Developments in many fields of science and technology occur at such a pace that frequently there is a long delay before information about them becomes available and usually it is inconveniently scattered among several journals. Developments Series books overcome these disadvantages by bringing together within one cover papers dealing with the latest trends and developments in a specific field of study and publishing them within six months of their being written. Many subjects are covered by the series including food science and technology, polymer science, civil and public health engineering, pressure vessels, composite materials, concrete, building science, petroleum technology, geology, etc. Information on other titles in the series will gladly be sent on application to the publisher.

Edited by

W.M.LEWIS M.Chem.A., C.Chem., F.R.I.C., F.I.W.E.S. WHO Consultant EURO, Environmental Health—Drinking Water Quality, Copenhagen, Denmark Managing Director, Coventry Chemical Consultancy Ltd, Coventry, UK


electronic. Barking. Series 628. Essex. “To purchase your own copy of this or any of Taylor & Francis or Routledge’s collection of thousands of eBooks please go to http://www.tandf.M. mechanical. 2005. stored in a retrieval system. Applied Science Publishers Ltd. ESSEX.ebookstore.—(Developments series).1′6 TD430 ISBN 0-203-97492-1 Master e-book ISBN ISBN 0-85334-903-7 (Print Edition) WITH 24 TABLES AND 54 ILLUSTRATIONS © APPLIED SCIENCE PUBLISHERS LTD 1980 All rights reserved. BARKING. without the prior written permission of the England . W. II. or transmitted in any form or by any means.” British Library Cataloguing in Publication Data Developments in water treatment. 2 1. No part of this publication may be reproduced. Lewis. or ENGLAND This edition published in the Taylor & Francis e-Library. photocopying. Ripple Road.APPLIED SCIENCE PUBLISHERS LTD RIPPLE ROAD. recording. Water—Purification I.

PREFACE ‘Surveillance of Drinking Water Quality’ published by WHO in 1976 in its introduction stated that ‘Public health protection of drinking-water supplies should assure that each component of the system—source. as far as is practicable. Trent and Rhine. that the water supply is not only aesthetically acceptable. in part at least. On the other hand if the quality of the supply water is from a lowland river. and employing perhaps the majority of the techniques described. treatment. or absence. to mention but three. The problem is compounded due to the fact that the toxic effects of many identified chemicals are insufficiently understood. risks to health from microbially contaminated drinking water have been dramatically reduced. then it follows that a combination of individual processes. the length of the list being limited only by the capabilities of the analytical chemists and their instruments. Chemicals present in raw water supply range from simple ions extracted from soil and minerals in the watershed to (in some instances) unidentified waste products from the chemical industry. Since the universal introduction of disinfecting agents in water supplies in developed countries. the resulting treatment. such as the three previously mentioned. a unique commodity in that the general population is normally permitted no freedom of choice. by the rapid progress in analytical chemistry and the environmental awareness of the general public resulting in the demand for the creation of standards of quality for drinking water. expert in the particular field. The ‘treatment process’ is not a single identifiable parameter but is dependent upon the nature and quality of the raw material and may for example involve only simple filtration or filtration plus disinfection. together with the air we breathe. Thus the responsibility devolving upon the shoulders of personnel responsible for ‘Treatment’ is to provide a process (or combination of processes) which will ensure. who has introduced his topic with a brief .. With rivers of the calibre of the Danube. Some medical researchers proclaim that the presence. Within this series will be found the various important facets of treatment each written by an author. commencing with coagulation for the removal of suspended matter. needs to be very sophisticated. so the assurance that the water available for drinking is of the highest quality is of paramount importance. Drinking water is perhaps. will be essential to provide the required quality of drinking water. Today the problem confronting personnel responsible for ensuring the public’s water supply is perhaps of a much more subtle character brought about. of a certain substance in drinking water is directly associated with the differences in death rates from specific diseases or the incidence of morbidity. etc. to provide drinking water whose quality is beyond suspicion. but also of the best chemical standard and in a condition which will not damage the integrity of the distribution system which could result in subsequent and additional contamination. storage and distribution—functions without risk of failure’.

to enable people to overcome the financial constraints laid upon them. W. The aim of the latter is to encourage and assist all countries of the world to adopt programmes with realistic standards for both quality and quantity and to provide water to all people by 1990.LEWIS . 1981–1990’. if possible. To achieve the above objectives will therefore strain the ingenuity and professional expertise of all concerned with the task of supplying the community with drinking water. It is a salutary thought that in 1975 (latest information available) some 78% of the world’s rural population and even 22% of the urban population were without an adequate water supply. many countries—not only the developing ones—are experiencing financial constraints of varying magnitude. It is unfortunate. but nevertheless true that at present.historical background before providing the reader with the most up-to-date information available on the subject. and for how long into the future we know not. Conscious of the urgent need to rectify these shortcomings. for within their pages will be found that information on ‘Treatment’. Of the urban population of the world having access to a piped water supply (77%). March 1977—urged the adoption of ‘The International Drinking-Water Supply and Sanitation Decade. 57% only had house connections and 54% of the population served by public piped supply received it only on an intermittent flow basis. the UN Water Conference—Mar del Plata.M. It is consequently singularly appropriate that these first two volumes on ‘Developments in Water Treatment’ should be available at this time. appropriate to the needs.


Disinfection A.D. Filtration T. Desalination M.H.A.HILSON 7.BURLEY and J.SHORT 3.TEBBUTT 2. Removal of Nitrogen Compounds R.PALIN 6. Sludge Treatment and Disposal M.S.COPE Index 1 22 53 79 122 142 162 189 .MORLEY and J.Y.J.B.J.CONTENTS Preface List of Contributors v x 1.T. Water Quality Monitoring P.MELBOURNE 5. Removal of Organic Compounds C.GAUNTLETT 4.


Sir M. M.COPE Scientific Officer.PALIN Consulting Chemist. NE3 4JL. B3 1SE. North West Water Authority. LS12 6DD. Olympia House. Station Road. A.O. Avon House. Box 363. Birmingham. UK. SL7 2HD. .TEBBUTT Senior Lecturer. Cannon Park.MELBOURNE Managing Director. Severn-Trent Water Authority.T.HILSON Principal Scientist. WA5 3LW. Newcastle upon Tyne.J. Oxon. P. Birmingham. UK.H.J. Newhall Street.S..BURLEY Consultant.A. B15 2TT. Department of Civil Engineering. UK.B. Water Research Centre. J.SHORT Yorkshire Water Authority. UK. UK. 165 Reading Road. Leeds. Bucks. CB1 2RS. Avon Division. Cambridge. Dawson House. Tame House. Demeter House.Y. Warrington. Melcon Water International Ltd. Medmenham. R. Henley-onThames. CV4 7EJ. Severn-Trent Water Authority. J. De Montford Way.GAUNTLETT Treatment Division. UK. Marlow. Headquarters Staff. UK.D. C. The University of Birmingham. T. UK. Gelderd Road. P. RG9 1DP. Montagu Avenue. UK. 7 Montagu Court.MORLEY Principal Scientist.Mac Donald & Partners.LIST OF CONTRIBUTORS M. Water Treatment and Supply. Coventry. Great Sankey.

TEBBUTT. to be shortly followed by the rapid gravity filter whose basic design has not changed greatly to the present day. A consequence of obtaining deeper penetration of suspended matter into a filter bed is the need to ensure adequate cleaning arrangements. By 1870 the rapid pressure filter concept made its appearance.S. . since the introduction of filtration as a water treatment process a considerable amount of knowledge has been accumulated about the behaviour and performance of the process. Indeed.C. Good filtrate quality can be achieved at higher loadings than would have been considered possible some years ago and the advent of dual and multi media beds has brought economic benefits. the principle of filtering rain water through a layer of porous material to remove suspended matter has been used for centuries although the first recorded purpose-built sand filters for a public water supply were not installed until 1804 in Paisley. M.Y. The early installations were of the slow filter type and their considerable purification ability in no small way contributed to the great improvement in public health which occurred during the second half of last century. S.I. in operational and economic terms. The University of Birmingham. Filtration through porous media is however a process of great complexity and it is not yet possible to produce a completely satisfactory theoretical model. INTRODUCTION Some form of filtration is almost certain to be incorporated in the treatment used to produce potable water from most surface water sources. Senior Lecturer..Chapter 1 FILTRATION T... B. Birmingham. M. Ph.E. Department of Civil Engineering. The complexity of the filtration process is such that mathematical models cannot as yet provide a universal solution for any situation but their existence is of value in helping to develop more efficient filtration plants.H. 1.D. and the demands for higher quality filtrates have meant that a variety of developments to and modifications of the conventional filtration process have been introduced.Sc. UK SUMMARY Developments in water filtration have enabled a more efficient use of the process and have provided a better understanding of the mechanisms involved..I. The continuing pressures to require more efficient treatment. However.1.M.W. A consequence of more effective use of bed capacity is that the process is more likely to be influenced by the nature of the suspended solids in the feed.E. Coupled with these developments has been an intensive study of the actual mechanisms involved in filtration with the aim of providing a better understanding of the process to aid in future design.

Developments in water treatment—2 2 1. The adoption of tertiary filters has encouraged a considerable amount of research into design and operational factors which has enhanced knowledge of the filtration process. In the USA the National Interim Drinking Water Standards lay down a mandatory turbidity limit of 1 unit for most surface-water-derived supplies. With high turbidity raw waters. With low turbidity raw waters direct filtration using either gravity or pressure rapid filters aided by chemical coagulation is widely used and in parts of the UK and Europe slow sand filters are used either as a single stage of treatment or as a second stage following rapid filtration used as a roughing or preliminary stage of treatment. sometimes almost exponentially. even high quality impounded waters would need turbidity removal for much of the time and all lowland river derived supplies would necessitate comprehensive treatment for turbidity removal.2. removes a considerable amount of the suspended solids which escape from final settling tanks together with the organic matter associated with these suspended solids. It is of interest to note that developments in wastewater purification have resulted in the adoption of filtration as a tertiary treatment stage in situations where the effluent is discharged to a receiving water with little dilution or which provides a raw water source some distance downstream of the outfall. at least at times. In such circumstances sand filtration. including filtration. EEC standards set out a guide level of 5 FTU with a maximum admissible concentration of 10 FTU. follow a law of diminishing returns in that the unit cost of successive increments of purification increases. The American Water Works Association has adopted a turbidity goal of 0. Before setting stringent turbidity levels it should therefore be considered whether such levels are achievable by normal means of treatment and whether the cost of such treatment is justifiable in respect of the marginal improvement in water quality which they would produce. Whilst all these types of filtration should be able to produce filtrates with turbidity less than 1 unit the reliable production of turbidities less than 0·1 or 0·05 units is another matter. With coloured upland sources. chemical coagulation and sedimentation are commonly employed to remove the bulk of the turbidity with filtration providing the final polishing stage to bring turbidity down to around 1 unit. usually in rapid gravity units. . Thus a normal secondary effluent of 30 mg/litre suspended solids and 20 mg/litre biochemical oxygen demand can be polished by filtration to give a final effluent of around 10 mg/litre suspended solids and biochemical oxygen demand. turbidity in the raw water may not be a serious problem but chemical coagulation is frequently used to remove the colour by what is in effect a precipitation process so that here again filtration is necessary following sedimentation. It is important to appreciate that most treatment processes. APPLICATIONS OF FILTRATION Except in rare cases all surface waters will contain.05 units. The rationale behind the adoption of such low turbidity levels is not that the turbidity itself is likely to be harmful but that its presence may inhibit disinfection processes.1 units and it has been suggested that this may in the future be reduced to 0. sufficient suspended matter to given turbidities in excess of 5 units which is the highest desirable level stipulated in the World Health Organisation International Drinking Water Standards. With such limits for turbidity being required.

Filtration 3 1. The long interval possible between cleaning procedures enables biological activity to become established in the bed particularly in the surface layers where a biological slime. the schmutzdecke. 1. Because of this low hydraulic loading there is only superficial penetration of suspended matter into the bed and filter runs of several weeks or even months are TABLE 1 CHARACTERISTICS OF CONVENTIONAL FILTERS Characteristic Filtration rate Size of bed Depth of bed Sand size Uniformity coefficient Head loss Length of run Cleaning water consumption Slow filter Rapid filter 1–4 m3/m2d About 2000 m2 1m unstratified 0·5–1·0 mm 2·0–2·5 Up to 1 m 20–90 days 0·2–0·6% of output 100–150 m3/m2d About 100 m2 0·5–0·8 m stratified 0·5–1·5 mm 1·2–1·5 Up to 2·5 m 1–5 days 1–6 % of output possible before excessive head loss terminates operation. so called because of its relatively low hydraulic loading of 1–4m3/m2d. the first form of sand filter was the slow type. Nitrification of ammonia is also usually a feature of slow sand filtration and this can make the ensuing disinfection stage more reliable. CONVENTIONAL FILTRATION Before discussing recent developments in the filtration of water it is useful to briefly outline what may be considered as conventional usage which had not changed greatly until the early 1970s and which is summarised in Table 1. The usual depth of water above the sand surface is 1·0–1·50 m so that when the head loss approaches this figure filtration must be stopped to prevent the possibility of sub-atmospheric pressures being created within the bed with consequent deterioration in performance. In addition the biological growth utilises organic constituents in the water as a food source oxidising them to inorganic end-products and often preventing or reducing possible taste and odour problems in the finished water.1. which would be all that would be likely to be present in a potable water source. the small addition of nitrate to the .3. contributes significantly to the removal of fine suspended matter.3. Slow Filters As indicated earlier. With small levels of ammonia. The bed can be restored to operation by scraping off the top few cm of sand which can be washed and later used to replenish the bed.

For low turbidity raw waters rapid filtration alone. Alternatively. Fortunately. In the UK.3. For this reason it is imperative that they are only used for relatively low turbidity (10–20 units) raw waters. This does of course mean that a much larger . the bulk of the turbidity is removed by preliminary coagulation and sedimentation processes which prolong filter runs. Rapid Filters The introduction of rapid sand filters no doubt arose partly from the seemingly inevitable trend to increase the capacity of treatment units and the need to handle high turbidity raw waters. rapid pressure filters with direct injection of coagulants find favour in hilly areas where their hydraulic characteristics prove useful when siting treatment plants but in other parts of the world pressure filters tend to be mainly used for industrial water supplies. penetration of solids into the bed is considerable and clogging to a maximum allowable head loss takes only a day or two depending upon feed quality. The result was the rapid filter with a hydraulic loading of around 100 m3/m2d. the cleaning of slow filters is a costly operation. At this rate of flow. The deep penetration of solids and frequent need for cleaning would of course rule out the type of cleaning operation used for slow filters. by chemical coagulation and sedimentation units. possibly with the addition to the raw water of a small dose of coagulant. 1. Because of this limitation. As mentioned in the previous section. can provide a filtrate of satisfactory quality. rapid gravity filters are also used as the primary stage in a double filtration process. penetration of turbidity may be complete resulting in breakthrough of suspended matter in the filtrate which will terminate the run even though the head loss limit may not have been reached. In the Netherlands slow filters have found considerable application as the final treatment stage when purifying heavily polluted river waters such as those from the Rhine.2. backwashing results in a stratified bed which is not desirable from the point of view of optimum utilisation of bed capacity but which has been generally accepted as a characteristic of rapid filtration. The bulk of filtration capacity worldwide is in the form of rapid gravity filters preceded. however. where appropriate. In most cases.Developments in water treatment—2 4 finished water is unlikely to be objectionable although of course levels of nitrate nitrogen of more than a few mg/litre are to be viewed with suspicion. the incorporation of backwashing systems was able to provide a practical and economical means of cleaning rapid filters. slow filters are not normally suitable for sources such as lowland rivers with high turbidities which usually require chemical coagulation since the additional carry-over of floc from settling tanks would be sufficient to rapidly clog the filter surface. When using the normal bed of graded media. however. The land area required for slow filters became a factor when constructing treatment plants for large communities so that considerable pressures were exerted on designers to develop more compact units. The increased dependence on lowland sources has resulted in a decline in the use of slow sand filters in many parts of the world. Because of their large size slow filters are labour intensive as regards cleaning operations and although a number of plants have been equipped with mechanical scraping devices. In the case of pressure filters separate coagulation and sedimentation tanks are not feasible so that the coagulant is dosed directly into the raw water and flocculation takes place largely within the filter bed. However in the UK much of London’s water is treated by slow filters which follow primary rapid filters.

1. Thus in a sand bed with grain size of 0·5–1·0 mm the voids are likely to be of the order of 100–200 µm. therefore. These units can give excellent turbidity removal and are found suitable for small potable supplies in some parts of the world. The units are relatively small in size and can provide an economic form of treatment for low turbidity supplies. In operation it may be beneficial to dose the raw water with a small concentration of the filtering medium. An important feature of rapid gravity filters is the arrangement made for backwashing and in particular the design of the underdrain and filter floor. Removal of suspended particles is controlled by a number of transport and attachment mechanisms. . The transport mechanisms move particles into the vicinity of grains of medium in the bed when the attachment mechanisms can operate to trap the particle. Clearly. THE FILTRATION PROCESS At first sight the manner in which a bed of porous medium removes suspended particles from a fluid passing through the bed might appear to be easily explained as some form of straining action. employs diatomaceous earth or cellulose powder deposited on rigid formers as the filtering medium. if the suspended particles are larger than the voids in the bed they will be removed in the same way as a sieve prevents the passage of particles larger than the mesh size. It is important that the active filter medium is supported in such a way that it is contained within the filter shell whilst preventing any short circuiting of flow during filtration or backwashing. removal of fine colloidal particles such as silt and bacteria with sizes of about 1 µm are readily demonstrated. The commonest system in the UK is to employ a concrete floor with plastic collection and distribution nozzles covered by a layer of graded gravel but there are a considerable number of proprietary filter bottoms. In such a bed. It is evident. A variation of the pressure filter. that particles very much smaller than the voids in the bed are effectively removed. used quite widely in the UK for swimming pool water treatment. The omission of these units does however give a cost reduction to offset the shorter filter runs and more frequent washing required by pressure filters. At the end of a run the medium together with the trapped suspended matter is discharged to waste and the filter element recoated with powder. There are also variations in the form of filter control and backwash procedures adopted by different manufacturers and designers. Examination of the solids removal performance of a granular bed shows. notably in the USA. Such a removal mechanism would mean that no penetration of solids into the bed could occur and that there would therefore be no need for a deep bed of medium. Some of these are of complex and costly design and it is by no means certain that any advantages they may have are cost effective.Filtration 5 amount of suspended matter is trapped by the filters and thus filter runs are much shorter than if the same water were treated by conventional gravity filters preceded by coagulation and sedimentation units. however.4. that straining cannot be the only mechanism operating in a bed of granular medium and indeed in most situations straining plays a relatively insignificant part in the overall removal of turbidity.

Sedimentation: gravitational forces acting on particles can move them across streamlines and bring them to rest on upward-facing grain surfaces. molecular forces are only likely to be important when the particle has approached very close to the grain surface. 3. In practice. changes in temperature can significantly alter the effectiveness of transport mechanisms. It is postulated that attachment is due to the interactions between the approaching particles and the bed grain as a result of the molecular attractive forces and the electrokinetic forces. 2. These can be modified by alterations in the ionic strength of the system resulting from the addition of coagulants or pH control. Diffusion: colloidal particles are influenced by random Brownian movements which may bring them into the vicinity of the grain surface.4. Thus the concepts of bridging and double layer formation in coagulation can be used to explain the entrapment of particles in a granular bed. This mechanism is only important for very small particles (<1 µm). 4. Hydrodynamic: particles in a velocity gradient tend to rotate and are thus subjected to lateral forces which can move them across streamlines. Interception: streamlines may pass close enough to bed grains so that suspended particles actually come into contact with the grain surface. Transport mechanisms thus have to be able to move suspended particles out of the flow streamlines into lower velocities near the bed grains. Thus particles which are not successful in reaching a grain surface in the upper layers of a bed may so change in characteristics that they become trapped lower down in the bed. 1. The nature of the voids in a granular bed provides continual changes in direction and velocity of flow so that particles may grow in size owing to flocculation as they penetrate into the bed. .Developments in water treatment—2 6 1.2. Transport Mechanisms In most filters laminar flow conditions prevail and thus the velocity in a void within the bed varies from zero at the grain surface to a maximum at the centre of the void. Thus the forces between the charged particles are mainly responsible for controlling the progress of the attachment process.1. Because of the relation between viscosity of water and temperature. Variation of the electrokinetic force depends upon the sign and magnitude of the surface charge and the thickness of the double layer. probably within 0·1 µm. In addition the use of polyelectrolytes can introduce bridging mechanisms which can bind particles to the grain surfaces.4. The important transport mechanisms in water filtration are: 1. attachment can take place under the influence of physico-chemical and molecular forces similar to those which operate in the coagulation process. With most natural waters containing significant dissolved solids the charges on suspended particles and filter grains are probably fairly small so that only weak repulsive forces are produced. Attachment Mechanisms Once suspended particles have been brought into close proximity to grain surfaces or existing deposits.

4. R=Reynolds Number (υd/v).3. v=kinematic viscosity. Ives and Gregory2 have shown that this additional head loss is a linear function of the specific deposit. When a filter receives water containing suspended matter some or all of these solids will be trapped in the bed thus reducing the void space and increasing the head loss (Fig. where E=150[(1−f)/R]+1·75. Schematic arrangement of gravity filter. . f=bed porosity. 2). 1. ψ=particle shape factor=(surface area of sphere volume V/surface area of bed grain volume V). d=characteristic dimension of bed grain. Filter beds are normally composed of a graded medium so that eqn (2) must be solved as a stepwise integration between adjacent sieve sizes. σ. The Carman-Kozeny equation predicts the head loss characteristics of a clean bed with single-size medium. In these circumstances the total head loss across a bed is the composite of the ‘clean’ head loss plus an additional head loss due to deposits within the bed. D’Arcy’s relationship for head loss per unit depth is (1) where h=loss of head in a bed of depth l with face velocity υ. 1.Filtration 7 1. in the bed. and k =coefficient of permeability. A more comprehensive relationship was developed by Carman1 based on the Kozeny equation (2) FIG. and g=acceleration due to gravity. Hydraulic Considerations A basic understanding of the hydraulics of filtration can be made by assuming a singlesize medium in the filter shown schematically in Fig.

Solids Removal In many respects it is the performance of a filter in removing suspended matter which is of primary importance and this is an area which has received considerable attention from research workers. H. across a bed containing deposited particles is given by (3) where H0=Carman-Kozeny head loss.4. and t=time. 2.Developments in water treatment—2 8 FIG.4. Head loss during filtration. 1. that the removal of suspended particles with depth in a filter bed is proportional to the concentration of particles in suspension. .e. (5) where c=concentration of particles at depth/in bed. For graded medium the expression is basically similar but replaces K with another factor to express the effect of size grading. If the bed retains the majority of the particles in the feed Ives and Gregory2 showed that an approximate solution of eqn (3) for a unisized medium is (4) where C0=feed concentration to bed. and λ=a constant termed the filter coefficient. and K=a constant. Specific deposit is defined as the volume occupied by deposit in the bed per unit bed volume. Most considerations are based on the proposition. Thus the total head loss. i. originally formulated by Iwasaki3 for slow filters.

11 is customary to remove about 10 mm of the sand which contains virtually all of the deposit and this material is washed and replaced on the bed when necessary. and fe=porosity of expanded bed. In the final stage of a run velocities in the voids increase to the point where previously deposited material is scoured. Nevertheless the models which are available can be useful in helping to produce more economical design and operating procedures. Further increase in backwash flow will increase the expansion of the bed but will not necessarily give better cleaning action since the scouring effect may be reduced at large expansions. As the backwash starts the bed begins to expand and the head loss increases until the whole bed is just suspended in the upflow. The upward flow of water produces an expansion of the bed to give a fluidised state in which the voids are increased in size and a considerable scouring action occurs with resultant release of deposits from the bed grains. Filter Cleaning In all filters the accumulation of deposits in the bed will eventually terminate the run either owing to a maximum allowable head loss being reached or owing to breakthrough of suspended matter with consequent deterioration in filtrate quality.6 Camp. 1.Filtration 9 Ives4 has developed this concept to permit modelling the filtration process in three stages. In hot climates higher upflow velocities are used because the reduced viscosity at elevated temperatures hinders expansion.7 Mohanka8 have produced variations on the theme of a physical model of the filtration process but in spite of intensive study the complex nature of filtration has meant that it is not yet possible to obtain a reliable predictive model for universal application.5. This drag force is a function of the velocity onto the bed and the . With slow filters breakthrough is unlikely so that the run will be terminated on a head loss criterion. ρw=mass density of water. and β. An initial spherical grain format changes to a situation analogous to flow through capillary tubes as deposits accumulate in the voids. Backwashing of rapid filters is achieved by introducing filtered water into the bottom of the bed at relatively high rates of flow to give superficial velocities of 0·3–0·5 m/min. The bed grains are kept in suspension because of the drag force exerted on them by the upflow of water. y.5 Deb.4. x. ρs=mass density of bed grains. z are empirical constants. At this point the upward force of water balances the gravitational force on the grains suspended in water. The mathematical expression of this concept can be developed to give the relationship between the filter coefficient at some stage of the run and the initial filter coefficient (λ0) at the start of the run (6) where σu=ultimate specific deposit. At the point of fluidisation hegρw=le(ρs−ρw)g(1−fe) (7) where he=head loss in expanded depth le. notably Minz. Several other workers.

An empirical relationship for the expansion of a unisize grain bed of normal depth l given by Fair et al. With a conventional graded bed each layer is carried into suspension in turn as the wash rate increases and an arithmetic integration of eqn. will be reached long before the majority of the voids have been utilised. prior to and sometimes together with the water wash. Most of these developments have been related to rapid filters since the nature of the slow filter gives less scope for useful change.5. Effective Use of Bed Capacity The inevitable consequence of backwashing a bed of graded medium is that the grains settle to give a stratified bed with the finest particles at the top and the coarsest at the bottom. This does not give efficient use of the voids in that a limiting terminal head loss. The use of larger media in itself does not alter the basic characteristic of a downflow bed of graded material in that the bed becomes less efficient in terms of solids . In the USA. Over the last few years there have been a considerable number of developments in configuration. It will be apparent that the process is one of considerable complexity and as such the performance of a filter is likely to be influenced by many parameters.Developments in water treatment—2 10 expanded porosity. TRENDS AND DEVELOPMENTS IN FILTRATION The preceding sections have set out some of the basic factors governing the process of filtration as it is conventionally used for the production of potable water. A number of modifications to the conventional filter could provide a means of increasing the penetration of solids into the bed and hence providing fuller utilisation of the void capacity. 1. largely due to clogging of the relatively small voids in the upper layers of the bed. and υs=bed grain settling velocity.9 is (8) where υe=wash rate as superficial velocity. give efficient cleaning. The use of larger filter media allows increased penetration and the size of individual voids will be greater. The total volume of voids will however remain the same if the grain shape and packing are unaltered. air scour was not common in the past and it was customary to use much higher wash rates to give bed expansions of up to 50% often supplemented by surface wash arrangements. design and operation of filters aimed at improving their efficiency and cost effectiveness whilst maintaining or even improving filtrate quality. 1.5. (8) between sieve sizes is necessary to determine the overall expansion produced by a particular wash rate.1. There seems little justification for such excessive expansions which must be costly to provide both from capital and operational aspects. The specific surface of the larger grains will be less so that particles of suspended matter are less likely to be trapped in any given void. UK practice is to operate with bed expansions during backwashing of around 20% which when supplemented by air scour.

both of which techniques are now well established. to improve utilisation of bed capacity. Provided the characteristics of the suspended particles are suitable in respect of size. In operation the bulk of suspended particles should TABLE 2 TYPES OF FILTER MEDIA Material Polystyrene beads Anthracite Sand Garnet Ilmenite Specific gravity 1·04 1·4–1·7 2·5–2·6 3·8 4·8 Typical size range (mm) 1·5–3·5 1·0–2·5 0·5–1·5 0·3–0·7 0·3–0·7 be trapped in the anthracite layer with its relatively low head loss per unit depth. floc strength and physicochemical properties. Table 2 gives examples of types of media which have been used in water filtration for this purpose. These aims can be achieved in several ways. With such an arrangement good separation of the layers can be maintained even after vigorous backwashing. By far the most popular combination of media is anthracite and sand usually aranged as about 0·3 m of 1·25–2·50 mm anthracite above a similar depth of 0·50–1·00 mm sand. by selection of appropriate materials and gradings.Filtration 11 removal in the direction of flow. the filtrate quality from a dual media bed is usually the . Increased specific surface in the direction of flow can be achieved by using dual or multi media downflow beds or by using a graded single medium in an upflow configuration. Dual and Multi Media Beds By using more than one medium in a bed it is possible. The essential need is a way of either increasing the specific surface in the direction of flow or of reducing the velocity in the direction of flow. There are also clearly limits as to the amount by which grain size can be increased before breakthrough of solids becomes a problem. Reduction of velocity in the direction of flow can be obtained in radial flow filtration which to date has had only limited application. Figure 3 shows the advantage of a dual media filter over a single layer unit in terms of run length for a specified terminal head loss. the sand layer in effect serving as a second stage filter.

The latter approach has achieved some popularity in the USA in the form of a proprietary filter incorporating carefully sized layers of anthracite. Tebbutt.10 However it should be appreciated that at high filtration rates more of the particles may penetrate into the sand layer causing a more rapid increase in head loss and/or early breakthrough. The influence of filtration rate on removal of suspended matter does not appear to be great at least when relatively large floc particles are concerned. This can be accomplished by adding a coarse polystyrene bead layer to the top of an anthracite-sand bed or placing a layer of fine garnet or ilmenite at the bottom of an anthracite-sand bed.11 A natural extension of the dual media principle is to add a further layer or layers to the bed in an effort to produce the desired decrease in void space with increasing depth into the bed. sand and garnet in such a way that there is a degree of intermixing between layers and sharp . In this way it may be possible to double the capacity of a filtration plant at a cost much less than the construction of duplicate single medium filters. Head loss relationships for single and dual media beds of same overall depth. A comprehensive review of the use of anthracite in water filtration has been produced by the Water Research Association. or alternatively permit operation of the dual media bed at higher filtration rate for the same length of run. 3. This latter feature can be of particular value in uprating the capacity of an existing filter installation by removing half the original sand and replacing it with a layer of anthracite.Developments in water treatment—2 12 FIG. The lower initial head loss and more efficient usage of the voids in a dual media bed permit longer filter runs than with a single medium bed at the same filtration rate. same as that produced by a single layer bed of the same overall depth using the same sand.

The three layer bed gave up to twice the length of run achieved by the dual layer bed for the same filtrate quality (<0. 180–360 m3/m2d. against which the bed grains arch under filtration. . The basic problem in upflow filtration is that of preventing the upward flow of water from expanding the bed as occurs during backwashing. in effect. Conley and Hsuing12 have described the design of such beds which are stated to be more efficient than dual media installations. Upflow Filters To overcome the undesirable effect of stratification produced by backwashing of a graded bed an obvious solution is to alter the direction of filtration from downflow to upflow so that the small voids on the top of the bed will only receive particles not trapped in the lower regions of the bed. and it was noted that differences in performance between the two beds were not apparent at the higher rates because then more suspended solids were carried through to the sand layer in both units. Fig. It is thus necessary to limit the filtration rate to avoid this effect or to provide some means of holding the bed in place to prevent expansion during filtration. The studies were carried out over a range of filtration rates. The principle of upflow filtration has been known for a considerable time and indeed some units were in operation in the eighteenth century.5 FTU) owing largely to prevention of surface clogging which took place in the dual layer unit. Some pilot scale studies have recently been undertaken in the UK and have been reported by Lekkas et al. The Immedium filter achieves this end by the insertion of a coarse grid in the top of the bed. In practice it would appear that dual media beds are the most cost effective way of improving the utilisation of a downflow filter but it should be realised that such a bed may be more sensitive to changes in loading and nature of suspended solids than a conventional single-medium bed which has. Since then a considerable number of Immedium filters have been installed for both potable water treatment and tertiary treatment of effluents. At the higher backwash rates the arched grains are no longer able to resist the upward force so that expansion can proceed normally.13 In this work the performance of anthracite-sand and polystyrene-anthracite-sand beds were compared when treating low turbidity (usually about 3 FTU) stored water. Multi media beds have received little interest in the UK partly owing to the increased cost and also to the law of diminishing returns which affects all treatment processes. It was however not until the advent of the Immedium unit in the 1950s that upflow filtration became more than a curiosity. 4(a).Filtration 13 interfaces are thus avoided. a fairly high inbuilt factor of safety.

4. The downflow portion of the bed is usually about a quarter of the total bed depth and it is claimed that the biflow process gives savings in capital and operating costs of 15–30% as compared with conventional downflow filters. There may however be need for care in operation to prevent sudden breakthrough and variable quality raw waters could cause problems in this respect. with retaining grids above both layers. Studies by Gregory et al. Ray16 reports that by using dual media biflow units. flow rates of up to 350 m3/m2 d were used successfully and good filtrate turbidities of less than 1 FTU were obtained from a variety of raw waters. An American upflow unit. Pilot studies showed that a filtrate of less than 0·1 FTU could be produced from polyelectrolyte-dosed Mississippi water at filtration rates of up to 500 m3/m2d. (b) AKX or biflow filter. 4(b). 0·9 m of 1·8 mm and 0·9 m of 0·95 mm. filtration rates of up to 430 m3/m2 d have been achieved in the USSR.Developments in water treatment—2 14 FIG. has been described by Haney and Steimle. Because of the high bed capacity and full solids penetration efficient backwashing is particularly important for upflow filters. It was however felt that because of the nature of the upflow filter its use as the final filtration stage in place of rapid gravity units would not be really suitable. Here a portion of the flow is fed into the top of the filter as in a normal downflow unit and serves to prevent expansion of the remainder of the bed under the influence of the upflow. Fig. (a) Immedium type upflow filter. A rather different approach to upflow filtration has been developed in the USSR as the biflow or AKX filter. Radial Filters In a radial filter with inlet at the centre and outlet round the periphery there is a decrease in velocity of flow as the water moves outward through the bed. In the investigations.14 show that upward flow filters do have a high bed capacity thus allowing long filter runs. which were carried out on a pilot scale Immedium type unit. L’Eau Claire. This velocity distribution .15 This uses a dual-layer sand bed.

5. There are however operational problems with a fixed-bed radial flow system in that conventional backwashing cannot be carried out and thus some other form of cleaning would have to be devised.5. Radial flow filters in the form of fixed beds have received some experimental attention on a laboratory basis. A study in the USA by King et al. Typical radial flow filter with fluidised bed and continuous desludging by air lift. 5. Studies by Ives4 suggest that the performance of a radial flow bed would compare favourably with a FIG. Process Modifications In efforts to produce less costly forms of water treatment some interest has developed in the use of high rates of filtration. Ray16 quotes the use of fluidised-bed radial flow units for removing inorganic turbidity from a groundwater to give a finished water of about 50% lower turbidity than the feed which averaged 1·2 units.17 reported that many . 1. conventional vertical flow bed. Because of the cleaning problems associated with fixed beds. commercial development of the radial flow filter has been directed towards the use of fluidised bed units with continuous washing and recycling facilities. The Tenten unit is an example of this concept which is shown diagrammatically in Fig.Filtration 15 encourages greater penetration of suspended solids into the bed and thus should improve the utilisation of bed capacity.2. The commercial units are factory built and occupy relatively small floor area having a typical surface loading of around 300 m3/m2 d depending upon type and concentration of suspended solids.

Logsdon19 pointed out that the process was normally only suitable for relatively low turbidity raw waters. Work in Thailand by Komolrit et al. Culp. average turbidity for US plants was 25 FTU with average colour 20°H. Stump and Novak21 have emphasised the importance of the correct polymer to obtain optimum performance in direct filtration and found cationic high molecular weight compounds to be most satisfactory. and this work is continuing. the filtration of raw water usually with the addition of coagulant and polyelectrolyte. The more recent studies have been concerned with determining the potential of direct filtration when aided by the modern armoury of polymers. It seems likely that the water supply needs of developing countries can in many instances . Increasing Gt values of up to 2·7×105 gave no further improvement in filtrate quality although the floc particles so formed were visibly larger. Pilot scale studies by Vianna23 have shown that when treating the same raw water a direct filter may be able to produce a better quality filtrate than a conventional plant. Paramasivam and Sundaresan24 have shown from studies in India that slow filters operating at rates of between 2·4 and 7·2 m3/m2 d will produce a filtrate of less than 1 FTU from an input of up to 30 FTU. i.20 however.18) where at filtration rates of up to 800 m3/m2d little correlation was found between filtration rate and suspended solids removal. The importance of the correct type of floc for input to a direct filter has been emphasised by Treweek22 who found that a Gt value of 4·2×104 was adequate to produce a filtrate turbidity of less than 0·1 FTU. Economic advantages could result from the abandonment of the sedimentation stage with at least certain types of water currently using conventional treatment.25 has shown that input turbidities of up to 50 FTU can be handled by slow filters but that capital costs are still high. Frankel26 has described a two stage filtration system capable of dealing with raw waters of 100–400 FTU without the need for chemical coagulation. Here the simplicity of construction and operation may counterbalance the high capital cost. suggested that direct filtration could satisfactorily handle poorer quality raw waters and indicated practicable limits of 100–200 FTU.Developments in water treatment—2 16 regulatory authorities viewed filtration rates in excess of about 175 m3/m2d as being high rate but that some authorities were prepared to approve filtration rates of up to 570 m3/m2d. A revival of interest in slow filtration has resulted from WHO-sponsored studies in a number of developing countries.13 There is clearly need for comparative studies to be undertaken on the performance of conventional coagulation. The first roughing filter operates at 30 m3/m2d and the second polishing filter can operate at 2–30 m3/m2d. Final filtrate quality of less than 0·3 FTU was achieved and the inexpensive media could be replaced about once a month in the roughing filter with the polishing filter only requiring removal and replacement of the superficial layer about 30 mm deep at the same frequency. To reduce capital cost local media such as shredded coconut husks or burned rice husks have satisfactorily replaced sand. sedimentation and filtration plants with those using coagulation and direct filtration. The process is not of course new in that pressure filters must operate in this manner and direct filtration of good quality raw waters on rapid gravity filters has been employed for years. 100°H.10 West et al.e. In the UK most studies of high rate filtration have been carried out for tertiary treatment purposes (Tebbutt. Considerable interest has appeared recently in the USA in the direct filtration process. with turbidity and colour together not exceeding 25 units each. Recent UK pilot studies on direct filtration of stored water of about 3 FTU turbidity have been reported by Lekkas et al. Of 16 plants surveyed only one had average filtrate turbidity greater than 1 FTU although five exceeded 1 FTU at least once a year.

filter runs are longer and capital and operating costs are lower.3. It seems likely that this type of control would certainly be more appropriate than the conventional constant-rate method for developing country situations. The additional capital cost of the extended shell depth is a disadvantage of this type of operation. 1. The optimum porosity for cleaning was found to be about 0·70 which for a graded sand would be likely to occur at 40–50% expansion of the top layers. Provided the backwashing of beds is staggered. In particular a decline in filtrate quality towards the end of a run does not occur. a reasonably constant output will be maintained from a battery of several filters and the process is claimed to offer a number of advantages over constant rate operation.5. In the case of rapid filters virtually continuous adjustment of control valves is necessary to maintain constant filtration rate.Filtration 17 be best satisfied by the adoption of such forms of appropriate technology using local materials and skills wherever possible. As the run proceeds and filter head loss increases the hydraulic control is gradually relaxed so that the overall head loss through filter bed and controller remains constant. Constant rate filtration can be achieved by using a deeper filter shell and allowing the top water level to increase as the head loss in the bed builds up. Various proprietary devices are available which provide a high head loss at the start of a run when the filter head loss is low.4. In declining rate filtration using a battery of filters a fixed top water level is used so that as the bed clogs the output declines. In spite of these claims relatively few declining rate installations have been built in the UK although they are more popular in the USA and Japan. Arboleda27 has discussed the various forms of hydraulic control techniques used in filtration and concluded that declining rate filtration did offer advantages over constant rate operation. . Backwashing The development of more effective filtration techniques with greater penetration of suspended solids into the bed leads inevitably to the need to ensure that the bed is efficiently cleaned. Flow to the filter is set at a constant rate with free discharge over a weir into the shell. This feature of rapid filtration has normally been catered for by provision of some form of automatic flow controller to ensure constant output. These flow control units are relatively expensive and are not always trouble free so that simpler forms of filter control are becoming more popular. 1. In a basic study by Amirtharajah28 it has been stated that the main cleaning mechanism in a backwashing situation is hydrodynamic shear and that abrasion between grains is negligible. Filter Control Because of the long runs achieved by slow filters the hydraulic characteristics do not change significantly from day to day and thus manual adjustment of the throughput is satisfactory. The growing use of granular beds for the filtration of wastewater effluents has also placed increased demands on cleaning arrangements since the organic nature of the deposits can result in difficulties in their removal from filter media.5. At the other end of the scale the automation of filtration plants is becoming increasingly common with large installations being equipped with process control and monitoring facilities to handle both filtration and backwashing stages of operation.

media type. These include: feed water characteristics. etc.5. The cost of a filtration plant will be influenced by such factors as: number of units. backwash arrangements. The last method was found to be most effective for relatively coarse sand beds although there was some danger of loss of media because of the violence of the air and water action. The intersection of the two curves . Gould and Patterson30 studied three backwash methods on a laboratory scale using an iron floc to provide the deposit. It was felt that the simultaneous air and water wash was likely to give the best long term performance. Both filtrate turbidity and head loss have limiting values the exceeding of which will necessitate termination of a run. required filtrate quality. required output per cycle. valves. The first and third techniques gave better cleaning than the water only wash even though a high velocity wash was employed.5. Optimum operational performance will occur when both of these limits are reached simultaneously. Amirtharajah and Cleasby31 have described a modified model of backwashing which predicts the required wash rate from knowledge of media characteristics and the density viscosity of the backwash water. controls. rate of flow. air scour followed by water. surface and subsurface wash before and during main wash. water at 0·8 m/min for 5 min. simultaneous air scour and subfluidisation water wash. 6 which relates the depth of bed and the length of run to satisfy the filtrate quality and head loss criteria. length of run. and air at 0·9 m/min with water at 0·32 m/min for 5 min with the water continuing alone for a further 5 min. Design Methods Because of the complex nature of the filtration process many parameters can affect performance. 1. Cleasby and Lorence29 carried out a long term study of backwashing techniques for tertiary effluent filters. Procedures used were: air scour at 0·45 m/min for 3 min followed by water at 0·32 m/min for 5 min.Developments in water treatment—2 18 Backwashing with water alone was found to be an inherently weak process and air scour or surface wash were felt to be indispensable for effective cleaning. In terms of optimised design it is important to appreciate that in general there will be a gradual rise in filtrate turbidity as a run proceeds together with a rise in head loss across the bed. costs of construction for filter shells and for pipework. filter bottom and gravel layer. It is of interest to note that this simultaneous technique is popular in Europe although for it to be applied successfully care must be taken with the design of the underdrains. operating temperature range. Techniques studied were: water wash only. grading and arrangement. By using pilot-scale filters or mathematical models it is possible to produce plots of the form shown in Fig. available head.

(Fixed filtration rate and single-size medium.34 A problem which arises in filtration work is that of characterising the . Adin33 has described a technique for predicting filter performance in an optimum design using the similarity which exists between turbidity breakthrough in a filter and the breakthrough pattern in an adsorption bed. The design of such studies has been detailed by Ives. 7). Since the various mathematical models of filtration which have been produced tend to be restricted in application to special circumstances it is generally agreed that information for use in optimising models is best obtained from pilot studies using the actual media and water under consideration. Ives32 has recently given a full description of this procedure and has considered in some detail the economic optimum design of filters. Additional points are obtained for different filtration rates and different media with the end-product being capable of expression in the form of a response surface which shows the operational optimum conditions (Fig.Filtration 19 FIG.) provides the optimum solution for a given filtration rate and medium. Determination of optimum bed depth and filter run based on head loss and filtrate quality criteria. 6.

J. D. GEYER. TEBBUTT. nature of the suspension to be treated. J. 81. 1937. 95. K1.. Sanit. A.Instn Chem. P.J. J. Water Treat. 16. This concept can also be used to relate the filterability of a suspension to filter media taking into account clarification clogging and flow rate as described by Ives. Water Supply Assoc.A.. K... 1971.M. Medmenham. J. and HSUING. 1967. 61. 8. 15. Water Res.Developments in water treatment—2 20 FIG. 8th Congr. 7. 1969. 399. Soc. W. CAMP. 1. 1. 1079. Waste Water Engineering. Int. Water Supply Assoc.Y.H.. This factor was appreciated during the development of microstrainers with the introduction of the filterability index. Soc.C. Engrs. Proc. CONLEY. Sanit. Response surface for optimum filter design. 150.. 2. Div.. 1972. Anthracite Sand Filtration. 6th Congr. WRA. 1967. Trans. 1591. Eng. G. Int. 4. and GREGORY. Water Works Assoc. 1964.35 REFERENCES 1. IWASAKI. Proc. Water Purification and Waste-Water Treatment and Disposal.J. New York.. Civil Engrs. Div. MOHANKA. IVES. E1. Amer. Vienna. Div. J. Soc.... Sanit.. FAIR. 9. J. 2. Conference Papers. T. Am. K. Exam.Amer. J. 90. 5. 1964... Eng. 1969. Proc. IVES.. Am..M. 1937. and OKUN. DEB. John Wiley. 3. 10. 12. 1969..C. S. 95. K. 1969. 6. CARMAN. Stockholm. 97. T. Water Works Assoc. 1.R. 7. Eng. UK.. MINZ. Civil Engrs. 11.. Water Research Association. Soc. T.R. . 29. 5.K. Civil Engrs. Am... 147. D.

239. Eng. 339. WRA. IVES.. and MILLER.C. 1978.G. R. Separn..H. Div.W. STUMP. and NOVAK. K. G. 28.. Water Works Assoc. Amer. A. Water Works Assoc.Sc. 66. 479. in Mathematical Models in Water Pollution Control. and CLEASBY.. J. 1978. Div. 20. 375. 749. R. W. 30... UK. IVES. and SUNDARESAN. 83.S. 35..J... 552. LOGSDON. and REHBERGER. CULP. J. Effl. 1978. 12. Aqua. A. A comprehensive review of filtration is presented in The Scientific Basis of Filtration. J. S. Thesis. K.and PATTERSON. AMIRTHARAJAH. John Wiley and Sons. ADIN. 1974.. Soc.. Am. 101. 10th Congr. 1978. J. PARAMASIVAM. 45. B. Instn Water Engrs & Scientists. J. ARBOLEDA. IVES. and BUASEEMUONG. 24. Aqua. 1979. 18. J. B1. 591. 25. 339. 22. Am. 27. Civil Engrs.T. GOULD. 48 (July).L.. 124.. 1979. J... 917. R. 13. and STEIMLE..C... J. G. Amer. Amer.G.). 69. 6. Proc. AMIRTHARAJAH. (3). GREGORY. S. J.J. 1979.. Water Works Assoc. J.L. 1.. 15. Water Services. G. 55. TREWEEK. Instn Water Engrs & Scientists. 101.James (Ed.. M. G.Ives (Ed. B.. Leyden. TP 102. Civil Engrs. 52. 489. Amer. Soc. Fox. 32. P. 87. M. 123. 1972. 23. M. (4). MCNAUGHTON.J.. 31.J.J. 1978...B. K. WEST.J. 104.L.. J. T. Water Works Assoc. J. 32. Civil Eng. Soc. Civil Engrs. 1977. VIANNA. Amer. J. Filtrn. and LORENCE.H. K. 33.Filtration 21 13. 1966.).. J. RANDALL. J. Am. CHAINARONG. 573.. J.. LEKKAS. 19. K.J. 71.B. Environ. A. C. HANEY. Div.T. CLEASBY. D. Environ. Water Supply Assoc. 1979.D.. Environ. R. University of Birmingham. 10. KOMOLRIT. and Cox.P. RACHWAL. FRANKEL.. 71. J.. R. Div. 1974. 1975. 64.F.. Performance Relationships in Water Treatment. .J. Water Tech. 1973. 1979. 17. J. J. V.L. A. 104. 14. 26. 29.. 1979. Water Works Assoc. Brighton. Noordhoff. Water Works Assoc. Amer. A. Medmenham. J. Int. 21. Johnson. Environ. Prog. G. 1975.. 68. 34. Experiences with Upflow Filtration... 16.D. Eng. and MCNAUGHTON. 1978.. RAY. Soc.. 1974.. Eng. L. 96..J. 1979. Am.J. J. P. 66.. 1978. 15.G. 33. 1975.L. Chichester..S. Civil Engrs. Eng.W. KING. Water Treat.

Yorkshire Water Authority. absorption. C. It is concluded that activated carbon adsorption is the process of choice for many duties from taste and odour removal to the general reduction of synthetic organics. The high organics removal performance of reverse osmosis has been demonstrated but it remains prohibitively expensive.W. UK SUMMARY The use of activated carbon for municipal water treatment continues to grow as water quality standards are raised and polluted sources are increasingly drawn on. M. The most common naturally occurring organic compounds are humic and fulvic acids derived from vegetation. but are rarely found in significant quantity in groundwaters. Leeds. ORGANIC COMPOUNDS IN WATER Organic compounds are present in most surface waters.1 . the most advanced current analytical techniques cannot identify more than 10 to 20% of the individual organic compounds present in polluted surface waters.I. Many individual substances have been detected. but these are not at present competitive with carbon for potable water treatment.particularly because of the problems associated with liquid regenerants.SHORT B.E. 2..Chapter 2 REMOVAL OF ORGANIC COMPOUNDS C... generally at very low concentrations.v.S.1. However. In addition.Sc.Eng. Development of high performance liquid chromatography in conjunction with mass spectrometry will allow the detailed investigation of the remaining fraction. while the related process of ultrafiltration is cheaper but effective only for removing the larger organic species. Ion exchange resins will continue to be used for the removal of naturally occurring organic acids in the production of deionised water.I.Chem. Minor developments in technique have been introduced in the 1970s. principally in regeneration furnace design. Total levels of organic matter can be determined in terms of organic carbon. or indirectly in terms of u. New resinous adsorbents have been developed for removing a wide range of organics.S.E. rivers receiving sewage and industrial effluents and run-off from agricultural and urban catchments may contain a very wide range of synthetic organic compounds. M.

during the disinfection process. However.3. a considerable expenditure on organics removal for health reasons may be anticipated in the next decade. whereas for others specific compounds or groups of compounds must be removed.2. Furthermore. Slow sand filtration may be expected to remove colloidal material very TABLE 1 OBJECTIVES OF ORGANICS REMOVAL Application Potable water supply Organic compounds of concern Reason for concern Maximum level recommended Organics arising Possible health Reduce to from industrial effects lowest effluents practical level (EPA) PV 5 mg/litre (EEC) Carbon chloroform extract 0. Table 1 indicates the organic compounds of concern in a number of applications. OBJECTIVES The objectives of organics removal depend on the application. to form a variety of chlorinated organics some of which are thought to be potentially hazardous. as will be discussed in later sections.1mg/litre (EEC) . THE PERFORMANCE OF CONVENTIONAL AND OXIDATIVE PROCESSES Both colloidal and dissolved organic matter are removed to some extent by conventional processes. this has given rise to concern. but a limited amount of information is available on their performance except in respect of colour removal. 2. As organics removal can be expected to add considerably to treatment costs. where a water source is known to contain significant amounts of industrial effluent. In the meantime. if the current (1979) requirements of the United States Environmental Protection Agency (EPA) and the EEC are to be met. Knowledge of the health effects of organic compounds at the low levels found in water supplies is very limited. there is an urgent need to improve our knowledge of the relationships between organic compounds and health. However. For some uses organics in general are undesirable. naturally occurring organic compounds have been found to react with chlorine.Removal of organic compounds 23 2. currently available treatment methods can be made specific for given types of compound only to a limited extent.

Developments in water treatment—2 24 Organochlorine Possible health 0·1 µg/litre pesticides effects each.5-TP 10 µg/litre (EPA) Polynuclear Possible health 0·2 µg/litre aromatic effects (EEC) hydrocarbons Trihalomethanes Possible health 0·1 mg/litre effects (EPA) Compounds Consumer causing tastes reaction and odours Compounds Consumer 15 Hazen units caus-ing colour reaction (EPA) Detergents Taste.4. or electrodialysis resins or PV/TDS 0·002 membrane Electronic Colloidal Affects – components material performance of manufacture components Soft drinks Polysaccharides Form – manufacture (products of precipitate at algal decay) low pH .4-D 100 µg/litre (EPA) 2. 0·5 µg/litre total| (EEC) Endrin 0·2 µg/litre (EPA) Lindane 4 µg/litre (EPA) Methoxychlor 100 µg/litre (EPA) Toxaphene 5 µg/litre (EPA) 2. 200 µg/litre appearance (EEC) 500 µg/litre (EPA) Biodegradable Substrate for Total Organic organics microbiological Carbon (TOC) growth in 0·5 mg/litre mains Boiler Weak organic Increase in Total feedwater acids conductivity conductivity 0·1 µS/cm for high pressure boilers Pretreatment Weak organic Cause 0·4 kg PV per for ion acids irreversible m3 resin per exchange and fouling of cycle.

results from the River Trent water treatment study5 indicated that. the Threshold Taste Number was reduced by up to 90% in summer. (From Houghton. Virtually complete removal is achievable from those raw waters containing moderate amounts of humic colour.8 Ozonation at 8 mg/litre. that passing through a 0·45 µm membrane filter) depends largely on the coagulant dose. Reference 2) Nov. At 2 mg/litre. as reported by Rook. soluble and colloidal) may be expected.6 The removal of pesticides by coagulation treatment is reported to be negligible. It also appears that volatile organic substances may be lost to the atmosphere by desorption. ESSEX WATER Co. total dissolved organic carbon was removed in varying degree. with 2 min contact. even with pre-chlorination.4 during storage of approximately 20 days.7 The organics remaining after coagulation and clarification are sufficient to form measurable amounts of haloforms on chlorination. Again from the Trent study. for instance as a result of the growth and decay of algae. the . but up to 40% reduction could be expected. Slow sand filters are effective in reducing some tastes and odours. Over 90% removal of polynuclear aromatic hydrocarbons (PAH) may be expected as these are very insoluble. Residuals of less than 10 ng/litre were achieved at several treatment plants examined by Lewis. suppressed the formation of haloforms by 50%. 1965– April-Oct. Reductions of Permanganate Value (PV) reported by Houghton2 apparently show the adverse effect of low temperature on a biological process (Table 2). a significant amount of colour remained after coagulation treatment of this water containing industrial effluents. Over 80% removal of ‘apparent’ colour (i. 75% in winter. CHIGWELL Row SLOW SAND FILTERS. but are also known to cause them under certain circumstances.e. March 1966 1966 Raw water PV mg O2/litre Filtered water PV mg O2/litre Removal (%) 2·0 1·5 25 2·2 1·3 40 Storage of raw water in open reservoirs may change the organic content. The removal of ‘true’ colour (e. Coagulation.3 TABLE 2 PV REMOVAL.Removal of organic compounds 25 Preparation of Pyrogens injections and pharmaceuticals Cause pyrogenic reaction in patients – effectively. However. Similar results were obtained when precipitation softening was practised.g. 8 min contact. sedimentation and rapid filtration reduce organic content by precipitation and adsorption onto coagulant flocs. while about 30% reduction of dissolved humic matter is achieved probably by biological oxidation.

v.10 Chlorine dioxide is used for disinfection as an alternative to chlorine when phenols are present in the raw water. if a longer contact time occurred between ozonation and chlorination. in 1978 the US Environmental Protection Agency (EPA) proposed that all municipal water treatment systems in the . In the municipal field. Recent studies11. the products of ozonation may be no more acceptable than the original compounds. Introduction The use of activated carbon for municipal and industrial water treatment is well established.9 Ozone was found to render various river water odours less unpleasant. chlorine dioxide and potassium permanganate break down organic molecules incompletely and therefore do not necessarily reduce any health risk.12 indicate that the action of ozone and u. Some results are given by Gomella. Chlorine dioxide and potassium permanganate are reported to reduce various natural organic odours but at rather high doses. Because odours often occur intermittently and are associated with very low concentrations of the odorous substance. 2. radiation together readily oxidises some organics to carbon dioxide and water. while not sufficiently reducing odour intensity. Ozone.Developments in water treatment—2 26 reduction was about 65%. notably on river abstractions suffering continuously from odours originating in industrial and municipal effluents. as indicated in Table 1. for which purpose it is often the most. As with ozone. effective treatment.4. this is discussed in a later section. as discussed above.1. such reduction as is achieved incidentally to the normal clarification and colour removal role of these processes may significantly reduce the cost of subsequent organics removal processes. that this would be economically acceptable on a practical scale for municipal water treatment. other oxidising agents such as chlorine. However.13 To summarise. or for potable water when polluted sources are used. Indeed. Nevertheless. appears to be capable of only partial oxidation of many organic compounds.10 From the point of view of health. Very few carbon plants have been installed specifically for the removal of organics to reduce the possible health hazard. or only. though a powerful oxidant. the haloform levels were not reduced. chlorine at normal disinfection doses forms possibly undesirable substitution products with organic substances. ACTIVATED CARBON 2. There are therefore many examples of its use throughout the world on reservoir and river abstractions where odour problems are common. as it does not form chlorophenol tastes but partially oxidises the phenols. however. it has been economical to use powdered carbon in the majority of these plants. they may be more readily biodegraded in subsequent activated carbon beds.4. There are a growing number of granular carbon installations. Oxidants modify rather than remove organic matter and their application is limited to the removal or avoidance of tastes and odours except for their possible use to enhance the performance of activated carbon beds. However. However. It is unlikely. the reduction in the level of organic compounds achieved by conventional processes is generally insufficient to meet the latest requirements for industrial water treatment. carbon has been applied almost exclusively to the removal of odorous substances.

For the case where intraparticle diffusion is rate-controlling. The solute molecular weight. Carbons activated at high temperature usually have a net negative (basic) charge. However.e. at the feed concentration. much of the existing knowledge was brought together at a Water Research Association conference in 1973. n is less than one for most organic solutes. the uptake of solute per unit weight of carbon increases with increasing concentration of the solute in the solution. and frequent reference will be made here to the proceedings. There is a very extensive literature on the use of carbon for water treatment. transport of solute to the carbon particles can be appreciably slowed by the occluding effect of coagulant flocs as in the case where powdered carbon is dosed upstream of floc blanket tanks or where granular carbon is used in the dual role of adsorber and filter. surface chemistry and charge play a smaller part. and K and n are constants for each solute/carbon system. implying that a greater proportion of the solute will be adsorbed from a dilute solution than from a concentrated one. However.Removal of organic compounds 27 USA serving populations greater than 75 000 should use granular carbon for this purpose. which can be expressed as the equilibrium equation where Cc is the concentration of solute in the carbon at equilibrium. an empirical equation of the form dy/dt=−KC ln y .4. design and performance of powdered and granular carbon systems with emphasis on practical applications and recent developments. Rate of adsorption depends on diffusion both to and within a carbon particle. It follows that activated carbon is well suited to the treatment of dilute solutions. On the other hand. but for maximum use of carbon it should achieve equilibrium with the solute at its most concentrated. Cw is the concentration of solute in the water at equilibrium. which is generally the rate-cootrolling step. physical (van der Waals) and chemical combination. i. Adsorption decreases with increasing polarity and therefore with increasing water solubility.14 The plan of this section is to cover the theory. 2. adsorption of many solutes from single component solutions in laboratory batch tests is found to follow the Freundlich isotherm. The principal properties of the activated carbon affecting adsorption are pore size distribution and surface area.15 The Carbon Adsorption Handbook16 is another encyclopaedic reference. Adsorption rates may be determined by stirred batch tests or by granular carbon column tests.15a Major factors in the degree and rate of adsorption of individual solutes are the polarity of the solute and the molecule size.2. carbon particle diameter and pore size distribution all affect the rate of intraparticle diffusion.16a At the low concentrations of solute normally found in water supply applications. Details of the preparation and chemistry of activated carbons are given by Cookson. Theory Adsorption of solute molecules onto activated carbon is considered to result from a combination of forces: electrical (ionic attraction).

y can be regarded as the fractional saturation of the carbon). unlike the usual methods of applying powdered carbon. For instance. where C is the concentration of solute in the solution at any instant. In either case the carbon must have a sufficiently long contact time to allow equilibrium to be achieved with the solutes of concern. However it is not always cheaper to install granular rather than powdered carbon as capital costs of granular systems are higher. Granular carbon plants should not be designed from the results of batch tests alone as these do not take into account the effects of microbiological activity. The upstream layers of the bed will eventually become saturated with solute at the feed concentration.3.Developments in water treatment—2 28 may be used to fit the data. provided that equilibrium is approached at each stage. and consequent backwashing all of which occur in granular carbon beds. whereas powdered carbon added before clarification is well mixed with the water and becomes saturated with solute at the treated water concentration.18 Gomella19 has shown the economies that may be expected if powdered carbon is added at two or more positions.20 proposed a fluidised bed system which would permit greatly improved powdered carbon utilisation if the fluid bed could be divided into several separate stages.4. coagulants and oxidants including chlorine. and batch and/or column tests are invariably required to determine the equilibrium and rate constants for a particular carbon/water/solute system. Powdered Activated Carbon The Material Powdered activated carbon has been widely used for many years and is available in a range of qualities. Removal by flotation would be rapid and the contact time practically limited to that provided in the flocculation stage. expressed as a fraction of the equilibrium concentration in contact with a solution containing the solute at concentration C (i. It is typically a powder of bulk density around 700 kg/m3 and particle size less than 75 µm The performance depends on the raw material and the method of activation. Performance is adversely affected by the concurrent addition of softening chemicals. and a carbon based on anthracite. However. and K is the rate constant. y is the concentration of solute in the carbon at the same instant. this would require an expensive special vessel. Selection and optimisation of carbon systems are discussed later in this section.16a. Lettinga et al. Recent developments include a water treatment carbon comprising a mixture of coal-based and peat-based material to obtain a wide spread of pore sizes. The relationships in the above equations are empirical. Point of Addition Powdered carbon may be added before sedimentation or immediately before rapid filtration.e. 2. occlusion by suspended solids. activated by steam at 950°C in a fluidised bed furnace. it can be seen that granular carbon beds must be used to achieve maximum carbon use. . These concepts of adsorption rate and capacity are valuable for the comparison of different carbons and also suggest ways in which the efficiency of use of activated carbon could be maximised.17 In some Japanese plants contact time before flocculation is provided.

Reference 15c). storage and dosing of the carbon depends to some degree on the size of the installation.Removal of organic compounds 29 Regeneration Powdered activated carbon is at present regarded as non-regenerable. preferred systems and costs. Figure 1 gives some indication of the relationship between size. the powder. Costs of powdered carbon dosing systems (from Burley and Short. FIG. Rigorous dust control is required to protect operators and equipment. However. and it is therefore used once only before being discarded as part of the sludge arising from clarification. In larger installations a dry feeding system will often be required either for dosing direct to the process or for making up a slurry of known concentration. is expensive enough to have prompted investigations of possible methods of regeneration and re-use. Either method is subject to inaccuracies resulting from variations in bulk density in the case of volumetric feeders and from variations in moisture content in the case of gravimetric feeders. Engineering of Dosing Systems A comprehensive review of design considerations and systems for dosing powdered carbon was made by Aldrich. Successful regeneration of an activated sludge/powdered carbon slurry by wet oxidation has been reported.15b The choice of equipment for delivery. though considerably cheaper than granular carbon. 1. . Dry feeders may be batch or continuous and deliver a measured volume or a measured weight of powder. Separation of the carbon from coagulant sludge would be a considerable problem.16b but the technique is unlikely to be economical at the dose levels normally associated with potable water treatment.

The mid 1979 cost of the mechanical and electrical equipment was about £65000. gravimetric dry feeding to produce a slurry of known concentration. Kennett22 reported that at times doses of up to 80 mg/litre could not sufficiently reduce tastes in the Derbyshire R. At one plant a minimum dose is added of 12 mg/litre in summer and 8 mg/litre in winter. the persistent tastes in this source eventually led to the installation of granular carbon beds. Slurry preparation and dosing is fully automatic. This implied that powdered carbon should if possible be added at a late stage of treatment after organic material has been substantially reduced by coagulation and sedimentation. anthracite/sand filters could cope with doses of 60 mg/litre with no significant increase in head loss development. The superiority of powdered carbon to oxidants for treating a range of surface water odours was shown by Gauntlett. Tubular screw conveyor casings are used to prevent the free flow of powder which has caused ‘flooding’ in some installations. This comprises bulk delivery to storage silos. to afford a degree of protection against occasional pollutions as well as for taste and odour reduction.Developments in water treatment—2 30 but powdered carbon is not thought to represent a significant fire or explosion hazard in British practice. However.15c Sumner21 described the continuous use of powdered carbon at the River Dee treatment plants. with the notable exception of the Federal Republic of Germany where only granular carbon beds have been employed. Gauntlett17 demonstrated the adverse effects on phenol adsorption of humic and fulvic acids and alkyl benzene sulphonate. A recently installed system for dosing up to 350 kg/h is illustrated in Fig. Doses are typically in the range 5 to 50 mg/litre. 2. Indeed.10 Gardiner15d reported that the filter run length of rapid sand filters became unacceptably short at carbon doses above 25 mg/litre. The choice between powdered and granular carbon for a given application is often an economic one and a cost comparison was made by Burley and Short. . It must be appreciated that carbons are not highly specific for odorous substances and part of their capacity will therefore be used up in adsorption of non-odorous organics.Derwent. Applications and Performance Powdered activated carbon is used in many countries for taste and odour control. and metered pumping of the slurry into a stream of carriage water which conveys the carbon to the point of application at a suitable velocity to prevent blockage or erosion of the pipeline.

Transport water pumps. Slide plate isolating valve. 6. Aeration pads supplied with air at 35 kN/m2. Load cells. Duplex slurry metering pump. 12. 3. 7. Air vent incorporating automatically cleaned bag filter. Screw conveyor. 15. Pneumatic delivery from bulk tanker. Key to details: 1. Pneumatically operated butterfly valve. 8. Elvington water treatment plant (by courtesy of Yorkshire Water Authority and Portasilo Ltd). 5. Low speed agitator. 2. PVC pipes. Vortex mixing cone. Schematic of powdered carbon dosing system. Pneumatically operated swing valve. 13. . 14. High speed mixer.Removal of organic compounds 31 FIG. 11. 4. Two-speed screw conveyor. Duplicate 50 mm dia. 9. 2. 10.

It is inevitable that during the upflow washing the arrangement of carbon particles in the bed is somewhat altered. This is referred to as non-regenerable carbon.23 However. The risk of occlusion of the carbon by particulate matter and coagulant floc is minimised. 2. and have shown reasonable agreement with the observed adsorption of single and binary solute systems. Adsorber designs are therefore generally based on the results of pilot column tests in which samples of water are taken from a . This arrangement has several advantages.4.Developments in water treatment—2 32 2. 1. for speed and cheapness of installation. Adsorption efficiency and the operating life of a bed could therefore be significantly reduced. However. Adsorber System Design A number of predictive mathematical models of granular carbon adsorbers have been developed. The surface area of typical water treatment carbons is in the range 500–1500 m2/g as measured by the standard BET method (based on the adsorption of nitrogen). The corresponding oxidation of the carbon surface may have an adverse effect on the adsorption of many organics of concern. formed by extrusion. it may sometimes be economical to use a cheaper. The shape is normally irregular. chlorine levels entering the carbon beds are normally kept to a minimum. some reported results are reviewed below. Some organic matter is removed by coagulation and clarification. Particle sizes giving the best combination of adsorption kinetics and head loss characteristics are in the range 0·5–2 mm. there are a number of plants where. but one carbon is available as uniformly sized cylindrical pellets 0·8 mm diameter. Chlorine coming into contact with the carbon will be reduced to chloride. Particle strength should be sufficient to allow regeneration of exhausted carbon with attrition losses of not greater than 5%. the cost of restoring the lost chlorine after the carbon beds must be considered. reducing the load on the carbon and extending its operating ‘life’ between regenerations. Where pre-chlorination is used. carbon has been substituted for sand in existing rapid gravity filters. 3.16a Also. Those grades most suited to water treatment are generally produced by high temperature steam activation. Irregularly shaped granular carbon is an effective filtration medium and its low density compared with sand makes it economical to backwash. However.4. Points of Application Granular carbon adsorbers are preferably installed following clarification processes. It is possible that the exhausted material could be reprocessed into powdered activated carbon. Backwashing frequency of the carbon units is minimised. Granular Activated Carbon The Material Many grades are available to cover a wide variety of industrial uses. softer grade on a throw-away basis. it is likely that some important factors in carbon bed performance will remain unquantifiable. This tends to disrupt the desirable adsorption profile in which the relative exhaustion of the carbon varies inversely with distance from the bed inlet.

24 Pilot column tests should therefore include parallel trials at different velocities in the suggested range 2 to 25 m/h. The carbon system must be designed to accommodate the worst anticipated organic loads. The concentrations of the solutes of interest are measured in each sample and the data can be presented as a plot of concentration against either time at each depth (‘breakthrough curve’) or depth at each interval of time (‘adsorption front’). The effect of water velocity (surface loading) on minimum contact time and carbon utilisation appears to vary according to the particular solutes/sorbents in reported studies. Three systems which ensure a high efficiency of carbon utilisation are illustrated in Fig. the minimum depth of bed to give the required treated water concentration is readily determined. However. Idealised adsorption front curves. and the progressive saturation of the carbon is illustrated. These data are used to evaluate the effectiveness of alternative adsorber designs in respect of carbon utilisation. FIG.Removal of organic compounds 33 number of depths within the bed at regular intervals of time. measurements should be made during column tests to . 3). Head loss and backwash data are provided by suppliers for each grade of carbon. Using the latter (Fig.16c.23. 3. Carbon removed for regeneration or disposal should as far as possible be saturated with respect to the organic solutes of concern. 4. Gomella19 suggests using carbon beds for base-load operation with powdered carbon dosing to reduce peak concentrations.

Flow velocities range from 4 to 24 m/h and contact times from 3 to 15 min.15c The full-scale installations for municipal water treatment which have been identified all employ adsorbers in parallel. Adsorber Installations A small number of pulsed-bed adsorbers have been installed for wastewater treatment. engineering details are given by Culp. Also. as demonstrated by the results of Hyde. washwater temperature is probably the most significant factor affecting bed expansion during backwashing. Burley and Short15c developed a computer program permitting the rapid evaluation of many alternative systems for a given application. As noted above. Granular carbon adsorber configurations. a cost comparison of gravity adsorbers used singly or in reversible two-bed series indicated that the series combination could be considerably cheaper when long contact times are required. 4. taking into account capital costs (number and size of adsorbers and pumps). The effect is mitigated by using two or more beds in series. However. Plants at Zürich and Düsseldorf16d use ozonation followed by pressure filters/adsorbers. observe the effect of feedwater turbidity and biological growths on head loss development.Developments in water treatment—2 34 FIG. the choice between systems and surface loadings is principally economic. no examples are known in potable or industrial water treatment applications. and power costs (related to pressure drop and backwash requirements). Nor have any installations of beds in series been reported. for instance at Göteburg27 and several USA plants. backwashing can adversely affect carbon utilisation as it tends to disrupt the adsorption front. though their efficiency has been demonstrated in a number of pilot column investigations. and the variation of backwash efficiency with time.24 Given the required data. carbon utilisation. Pressure vessels are .26 However.15e Some of the latter have carbon on top of a thin layer (150–300 mm) of sand. There are a number of examples of combined filtration/adsorption in rapid gravity filters. Bossy and Sanchez25 attributed such variations to changes in carbon density and particle size.

Church Wilne water treatment plant (by courtesy of Severn–Trent Water Authority and Humphreys and Glasgow Ltd). as carbon utilisation rates are strongly influenced by feedwater quality and the desired treated water quality. 5). sedimentation and sand filtration at Nottingham. Performance of Granular Activated Carbon Adsorbers It is difficult to compare and summarise the reported results of batch.30 This is intended for industrial wastewater treatment but could also find an application in the provision of temporary water supplies from low quality sources.28 Turin27 and Buckingham. One carbon supplier offers prefabricated adsorption systems for hire. The requirements of a complete adsorption/regeneration system are exemplified by the Church Wilne plant at Nottingham (Fig. column and fullscale operation. including periodic replacement of the carbon. 5.15f A similar treatment sequence is employed at Mulheim and Rouen.Removal of organic compounds 35 used to contain carbon beds preceded by coagulation. techniques are described by Janecek. with the addition of pre-ozonation. Granular activated carbon adsorption/regeneration system. FIG.29 Vessels for receiving exhausted and fresh carbon may also be provided. Utilisation rates between 2 and 200 g carbon per m3 water treated have been reported for applications varying from taste and odour removal to .16d Provision is usually made for the removal of exhausted carbon from the beds by eduction into a stream of water.

(b) Total organic material is readily reduced but has a comparatively high carbon utilisation rate. threshold odour number. Carbon beds after coagulation.15g The performance of the adsorber preceded by sand filtration was markedly better than that of the dual-purpose beds in terms of the removal of both general and specific organics. Taste 28 TOC. PV. when prechlorination was applied to River Trent water. (c) Most soluble polyaromatic hydrocarbons. the bed becomes an ideal growth medium for micro-organisms. the useful life for taste removal was almost doubled. detergents. the low TABLE 3 KEY TO REPORTED DATA ON ORGANICS REMOVAL BY GRANULAR CARBON Reference 15 System Foxcote waterworks. particularly chloroform. For example. sedimentation and sand filtration Church Wilne waterworks. Table 3 indicates where detailed operational and experimental results can be found for various organic parameters. (d) Colour. Carbon beds following coagulation. non-ionic pesticides. absorption . organochlorine and organophosphorus pesticides are well adsorbed.Developments in water treatment—2 36 general organics reduction. chlorination. General conclusions are: (a) Earthy/musty and pesticide tastes and odours are readily removed and have a low carbon utilisation rate even in the presence of a considerable amount of humic matter. though their carbon utilisation rates may differ considerably.v. For instance. If biodegradable organic material is adsorbed in a granular carbon bed. Chemical Oxygen Demand (COD). and there is usually a significant fraction which is not adsorbed by the carbon however long the contact time. The performance of carbon adsorbers with and without prior sand filtration was investigated in full-scale trials at Vigneux-sur-Seine. are among the compounds less readily adsorbed by common water treatment grades of activated carbon. Organics investigated TOC. phenols and anionic detergents are well adsorbed despite their polar character. haloforms 16d COD u. (e) Trihalomethanes. sedimentation and sand filtration Lengg waterworks.

COD. 2R. phenols. absorption. bromodichloromethane. 2-methyl columns isoborneol in presence of humic acids Carbon Organochlorine .v. 5-T ester Pilot columns TOC. absorption. monohydric phenols. u. u. TOC. TOC.v. u.v. ozonation. Seine fullPV.Trent colour. 4-dioxane Small Geosmin. Silvex.Threshold taste value. 4.v. n-butanol. α-BHC. u. R.Thames dichlorobenzene. PV. γ-BHC. Carbon beds after ozonation Dohne COD u. pesticides experiment with and without sand filtration Pilot columns. 1. 2. absorption. absorption waterworks. methyl ethyl ketone. Mülheim. anionic and non-ionic detergents. Carbon beds after coagulation. haloforms Pilot columns Haloforms. Lindane. Amsterdam colour Pilot columns Endrin. Toxaphene. nitromethane. 1. phenols.Trent colour. sand filtration Vigneux-sur. anionic scale detergents. pesticides Pilot columns. threshold odour number. sedimentation.Removal of organic compounds 37 16d 15 5 31 24 16d 7 8 23 32 33 Zürich. pesticides Pilot columns. chloroform. absorption. PAH. carbon tetrachloride. R.v. Dieldrin Pilot columns.

Several stages have been identified in this process: 1. presumably because in this case the filtration effect of the carbon was greater than the growth effect. changing from pre-chlorination to pre-ozonation extended the useful life of activated carbon beds at Mülheim from 1 to at least 20 months. Rouen) microbiological activity within carbon beds is deliberately promoted by ozonating the water upstream of the adsorbers at doses of 1 to 5 mg/litre.15f. .g. A comprehensive review of regeneration methods and systems34 suggests that only high temperature thermal reactivation is practicable for water treatment applications. Pyrolysis of non-volatile organics—200 to 650°C. 3. 2. (iii) The biological activity thus encouraged oxidises biodegradable organic substances and effects a continuous partial regeneration of the adsorptive potential of the carbon. Nottingham and Göteburg—high levels of chlorine are continuously applied so as to penetrate the carbon beds and prevent microbiological activity. Gasification of pyrolysis products—800 to 1000°C. Biologically active carbon beds can support the development not only of chlorineresistant bacteria which may lead to odour problems in distribution. or 0·3 g per m3 carbon per hour. (iv) Ozone does not form trihalomethanes as does chlorine. Mülheim. but also of algae and invertebrates.16d Regeneration System Design and Operation Spent granular carbon can be returned to the manufacturer for regeneration but in some circumstances—particularly where large quantities of carbon are involved—it may be economical to provide on-site regeneration facilities. Loss of volatile organics—100 to 300°C. However. in a number of European water treatment plants (e.Developments in water treatment—2 38 extraction pesticides apparatus Organophosphorus (minisampler) pesticides numbers of surviving bacteria entering a carbon bed were considerably increased in the outlet.g.28 In some installations therefore—e. ozone must be preferred to chlorine for disinfection. The chlorine demand of the beds at Nottingham is about 0·7 mg/litre. This appears to enhance organics removal by a combination of the following factors: (i) Non-biodegradable substances may be broken down into biodegradable components by ozone. and it is necessary to disinfect the water at an early stage of treatment. Düsseldorf. Drying—up to 100°C. but may indeed reduce the concentration of trihalomethanes if these are present in the raw water. Therefore if trihalomethanes are an important criterion of treated water quality. 4. (ii) Residual ozone may provide additional oxygen for bacterial respiration and biological oxidation of organics. Zürich. Thus.5 Conversely if high levels of bacteria were presented to the carbon bed these were attenuated. thus extending the operating life of a bed.

it is also improved by increasing the gasification temperature. A detailed account of design and operational factors and an economic study of multiple hearth furnace regeneration will be found in references 16e and 15c respectively. Reference activation per re. hearth Göteburg.heat input. Juhola15h showed that slow drying improved the final activity of the carbon. The provision of an afterburner to destroy possibly noxious components in the waste gas adds appreciably to the cost per kg carbon regenerated unless the resulting heat in the stack gas can be reclaimed for use. Multiple hearth and fluidised bed furnaces have been installed at a small number of water treatment plants. Carbon after six regenerations in the multiple hearth furnace at Church Wilne28 was equal to fresh carbon in bulk density. Nottingham. The degree of reactivation is often enhanced by injecting steam at the gasification stage. but higher carbon losses and fuel requirements have been reported. A furnace heated by infrared radiation is also being developed. The system TABLE 4 PERFORMANCE OF REGENERATION FURNACES Plant Type Re% losses Approx. methylene blue adsorption and taste/odour removal performance. Iodine number (representing small diameter pores) was reduced by 20%. This type can also have considerable flexibility of operating temperature profile. UK Multiple 950–975 hearth with steam injection and afterburner Alelyckan Multiple 900–1000 waterworks. Very exacting control is required to minimise the loss by overheating of the carbon itself and to preserve the refractory lining of the furnace. but could probably be restored to the fresh carbon value at the expense of slightly higher carbon losses by raising the oxygen level in the furnace gas.Removal of organic compounds 39 The two middle steps occur rapidly but adequate time must be allowed for drying and gasification. Rotary kilns are also attractive in terms of first cost and reliability. but increased capital costs may make this uneconomical. The multiple hearth type has an efficient counter-current flow of hot gas and carbon such that the incoming carbon is dried by the gas leaving the reactivation hearths. Some performance data are given in Table 4. The principal advantage associated with the use of a fluidised bed furnace is the lack of mechanical rotating equipment with consequently lower maintenance and downtime and less attrition of the carbon. temperature generation 106 kJ/t carbon regenerated 4·5–5 20 (10·5 at 28 Private 100% load communication and with air cooling) Church Wilne waterworks. with steam Sweden injection and 6 8·5 Private (excluding communication steam) . Heating is normally achieved by burning gas or oil in a stream of air which then passes over or through the carbon.

On-site carbon regeneration will also be attractive for such duties. is reported to have comparatively low fuel requirements. steam Mississippi. . from naturally occurring tastes and odours to industrial pollutants. injection USA and waste gas recycling Hypothetical Any type (EPA cost with estimates) afterburner and scrubber 900–925 Av. USA and occasional afterburner Zürich Fluidised waterworks. Thermal regeneration has the important advantage of completely destroying the organics removed from the water. afterburner and vacuum drier Industrial Two-stage wastewater fluidised treatment bed with plant. bed with Switzerland steam injection. plus partial recirculation of waste gases to the gasification stage. and that series beds or pulsed beds will be used for greater economy of carbon use. heat extracted from the waste gases is used to raise steam for injection and to assist drying. 5% 6–12 26 900 3·5–5 – 35 815–980 6–8 5 36 – 7 8·6 14 installed at Zürich waterworks35 includes a vacuum drier prior to the reactivation furnace. even if required fulfilling the dual role of adsorbent and filter medium. Another system using two fluidised beds in a vertical series.Developments in water treatment—2 40 afterburner South Tahoe Multiple advanced hearth wastewater with steam treatment injection plant. It is likely that granular carbon beds will be applied to heavier and more stringent organics removal duties in the production of potable water. Its flexibility is illustrated by the many ways in which it can be integrated into a sequence of water treatment processes. Developments in furnace design may considerably reduce operating costs.36 Granular Activated Carbon Applications Activated carbon is an effective flexible and economical method for the removal of a wide range of dissolved organic substances.

Resins for Organics Removal Synthetic polymeric resins of all the above-mentioned types have been evaluated in recent years specifically as a means of removing organic compounds from water.1.2. Experience has shown that for demineralisation of boiler feedwater.37 reference may also be made to McWilliam. Both macroporous and isoporous resins allow organic solutes to be adsorbed. One such adsorbent is described as being produced by partial pyrolysis of beads of a macroporous synthetic polymer with specially designed surface . It was found that organic substances—in particular. At the same time. carbonaceous and cellulosic. they can economically combine the removal of organic acids and of anions of strong acids. To some extent their properties—in particular.38 A pilot-scale evaluation of isoporous and macroporous resins for the deionisation of R. in some circumstances macroporous resins may be used to reduce the organic load on following gel type strong base anion exchange resins. which have a more regularly cross-linked structure than conventional gel type resins. strong base macroporous resins are effective in removing the organic acids responsible for fouling. ION EXCHANGE AND POLYMERIC ADSORBENTS 2. hydrophobic (non-polar) resins are available which are designed to adsorb non-polar solutes.5. For instance. open pore structure. Macroporous resins used in this way are commonly known as organic scavengers.Removal of organic compounds 41 2. Two new types of anion resins were developed to overcome the fouling problem: macroporous. A detailed account of the causes. effects and control of organic fouling in demineralisation systems is provided by Tilsley.Trent water is described by Brown and Ray. but make no contribution to the deionisation as anions in the feedwater are exchanged for chloride. Weakly basic macroporous resins have been developed for their ability to regenerate effectively with sodium hydroxide. humic acids—were strongly adsorbed. However.39 2. and subsequently removed during regeneration. and isoporous. polarity and pore size—can be varied to improve performance with respect to specific groups of compounds. Introduction The use of ion exchange resins for organics removal derives from observations of the fouling of synthetic anion exchange resins in boiler feedwater treatment systems. and insufficiently desorbed during regeneration.5. Two additional types of resin have been developed specifically for the removal of organic substances from liquid and gas streams. which have a large. the isoporous strong base anion exchange resins are more economical than macroporous in terms of both capital and operating costs. With the development of high pressure boilers the problems caused by fouling became more acute.5. Carbonaceous adsorbents are said to have a structure between those of polymeric resins and activated carbons. and may be used to precede strong base resins in either separate or stratified beds. practieally complete removal of the organic acids was necessary as a significant residual concentration would raise the conductivity of the treated water to an unacceptable level. Regenerated by caustic brine.

acetone or methanol. They have extensive macropores and are particularly effective for the removal of very large molecules. which in turn depends on the size of the solute molecule. the porosity of the resin and the distribution of pore sizes.5. The regeneration of non-polar resins may require the use of organic solvents. For the removal of humic acids from water. haloforms and pesticides.g. A non-polar variety is suggested for the removal of halogenated organic compounds. from aqueous solutions. The development and preparation of cellulose based resins are described by Grant. The capacity of a resin for a given solute depends on the surface area presented to the solute. Alternative regenerants could be similarly screened by contacting with exhausted resins. When the removal of a solute is by ion exchange predominantly. A number of resins may be tested in parallel. These concepts are sufficient to indicate the resins most likely to provide effective removal of given organic substances. More detailed predictive models and associated data are not available for the design of systems. e. They are reported to have a high capacity for specific organic and inorganic components. Gauntlett41 noted that fresh resins imparted organic matter to the test solution and described a procedure for extracting this prior to equilibrium tests. The regenerants of choice for strong and weak base anion exchange resins will normally be caustic brine or sodium hydroxide solution.5. e. the mechanism depending on the polarity of the solute and of the functional groups in the resin. Cellulosic ion exchange resins are based on a cellulose matrix rather than the more expensive polystyrene or acrylic ester on which conventional ion exchange resins are based. . resin performance will be sensitive to the pH of the solution as this affects the degree of ionisation of the solute.40 Various ionic forms corresponding to the main types of conventional resins are available. strong or weak base varieties are indicated. Resin selection and plant design therefore require experimental data from laboratory evaluations. for instance proteins and enzymes.g. and rinse volumes should be determined in the column tests.3.23 Carbonaceous adsorbents are available in a variety of polarities and pore size distributions. The importance of thorough rinsing in potable water applications can readily be appreciated. 2. More polar molecules such as phenols require a hydrophilic (polar) variety.Developments in water treatment—2 42 functional groups. It is essential to evaluate promising resins by column tests over several exhaustion/regeneration cycles to obtain information on the capacity of fresh and regenerated resins for the solutes of interest. 2. Methods of Evaluation Rapid screening of a range of resins may be carried out by contacting known quantities of resin and solution in batch tests and measuring the equilibrium concentration of the solutes of interest in the solution. Theory It will be noted from the foregoing that removal of organic solutes takes place by a combination of ion exchange and adsorption.4.

low turbidity waters.5.6. in combination with. Large column tests may be required when investigating the removal of certain compounds for which potable water standards have been set at the µg/litre level (see Table 1). The desorption from weak base resins is very low but according to Oehme and Martinola47 levels of up to 0·3 mg anionic detergents per litre can be tolerated if sodium hydroxide regeneration is applied. giving superficial residence times of 5 to 1 min in beds 400 mm deep. When treating river water or highly coloured moorland water. 2.Removal of organic compounds 43 25 mm diameter glass or perspex columns are suitable for laboratory tests. Superficial velocities of 5 to 25 m/h may be used. but somewhat inferior for another. or preceding. in order to obtain sufficient treated water for analytical purposes. with the best performance at pH 5. However. clarification and scavenger resin for the treatment of highly coloured. The salient conclusions are as follows: All types of macroporous and isoporous weak and strong base resins are effective for the removal of humic acids. 2. Non-polar polyacrylic and polystyrene adsorbents (‘white carbons’) were found to be inferior to activated carbon in respect of a variety of solutes. phenols and anionic detergents.42 As with granular activated carbon studies as described in the preceding section. Test Results Table 5 is a key to recently published test results for a variety of resins and solutes. Grant has suggested40 that the low costs and high organics capacity of cellulosic ion exchange resins make it possible to consider these as an alternative to coagulation. The performance of a non-polar carbonaceous resin was comparable to that of activated carbon. anionic detergents are so strongly adsorbed by basic resins that they are hardly desorbed at all from strong base resins by conventional regeneration. The uptake of phenol by a weak base phenol-formaldehyde resin was found to be highly pH dependent. The use of ammonia as a recoverable .5. For potable water treatment it appears that resins are generally not competitive with activated carbon. it is important when evaluating resin adsorbents to obtain breakthrough data for design purposes.5. demineralisation of boiler feedwater. Applications Macroporous and isoporous weak base and strong base resins are well established for the removal of weak organic acids. Ammonia was found to be as effective as sodium hydroxide for regenerating one weak base resin. However. the resins would normally be preceded by coagulation and clarification. Further details of laboratory test procedures are given by Brown and Ray39 and Chriswell et al. The advantage of in-situ regeneration is outweighed in most circumstances by the difficulty and cost of disposing of the spent regenerant solution.

absorption – – – – 2·1 2·1 – – – – – – 2·1 – – 41 – – – – – – – – – – – – – – – – – – .Developments in water treatment—2 44 TABLE 5 SUMMARY OF REPORTED DATA ON ORGANICS REMOVAL BY ION EXCHANGE AND ADSORBENT RESINS Refe Type Trade rence name Test Solutes /Parameters Rege nerants Column test conditions Velocity Contact (m/h) time (min) – 18 – 2·7 42 31 M np XAD-2 Batch/column pD (A) hybrid M sb IRA Large column pD 904 (A) M – Column wb ce M an WRL Column ce 200A M Duolite Equilibrium wb S37(D) and column pf M np XAD-2 Column pD (A) M XAD-7 Column mp (A) ac M np XE-340 Column ca (A) M sb MP 500 Equilibrium pD (L) and column M MP 62 Equilibrium wb (L) and column pD M sb IRA Equilibrium pD 904 (A) and column M IRA 93 Equilibrium wb (A) and column pD I sb XE 258 Equilibrium ac (A) and column I wb XE 236 Equilibrium ac (A) and column M Duolite Equilibrium wb S37(D) and column pf I sb FF/IP Equilibrium po (P) and column 100 various TOC – Caustic brine 50°C Caustic brine Caustic brine – 40 Total organics Colour p-nitrophenol – – 43 44 10 2·7 1·5 4 23 n-butanol methyl ethyl ketone nitromethane 1.4-dioxane u.v.

Such a system has been used for the recovery of a wide range of organics from water samples prior to analysis.v. However.4-D γ-D – – – – Caustic brine 40°C Sodium hydroxide 40°C Caustic brine 40°C Caustic brine 40°C Ammonia 20°C NaOH 20°C PV Organic carbon Caustic brine (reused) – – – – 2. . if a very high standard of organics removal is required the series combination of activated carbon and a macroporous anion exchange resin would be a powerful one.absorption TOC DBS 2.Removal of organic compounds 45 I wb H/IP Equilibrium po (P) and column I wb M/IP Equilibrium po (P) and column M np XAD-2 Equilibrium pD (A) only M np XAD-7 Equilibrium ac (A) only M sb MP 500 Extended pD (L) column test M wb pD I sb ac MP62 Extended (L) column test XE 258 Extended (A) column test u.4 – – – – 12 2·4 12 2·4 12 I sb TR (P) Extended po column test M MP 62 wb (L) pd M Duolite wb S37(D) pf M sb MP500 pD (L) Extended column test Extended column test Column test – – 2·4 12 2·4 12 45 67·5 1·1 46 M wb Grantex Column (E) test PV Organic carbon Caustic brine 6 10 Key to abbreviations M macroporous I isoporous np non-polar mp medium polar an anionic wb weak base sb strong base po polystyrene pD polystyrene-DVB acrylic ce cellulosic (viscose) pf phenolformaldehyde ca carbonaceous A Amberlite (Rohm and Haas) D Diamond Shamrock L Lewatit (Bayer) P Permutit E Ecotech regenerant is of interest. but a concentrated waste liquor would remain to be disposed of.

Removal Mechanisms Organic species may be rejected either because they have a low solubility in the membrane material or because. as developed for desalination of water. The feedwater has to be applied to the membrane at a high pressure to overcome the natural osmotic pressure (which increases with the salinity of the feed) and provide an adequate flux (rate of permeate production per unit area of membrane).6. viruses and larger particulate matter. 6. The rejected species are therefore concentrated into a waste stream as illustrated in Fig.2.1. design and operation of RO plant in depth. It is necessary here to make only brief reference to the fundamental concept of RO and to define certain terms. 2. whatever their solubility. Introduction The process of reverse osmosis. FIG. . REVERSE OSMOSIS AND ULTRAFILTRATION 2.Developments in water treatment—2 46 2. Water is forced through a membrane which retains (rejects) dissolved inorganic and organic compounds as well as bacteria. Reverse osmosis schematic. and they are therefore concentrated in the waste stream. 6. their size hinders their passage through the membrane. Chapter 4 describes the application of reverse osmosis (RO) to desalination and covers the theory.6. In either case the organic molecules permeate the membrane at a much lower rate than do the water molecules. is also effective in removing organic compounds from water.6.

The theory predicts that in general aldehydes. It appears that odorous compounds present in the Trent water were less readily rejected than the bulk of the organic matter present. This type of membrane can also be operated at extremes of pH which would rapidly hydrolyse cellulose acetate. The rejection of total dissolved solids under these conditions was 95% or higher. Experimental Results The rejection of many organic compounds has been studied mainly in laboratory units using the common cellulose acetate membrane material. This regime permitted a flux of about 0·013 m3/m2 atm to be maintained at 28 atm feed pressure with either tube or spaghetti modules. but also to reduce the permeate flux rate. Cellulose acetate membranes were also used in continuous operation on River Trent water. 2.6. if particular compounds or groups are to be removed. adsorbed solutes should rapidly saturate the membrane and thereafter be rejected according to their solubility and size. About 80% of organic matter (as TOC) was rejected from Cincinatti tap water by cellulose acetate membranes. certain organic substances permeate the membrane more readily than water and their concentration is therefore higher in the permeate than in the feed. it was concluded that daily flushing with Calgon solution was the most effective of the methods tried. notably aromatics including polynuclear aromatic hydrocarbons (PAH). are adsorbed onto the membrane and are thereby attenuated in the permeate. that is. ketones.4-D are summarised by Love.31 This gave valuable experience on the practical operation of both tubular and ‘spaghetti’ type RO modules. polyethers and long chain fatty acids. To remove the former groups the theory indicates that an aliphatic nylon membrane would be effective. The removal of organic materials is illustrated by Table 6. however. ethers and esters will be rejected less effectively than will ionised compounds or highly hydrogen-bonding compounds. phthalates. Adsorption of large quantities of some organics might be expected to improve the rejection of other species.49 The concentrate included hydrocarbons. perhaps operated at diiferent pH values. Results for the removal of the pesticides Lindane and 2. could therefore be used to obtain a very comprehensive concentrate of organic materials from water for analytical investigation. It should be noted that treatment of the river water prior to RO was limited to rapid sand filtration and pH adjustment to about pH 6 using sulphuric acid. This has implications for the use of laboratory batch tests for the prediction of RO performance. It has also been observed in laboratory tests that certain organic compounds. the product to feed flow ratio was 75%. Product quality is satisfactory compared with the potable water quality requirements of Table 1 except in respect of threshold odour number. The implications for full-scale treatment are that.7 concentrations and/or pressures used in the reported studies do not however appear to accord with expected full-scale conditions. as would be . chlorinated compounds. the selectivity of various RO systems could be considered. Klein et al. A series of RO modules with different membranes.48 describe the use of solubility parameters to predict the rejection of organic compounds by cellulose triacetate and ethyl cellulose membranes. On the basis of product flux recovery and product quality. In continuous processing.Removal of organic compounds 47 Negative rejection is also possible.3.

4.5.Developments in water treatment—2 48 predicted from their aromatic nature. three other configurations are available: flat plate. spiral wound and the very high specific surface area hollow fibre system using aromatic polyamide material. However. Hollow fibre units are susceptible to organic fouling and are not guaranteed for use on feedwaters with more than 5 Hazen units of colour. Other applications which have been suggested include: . It is unlikely that RO would be the process of choice specifically for organics removal in the production of potable water. Applications The high cost of RO derives from the sophisticated technology.31 by courtesy of Water Research Centre Parameter Concentration Concentration in feedwater in product Colour (optical density at 400 nm) Optical density at 300 nm Total organic carbon (mg/litre) Anionic detergents (mg/litre) Monohydric phenols (mg/litre) Threshold odour number Pesticides αBHC (µg/litre) γ-BHC (µg/litre) 0·048–0·093 0–0·01 0·24–0·87 0–0·3 4·27–21·4 0·1–0·64 0·13–0·54 0–0·1 0–0·004 0–0·002 20–100 0·008–0·172 0·033–0·21 5–24 0–0·12 0–0·14 2. There is a possible application in the preparation of samples for organic analysis.6. as mentioned above. the high pressure required.50 2. TOC was reduced by 97% on average by the tubular modules. After Melboume. Membrane Configurations Besides the tubular and ‘spaghetti’ systems already mentioned. and the difficulty of disposing of the reject stream. it could be competitive if the removal of inorganic salts was also required.6. TABLE 6 PERFORMANCE OF TUBULAR RO ON RlVER TRENT WATER.

Adsorbent resins. the UF membrane is more ‘open’ so that only large molecules are rejected. As an intermediate stage in boiler feedwater treatment.g. humic acids would be removed and one possible application would be the reduction of humic colour prior to RO of the hollow fibre type. have not yet found practical application in potable water supply. The mechanism may be thought of as sieving. Product flux rate is considerably higher in UF.51 The concentration of regenerant liquors from organic scavenger resins. Activated carbon is generally the most cost-effective treatment for the removal of specific organic compounds and groups of compounds including taste.Removal of organic compounds 49 The removal of pyrogens in the preparation of pharmaceuticals and injections. to remove organics and reduce the inorganic ion load prior to a final ion exchange stage.6. e. UF has been used to concentrate large organic species. disinfection and chemical oxidation remove organic matter to some extent. . 2.6.52 In water treatment.7. whereas RO of waters containing up to 10 000 mg/litre salinity requires pressures of 20 to 40 atm. Ultrafiltration is considerably cheaper but effective only for the removal of large organic molecules. viruses and polypeptides. though widely used in boiler feedwater treatment. Thermal regeneration has the advantage of completely destroying the organic matter removed from the water. Reverse osmosis is extremely effective for the removal of a wide range of organic compounds but is prohibitively expensive except for small specialised duties or where its deionisation capability is also required. The removal of algal products (polysaccharides) which can cause problems in soft drink manufacture. but insufficiently to meet the latest stringent requirements for industrial and municipal water quality. granular activated carbon beds offer considerable economies and the opportunity to employ on-site regeneration of exhausted carbon in high temperature furnaces.and odourproducing substances. Ultrafiltration Ultrafiltration (UF) is closely related to reverse osmosis. 2. proteins. There are many installations of powdered carbon for the removal of tastes from potable water. For heavier or more stringent organics removal duties. Dissolved solids of molecular weight greater than 1000 were found to be removed in the study of Hardt et al. Resins and membrane processes suffer from the disadvantage of a concentrated liquid waste which must be disposed of. Inorganic salts are not rejected so there is little osmotic pressure to be overcome and operating pressures are normally below 7 atm. Compared with RO. often with considerable difficulty at high cost. CONCLUSIONS The processes of coagulation.

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93.J. 1975.L. J. MCGUIRE. 69. paper presented to American Chemical Soc.J. 23. C.. 1973. TR 74. HERZING. 1975. and WOOD.H. 50. in Activated Carbon Adsorption of Organics from the Aqueous Phase. 25. TILSLEY. 1977. 1979. Water Research Centre. Effl.J..L. J. July/Aug. & Scientists. V.. 1979.I. 669. 1975. Water Engrs. W.L. 33. Amer.W. Pergamon Press.. ROBERTSON.D. 36. 30. R. 33. 1978. 1979. and KENNETT. R. Instn Water Engrs. 18. ROWE. R. MELBOURNE.C. 1978. 68. R. 1978. 2135.. Engng. J. JUNK.L. Water Treat. Van Nostrand Rheinhold Co. La Technique de l’Eau. 1978. Northern Section. J. 15.A. Sept.A. 69.. HARDT.. Amer. GRANT. 1976. 1979.R.. 37.. 2.. 47. 38. E.F.A. in New Processes of Waste Water Treatment and Recovery. 27.. 40. Chem.). and SVEC. J. 70. MCWILLIAM. G. Chemy Ind. 1973. Water Supply & Management. and RAY. Water Research Centre.W. 1970. S. p.. CULP. 799.. June 18. 1975. MELTON. N. J. Water Pollut. 807. ERICSON.D. and SMITH. H. and SAUNDERS. Engng. 69. 1. 621. J. Vol.L. G. D. ANON. R.. 1971. C. Bucks. and MITCHELL. J. Effl... HYDE. and WASHINGTON. J. DIENZER. Water Res. C... Water & Sewage Works. SUMNER. J. 1978. J. M. 1977. Chichester.. KOLLE. Y. 120.. N. BROWN.. LEE. 52. Water Treat.. 35. Medmenham. J...A. June 4. Mattock (Ed. Water Works Assoc. and SANCHEZ.D. Water Works Assoc. 44. Marlow. 15.J. 42. Instn. 581.. 417.. GAUNTLETT. KIM. 28. M.P. SNOEYINK.. 1975. Bucks. D. J.. TREANOR. 823.. M.M. R. 46. published for the Commission of the European Communities.‘A Comparison between lon-Exchange Resins and Activated Carbon for the Removal of Organics from Water’. 29. 49. S. Advanced Wastewater Treatment. May 1979. L. ROBINSON. 1971. 16. papers presented to US Environmental Protection Agency Conf.. 28. K. C. Water Pollut. J. Treat. Mich. Ellis Horwood Ltd.. Effl.. 27. 9. K. Water Purification in the EEC. WATER RESEARCH CENTRE.. Suffet (Eds. Control Fed. 39... SCHALEKAMP. ANON.. R. M. Ann Arbor Science Publishers Inc.S. 9. CLESCERI. 142.W. 56. LOVEN. ‘River Trent Treatment’. Control Fed.R.W. 45. B. 1978. 1972. 15. ADAMS. BOSSY. OEHME. A.. I. EICHELBERGER.D. Ann Arbor. Adsorption Techniques—Practical Application of Adsorption Techniques in Drinking Water. and BAKKER. and MARTINOLA. G.R. 51.H.M. 48. EYER. Water.J. JANECEK. Oxford. J. 31. and LICHTENBERG. 41. Miami Beach. A..S. and SUFFET... Chemy Ind. 1978. p.. Marlow. Engng Prog. J. and KENNETT... 26.. Water Works Assoc. . p. p. 24..M. J. R. Water Works Assoc.J.. Water Treat. 43. Water Services.A. N.L. Effl. Amer..E. 223.. 519.. 79. 14. OSBORNE. May 22.B. F. C. TR 10. Symposium. Chemy Ind. (In press). J. Chem. (11). 431. 22.. Sep. 2... V.. 126. Amer. Chem. CHRISWELL. March 3.F. A. paper presented to the Institution of Water Engineers and Scientists. 516. NEMEROW...Removal of organic compounds 51 21. 1980. 1977. p. Va. p. p. F. 63. D. J.. Reston. JØRGENSEN. Amer. D.).... J. Water Works Assoc. Medmenham. 1974. 80. New York.. G.. W. SNOEYINK. 48. KLEIN. EICHELBERGER. 475. 1975. 42. FRITZ. 15. Water Res. J. 1977. and CULP. 32. 70.. 1973.J.W.. G. F. 1978. 34. 455. McGuire and I. M. 25.


The best method to use will depend on the particular circumstances at the treatment site. UK SUMMARY Improvements in sewage and water treatment processes are reducing the need for removal of high concentrations of ammonia for potable waters.W. Nitrate levels in both surface and underground water supplies are tending to rise due to the use of agricultural fertilisers. Bucks. Medmenham.. The World Health Organisation (WHO) European Standards recommend a level of not more than 0.05 mg/litre in supply. INTRODUCTION The two forms of nitrogen that may require removal during potable water treatment are ammonia and nitrate. ammonia removal has been carried out by breakpoint chlorination. while high nitrate levels can cause methaemoglobinaemia in infants and there has been some suggestion that they may also give rise to the formation of carcinogenic nitrosamines in the stomach. incompletely treated sewage or possibly industrial effluent may be another. Ammonia can interfere with the disinfection of water by chlorination. Water Research Centre.S. however.. Work in the Netherlands has shown. B.Chapter 3 REMOVAL OF NITROGEN COMPOUNDS R. while in populated areas. and the relative advantages and disadvantages of ion exchange and biological treatment are reviewed in the chapter. but usually at levels too low to be of consequence. Ammonia occurs in surface waters as the result of pollution. Ammonia in its undissociated form is toxic to fish at quite low levels . There is now. however. No direct hazard to health has been demonstrated due to ammonia in drinking water. Nitrite may also occasionally be found in water.A. The excretions of wild or farm animals may be one source. Biological methods are however being developed and these are expected to find their principal application in the treatment of surface waters.GAUNTLETT. M.E. At present ion exchange is sometimes used for nitrate removal from underground waters before they enter supply. 3.I.B. an increasing acceptance of biological methods for ammonia removal because of trihalomethane formation resulting from the application of high chlorine doses to surface waters.1. that levels of ammonia in excess of 0·3 mg/litre can lead to aftergrowths in the distribution system with associated taste problems. Ammonia is sometimes found in groundwaters as a result of biological denitrification or from the breakdown of proteinaceous organic material by saprophytic bacteria and fungi. Traditionally.

for example. More polluted rivers such as the Trent or Rhine now have an average of 1–1·5 mg/litre ammonia. due to bacterial or algal action in the reservoir. and give rise to concern in relation to methaemoglobinaemia in infants. for example. the natural nitrification processes taking place in rivers slow down and sewage works may also have difficulty in producing a nitrified effluent. In highly populated areas. at least seven times its own weight of ferrous iron to reduce it to nitrous oxide and ammonia.5 mg/litre) and its removal can be important for fish farming. In winter. nitrified sewage effluent has in a few cases been found to contribute a significant amount of nitrate to the river it discharges into. On the Continent. Nitrate-nitrogen levels above 11·3 mg/litre have been experienced at a number of boreholes. Some reduction in nitrate levels is also often found on storage.Developments in water treatment—2 54 (<0. such as nitrogen trichloride from . Nitrate levels on the other hand have been rising in the United Kingdom as a result of an increase in the use of fertilisers and in the proportion of land used for arable cultivation. Ammonia is the most reduced form of nitrogen and requires a 7·6:1 weight ratio of chlorine: ammonia-nitrogen for oxidation to nitrogen. Nitrate levels in several rivers such as the Thames and Great Ouse now regularly exceed 11·3 mg/litre for periods during the winter months. however. physico-chemical and biological. The treatment methods available for the removal of ammonia and nitrate will be described individually in more detail later. At particular locations or times the level may be at least twice the average. but treatment can often be avoided where water from a nearby low nitrate source can be used for blending prior to putting the water into supply. Thus the amounts of oxidant or reductant required tend to be large. has been found to require. Nitrate on the other hand. levels above 2 mg/litre are not uncommon and boreholes containing as much as 8 mg/litre are used for potable supply after treatment for ammonia removal. particularly where a high proportion of the water is recycled. The proposed EEC maximum admissible concentration for drinking water is 11·3 mg/litre of nitrate-nitrogen. which corresponds to the maximum ‘recommended’ WHO level. Ammonia is seldom a problem in groundwaters in the United Kingdom. Levels above 22·6 mg/litre nitrate-nitrogen are ‘not recommended’ by WHO. High nitrate levels in some underground waters have already become a problem in the United Kingdom and treatment is being practised at two borehole sites in East Anglia. Where raw water storage reservoirs are used. particularly at times of low flow. it may be possible to cease abstraction from the river during periods of high river nitrate levels. The occurrence of nitrate in both surface and groundwaters is associated with arable farming practice and the application of nitrogenous fertilisers. The current trends in the ammonia and nitrate levels found in sources used for potable supply are in opposite directions: while river pollution becomes subject to closer control and sewage treatment becomes more efficient. Ammonia levels in relatively unpolluted rivers such as the Severn or Thames are under 0·5 mg/litre on average. but in each case they can be divided into three main categories: chemical. ammonia levels in rivers have tended to fall. thus causing ammonia levels in rivers to rise. Most nitrate is released after the soil has been ploughed. allowing organically bound nitrogen to become oxidised to nitrate which is then washed into the watercourse or aquifer by rain. being the most highly oxidised form of nitrogen. and there is always the possibility of undesirable end-products appearing.

In practice. large nitrification plants have been in operation for many years in France and Holland treating groundwaters whose . Biological methods also have the advantage of producing few. These disadvantages are most marked in the case of nitrate reduction. depending on conditions. particularly for nitrate removal. per unit volume of treatment vessel. Biological treatment methods rely on processes already occurring to some extent in nature. This involves the use of high concentrations of bacteria in the form of small flocs or as a thin film covering a finely divided medium such as sand. using the oxygen dissolved in the water to do this. Air-stripping seems an obvious possibility for ammonia removal but. which may occur at different locations in a river or reservoir. If however the nitrate so produced results in an unacceptably high nitrate concentration. is added to give good reaction rates. but produce waste streams that are often difficult to dispose of in an acceptable manner. The basic requirement for achieving this is the attainment of as high an interfacial surface area as possible. and ultimately also nitrate. In contrast. unwanted side products and no environmentally undesirable wastes. and require a suitable source of oxidisable organic carbon. the growth of nitrifiers is slow and the cell yield is small. As regards reliability. such as methanol or ethanol. Reverse osmosis is unlikely to be an economic choice in most cases. They do not adhere as readily as denitrifiers to surfaces and are more susceptible to poisons. They carry out the oxidation. their performance has been found to be almost unaffected by the variations in the quality of a lowland river such as the Thames. between the water and the bacteria. so that there is no difficulty in maintaining the bacterial mass or film. apart from its high cost. a simple easily oxidised organic compound. Thus the two processes. Indeed. in the absence of further pollution. The denitrifying bacteria also derive their energy from oxidation. Nevertheless. denitrifying bacteria grow easily and adhere well to solid surfaces. In fact they can usually be made to operate much faster than chemical methods. denitrification may also be required. the bound oxygen in the nitrate. Reaction times can also be long. Where only ammonia removal is needed. Physico-chemical methods such as ion exchange or reverse osmosis are usually able to treat the water in a shorter time. whereas ion exchange often merits consideration. and then. it can suffer from freezing problems at low air temperatures and from calcium carbonate precipitation if the water is hard. can ultimately convert inorganic nitrogen compounds to nitrogen gas. Algal activity can also result in a significant reduction in nitrate levels in raw water storage reservoirs. the nitrification step alone will usually suffice. when conditions have become anaerobic. Biological treatment methods are often given little consideration because they are thought to be slow and unreliable. if any. For denitrification.Removal of nitrogen compounds 55 ammonia oxidation or ammonia from nitrate reduction. via nitrite. first using the free oxygen available. water in a river or reservoir can be expected to lose ammonia. by biological action: The nitrifying bacteria derive their energy from oxidising ammonia to nitrate.

Developments in water treatment—2


composition can be relied upon to remain reasonably constant. With river waters, on the other hand, experience has shown that seasonal variations can be expected in the bacterial population of a nitrifying unit; for instance, a decline is often observed in the autumn. The reasons for this are not clear and there is scope for more research into ways of improving the reliability of river water nitrification. Biological methods compare very favourably in cost with other methods. In view of this and their other advantages they will be discussed in some detail in the following sections dealing separately with ammonia and nitrate removal.

3.2. AMMONIA REMOVAL 3.2.1. Breakpoint Chlorination This is the most frequently used method for ammonia removal. It is usually applied in the treatment of surface waters; and has the advantage of being cheap to install and simple to operate. The basic chemistry of the process is now well known1 and will not be described here. In essence, a sufficient chlorine dose is applied prior to clarification to react with all the ammonia present to give predominantly nitrogen and a minimum of chloramines and nitrogen trichloride. If no organic nitrogen compounds are present, this occurs at the Cl:N weight ratio of 7·6:1 (the breakpoint) that varies slightly with pH. The time spent in the clarification stages of treatment should be sufficient for completion of the chlorination reactions prior to final chlorination of the water before it enters supply. Sometimes excess chlorine is applied initially so that dechlorination (e.g. with sulphur dioxide) is used to regulate the residual entering supply. It may not always be easy, however, to control the overall chlorination procedure so that an adequate chlorine residual is maintained in supply for disinfection. This is particularly the case when organic nitrogen compounds, as well as ammonia, are present thus increasing the variety and duration of the chlorination reactions. Also, nitrogen trichloride or dichloramine can be formed under many conditions, giving rise to taste and odour problems in supply. The disadvantages of breakpoint chlorination become most evident when ammonia levels are consistently high. The process then becomes much more expensive to operate in comparison with the biological method (see Fig. 1). Breakpoint chlorination has then been advocated2 as a back-up

Removal of nitrogen compounds


FIG. 1. Estimated costs of ammonia removal processes.
process to supplement biological nitrification where the latter cannot always be relied upon to remove all the ammonia. High ammonia levels also increase the likelihood of unacceptable amounts of nitrogen trichloride being formed, especially when the chlorine dose exceeds that required to reach the breakpoint and if the pH is low. In practice, the chlorine dose will almost certainly be in excess of that required to reach the breakpoint, if only to guard against variations in ammonia level. Where dechlorination is then applied, the excess free chlorine will be removed before the dichloramine and nitrogen trichloride, which may remain. With further dechlorinating agent, the chloramines and nitrogen trichloride are converted back into ammonia. Thus dechlorination cannot entirely remedy the effects of chlorinating beyond the breakpoint. It is perhaps worth noting that activated carbon can be used for dechlorination.3 It can only be used for total dechlorination, however, so that the required chlorine residual for supply would have to be added after dechlorination by carbon. Active carbon has the advantage over sulphur dioxide of being able to convert nitrogen trichloride and dichloramine into nitrogen instead of ammonia,4 while monochloramine is converted to a

Developments in water treatment—2


mixture of nitrogen and ammonia. Thus the possibility of ammonia reappearing during dechlorination is substantially reduced. Variation in the ammonia level of the raw water can of itself present problems when breakpoint chlorination is practised, even if ammonia levels are quite low. Saunier5 maintains that chlorine doses beyond the breakpoint can give rise to objectionable amounts of nitrogen trichloride at ammonia levels above about 0·2 mg/litre. If, on the other hand, the initial chlorine dose is insufficient to reach the breakpoint, final chlorination may result in a continuation of the chlorination reactions, and make it difficult to regulate the free chlorine residual. The breakpoint chlorination method therefore requires an accurate adjustment of the chlorine dose according to the variations of ammonia level in the raw water. Apart from accurate chlorine dosing an essential requirement for the success of breakpoint chlorination is an adequate contact time with the chlorine before either dechlorination or final chlorination. An inadequate contact time renders the result of the initial chlorination uncertain and may result in ammonia or dichloramine remaining in the water after dechlorination. Where dechlorination is not practised, the chlorination reactions may continue in supply, thus rendering the chlorine residual impossible to control. Saunier5,6 has found from theoretical predictions and practical tests carried out at 15°C that an effective contact time of 2 min was required to eliminate 20 mg/litre of NH3–N, and 40 min to eliminate 1 mg/litre NH3–N, at pH 7·3. A lowering of temperature, or a pH outside the range 7 to 8, resulted in longer contact times being needed. The effect of temperature and pH was studied by Wei and Morris7 who found that a temperature drop of 10°C almost doubled the time required for reaction. The combined effects of low temperature, a pH below 7, and short circuiting in clarification or holding tanks can result in a long actual residence time being required. This could well amount to two or three hours. High chlorine doses can have undesirable consequences quite unconnected with the presence of ammonia, since it may react with the organic material in surface waters to form trihalomethanes (THM). This has been found8,9 to take place with naturally occurring humic and fulvic acids to a degree dependent on the chlorine dose. The results of a national survey carried out on THM formation during water treatments in the USA showed10 that there was a fair degree of correlation between the chlorine demand of a water and its THM content after chlorination. Rook has also shown11 how the THM formed in a surface water after 1 h increased with chlorine dose. Once formed, THMs are not easily removed, since they are poorly adsorbed by active carbon, for instance. Breakpoint chlorination may also adversely affect later treatment stages: Sontheimer found12 that it lowered the overall efficiency of organics removal by biologically active carbon as a result of the formation of organochloro compounds. The current trend on the Continent, where active carbon is often used and ammonia levels in surface waters may be high, is therefore away from breakpoint chlorination as the principal means of ammonia removal. Instead, biological methods are preferred for removing the greater part of it. Chlorine is the only oxidant that has found practical use for ammonia removal. Ozone reacts too slowly with ammonia under normal circumstances, although solid catalysts have been found13,14 to increase the reaction rate. Ozone reacts only with free ammonia

Removal of nitrogen compounds


forming nitrate and the rate of reaction therefore increases as the pH is raised through the range 8 to 10. However, carbonate ions and organic solutes interfere strongly with the reaction above pH 9, by competition with ammonia for the available ozone. It has been estimated15 that for a typical surface water of pH 8 containing 1 mg/litre NH3–N, the ozone would react at least an order of magnitude faster with the other solutes present. 3.2.2. Physico-chemical Methods Physico-chemical methods of ammonia removal have found little application in potable water treatment, but have been given more serious consideration for wastewater treatment, where ammonia levels can be much higher. Considering first ion exchange, a comparative study carried out by Jorgensen on several different types of cation exchanger16 showed that clinoptilolite, a natural zeolite, had the highest ammonia removal capacity. It was also less expensive than conventional synthetic cation exchangers. A direct comparison of the selectivities of Hector clinoptilolite with a strong acid polystyrene ion exchange resin has shown17 that the latter preferred calcium ions to ammonium ions whereas for clinoptilolite the opposite was true. It is therefore possible to regenerate clinoptilolite with relatively inexpensive lime and calcium chloride. Pilot plant tests carried out on a wastewater containing 10 to 20 mg/litre NH3–N by the US Environmental Protection Agency18 have shown that columns of Hector clinoptilolite brought the ammonia level down to 0·5 to 1·0 mg/litre NH3–N. Further treatment by breakpoint chlorination might therefore be required to produce a potable water. As much as 99% ammonia removal has been demonstrated17 using two laboratory columns in series. The regenerant used in the pilot plant study was a mixture of sodium and calcium chlorides adjusted to pH 11 with lime. Regenerant recovery was also studied, using either air stripping to blow off the ammonia, or electrolysis which generated chlorine to react with the ammonia and so convert it to nitrogen. An advantage of the electrochemical method of removing ammonia from spent regenerant was that neutral regenerant solutions could be used, thus avoiding precipitation and scaling problems associated with the use of lime. Ion exchange using clinoptilolite was found to be a more expensive process than direct air stripping. Most studies of ammonia removal by air stripping have been carried out on wastewaters. Since ammonia is very soluble in water, an air: water volume ratio of about 3000:1 is required for 90% removal at 10°C in a counter-current air stripping tower. As the temperature falls, the amount of air required increases. For air stripping to be successful, the greater part of the ammonia must be converted into its free form by raising the pH of the water. Several studies have shown that ammonia removal efficiency increases considerably as the pH is raised to 10·5, but that little further improvement can be expected beyond pH 11. The lime dose needed to achieve pH 11 depends on the alkalinity of the water, being about 400 mg/litre Ca(OH)2 for an alkalinity of 200 mg/litre. Scaling can often cause problems when alkaline waters are treated. A pilot plant study of air stripping for potable water treatment has been carried out19 using a feedwater containing 3 mg/litre NH3–N and a tower packed with serrated wood slats. Water flowrates of up to 2 m/h were used and under the most favourable conditions an HTU of 2·3 m was obtained at 15–20°C. This implies a tower packing height of at least 7 m for 95% ammonia removal. The estimated cost of air stripping, compared to

Chedal2 has described how at Mery-sur-Oise nitrification in the flocculators is encouraged by sludge recirculation. depending on the backwash procedure employed. Below 5°C the performance fell off rapidly. Ammonia removal by bacterial nitrification on rapid sand filters has also been studied by Taylor20 who found that residual chlorine present in excess of 0·2 mg/litre adversely affected the process. 1. This was entirely due to bacterial action in the bed since carbon cannot adsorb ammonia. It was observed that during the prolonged frost of the 1962/63 winter. Madsen has stressed21 the importance of maintaining the water as close as possible to 100% saturation with oxygen to assist performance at low temperature. His results showed that about 75% ammonia removal was achieved on the filters over a period of a year. which contained ammonia levels varying seasonally between 0·2 and 2·0 mg/litre. 3. He also demonstrated with a . The major cost item was electrical power for the air blowers. Chemical costs for pH adjustment were not included in the estimate. nitrification can occur at almost any stage within an existing river water treatment plant. Normally. is biological nitrification. This is usually accomplished by forced aeration through fixed beds of sand or granular material to which the nitrifying bacteria adhere. The results of lower removal efficiency (due to higher ammonia solubility) at low temperature and the possibility of freezing need also to be taken into account when deciding if air stripping would be a feasible process in practice. The ammonia removal performance of a number of different types of filter has been studied by Madsen21 using water from the River Weser. Biological Nitrification The cheapest process capable of reducing high ammonia levels (>0. since the ammonia levels in rivers also tend to be highest at this time. Usually. nitrification in the rapid sand filter ceased and did not resume until the temperature had risen again to 10°C. Small-scale tests using granular active carbon or limestone of similar particle size to rapid sand (~1·5 mm) showed better nitrification performance than rapid sand.3. Up to a further 1 mg/litre NH3–N is then removed by nitrification in the rapid sand filters. is shown in Fig. provided the water has not already been chlorinated. to compensate for the lower rate of bacterial activity. although during several other winters over 80% removal was maintained. so that after about two weeks operation 60% of the ammonia is removed. Nitrifying bacteria utilise about 4·6 mg/litre of dissolved oxygen to oxidise 1 mg/litre NH3–N. The diminished nitrification performance of filters at low temperature is unfortunate. The performance of a slow sand filter was similarly affected. however.Developments in water treatment—2 60 other methods of ammonia removal. there was a tendency for ammonia removal performance to deteriorate when temperatures fell below 4°C. during which the NH3–N level in the raw water varied between 0·1 and 4 mg/litre and the temperature fell as low as 1°C on one occasion. A 3 m deep granular carbon bed run at a flowrate of 10 m/h was able to almost totally remove the ammonia at temperatures down to 5°C.2. and could result in a doubling of the total cost for highly alkaline waters. Therefore if it is required to remove more than about 2 mg/litre NH3–N special measures must be taken to oxygenate the water during the nitrification process. It was also found advantageous to reduce the filtration rate from 6 m/h in summer (20°C) to 3 m/h in winter (4°C).3 mg/litre NH3–N) to a point (<0·1 mg/litre NH3–N) where problems arising on chlorination are unlikely.

The work done with the River Thames pilot plant25 indicated that upflow rates as high as 24 m/h could be used in a tank with vertical sides. although this may not be necessary at times of high river turbidity. by bacterial action on its surface. Usually more than 90% of the ammonia is removed. This ability has been put into practice at Müllheim12 where filtration through granular active carbon is now preceded by ozonation in place of breakpoint chlorination.24 and the process has also been studied on pilot plants treating water from the Thames25 and Trent. depending on conditions.Removal of nitrogen compounds 61 carbon filter that low temperature performance could be better maintained if the filter had already been acclimatised to removing the higher winter ammonia levels before the temperature dropped. and dissolved organic matter by a combination of bacterial action and adsorption. A combination of temperatures below 8°C and upflow rates higher than 24 m/h caused excessive expansion of the fluidised bed and a significant drop in the reaction rate. as may be seen from Fig. Two waterworks on the River Severn use fluidised beds for ammonia removal23.26 The average ammonia levels are about 0·3 mg/litre in the Thames and Severn. Granular active carbon is capable of removing both ammonia. and 1 to 1·5 mg/litre NH3–N in the Trent. although sudden increases in the ammonia level of the river have resulted in short periods of poorer performance. This was done by dosing ammonia into the water while the temperature was still above 10°C and before the ammonia level had risen in the river. The time taken to establish a fully active biological bed can vary from a few weeks to as much as three months. Effective operation of the bed required a fluidised solids concentration of over 35% by settled volume. A similar 2000 m3/h plant in France22 achieves over 80% ammonia removal on active carbon from ozonised water containing 1·5 mg/litre NH3–N. giving residence times of 14 and 19 min. 2. Similar upflow rates and residence times were used for the River Trent pilot plant and its performance was also very similar despite the higher (0·5–2 mg/litre) NH3–N concentration in this river. . When starting up the beds it has usually been found advantageous to charge the beds with fine (0·05–0·2 mm) sand. particularly when the temperature was low. The waterworks use inverted pyramidal tanks with upflow rates of 7 and 10 m/h at the top. In all cases the fluidised beds were composed of river silt which formed the support medium for the nitrifying bacteria. in treating water from the River Dohne. The fall-off in nitrification performance at low temperatures that is observed in sand filters can be largely overcome by the use of fluidised beds in place of fixed beds. At the same time the ammonia (~1 mg/litre) is now removed by bacterial action in the carbon filters. which are 2·5 m deep and are operated at a flowrate of 10 m/h. This has improved the removal of organic matter by the carbon since poorly adsorbed chlorinated organic compounds have been replaced by the readily biodegradable products of ozone oxidation.

4. The value of K.Developments in water treatment—2 62 FIG. 2. The rate of reaction was found to be approximately first-order with respect to ammonia concentration. the rate constant. . Using the lower figure of 0·5 min–1 for K. was found to be between 0·5 and 1·5 min−1 depending on conditions such as temperature within the range 5°C to 20°C. Thus: where C is the concentration of NH3–N. 3. The better performance attained by fluidised beds compared with fixed bed filters is due to their higher bacterial mass per unit volume. Effect of fluidised bed solids concentration on nitrification performance. as indicated by the gradient of unity in Fig. the calculated residence times to achieve residual NH3–N concentrations of either 0·1 or 0·04 mg/litre are shown in Fig.

This would enable up to 8 mg/litre NH3–N to be removed. Thus far. has been described. If it is desired to remove more than this amount of ammonia. A fluidised bed system capable of removing 20 mg/litre NH3–N from a wastewater at Bay Park.27 It involved recycling just over two-thirds of the nitrified effluent from the unit back to the inlet. the dissolved oxygen content of the raw water may be increased to 40 mg/litre by equilibrating the water with pure oxygen gas at the maximum hydrostatic pressure available at the base of the nitrification unit. USA. only the performance of nitrifying systems relying on thedissolved oxygen already present in the raw water has been considered. Hence the combined . where it re-entered after being mixed at a ratio of 2·3:1 with the raw wastewater. Variation of nitrification rate with ammonia concentration. 3.Removal of nitrogen compounds 63 FIG. They are therefore only capable of removing 2 to 2·5 mg/litre NH3–N at most.

two borehole-derived waters containing 7 mg/litre NH3–N in one instance and 16 . Residence time required in fluidised bed. The operation of ‘dry’ sand filters has been described by Boorsma. The best published performance was found by Rossner30 of Hamburg waterworks. Operated at flowrates of from 4 to 9 m/h. the ‘dry’ filters at Hillegom were able to reduce NH3–N levels of 3–3·5 mg/litre to less than 0·15 mg/litre. although sand graded down to 0·5 mm has been used. For most potable water treatment purposes. They have been employed mainly for the treatment of groundwaters on the Continent where ammonia levels of 8 or even 16 mg/litre are not unknown. iron and manganese. To date. the removal of more than 2 mg/litre NH3–N from potable waters has been accomplished using two types of aerated fixed bed. obtained by equilibrating the influent with oxygen gas. The two types of aerated fixed bed are the ‘dry’ sand filters favoured in Holland and the aerated pumice stone beds used in France.Developments in water treatment—2 64 FIG. the use of either oxygen equilibration or partial recycling with re-aeration would be sufficient. 4. using sprays to distribute the water and blowers to introduce the air. The beds are totally enclosed so that in service both air and water can be passed downwards through them. Kegel29 quotes two examples of ‘dry’ filters operated at 12 m/h and an air: water volume ratio of 2·5:1 which brought ammonia levels of 1·4 and 4·5 mg/litre down to less than 0·05 mg/litre. Using two ‘dry’ filters in series at flowrates of 10 m/h and an air: water volume ratio of 3:1. They usually employ a 1 to 2 m bed depth of 1–2 mm sand. influent to the fluidised bed unit contained only 6 mg/litre NH3–N which was completely removed in presence of 36 mg/litre of dissolved oxygen. The treatment of these waters by nitrification is facilitated by their comparatively constant ammonia level and temperature. The beds are backwashed periodically in such a way as not to significantly impair their performance when brought back into service.28 who studied their performance for the simultaneous removal of ammonia.

In the latter case. the aeration is only applied intermittently to avoid expelling too much carbon dioxide. while the air flowrate is adjusted to provide sufficient oxygen to complete nitrification without producing a water that precipitates chalk.e. However. lasting several months for a groundwater or at least a year for a surface water. Thus where the removal of nitrate only is required. Both the air. supplied by compressors. NITRATE REMOVAL 3. Water flowrates of up to 10 m/h are used. reverse osmosis or a two-bed ion exchange system). Possible Methods Before considering treatment methods for nitrate removal alone. Despite the successes that have been achieved with biological nitrification. removing both cations and anions from the water (e. the fact remains that it is at present a less reliable (i. and the water are passed upwards through open 2 m deep beds of 8–15 mm pumice.3. Reverse osmosis membranes do not reject nitrate preferentially to other common anions. There remains a need for fundamental research to better determine all the factors affecting the process. will greatly reduce or eliminate the nitrate content. Economically. reverse osmosis only becomes competitive with ion exchange when the total dissolved solids content of the water exceeds about 1000 mg/litre. In a short but comprehensive review of nitrate removal methods.g. whereas anion exchange resins retain nitrate in preference to both chloride and bicarbonate. One plant treats water containing 4 to 6·5 mg/litre NH3–N while the other treats water with about 2·5 mg/litre. It was found necessary to add a trace of phosphate to the raw water in order to maintain satisfactory bacterial performance. so raising the pH. The size of the pumice medium was chosen to be small enough to present a large surface area per unit volume for the bacteria to grow on without at the same time causing an unacceptably large pressure drop through the bed. Before any nitrification plant is built for treating water going into supply it is essential that pilot plant trials be carried out. less predictable) process than biological denitrification.Removal of nitrogen compounds 65 mg/litre in another were thereby treated to produce a water containing less than 0·125 mg/litre NH3–N. . ion exchange possesses this advantage over reverse osmosis. Sorg32 states that neither electrodialysis nor reverse osmosis systems have yet been installed solely for the removal of nitrate from water. 3. The water then overflows onto sand filters to remove the bacterial matter it carries over. it may be noted that any demineralisation process. The period required for start-up may be long and can best be shortened by seeding the bed with bacteria from another similar plant already in operation. since nitrification tends to lower the pH: it was found possible to balance the two opposing effects and thus produce a stable water.3.1. The water has an alkalinity of about 300 mg/litre and aeration inevitably removes some carbon dioxide. Devillers has described in some detail31 the aerated pumice stone beds used at two 5000 m3/h waterworks near Paris.

and the reduction of nitrate has been achieved in the laboratory using simple molybdenum .34 This reductant was chosen after carrying out an extensive literature survey followed by feasibility tests on a number of reducing and deamination agents. A possible future method for nitrate reduction could involve the use of immobilised enzymes. three main methods of nitrate removal have received attention in the past: chemical reduction. These are illustrated schematically in Fig. Some work has been carried out to elucidate the enzyme mechanism used by bacteria for denitrification. and the constituents added to the water as a result of treatment at the right. 5 which shows in each case the chemical requirements of the method entering at the top. The possibility of reducing nitrate chemically using ferrous hydroxide precipitated in situ has been investigated in some detail by Gunderloy33 and Buresh. The presence of cupric or silver ions was found to catalyse the reduction by ferrous hydroxide.Developments in water treatment—2 66 Disregarding demineralisation. bacterial denitrification and ion exchange using a strong base resin. But the time still required for the reaction. the variety of possible end-products and the voluminous sludge produced made the method look unattractive as a practical treatment. the waste products leaving at the bottom.

In the presence of a suitable organic substrate. 5. Biological denitrification by naturally occurring denitrifying bacteria has been studied extensively for the purification of wastewaters and sewage effluents. Michigan36 Universities. Nitrate removal methods. This work is still however at an early research stage. these bacteria can reduce nitrate to nitrogen gas. complexes at both Manchester35 and Oakland. The most usual substrate used has been methanol since it is relatively cheap and easy to handle.Removal of nitrogen compounds 67 FIG. The only waste product is the excess bacterial growth which must be removed from the .

Organic fouling of the resin could well be a problem if ion exchange were used for this application. iron and to a lesser extent silica can cause resin fouling when present. provided the water is not pre-chlorinated. the rate of bacterial action declines at low temperatures.Developments in water treatment—2 68 unit for disposal. it is less expensive to install and operate. Although a denitrification plant may not be as convenient to operate as a single-bed ion exchange plant. It has not however yet been used in practice as has ion exchange.39 A 0·25 mgd fixed bed plant with the capacity for treating at least double this flow has been undergoing trials in Suffolk. The bacterial growth also requires time to become established in the unit after start-up. USA. however. A 2 mgd continuous ion exchange plant has been used at Long Island. The gradient of the lines is proportional to the operating costs which can be high for ion exchange. so that biological denitrification would be the more promising alternative. Apart from organic matter. thus making necessary a longer residence time in the treatment unit. Complete resin replacement has been assumed every five years. In any biological treatment method. Thus denitrification needs to be followed by aeration and filtration. and at least two weeks are usually needed to attain full performance. this process has been studied37 on a pilot plant for nitrate removal from River Thames water.38 and a similar plant of 0·37 mgdcapacity is operating in Lincolnshire. Fig. The intercept on the cost axis represents the annual capital cost amortised at 10% over 15 years for ion exchange and over 20 years for denitrification plant. 6 also includes the cost of blending the high nitrate water with a low nitrate water piped in from a distant source using 3:1 and 1:1 blend ratios to lower the nitrate level in supply.40 Pretreatment for iron removal may therefore be required with some waters.39 There is as yet no nitrate removal plant treating a river water. Figure 6 compares the estimated costs of the two processes. Treatment for nitrate removal may therefore not be needed during the summer months. As an alternative to treatment. Any residual methanol may be removed by evaporation in the aerator and. Ion exchange has already been used for the removal of nitrate from groundwaters. In the UK nitrate levels in rivers tend to increase in late autumn and winter when the rain washes it out of the soil. Ion exchange has the advantage of being a process that is predictable in performance and little affected by temperature change. Hence it is . The denitrified water is always anaerobic. not including nitrate or methanol monitoring costs. More recently. by further bacterial action in the clarifier or filters. may contain traces of residual methanol and will also carry over some bacterial floc with it.

it may only be necessary to treat a proportion of the water.3. the operating cost of the plant could be at least doubled. (mls=miles. 3. therefore. 6. The treated portion can then be blended with the remaining untreated portion to give the required nitrate level in supply. to the coast for instance. It is not. resulting from regeneration of the resin with brine. Costs for nitrate removal per 1 mgd (December 1976). Since biological denitrification and ion exchange are the only two practical methods of nitrate removal at the present time.Removal of nitrogen compounds 69 FIG. 6.2.Since ion exchange removes almost all the nitrate from the water being treated. nitrate and sulphate. Ion Exchange The aim of treatment will usually be to reduce the level of nitrate in the water put into supply to below 10 mg/litre as N. these will now be considered in greater detail. If this waste has to be tankered away. at present possible to .) amenable to automation and should be capable of working at a borehole site with little supervision. as indicated in Fig. On the other hand a troublesome waste disposal problem is usually presented by the exhausted regenerant and rinsewater which consist of a mixed solution of sodium chloride. It has been found40 that commercially available strong and weak base resins show greater selectivity for sulphate than for nitrate over the concentration range (<5000 mg/litre TDS) normally found in ground-waters. commencing with the longer established ion exchange method.

bicarbonate. Any sodium chloride present in the raw water is then not retained by the resins. replaces these anions by chloride ions. A wide range of styrenedivinylbenzene resins and some macroporous acrylic-amine and phenol-formaldehyde resins were recommended as a result of their tests. The large variation in chloride level and also in alkalinity (and hence pH) during the run would be unacceptable for a water going into supply. If an increase in chloride concentration is unacceptable or if calcium and magnesium removal (i. This process employs a strong acid resin. chloride and sulphate selectivities of the resin. are therefore required in practice to supply a water of uniform composition. Alternatively. in practice first consideration is usually given to the single-bed process if nitrate removal alone is required. using a strong base resin in the chloride form. However. this treatment may produce a water containing a high enough ratio of chloride to bicarbonate for it to dezincify domestic brass fittings. softening) is also required. the regenerant requirement may be reduced by postponing regeneration until divalent metal breakthrough occurs on the acid resin and nitrate breakthrough on the basic resin. The resin is then regenerated with sodium chloride which is a relatively cheap chemical. The combined spent regenerant could then be given away as fertiliser on account of its ammonium nitrate content. regenerated with mineral acid. a two-bed ion exchange process which at least partially demineralises the water may be used. regenerated with alkali. Clifford and Weber41 have compared the performance and cost of the single and two bed processes and found the latter to be up to twice as costly to install and operate. but is allowed to break through before termination of the service cycle.e. Carbon dioxide gas is formed as the water passes through the strong acid resin bed so that a degasser must be included at a later stage to remove it. The single-bed process. Figure 7 shows the nitrate. and these all performed very similarly. followed by a weak base resin. The sulphate was totally removed until well beyond the point of nitrate breakthrough where a service run would normally be terminated and regeneration carried out. combined perhaps with a treated water blending tank. using water containing equivalent amounts of each of these anions.38 In one section of the loop resin treats the water. and chloride levels found in the column effluent during an exhaustion run. as in the ‘Ducol’ process. while exhausted resin is regenerated and rinsed in another. Several resin beds run in parallel and regenerated in sequence. However.Developments in water treatment—2 70 remove nitrate by ion exchange without also removing sulphate. The problem of variation in treated water quality can also be largely overcome by use of a continuous ion exchange plant such as the Chemseps continuous loop.42 Also. The resin is periodically (every 20 min or so) pulsed round the loop so that a portion of exhausted resin leaves the top of the treatment section and is replaced by freshly regenerated resin entering the bottom of the section. They also determined how the performance of the anion resin bed in each process was influenced by the nitrate. Thus the variations in treated . The performance of some commercial strong base resins treating two model hard waters having the same nitrate content (14 mg/litre as N) but differing sulphate contents (20 and 120 mg/litre) has been studied43 using laboratory columns. the cost of regeneration could be lowered by using lime slurry to regenerate the weak base resin. To reduce spent regenerant disposal costs for the two-bed process it has been suggested41 that ammonium hydroxide and nitric acid be used as regenerants.

The regeneration efficiencies that are then obtained. 7. Similar regeneration efficiencies were found using a continuous loop instead of columns. Treated water quality from an ion exchange column. expressed as equivalents of nitrate removed per equivalent of sodium chloride regenerant used. To minimise regenerant consumption. When treating a high sulphate water (>120 mg/litre).Removal of nitrogen compounds 71 water quality. The major problem that they anticipated was in the means by which a liquid resin could . The effect that high raw water sulphate levels have in raising regeneration and waste disposal costs could be overcome by the development of a resin that was more selective for sulphate than for nitrate. Grinstead and Jones44 have achieved this objective with liquid amidine resins for which they proposed ammonium hydroxide as regenerant. To minimise spent regenerant disposal costs. Treating low sulphate water FIG. fixed beds are usually partially regenerated in a direction counterflow to the direction of the water flow when in service. In this respect. Partial regeneration involves using 0·8 to 1·0 bed volumes of 10% brine or twice this volume of 5% brine. it is important to keep the spent regenerant and rinse water volumes to a minimum. (20 mg/litre) results in the volume of water treated per regeneration being doubled and hence in halving the regenerant and waste disposal costs of either ion exchange system. were found to be43 0·24 and 0·12 when treating waters containing 14 mg/litre NO3–N with 20 mg/litre SO4 and 120 mg/litre SO4 respectively. This is because the continuous loop can use saturated brine for regeneration and because the volume of rinse water it uses can be kept small. occur over a period of a few minutes instead of several hours. whereas a continuous loop produces a waste volume of under 0·5% of the volume treated. which are less marked than with fixed beds. partial regeneration of a fixed bed may be expected to give a volume of waste for disposal in excess of 2% of the water treated. the continuous loop has an advantage over the conventional fixed bed system.

The methanol level in the treated water was however required to be kept very low (<0·5 mg/litre). when it filled . Three types of denitrification unit were studied: fixed beds. The suspended layer increased in depth until. Since both temperature and methanol concentration were rate-limiting. the naturally occurring denitrifying bacteria formed grey gelatinous globules which remained suspended as a fluidised layer in the tank. The water was derived from the River Thames with provision for dosing extra nitrate when required. and fluidised sand units. without necessarily removing the nitrate completely.Developments in water treatment—2 72 actually be employed to treat water and in preventing an unacceptable concentration of the resin itself appearing in the treated water. if not also on that in the water leaving the denitrification unit itself. The data presented here are based on the results of this study in which methanol was used as the source of organic carbon for the denitrifying bacteria. these conditions greatly affected the residence time required in the denitrification unit.3. Water flowrates of 0·7 to 2·8 m/h were used during treatment. However. and another 2 m depth of 25 to 40 mm gravel. More recently45 the introduction of amidine groups onto conventional acrylic resin beds has resulted in a resin with significantly reduced sulphate selectivity and which can be regenerated with brine. it also exhibits a low capacity and low ‘regenerability’ and it is therefore doubtful if it will possess any net advantage over existing commercial resins. since it was anticipated that in practice strict limits would be placed on the methanol level in the water entering supply after filtration. After initial seeding with fine sand or river silt as a basis for attachment. Biological Denitrification A comprehensive study has been carried out37 to assess the performance and applicability of biological denitrification to the treatment of water for potable supply. but some were as large as 6 mm.3. The suspended growth unit was a tall tank in which the water flowed vertically upwards. The treatment objectives were to obtain design criteria for a plant capable of reducing the nitrate level by 10 mg/litre (as N) at temperatures below 5°C. The bacteria grew as a film on the gravel surface and the excess growth had to be removed periodically by back-scouring to prevent the beds from clogging. One fixed bed contained 1 m depth of 10 mm gravel. suspended growth. 3. Most of the globules were 1 to 2 mm in diameter.

Concentration profiles (fluidised sand bed).Removal of nitrogen compounds 73 FIG. the tank. Upflow rates of up to 24 m/h could be used. the excess bacterial growth was carried over in the denitrified water. The lower rate was . 8. although 12 m/h was more usual.

expressed as the weight of NO3–N removed per cubic metre of the unit per hour. 8 reflects this effect. To prevent carry-over of sand by the denitrified water. After a week or two of operation a thin film of bacterial growth became established on the sand surface causing further expansion of the fluidised layer.Developments in water treatment—2 74 necessary at low water temperatures to allow an adequate suspended solids concentration to be maintained in the unit. The rates of denitrification were found to be independent of nitrate concentration down to very low nitrate levels (less than 1 mg/litre as N). Only when the oxygen had been almost totally removed did the bacteria start to utilise the chemically bound oxygen in nitrate for the same purpose. They were however dependent on the methanol concentration. becoming approximately first-order with respect to methanol at low (less than 5mg/litre) methanol concentrations. DO and nitrate through a denitrification unit is shown in Fig.5 10–15 700 3000 .2–0. Unlike nitrate removal by ion exchange which takes place rapidly. A typical set of profiles for methanol. The methanol dose required depended on the dissolved oxygen content of the water and on the nitrate removal required. It may be seen from Table 1 that the denitrification rates were related to the bacterial film areas per unit volume. (mm) 25–40 Bacterial matter concentration (4–8) (kg/m3) Bacterial film area 120 per unit volume (m2/m3) 10 (5– 10) 360 1–2 5–20 0. The denitrifying bacteria first utilised the dissolved oxygen (DO) to oxidise the methanol to carbon dioxide and water. 8 and the following relationship was found to hold: CH3OH consumed=1·1 DO+2·47 NO3–N removed (mg/litre). The curvature of the methanol and nitrate profiles in Fig. Table 1 shows the denitrification rates that were obtained in the different types of unit. The fluidised sand unit was similar except that it was initially filled to one third of its depth with 0·2 to 0·5 mm settled sand. which in turn were governed by the particle sizes of the media used. The volume of each type of unit required to perform a given denitrification duty is then inversely proportional to the rate. The sand became fluidised to about twice its settled depth when an upflow rate of 20 m/h was used. The methanol requirement was about 30% above that stoichiometrically needed for its oxidation since the bacteria utilised some methanol for cell and slime synthesis. The denitrification rates given in TABLE 1 DENITRIFICATION UNIT CHARACTERISTICS Fixed Fixed Suspended Fluidised bed bed growth sand Media dia. the top of the fluidised layer was scoured periodically with a high speed stirrer. denitrification rates tend to be low and determine absolutely the residence times and hence size of unit required.

A 10°C drop in temperature approximately halved the denitrification rates. about 36 mg/litre being required for example to remove 10 mg/litre DO and 10 mg/litre NO3–N. which was carried out every few weeks. In the case of the fluidised sand unit. . The period required to start up a bed and establish bacterial growth can be reduced if the water leaving the unit is initially almost totally recirculated to the inlet. 9 by a factor of 0·75). 9. thus retaining within the system any fine bacterial floc not yet adhering to the bed and preventing unutilised methanol from being discharged. Some mechanical device was also needed to keep down the top of the fluidised sand bed to a constant level by continuously or intermittently stripping excess bacterial growth from the sand surface. this bacterial concentration was controlled by adjusting the amount of sand held in the bed. The effect of temperature is indicated in Table 1 and further illustrated in Fig. assuming that an effluent methanol concentration of not more than 0·2 mg/litre is required (thus lowering the average denitrification rates shown in Fig. An operational suspended growth or fluidised sand unit usually contained about 12.Removal of nitrogen compounds 75 Denitrification 10°CM rate (gN/m3h) 20°CJ 2. The fixed beds therefore exhibited the lowest rates and would consequently need to be unacceptably large in practice. A lower final methanol concentration would result in a lower average denitrification rate. The coarsest media gave the lowest denitrification rates and vice versa. Considering therefore the requirements for a practical suspended growth or fluidised bed denitrification unit: the incoming water. which must not be chlorinated. is dosed with methanol.5 5 12 24 60 120 160 310 Table 1 were average rates found for a methanol concentration drop from 20 mg/litre to 1 mg/litre. particularly in warm conditions. They also had the disadvantage of giving impaired performance for a time after each scouring.15 kg/m3 of bacterial matter (volatile suspended solids). The flow distribution arrangement at the base of the denitrification unit must be adequate to totally fluidise the bed since unfluidised pockets can turn black and emit hydrogen sulphide. Table 2 shows the effective depths and residence times of the beds required to remove 10 mg/litre DO and 10 mg/litre NO3–N at 2°C.

biological denitrification compares very favourably in cost with ion exchange for nitrate removal. Even so. Effect of temperature on performance of suspended growth (SG) and fluidised sand (FS) biological denitrification units.Developments in water treatment—2 76 FIG.46 Monitoring requirements are likely to be more stringent for potable than for wastewater treatment applications. 6. and the equipment for this could more than double the capital cost of the plant shown in Fig. TABLE 2 DENITRIFICATION UNIT OPERATING REQUIREMENTS FOR REMOVAL OF 10 mg/Htre NO3–N AT 2°C Type of unit Suspended growth Fluidised sand Upflow Bed rate (m/h) depth (m) 12 20 5·0 3·6 Residence time (min) 25 11 The fluidised sand bed is clearly the fastest type of denitrification unit.27 and their use has now been patented. The unit used in this study37 was a 0·3 m diameter column with a throughput of about 35 m3/day. 9. Larger fluidised sand pilot plants (150 to 300 m3/d) have been used for both ammonia and nitrate removal from municipal wastewater. .

. 70. C. 1976. 1971. J. OWENS.. SAUNIER. L. F. 1977.. J. 68. C. 14. B. 2290.L. 103. PARKER. M.D. PALIN.J. 17. MELBOURNE. Wiesbaden. Water Research Centre. Civ.S.T. 1979.. Wasserfach. Engrs. R. NOLTE.. Bucks. P.. 45. Technol. 22. 49.B. R.. HYDE.. and SNOEYINK. SYMONS. B. 6. SHORT. EEX. 1975. 13. 9.. 253.L. Water Treat. R. GNIESER. 180. Tech. and HICKEY.W. 34. J. T. Nature. GARNER.C. 1976.G. Bucks. Tech. Rep. Wasserwirtschaft. 1976. 23.R. 816. 30. BABCOCK. R. Water Works Assoc. 1972.J. KEGEL.A.R. Westvaco Corp. 149. 29. 8. 1977. 151. J.B. 71. Amer. Bucks.T.. K. M.. 295. 5. and STEVENS. R. ROBECK. H. Water & Water Engng.. WAGNER. and MORRIS. M. 74. 202. 396..B..H. SMITH. R. and DAYAN. R. JEKEL. TAYLOR. 1975. 363. H. USA.W.. 1973. 259. Medmenham. J. S. Water Works Assoc. Rep. J. 1974. SEEGER. L’Eau et L’Industrie. 42. 79. L’Eau et L’Industrie. 1975.J..A.Removal of nitrogen compounds 77 REFERENCES 1.. W. H. GAUNTLETT. Vom Wasser... Instn. BOWLES.L.. 164.M. Tech.. A. 1973. J.. 26. Amer. Paper No.. D. Techniques et Sciences Municipales. J. 32. 1978. 315. 1972. 70. J. E. 1979. SORG.. Control Fed.L. JERIS. 19.. Water Res.L.. Ch. Environ. Water Research Centre. 71.J. 1950. 3. Va. Medmenham. Sci. HOIGNÉ. Project 17010. MERCER. F. 15. 634. V. Amer.J..W. Water Pollut. BURESH. C.I. B.C. 38. Water Pollut. 1978.. H. 1962.. Control Fed. F.S.. R95. BELLAR. 1976. HEILKER. KROPP. J. GINOCCHIO. C. D. Amer.. US EPA. C. P. and MORAGHAN. ROOK. 101. 36. 173. 189.A. 1975. Techniques et Sciences Municipales. 3. Chemistry of Supply.. GUNDERLOY. J. B.J.. J. R. 1953. No. 67. 2. B. 21. 1979. 1975. Washington. 16. 12. 45. 393. 28. 1970. WEI. J. D.A. G. Civ. D. 8. 43. 24. OLIVER. and CRAFT. 98... Water Pollut. KETCHUM. No. MADSEN. 168. 4.. Ann Arbor Science Publishers.. Water Research Centre. D.. Washington..C. and MABBS.. 103. 35. Water Works Assoc. 33. and SELLECK.K. 1977. Water Quality Office. 21... 1978. J. 13. S.. Water Pollut. Wasserfachliche Aussprachetagung des DVGW und BGW. Chemische Rundschau. Water Treat. 27. Water Works Assoc. DE MARCO.. J. 9. No. Gas.. US EPA.. TAYLOR. Medmenham. 20.W. Medmenham. CHEDAL. Treatment and Distribution. 248. 7. Envir. J. GOMELLA.Y... 11. Qual. J. 398. Control Research Series. E. 3. Bucks.X. 60. SONTHEIMER. SAUNIER. 31.S. J... Ann Arbor.D. 161.. Control Fed. Amer. 1971. 2. 318.J. J. 34. J. 78. Project 17010. 5. and BADER.E. ROSSNER. Water Works Assoc. K.S. Proc.. 54.. 21. 1976.. J. S.. 37. and SINGER.. 10. .E. Engng. 1973.M... J. 105. 45. 1976.. F. DEVILLERS.. Exam. 25. Amer.u.C. 320. 1978.ToUHILL. Tech. 623. 1975. BAUER.R.C. Rep. 1970. Exam. GREGG.. T. 1978.D.G. SLOCUM. V... 12. W. 71.. SHORT.. Water Works Assoc.A. Water Pollut. H2O..J. C. 70. G. 18. 10. 1979. 71. and YOUNG.. J. Water Works Assoc..AMES. and VOLLMER. JORGENSEN. R. C. Taste & Odour Control J. J. Water Quality Office. No.. Covington.VANSLYKE. and BRETT.. R.. Nature. CARSWELL. J.E. BOORSMA. and DEAN. and LAWRENCE. ECZ. HYNDSHAW. MILLINER. A.. 16. 1975. 41.. 213. Amer. Water Research Centre. Control Research Series. 68.

J. and SYMONS.A. R. WITHERED. 41. 1430410.R. Control. 1973. Control Research Series. Brit. J.. BUELOW. 1971... Water Treat.W. 528. KROPP. CLIFFORD. 40. 15.. GREENE. Diaprosim Ltd.. 42. 172. J.. 77. 1975. 632.B. 24.M.. Control Fed. 46. K. Water Research Centre.C. 43. and WEBER. Project 17010. 478.W. Ind. S. 1973. 67. Amer. GRINSTEAD. 1978. Water Works Assoc.. R. R.Developments in water treatment—2 78 39. J. Medmenham. Exam. US EPA.. 1975. EVANS.. Water Pollut. Contract Report. GAUNTLETT. Water Quality Office. D. Water Pollut. J. 45. Pat. 45. 1978. 18. 44. K. FSJ.. L.A. Water Pollut. and JONES. Bucks.L. Water Engng. 1979. . Washington.

.Sc. in a simple form. Improved scale control and use of materials have been the major developments with this process. This market spurred several governments to finance research and development in the field of desalination and foremost of these programmes was that of the United States Office of Saline Water. Developments with reverse osmosis membranes have also led to a capability of desalting sea water and several small commercial plants have been installed..Eng. C.Mac Donald and Partners.D. with the development of oil communities in the Middle East and the Caribbean that demand arose for large-scale land-based plant. After the initial 4500 m3/day multi-stage flash (MSF) distillation plants were installed in the late 1950s.I.W..E.D. Works of the 1970s involve units of up to 35000 m3/d capacity and countries . particularly in the Middle East. Oxon. M.S.) Melcon Water International Ltd.. However it was not until the late 1950s. is now considered to be technically and commercially reliable. Distillation is normally now only applied to sea waters and the most successful. A new technique using fluidised bed heat exchange may lead to cost reductions. reverse osmosis has been the more successful and. B. UK SUMMARY Desalination has progressed significantly since the simple distillation techniques first used for producing small quantities of drinking water from sea or saline ground waters. 4..Chem. Reverse osmosis and electrodialysis. Ph.E. both membrane techniques.Sc. are the two most commonly applied processes for the desalination of brackish waters. reliable and widely applied technique is the multi-stage flash process.(Chem) (Aust). Cambridge. INTRODUCTION Distillation processes.E.(Cantab. Electrodialysis also has the capability of treating sea water but this is not yet commercial.MELBOURNE.Chapter 4 DESALINATION M. It is possible that the slightly more attractive economics of sea water reverse osmosis will result in a decrease in sea water distillation applications. but this will not be fully commercial for several years. Sir M.E.I.J. M. have been employed for over a century as a means of producing drinking water from the sea. the process was rapidly established as the foremost desalination technique. Demeter House. Henley-on-Thames. The other techniques of freezing and ion exchange have had little commercial impact in the desalination field. although a relatively new process. B. Of these. UK AND J. M.1.BURLEY.

During the 1970s the major changes which have occurred are the gradual improvement of membrane properties. As early as 18651 the water supply for General Napier’s expedition into Ethiopia was provided by two 30 ton/day units installed at Alexandria. In general. Whilst the use of electrodialysis for the treatment of brackish waters with total dissolved solids contents up to about 5000 mg/litre has continued to grow. SEA WATER DISTILLATION The boiling of saline water and condensing of steam to produce potable water has been employed for centuries but it is only in the last 30 years that the factory-built plants to produce large quantities of water have been developed. if not ceased. the application of the process has clearly suffered from the competition of the simpler reverse osmosis process. Two systems are being used: one based upon spirally wound membranes and the other upon selfsupporting. 4.2. fine. a factor of economic importance in situations where the costs of imported chemicals are high. The use of frequent current reversal to counteract polarisation effects and consequent scaling problems is the most significant single development during the 1970s since this reduces the need for pre-treatment and the use of chemicals.Developments in water treatment—2 80 such as Kuwait and Saudi Arabia have total installed capacities of about 500000 m3/d. The progress in the manufacture of membranes and modular support systems has led to the establishment of the technique as a reliable and economic means of brackish water treatment which is now being widely employed on a commercial basis. flashing brine characteristics and materials has limited the ever rising costs and allowed more reliable operation. and the development of membranes capable of treating sea water in a single pass. For the future. The process was basically similar to the multiple-effect submerged tube distillation which was employed through to the 1950s. during the 1970s. Reverse osmosis has continued to develop rapidly since its beginnings in 1960. The performance ratio R (mass of product water per . Despite the potential of lower energy consumptions it seems unlikely that these desalination methods will be developed to a commercial stage for large-scale use. a better understanding of membrane fouling and the measures required to eliminate the associated problems. Whilst sea water treatment by reverse osmosis has not yet been widely used it is clear that the process will develop and become an economic competitor of distillation for large-scale sea water treatment. The steam produced from the vessel is passed as heating steam to the next effect. In this type of plant feed steam is condensed on the inside of coils or tube banks suspended below the surface of the feed sea water held in the first effect. The process remains relatively unchanged from the original concept but the better understanding of aspects such as scale control. Other processes under study in the 1960s included solar distillation. ion exchange and freezing techniques. submerged tube plants consist of no more than three effects and therefore have a poor efficiency in terms of energy use. The development of these processes has slowed down. hollow fibres. techniques such as the use of fluidised bed heat exchange systems show promise for cost reduction but the basic MSF process seems likely to remain the major sea water distillation process.

(2) Scale which forms on the outside of the tube bundles is extremely difficult to remove. and has led to the construction of works similar to that shown in Fig. 1. This development arose directly as a result of the large demands for drinking water which were created by the post-war growth of the Arabian Gulf Oil States and similar demands in the Caribbean and developing island communities FIG. 1. Thus large areas of expensive nonferrous heat transfer surface are required. economic and relatively trouble-free means of supplying drinking water.Desalination 81 unit mass of feed steam consumed) is typically only about two. The introduction of multi-stage flash (MSF) distillation in the late 1950s revolutionised desalination and provided a practical. The process has two other serious defects: (1) The rate of heat transfer between condensing steam and evaporating water is very low owing to poor turbulence outside the tubes—the overall heat transfer coefficient is typically 500 W/m2 °C (100 Btu/ft2 h °F). The major benefits of MSF distillation over the submerged tube process are as follows: (a) Sea water passes at high velocity over heat transfer surfaces thereby allowing the heat transfer coefficients to be increased by a factor of about five to 2800 W/m2 °C (500 Btu/ft2h °F). . 22750 m3/d MSF Evaporator (one of four units constructed by Weis Wertgerth Ltd for Quatar).

(c) The plant design allows the use of a large number of evaporation stages which has the effect of increasing the efficiency. Multi-Stage Flash Distillation The multi-stage flash process can be illustrated as shown in Fig. TFO. .S. These achievements were the direct result of the development work of R. 2. After discharge of the concentrated waste stream. On emerging from the condensers of stage 1 the recycle stream is heated to its highest temperature. Therefore MSF distillation has been selected for detailed consideration.Silver and A. 4. by heat exchange with feed steam in the brine heater. 2. the multistage flash distillation process is still used almost exclusively for the large land-based sea water desalination plants (greater than 5000 m3/d capacity). Cooling water is fed to the condensers of the heat rejection section of the plant. Performance ratios of 10 became a reality overnight.2. is passed to the inlet of the recycle pump where it is mixed with flashing brine withdrawn from the final stage (stage 7 in the works illustrated). a portion of the cooling water is separated and. including various forms of multiple effect (ME) and vapour compression (VC) processes. private communication) who both came to almost identical conclusions while working independently. the recycle flow MR is passed through the condensers of the heat recovery section where it is successively heated by condensing steam.Frankel (Silver. On FIG. Simplified flow sheet MSF. MB. as a result.1. after chemical treatment. emerging. Whilst several other means of sea water evaporation have been developed.Developments in water treatment—2 82 (b) Sea water is not boiled at the heat transfer surface and. scale formation can be more readily controlled.

Since the lower temperature TRI is fixed by the temperature of the sea.Desalination 83 The heated brine then enters the flash chamber of stage 1 which is held at such a pressure that a portion of the brine stream flashes off thereby cooling the flashing stream to its boiling point at the stage pressure. (ii) Reducing the stage temperature drop ∆t. Developments in scale control have been aimed at increasing the top temperature whilst avoiding undue corrosion. This can only be achieved by increasing the number of stages employed and hence increasing the capital cost of the plant. ∆TT can only be increased by raising the top temperature TF0. 3. can readily show that the performance ratio R approximates to the following:2 (1) Thus the energy consumption can be reduced by the following means: (i) Increasing ∆TT the total flashing range. . 3. As the flashing brine stream passes from stage to stage it is successively cooled with a portion of the flow flashing off. The temperature distribution is shown in Fig. Mass and heat balances FIG. to be condensed as distillate in each stage. Temperature distribution MSF.

. Heat transfer requirements MSF. α is the temperature difference between flashing brine and condensing distillate and is the sum of the boiling point elevation and the temperature difference caused by pressure losses. U is the mean heat transfer coefficient. λ is the mean latent heat of evaporation over the flashing temperature range. ∆TT is the flashing temperature range.Developments in water treatment—2 84 (iii) Reducing the value of . Using typical values. represents the heat transfer area per unit of product water output. the specific heat transfer area. 4. This is shown by the following approximate relationship: (2) where As. From points (ii) and (iii) above it is clear that plant design can be optimised to achieve a lowest water cost by balancing capital with fuel costs (or balancing heat transfer area and number of stages with performance ratio). This can be achieved by use of more heat transfer area in each stage or increasing the heat transfer coefficients. and R is the performance ratio. this relationship has been plotted as shown in Fig. n is the number of stages. FIG. the stage approach temperature (the temperature difference between recycle brine leaving the stage and condensing steam). Little can be done to reduce the value of α. 4.

4. . The use of these materials limits the top temperature to about 90°C since at higher temperatures the phosphates break down and become ineffective. (b) Pretreatment of the feed water by dosing of acid. the negligible buffering capacity of the recycle brine makes the control of pH difficult and therefore the risk of corrosion will always be present when acid dosing is used for scale control. The benefit of this higher temperature can be illustrated as follows: If the temperature of sea water controls the bottom flashing temperature to 38°C. (3) Use of cheaper heat transfer and shell materials. Scale Control The flashing temperature range is limited by the maximum brine temperature at which scale formation can be satisfactorily controlled.Desalination 85 From eqn (2) and Fig. Even so. caused by the breakdown of bicarbonates in sea water to deposit calcium carbonate and magnesium hydroxide scales. By the use of acid. effectively removes the scale-forming bicarbonates with evolution of carbon dioxide. Periodically it is necessary to acid flush the condenser tubing in order to remove the sludge build-up which will otherwise cause a deterioration of plant performance. 5. the total flashing range with acid treatment will be 77°C (=115 −38) as compared with 52°C (=90−38) for operation with polyphosphates.2. Substitution of these values in eqn (2) will show that the heat transfer area can be reduced by about 47% by the use of acid dosing while still retaining the same number of stages and performance ratio. does not completely eliminate scale formation but rather causes scales to form as sludges which do not adhere strongly to the heat transfer tube surfaces. (5) Use of cheaper energy sources. The approximate relationship is shown in Fig.2. (2) Increasing the heat transfer coefficient U. 5 to 10 mg/litre. otherwise severely corrosive conditions will be created within the evaporators. 4 it can be seen that costs of MSF distillation can be reduced by the following means: (1) Increasing the flashing range ∆TT. top temperatures of 110−115°C can be achieved without serious scale formation. It is therefore of value to consider the developments in distillation in terms of their effects upon these factors. at a concentration of about 120 mg/litre. A rigorous evaluation will show the difference in costs between polyphosphate and acid dosed plants to be greater at high performance ratios. has traditionally been controlled by one of two alternative means: (a) The dosing of polyphosphates at low levels. Alkaline scale formation. The gas is removed by air or steam stripping prior to entry of feedwater to the plant. (4) Use of improved designs to permit smaller flash chamber.

so much so that the cost of replacements and repairs has outweighed the initial benefits. Belgarde for Scale Control One of the most significant improvements of recent years is the development of additives which effectively control scale at high temperatures without the creation of corrosive conditions. Whilst many of the chemicals developed have shown only marginal benefits over the traditional polyphosphates the Belgarde range of chemicals. 9000 m3/d capacity. is typical of several authorities who have deliberately avoided the use of acid and in so doing have maintained a high standard of reliability. Kuwait. Dosing with 7·5 mg/litre of Belgarde over a five-week monitored test period showed no increase in fouling factor with a top temperature of 110°C and an output of 11 800 m3/d. Trials with Belgarde at Qatar are typical of many uses of the chemical. had previously been operated with polyphosphates at a maximum temperature of 85°C and intermittent acid cleaning at six-monthly intervals. Top temperatures of 105–110°C have been successfully achieved over many months of operation with insignificant rates of fouling of heat transfer surfaces and with iron and copper dissolution rates typically 10% and 30% of those experienced in acid dosing plants. 5. Plant capital costs— polyphosphate/acid.Developments in water treatment—2 86 FIG. an increase of 30% above that for polyphosphate operation. In a number of cases poor pH control and the use of unsuitable materials has caused premature failure of heat exchange tubing and steelwork. The Ministry of Electricity and Water. This capital cost saving has led many users to select acid dosed plant in preference to the more expensive polyphosphate dosed works. In this case the plant. Extended operation of 150 days at a top temperature of 105°C and a Belgarde dose of 6 mg/litre showed the fouling . developed by CibaGeigy Ltd have been found to be most effective.

2. (4) To achieve scale control without incurring the costs associated with the use of chemicals. 4. The purpose of the fluidised bed is fourfold: (1) To create sites for scale precipitation and thereby minimise deposition on heating surfaces. 6). The recycle brine is pumped vertically up the condenser tubes at a velocity adequate to fluidise glass particles typically of 2 to 4 mm diameter. the stages of a multi-stage flash evaporator are mounted vertically with condensers located at the side of the flashing chambers (Fig. Whilst the development of the process is by no means complete the . Fluidised Bed MSF A second development which permits the use of high temperatures without resort to acid dosing involves the use of a fluidised bed of ‘seeds’ within the recycle condenser tubes. Without doubt the high maintenance cost often associated with high temperature plant will be minimised in the future by the use of scale-control polymers such as Belgarde.3 In this process. (2) To abrade the surface in order to remove what scale does deposit.Desalination 87 factor to remain constant whilst the output was maintained at 10 900 m3/d.3. (3) To take advantage of the high film heat transfer coefficients experienced with fluidised beds. an increase of 21% over the production rate when polyphosphates were employed.

Developments in water treatment—2 88 FIG. like the basic MSF process. In addition to the benefits listed above. jointly by Delft University. . in high performance ratio plant. Thus overall a capital cost reduction of some 40% may prove possible and since the process. It is anticipated that the continuing development. will lead to the use of this process in the later 1980s. 6. could reduce area requirements by 5%. is amenable to capital/operating cost optimisation. Esmil Ltd and the Dutch Government. significant economies are likely owing to the reduction in stage steelwork requirements in the use of a vertical layout. The potential high temperature operation could lead to a 10% saving and improvements in heat transfer a further 10%. Fluidised bed evaporator MSF. Wire mesh demisters to reduce the carry-over of entrained brine droplets into the distillate have been found to be unnecessary and a very close approach to flashing equilibrium has been found possible. These effects could have the effect of reducing the value of α (eqn 1) by about 0·6°C which. results of trials undertaken with a 50 m3/d experimental unit have been sufficiently promising4 that a 500 m3/d trial unit has been constructed and started operation in 1979. this advantage can be shared between capital and fuel costs. The reduced steelwork costs could give a further 5–10% saving.

6 that the multiple effect cycle is potentially more economic than the MSF. this practice has continued. . creates local points where the tube wall temperature rises and the rate of scale formation increases. In contrast to the above practice for polyphosphate dosed plants. Materials for Evaporators7 The early MSF plants followed normal marine practice. that are theoretically possible with falling film. Thus the Kuwait MSF plants normally use 70/30 cupronickel tubing for the heat reject. Approximately 25% of the tubes are cupro-nickel and the remainder aluminium brass.2. Maldistribution of the film. All of these types have a single common design feature—steam is condensed on one side of the heat transfer surface and water is boiled on the other. can be reliably maintained in practice. Multiple Effect Distillation Multiple effect distillation has been employed in several forms. therefore. multi-stage flash distillation is likely to remain the only serious contender for the large-scale sea water evaporator market. apart from the USA. where standard 70/30 cupro-nickel has been specified. created either by blockage of the sensitive water distribution nozzles or by slight scale deposits formed at the sites of imperfections in the heating surface.5. there has been a tendency to use 90/10 cupro-nickel instead of aluminium brass in acid dosed plant. particularly if the high heat transfer rates. with the use of copper-base alloys for heat exchanger tubing and. The cupro-nickel alloy used in the first plants was the 2% iron 2% manganese version. in general. Despite the theoretical potential of multiple effect systems.2. Overall.4. and some units have been built with this alloy in all sections—an example of this is Jeddah 1. there has been an increase in usage of 90/10 cupro-nickel at the expense of aluminium brass. spray film and fluted tube systems. brine heater and high temperature stages with aluminium brass used elsewhere. Tube plates for the plants are usually Naval brass or 90/10 cupro-nickel.Desalination 89 4. for many years as a part of the US Office of Saline Water test programme. The laminar flow conditions within the film provide insufficient turbulence to remove deposits and hence accelerating scaling develops. Vertical tube climbing film evaporators have been tested and horizontal tube multiple effect evaporators have been employed. particularly in combination with vapour recompression cycles in situations when high performance ratios are called for. 4. Texas. Some data8 show the overall picture of about 65% aluminium brass in 1971 and about 35% in 1975. It is unlikely that the consequent instability of heat transfer performance can be avoided particularly since the feed sea water is always somewhat variable in quality and contains suspended matter. Data from the AD 1972 Little Survey9 shows 90/10 cupro-nickel to perform significantly better than aluminium brass in acid dosed plants so that this switch to 90/10 cupro-nickel is probably based on an increased usage of acid dosed plants during the 1971–75 period. This practice has continued and has spread to most other areas. It has been shown in several cases5. Unfortunately the thin films employed to achieve high heat transfer rates tend to be unstable. A vertical falling film process was employed at Freeport.

For large plants clad steel plate is used for economic reasons and this circumvents external corrosion problems where stainless steel is specified. but as this represents less than 0·5% of the market it does not affect the overall trends. For ejector condensers. the most common being 90/10 cupro-nickel (either as solid or clad plate). Aluminium bronze is the usual tube plate material where titanium tubes have been used. have performed poorly are no longer widely used. but elsewhere only the raw sea water and high temperature boxes have been protected. however. It can in general be concluded that over the last 10 years no new materials have been employed in evaporators but rather the practice has been to upgrade materials used and consequently fewer problems tend to be experienced.6. as stainless steel would suffer problems externally. Cost of Sea Water Evaporation Capital Costs The capital costs of sea water evaporator installations are comprised of three elements: (1) The evaporators. cupro-nickel is the normal choice where an alloy material is specified. where the shell thickness is low. suffer severe corrosion and most plants now employ protection of some kind. However. Rubber linings are sometimes used for raw sea water but epoxy and similar coatings which. In low oxygen conditions. Flash Chambers Following the trend in water-boxes many acid dosed plants are now lined with corrosionresistant material. This trend towards the use of alloy lined chambers is probably the most significant change in material usage in desalination in recent years. as Jubail II has reverted to 90/10 cupro-nickel this does not seem to represent a breakthrough for titanium. In some cases all water-boxes have been metal lined. 90/10 cupronickel is not prone to these problems but is more expensive than stainless steel. The two commonly used materials are 90/10 cupro-nickel and stainless steel. Both appear to perform satisfactorily but experience with completely lined stainless steel chambers is sparse and time is needed to be sure that this alloy can withstand the varying conditions and in particular oxygen levels to be expected in MSF plant. where vapour side conditions are unfavourable to copper-base alloys titanium has often been used. Some linings of 70/30 cupro-nickel have been used but this is much less common and seems to be declining. in general.2. Elsewhere deposits of carbonate and hydroxides on the steel surface seem to markedly reduce corrosion of the underlying metal. stainless steel can be expected to perform well. For smaller units. hence the use of both materials for this application. even in polyphosphate plants. . at high oxygen levels pitting and perhaps cracking may occur. usually type 316L. Water-Boxes Experience has shown that bare carbon steel water-boxes. For polyphosphate plants alloy linings are not normally used apart from local areas around weirs and nozzles.Developments in water treatment—2 90 There has been no significant usage of titanium for tubing apart from Jubail I (still under construction). 4.

The costs are presented in terms of pounds sterling per unit of plant size and performance ratio. FIG.Desalination 91 (2) The feed steam system—self-contained boilers or. It can be seen that a typical evaporator of 10000 m3/d capacity with a performance ratio of 10 will cost about £5·8 million at 1979 prices. (3) Ancillary works—civil works for the evaporators. 7. low pressure. the performance ratio for a single purpose plant is optimised at 12 whilst that for corresponding dual plant is 10. as shown in Fig. the supply system from combined power generation plant. water-tube boilers installed together with auxiliary equipment has been taken as £30 per kg/h of steam raising capacity. more commonly. Clearly such costs can only serve as a guide since site conditions and the state of the market as well as specific design details will influence the precise cost in an actual case. acid or Belgarde dosed evaporators are shown in Fig. Typical costs for high temperature. 7. Costs of polyphosphate dosed plant are higher. For the fuel costs assumed. The civil works directly associated with the evaporator typically add 15% to the cost of the installation but if post treatment works to artificially harden the distillate prior to distribution are employed higher additional costs will be incurred. post treatment or blending facilities. Operating Costs . The total cost of self-contained. Capital costs MSF evaporators (acid dosed) 1979. Thus typical capital costs for a 10000 m3/d installation are shown in the following table. storage and distribution works. 5.

performance ratio (12) Distiller cost 6·90 Boiler cost 1·23 Civil cost 1·03 Total capital 9·16 Operating costs (£ £mpa p/m3 £mpa 3 million p.75% (10% interest. Probably the lowest economic value which can be placed on feed steam is that part of the costs associated with generation of steam which can be attributed to low pressure use after expansion from high pressure in the generation of electricity. Fuel at $20 per barrel 0·83 32·5 0·50 (half cost for dual purpose) 3. Such a case is shown in Table 1 with oil priced at $20/barrel and a boiler efficiency of 85% assumed.Developments in water treatment—2 92 The major items contributing to the running costs of evaporators are as follows: Fuel for steam raising Auxiliary power Chemicals Maintenance and operation Steam supplies. Chemicals Polymer 0·09 34 0·09 (10) 5·80 1·52 0·87 8·19 p/m3 37·7 Dual purpose 19·5 3·4 . Fixed charges 1·08 42·3 0·96 11. being dependent upon the source of energy. The highest values are those associated with the raising of steam in self-contained boilers where the effective cost of the steam is directly related to the world market rate for energy. The largest single operating cost is that of fuel for generating feed steam. The lowest values quoted in the literature tend to be based upon the use of free or very low priced gas which would otherwise be flared off. An authority may wish to set a low price for such a fuel but this can only be considered as a subsidy and does not reflect a realistic value.a and p/m ) 1. Similarly ‘waste heat’ from incinerators or the exhausts from gas turbines or diesels cannot be realistically valued at zero cost. 20 years) 2. This cost is extremely variable. In such cases the allocation of fuel costs between electricity and power is somewhat arbitrary. TABLE 1 COSTS OF MSF DISTILLATION (1979–70% LOAD FACTOR) Single purpose Capital costs (£ million) Opt. In the second case quoted in Table 1 50% of steam raising costs have been allocated to the low pressure steam employed for desalination.

membrane desalination process which has undergone the most rapid development of any desalination technique. blowdown and condensate pumps and site instrumentation and services. It can be seen that for the conditions assumed total water costs range from 78·5 p/m3 for the dual purpose works to 96·5 p/m3 for the single purpose case.Desalination 93 £2000/tonne. REVERSE OSMOSIS Reverse osmosis is a pressure driven. for a 10000 m3/d plant will approximate to 1600 kW. being slightly lower for the lower performance ratio plants. Chemicals. The annual cost of maintenance typically contributes some 1·5% of the capital cost of the distiller whilst operation is approximately double this value for a plant of 10000 m3/d. Capital costs and capital charge rates quoted reflect these different efficiencies. also known as hyper filtration. The process. has now . Maintenance operation. Typical costs quoted by Wade10 are: Polyphosphates Polymer Acid £500/tonne £2000/tonne £120/tonne With typical doses of 7 mg/litre for polymer and 120 mg/litre for acid there is little between the costs of these two chemicals for high temperature operation. the running of distillate. thereby limiting the concentration of the brine blowdown to 1·7 times that of the feed sea water. Prices for chemicals for scale control are extremely variable. Thus the combined cost contributes about 10 p/m3 to the cost of water. The polymer cost quoted in the table of operating costs is based upon the use of a feedwater rate 2·4 times that of the product. staff and materials Total annual cost (£m) Total water cost (p/m3) 0·20 7·9 0·20 7·9 0·25 10·0 0·25 10·0 2·45 – 2·00 – – 96·1 – 78·5 The variation in fuel price for the two cases would lead to the selection of difference performance ratios. Major power consumption includes the pumping of recycle brine. With a 10% interest rate and repayment over the 20 years life of the plant and an average load factor of 70% of the optimum performance ratios become 12 for the single purpose plant and 10 for the dual purpose plant. dependent upon the location of the works. 4. Water costs.3. 7 mg/litre 4. Auxiliary power (at 2p/kWh) 5. To some extent this has been due to substantial funding of research and development by the United States and other international governments. Auxiliary power. This. The selection of steam turbine drives for major pumps for single purpose plant can save up to about 4 p/m3 on the cost quoted by raising steam at an adequate pressure to drive the turbines before being employed as feed to the brine heater. Maintenance and operation.

Basic principles of reverse osmosis. The reverse osmosis process operates at ambient temperature by sufficient pressure being applied to a saline water to overcome the osmotic pressure and to force fresh water through a thin semipermeable membrane at a realistic rate (Fig. 8). Engineering developments have occurred in the packaging of membrane and the overall system designs but these have basically been refinements to the original designs. During this time membranes have been improved and developed to achieve excellent performances in brackish water treatment and finally to be capable of desalting water of up to sea salinity.Developments in water treatment—2 94 been commercially available for the treatment of brackish waters for approximately 10 years. FIG. (2) Polyamide (PA). . Sea water systems have been commercially available to a limited extent for the past three years but research and development is continuing in this area. (3) Composite membranes employing a thin film of polyamide or similar desalting layer formed upon a porous substrate of a material such as polysulphone (TFC). The membranes are ideally permeable only to water but in practice a small amount of salt transfer also occurs. There are three basic types of membrane in use: (1) Forms of cellulose acetate (CA). 8.

Desalination 95 The CA and TFC membranes have normally been employed in the form of a flat sheet and the polyamide as thin hollow fibres. fulvic and humic acids. from water. and is applied to solutions with dissolved solutes with molecular weights above 1000. there is one hollow fibre system with cellulose triacetate membranes. although it will not be discussed in any detail in this chapter as it has had very little application in the water treatment field. It is an extension and development of reverse osmosis using more open high flux membranes (4–8m3/m2/d) which will only reject larger molecules. The scheme is to maintain a satisfactory quality in the Colorado before it passes to Mexico. In addition it has been applied in a few instances for the direct removal of colour. Its main potential as a water treatment process is for the removal of colloids and high molecular weight dissolved organic substances in the feed water to reverse osmosis or ion exchange plant. single pass systems can be employed using membranes which give 99% salt rejection. It is estimated that UF applications in Europe may have a total installed membrane area of 25000 m2 mainly in the electropaint and dairy industry. The total world installed capacity of sea water RO systems to June 1979 is approximately 19 Ml/d. The largest of these is a 12·5 Ml/d plant in Jeddah in Saudi Arabia. Within a year it is expected that the total installed capacity will be approximately 45 Ml/d. a number of plants are under construction and the largest of these is a 13 Ml/d plant for treating the Caspian Sea in Russia. i.e. The largest installation proposed is the 360 Ml/d plant for Yuma in Arizona. . The largest installed plant at this time is at Salbukh in Saudi Arabia and has a capacity of 46 Ml/d. The osmotic pressure of brackish waters would typically be in the range 140 to 350 kN/m2 (20 to 50 psi) and that of sea water 2450 kN/m2 (350 psi). lower rejection membranes have been employed in a two pass system in which the product from the first pass is used as feed for the second pass. The osmotic pressure for these systems is thus very small and operating pressures are usually between 175 and 700 kN/m2 (25–100 psi). However. Hence operating pressures for brackish water systems are typically 2800 kN/m2 (400 psi) but can vary through the range 1400–4200 kN/m2 (200–600 psi) dependent on the application. No doubt the installed area in the USA would be significantly higher than this. The total salt rejection in brackish cases can be controlled to some extent by the type of membrane applied but typically 95% plus would be expected in a single pass system. Pressures of 5600–7000 kN/m2 (800–1000 psi) are required for sea water. In practice it is necessary to apply a sufficient pressure above the osmotic pressure to provide satisfactory product water rates. USA. The total world installed capacity for brackish water RO systems can be estimated as 1550 Ml/d. This is based on the 1977 Desalting Plants Inventory of the US Department of the Interior11 with allowance being made for small plant not included in that inventory and the growth in the market to June 1979. Dissolved inorganic salts and small organic molecules will pass through the membrane with the permeate fluid. however. This is to desalt saline drainage water from the Wellton Mohawk irrigation and drainage area before it discharges into the Colorado River. However. Ultrafiltration (UF) is also a pressure-driven membrane process worth noting. This may be a potential area of increased application but unless costs are significantly reduced it will only be used where performance is more important than cost. For sea water.

thin dense active layer. plus the ability to vary the layer thicknesses for different applications. 9. The polyamide hollow fibres of DuPont are no thicker than a human hair and are self-supporting. supported by a thicker porous layer of the same material. released in 1970. Plastic Products and Resins Department. Fluid Systems Division. dry store for their cellulose acetate membranes. Hydranautics Water Systems offer a form of this property with dry ship.Developments in water treatment—2 96 4. It can be seen that the membranes have pH and temperature limitations which at times can restrict the direct application of the process. The cellulose acetate membrane is cast onto a supporting fabric to provide mechanical strength for handling. This means that the membrane is formed in a one stage process with an outer. The construction details of all three membrane types are shown in Fig.1. Typical performance characteristics of the various membrane types are detailed in Table 2. They are dry processed and can be wet-dry cycled with no effect on membrane performance. FIG. was the only real commercial alternative to cellulose acetate or modified forms of it until 1977. At this time the first commercial thin film composite membranes became available from Universal Oil Products (UOP). Both the cellulose acetate and polyamide membranes are asymmetric. Membrane configurations. typically 0·1 to 1 µm thick for desalination. Although it was anticipated that cellulose acetate would be rapidly superseded. following their CA membrane. The thin film composite membranes consist of a very thin active layer of polymer deposited onto a porous support of a different polymer and thus fabrication is a two stage process. the ‘Permasep’ polyamide hollow fibre of the DuPont Company. The fabrication advantages of composite membranes include the independent selection of polymers from which to optimise the properties and fabrication of each layer. Membranes The first commercial reverse osmosis desalination membrane was an asymmetric cellulose acetate membrane which emerged from the work of Loeb and co-workers in 1962. CA membranes are subject to hydrolysis .3. 9.

0·1 0·1 Nil Nil pH 5 and 6 where minimum hydrolysis occurs. TFC membranes can be seen to have the widest range of pH resistance. Inorganic Flat Allowable type range Temp.Desalination 97 but within the range specified this is not excessive. All membranes have temperature limitations with the TFC offering the most flexibility. Owing to the upper limits it is necessary in the Middle East where groundwaters can emerge at 50–55°C to cool the water before treatment. In addition the temperature of the feedwater affects the productivity of the membranes although it has . recovery for brackish water and 30% recovery for sea water. For hollow fibre polyamide membranes there is no membrane life or performance advantage in operating at any particular pH within the allowable range. Longer membrane life can be achieved by operating between TABLE 2 TYPICAL CHARACTRISTICS OF OSMOSIS MEMBRANES (2800 kN/m2 (400 psi) FOR BRACKISH WATER AND 6000 kN/m2 (850 psi) FOR SEA WATER) Membrane pH Max. The rejection of divalent salts is largely independent of pH. salts sheet free Cl in (°C) rejection flux feed (%) (m3/m2d) (mg/litre) Cellulose acetate (a) Brackish (several types) (b) Sea 3–8 40 98 95 3–8 35 98 0·73 0·85 0·6 0·5 above 25°C 1·0 below25°C 0·5 above 25°C 1·0 below 25°C Polyamide hollow fibre (a) 4–11 35 95 Brackish (b) Sea 5–9 35 98·5 TFC (a) 2–12 45 98 0·7 Brackish (b) Sea 2–12 45 98·5 0·7 Note: These data refer to plant performance of 75%. although the rate does increase with higher operating temperatures. Again there is no membrane advantage in operating at any particular pH within the range but optimum rejection appears to occur between pH 5 and 7 for monovalent salts.

Partial second stages will be necessary with some membranes and for some high salinity sea waters. 10. For single pass sea water desalination with a product requirement of 500 mg/litre TDS or less. This occurs for all membrane types. The overall salt rejection achieved by the membranes for brackish and sea waters can be in excess of 98%. although the major part of the decline would occur in the first year of operation. . Typical performance data from cellulose acetate membranes operating at 2800 kN/m2 (400 psi) and 50% recovery on a brackish water are shown in Table 3. The higher the operating temperature the greater the decline. However this is not always necessary for brackishwater treatment of up to 5000 mg/litreTotal Dissolved Solids (TDS) and membranes with a 95% rejection are adequate. Flux decline in hollow fibre membranes (by courtesy of DuPont). The flux decline over the membrane life also varies with operating temperature. 10 for DuPont hollow fibre membranes. rejection the more raw water that can be blended to achieve a 500 mg/litre TDS potable supply.Developments in water treatment—2 98 little effect on product quality. This does vary marginally for the different types of membrane but could be taken as a realistic average. a rejection of greater than 98% is necessary. Membrane product flux at 25°C is rated as 100% and over the operating temperature range the flux varies almost linearly by approximately 2·8% per degree Centigrade. However the higher the FIG. as shown in Fig.

8 41200 520 1460 125 22000 2960 Product (mg/litre) 7. bacteria and pyrogens and hence overall a high quality water can be produced. heavy metals.Desalination 99 TABLE 3 RO TREATMENT OF BRACKISH WATER AT YUMA—USA BY SPIRAL WOUND CELLULOSE ACETATE MEMBRANES12 Feed (mg/litre) TDS Ca Mg Na K Total Fe Sr Total Alk as CaCO3 Cl SO4 pH 2900 113 70 836 8 <0·06 2 9 1036 826 5·5 Product (mg/litre) 85·0 0·87 0·54 31·0 0·15 <0·06 0·2 6·5 44·0 2·0 5·2 In addition it is known that such a membrane would have approximately an 86% rejection of nitrate ands would largely reject organic compounds with a molecular weight down to approximately 200. RO membranes can also almost completely reject aluminium. WITH SPIRAL WOUND TFC MEMBRANES14 Feed (mg/litre) Temp. TABLE 4 RO TREATMENT OF SEAWATER— JEDDAH. Hollow fibre membranes would have very similar rejection capabilities. The improved organics rejection could be significant if chlorinated and other low molecular weight organic compounds must be removed from drinking water. TFC membranes operating on a brackish water would also provide similar rejections except that improved nitrate and organics rejection would be expected. SAUDI ARABIA. However more data need to be generated to determine the full potential of organics removal with TFC membranes. (°C) PH TDS Ca Mg HCO3(asCaCO3) Cl SO4 32 max.13 A rejection of up to 99% could be obtained for nitrate. It may also be possible to tailor the membrane properties to reject different types of organic compounds.5 ~800 20 ? 65 600 20 .

Hence very low or zero chlorine must be present in their feedwaters. However. The TFC membranes have minimal compaction since it is possible to optimise the support layer during fabrication. while non-cellulosic chlorine resistant membranes with their wider range of properties are highly desirable. This decrease is due to compaction or densification of the polymer support layer which occurs from operation at high pressures. Biological activity can develop in RO modules and to prevent attack on cellulose acetate membranes a free chlorine residual in the feed water is often recommended. All membranes are subject to compaction but this is relatively low below a 2800 kN/m2 (400 psi) operating pressure.Developments in water treatment—2 100 SiO2 Total Fe 0·4 0·2 For sea water treatment with systems operating at approximately 7000 kN/m2 (1000 psi) and 30% recovery typical data are shown in Tables 4 and 5 and for single pass operation. The hollow fibre and TFC membranes are non-biodegradable and hence do not require this form of protection. The flux per unit membrane area from flat sheet membrane can be seen in Table 2 to be in the region of 0·5–0·75 m3/m2d for brackish water at 2800 kN/m2 (400 psi) or sea water at 5600 kN/m2 (800 psi). WITH POLYAMIDE HOLLOW FIBRE Feed (mg/litre) pH TDS Ca Mg Na HCO3 (as CaCO3) Cl SO4 Fe 7·4 42000 600 1118 16000 190 25000 2900 3·8 Product (mg/litre) 6·5 435 8 1 133 20 210 1 0·2 output. A membrane of this type should be commercially available in the near future and ultimately similar benefits are likely to be achieved for sea water membranes. In fact the polyamide or similar polymers are very sensitive to chlorine and can be readily oxidised. the sensitivity of the present membranes . this cannot be compared directly with hollow fibre membrane which has much lower unit fluxes but much greater surface area to achieve the required TABLE 5 RO TREATMENT OF SEAWATER— SOUTH CAICOS ISLAND. The fluxes quoted are for new membrane but these do decrease over the membrane life as seen in Fig. BRITISH WEST INDIES. Significant progress is being made in the development of TFC membranes which have the above flux and rejection characteristics for brackish waters but which will operate at 1400 kN/m2 (200 psi). 10. The chlorine also controls this type of activity in the other components of the overall plant. However.

One form of the tubular module concept typically consists of 13 mm internal diameter porous tubes up to 3660 mm long. The ‘rod’ system was developed by the United Kingdom Atomic Energy Authority. Saline water under pressure is pumped at the required velocity through these tubes in the modules. In many cases they would expect the life to be substantially longer. and. namely tubular. The feed liquid is pumped through the pressure vessel at an appropriate velocity and . Reverse Osmosis Modules Not only must reverse osmosis membranes have satisfactory desalination properties but they must be produced in such a form as to be capable of withstanding the high forces created under operating conditions.Desalination 101 should not technically limit their applications. when necessary. the packaging of large areas of membrane in this way is not economically competitive with the alternative spiral wound and hollow fibre systems. can be mechanically cleaned by foam swabs without dismantling the equipment. spiral wound.16 and in terms of packed membrane area per unit volume of module it falls between the tubular and the higher packed density of the spiral wound and hollow fibre configurations. They do however find extensive use for special applications in the dairy industry and are offered by Paterson Candy International Ltd in the UK. 4 or more metres long with one end sealed and the other mounted in a header block.3. The more recent sea water and TFC membranes have yet to be fully proven in large installations but again manufacturers are confident of a minimum three-year life. In fact polyamide hollow fibres have been widely applied and for chlorinated feedwaters a dechlorination stage is readily included. Tubular systems have well defined open flow channels and are very tolerant towards suspended solids and are difficult to block. The plate and frame concept. is a viable approach technically but again is not applied in the water field as it also is not competitive economically. The paper membrane tube is then inserted into the support tube. Fresh water passes through the membrane and porous support and is collected by an outer shroud surrounding the tube bundle. In its latest concept the rod system is based upon a 3 mm diameter microporous polypropylene tube onto which the membrane can be cast directly and continuously. similar to a filter press. For brackish waters most major manufacturers now have sufficient experience and confidence to offer a three-year guarantee provided the feedwater specifications have been met. Whilst the fine hollow fibres are mechanically selfsupporting all other types of membrane have to be provided with some form of porous support. Bundles of 37 or 109 of these rods. There are five different module designs which have been considered seriously. However. For a relatively new process such as RO the membrane life is a key factor in the operating costs. and therefore tubular membranes are not often employed for municipal water treatment. They are particularly amenable to cleaning by water flushing and chemicals. 4.2. Harwell. hollow fibre and the rod type. These tubes are the membrane support and must be capable of withstanding the operating pressure of the system. Cellulose acetate type membranes have been generally used and can be cast directly onto the inner surface of the tube or more usually the membrane is cast onto the inner surface of a synthetic paper tube. are placed in tubular pressure vessels. The advantage of this approach is that the modules can be very simply and economically remembraned where necessary. connected in series in a repeating ‘S’ configuration with up to 18 tubes per module. plate and frame.

Hence at the present time it has limited application. Membrane bundles can be quickly and easily replaced and are disposable. A more open porous mesh approximately 1 mm thick is placed on the outside of the membranes. It also has the advantage that in the event of severe malfunction the membrane rod bundle can very easily be removed for some form of physical cleaning. The membrane element usually consists of several membrane leaves attached to a central product carrying tube. typically Hydranautics and Envirogenics. The spiral wound element was developed by General Atomic of the Gulf Oil Corporation. However. The feedwater at pressure passes . Spiral wound membrane module. the spiral wound and the hollow fibre. differ significantly in designs. The system is more tolerant to suspended solids than spiral wound and hollow fibre modules but less tolerant than tubular designs. polymer sheet less than 1 mm thick which supports the membranes under pressure. the porous support tubes are not suitable at this time for operating pressures greater than 600 psi which would limit the system to brackish water applications. Three sides of the ‘envelope’ are sealed with a suitable glue and the fourth side is glued to a porous section of the central tube. A basic leaf is shown in Fig. However. now the Fluid Systems Division of Universal Oil Products (UOP) Inc. as their basic configuration. Up to six elements can be inserted in series into each fibreglass pressure vessel. Permeate passes through the membrane and porous tube and is collected from the header block end. Then this leaf and others attached in the same way are rolled around the centre tube. The membrane elements are usually 1 m long with diameters of 4 in or 8 in being generally used although UOP can supply 12 in diameter elements. Two flat membrane sheets with their desalting skin facing outwards are separated by a very fine. porous. under US Government sponsorship.Developments in water treatment—2 102 pressure on the outside of the rods. An 8 in diameter element 1 m long would have an effective membrane area of approximately 320 ft2. 11. FIG. The two most extensively used module types.. although the system has significant potential it is considered to be not commercially competitive for municipal water treatment by Paterson Candy International Ltd who hold the marketing rights for the process. 11. It has since been adopted by other US companies.

The Permasep polyamide. Each end of the fibre bundle is then encapsulated in epoxy resin. Permasep permeator.Desalination 103 through the porous mesh channels parallel to the membrane and the fine mesh supporting the membrane is the product water carrier to the centre tube. outside. would be approximately 68 m3/day. Pretreatment of Feedwater For reverse osmosis equipment to operate satisfactorily there must of course be an adequate engineering design. Hence in this case each hollow fibre membrane bundle has its own pressure vessel. treating a brackish water. whichever is required. The maximum back pressure from the product water which this type of module can safely withstand is 120 kN/m2 (14 psi). 4. the most important operational factor is to keep the membranes in a functional condition and therefore they must be protected from . 1 m long. Saline feedwater at pressure is pumped into the central distributor tube where it passes out radially between the fibres pressurising them from the FIG. It is collected by the porous block and is removed via a central tube. The module basically operates under laminar flow conditions. This continues until the overall diameter of the fibre bundle is 4 in or 8 in. These are wound around a plastic mesh material approximately 1 mm thick and 450 mm long which in turn is wound around a central porous tube. This is then wrapped with a fine cloth to keep the fibres in place. One of these ends is machined back to cut off one end of the fibre bundle to leave fibres in a ‘U’ shape and open at the two exposed ends. hollow fibre module was developed by the DuPont Company and consists of millions of the hair-like fibres bundled together. 25°C and a total 60% recovery treating a brackish water would be approximately 185 m3/day of permeate. 25°C and 75% conversion. The output capacity for 6×8 in diameter membrane elements.3.3. This tube bundle is then inserted into a fibreglass pressure vessel as shown in Fig. The output from an 8 in diameter module operating at 2800 kN/m2 (400 psi). operating at 2800 kN/m2 (400 psi). Fresh water passes through the fibre wall into the hollow centre where it moves towards the open ends of the fibres. 12. The brine outlet removes the remaining concentrate. These are all held in place by circlips. End plates with ‘O’ ring seals are fitted and on the product end a porous support block is also fitted. 12. Accepting that.

Its solubility in pure water at 25°C is approximately 105 mg/litre as SiO2. This is an increasing linear function with increasing temperature. However the solubility of calcium sulphate increases with ionic strength of the solution and therefore this should be taken into account when determining the maximum allowable calcium concentration in the RO concentrate for the particular plant conversion. There are several types of fouling which can occur and some of these are important to greater or lesser extents in the various membrane module configurations. However.Developments in water treatment—2 104 fouling constituents in the feedwater. it is very difficult to remove. Doses of 10 mg/litre have allowed the concentrations of calcium and sulphate ions in the concentrate to be raised to such levels that their product is as high as 10–3 mol2/litre2 without calcium sulphate scaling becoming a problem. will largely remove calcium and other divalent scale-forming cations. It is important to achieve the correct feedwater quality and operating conditions in order to avoid calcium sulphate scale formation as. Membrane fouling from calcium carbonate and/or sulphate scale is a common consideration for all. It may be preferable to control calcium carbonate scale by acid dosing to achieve a negative Langelier Index which would occur in the pH range 5–6. To prevent calcium sulphate scale without further treatment. either chemically with lime/soda or by ion exchange. Silica can be removed from feedwaters by . barium sulphate and calcium fluoride can also cause scaling. Softening. However. once deposited. Problems due to silica scaling from the concentrate are also common to all module types. this is usually not practical for large plant and the scaling can be controlled by pretreatment to remove one of the ions of the scale-forming compounds or by chemical dosing to control salt precipitation. However this is not always viable unless high conversions are required. Solutions can become supersaturated with silica whereupon it can polymerise to form colloidal silica or precipitate as calcium silicate if calcium is present. In addition the water must be treated to satisfy other membrane limitations: pH control for cellulose acetate membranes and dechlorination for polyamide hollow fibre and composite membranes may be necessary. supersaturated silica solution. strontium sulphate. If the plant is shut down then the concentrate must be flushed from the RO modules to remove the scale-forming. the ionic product of the calcium and sulphate ions should not exceed the solubility product Ksp for calcium sulphate. can be concentrated by a factor of two to five times depending upon the plant conversion. silica scale does not precipitate rapidly and operating experience indicates that levels of 150 possibly up to 200 mg/litre can be tolerated in a continuously operating plant. To prevent calcium carbonate scale formation the Langelier Index of the RO concentrate must be negative. Adequate pre-treatment is thus essential to limit the concentration of potential foulants in the feedwater. In these circumstances calcium sulphate scale would be controlled by dosing a scale inhibitor such as sodium hexa-metaphosphate. Calcium carbonate and calcium sulphate are the most common salts which can cause problems but silica. If the solubility products are exceeded fouling will occur owing to precipitation. depending on their concentration. These constituents are present in the feedwater and. It would appear that the silica solubility is not affected by the solution ionic strength but it is dependent upon pH. In pure water at 25°C this is Ksp=2·4×10–4. Scaling can be controlled by operating the systems at low conversions so that the solubilities of the problem salts are not exceeded.



being adsorbed on precipitated magnesium hydroxide in the cold lime or cold lime-soda softening process. Fouling of RO membranes can occur by the oxidation of soluble species in the feedwater which if not removed can then precipitate as insoluble hydroxides on the membrane. Iron and manganese fouling can occur in this way. This type of fouling can normally be avoided by removing the oxidisable species from the water or by keeping the feedwater out of contact with air and so avoiding the oxidising conditions. Iron fouling is the most common and this can be removed from groundwaters after oxidation by sand filters before passing to the RO modules. Fouling could also occur from well oxidised surface waters containing precipitated ferric hydroxide. Hence in this case the iron would also be removed by filtration or by two stage treatment employing both clarification and filtration if necessary. If there is no oxygen in the feedwater and oxygen can be excluded, levels of 3–4 mg/litre of iron can be tolerated for hollow fibre membranes. Otherwise the level of iron should be kept below 0·05 mg/litre in the RO feed. Cellulose acetate spiral wound membranes are slightly more tolerant with levels of up to 5 mg/litre and 0·1 mg/litre being acceptable for oxygen-free and oxidising conditions respectively. Hydrogen sulphide which is frequently found in groundwaters may also cause problems if oxidised. Very fine colloidal sulphur could then irreversibly foul the membranes. Hence if possible the feedwater should be pumped through the system without exposure to air with the hydrogen sulphide then being removed from the permeate by degassing. Cellulose acetate membranes are susceptible to biological fouling and attack and hence to prevent this the membranes have to be frequently disinfected in a cleaning sequence or protected by continuously dosing up to 0·5 mg/litre free chlorine to the feedwater. The hollow fibre and TFC membranes however are completely free from bacterial attack and hence no disinfection of the feedwater is required. These membranes in fact can be readily oxidised by chlorine and hence any chlorine must be completely removed from the feedwater. This would normally be done by passing through an activated carbon bed where it would be absorbed or by dosing with sulphur dioxide. A very important fouling consideration, particularly for hollow fibre membranes, is the potential plugging of the membrane by coagulated ultrafine colloidal particles. Even though a feedwater may have been clarified and sand filtered it may still contain significant material with a size range of approximately 0·2 to 1·0 µm which can cause severe problems. These particles are usually hydrophobic and may be inorganic or organic in nature. An empirical fouling index test has been devised by DuPont17 to determine whether the colloidal content of the water is likely to cause a fouling problem for their hollow fibre membranes. Variations of the test have been used by other manufacturers. Turbidity measurements cannot indicate the presence of colloidal material. DuPont determine what they call a ‘Silting Density Index’ (SDI) from the following equation when the feedwater is passed through a 47 mm diameter 0·45 µm filter at 30 psig.

Developments in water treatment—2


where ti=initial time (s) to obtain a sample of say 100 ml; tf=time (s) required to obtain a 100 ml sample after time T (min) of operation; and T =time (min) total test time, usually 15 min. The colloidal content is considered to be low enough to avoid fouling problems if an SDI of three or less is obtained. Groundwaters usually fall into this category. However surface waters even after treatment can have an SDI in the range of 10 to over 100 which can lead to severe fouling problems. Spiral wound modules are considered to be much more tolerant to suspended solids and colloidal content in the feedwater. At the present time a turbidity of less than 1·0 FTU is considered to be adequate to feed spiral wound modules. However it is possible that the new TFC membranes with their polyamide thin film desalting layer may need to have a feedwater which conforms to an SDI not significantly greater than that required for polyamide hollow fibre membranes. Fouling by colloids can be reduced by either removing them from the feedwater or by increasing their stability. Coagulation and filtration techniques can be used to reduce the SDI of a water. DuPont suggest that for an SDI above 50 either aluminium or ferric sulphate coagulants can be used with sedimentation followed by rapid gravity filtration to remove colloidal material. However there are cases where even this treatment is insufficient and further filtration with polyelectrolyte addition is necessary. The technique of dosing with polyelectrolyte followed by pressure filtration is the recommended method of reducing the SDI to below three for feedwaters which have an initial value below 50. It should be pointed out that clarification by dissolved air flotation rather than by sedimentation has considerable potential when two stage treatment is necessary. Flotation is a much higher rate process than sedimentation and therefore in a more compact plant can be employed. In addition it is a process where solids are removed by being floated to the surface by micro bubbles of air. This should be beneficial in removing material such as colloids which typically will not settle. DuPont also suggest that measurement of the zeta potential of a solution is an effective guide to colloid stability. If, for example, the zeta potential can be increased from −10 mV to −30 mV colloidal fouling will be significantly reduced. The zeta potential can be approximately doubled by softening to below 5 mg/litre as CaCO3 which increases the stability of the colloids and reduces their tendency to coagulate. Thus if larger particles are not formed they will not foul the membrane and the small colloidal particles will be purged from the system with concentrate. Fouling of membranes can also occur from severe organic contamination in the feedwater. This is largely reversible for cellulose acetate membranes and to a lesser degree for non-cellulosic membranes. If necessary some organics can be removed by clarification and filtration but usually routine cleaning can cope with the problem. If absolutely necessary activated carbon could be considered as a further pretreatment stage following filtration. Even though membranes may be fouled during operation, in many cases it is possible to remove this with suitable cleaning techniques. Hydrated metal oxides can be removed by types of ammoniated citric acid solution and calcium carbonate removed by a solution containing weak hydrochloric acid both at pH 4. Calcium sulphate can be removed in part by an ammoniated citric acid, or EDTA solution at pH 8 and organics can be removed by detergent at pH 8 or higher depending upon the membrane. Inorganic colloids and silicates can be removed by detergent or caustic solutions also at pH 8 or higher. Bacteria



can be removed by a mixed detergent, formaldehyde solution. It is sound practice to build routine cleaning cycles into the operation of any plant and the type of cleaning may vary depending upon the feedwater quality. 4.3.4. Reverse Osmosis Systems Design The basic individual components in reverse osmosis systems are all relatively simple apart from the sophistication of the associated electronic controls. Ignoring pre- and posttreatment considerations, a simple system consists of a 5–25 µm pre-filter to protect the high pressure pump and module, the high pressure pump itself, the single desalting membrane element in its pressure vessel and the reject flow control valve. In systems of this size design considerations are limited but they become more important with increasing size. The important factors will be briefly discussed for larger systems. The micron filters are usually of the cartridge type where up to fifty cartridge filter elements may be contained in the one pressure shell. On a large plant there may be tens of these pressure shells to provide the capacity for the plant. The cartridge particle size cut-off rating will vary depending upon the type of membrane element being used. For hollow fibre permeators which are more sensitive to suspended material ratings of 5–10 µm are normal, while for the spiral wound 25 µm is common. With satisfactory pretreatment these filter elements have an extended life and hence filter changes are not too frequent. However when they do require changing this operation is somewhat labour intensive. Interest is currently being shown in continuous screen filters.18 These potentially can provide a particle size cut-off down to 5 µm, can be automatically backwashed on pressure drop or time and can pass large volumes per single unit. These continuous filters with coarser screens might also replace the pre-treatment sand filters. Several small units are being evaluated. The high pressure RO feed pumps require sufficient feedwater at a small positive pressure to operate properly. A low pressure cut-out control is normal to guard against any deficiency. The selection of these high pressure pumps also depends upon the size and duty of the plant. Typically for small plants, single stage, stainless steel, high speed centrifugal pumps are used for pressures in the range 2800–4200 kN/m2 (400–600 psi). They can develop up to 6300–7000 kN/m2 (900–1000 psi) if necessary. However the efficiency of these pumps is only 40–50% resulting in a higher power consumption than for more efficient pumps. For larger installations multistage turbine or centrifugal pumps can be used to develop up to 4550 kN/m2 (650 psi) and these have higher efficiencies of up to 75%. Although reciprocating pumps can have an efficiency in excess of 90% they are not particularly popular for brackish water applications as they generally have a higher maintenance cost. However for large sea water applications the reciprocating pump has the advantage of being able to readily develop the required pressures whereas the others cannot and hence it would usually be selected. An accumulator should be used with reciprocating pumps to dampen out pulsations. In choosing a suitable high pressure pump it is important to select one with a performance specification as close as possible to the required duty. Pumps which have a higher pressure and volume specification than required, and are merely throttled back, consume unnecessary energy. This also applies to reciprocating pumps as although they cannot be throttled directly water can be recirculated through the pump. In addition in determining the energy required to drive the

Developments in water treatment—2


pump the normal viscosity of the water should be taken into account so as not to unnecessarily overrate the motor. Both brackish and sea water pumps would typically have materials of construction of stainless steel or aluminium bronze. With the increasing need to conserve energy and reduce costs more consideration is currently being given to energy recovery from high pressure brine, particularly on sea water systems operating at 7000 kN/m2 (1000 psi) and only 30% conversion. Some pump manufacturers are proposing an energy recovery turbine coupled directly to a double ended shaft of a motor that drives the high pressure feed pump. In this way the net electrical power input required by the motor to pressurise the water can be reduced by possibly over 50% for sea water plants. An important aspect in designing reverse osmosis systems is to optimise the conversion to product water without creating scaling and concentration polarisation conditions. Adequate pre-treatment allows higher conversions to be obtained without scaling but there is a limit as 100% conversion is not possible. Concentration polarisation is the condition where a much higher salt concentration is created at the membrane surface than in the bulk stream. This significantly increases the osmotic pressure of the system and decreases performance. It is caused by the removal of fresh water through the membrane, increasing the surface salt concentration and reducing the flow to the point where the velocity at the membrane surface is too low to cause adequate mixing between the concentrated layer and the bulk flow. There is then also the possibility of precipitation from the concentrated layer causing scale formation on the membrane surface, even though the bulk flow may be unsaturated. To avoid these conditions on a large plant, the pressure vessels are connected in arrays, with the concentrate from a bank of modules operating in parallel being passed as feed to secondary banks containing fewer modules. Thus the required minimum velocity conditions can be maintained in the membrane elements and up to 90% conversion can be achieved. Popular arrangements are 2, 1 or 8, 4, 2 arrays as shown in Fig. 13.

FIG. 13. RO arrays.
RO systems are now more commonly designed to operate at variable pressures in order to maintain a constant product output. However the systems can readily be operated at

This is not however possible for components exposed to high pressures. The post-treatment may consist of degassing the product of some carbon dioxide produced from acid dosing the feed and destroying the alkalinity. Instrumentation related to critical parameters is connected to alarms to allow abnormal conditions to be promptly observed and remedied. When this occurs there is often concern that the brine may percolate through the ground strata and contaminate any groundwater below.Desalination 109 constant pressure. since the product is usually of a higher quality than necessary. if it is prior to the membrane elements. Reverse Osmosis Plant As with any new technology. For constant output operation the systems are commonly designed with automatic valves to control the feedwater and reject water flow rates. pH. pressure. large process plants are not built until smaller plants have been installed and the process performance and reliability established. Brackish water RO has passed through this phase and large plants are now being ordered and installed.3. . The post-treatment of the product water can be an integral part of a system design. The last very important consideration in an RO system design is the disposal of the brine concentrate which would normally vary from 10 to 25% of the total flow for brackish water and up to 70% for sea water.5. to alleviate all fears of this. If corrosion occurs not only is there an eventual failure of the component but. Owing to the high concentrations of chlorides commonly found in these streams. In typical designs instrumentation is provided to monitor temperature. The controls and indicating instrumentation can be mounted on the equipment or in a local control panel. mainly in response to the water demand in the Middle East. However in other situations it may be necessary to collect the brine in ground level ponds and in hot climates evaporate it away. As far as possible to minimise corrosion it would be recommended that non-metal components be used whenever they are practical and economical. This degassed water would pass to a clear well where it could be blended with raw water. conductivity and other parameters to ensure correct operation and control. 4. care is required in the selection of appropriate grades of stainless steel and the standards of welding. Stainless steel is commonly employed for both feed and reject pipework. When considering the costs of the process for a specific case the disposal costs for the brine and any pre-treatment residues should be included. pickling of weld areas with passivating solutions being often necessary. In addition. ponds with rubber liners have been proposed. it is blended with raw water to provide a higher volume with an acceptable quality. the corrosion products can foul the membranes. However. In some circumstances disposal can be simple by returning the brine to the sea. Care should also be given to selecting suitable corrosion resistant materials of construction for all process items and pipe work. flow. The blended water would then have the pH adjusted to approximately 8 by lime or soda ash dosing and be chlorinated before being pumped into a distribution system. When significant calcium sulphate is present in the brine the danger of this occurring is minimal as the calcium sulphate will precipitate out on the floor of the pond in a very hard impervious layer. Some alkalinity may be formed from the lime and residual carbon dioxide in the blended water which would help control corrosion in a distribution system.

A typical RO plant would consist of multiple blocks of pressure vessels with membrane elements to make up the required capacity plus pumps and controls. Extensive pretreatment and desalination trials have been conducted for several years. as shown in Fig. Pre-treatment of partial lime softening followed by multi media filtration has now been chosen for the final design.Developments in water treatment—2 110 The largest operating RO plant at the present time is that installed by Degremont at Salbukh in Saudi Arabia. softening with silica removal. The total investment cost per m3 of . 14. The largest RO plant yet considered has been approved for installation at Yuma in Arizona. Nine RO and electrodialysis manufacturers conducted desalination trials and from a performance and economic standpoint two RO spiral wound module manufacturers have been selected to supply the desalting equipment. At January 1979 prices the total cost of the desalting complex has been estimated to be US $190 million.19 Hydranautics has several 15 Ml/d plants and Paterson Candy International Ltd. to treat 360 Ml/d of a 3000 mg/litre TDS brackish irrigation water before it drains into the Colorado River. This will maintain the quality of the Colorado before it passes to Mexico. This plant uses spiral wound modules from UOP. filtration and acid and polyphosphate dosing as a pre-treatment before the RO units. This uses DuPont hollow fibre modules to produce 46 Ml/d from a 1500 mg/litre TDS brackish water. A marginally smaller plant of 45 Ml/d on a similar water has been installed at Buwayb in Saudi Arabia by Ames Crosta Babcock and is currently being commissioned. Envirogenics and other companies have numbers of smaller plants installed on brackish water in the Middle East. This has cooling. UOP Fluid Systems are to provide 276 Ml/d capacity and Hydranautics 84 Ml/d. The final design of the project is proceeding with the initial operation of the plant scheduled for 1982. There are four other RO plants so far in the Riyadh water treatment complex with an average capacity of 32 Ml/d each which are due to be commissioned in 1980. USA.

Typical components for a Hydranautics plant to produce 1 Ml/d from brackish water.Desalination 111 FIG. . 15. 14. 1·7 Ml/d section of the UOP Fluid Systems’ Jeddah sea water RO plant. FIG.

There. 16. a number of much smaller sea water or highly brackish water plants installed with the B10 modules have been successfully operating for several years.20 Sea water RO technology is more recent and the largest plant installed is for 12·5 Ml/d at Jeddah in Saudi Arabia.Developments in water treatment—2 112 product per day of installed capacity would be approximately US$0·53/m3. A 2·3 Ml/d plant using DuPont hollow fibre sea water modules. 16. 15. . However when the specified limit of 1000 mg/litre is exceeded a partial second stage will be used. This was supplied and installed on a turn key basis by UOP Fluid Systems and uses their TFC spiral wound membrane elements operating at 6100 kN/m2 (870 psi) and 30% recovery. It is expected that product water of 800 to 900 mg/litre will be produced in a single stage for up to two years. A typical plant installed by Paterson Candy International Ltd in Bahrain to produce 2·3 Ml/d of fresh water from a 10000 mg/litre TDS feed is shown in Fig. A section of the plant is shown in Fig. The pretreatment for the plant consists of dual media filters only followed by acid and polyphosphate dosing before the final pre-treatment cartridge filters. installed by Paterson Candy International Ltd. FIG. A slightly larger plant for 13·0 Ml/d with DuPont B10 hollow fibre sea water modules is being installed in Russia to treat the Caspian Sea and should be operating in 1980.

Membrane replacement 3-year life (a) Brackish 0·053 4·0 0·27 4·0 (b) Sea 0·32 24·4 1·53 24·4 5. Power(at 3·2 p/kWh) (a) Brackish 0·076 5·8 0·38 5·8 (1·8 kWh/m3) 0·34 25·6 1·70 25·6 (b) Sea (8·0 kWh/m3) 3. Maintenance. staff and materials Total annual 0·26 – 1·24 – 0·94 – 4·54 – cost (£ million) Total water cost – 19·9 – 18·1 – 71·2 – 70·1 (p/m3) . Fixed charges 0·065 5·0 0·28 4·3 0·20 15·5 0·97 14·8 11·75% (10% interest. (860 psi) 25°C.a 3 and p/m ) 1. 6020 kN/m2 (400 psi) 25°C. Chemicals Acid Polyphosphate Chlorine Detergent Formaldehyde (a) Brackish 0·033 2·5 0·17 2·5 (b) Sea 0·041 3·1 0·20 3·1 4. 2800 kN/m2 prod.28 million) £mpa £mpa £mpa £mpa Operating costs p/m3 p/m3 p/m3 p/m3 (£ million p. 20 yr plant life) 2. 0·035 2·6 0·14 2·2 0·035 2·6 0·14 2·2 operation. 75% conversion 30% conversion 4 Ml/d 20 Ml/d 4 Ml/d 20 Ml/d Capital costs (£ 0·56 2·4 1·73 8.Desalination 113 TABLE 6 TYPICAL REVERSE OSMOSIS COSTS Q3 1979 FOR A 90% LOAD FACTOR Brackish water Sea water 1500 mg/litre 35000 mg/litre TDS feed 50 TDS feed 500 mg/litre TDS mg/litre TDS prod.

e. 4. 17. ELECTRODIALYSIS Electrodialysis (ED) is a membrane process which has been used commercially since the mid 1950s for the removal of inorganic salts from water. The diluate and concentrate streams are pumped in co-current flow through their respective cells. Different bases and assumptions can be used for estimating if desired. Similarly if power has to be generated at site or product water has to be pumped to supply. the solution between one pair of membranes becomes depleted in ions while the solutions on either side become enriched. The cell thicknesses are . the total capital cost can be more than double the figures quoted. this technique will gradually replace distillation for many applications. salts dissolve to form positively charged cations and negatively charged anions.3. The costs quoted in Table 6 should not be compared directly with the distillation costs quoted earlier since the bases employed are not identical. It has also been used in Japan as a brine concentration process. This situation arises because different cost elements need to be included or excluded depending upon the site and the process being considered. as a desalination process. With permselective ion exchange membranes. and waste disposal are included. civil and building works. In time it is probable that.6. The basic cell pair can be seen to consist of a feed or diluate stream between a cation and anion membrane plus a concentrate on the other side of each membrane. For a particular application for sea water desalination. it will usually be found that the estimated total costs are similar whether desalting is performed by distillation or reverse osmosis. significant additional costs will be incurred. one cation and one anion placed between the electrodes. These RO costs must be used with caution since they only constitute the desalination element of the total water supply cost. pre-treatment works. alternately cation and anion. If the costs of wells or an intake. If a d. is placed between the electrodes. distillation plant will largely not need to be housed in a building while housing will be essential for reverse osmosis.4. as shown in Fig. In water. cations migrate towards the negatively charged cathode and anions towards the positively charged anode. 4. product post-treatment and storage. If now a stack of membranes. electric field is applied across the solution. For example. Hence it must be decided what cost elements need to be considered and included for overall cost estimates.c. In a commercial configuration there can be several hundred cell pairs per stack. with the RO costs usually being the lower.Developments in water treatment—2 114 A significant growth in the application of sea water RO can be expected in the future. owing to the apparently more favourable economics. the permselective property ideally allows the cation membrane to only pass cations and the anion membrane to only pass anions. i. particularly for small plant. between the two electrodes. clamped as in a filter press. Costs of Reverse Osmosis Typical estimated costs for installed reverse osmosis plant alone can be presented for both brackish and sea water systems at third quarter (23) 1979 for small and intermediate plant sizes (Table 6).

For the past 3–4 years they have almost exclusively offered plant with polarity reversal as the means of controlling scale formation. The membrane electrical properties of high conductance and ion selectivity control the process through the application of Ohm’s Law for stack resistance and Faraday’s Law for salt passage. There are two types of electrodialysis systems commercially available. although simple chemical cleaning every two or three weeks may be required. The first that of Ionics of the USA who have probably supplied over 75% of the world’s installed electrodialysis plants. 17. They manufacture their own membranes and have a tortuous path spacer design where the liquid follows a continuous compressed ‘S’ shape across the cell. chemical dosing is not necessary. For normal brackish water treatment the polarity reversal occurs automatically three or four times an hour and by means of motorised valves reverses the product water. concentrate and electrode streams.Desalination 115 approximately 1 mm and a plastic mesh or spacer separates the membranes as well as acting as a turbulence promoter within the flow channels. Thus desalting energy requirements are proportional to the quantity of salts removed. With this mode of operation plant is normally operated with approximately 80% recovery. The fluid velocity along this path is approximately 0·5 m/s. The reversal purges membrane and electrode surfaces of scaling and fouling materials which may have deposited during the cycle. . Mixing is accomplished by ‘bridges’ across the flow path. The ion exchange membranes are cast as flat sheets typically 0·6 mm thick around a woven fabric to provide mechanical strength. With this facility. Owing to the economy of the process being directly linked to the amount of salt removed the upper economic limit for treating brackish waters is 7000 mg/litre TDS. FIG. Principles of electrodialysis.

Electrodialysis systems are relatively sensitive to feed water quality. The cross-sectional area of large electrodialysis stacks has usually been limited by the size of the membrane which can be fabricated and readily handled. increasing the electrical resistance of these streams. The limitations of these systems are very similar to those of Ionics. The blowdown typically varies between 5 and 20% dependent upon the feedwater quality. concentrate and electrode streams through the stacks. However. The current which flows is proportional to the salt removed and at ambient temperature from Faraday’s Law for each 1000 mg/litre TDS removed per m3 the actual desalting power requirement is approximately 0·7 kWh/m3 of product. However if two stages are operated with one common electrode in a single stack the current will be constant. The use of two or more stacks in series for electrodialysis is quite common. It is then common for progressive stacks to operate at lower currents to reduce the formation of excessive resistances in the diluate streams. chlorine. The maximum commercial membrane size is typically 0·5 ×1·5 m. In addition to the power for the actual desalination for tortuous path spacers a further 0·5–0·75 kWh/m3 of product would be required for pumping the product. The Japanese and UK systems use Japanese membranes and are based on a mesh type spacer to separate the membranes and induce turbulence. Hence multistage/stack plants are required. Often for a given duty and with satisfactory operating parameters the residence time is insufficient for adequate desalination to occur. Scale formation and fouling are controlled by acid dosing of the feed and adjustment of the blowdown rate to prevent excessive concentrations of salts which potentially precipitate on the membrane surfaces. Fewer cell pairs in the second stage allow the use of higher flow velocities which help reduce cell resistances.Developments in water treatment—2 116 The membranes for this duty have an upper temperature limitation of 43°C and can tolerate a pH range of 1–12. with the polarity reversal system it should be possible to achieve a product quality of 50–100 mg/litre TDS as the high resistance layers are frequently broken up by the polarity/flow reversals. There is usually a current limit of 130–150 A between electrodes and if this is to be exceeded a further stage or stack is required. The pressure drop is higher through the tortuous path spacer systems. They typically operate at 0·1 m/s open cell velocity across the width of the cell. When a voltage is applied across a stack the diluate streams are depleted in ions. For the Japanese/European systems the lower practical limit of salinity of the product water which electrodialysis can produce would be in the range 2–300 mg/litre TDS. It is possible for them to be depleted to the point where the stack resistance is excessive and operation of the stack impractical. In addition hydrogen sulphide. Russians and Permutit-Boby of the UK. In general terms the voltage applied to brackish water electrodialysis plant can be between 1 and 2 V/cell pair. The basic specification for all manufacturers would be as follows: The feedwater should have a turbidity of less than 2·0 FTU to give a reasonable life to the following 10 µm prefilter and contain less than 0·3 mg/litre iron and less than 0·1 mg/litre Mn. These plants often have the capability of polarity reversal but this is done at possibly monthly intervals and the change over is manual. However one membrane manufacturer does report a membrane which has good electrical and mechanical properties and excellent resistance against high temperature and . organics or other polymeric material which may cause membrane oxidation or fouling must be removed to very low levels. The second type of electrodialysis system is that of the Japanese.

18.21 It is claimed that any foulant on the membranes can be completely removed by a high concentration of acid and/or alkali cleaning. The largest polarity reversal plant is a 15 Ml/d plant on the island of Corfu.4 2969 7.25 3540 Product (mg/litre) 54 61 13 53 81 170 0.Desalination 117 chemicals. The total world installed capacity of ED to June 1979 is approximately 300 Ml/d. 25°C) 170 508 188 340 211 1550 2.05 650 .95 433 7. The process has not typically been applied to the desalination of sea TABLE 7 PERFORMANCE OF POLARITY REVERSAL ELECTRODIALYSIS ON A 3000 mg/litre TDS BRACKISH WATER22 Feed (mg/litre) Na Ca Mg Cl HCO3 (as CaCO3) SO4 F TDS pH Conductivity (µS/cm. A small polarity reversal ED plant can be seen in Fig. There is considerable experience with smaller plants of this type and a typical performance on a brackish water can be seen in Table 7.

18. However the Japanese developments originated from concentration of brine by electrodialysis which is now a standard commercial technique.1. dependent upon the feedwater quality and the site. must be added to obtain total water supply capital costs.4. the process could not be considered to be commercial at this time.). water since it has been uneconomic. brackish water. . As for reverse osmosis. 4. However recent development work in the USA with high temperature electrodialysis23 and in Japan with large plant24 at ambient temperatures has led to cost estimates for large-scale desalination of sea water which appear to be similar to those for sea water reverse osmosis. An Ionics 0·5 Ml/d polarity reversal. they only represent the desalination element of the total water supply costs and hence must be used with caution. Hence commercial sea water desalination plants can be expected in the near future. While small batch or development plants have been installed for sea water. The additional costs for associated plant site works and buildings. ED plant (by courtesy of Ionics Inc.Developments in water treatment—2 118 FIG. Costs of Electrodialysis Typical estimated costs for installed brackish water electrodialysis are presented in Table 8 for Q3 1979.

Although plastics have been tried as still covers the limited . 200 mg/litre TDS product.a and p/m3) 1. Solar energy has been employed to distil sea water. The costs for RO however on this feedwater would not greatly change. Membrane replacement 7-year life 5. Few ED plants have been installed with capacities greater than 16 Ml/d while significantly larger brackish water RO plants have been installed. cost estimates have not been presented for this. but as the feed salinity rises RO can become the more attractive process. OTHER DESALINATION PROCESSES A number of other desalination processes have received attention but none has been developed beyond the pilot-scale or very small full-scale capacity. 1·12 kWh/m3 Pumping 0·7 kWh/m3 Total 1. If a brackish feedwater of 4000–5000 mg/litre TDS was to be treated by ED then the capital costs would increase as extra membrane area would be required. Maintenance. staff and materials Total annual cost (£ million) Total water cost (p/m3) 20 Ml/d 0·7 2·8 £mpa p/m3 £mpa p/m3 0·082 6·3 0·33 0·076 5·8 0·38 5·0 5·8 0·005 0·4 0·026 0·4 0·050 3·8 0·25 0·046 3·5 0·20 0·26 19·8 1·12 18·1 3·8 3·1 These ED costs are very close to those for a similar RO feedwater with in general the capital costs being higher than for RO. 78% recovery) 4 Ml/d Capital costs (£ million) Operating costs (£ million p. However the higher capital costs are partly offset by a longer membrane life and a reduced cost per m3 for membrane replacement. Power (at 3·2 p/kWh) Desalting 0·7 kWh/m3 per 1000 mg/litre TDS removed. Hence there is also more confidence in RO for large-scale applications. 21°C. operation. Hence for low TDS waters RO and ED are competitive. Chemicals Provided polarity reversal used 4. Fixed charges 11·75% 2. In addition the power requirements would more than double. i.82 kWh/m3 3. Since sea water electrodialysis is not yet commercial.e. 4.5.Desalination 119 TABLE 8 TYPICAL ELECTRODIALYSIS COSTS Q3 1979 FOR A 90% LOAD FACTOR (1800 mg/litre feedwater.

Symposium on Fresh Water from the Sea.Developments in water treatment—2 120 life of the material has led to the preference for glass covers. considerable effort was devoted to the development of freezing desalination processes which rely upon the melting of salt-free ice formed from saline solutions. VEENMAN. The Sirotherm ion exchange process was developed in Australia as a means of desalination for brackish waters. A. Whilst consideration has more recently been given to the use of absorption refrigeration cycles as a means of overcoming the practical limitations of compression in vacuum freezing. BURLEY. The direct contact vapour compression freezing process involves the formation of ice and simultaneous evaporation under vacuum conditions. Marlow.J. Israel and the UK. Proc. The secondary refrigerant process employed an organic refrigerant such as butane. 1978. MOORHEAD. Dell. . The provision of this storage adds significantly to the high capital costs of solar distillation works. without the use of chemicals. P. the high construction costs and limitations in performance have restricted the use of the process. Bucks. the Commonwealth Scientific and Industrial Research Organisation in Australia and Portham Ltd in the UK led to the construction of a number of solar stills for the supply of small communities in the 1965 to 1970 period. The Blue Nile. washing ice free of salt. 1967. and BROEKENS. Whilst reliable operation of the process was proven in Israel and the United States it was found to be impossible to scale-up the vapour compressors owing to the massive volumes of vapour to be handled. at a temperature of 90°C. In both the United States and the UK initial optimism for the process was never justified by results.D. M. and separation of ice/salt solution/refrigerant mixtures led to plants becoming excessively complex and unreliable in operation.W. The output of a still is typically five times greater in the summer than in the winter. it is rather unlikely that the process will be developed to a stage where it can compete with the alternative sea water desalination processes... REFERENCES 1. New York. TP50. Since this pattern of output does not match demand.A. 1967. This process relies upon the change in ion exchange properties of synthetic resins when they are exposed to different temperatures and by this means regeneration is achieved. Work by the Battelle Memorial Institute in the United States.. The vapour produced after compression was used as a direct contact heat source for melting washed ice. 53. and MAWER. 6th Int. Assoc. In the freezing section of the plant butane liquid was vaporised whilst in the melter the compressed butane vapour provided the heat source for the melting of ice to form water. However. A. and consequently plant capacities were limited to about 1000 m3/d. In the United States. This process has not yet been employed to any significant extent although there may be some requirement for small-scale units of this type in remote locations where chemicals are not available. For these reasons development of the process virtually ceased during the first half of the 1970s. season to season storage is required. Difficulties in handling ice. The attraction of the processes has been the theoretically low energy demand involved in ‘heat-pumping’ the latent heat of fusion. J. Las Palmas. 3. Water Research Centre. 2. Water Res. 2.

TODD. EL-RAMLY. Desalting Plants Inventory No. June. 1978. B. M. Proc.. paper 16.G. 14/30/2721.Desalination 121 4. 1.. 8. 6. J. KLAREN. R. Presented at the Comision Federal de Electricidad. Inst. Technical Bulletin on Self Cleaning Filters. 23. WADE.M. and DE BUSSY.. USA. SEROY. 23. H. Las Palmas.. R.P. Newbury. 15. 1977. . Dept. W. S.. R. T. Office of WaterResearch and Technology. National Water Supply Improvement Association J.. N. UK. 10 pp. M. 1977. Las Palmas. Mexico City. KISHI. International Nickel Co. and TAGAMI. E. 3. J. 4. and WINDT. October 1977. BIRKETT. and ERRICSSON. LYONS.. SATO. Symposium on Fresh Water from the Sea. 2. Amsterdam. 13.M. 1979. C. BURLEY. 12.. 14. GHULAIGAH. 11–1. 95. Proc. Permasep Products. Proc. A. 1973. 1978.M.. Proc.S. JHA.. Report to U. MILSTEAD. and DELUE. Proc. T. Birmingham. 101. Symposium on Fresh Water from the Sea. Congress on Desalination and Water Re-Use.. 3–301. 2. First Desalination Congress of The American Continent 1. ASAKA. 1979. 1978. and O’DONOGHUE. Nice. NEWTON. GANZI. Int. (2).W. M. Japan.. 307. U.. K. C. 327. Proc 2nd Int. Proc. Congress on Desalination and Water Re-Use..H. Metals. 1977.J.. Contract No. GROVER. 21. A. Tech. 9. J.A. R.. Desalination. 18. 10. 22. 1. 6th Int. 24. J. March 1972. J.L. The Plenty Group. 15. NWSIA.E. Bull.E. G. 575. N. Ionics Inc.. 1979. LOPEZ. and NAKARO. 17. 349. K.M. AL-GHOLAIKAH. Symposium on Fresh Water from the Sea. RILEY.R. A. May 1967. Plastic Products and Resins Dept.. Las Palmas. Fox. Office of Saline Water. W.A. McRAE. WADE. Athens. 6th Int. M. UK. 4th Int.J. 1. 1977. R. 203. Jan. of the Interior.R.. and SEATON.D. B. GAYLER.. DuPont Company.. and KETTERINGHAM. 367. SERIZAURA. 6th Int. Proc. 6. 1978. 309. Private communication. JAMJOON. 491.. M.H.. 1978... 7. Bull. 1–15. 3.. 1976. Symposium on Fresh Water from the Sea.L. E.S. Desalination. I. 1978. Elsevier Scientific Publishing Co. Bulletin TP. and SUZAKI. KAWAHARA.. 11.. 16. Symposium on Fresh Water from the Sea.. 20.. 19. Las Palmas. 5. 6th Int. M. Desalination. W. Heidelberg.. CARMONA. 1979. PARSI... W. 1976.. 23..E. Nice. D.. DESAI. KALZ.. Int. Symposium on Fresh Water from the Sea. N. 31.

In addition. these disinfectants are dealt with in turn with reference to such aspects as historical development.Sc. viruses and other disease-producing organisms.S.Chapter 5 DISINFECTION A. may produce undesirable traces of chloroform. Nevertheless considerable use is still made of the chloramine process and it may.1. a chemical first introduced for regular water treatment at about the turn of the century. UK SUMMARY The principal disinfecting agents used in water treatment are chlorine. B. Ph. F. an outline of the DPD analytical tests for treatment control is presented of which a special advantage lies in their ability to determine mixtures of disinfectant residuals in the treated water. The only other disinfecting agents used in water treatment on any appreciable scale are chlorine dioxide and ozone. was widely practised during the 1930 to 1940 period but gradually became less popular because of its much slower rate of disinfection compared with that of chlorine and its inability to provide other desired quality improvements. In the vast majority of cases the disinfectant used at the present time is chlorine..E.W. Consulting Chemist. chloramine.D.PALIN. Demand for these is likely to increase in view of the attention now being paid to the possibilities of using one or other in conjunction with or alternative to chlorine..I. and even those containing natural organic colouring matter. for certain types of water. F.. a recognised carcinogen. a form of combined chlorine.R. 5. After a preliminary discussion of their relative importance. These developments arise from the findings of recent years that the chlorination of polluted waters. Newcastle upon Tyne. remain the preferred method.I. especially when dealing with the more polluted sources. chlorine dioxide and ozone. renewed interest is being taken in the chloramine process and in those advantages it possesses compared with straight chlorination. Finally. and similar potentially carcinogenic .C.T. Consideration is given to the influence of these findings on future developments. While chlorination remains the most widely used process at the present time..E.B. studies of recent years have revealed problems associated with the possible formation in some waters of traces of harmful carcinogenic by-products such as trihalomethanes. O. INTRODUCTION The process of disinfection is applied to water for the purpose of destroying or inactivating pathogenic bacteria. Treatment by chloramine. chemical and bacteriological properties and practical application.

It may be mentioned that for emergency use on a small scale boiling the water is completely effective. History In the earliest applications of chlorine for water disinfection the chemical was applied in the form of hypochlorite. Reference will also be made to such modifications to treatment as might be required to minimise risks of harmful by-products being produced in the finished water. In considering developments in disinfection the present discussion is concerned only with those agents having any significant large-scale application in the field of water treatment.Disinfection 123 trihalomethanes. resulting from its oxidising power. iodoform or chlorophenol. Its excellent bactericidal properties became firmly established and additional benefits. It is this aspect of disinfection to which most research is directed at the present time.2. From the public health point of view the benefits derived from the use of chlorine as a disinfectant were unquestionable so that further investigation up to about 1935 was directed more towards improvements and modifications of treatment aimed at overcoming any possibly undesirable side-effects on general water quality. bactericidal efficiency. These were due to reactions of the chlorine with trace amounts of phenols and similar compounds. Other disinfectants such as ultraviolet radiation. these being compounds formed in the water by reaction between chlorine and ammonia.v. During this period attention was paid to the use of chloramines. mode of application. 5. bromine and iodine are not regarded as practical for drinking water treatment except possibly on a very small scale. and iodine. while satisfactory for emergency purposes. U. or it can be added if required in the form . can impart taste. bromine is difficult to handle and is expensive. became evident such as removal of iron and manganese. chlorine and the related chloramines. From about 1915 increasing use was made of chlorine gas contained under pressure as liquid in cylinders. CHLORINE 5. usually as a consequence of pollution.1. and the necessary treatment control to ensure full compliance with chemical and bacteriological standards of drinking water quality. The survey will cover their chemistry. and of tastes and odours. does not provide an active disinfectant residual in the water. On the other hand it was found that chlorination itself could impart to some waters undesirable tastes variously described as medicinal. odour and colour to the water and also is very expensive.2. Such processes provide the further advantage of physically removing a substantial proportion of the micro-organisms thus reducing the pollution load at the disinfection stage and the general chlorine demand of the water. that is the amount remaining in the water after treatment. Ammonia is present in many raw water sources. Furthermore the use of too much chlorine could itself give a chlorinous taste because of the presence of excessive amounts of ‘residual chlorine’. Clarification by filtration is therefore essential usually preceded by coagulation and sedimentation. In the case of turbid waters the presence of suspended particulate matter may interfere with disinfection by affording protection to embedded bacteria from the action of the disinfectants. chlorine dioxide and ozone. that is to say.

. This research received much impetus from the reported discovery in 1939 of so-called ‘breakpoint’ chlorination by Faber1 and Griffin. The chloramine or ammonia-chlorine process had the advantage. the so-called ‘hump and dip’ curve. and had begun to increase more or less in line with progressive increases in chlorine dose. often with a minimum of firm supporting experimental evidence. from a practical point of view. from liquid ammonia under pressure in cylinders. It thus became necessary in practice to make provision for an adequate time of contact to ensure complete disinfection of the water. possibly to compensate for short contact time.6.Developments in water treatment—2 124 of ammonia. These developments towards greater flexibility in methods of chlorination were coupled with an awareness of the need for more fundamental research into the chemistry of water chlorination. especially their ability to react both among themselves and with free chlorine. The results emphasised the need. Other modifications of treatment to be developed at that time included ‘superchlorination and dechlorination’ signifying the use of much higher chlorine doses than required normally. of greatly reducing the risks of producing undesirable tastes and odours but at the same time its bactericidal activity. The indications were that the presence of ammonia was a principal factor contributing to these unusual dose-residual relations.2 a phenomenon which had in fact been described in the literature as long ago as 1914 by Ruys3 and again by Holwerda in 1930. referred to as the ‘breakpoint’. or its ‘rate of kill’ was much lower than that of chlorine itself. The behaviour of such compounds.4 It was found that as the rate of application of chlorine to some waters was increased the residual chlorine after a period of contact could behave in an erratic manner. for suitable water chlorination control tests since it had become clear that an indication of the chemical nature as well as the amount of the residual chlorine in the treated water was essential. Ample confirmation was thus provided for the earlier work to which may be added that of Gerstein5 who had also reported in 1931 that in the chlorination of water containing ammonia a point was reached where with increasing chlorine dose the residual chlorine began to break down and disappear more rapidly than if a lower dose were used. the removal of tastes and odours was complete in such cases only when the residual chlorine had passed the minimum point. with subsequent dechlorination to remove the excess residual chlorine. because of its lower reactive and oxidising power. In the continuing work from 1940 onwards several workers demonstrated the close relation between the presence of ammonia and this characteristic type of chlorine dose-residual curve.7 Subsequent researches then revealed that residual chlorine in water could exist in different chemical forms with different oxidising and bactericidal powers. Furthermore. With polluted waters a high chlorine dose might well give a lower residual than that obtained from a low dose. Many theories were presented to account for the breakpoint in chlorination. or in smaller installations as ammonium sulphate in solution form. thus provided a rewarding field for further exploration eventually made possible by the advances made in analytical methods. A full explanation of the chemistry of the chlorine-ammonia and similar reactions awaited the development of suitable analytical techniques for the determination of both the type and the amount of the residual chlorine compounds at these relatively minute concentrations in water. With these refinements in test procedures the chlorination process could be applied to give optimum results under all conditions of raw water quality.

Similarly chlorine dioxide although first introduced as being two and a half times more powerful than chlorine is in fact considerably weaker in some reactions. the final reduction product. . Similarly the concentration of residual chlorine in water is always expressed in terms of available chlorine no matter in what chemical form it might be present. To illustrate the application of the available chlorine concept the following four cases may be considered using potassium iodide KI and hydrochloric acid HCl. this remains the standard form of expression for the strengths or capacities of the various forms of chlorine as well as for the doses in which they are applied and for the residues that remain in the water. NH2Cl—137% and ClO2—261%. A knowledge of the available chlorine content is of value in assessing the comparative costs of chlorine from different commercial products and in checking for any gradual loss on storage (Table 1).) By calculation from molecular weights it may be demonstrated that the amounts of iodine liberated from 1 g of each of the above chemicals are 3·6 g.Disinfection 125 5. (In practice another acid. the available chlorine contents become HOCl—134%.2. Any chlorine that eventually appears as chloride. For the present purpose it enables the reactions to be presented more simply. say acetic acid. In terms of percentages. Monochloramine is far less reactive than hypochlorous acid.2 Forms of Chlorine In any comparison of strengths of chlorinating chemicals in terms of chlorine yield it is standard practice to refer to their ‘available chlorine’ content. The expression ‘available chlorine’ is defined in precise chemical terms and relates to capacity rather than oxidising or disinfecting power. 4·93 g and 9·41 g respectively. Since the available chlorine content of pure chlorine is 100% the corresponding figures for other compounds may be obtained as a percentage by comparing the amounts of iodine thus liberated with the amount liberated from the same weight of chlorine. As previously noted it would be incorrect to equate these figures to oxidising power and bactericidal efficiency. taking chlorine as 100%. It is based upon the determination of the equivalent amount of iodine liberated from iodide in acid solution by a known amount of the chlorine compound. 4·84 g. represents a complete loss of available chlorine. would be used in the determinations since HCl itself may contain traces of chlorine. While regarded by some as a misnomer.

First. the product being sodium hypochlorite. Of the solid hypochlorites one of the best known is bleaching powder or chloride of lime. A superior form of solid hypochlorite is available under the name High Test Hypochlorite. In full containers most of the chlorine is present in liquid form. In practice the solution may require dilution to provide more convenient application with solution-feed dosing equipment.3. usually by means of an injector. When fresh the available chlorine content is up to 15% by weight but gradual loss occurs on storage.2. For application the chlorine is withdrawn as gas with the rate of flow being set to the desired level by suitable metering equipment. the chlorine hydrolyses to form hydrochloric acid and hypochlorous acid thus Secondly. The essential constituent is calcium oxychloride which is decomposed by water to produce calcium hypochlorite. Chlorine solutions as supplied are usually prepared from chlorine and caustic soda. Chemistry of Chlorination When chlorine is dissolved in pure water two practically instantaneous reactions occur. before mixing with the main flow. the hypochlorous acid partly dissociates to give hydrogen ions and hypochlorite ions thus: .Developments in water treatment—2 126 TABLE 1 AVAILABLE CHLORINE CONTENT OF DIFFERENT FORMS OF CHLORINE AND THE QUANTITIES REQUIRED TO GIVE 1 lb OF AVAILABLE CHLORINE Form of chlorine Chlorine gas High Test Hypochlorite (calcium hypochlorite) Bleaching Powder (chloride of lime) Sodium hypochlorite Sodium hypochlorite Sodium hypochlorite Available chlorine 100% 65–70% Equivalent quantities 1 lb 1·5 lb 30–35% 15% 10% 5% 3·0 lb 0·5 gal 0·8 gal 1·6 gal Chlorine gas is produced commercially from sodium chloride (common salt) by an electrolytic process and is supplied under pressure in cylinders and drums. This consists of solid calcium hypochlorite in the form of free-flowing granules which dissolve readily in water or as tablets for smaller-scale use. 5. The gas is then dissolved in a minor flow of water. When fresh its available chlorine strength is about 33% by weight but there is fairly rapid loss on storage unless conditions are cool and dry. The available chlorine content is up to 70% by weight and the shelf life is considerably longer than that of bleaching powder.

1. hypochlorous acid HOCl and hypochlorite ion OCl−. Its reactions with chlorine may be represented as follows: .e. A balance exists between these forms and at any given time the relative proportions are governed by water temperature and pH of which by far the more important is pH. namely molecular chlorine Cl2. The small amount of hydrochloric acid produced in the above hydrolysis of chlorine is neutralised by the natural alkalinity of the water. It may be seen that within the pH ranges encountered normally in drinking water only two forms are present. in-built resistance to pH change).Disinfection 127 Three forms of available chlorine are involved in these reactions. These together comprise what is defined as ‘free available chlorine’. Having considered the reactions that occur when chlorine is dissolved in pure water it is necessary next to examine the effect of those impurities whose presence is to be expected in the chlorination of natural and polluted waters. namely HOCl and OCl−. As already noted. The resulting effect upon pH is insignificant except for relatively soft waters low in buffering capacity (i. This relation is shown in Fig. the presence of ammonia has a particularly marked influence upon the chemistry of water chlorination. The equilibrium is independent of the form in which the chlorine is initially added assuming that such addition does not itself alter the pH.

that is the combining weight ratio is 5 of Cl2 to 1 of NH3 calculated in terms of nitrogen. The lower the pH of the water and the higher the ratio of chlorine to ammonia the greater is the tendency to produce the more highly chlorinated derivatives. Effect of pH value on form of free available chlorine in water. however. For conversion of all the ammonia to monochloramine about five times as much chlorine is required.Developments in water treatment—2 128 FIG. Within the normal pH range of water. continuing oxidation reactions occur at a slower rate eventually producing mainly nitrogen thus: 2NH2Cl+HOCl=N2+3HCl+H2O Small amounts of dichloroamine and nitrogen trichloride may also appear during the course of the breakpoint reactions especially in the zone corresponding to chlorine doses . 1. the product consists almost entirely of monochloramine and the reaction is complete within one minute. If more chlorine is applied than is required for this rapid initial reaction.

FIG.Disinfection 129 above the 5:1 ratio. 3. where appreciable amounts of ammonia are present the distinctive breakpoint curve will be obtained as in Fig. On the other hand. but the net result as the chlorine is further increased and adequate contact period is allowed corresponds to the following overall equation: 2NH3+3Cl2=N2+6HCl According to this equation the amount of chlorine required to oxidise one part by weight of ammonia-nitrogen is 7·6 parts by weight. In natural waters there may be additional chlorine absorption by other types of impurity giving a ratio about 10:1. Breakpoint curve for water with ammonia-nitrogen 0·06 mg/litre. For polluted waters the ratio could be much higher. 2. . If the water contains only a small amount of ammonia the curve obtained will be similar to that of Fig. The chlorine dose-residual curve may be plotted for a given sample of water by treating a series of aliquots with increasing doses and determining the residual chlorine values after a predetermined period of contact. 2. While nitrogen is the main end-product small amounts of nitrate and possibly nitrogen trichloride may also remain with the result that the observed ratio becomes somewhat higher at about 8·3:1.

Breakpoint curve for water with ammonia-nitrogen 5·2 mg/litre. 4. FIG. .Developments in water treatment—2 130 FIG. Chlorine dose-residual curve at pH 6·0 after 1 day. 3. Initial ammonia 0·5 mg/litre (N).

Disinfection 131 FIG. Initial ammonia 0·5 mg/litre (N). In these systems. 6. Chlorine dose-residual curve at pH 7·0 after 1 day. . Initial ammonia 0·5 mg/litre (N). FIG. 5. The ammonia was added as ammonium chloride. Chlorine dose-residual curve at pH 8·0 after 1 day. 5 and 6. the water used being otherwise of zero chlorine-demand. The effect of pH on the composition of the residual chlorine at different stages of the breakpoint curve is shown in Figs. 4.

4. This may impart to the water an objectionable chlorinous-type odour for the eradication of which additional treatment may be necessary.2. The chlorine demand of a water is the difference between the applied dose and the residual chlorine. It is necessary to specify the conditions. The production of residuals of known composition by suitable control of chlorination has been made possible by the methods of chlorine residual differentiation now available. that is combined chlorine.8 5. The most important feature of the curves is that before the breakpoint the residual chlorine is present in the form of chloramines. The modern approach to the classification of chlorination methods is based upon this distinction between free and combined chlorine. Both free and combined chlorine are destroyed thus: SO2+H2O=H2SO3 (sulphurous acid) H2SO3+HOCl=H2SO4+HCl H2SO3+NH2Cl+H2O=NH4HSO4+HCl . exhibit a breakpoint.Developments in water treatment—2 132 therefore. The two main types of process therefore are free residual chlorination and combined residual chlorination. that is whether the residual produced is in the free or combined form. Variations may be introduced to meet particular requirements but the results obtained under any given conditions will always depend upon the nature and amount of the residual chlorine produced in the water. The chlorine dose also should be specified. Recognition of these two forms is of vital importance in the control of water chlorination since the bactericidal and virucidal properties of free chlorine are vastly superior to those of combined chlorine. Combined available chlorine is residual chlorine existing in combination with ammonia or organic nitrogen compounds. Where dechlorination is required it is usual to apply sulphur dioxide which reacts rapidly to destroy the residual chlorine in an approximate 1:1 ratio. Modern Chlorination Practice From the foregoing review of the chemistry of chlorination it is clear that the following definitions are fundamental to modern practice. possibly involving complete dechlorination with a final stage of ammonia-chlorine treatment. After the breakpoint it is present mostly as free chlorine. that is to the point of establishing free chlorine. Dosing equipment is similar to that used for chlorine. A disadvantage of breakpoint chlorination lies in the possibility of producing traces of nitrogen trichloride unless the pH is fairly high. In those cases where the chlorine demand is due mainly to nonnitrogenous matter or oxidisable inorganic impurities the chlorine dose-residual curve may not. Free available chlorine is residual chlorine in the form of hypochlorous acid and hypochlorite ion. Sulphur dioxide is a gas under normal pressure but may be compressed to liquid for supply in cylinders and other containers. as already noted. Nevertheless after the demand has been satisfied free residual chlorine will appear and continue to increase with increasing dose. the reactions involved only chlorine and ammonia. Therefore for maximum safety in the disinfection of water it is generally desirable to chlorinate beyond the breakpoint. and the time of contact.

10 it was established that within the same contact period about twenty-five times as much chloramine as free chlorine was required for complete destruction of bacteria. . for residuals of the same amount about 100 times the exposure period was required with chloramine compared with free chlorine. 50% and 25%. TABLE 2 MINIMUM CYSTICIDAL AND BACTERICIDAL RESIDUALS (AFTER 30MINUTE CONTACT) pH Combined chlorine Bactericidal Cysticidal Cysticidal Bactericidal 0–25°C 22–25°C 2–5°C 0–25°C 0·2 0·2 0·2 0·6 2·0 2·5 5·0 20·0 7·5 10·0 20·0 70·0 2·0 2·5 3·0 3·5 Free chlorine 6·0 7·0 8·0 9·0 especially if the first is high and the second low. sodium sulphite and sodium bisulphite. From studies carried out originally by the US Public Health Service9. Under favourable conditions free residual chlorination may require no more than a few minutes whereas combined chlorine under similar conditions might require from 30 minutes to 2 hours.0. Whatever the conditions the final test resides in microbiological examination of the treated water. If in addition to the free chlorine reading the pH is known it is possible to calculate the residual HOCl quite simply from the established dissociation factors. Where treatment is concerned it may be necessary in practice to work to higher free chlorine residuals at the higher pH values. The bactericidal power of both free chlorine and combined chlorine decreases as the water temperature falls. Furthermore. 7·5 and 8·0 the HOCl proportions are very approximately 75%. At pH values of 7·0.Disinfection 133 Passage of the water through granular activated carbon filters provides another means of dechlorination. With pH rising above 6·0 the proportion as HOCl declines from virtually 100% down to almost zero at pH 9. Since the bactericidal activity of HOCl is something like 80 times more powerful than that of the OCl− ion it is evident that in free residual chlorination the higher the pH the less active is the residual. There is evidence that the killing power of combined chlorine diminishes also with rising pH. Thus pH and temperature. may together have an important bearing on the period of contact required to achieve satisfactory disinfection. the principal reaction being as follows: C+2Cl2=2H2O=4HCl+CO2 For small-scale dechlorination use can be made of such chemicals as sodium thiosulphate (‘hypo’). The pH of the water governs the relative proportions of hypochlorous acid and hypochlorite ion in the free chlorine residual. The bactericidal and virucidal power of free chlorine may be influenced by other factors of which one of the most important is pH.

known as the CIFEC method. based on 30-minute contact.2. with additional recommendations regarding cysticidal chlorine residuals (Table 2). During this period some unreacted free chlorine will be present thus giving a significant improvement in bacterial kill.1.13 For smaller installations other methods may be used in which the chlorine dioxide is generated under controlled conditions from mixtures of sodium chlorite and either hydrochloric or sulphuric acid or from similar mixtures with the addition of hypochlorite. as delivered from the normal type of chlorinator.3. Although its use has expanded considerably. whereby the chlorine water is recirculated around an enrichment loop to ensure almost 100% production of chlorine dioxide after admixture with the sodium chlorite solution. History Chlorine dioxide was first applied as a water treatment chemical in 1944 at a plant in Niagara Falls. with a solution of sodium chlorite when the following reaction occurs: Cl2+2NaClO2=2NaCl+2ClO2 If the pH of the mixture is not low enough the reaction may not go to completion thus leaving unreacted chlorine and chlorite in the discharge to the water. It was found to be effective in controlling unpleasant tastes and odours especially those of phenolic origin. 5. . CHLORINE DIOXIDE 5. It was subsequently investigated in the UK by the author12 with particular reference to its decolorising effect on peaty moorland waters.3. During this work its general chemical properties were examined and this led to the discovery of its inertness to ammonia. it is now fully accepted as a disinfectant in its own right. While originally its effectiveness as a disinfectant was open to some doubt. It can provide a longer-lasting residual than chlorine which is advantageous where it is desired to maintain residual disinfectant throughout the water distribution system. In practice the performance of chloramine will be rather better than is indicated because a short period of up to one minute is required for completion of the reaction between chlorine and ammonia after their addition to the water.3. This position may change in view of current researches into the trihalomethane problem. Because of this chlorine dioxide does not give a breakpoint type of dose-residual curve. Generation Chlorine dioxide is produced on site by mixing strong chlorine solution.Developments in water treatment—2 134 In 1956 the National Research Council11 re-analysed the earlier data and submitted revised recommendations for minimum safe residuals. it still remains relatively small compared with that of chlorine. In addition to its use in the control of tastes and odours it now finds application in the oxidation of iron and manganese and some forms of organic impurity. and thus it was always used with an excess of chlorine. 5. USA. A system has been devised.

Thus in the majority of reactions chlorine is a better oxidant than chlorine dioxide except in special circumstances. when the advantage lies with the dioxide. which must be clean and dry. This relatively low concentration coupled with its low solubility requires very intimate mixing and dispersion of the ozonised air throughout the water in order to achieve the highest possible degree of transfer from the gas to the liquid phase. As a general rule chlorine dioxide is as effective a disinfectant as chlorine and is less sensitive to changes in the pH of the water.4. In the generation process the air.3. Chemical and Bactericidal Properties As previously noted chlorine dioxide. History The earliest recorded use of ozone as a water disinfectant occurred in France in 1886. is passed between electrodes separated by an air gap across which a very high voltage is maintained to produce a silent electric discharge. that at Nice where the process has operated continuously from 1906. Thus ozonation has a long history of use but never on so extensive a scale as that of chlorine.1.4. unless the dose is high enough. does not react with ammonia to form chloramines. such as the presence of phenols. This is equivalent to no more than one-fifth of its total available chlorine as expressed normally. iron and manganese oxidation and organics removal. porous diffusers or mechanical mixers. Apart from disinfection it may be applied for other purposes such as taste and odour control.3. As a result of further pilot studies a number of treatment plants adopted ozonation in the early years of the present century including.2. In water treatment only a part of the full oxidising capacity of chlorine dioxide is used because in most of its reactions it undergoes only a first-stage reduction corresponding to the change from chlorine dioxide to chlorite. as is more usual in large-scale commercial production. For this purpose the methods used may take the form of injectors. The amount of ozone produced may be up to 30 g/m3 of air. Generation and Application Ozone is generated on site from oxygen or. for example. 5. becomes converted to the slow-acting chloramines. unlike chlorine. For maximum efficiency the aim must be to produce as small a bubble size as possible. from the air. As . OZONE 5.4. Thus with pH rising over 7 it is better able to maintain its disinfecting power unlike chlorine which gradually becomes less effective because of the shift from hypochlorous acid to the much less active hypochlorite ion. The strong disinfecting and oxidising action of ozone is due to the release of the very reactive third atom of oxygen with reversion to oxygen O2 thus: 2O3=3O2 There are today possibly more than one thousand plants using ozone.Disinfection 135 5. In waters of high ammonia content this lack of reactivity is beneficial compared with chlorine which. 5.

Developments in water treatment—2 136 the dispersed bubbles gradually grow in size so the efficiency of transfer falls away with the decreasing interfacial area of contact. Selection of points of application will .5. As well as chemical pollutants the naturally occurring constituents of peaty water. In calculating applied doses it is assumed that all the ozone is transferred from the air to the water although in practice the proportion of ozone dissolved may range from 60% to possibly better than 90%. chlorine dioxide and even chloramine where conditions are suitable for its application. respectively.6. This is not the case where chloramine is concerned and it may be necessary to allow further for additional disinfection unless high quality waters are being treated. for example. While the results varied with design capacity the general indication was that chlorine dioxide. 5. The slow-acting chloramines do not form these compounds. chlorine plus chlorine dioxide and ozone plus chlorine are likely to receive more attention. Environmental Protection Agency who are urging that modified treatment practices be adopted to minimise chloroform and similar trihalomethane formation from the organic materials found in natural and polluted waters. such as humic acid and similar organic matter.S. The ozone disappears very rapidly from the water and it is therefore not possible to maintain an active residual as is the case with chlorination. can act as precursors of the trihalomethanes. more than chlorination. Recommended dosage rates for drinking water are generally within the range 0·2 to l·5 mg/litre. While there is at present no acceptable substitute for chlorine for general use in water disinfection there is no doubt that increased consideration will be given to ozone. The carcinogenicity of chloroform has now been acknowledged by the U. Satisfactory disinfection by ozonation is assured normally by 0·4 mg/litre or more of residual ozone acting for a minimum contact period of 4 to 5 min. In the case of chlorine. operational and maintenance costs. In practice the presence of ozone residuals of about 0·1 mg/litre at the outlet of the ozonation chamber is generally effective. The absence of any lasting residual disinfecting action is a disadvantage of the process and for this reason a supplementary stage of chlorination is usually applied.14 The basis of these estimates includes capital. RELATIVE COSTS Unit costs for five disinfection processes have been developed by the U. DISINFECTION BY-PRODUCTS The problems associated with the formation of traces of chloroform and other trihalomethanes as possible by-products of chlorination have led to a review of the entire subject of drinking water disinfection. Such traces have been detected in polluted waters after chlorination and also where chlorine has been applied with long contact period for colour removal. Environmental Protection Agency.S. chloramine and ozone cost about 65%. 20% and 100%. chlorine dioxide and ozone it is assumed that the specific doses have equivalent disinfecting capability. In addition. 5. mixed treatments such as.

Multiply by 5. BAC is an effective process for ammonia removal. to use other disinfectants in conjunction with chlorine so as to enable chlorine doses and contact times to be reduced. by improved or modified pre-treatment prior to chlorination. As normally produced for water treatment by reacting sodium chlorite with chlorine. To express as ClO2. Chlorine dioxide G 1 5. Secondly. to reduce. can result in substantially reduced chloroform production. Results indicate that formation of trihalomethanes can then occur with these mixed residuals but at lower concentration than would be produced from an equivalent amount of chlorine alone. some excess of chlorine remains. for instance after coagulation and sedimentation. Shortening of pre-chlorination contact periods or applying the chlorine at a later stage of treatment. This result is in terms of available chlorine. First. Improved results are obtained by pre-ozonation which assists by breaking down those organic materials not readily adsorbed into more readily adsorbable and biodegradable compounds. Combined 1 3 Reagents 1 and 3 added together may be used in place of reagent 4.Disinfection 137 require further thought. Trace amounts of chlorite may appear as a by-product of chlorine dioxide treatment either because of TABLE 3 OUTLINE OF DPD TESTS FOR FREE CHLORINE AND OTHER DISINFECTANT RESIDUALS Test 1. Free chlorine 2. Result gives onefifth chlorine dioxide. There are two general approaches to the problem from a treatment point of view. To obtain free chlorine from reagent 1 reading. Free chlorine Combined chlorine 3. Chlorine dioxide plus free chlorine. the level of organic pollutants acting as precursors of the trihalomethanes. multiply instead by 1·9. This process in which the use of ozone is combined with biological activated carbon (BAC) is receiving much attention with very promising results. Chlorine dioxide treatment appears not to produce trihalomethanes when prepared free of chlorine. deduct one-fifth . A favoured approach in attempting to achieve the first objective is adsorption by passage through granular activated carbon (GAC) filters. Total available chlorine Reagents (in order of use) 1 1 3 4 Notes 4. It is now recognised that the carbon becomes biologically active.

An outline of the procedures is given in Table 3. Deduct four-fifths chlorine dioxide in terms of available chlorine as obtained from test 4 to obtain chlorite. Provides for separate determination. In the control of these modified disinfection processes involving mixed treatment by chlorine. Reagents 1 and 3 added together may be used in place of reagent 1. The possible toxicity of chlorite has not been ruled out and preliminary indications so far suggest that it is about the same as that of nitrite. Chlorite (continuation of test 5) A N 7. by using quite simple modifications of the method they are here included together as combined chlorine. chlorine dioxide and ozone a suitable residual control test capable of their separate determination is essential. can meet these further analytical requirements. Free chlorine plus ozone 4 G 4 1 chlorine dioxide as given in test 4.15. Total chlorine plus ozone 3 Key to Reagents 1—DPD indicator+buffer 2—for differentiation of combined chlorine (not included here) 3—potassium iodide 4—1 and 3 combined G—glycine A—acidifying agent N—neutralising agent incomplete conversion or because of reversion in the treated water. The preparation of the various reagents is given in standard manuals of water analysis and in the author’s published papers.18 Standardised tablets and powder reagents are available commercially. Combine with test 8 for complete differentiation. Ozone 4 8. Ozone response is incomplete but difference gives combined chlorine.17. if required. Total chlorine plus ozone Total chlorine only 9. Although monochloramine. bearing in mind that chlorite is the first reduction product of chlorine dioxide. 7 and 8. Only the DPD test.Developments in water treatment—2 138 chlorine 6.16 adopted as standard in many countries for free chlorine and combined chlorine compounds. . dichloramine and nitrogen trichloride may be determined separately.19 These are used with colour comparators in test kits as shown in Figs.

Tintometer Lovibond test kit for residual chlorine. . 7. pH value and alkalinity.Disinfection 139 FIG.

10. A. 157. England. and WATTIE. 7. 3. 1956.T. Thesis. J... 1949. RUYS. 1931. Ph.. 1939. K.B.E.. Water Works Assoc. H. 1946.. J. 1948. Water Works Assoc.D. A. W. J.). 1837. Public Health Reports. Inst.. 1334. 100. 8. 3.. 63. 1949.. Amer. J. 5.. LaMotte test kit for residual chlorine and pH value. H.. BUTTERFIELD.D.. BUTTERFIELD. 1510. A. PALIN. 61. 1914. PALIN. 1943. 1948. 9. 934. GRIFFIN. REFERENCES 1.T. Notice No. 61. J. 12. 8. Amer. 41.. 1949. . SNOW.B.T. Water Works Assoc. Chlorine Dioxide Generator: The French Method with Enrichment Loop.H. Water Works Assoc. GERSTEIN. Water Engrs.. 1930. 1539. J.Developments in water treatment—2 140 FIG. 1976. Inst. 19.A. 2.. Amer. 167. Water Works Assoc.T. Paris. 31. Water Engrs. FABER. 325. 441. 13. J. 23. WILLIAMS.. Public Health Reports. Mededeelingen van den dienst der Volksgezondheid in Nederlandsch-Indie. Nov. University of London. 1939. A. 11.T. PALIN. 58. 31. 4. C.. D.. HOLWERDA.. 48. C. CIFEC (Cie Industrielle de Filtration et d’Equipment Chimique S. Drinkwater-reiniging met Hypochlorieten.A. 6. Amer. 2121. 2. Amer. E. J.

Washington. 1975. A. Revised April 1978. 19.. 16. Ozone. 1957. DC. American Public Health Association. UK Department of the Environment. Water Engrs.T. 1974. J. Gateshead. 18. 17.T. Ltd. 2nd Edn. 28.Disinfection 141 14. USA. USA. England. 873. Chlorine Dioxide and Chloramines as Alternatives to Chlorine for Disinfection of Drinking Water. Standard Methods for the Examination of Water and Wastewater. England. 1980 (in preparation). J. A.. . Analysis of Raw. PALIN. 1972. 14th edn. London. Wilkinson and Simpson. Amer. Water Works Assoc. US Environmental Protection Agency. 49. Potable and Waste Waters. PALIN. Tablet Tests and Reagents for Water Analysis and Treatment Control.. Cincinnati. Inst. 15. 139. American Water Works Association and Water Pollution Control Federation.

The term sludge can be taken as describing any suspension of solid material in a liquid. Quantities of sludge arising and operational procedures for sludge treatment installations are then dealt with.A. The dewatering of sludge is considered as two separate processes: initial thickening or increase in concentration to minimise the size of treatment equipment required followed by a review of the various methods available for further dewatering. Recently introduced water treatment processes are then considered with particular reference to their impact on sludge treatment. Increasing interest in environmental matters together with pressures on land use and concern for public safety have escalated the problems of waste disposal. F. Such areas ultimately become filled with gelatinous sludge which presents a safety hazard as well as a visual eyesore and merely postpones the day when a viable sludge treatment and . The methods of water treatment plant operation aimed at producing the minimum volume of sludge for subsequent treatment are then discussed. Water Treatment and Supply. It is produced in large quantities and presents the industry with a very significant disposal problem. This philosophy has resulted in large areas of land in the vicinity of water treatment plants being given over to sludge-holding lagoons.HILSON.S. F.Chem.Chapter 6 SLUDGE TREATMENT AND DISPOSAL M. C.I.R. INTRODUCTION Sludge is the waste product produced in a water treatment process and as such is a material of little or no intrinsic value.1. North West Water Authority.. It is apparent that in the past insufficient thought was given to the disposal of waste products at the design stage of a water treatment plant. 6. the problem being left in abeyance pending operational experience.I. Warrington.E.W. but attempts have been made to point out where differences may arise when dealing with sludges produced from waters of various types.C. In the context of water treatment processes the liquid phase of the sludge is invariably aqueous whilst the solid phase will consist of any materials derived from the raw water together with the residues of any chemicals added in the treatment process. Much of the material in this chapter is drawn from the experience of the author and his close colleagues and as such is perhaps inclined towards the problems of the treatment of sludge arising from peaty upland waters. Principal Scientist. UK SUMMARY The various types of sludge arising from water treatment processes are considered and this is followed by a consideration of disposal methods..

should be an integral part of the plant design. contain quite high concentrations of suspended solids since the backwashing will be carried out at time intervals depending on filter performance and solids load in the raw water. settled from the raw water. 6.1.Sludge treatment and disposal 143 disposal system has to be provided. TYPES OF SLUDGE The properties of different sludges will vary considerably dependent upon their origin and the type of treatment applied to the raw water. In other words the liquid component must be of such a quality that it can be either recycled or discharged to a watercourse and the solid component reduced to a form in which it is readily transportable for disposal and which will not. The washwater produced will contain algal remains and some larger particulate matter. Washwater from Microstrainers and Filters used Without Coagulant When a raw water is of an acceptable colour but contains small amounts of suspended matter such as algae it is often possible to remove this suspended material by either microstraining through fine wire mesh fabric or by filtration through sand filters without the use of coagulant. Since the costs of sludge treatment can amount to up to 17% of the total costs of the water treatment process it is apparent that sludge treatment should be worthy of rigorous attention to detail during the design stage of a treatment plant. however. As such they should be relatively free draining and present few or no problems of separation into their two components. such as sand and coarse silt. The washwater from a microstrainer installation will generally be of quite low solids content since the backwashing of such installations is carried out on a continuous basis. Sludges of this type will generally accumulate in channels and sumps at the inlets to treatment works. The .2. Washwater from rapid gravity sand filters used without coagulant can. Indeed in the long term such an interim scheme compounds the disposal problems in that any new process for disposal must be capable not only of dealing with the sludge produced from the treatment plant but also capable of gradually dealing with the old sludge from the lagoons to enable such areas to be made safe and put to a more productive use. 6. The objective of a sludge treatment process should be to separate the liquid and solid components in a manner in which both are capable of re-use or disposal. Such processes are often used prior to slow sand filtration. give rise to a hazardous environment. Sludges can conveniently be grouped into two types: (1) Sludges produced without chemical treatment. It is therefore recommended that sludge treatment. and where practicable wastewater recycling.2. Sludges Produced Without Chemical Treatment Primary Sedimentation Sludges In general such sludges will consist of the coarser solid materials. (2) Sludges produced from a chemical treatment process. as a result of such disposal.

Other sludges in this category may find application for treating agricultural land in place of ground limestone. Sludges Produced by Iron and Manganese Removal Plants Sludges derived from such plants generally have similar characteristics to coagulant sludges.2. 6. being more particulate.Developments in water treatment—2 144 batches of backwash water when they arise will therefore contain the accumulated suspended solids from a considerable volume of throughput water. will usually be within the range 100–500 mg/litre. to those containing suspended matter from the raw water mixed with the softening products together with the residues of any coagulant used in the process. Sludges Produced from a Chemical Treatment Process Sludges Produced by Coagulation Sludges produced from water treatment processes utilising coagulation by means of aluminium or iron salts can vary considerably depending on the chemicals used and the type of treatment plant. Given efficient management of desludging a concentration of 0·5% (5000 mg/litre) should be attainable from plants treating soft upland water whilst higher concentrations may be obtained from plants dealing with lowland river waters. which form a very small proportion of the total water treatment sludge production. or rapid gravity filters used after sedimentation. they are more easily dewatered. Softening sludges are normally of a higher solids concentration than coagulant sludges and. Sand-Washing Plants When slow sand filters become partially blocked by solid matter in the upper layer of sand. ranging between pure calcium carbonate. Whatever the coagulant used there is a physical and chemical bonding of water to the sludge particles which makes dewatering difficult. 6.2. Of these sludges pure precipitated calcium carbonate may have some commercial value to the pharmaceutical industry. the disposal method usually . The suspended solids concentration of the effluent from the sand-washing process can be quite high and will normally consist of organic material from the removal of algae. Sludges Produced by Precipitation Softening The quality of sludges will vary widely. through mixtures of calcium carbonate and magnesium hydroxide. The suspended solids concentration of backwash water from sand filters employed after coagulation whether they be pressure filters in use as a single stage treatment. the hydrated oxides of certain metals present in the raw water together with fine sand particles. Effluent from Slow Sand Filter.3. CHOICE OF METHOD FOR DISPOSAL Apart from the case of the softening sludges mentioned above. The sludge obtained from desludging sedimentation tanks will vary considerably in suspended solids content. this sand is skimmed off and washed free from debris by some mechanical process.

Consideration of sludge disposal should be one of the factors taken into account at the design stage of a new waterworks and location of the works relative to the sewerage system should receive due consideration at this stage. Much depends on the proportion of the sewage works capacity taken up by the waterworks sludge. Discharge of waterworks sludge to sewer is not therefore an end in itself. As has been mentioned earlier. This is often not the case as the majority of water treatment works tend to be removed from centres of population and hence from sewers of significant size. If this is the case then the provision of suitably sized holding or balancing tanks at the waterworks together with means of maintaining the sludge in suspension will be another economic factor which must be allowed for in the appraisal of sludge disposal strategy. Provision of a suitable sewer for sludge disposal should be the subject of an economic appraisal against the costs of sludge treatment on the waterworks site followed by transport to a suitable tip. after suitable treatment. to agricultural land then it may be that the introduction of a considerable inorganic component to the sludge. This can be achieved either by discharge to sewer. However at this concentration even with a 75% moisture content the sludge . This should not be a serious problem in the case of coagulant sludges since the density difference between the suspended matter and the water carrier vehicle will be quite small. nor is it desirable to incur transportation costs of large quantities of water.Sludge treatment and disposal 145 applied is one of ‘throwing away’. in the case of coagulant sludges. If the sludge has to be disposed of to tip after suitable treatment at the waterworks then the problem resolves itself into selecting a suitable method of dewatering. If the sewage works sludge is disposed of. Another factor which must be taken into account when considering this method of disposal is the avoidance of deposition of solids within the sewer. Discharge to sewer is a convenient method of disposal if sewers of sufficient capacity are available in the vicinity of the water works. Discharge of waterworks sludge to sewer will of course only be possible if the treatment processes employed at the sewage works are amenable to the reception of sludge of this type and the necessary hydraulic capacity is available. would render this method of disposal less attractive to the agricultural industry. It is not economic to produce a solid of lower moisture content than is necessary at a high cost. The degree of dewatering required is that which produces a solid component which is suitable for tipping. it is merely transferring the disposal problem from one place to another. The subsequent sludge treatment and disposal practice at the sewage works will also play a part in determining whether or not waterworks sludge is acceptable. The objective should be to produce a solid component which when placed on a tip will not revert to a gelatinous condition and which has sufficiently high load bearing characteristics to enable the tipping area to be reclaimed by the application of topsoil followed by reseeding. The process should seek to strike a balance between disfigurement of the environment and the economics of disposal. there is a physical and chemical bonding of water to the sludge particles which makes dewatering difficult. from the coagulant residues. It may also be necessary to avoid intermittent ‘slug’ disposal because of possible effects on the processes at the receiving sewage works. Indeed the ultimate dewatering that can be achieved for a sludge produced from a soft upland coloured water treated with aluminium sulphate as coagulant is only about 25% solids w/w. possibly after some pre-treatment or transport direct from the waterworks to a suitable tip after local treatment.

after a few weeks atmospheric exposure. Sludge cake of 20–25% solids content will. Before considering methods of thickening and dewatering it is worth considering the way in which the sludge to be handled is produced from the water treatment plant and what operational practices can be used to minimise the subsequent problems of sludge dewatering. the operation of two separate sludge separation and thickening processes which can increase both capital and operational costs.Developments in water treatment—2 146 cake is quite dry and hard to the touch and indeed its ‘feel’ resembles that of a piece of softwood. As has been mentioned earlier when considering the various types of sludge. lose additional water by evaporation to produce a dry friable solid which is quite suitable as land-filled material. thickening followed by further dewatering. If this is not being achieved then attention should be given to the desludging operation to increase the sludge bleed concentration to the maximum possible level. It is important that any sludge thickening process employed must not only result in the production of a sludge of the desired concentration but must also produce a supernatant water of a quality suitable for either recycling through the water treatment plant or discharge either to drain or a local watercourse. if the solids content of the sludge cake exceeds 18–20% then there will be no tendency for the sludge to revert to a gelatinous nature on exposure to the atmosphere even after heavy rainfall.4. 6. as would be the case when treating water from lowland rivers. The presence of increased amounts of suspended solids in the raw water. The sludge should be thickened to the maximum concentration at which it is still capable of being pumped. It is better where possible to use the existing structures of the water treatment plant to achieve as much sludge thickening as possible. the sludge produced from sedimentation tanks is at a considerably higher concentration than that arising from the backwashing of filters. Even when treating coloured upland waters of low turbidity it should be possible to operate the sludge bleeds from modern sedimentation tanks to yield a sludge of 0·5% solids concentration. This concentration will normally be not less than 4% in the case of sludges produced from coloured upland waters of low turbidity and could be higher for sludges produced from waters containing appreciable levels of suspended solids. Whilst it is perfectly feasible to separate the solids from filter backwash water and then treat these solids along with the sedimentation tank sludge this can involve. Dewatering of waterworks sludge can therefore be considered as falling into two separate stages. in effect. The upper limit of concentration to which a given sludge can be thickened is governed by the flow characteristics of the sludge. will enable sludge cakes of a somewhat higher solids content to be produced. This can be done by arranging for the dirty filter wash water to be collected in a holding tank and returned to the treatment plant . DEWATERING OF WATERWORKS SLUDGE The capital cost of any sludge dewatering process is influenced largely by the quantity of sludge to be handled. It is worth noting that in the United Kingdom a site licence may be required under the Control of Pollution Act 1974 for the tipping of waterworks sludge. for the case of sludge produced from soft upland waters of negligible turbidity. It has been found in practice that. There are great economic advantages if the sludge can be thickened and hence the volume reduced as much as possible prior to subsequent processes.

often 3–5% of the plant throughput. If it is intended to use a polyelectrolyte for sludge thickening and the resultant supernatant water therefrom is to be discarded. care must be taken that the desludging arrangements of the sedimentation tanks are not overloaded by the return of the filter backwash water. The advantage of this method of operation is that the only sludge arising for treatment is that arising from the sludge bleeds of the clarifier and the subsequent processes are simplified by only having to deal with what is in effect a single point source of sludge of a reasonably consistent concentration. then a wide range of polyelectrolytes is available from which the ultimate selection can be made. particularly those of high molecular weight. this being particularly useful when treating waters of low turbidity. Filter wash water return can assist the coagulation and flocculation of the incoming raw water by providing additional solids within the clarifier.5. only be used when the water treatment plant is based on a two-stage process of sedimentation followed by filtration. appear to have a voracious appetite for the solid sludge particles. resulting in possible blockages. 6. The nett result of this . and even then the dose which can be applied to the sludge may be governed by the maximum recommended dose which may be applied to the water being treated for potable purposes. overdosed whilst the remainder are underdosed. in view of the normally much larger quantities of solid material involved.Sludge treatment and disposal 147 inlet at a uniform rate without any separation of the solid material. In the case of single-stage water treatment plants consisting of filtration of coagulated raw water there is no option but to regard the starting point for sludge treatment as being the much larger quantity. It is more a case of trying a range of products and selecting the best one of that range for the job in hand. This is necessary because the molecular chains of the polyelectrolyte. This is particularly so where a polyelectrolyte is also being used as part of the treatment process. of course. In the present state of knowledge of the theory of the action of polyelectrolytes it is not possible to scientifically define an application and thereby select the best product for the purpose. The efficiency of action of any polyelectrolyte depends on the rapid and complete dispersion of the small dose applied into the bulk of the ‘dirty’ water or sludge being treated. If it is intended to recover the supernatant water then the choice of products will be restricted to those products which have been approved on toxicity grounds. Work carried out over twenty years ago1 showed that the sludge produced from the treatment of a coloured upland water could be thickened to about 2·5–3·0% solids by this method although the quality of the supernatant water from such thickening was often poor. If the dispersion is not rapid then those sludge particles which first encounter the polyelectrolyte molecules become. The rapid and thorough dispersion is necessary to ensure that all sludge particles are equally exposed to the action of the polyelectrolyte. The introduction of synthetic polyelectrolytes during recent years has had a great impact on sludge thickening both in terms of the solids concentration attainable and the quality of the supernatant water for disposal. of dirty filter wash water of low suspended solids concentration. in effect. It is also applicable to the operation of precipitation softening plants although in this case. SLUDGE THICKENING The most widely used method of sludge thickening is by slow stirring. This method of operation can.

The Stocks plant is a pressure filter installation which treats about 100 Ml/d and can produce up to 5 Ml/d of dirty filter wash water containing 0·03–0·04% solids. The problems associated with and the benefits obtainable from the use of polyelectrolytes can perhaps best be illustrated by a description of and comments on their use for sludge thickening at two water treatment plants of the former Fylde Water Board which is now part of the North West Water Authority. The dirty filter backwash water is returned to the plant inlet at a uniform rate and the sludge bleeds from the sedimentation stage give about 0. After the solenoid valve closes the stirring . The laboratory tests had shown that the use of polyelectrolyte could be expected to improve the thickening to such an extent that the capacity of the lower tank would be sufficient to achieve the degree of thickening required and the upper tank could be used as a balancing tank to iron out variations in flow and sludge solids concentration arising from the clarifier sludge bleeds.Developments in water treatment—2 148 is that the full action of the polyelectrolyte is not realised since overdosing is equally detrimental to the effect being sought as is no dosing at all. The dose of polyelectrolyte added is adjusted by varying the time for which the solenoid valve is opened. The sludge bleeds from the sedimentation tanks fed sludge on an intermittent basis into the upper tank. The original sludge treatment installation at Fishmoor consisted of two 9 m diameter circular sludge thickening tanks equipped with picket fence stirrers.1 Ml/d of sludge containing 0·6% solids as the starting point for treatment. The sludge is dosed with polyelectrolyte on a batch basis in 455litre batches. Some sludge thickening occurred in the upper tank and the sludge passed to the lower tank with a solids concentration of about 0·8–1·0% solids. This mixing tank is a circular tank of 1·2 m diameter with a conical bottom section leading to an outlet gate valve and discharge pipe. Although the same polyelectrolyte is in use at both Fishmoor and Stocks its method of application. Exhaustive laboratory tests showed that treatment with the same anionic polyelectrolyte of high molecular weight would give improved sludge thickening and supernatant water quality at both plants. The polyelectrolyte as a 0·15% solution is dosed into the sludge from a header tank the outlet of which is controlled by a solenoid valve. When the 455-litre quantity of sludge is in the mixing tank the stirrer starts up and after 5 s the solenoid valve opens to allow the preset volume of polyelectrolyte solution to run into the stirred sludge. in order to achieve rapid dispersion. Sludge is drawn from the upper tank by means of a pump on the time control to deliver 455-litre quantities into a mixing tank. It was felt that injection of polyelectrolyte solution into the pipeline between the two tanks would not give the required rapid dispersion and mixing. The supernatant water from this tank was returned to the plant whilst the sludge from the bottom was transferred by gravity flow through an| underground pipeline to the lower tank for further thickening. The mixing tank is fitted with a 130 mm propeller-type stirrer which operates at 960 rpm. These two tanks were arranged in series in order to perform a two-stage thickening process. The problem therefore became one of injecting polyelectrolyte into the sludge as it passed between the two tanks. In order to assist this rapid mixing and dispersion the polyelectrolyte is usually dosed to the sludge as a very dilute solution of about 0·1–0·2% strength. The Fishmoor plant treats 32 Ml/d by means of sedimentation and rapid gravity filtration. is quite different. experimental work was therefore undertaken which led to the system which has been in use for the last 14 years. the discharge being by means of a submerged weir.

the stirrer then stops and the outlet gate valve opens.1 These two sedimentation tanks had been installed originally when the throughput of the plant was 32 Ml/d and proved capable of dealing . nevertheless it has. It has been found in this process that the solids content of the final sludge produced from the bottom of the lower stirrer can be varied by varying the dose of polyelectrolyte applied. In order to produce a final sludge of 5% solids content it is necessary to inject polyelectrolyte at the rate of 1·5mg of polymer for each gram of dry solids in the initial sludge. At the Stocks plant the dirty filter backwash water is passed to two horizontal flow sedimentation tanks. It would appear that a stirrer speed of 960 rpm is ideally suited to size of propeller and mixing tank for the polyelectrolyte used and the sludge produced at the Fishmoor plant. It is important to stir the sludge prior to polyelectrolyte addition to ensure homogeneity and to continue stirring only until the polyelectrolyte solution added is completely dispersed in the sludge. such as the passage over a weir. There is sufficient turbulence in this main and at the submerged bell-mouth inlet to the sedimentation tanks to achieve the required degree of and rapidity of mixing. any free fall discharge at this stage again adversely affects the thickening. In this process the rate and duration of stirring are critical. this discharge takes place via submerged weir below the surface of the supernatant water in the lower thickening tank. been a method which has proved outstandingly successful at the Fishmoor plant and particularly suited to the configuration of the installed sludge thickeners. The dose of polyelectrolyte required to yield a final sludge of a given solids content is proportional to the solids content of the initial sludge being treated. Experiments were carried out with lower stirring speeds in the mixing tank but these did not give results as good as those obtained using the 960 rpm stirrer. On new treatment plants it is usual to design the sludge thickening facility so that polyelectrolyte solution is injected into the sludge at a point of high turbulence.Sludge treatment and disposal 149 continues for a further 5s. thereby aflfecting the subsequent thickening. If the stirring is continued for more than 5 s after the completion of dosing then the large floc particles which are formed rapidly by the polyelectrolyte are broken down by the shearing action of the stirring and only reform slowly once the sludge has been discharged. In this case the polyelectrolyte solution is injected into the main carrying the dirty wash water to the sedimentation tanks at a dose of about 1·5–2·0 mg/litre. 1. over the years. The sludge thickening by this process appears to be largely unaffected by the temperature of the sludge. the dosed sludge being discharged by gravity to the lower thickening tank. A great deal of experimental work was carried out into sludge thickening by slow stirring at this plant during the 1950s. The sludge thickening and polyelectrolyte dosing arrangements at the Fishmoor plant are shown diagrammatically in Fig. in an effort to achieve the desired rapidity and thoroughness of mixing thus avoiding the expense of the installation of a batch dosing system such as that described. The thickened sludge is withdrawn from the bottom of the primary section of these tanks. This work and a description of the horizontal sedimentation tanks has been described by Doe. For similar reasons it is also important that the dosed sludge be discharged below the water surface of the lower thickening tank. The above may appear at first sight to be a complicated method of achieving a rapid and complete dispersion of the polyelectrolyte solution in the sludge to be treated.

1. Whilst it must be realised that there will be differences in the thickening characteristics of different sludges. the Water Research Centre. Current Practice and Trends. even when operated in parallel. it is interesting to note the variation in dose of the polyelectrolyte required to produce a thickened sludge of similar solids content at the two . A seminar was held at the Water Research Centre early in 1978 on: Alum Sludge Disposal. Research Association carried out extensive pilot-scale investigations at the Stocks plant. At this seminar four papers were discussed including one on ‘Research in Alum Sludge Treatmen’ by the Water Research Centre staff. The proceedings of this seminar have been published3 and the research at the Centre into sludge treatment is continuing. The sludge thickening and polyelectrolyte dosing arrangements at the Fishmoor water treatment plant. The position was becoming so serious that consideration was being given to the construction of a third and possibly even a fourth sedimentation tank. By the latter half of the 1960s the plant throughput had further increased and the wash-water sedimentation tanks. The advent of the use of polyelectrolyte so changed the position that one of the original sedimentation tanks is now able to cope with the wash water arising from a plant throughput of over 100 Ml/d whilst achieving an improved sludge thickness (4·5% solids) and greatly improved quality of supernatant water. the results of which have been published by the Association’s successor. were becoming so overloaded that the sludge thickening (to 2·5–3·0% solids) was being impaired and the supernatant water quality passing to the river was outside the standard required by the local river authority.Developments in water treatment—2 150 with the wash water arising from an increased throughput up to 79 Ml/d.2 It is interesting to note that virtually all the conclusions arrived at during the original investigations and experiments carried out at the plant over a period of years were verified during the above pilot-scale experiments. During the period September 1972 to October 1974 the then Water FIG.

It is apparent from this equation that the sludge properties which control the dewatering process are S the compressibility index and r0 the specific resistance of the sludge at unit pressure. If all connections are a good fit. 3. A=area of filter.Sludge treatment and disposal 151 plants which both treat waters of an essentially similar type but using different mixing techniques. It is undesirable to attempt to adjust the vacuum by manipulation of the valve B during the . The dewatering takes place according to the following equation. The rate of dewatering by filtration is therefore governed by the properties of the sludge itself. As mentioned above the grade of filter paper used does not matter. Close valve B. and C=initial concentration of solids in sludge. t=time. These properties are readily determinable on a small scale in the laboratory. 2. To yield a final sludge of 4.5% solids the polymer dose used at Stocks is of the order of 4·5 mg of polymer per g of dry sludge solids whilst at Fishmoor it is only 1·5 mg/g. Most of these processes involve some form of filtration of the sludge and it is only during the very early stages of such filtration that the filtering medium has a controlling effect on the rate of dewatering. which is derived from the Carman-Kozeny and D’Arcy equations: where V=volume of filtrate. Glass fibre filter paper is used because of its wet strength. 2. THEORETICAL BASIS OF SLUDGE DEWATERING Before giving detailed consideration to the various methods available for further dewatering of coagulant-based waterworks sludge it is necessary to consider the mechanism of such dewatering which is applicable to most of the processes to be considered. since it plays no part in the dewatering except in the very early stages. Open valve B until the required vacuum shows on the gauge C (allow about 5 cm higher vacuum than is desired for the experiment). 2 with valve B and tap E both closed. Turn on the water to vacuum pump A at a rate in excess of that required to obtain the desired degree of vacuum. 6. the vacuum should hold constant for the duration of the experiment. P=applied pressure. After a very short time the filter medium becomes blinded by a layer of the sludge and it is this increasingly thick layer of solids which governs the subsequent rate of dewatering. and is virtually independent of the characteristics of the filter medium provided such medium is capable of retaining a layer of sludge which is of course necessary if the quality of the filtrate is to be acceptable. The apparatus used for this laboratory determination is shown in Fig. Place a filter paper in funnel G and make sure it is thoroughly bedded down by drawing a little distilled water through. 4. The procedure used is as follows: 1. η=viscosity of filtrate. S=compressibility index.6. r0=specific resistance of sludge at unit pressure. Assemble the apparatus as shown in Fig.

Developments in water treatment—2


experiment, since slight changes in vacuum produce a marked momentary effect on the rate of filtration. 5. Place the sludge in the funnel G. 6. Open tap E and start a stop watch. (The vacuum will fall slightly.) 7. Note the volume of filtrate collected at minute intervals for 10 minutes or up to the 50 ml mark, whichever is the less. Whilst taking these readings keep the level of sludge in the funnel G topped up to a reasonably constant level, in order to simulate a constant feed of sludge to the filter. The filtration rate is normally determined at four different pressures, i.e. levels of vacuum. It is important that the units used are systematic and it is recommended that the cgs system is employed, i.e. V=volume in ml; P =pressure in g/cm2; A=area of filter in cm2; t=time in s; η=viscosity of filtrate in poise (see below); and C=initial concentration of sludge in g dry solids per g sludge.

FIG. 2. Apparatus for determining the compressibility index and the specific resistance of sludge.
A=water-driven vacuum pump B=Saunders valve C=vacuum gauge D=vacuum reservoir (500 ml) E=glass stopcock F=50 ml graduated measuring cylinder G=Buchner funnel to take 5·5 cm filter paper. The viscosity of the filtrate will vary with the temperature of the sludge. Temperature of sludge Viscosity of filtrate (°C) (poise)
0 5 10 1·79×10−2 1·52×10–2 1·31×10−2

Sludge treatment and disposal


15 20

1·14×10–2 1·01×10–2

The value of S and r0 are obtained from the experimental data by means of the following treatment:

therefore log(V2/t)=(1−S) log P+log(2A2/ηr0C). A plot of V2. against t for each pressure examined gives gradient g. A plot of log g against log P gives a straight line of gradient (1−S), hence S is determined. This straight line gives the value of log(2A2/ηr0C) from its intercept on the y axis at log P=0 (i.e. P=1), therefore r0 can be calculated. The conditioning of a sludge prior to dewatering in order to increase the rate of dewatering involves treatment by polyelectrolyte or other means to alter the values of S and r0 and so the above experiment yields valuable predictive information on a laboratory scale on the benefits likely to be obtained on a full scale. Details of the above experiment have been described by the author4 along with other information on the conditioning of sludge by means of polyelectrolyte. A simpler method of predicting changes in the dewatering characteristics of sludge is by means of the capillary suction time method developed at the then Water Pollution Research Laboratory,5 but this method has the disadvantage that it is performed at a single pressure equivalent to the capillary suction pressure of the paper being used and hence does not take account of changes in the compressibility index S with pressure, which can be important when the sludge is to be dewatered at elevated pressures as in a filter press.

6.7. METHODS OF FURTHER DEWATERING There are six principal methods of further dewatering of coagulant based sludges, each of which is examined below. 6.7.1. Drying Beds A sludge drying bed is a development of a simple sludge lagoon in that it incorporates a system of underdrains overlain by a permeable filtration medium to facilitate drainage and dewatering of the sludge. Many different materials have been proposed and used as the permeable filtration medium in drying beds, the main ones being sand, ‘no-fines’ concrete and specially woven wire fabric known as ‘wedge-wire’. Whichever permeable medium is used it is essential that it should not become blocked by the sludge particles. If

Developments in water treatment—2


blockage does take place then the drying bed merely acts as a lagoon and the only dewatering achieved is that which takes place by evaporation. This system has been investigated by Gauntlett and Packham6 who conclude that drying beds of suitable construction provide an effective means of drying waterworks clarification sludge during those months of the year when evaporation proceeds at a reasonable rate. They also stated that drying proceeds at a very slow rate indeed during the winter months. From this it is apparent that evaporative loss of water plays a significant part in the sludge drying and as such it is not a process which is of much use in temperate climates such as the UK but may be of use in the hotter and drier parts of the world. 6.7.2. Rotary Vacuum Filtration The rotary vacuum filter consists of a large drum or cylinder the circumference of which is covered with a suitably fine filtration fabric. The drum is mounted in a frame and motor driven so that it rotates slowly about its cylindrical axis. A partial vacuum is applied to the interior of the drum, the lower part of which passes through a trough into which the sludge is fed. The partial vacuum causes a thin film of sludge to adhere to the filtration fabric as it passes through the sludge in the trough. Water is drawn from this film of sludge, by the vacuum, during the remainder of the rotational cycle. The water drawn into the centre of the drum is collected in a drainage trough and hence to waste whilst the dewatered sludge on the outside of the drum is scraped from the fabric by means of a horizontally mounted knifeedge just before it re-enters the sludge trough. This type of machine has been established for many years and has proved useful for the dewatering of many types of sludge. It suffers however from the fact that the maximum pressure which can be used in the dewatering process is limited to the level of vacuum which can be maintained in the interior of the drum which is of course something less than one atmosphere. Additionally the maximum time which can be allowed for dewatering to take place is the time taken for that part of the revolution of the drum between leaving the sludge trough and the sludge being scraped off the fabric, i.e. it is governed by the rotational speed of the drum. Difficulties can also be encountered in the selection of a suitable filtration fabric capable of supporting the sludge to be dewatered without allowing an excessive quantity of fine sludge particles to pass through with the filtrate. This can be overcome by the use of a precoat material, which in effect is a material the particles of which are of a size and shape that are retained on the filter fabric and then act as the support for the sludge particles. The precoat is applied by allowing the circumference of the drum to pass through a trough containing a suspension of the precoat material immediately prior to the sludge trough. The use of a precoat adds to both the cost of dewatering and the quantity of sludge for ultimate disposal. The rotary vacuum filter has found the widest application in the water supply industry for the dewatering of sludges of the more particulate type such as those produced in water softening processes. Because of the limitations mentioned above it has not found great favour for the dewatering of coagulant-based sludges.

Sludge treatment and disposal


6.7.3. Belt Pressing During recent years a number of pieces of sludge dewatering equipment have become available which can best be described as belt presses. In some respects they resemble vacuum filters but are provided with additional means of achieving a greater level of dewatering than is possible on a normal vacuum filter. They consist of a belt of fine filtration fabric of considerably greater length than the circumference of a rotary vacuum filter. The belt passes through a trough of sludge or is fed with sludge from above and passes over a drum or chamber in which a partial vacuum is established. This results in a film of sludge adhering to the belt which is further dewatered by passing between a series of rollers at gradually increasing pressures so that further water is squeezed out of the sludge. The limitations of pressure and dewatering time inherent in the rotary filter are thereby alleviated to some extent but the problem of selecting a suitable filtration fabric for the belt remains, if the use of a precoat material is to be avoided. Such belt pressing equipment has found more application in dealing with the more fibrous type of sludges produced from sewage than with coagulant-based sludges. 6.7.4. Filter Pressing The filter press or plate press has been in use for many years in various process industries as a means of dewatering suspensions of solids in liquids. It comprises a multiplicity of recessed plates the surfaces of which are covered by a detachable filter cloth; each plate has a hole of about 100 mm diameter in the centre which forms the sludge inlet system to the press. The plates are mounted on a heavy cast-iron frame either slung from a top beam or supported on side bars. The frame is of such a length that the plates can be moved successively along their supporting beam to enable the pressed sludge cakes to be removed, and is fitted with hydraulic or mechanical equipment to enable the plates to be held tightly together during the dewatering cycle. The principle of operation is that the press is closed up and sludge is pumped into the central core and hence into each chamber formed between adjacent plates. The solids in the sludge are retained in the chamber to form a sludge cake whilst the water passes through the filter cloth and drains away through channels in the plate itself. Plates can be obtained with different depths of cavity to yield sludge cakes of different thicknesses, the normal thickness being 25–30 mm. Filter presses normally operate at pressures of up to 6·7 bar, but equipment working at even higher pressures is now available. It does not necessarily follow that the dewatering is more rapid if a higher pressure is used. This depends to a large extent on the compressibility index of the sludge in question and its effect on the rate of filtrate production according to the Carman-Kozeny equation. The cake thickness chosen for a filter press installation will again depend on the dewatering characteristics of the sludge itself and should be selected to give the desired degree of dewatering in a reasonable press cycle time. Many coagulant-based sludges in the past did not prove amenable to filter pressing, merely producing a sludge cake with a hard outer skin and a soft centre. To overcome this problem the selected cake thickness would have had to be so small as to render the

Developments in water treatment—2 156 number of plates required for a given sludge throughput excessive and beyond the bounds of economic feasibility.8 and the reader is recommended to refer to them for further practical details. but it suffers from the fact that it depends for efficient separation of solid and liquid on difference in density between the solid and liquid phases which is often very slight in the case of coagulant-based waterworks sludges. Whilst this is undoubtedly true it aggravates the disposal problem since the addition of lime increases the quantity of sludge to be disposed of to tip and the increased pH value of the sludge can result in poorer filtrate quality. allowing as it does the optimisation of the variables of cake thickness. In spite of these limitations centrifuging can prove an economically attractive process for dewatering certain types of waterworks sludges.6. Several papers have been written on the development of filter press systems for this purpose7. applied pressure and cycle time. offers one of the most economical and controllable methods of dewatering coagulant-based sludges produced by water clarification processes. This tends to limit the degree of dewatering attainable to about 14–17% solids content and often produces an aqueous phase of a quality unfit to discharge to a watercourse because of its high residual suspended solids. 6. the solids are changed to a granular nature which allows the water to drain away freely when deposited on a tip provided with underdrains. for some reason. The solids so deposited have sufficiently high load bearing characteristics to enable the tip to be reclaimed by topsoiling and seeding.9 The process has the advantage that it is a continuous rather than a batch process.7. The solids are scraped from the wall by a scroll revolving at a slightly slower speed than the drum itself and directed to an outlet chute. The freezing must proceed slowly if the required benefits of the process are to be obtained. 6. coagulant-based water-works sludge can be dramatically altered by freezing and thawing. The advent of polyelectrolytes with their ability to so condition coagulant-based sludges as to vastly improve their dewatering characteristics has meant that filter presses are now an economic proposition for even the most intractable of sludges. If the process is carried out correctly and completely the filtrate from the thawed sludge is of a .7.5.3. Several experiments and full-scale operations have been reported. flash freezing does not produce the desired results. after suitable conditioning with a polyelectrolyte. It has been claimed in the past that the addition of lime to the sludge will considerably improve the dewatering characteristics and enable shorter pressing cycles to be achieved. If the sludge is frozen slowly to a solid block and then allowed to thaw. the solids adhering to the wall of the drum and the water overflowing a ‘beach’ at the far end of the drum. There is no doubt that filter pressing. claiming various degrees of success. Freezing The dewatering characteristics of a gelatinous. into one end of a drum which is spinning at a rate of several thousand revolutions per minute—the principle being that the solids and water are separated by centrifugal force. Centrifuging In this process the sludge is fed.

then it is possible to obtain sludge concentrations in excess of 2% solids direct from the flotation unit. it may indeed worsen the problem since the sludge will be at a very low solids concentration and a thickening process capable of dealing with quite a high throughput will be required. The flotation process is carried out in a tank equipped with mechanical means of skimming the floating sludge layer from the surface of the clarified water. Continuous removal of the sludge from the surface of the tank. The skimming process can be either on a continuous or an intermittent basis. the sludge skimming is intermittent and the layer of sludge can be allowed to remain on the surface of the tank for a period of hours then a considerable amount of dewatering of the sludge takes place by water draining from the aerated sludge layer back into the tank. If the sludge removal from the surface of the flotation tank can be carried out in this intermittent manner without adversely affecting the quality of the clarified water passing forward for filtration. Apart from the use of a polyelectrolyte for sludge thickening to minimise the size of freezing plant required. do in fact minimise its handling problems by producing the sludge from the water treatment process at a higher concentration and thereby simplifying subsequent processing. thus avoiding the operational complexity of solids handling equipment. The fact that sludge of this concentration from a . does not provide any benefits in the way of simplifying the sludge treatment and disposal. if.8.10 6. however. The two most notable of such recent processes are flotation and lamella sedimentation. The freeze-thaw process has been developed to full-scale operational plant at three waterworks locations in the UK. There are however certain water treatment processes which have been developed in recent years which. the process does not depend on any sludge conditioning. the freezing is not complete and small pockets of sludge remain unfrozen then the filtrate quality is greatly impaired. In this process the suspended particles produced by coagulation and flocculation of the raw water are induced to rise to the surface by the attachment of minute air bubbles. 6. however. but owing to increasing running and maintenance costs has been discontinued at two of those locations where the advent of polyelectrolytes for sludge conditioning render filter pressing both feasible and more economically attractive. A great attraction of the freeze-thaw process is that the sludge remains transferable by pipeline through to the tip.8. working equally well on sludges whether or not they contain a polyelectrolyte. where the final dewatering takes place.1. If. Flotation The flotation process as applied in water treatment is normally the dissolved air flotation process of solid-liquid separation. whilst not necessarily reducing the quantity of sludge.Sludge treatment and disposal 157 very good quality. by whatever means. OPTIMISATION OF WATER AND SLUDGE TREATMENT PROCESSES The foregoing has been mainly concerned with the handling and treatment of sludge from existing or ‘conventional’ water treatment processes.

however. as a single-stage treatment for a particular water.3 At least one other treatment plant incorporating dissolved air flotation followed by filter pressing of the sludge is in the course of construction and details of its performance will no doubt be published in due time. dissolved air flotation is being used at at least one treatment plant in the UK for treating the backwash water arising from rapid gravity filters.8. Unfortunately the development of such cationic polyelectrolytes is still in its infancy and the types currently available are only applicable to certain types of raw waters. a dose of 40 mg/litre of block alum will result in 8 mg/litre of dry solids in the sludge. In addition to new processes which minimise sludge treatment there are two additional developments which minimise sludge production and hence minimise the problems of sludge treatment and disposal. The operational aspects of the dissolved air flotation process. In addition to this the cost of .e. Lamella Sedimentation The lamella sedimentation process is a continental development and has not been much utilised in the UK.2. the experiences of one operational plant incorporating dissolved air flotation as part of the water treatment and sludge treatment by centrifuging have been described.3. used without coagulation. An example of this is the use of aluminium sulphate in which approximately 20% of the dose level as ‘aluminoferric’ or block alum contributes to the sludge as aluminium hydroxide. This can often mean that 50% of the sludge produced in the treatment process arises from the chemicals introduced. i. They are coagulant replacement and coagulant recovery.8. The partial or total replacement of the hydrolysing coagulant by a suitable cationic polyelectrolyte is claimed to reduce sludge production considerably.Developments in water treatment—2 158 flotation unit contains considerable quantities of air does not appear to significantly affect its subsequent handling and dewatering characteristics. 6. both as a method for the clarification of raw water and its effect in subsequent sludge handling. At the present time there is little full-scale operational experience in this field. A similar process is being incorporated at two other water treatment plants of a similar type which are at present in the early stages of design and construction. 6. have been the subject of considerable investigation by the Water Research Centre. It is a high rate sedimentation process which takes place in tanks equipped with inclined plates which form in effect a series of very shallow sedimentation tanks. Coagulant Replacement The use of a traditional inorganic hydrolysing coagulant in a water treatment process in itself produces a considerable quantity of sludge in addition to the materials removed by such coagulant from the raw water. In addition to the above. This claim is undoubtedly true if such a polyelectrolyte can be found which will produce results as good as the traditional coagulants at a reasonably economic cost. It is claimed that sludge concentrations of the order of 4% can easily be obtained from such equipment. The clarified water rises between the plates whilst the sludge solids settle on the plates and run down the plate surface into the bottom of the tank which is equipped with what in effect is a totally submerged picket fence slow stirring sludge thickener.

with a view to formulating firm proposals for sludge treatment and disposal after initial operational experience of the water treatment plant has been obtained. The operation of such a process requires careful control of sulphuric acid dosage to avoid recovery of undesirable metals from the sludge along with the aluminium or iron salts.9. there has not been the opportunity to study in any great detail the handling and dewatering characteristics of the sludges produced.8. It is indeed a philosophical question as to whether it is correct to go to considerable expense to treat a water with a coagulant to remove undesirable materials and then extract the sludge with acid and return the acid-soluble fraction to the water undergoing treatment. The pilot plant work on which this plant design was based has been described in the literature. This is indeed a problem if data on the quality of the raw water to be treated are limited and is often the reason why temporary disposal methods by lagooning are adopted initially.Sludge treatment and disposal 159 such materials is such as to render their use uneconomical as compared with the use of a hydrolysing coagulant together with a polyelectrolyte as a coagulant aid.11 Coagulant recovery is an expensive process since it involves the use of acid resistant materials in many parts of the sludge handling equipment and its economic viability depends on the relative costs of fresh coagulant. 6. In addition to the economic aspects of the recovery process there is always the doubt about what other materials will be recovered inadvertently from the sludge by acid extraction. Since the full-scale use of cationic polyelectrolytes as a replacement for the more traditional materials has been very limited. This recovery normally consists of thickening the sludge as much as possible and then extracting the used coagulant with sulphuric acid.4. It is also claimed that the dewatering characteristics of the residual solids after acid extraction are modified in a beneficial manner. Coagulant Recovery When a hydrolysing coagulant such as a salt of aluminium or iron is used it is possible to minimise the quantity of sludge for ultimate disposal by recovering for re-use as much as possible of the coagulant from the sludge. SLUDGE QUANTITIES A dilemma facing the designers of new treatment plants in which it is desired to incorporate sludge treatment at the outset is the estimation of the quantity of sludge which is liable to arise from the water treatment. All that is required is a knowledge of the suspended solids and colour levels in the raw water and their variability with time along with estimates of the coagulant doses likely to be . 6. The lead-in time to the development of a new water supply scheme or new treatment plant is normally sufficiently long to enable adequate data on raw water quality to be obtained allowing the sludge treatment facilities to be incorporated at the outset. sulphuric acid and suitable dewatering equipment at the site in question. It is claimed that coagulant recovery levels as high as 70% can be obtained and the quantity of sludge for subsequent disposal is greatly reduced. A coagulant recovery process is at present used at one waterworks in the UK where the recovery is allied to a sludge freeze-thaw dewatering system.

10. care must be taken to ensure that the whole of the various processes involved do not become too interdependent. The provision of such a system of hoppers and conveyors can also make for savings in manpower costs since the presses can be emptied and put back into the filtration mode immediately and only after this has been done is there a need for the same personnel to concern themselves with the actual handling and disposal of sludge solids.11. Neither should the loading rate of road transport vehicles be dependent on the rate of emptying of the filter presses. In such cases it is better if the filter presses are provided with hoppers below them capable of holding one press load of dewatered sludge cake and a means of loading the sludge from the hoppers onto the road transport at a reasonable rate either by means of screw or belt conveyors or a combination of the two. the emptying of the filter presses should not be dependent on the availability of road transport at the appropriate time. Another example of the possible interaction of various processes is between the dewatering and ultimate disposal of the sludge.Developments in water treatment—2 160 required. It is important at the design stage. to take account not only of the technical aspects of the design and .12 Having ascertained the quantity of dry solids expected to arise from the process it is a relatively simple matter to convert this into the volumes of liquid sludge at various stages throughout the water treatment and sludge handling processes and to design the necessary tanks and dewatering equipment accordingly. Sufficient capacity must be built into the system to allow for breakdowns on the sludge treatment being rectified before their effect is transmitted back to the water treatment. If the sludge is dewatered by filter pressing and the ultimate disposal is by road transport. the latter being required anyway to enable the chemical storage and dosing requirements to be specified. An obvious example of this is a problem arising on the sludge thickening system which results in an inability to desludge the sedimentation tanks at the required intervals and this in turn results in a deterioration in settled water quality passing forward for filtration. whether the sludge treatment facility is to be part of a new or an existing water treatment plant. CONCLUSION From the foregoing it can be seen that several processes are available for the efficient and economical treatment and disposal of waterworks sludge. 6. 6. OPERATIONAL ASPECTS OF SLUDGE TREATMENT Whilst it is recommended that sludge treatment and disposal should be designed as an integral part of the whole water treatment system. Sludge treatment must always be subservient to the primary purpose of producing a treated water of the required quality. The amount of sludge produced in terms of dry solids can be calculated from the suspended solids and colour in the raw water together with the solids arising from the coagulant dose envisaged along with the residues from any other chemicals used in the water treatment process such as coagulant aids and activated carbon. Equations have been published for this quantification.

233.. SANKEY.B. R. 10. TR62. and BAYS. 7. Instn Water Engrs. R. 19. 1966. Instn Water Engrs & Scientists. 5. BASKERVILLE. J. M. with the permission of the successor to that Institution. and PACKHAM. J. 12. 399. 1978. 25. 1958.. 26.. 1973. Water Research Centre Tech. 2. DOE. 417. Water Pollution Control. DOE. 1971. P. J. GAUNTLETT.F. R. 1971. J. WEBSTER. 402.. 251. 20. 67..L. 11. 409.. 33.W. J. R. 167. 367. 1977. and GALE. L. 1979. published in the Journal of the Institution of Water Engineers. Instn Water Engrs..A. R. 6. Instn Water Engrs. Rep. REFERENCES 1. Instn Water Engrs. 21.A. D. 25. Proc. J. Instn Water Engrs. 4. ACKNOWLEDGEMENT Figures 1 and 2 in this chapter are drawn from a paper by the author. 25.S. J. Instn Water Engrs. D. 12. P. J. WRC Seminar of Alum Sludge Disposal. 1968. J. J. 1971. Instn Water Engrs. . 9. 1967.W. 402.C. and BRIDGES. 1965.. 3.Sludge treatment and disposal 161 selection of the various components but to subject the proposed process to a degree of operational and systems research in order to produce a workable system. BENN. HILSON. BENN.. the Institution of Water Engineers and Scientists. F. 27. 80. 8. 185. Instn Water Engrs. 1972.A.

methods were considerably simplified to provide results quickly and cheaply from non-chemical personnel. such as plant control. In certain areas. Those first determined were dissolved oxygen. C. Although this gave useful information. boreholes and springs. C.C. has produced equipment capable of measuring only a limited number of parameters.I.D. UK AND J. UK SUMMARY The firstpart of this chapter deals with the historical aspect of water quality monitoring and the need for increased vigilance in recent years.R.Chem. Ph. Scientific Officer. it led to many rough imprecise data being accumulated. M. The latter can provide reliability and a variety of analyses. Predictions of much higher water consumption created a need for information relating to the quality of our rivers. The development work so far. In the early 1960s there was an acceleration of interest in the environment and a growing awareness that raw water supplies were at risk from a variety of sources. 7.Chem. electrical .Chapter 7 WATER QUALITY MONITORING P. however. The analytical techniques involved frequently required considerable skill and time from their staff.COPE. This has taken two courses—the use of continuous monitors. Coventry. M.. INTRODUCTION Historically quality control of the water cycle was the responsibility of such agencies as the Public Analyst and the River Authority. canals..C. when used in context of how it was gained. The data available were in many areas unreliable and the acquisition of new records promised to be labour intensive and consequently very expensive. lakes. but needs a high capital outlay and suffers from doubtful reliability and a lack of versatility. The former offers rapid answers. The two approaches are discussed in detail together with their relative merits and future development. Severn-Trent Water Authority. Principal Scientist. The need for a cheap instrumental monitor to continuously gauge water quality at source unattended is obvious.. but has the disadvantages of errors caused by transport of samples and the time delay before results are available.J MORLEY. Birmingham.R. Avon Division. and modern automated laboratory analyses.1.I. The approach to the problem has taken two courses—the use of modern laboratory techniques and continuous monitoring on site. Severn-Trent Water Authority.

The approach to the handling of results has also been considerably revised with the help of advancements in the fields of data capture and computing. Samples are transferred into a reaction vessel together with. The samples are thus part of a continuously moving stream with reagents being added at controlled rates at specific points. additions of reagent. The later generations of monitors. that either will present itself as the complete answer. filtered. in the foreseeable future. although the cost of equipping and staffing such an establishment is high. heated. Their main advantage of instant response at the point of sampling has to be balanced against a number of other factors. 7. The main advantage of laboratory analysis is that the number of parameters analysed can be much greater. have also found considerable areas of application. The sample stream may be split for multiple analyses. This has taken the course of the use of equipment to automate manual techniques and the development of instrumentation capable of measuring trace quantities previously unattainable. is extremely versatile. which utilise such sensors as the ammonia and fluoride specific ion electrodes. The vessel can then be heated for a fixed period of time and a portion removed to the colorimeter or other detector. all of which are best measured on site and such instruments have found wide use. the last twenty years has produced an ideal climate for improvement in the laboratory. Both the use of a continuous monitor or a modern laboratory facility share the same serious problem. The batch analyser treats each sample as a discrete unit and therefore does not suffer the same degree of cross-contamination. The stream then flows to a measuring device which is commonly a colorimeter or specific ion electrode.Water quality monitoring 163 conductivity. above all others. They are expensive to install and service. The discrete analyser exhibits rates of analysis of up to 300 samples per hour compared with 40–60 per hour obtained from conventional air segmented continuous . still finds new areas of application. Currently the instruments manufactured and suggested for the analysis of large numbers of individual sample solutions can be classified into two areas—continuous flow analysers and batch analysers. The chief disadvantage is that each sample is liable to contamination from the preceding one and this limits the rate of throughput.2. At present these two methods of data collection complement one another and it is not likely. In continuous flow analysers the samples are pumped from their containers into a glass or plastic tube through which they move until the reaction is complete. This technique. at pre-determined intervals. dialysed. It is as difficult to present a representative flow to an in situ sensor as it is to obtain a bottle of sample which fairly reflects the state of a heterogeneous mass of water. extracted with organic solvent and distilled. pH and temperature. LABORATORY INSTRUMENTATION AND AUTOMATION As previously described. It is also very flexible and. after 15 years of intense development in the water industry. The recent trends are to utilise modern techniques and automation to minimise the cost and continuous monitors are constantly being improved and their range becoming more diverse. at trace levels they can lack sensitivity and much remains to be done to produce reliable sensors which maintain calibration between checks.

already well known in clinical biochemistry. 7.Developments in water treatment—2 164 flow analysis. considerably less versatile. however. 1. chromatography and mass spectrometry have brought about immense progress in these fields and will be discussed in more detail later in the chapter. These produce a FIG. It is. The analysis of ‘trace’ quantities is largely concentrated on toxic metal and organic contaminants. The production of large numbers of data from these analysers and other techniques introduces a high clerical involvement. This can be divided into two areas—data processing and laboratory organisation. The technique of air segmented continuous flow analysis1 is a simple way to automate any colorimetric or turbidimetric measurement and is now a common sight in water laboratories. Because of the rapidly changing nature of this field it should be read in conjunction with the more recent literature available. . A basic form of analyser is shown in Fig. CONTINUOUS FLOW ANALYSERS In the mid 1960s The Technicon Instruments Company Ltd introduced the Auto Analyser. has more moving parts to service and replace. A simple air segmented continuous flow analyser. The section dealing with laboratory data collection and processing will review the work already carried out in water laboratories and the possibilities offered by recent technological development. 1. Sample. and is much more expensive. into the field of water analysis. The developments in atomic absorption. reagents and air are pumped along fine-bore plastic tubing to glass mixing coils.3.

When two of these plates are screwed together. and a typical unit is shown in Fig. An important aspect of any colorimetric analysis is the separation of particulate matter even though this still leaves problems with natural colour and turbidity. separated by a polyethylene dialysis membrane. The required flow is pumped from the bottom of this separator into the flow cell and finally to waste. usually at the same speed. Early attempts at continuous filtration utilised a roll of filter paper fed between two spools in a manner similar to that of a tape recorder. of hemispherical cross-section. The sample stream is allowed to flow onto the paper and the filtrate collected underneath. A stream of water to be analysed is passed over the top of the polyethylene and a receiving stream flows. For example. oxidation or colour formation. The strip is driven continuously to provide a fresh surface. The plates are made of rigid plastic and have a flow FIG.Water quality monitoring 165 homogeneous mixture uniformly segmented between air bubbles which may be thermostatically controlled in oil or water baths to promote hydrolysis. machined on one surface. A far more effective means of removing particulate matter. was found by using the clinical technique of dialysis. This will remove turbidity and natural colour as well as filtrable solids. underneath. 2. Before the stream enters the flow-through colorimeter the air bubbles are removed in a glass T-piece. a solution of lower pH than the donor stream will be used to . channel. 2. Dialysis unit. The output from the colorimeter is generally fed to a flat-bed chart recorder. The nature of the receiving stream is chosen to encourage the transfer of the relevant constituent from the water sample. the unit is complete. reduction. however.

Replacement of the polyethylene with a thin sheet of silicone rubber gives a membrane surface that cannot be wetted by either of the streams. phosphate. nitrate. 3. The continuous distillation head has been introduced with particular success for these two parameters and is illustrated in Fig. This enables the transfer of gas and the determination of cyanide and sulphide has been carried out in this way. For example in the analysis of waters for free and simple complexed cyanide the air-segmented sample is mixed with acid and passed through a gas dialysis unit. The recipient stream is a solution of caustic soda and the cyanide is then determined by the standard pyrazolone or barbituric acid colorimetric techniques. The sample and a 10% v/v aqueous solution of phosphoric acid are mixed together and . It is thus possible to separate the ammonium ion. The use of continuous flow analysis together with dialysis enables a variety of determinations to be carried out at speeds up to 60 per hour (see Table 1). All molecular or ionic species other than the simple small variety will remain in the donor stream and flow to waste. nitrite and many others from colour and particulate matter in the main stream. chloride. TABLE 1 CONTINUOUS FLOW METHODS DEVELOPED FOR WATER ANALYSIS Alkalinity Aluminium Ammonia Anionic detergent Boron Calcium Chloride Cyanide Fluoride Hardness Iron Magnesium Nitrite Phenol Phosphate (total soluble) Silicate Sulphate Sulphide Sulphite Total oxidised nitrogen Manganese Organic nitrogen Organic phosphorus The manual determinations of phenol and total cyanide are good examples that can require a preliminary distillation stage.Developments in water treatment—2 166 effect the transfer of the ammonium ion.

The distillation head is connected to the flow at the exit from the heating bath and all the volatile constituents are collected FIG. The sample.Water quality monitoring 167 passed through a heated mixing coil at 165°C. Total nutrient concentrations. in the trap following the water condenser. tend to be very rigorous and limit the application. It should be noted here that COD is an arbitrary value derived from a set of empirical oxidation conditions. It is even possible to introduce an acid digestion into the continuous flow system by utilising a long glass helix. The phosphoric acid and nonvolatile portion flow to waste whilst the condensate is mixed with more air and the colour reagents. therefore. and digestion acid are mixed and dropped into the bottom of the helix. A continuous distillation head. The only disadvantage of this system is that a nonvolatile. The use of the heated helix gives a different value to the standard manual method but it can be effectively utilised to study trends in oxygen demand. thermally stable liquid such as phosphoric acid must be present to prevent the coil from becoming blocked and the conditions. temperature and speed of helix rotation the solution emerging from the other end of the tube will be completely digested. With optimum adjustment of acid conditions. The extraction of the methylene blue-detergent complex is . 3. such as nitrogen and phosphorus. A further illustration of the versatility of continuous flow analysis is its application to solvent extraction systems and the laborious manual method for estimating synthetic anionic detergent in waters was one of the first to be automated. can be monitored in this way and the equipment can also be used to automate the determination of chemical oxygen demand (COD). Rotation of the tube causes movement of the liquid from one end to the other across heater blocks. air.

5 The net effect is a reduction in carry-over but there are also a number of disadvantages. . via a syringe and septum. Early work with simple colorimetric reactions. has revealed that carryover between samples is caused by the extent of laminar flow prevailing.Developments in water treatment—2 168 carried out by introducing chloroform into the flow shortly before a mixing coil. The application to the water industry has so far been disappointingly small. into a turbulently flowing carrier stream of reagent. the necessity of removing bubbles before colour or turbidity is measured and the need to accurately control bubble patterns at fast sampling rates.6 suggests possible rates of 250–500 samples per hour. The presence of the air bubble in continuous flow systems is commonly believed to separate sample and alternated wash into well defined ‘slugs’. The two phases are sufficiently agitated to give an efficient extraction and the heavier solvent may be separated from the aqueous layer and air using a glass T-piece. which causes the stream to pulse rather than to flow regularly. The most promising advance of all has been the development of flow injection analysis. The chief ones are the compressibility of air. The chief disadvantage of the continuous flow analyser is cross-contamination of samples. The theory of flow within the tubes. such as the determination of chloride using iron (III) thiocyanate. 4. or expense and expertise involved. They range from the introduction of a calculated correction factor3 to computer regeneration4 of the recorded curve but have achieved limited application. Ruzicka and Hansen2 argued in 1975 that the theoretical maximum was approximately 40 samples per hour but recent suggestions. however. however. the air bubble no longer being necessary. Automation of sample presentation to an ion-selective electrode using flow injection. The presence of an air bubble causes friction at the tube walls and gives a turbulent flow even at very low pumping velocities. The technique suffers the disadvantage that it appears to be only suited to simple reagent addition and that long heating times for reaction development are difficult to accommodate. Ruzicka and Hansen2 exploited the fact that fast flows in sufficiently small diameter tubing are predominantly turbulent. mainly owing to the loss of precision and accuracy. It is. In flow injection analysis a small volume of sample (approximately 0·5 ml) is injected. are that this is 60 per hour. a very good system for presenting a buffered sample to ion-selective electrodes in that the response time of these sensors FIG. Rates higher than these lead to significant carry-over effects and a number of approaches have been used to circumvent the problem. mainly by manufacturers.

A diagram of the equipment required is shown in Fig. the depth of the cut normally increasing towards the centre. Susceptible to interruptions in sampling programme 5. BATCH OR DISCRETE ANALYSERS Discrete analysers have found wide application in the clinical field and have been available to the water industry for some years. Early experience with them. A preset volume of sample is automatically withdrawn by syringe from a tube and dispensed. until it reaches TABLE 2 A COMPARISON OF CONTINUOUS FLOW AND DISCRETE SYSTEMS Continuous flow 1.4. reagent addition. particularly in the area of pneumatic operation. Approx. have produced an extremely useful rapid laboratory analyser. Sample and reagents are placed individually into these arms and the whole disc is spun rapidly in a thermostatically controlled environment. which houses the reference electrode. The reaction mixtures are formed at the circumference and their optical densities can be measured as they pass through a light beam. £10000 for cheapest five-channel unit 3. One of the better instruments available at present is the Pye ACl system in which most moving parts are pneumatically driven. into a reaction vessel. mixing. 4. The manual simulation is considerably cheaper and at £12000–£15000 (October 1979) it is possible to buy a single channel unit which performs the functions of sample dilution. The other design uses a disc into which a number of radial troughs have been cut. together with the first reagent. Recent improvements in the mechanics of these systems. the temperature controlled by a variable water bath. 7.7 The flow injection stream of sample and buffer is allowed to impinge on the electrode surface and then falls in a continuous stream to a waste container. however. At present an instrument of this design is available but its cost will limit any application to the water industry. This then moves along a rack.Water quality monitoring 169 increases dramatically in fast moving streams. Susceptible to carry- Discrete 240–300 samples per hour £12000–£15000 for sequential analyser Low reagent consumption Not applicable (no ‘settling down’ period) Not applicable . There are at present approximately 10 discrete analysers available and they fall into two main groups. This stream maintains an electrical connection between the two electrodes and increases of response time up to a factor of four can be obtained. incubation and transfer at speeds of up to 240 samples per hour. High reagent consumption 4. showed poor reliability and few properly developed water chemistry methods. Maximum rate of 40– 60 samples per hour 2. The most common simulate manual addition and mixing and subsequently present the reacted solution to a spectrophotometer.

distillation and solvent extraction 9. costs the next reagent addition station which dispenses a fixed quantity of reagent and mechanically mixes the solution. yet not restrictive. Table 2 illustrates the main points of comparison of the two techniques. 7.g. This allowed rates of 120 metals per hour to be achieved.Developments in water treatment—2 170 over 6. As a general rule a discrete analyser should be used in a laboratory dealing with a large workload of ‘clean’ samples (e. The analytical speed. No limit to reagent Usually limited to additions four 8. With a possibility of three such stations four reagents can be added to the sample and. ion spectrophotometer specific electrodes) 11.g. Possible to automate Not possible filtration. The first step towards automation was a turntable feeding the samples to the instrument and a recorder or printout providing a continuous output of absorbance. Peaks must be Output available as a ‘picked’ from recorder digital display output before data can be processed 7. Can be used with Use usually restricted detectors other than to a colorimeters (e. Large number of water Limited number chemistry methods available developed 10. there is a total reaction time of 12 min.5. THE DETERMINATION OF METALS The technique of atomic absorption spectrophotometry is particularly useful for the monitoring of a variety of metallic contamination at trace levels. The final mixture is drawn into a spectrophotometer for measurement of absorbance. Low maintenance cost Higher. This speed can be reduced to increase the time. More recently improvements in nebuliser and atomiser design have made possible speeds in excess of . ease of operation and relative lack of interferences have made the method attractive for routine water quality analysis. potable and river waters) and where simple reagent addition alone is required. at a rate of 240 per hour. dialysis. The continuous flow systems find application where workloads have a high proportion of samples containing high suspended solids and organic matter and when the sample throughput is insufficient to support a discrete analyser. The manufacturer has with this instrument invested some time in providing simplicity of operation and rapid changeover for a number of water chemistry methods. It is interesting at this point to compare air-segmented continuous flow and discrete analysers and to specify their areas of application.

TABLE 3 COMPARATIVE DETECTION LIMITS (µg/litre) Element Inductively Flame Flameless coupled (electrothermal) plasma Al As B Cd Co Cr Cu Fe Mn Mo Ni P Pb Pt Se 10 15 2 1 2 2 2 1 0·5 5 5 30 15 20 15 20 100 1000 1 5 3 2 5 3 10 8 105 10 50 100 0·004 0·06 – 0·008 0·03 0·005 0·008 0·003 0·004 0·06 0·02 3·0 0·03 0·45 0·10 . Microprocessor units. An important advance with this technique has been the availability of a reliable automatic sampler. Further flameless methods which have achieved popularity are those of hydride generation and the cold vapour technique. into a flow cell with silica end windows. This removes many of the precision problems previously encountered with the method and enables simple application of the standard addition technique that is necessary for accuracy. A potential is applied across the tube in three stages. Alignment of the cell in the light beam allows mercury to be determined to 0·0001 mg/litre. One manufacturer has produced a microprocessor controlled sampler which has such facilities as multiple sampling from individual tubes and recalibration on request. The final step is a rapid increase to volatilise the metal in its ground state (temperatures up to 2600°C). Modern technological advancements have also made practicable the always promising technique of flameless atomic absorption.Water quality monitoring 171 600 per hour.9 and this is then allowed to pass into the flame. the first is a drying stage which involves a slow increase in temperature to approximately 100°C and this is followed by an ashing stage to 600°C to burn off organic matter. by the passage of air. In the cold vapour technique10 mercury ions in solution are reduced to the metal by the addition of stannous chloride and the element is then flushed out. There is a considerable increase in sensitivity over the standard method. Arsenic. In the most common design volumes of water of up to 30 µl are dispensed into a carbon tube through which a beam of monochromatic light shines. now integral in many instruments. The latter is essential because of the change in electrical characteristics of the tube with age. control automatic setting of machine conditions and process raw absorbance data to original concentrations. selenium and antimony can be estimated by generation of the respective hydride8.

The development of a stable plasma source has enabled fast multi-element analysis to be seriously contemplated and the high temperature of the plasma (10000°C) minimises the interference effects normally encountered. The quantity of this gas produced can then be measured either by infrared detector or titrimetrically.c. The multi-element analysis is carried out by using a number of pre-set photomultiplier tubes or by allowing the grating to scan. Measurement of the methane produced can be achieved with high sensitivity using a flame ionisation detector. Typically the TOC values for waters range from less than 1 mg/litre for some treated borehole supplies to greater than 5 mg/litre for certain surface waters. The sample is sprayed into the resultant plasma and the ‘tail’ of the flame is viewed through a monochromator. The combining of capillary column gas chromatography with mass spectrometry (GCMS) has produced an instrument with a very high performance in terms of resolving power and selectivity. either alone or combined.6. The tasks can be eased by the use of heated digester blocks. It has also been used for a wide variety of metals in qualitative and semiquantitative investigations using a medium quartz d. has led to the necessity to monitor the individual identity and quantities of the component compounds. A further sophistication is the instrument which will reduce the carbon dioxide by mixing with hydrogen and passing over heated Raney nickel. Approximately 20% of this organic fraction consists of man-made chemicals and these form the greatest cause for concern. spectrograph. capable of dealing with 15 samples per hour unattended. An alternative measurement of organic strength is to measure total organic carbon (TOC). Modern commercial . This work represents the most labour intensive effort remaining in the laboratory as the empirical nature of the tests resists full automation. The classical determinands of suspended solids—biochemical oxygen demand. Evidence of their impact on the environment. consists of an oxidation furnace in which all the carbonaceous compounds are converted to carbon dioxide.Developments in water treatment—2 172 Si Ti V Zn 10 1 75 1 60 50 7000 0·6 0·10 0·30 – 0·0007 Emission spectroscopy has always found use in the determination of the alkaline earth cations. Until recently effective separation and analysis at these trace levels would have been impossible. MONITORING OF ORGANIC CONTAMINANTS The organic fraction of raw water consists largely of naturally occurring compounds originating from land drainage or domestic sewage discharge. 7. permanganate value and chemical oxygen demand—are retained by most Water Authorities as measures of solid matter and organic strength. Table 3 shows the comparative detection limits obtained with a number of metals using the different techniques. dissolved oxygen electrodes and sophisticated electronic balances but they remain expensive. An RF with a power of the order of 5 kW is applied to an induction coil encircling an inert gas (usually argon). This instrumental technique.

Musty and Cope12 describe a system which uses a desk-top computer in combination with magnetic tape data recording.Water quality monitoring 173 instruments can produce GC peaks as narrow as two seconds and scan the eluant every second using the mass spectrometer. The sample can be booked in at the computer keyboard by typing sample location. benzaldehyde and benzyl cyanide. time. etc. Any manually produced data such as suspended solids. finished waters can contain haloforms. 7. The technique has been found particularly useful in identifying sources likely to cause taste and odour problems in areas of industrial pollution. A common criticism by the misinformed is that computer systems dehumanise the analyst and leave him without a ‘feel’ for the samples. The machine can be interfaced with a small desk-top computer and disc storage to enable fragmentation patterns produced to be compared against those associated with some thousands of known synthetic organic compounds. Leahy and Purvis11 describe a technique of extracting the organic fraction onto a macroreticular resin. transcription and arithmetic errors inherent in the manual equivalent. Similarly instruments capable of producing a digital output. LABORATORY DATA COLLECTION AND PROCESSING The automation of a laboratory to accommodate the analysis of a large number of samples produces a purely clerical problem. ‘draws’ calibration graphs. A simple program sorts through the computer disc store and brings together all data relating to an individual sample for report production. GCMS will only separate and quantify those compounds which are volatile or form volatile derivatives. Because of their high cost the number of these instruments available is small but their presence is essential unless the industry is to ignore the impact of this ever-increasing complex organic mixture on our population and environment. date. Commonly present in surface waters are phthalates. In addition to these. Although most of the synthetic chemicals fall into this category the remaining fraction could be identified with a high performance liquid chromatograph again linked to a mass spectrometer. Laboratory work sheets and an outstanding samples report can be produced at this point. This includes sample reception. They are merely a powerful aid and the system can be devised .7. The authors quote a number of compounds found in raw and finished waters including some which appear to have been introduced by the treatment process. corrects for base-line and sensitivity drift and computes final concentrations. e. Morley. may be keyed in by the analyst. By connecting the instrument recorders (fitted with re-transmitting slidewires) to a magnetic tape logger unit the continuous flow analyser output can be recorded and at the end of the analysis run the tape is replayed to the desk-top computer which picks peaks.g. progress chasing and report production. With some sacrifice of the most volatile compounds a further ten-fold increase can be achieved. chemical oxygen demand. sampler’s name and analyses required. There is an edit facility to allow dilution factors to be applied and for faulty data to be erased. can be monitored at a standard BCD (binary-coded-decimal) output and the data recorded and processed. processing of automatically produced and manually produced data. Atomic Absorption Spectrophotometers. After eluting with ether and further evaporating a 10000-fold concentration can be achieved before submission to the GCMS. organic phosphates and herbicides.. A worthwhile by-product of this system has been to largely eliminate clerical.

Developments in water treatment—2 174 which allows as much contact with the results as manual methods but eliminates the drudgery and error. not always very well programmed and it is advisable to find an answer to the question. In addition to performing this role the monitoring system could be used for routine historical water quality data gathering for use in water quality models and as future design data. as it is produced and when its priority rating in the system permits. Most commercial instruments which give a digital output are fitted with microprocessors to compute final sample concentration. In general its chief weakness is the delay in obtaining a result. The individual instrument can plug into a ‘ring main’ circuit and automatically convey data. ‘How are the results calculated?’ With a satisfactory instrument. They are. Much depends on how involved the analyst is with the design of the computer procedures. however. It is often possible in such environments to lose sight of the original objective and produce the analytical report for its own sake. . A number of instruments can be connected on-line to the computer in this way and the data collected and sorted in the background of normal keyboard activity.8. is extremely appealing. identify the pollutant and its concentration. then the system could interrupt the flow of water to prevent its passage into supply. The information can be combined with previous data and shown as a graphical trend or compared with historical limits permitting conclusions to be drawn relating to its significance. Because of the rapidly improving technology relating to this area the previously described approach is already becoming outmoded. however. 7. an accident or wilful intent. This concludes the part of the chapter dealing predominantly with laboratory based monitoring and the advantages and disadvantages of such systems have been highlighted. now allows the computer to act as a collator of information. to the disc store. Present-day monitoring systems are a long way from providing the user with information that he really requires and the reliability of many systems would require extreme care on behalf of the user before fully automatic control systems could operate on a foolproof basis. AUTOMATIC MONITORING OVERVIEW The concept of a monitor that will continually survey raw water. there is no need for the complex software to compute results. and water entering supply. With very little effort the analytical results can be combined with other data such as flow to produce useful operational information. whilst its main strength is the reliability and versatility of analysis. Should pollution occur by natural phenomena. The presence of a computer in the laboratory has another distinct benefit. The introduction of interface systems such as the Hewlett Packard Interface Bus. If the monitor was one of a chain of such devices then information as to the location of the pollution would also be available. Even the continuous flow analysers can be fitted with data processors to give an output of sample concentration. The next section deals with automatic stations and a combination of the two techniques should show a satisfactory approach to water quality monitoring.

ease of access and construction.9.Water quality monitoring 175 Broadly. The siting of the station for security. e. a further division can be made between those monitors offered as a multi-determinand package by a manufacturer and monitoring systems assembled by the user incorporating various discrete analytical systems and possibly simpler packaged monitors. Good laboratory analytical services are an essential part of the monitoring system and will remain so for a considerable time. BASIC TYPES OF MONITORS There are two basic methods of deployment of automatic water quality monitors. DESIGN CONSIDERATIONS When designing a monitoring system factors other than the determinands measured should also be given serious consideration. pH. Each type has advantages and drawbacks. that is. redox. Once a transducer signal has been obtained electronic treatment and data processing of this signal can now be carried out easily and with a reliability that will match and probably exceed that of all the other components in the water system.10.11. 7.g. SUBMERSIBLE MONITORS A submersible monitor is a monitoring system which can be wholly immersed in the water it is measuring. but even allowing for more specific sensors to be developed it seems that it would be virtually impossible to continuously monitor for all possible pollutants and be able to identify these. they may either be land-based on a fixed site or they may be submersible and totally immersed in the water they are measuring. In addition to the distinction between land-based and submersible types.. The design should be vandalproof but allow good access for users and allow maintenance and repair work to be carried out.g. The sampling system should be designed to take a representative sample in such a way that it does not degrade it for subsequent measurements (e. power supply and data recording system with the sensors exposed . lifting may affect dissolved oxygen). The data it measures can be recorded for subsequent treatment or relayed to another site via cable or radio. the problems arise from the lack of suitable sensors for many of the determinands that are required. the ease with which samples may be taken and the relevance of the readings obtained are very important. conductivity. together with sampling and fouling problems. etc. It will be seen that such a device consists of a waterproof housing containing the necessary electronics. The present range of sensors is limited and the determinands available to the user are often non-specific in identifying pollution. A burglar alarm system is recommended for unattended stations in remote sites. 7. or the device may act as a transponder. 7.

pier or jetty may also be considered. but this has the disadvantages that the monitor may strike the structure damaging itself. It can be easily transported and located at the point of interest. If the unit can receive no external power (i. lake or construction. a monitoring system may have indicated a pollution or suspect reading but it is highly unlikely that the precise cause of the pollution can be identified from the data given by the monitor.e. (The same is not of course true for oceanographic submersible monitors which are beyond the scope of this work. then the submersible monitor can only record historical data. In addition. It is also likely that changes in determinand levels were occurring before an alarm state was signalled. The sensors may be contained in an elaborate housing with a flow impeller to obtain optimum performance. The idea of a universal calibrant for all determinands of a submersible monitor is an appealing concept but in reality each determinand will probably require its own calibration solutions. The obvious requirements are for small amounts of calibration solutions to be required and for the calibration electronics to be readily accessible whilst calibration is being carried out. A radio beacon may help here. The anchoring of a submersible monitor also presents substantial problems.) Unless the unit is equipped with a means of data transmission to the outside world. 7. also such a unit could easily be replaced by terrorists by a similar looking explosive device.26. Data Logging). Calibration of submersible monitors may be a problem but designers should endeavour to simplify this. by the time qualified . as a leak would probably mean that the device would have to be written off. which is often impracticable or undesirable. Attachment to a bridge. This is satisfactory if the data are for modelling or archive work but of no use for pollution warning. Locating monitors at different sites enables profiles to be built up. it is not connected to a cable or acting as a transponder) then the design must optimise the power requirements of the unit to maximise power supply life. Care must also be taken with the seals and external connectors used on such a device. If no output to the external world is provided a recording real time clock on this type of device is essential (see Section 7.Developments in water treatment—2 176 to the surrounding water. A submersible monitor is by its nature a sophisticated and therefore expensive device and it is also vulnerable to vandalism. In an open lake or river there may be no convenient anchorage point and an anchor may have to be fixed to the river bed or lake bottom. The disadvantages seem to outweigh the advantages for most inland applications. If a buoy is fitted to identify the location then this invites vandalism and may hinder navigation. This may be extremely difficult and relocation of the monitor may be hampered if it has moved. and users of monitoring equipment must be prepared for some losses if using this type of monitor on open sites. The fixing may not be difficult if carried out within the confines of a works but a land-based monitor may be more convenient in this situation. SAMPLERS As has been discussed. The advantages of a submersible monitor are that it can theoretically be sited anywhere in a river.12. damage by boats or total loss during storms or flood.

13. . gas absorption and the effects of the measurement system may change the pH value significantly. Water for dissolved oxygen monitoring should be measured in situ or pumped using submersible pumps. The dissolved oxygen measurement should be taken before the sample is subjected to any chemical treatment. 7. The membranes may be cleaned by mechanical action although care must be taken not to scratch or puncture them. DISSOLVED OXYGEN Dissolved oxygen is most commonly monitored using either a sensor of the Mackereth type13 or a polarographic sensor of the Clark type. If no pollution occurs these may be discarded but when a pollution does occur the samples are retained together with samples at the time of the indicated pollution and subsequent samples. A very high input impedance measurement system is used and the measurement is amplified and scaled to give pH. Care should be exercised when measuring and interpreting pH data on low conductivity waters as electrode contamination. In these circumstances the value of measuring pH and its relevance should be borne in mind when interpreting these data. To help identify pollutants with present sensor technology a useful method is to automatically take samples of the water presented to the monitoring system and retain these for a set period after measurement. A more detailed explanation of the measurement system will be found in most physical chemistry text books. If fouling is a problem other sensors are available. These samples may then be submitted to a laboratory for further investigation by more sophisticated and specific techniques. the water may have returned to being unpolluted. When monitoring dissolved oxygen it is extremely important not to carry out any processes on the water which will affect the reading.14.Water quality monitoring 177 personnel arrive to investigate the pollution. a common one of which is the sacrificial thallium electrode. pH pH is a measure of the acidity or alkalinity of an aqueous liquid. An alternative electrode for the determination of pH. 7. This device often incorporates a mechanical scraper to expose fresh electrode material and is a useful system for automatic monitoring. The glass electrode is a delicate device and may encounter problems if used in a monitoring environment. Lift pumping will tend to lower the dissolved oxygen level whereas turbulence entraining air will increase the level.14 Both these sensors use gaspermeable membranes which may be subject to fouling. is the antimony-antimony oxide electrode. It is most commonly determined by measuring the potential between a reference electrode and a specially constructed glass electrode immersed in the water. where glass electrode failing is a problem. Present-day glass electrodes are relatively robust but exposure to abrasion or vibration may damage them irreparably.

17.15.g.17 The turbidity or lightscattering properties of the liquid may be determined using techniques based on classic optics and the result expressed in turbidimetric or nephelometric units.Developments in water treatment—2 178 7. The automation of this technique for monitoring poses many serious technical problems and is not practicable at present. the fluoride electrode and the chloride electrode. is consistent. Optical methods do not offer any method of establishing the weight per unit volume of solids. then weight per volume figures can be inferred from optical data. very few of these devices can be used without sample pre-treatment and complete specificity. It is probably one of the most difficult determinands to evaluate but indications as to changes in the system will often show a change in redox potential and it can help in verifying trends shown by other sensors. The laboratory test for suspended solids involves the filtering of a known volume of sample through a pre-weighed filter paper. SUSPENDED SOLIDS There are two ways of interpreting suspended solids and it is important to be aware of this when considering automatic methods for their determination. Optical suspended solids meters which are scaled in weight per volume units should not be believed blindly. drying the paper and re-weighing to est ablish the weight of solid the volume of sample contained. The opacity of liquids containing suspended matter is easily observed by eye and this property is frequently used to assess suspended solids levels. colour. 7. If the nature of the solids. OXIDATION-REDUCTION POTENTIAL (ORP) OR REDOX POTENTIAL This is sometimes measured in pollution monitoring systems often using a platinum and a calomel reference electrode. etc.16 Whilst manufacturers may list electrodes for a wide variety of determinands. 7. but in absolute terms there is no optical property which relates to the weight of the suspended matter. and that the system being measured will not present any interfering species to the electrode system. Unfortunately.16. The interpretation of these results requires care but does enable one set of results to be compared with another (as do those from gravimetric determinations). spatial scatter. ION SELECTIVE ELECTRODES Devices of this type have been available for many years. Before installing detectors of this type a user should ensure that provision is made for the correct sample pretreatment if required. users must ensure that they can be successfully applied to the media being measured. the most widely used example of which is the glass electrode used in pH measurement.. e. Electrodes which find common use are the ammonia gas permeation electrode. This yields a result in weight per unit volume which is the way solids levels are most commonly expressed. The concept of an electrode which may be immersed in water and give a readout of a specific determinand is very appealing. but the user should ensure that .

It is essential that when a pollution has been indicated by a biological sensor.15 Care must be taken when applying temperature corrections to conductivity measurements and it is preferable to record the absolute conductivity together with the temperature of the sample. A pollution will cause the metabolic rate to drop and this can be measured relatively simply and the metabolic rate displayed on a chart recorder.Water quality monitoring 179 he has a clear knowledge of the operating principles of the meters and the nature of the samples under investigation before placing reliance on indicated readings. electrical bridge system operating at either 1000 or 1592 Hz. Such systems may also give results which are at variance with reality if ‘artificial’ standards such as formazin or fullers’ earth are used as calibrants rather than the solids being measured.19. 7.c. D. Electrode designs vary but it is common to use ring-type electrodes for monitoring work. The pump rates and therefore reagent usage are lower than in conventional laboratory systems and the instrument receives sample from one source only. especially human life. If the pollution level in the water rises then the fish behaviour will become more agitated and this is monitored electronically and assessed by computer. CONDUCTIVITY Conductivity is a determinand that is easy to measure and is thought to give an indication of an ionic pollution. samples of the suspect water are taken for subsequent laboratory investigation. In an attempt to assess water conditions which may endanger living species. A pollution detected by biological sensors of these types still has to be identified. These electrodes are easily cleaned or kept free of fouling by high flow rates. BIOLOGICAL SENSORS As has been previously discussed. These are arranged as rings on the inside of a tube and guard electrodes are often incorporated in the design.c. It is postulated that the fish have an established behaviour pattern in unpolluted water.18 One such method is to record the behaviour of fish living in the water to be monitored. and this may prove a difficult task requiring substantial laboratory facilities and expertise.18. measurements should be avoided owing to electrolytic and polarisation phenomena. it is impossible to provide physical and chemical automatic sensors which would provide total coverage of pollutions hazardous to life.20. Biological sensors which monitor the metabolic rate of lower organisms are also used. sensor systems have been designed which monitor the changes in behaviour of life forms when exposed to the water under examination. CONTINUOUS FLOW ANALYSERS The air segmented continuous flow analyser has been adapted to perform a continuous monitor function. Conductivity is normally measured with an a. The advantages of this unit are that continuous flow methods used in the laboratory . 7. 7.

If an automatic temperature compensator is used it may be impossible to establish the absolute conductivity of a water as measured from data so treated. Remote measurement techniques from satellites and aircraft commonly use infrared thermography. The correction is difficult as the temperature coefficient for a water at a specific time is seldom known accurately and large adjustments are made to the reading which can commonly be of the order of 50%. after cleaning. Most standard laboratory methods require conductivities to be determined at the standard temperatures of either 20 or 25°C. had it been determined at the standard temperature. then a temperature compensation can be easily carried out if desired but the integrity of the measured data is not destroyed. When an automatic cleaning system is used care should be taken in its choice in that it should not damage the monitoring assembly or the sensors and that. pH and selective ion measurements and redox potential are all affected by temperature variation but not as dramatically as is electrical conductivity. chemical agents or air. If a record is made of absolute conductivity and temperature. 7. and that it enables tests to be performed in a monitoring station which are not possible by other methods. Dissolved oxygen. When monitoring raw or supply water it is impractical to adjust the temperature to that of standard laboratory conditions. CLEANING SYSTEMS Where fouling of a monitoring system presents a problem there are several methods available which offer the user a means of substantially extending the time between complete overhauls of the system. Some of the cleaning systems available for use on automatic monitoring systems are given below. e. It is also essential to the correct interpretation of data from other sensors being used for water quality monitoring. A common practice is to measure the conductivity at the ambient water temperature and then to use a device known as an automatic temperature compensator to ‘adjust’ the conductivity to the value that it supposedly would be. An example of the second role is in connection with measuring electrical conductivity which is temperature-dependent. Temperature measurement serves two functions. It is an important determinand in its own right and an indication of possible thermal pollution.21. thermistor or thermocouple. In all cases where temperature-dependent measurements are made then a simultaneous record of temperature enables correct interpretations to be made at a later date and helps establish absolute integrity of data.Developments in water treatment—2 180 can be adapted to be used in a monitoring situation. 7.22. TEMPERATURE MEASUREMENT Automatic temperature measurement is usually performed by a device such as a resistance thermometer. .g. any causes of misreading of the sensors are adequately removed.

Various methods are available for doing this and the chemical method has already been discussed. 7.1. This works quite well with biocides. Radiation sterilisation offers perhaps the best way of achieving sterilisation.3. some pH glass electrodes and certain dissolved oxygen electrodes may be damaged by this treatment). Ultrasonic Cleaning This is a form of mechanical cleaning using ultrasonic transducers to generate ultrasound in the liquid in the monitoring system to detach fouling. Chemical Agents Substances such as sodium hypochlorite solution or detergents can be used to clean a system but they will be much more efficient if used in conjunction with a mechanical cleaning method. If the chemical agent used will interfere with a sensor reading then it should be properly removed before the system is allowed to produce real measurements.22. The same is true of ozone together with potential damage to components and the invalidation of several sensors. In practice it is found that this will reduce fouling but.22. 7. It may be used with the water being measured by the system or used in conjunction with a chemical cleaning agent or detergent.g.22.22. If a chemical agent is known to have no effect on a test being performed then a continual dosing of the chemical into the water being measured is a very effective way of reducing fouling. . Mechanical Cleaning A mechanically actuated brush or wiper is used to clear fouling. Again care should be taken that the sensors used can take this treatment and that the air is fully removed from the sensors after cleaning.Water quality monitoring 181 7.−C radiation) is one method.5.2. damage to the system will result. Sterilisation Methods If the water entering the monitoring system has been sterilised then fouling will be substantially reduced unless the problem is one of silt.v. Treatment with ultraviolet light (u. dissolved oxygen. but it may be undesirable to use this at an unattended station. but by its nature may cause chemical changes in the sample.4. if sufficient sonic power is used to remove all fouling. Care must be taken if sensors are cleaned this way to ensure they are designed to undergo this treatment (e.g.22. The operation may be continuous or intermittent. e. It would be bad practice to take sensor readings whilst an ultrasonic transducer was switched on. 7. Air Cleaning If the routine measurement cycle is interrupted and a mixture of compressed air and water (possible with chemical cleaning agents) passed through the system the agitation produced will give an effective cleaning action. 7.

21 Such a time standard would probably be one of the radio transmissions carrying digital time code information. Many other countries throughout the world provide similar transmissions. Station Design A monitoring system can be designed in such a way as to reduce fouling. 7. 7. REAL TIME With any automatic data logging record there is a possibility that readings may have been missed. The design of the instrument would probably allow sophisticated control to be used.F. liquid velocities should in any case be greater than isokinetic to prevent suspended material being deposited in the system.S. Light will often encourage the growth of algae and where possible systems should be protected from it. An associated field is the determination of metals from their atomic emission lines when excited in a high temperature plasma generated by radio-frequency power or d.23. The recording of real time together with a day indication is essential for data being logged from a monitoring station. call sign M. The real time clock should be independent of the station power supplies with standby batteries or should have the facility of being linked to a digital time standard so that when power is resumed it can reestablish the correct time. arc. in the United Kingdom the National Physical Laboratory transmits coded time information on the Post Office transmitter at Rugby on 60 kHz. If liquid flow rates are kept high through the unit it will be difficult for fouling to occur. as is a design which enables easy manual cleaning. With increasingly low cost data processing and optical developments such as fast Fourier transform systems and electronic image dissectors the plasma spectrometer may offer a means of determining a large number of elements on a continuous automatic basis. for example. Attention to pipework to have all smooth surfaces with no inaccessible corners is essential. power or electronic failures occur and if the data have been accumulated over a period and the number of readings obtained is found to be incorrect then it may be impossible to correctly assign times to the data. Sample filtering may help to reduce fouling.22. ATOMIC ABSORPTION SPECTROSCOPY AND PLASMA EMISSION SPECTROSCOPY At present atomic absorption spectroscopy is widely used for the laboratory determination of metals in water. but total automatic solids removal in an unattended system is difficult to attain unless solids levels are comparatively low. which would mean that the whole of the data must be discarded. instruments are being announced which offer similar ease of operation to atomic absorption systems.19 With the development of flameless systems and instruments which can be fully computer-controlled it should be possible to incorporate an atomic absorption instrument into an automatic monitoring system. . The advantage of this instrument is that it would offer a means of monitoring specific metal levels in water.6.c.24.20 At the time of writing.Developments in water treatment—2 182 7.

DATA LOGGING* Monitoring may simply be used to detect a pollution and activate an alarm. Devices of this latter type may be of very low cost giving bleeps to indicate numerical values or incorporate a talk out device to tell the user the status.Water quality monitoring 183 7. but this would be an extravagant waste of resources. Warning of failure of communication lines could also be given. to effect changes or control plant. but conversely it is unlikely that a water system will undergo a dramatic change in condition. An extension of telemetry is to provide the receiver of data with a means of retransmitting to the station. 7. data need to be relayed to interested parties by a telemetric system. archiving and establishing average levels of determinands.26. . The telemetry can be continuously transmitted via dedicated lines (electrical or optical). tables. corrected figures and archive data as required. A continuous link may prove expensive if the user cannot provide his own and has to hire or rent such links and this cost may be difficult to justify. A lower cost alternative is to use a ‘dial-up’ or on demand system. Various data recording mediums are available for use with monitoring systems and the situation is one which may rapidly change in the light of modern electronic developments. TELEMETRY The data obtained from monitoring systems have maximum value if they can be relayed immediately to enable correct plant operation. detection of pollution and other immediate consequential actions. no further use being made of the data. The manual transcription of data from recorder charts or even tally roll printers can be extremely tedious and prone to error. this being known as telecontrol. The prime record in the monitoring station will probably be on one or several recorder charts and data in this form are not suited to further analysis other than by simple visual observation. Status reports could be given at regular intervals or the equipment interrogated at will. radio or microwave links. This may use the voice switched telephone network or a private communication system. Unless the monitor is actually on the works. Telemetric systems will form an important part in the development of intelligent monitoring systems. There are two methods of telemetry available and the user must establish which is most cost effective for a particular application. For increased sophistication digital devices giving full status reports and possibly relaying data to a central data store are available.25. Further use can always be made of water quality data for modelling. In addition. should alarm conditions occur an automatic call out would be initiated alerting the user to the alarm. This has the advantage that current information is always available. This system becomes more important if security of communication is a high priority which ‘dial-up’ systems could not give. If the monitor is equipped with an efficient means of data logging the analytical results can be recorded onto some storage medium and when convenient these data can be recovered and used with a data processing system to obtain graphs.

It seems unlikely that few users would have a need for true analogue records of their data and the cost of such a system may be high. The premium paid for this random access and relatively high speed is that the system is a sophisticated high tolerance mechanical unit not ideally suited to monitoring environments. They incorporate high precision mechanical devices and often require reasonable amounts of power.22 It is obvious that this situation will soon change dramatically and that solid state storage either onto bubble memory or random access memory (RAM) will be readily available with cost and reliability benefits. therefore. Magnetic media offer well established data recording systems and the two that could be considered for water quality data logging are magnetic disk and magnetic tape. 7. Magnetic disks are normally used as medium speed random access devices on data processing systems. It would be useful. Disk drives incorporate some housekeeping electronics (which may itself be a computer) to ensure correct recording. A common use of magnetic tape logged data is to turn this back into a chart with more reasonable co-ordinates than the original record. The random access nature of a disk is of little advantage when recording monitoring station data unless there * There is some confusion over the term data logging. but such items are available. Magnetic tape is available in many forms which can and have been used for monitoring stations. Magnetic tape is a well established medium for both analogue and digital recording. to record its determinands in a different file. but often are not suitable to give a summary of results over. but this sort of data manipulation is easily and more effectively achieved when recovering the logged data with a computer system. The term often refers to a device scanning various sensors and outputting the data to a printer—this is not what is referred to here. Another disadvantage is the high power requirement and bulk of this system. Digital tape systems probably offer the most effective way of logging data from monitoring stations at the time of writing. CHART RECORDERS Data as commonly presented on chart recorders are satisfactory for continual surveillance. The relatively high data error rate and the highly mechanical nature of a paper tape punch means that they are not ideal in this application. It offers probably the only means of recording true analogue data to enable this to be replayed to a data processing system. The environment in which the paper would be kept may not suit this type of data logging system. a week. The high writing (and reading) speed of a disk offers no advantage on a system which is generating data at an incredibly low relative data rate. was a pressing reason. say. if chart . say. Here it refers to the recording of data on some medium which can subsequently be utilised as a direct input to a data processing system.27.Developments in water treatment—2 184 Data logging on punched paper tape is now regarded as obsolescent. It is difficult to see why anyone would wish to use magnetic cards for this task. Even with new low cost small floppy disk drives which are beginning to be commonly available the disk has little to recommend it for this type of work.

29. it could cross-correlate data from different sensors and detect possible sensor malfunctions. Further. curve correction and data processing by itself. as do some flow and meteorological recorders. First. controllers and data handling systems. similar in concept to a domestic ring main.Water quality monitoring 185 recorder manufacturers could produce a recorder with charts of a convenient size (say A4) with a grid marked in real time (and days if required) so that each week an easily filable graphical output of results was obtained. It could query readings from sensors and perform cleaning. Such a recorder may remove some people’s requirement for data logging. there is a requirement for increasing ease of interchange of data between instruments. The concept of the data bus ideally suits itself to a monitoring station. 7. All instruments and data recording devices together with a station controller would ideally be plugged into identical sockets on a common bus cable. INTELLIGENT INSTRUMENTATION The well publicised current growth in electronic technology is both increasing instrument reliability and making available at low cost sophisticated data handling systems. this would be expected to be accompanied by a change in conductivity but if this was not the case the system could self test and if operating correctly alert the user to this observed state of affairs. An example might be a dramatic change in pH. The other impact of increasingly intelligent devices will be that each individual instrument or sensor system will contain a unit of this type. (This may also be a lower cost option than current non-intelligent analogue or discrete logic technology. The intelligence of the system would enable it to examine data from its sensor units and evaluate this. INSTRUMENTATION BUSES As instrumentation becomes increasingly intelligent and we move towards intelligently controlled monitoring stations. but there does not appear to be an electrical input version with a rectangular format.23 These developments will have significant effects on water quality monitoring instrumentation in two respects.28.) The instrument will be able to perform calibration. The system would control routine operation and maintenance and such functions as sampling. calibration. The controller . perhaps even producing hard copy summaries of measured data. it will be possible to have an intelligent device controlling and collating individual sensor units and in overall control of the analytical system functioning. It follows that as instruments are becoming increasingly able to provide data for collation by a central system a practical universal system of instrumentation interconnection is developed and implemented by manufacturers and users. 7. It will then present a processed result which may be printed out or passed to some central data system. Circular chart recorders approach this idea. A master controller of this type could also undertake data processing and reduction tasks. zeroing and re-calibration steps before accepting the sensor reading as valid and perhaps initiating an alarm or controlling the abstraction process. cleaning and data collection.

It should be able to sense devices which have been plugged in or removed from the bus and react accordingly. Data from other sites could also be called up to establish trends or help identify the site of a pollution. Detailed elemental and cation and anion determinations are rarely carried out if at all by automatic systems although instrumental developments will make monitoring of these more feasible.30. etc. Keying or dialling a sequence of numbers a user gains access to the desired information by a process of successive branching. .23. checking recalibration and cleaning and outputting the data to the recording devices. The task of interconnecting instrumentation for such purposes as monitoring stations will be greatly facilitated by international standards being set and followed for the direct plug to plug connection of instrumentation. VIEWDATA The current and future implementation of viewdata systems in many countries offers a novel means of utilising data from water quality monitoring systems. A user could interrogate data on the computer at will or if an alarm status was triggered an automatic verbal telephone message would be sent to the user.24 One such implementation of this concept is the IEEE 488 Interface bus (sometimes referred to as GPIB or HPIB after the Hewlett Packard company who were responsible for devising the system). Parts of the display can be made to flash and update to show trends or historical data. Data would be fed to the viewdata computer via telemetric input from automatic monitoring system and via keyboard or automatic data input for laboratory data. Future developments may allow the user telecontrol facilities in addition to simply abstracting data.31. Restriction of availability of data is made possible by designing the system to require pass codes before restricted data are made available. together with other relevant data including that obtained in the laboratory.Developments in water treatment—2 186 manages the bus instructing readings to be taken. Data can be recovered as alphameric characters or displayed graphically in monochrome or various colours. CONCLUSION Laboratory methods and automatic monitoring systems are both essential to water quality monitoring. They complement each other and it is not likely that developments in the immediate future will render the laboratory measurement side redundant. 7. collecting and examining the data. On receipt of an alarm message the user could investigate current data for the suspect site and call on previous information to evaluate trends. 7.25 The viewdata system enables a subscriber to access data stored on a computer facility via the voice switched telephone network and a suitably modified domestic television receiver.

A. 19. 78. New laboratory techniques such as plasma emission spectroscopy offer means of performing analyses for a wide variety of species quickly and at relatively low cost. 11. Ltd. 12.A. It is unfortunate that sensor development for automatic monitoring systems has not made much progress in recent years. P. 33. In both the laboratory and the field instruments will become more reliable and capable of giving final corrected results to analyses. J. E. 1956/7. 1979.). 8. may be made by a monitoring system but sophisticated laboratory techniques such as mass spectrometry and spectroscopy together with experienced interpretation offer the only way to obtain correct and reliable compound identification. and MAYDAK. 2. Methods for the Examination of Waters and Associated Materials. Zh. . GERKE.R. D. 1971. 1964. 387– 396. 1976. 41. F. P. 5..Newsletter. REFERENCES 1.H.. J. J. W. and FERRARI. Sydney.. Merrow Publishing Co. 1976.T.. J.W.B. 1970. and COPE. 305. J.S. Artificial Internal Organs. No. 1973 (July-Aug.J. 7.A. J. 14. BAILEY. E.A. 1971. Instrum. Anal. 1969. HANSEN.2. Sci.Water quality monitoring 187 The identification of pollutants. 4. R. 15.S.. Clin. A.. J. 4. Ion Selective Electrodes for the Analysis of Natural Waters.. Clin.. VITKUN. M. and ZAGATTO. 2...J. Analytica Chim. Trans. 1576. Analytica Chim. and HANSEN. NATIONAL RESEARCH DEVELOPMENT CORPORATION and MACKERETH. 9. 32. 88. 1977.H. E.. POLUEKTOV. Ion Selective Electrodes.H. Watford.H. Acta. Technicon Symp. WALKER. 1969. 3. CLARK. J. E. HOLAK. 41. 10. P. National Bureau of Standards.. British Patents 19294(1962) and 12882(1963). Instn Water Engrs & Scientists (in press). and developments in fields such as mass spectrometry enable speedy identifications of compounds to be carried out. 13. 311. Amer. H. J.J.. Anal Chem. Heyden & Son Ltd. J. MUSTY.. 81. Acta. Analytica Chim. Instn Water Engrs & Scientists. ZELYUKOVA. Analysis with Ion-Selective Electrodes. especially if these are complex organic molecules. F. R. FERNANDEZ. MOODY. Handbook No. 145–157. Acta.. 1971. J. 16.H... Washington. RUZICKA. 1–16. C. SKEGGS. London. 1975. ‘The Measurement of Electrical Conductivity and the Laboratory Determination of the pH Value of Natural. 873. 1967. LEAHY. Treated and Waste Waters’. 1. MORLEY. Chem. Anal Khim. 42.).C.. L. Selective Ion Sensitive Electrodes. Technological developments will mean that automatic systems will be less prone to failure and enable the integrity of the results to be higher...J. STEWART. 1957.. and developments in telemetry and viewdata systems will enable better use to be made of these data. This is an area in which worthwhile research could be made. E. DURST. MACKERETH. P. Soc.and PURVIS. Acta. STANCHAK. L.L. 41–47. (Ed. J. WHITFIELD. Perkin Elmer A.R.. 1712.. Chim. 1964. 12.. Amer. Developments in data processing and communication systems will enable easier collation and handling of data. 311. 531.C.J.. Australian Marine Sciences Association. RUZICKA. 6. J. Pathol.J. M. RUZICKA. Her Majesty’s Stationery Office. 38. STRICKLER. 1978.and THOMAS.D. 28. and ZAGATTO.

WINGFIELD. and RITTER. WITTEN. Fluorescence and Flame Emission Spectroscopy. 1979 (Feb. 19. In addition to these references the reader will find much valuable information in manufacturers’ data and handbooks. 21. 713. 20. 24. D. Water Pollut. Control Fed.). I..W. J. S. 1979 (Dec. McARTHUR.).M. Atomic Absorption. 22. I. Spectrochimica Acta. 1972. 48. 47–51 et seq. GREENFIELD.C..H. THOMPSON. and in current journals and periodicals which are essential in order to keep in touch with the very rapid technological advances currently being made. GREEN.L. Wireless World.Developments in water treatment—2 188 17. 39. 1021–1024. Instrum. and REYNOLDS. 1975. Analyst. Water Research Centre Seminar on Practical Aspects of Water Quality Monitoring Systems.F. S. Sci.. International and Maritime Telecommunications Region.G... CROSS.) . J. 6th International Broadcasting Convention. COTTIS. 23. 2–7.. . Institute of Electrical and Electronics Engineers... E.D. G.I. London.). 82. ‘Non-contact Sensing of the Electrical Field surrounding Trout’.C. K.. 1977.. 46–56. University of Wyoming. 25. Wyoming. W.N. A. Wireless World. ‘Standard Frequency and Time Broadcasts. A. FEDIDA. K. 24.. 1975.F... 18. HELSBY. 70–74. 1955. Chem. 1976 (Aug.C. New Electronics. 7. WALSH.. R. Rugby Radio Station. Laramie. European Computer Manufacturers Association. V. Stevenage. 89. JONES. Anal. 20–24 Sept.. 1962.J. 1978.. C.B. Standard IEEE 488–1975. 30–35 et seq. 85. STENSEL. 41. POELS.H. 1964.. 46– 51.. and FASSEL. American National Standards Institute (A. HOLLAND. I.J.A... Thesis. and JONES. DICKINSON.S. ‘The Development of the Water Research Centre Water Quality Monitor using Fish’. and WITTEN.T. 1976. BRIGGS. STROUD. Rugby Radio Station’. R. 12. Charles Griffin & Co.J. Australian Patent 23041/53. 1969. N..1. 24. MILLER.C. Post Office. 82.L. 2343–2350.. N. 1976. 1976 (Feb. Standard Nos. M. in many of the standard texts on physics and physical chemistry. H. and BERRY. MARSHALL.. W. A. 108.). Water Treatment & Exam. 34 and 46.).Sc.D. Ltd. Wireless World. G.S. 81–119. Water Treatment & Exam. ‘The Application of Atomic Absorption Spectra to Chemical Analysis’. 1979 (Dec. C. 32–35 et seq... C.. Standard MC 1. A. Wireless World..A. A. McDowELL. 85. R. ‘Viewdata—an Interactive Information Medium for the General Public using the Telephone Networks’. WALSH.

78 Activated carbon. 158 granular. 144 Ammonium hydroxide. 36–41 Aluminium sulphate. 62–3 . 36 regeneration system design and operation. 35 Biological activated carbon (BAC). 46–51 Adsorption. 191 Bactericidal residuals. 30–2 biological. 75–7. 180 BET method. 43–5 powdered. 158 adsorber installation. 139 Acrylic-amine resins. 30. 28. 33–4 point of addition. 154 Batch analysers. 29–46. 191. 35–46. 199. 81 Anion exchange resins. 63–6 ion exchange resins. 197–9 BCD (binary-coded-decimal) output. 184 Ammonia. 59–63 removal. 32–3 Adsorbents. 158 Biological denitrification. 39–41 adsorber system design. 203 Belgarde range of chemicals. 36–9 applications. 67–74 breakpoint chlorination. 30–2. 66–7 physico-chemical methods. 46 Anionic detergents. 32–5 applications and performance. 143. 214 Automation. 63–74 biological nitrification. 41 points of application. 32 regeneration. 81–6 Biological methods. 49 Atomic absorption spectrophotometry.INDEX Absorption refrigeration cycles. 35 dosing systems. 98 Belt pressing. 64 adsorption of solute molecules onto. 66–7 Ammonia-chlorine process. 46 performance.

143. 154–5 dose-residual curve. 143. 53. 154–6. 146. 121 Cellulosic ion exchange resins. 63–6. 126 Bromine. 196 Chemseps continuous loop. 63. 212–13 Clinoptilolite. 145. 141. 152 solutions. 66. 46. 145–7 history. 158 available. 160 chemical and bactericidal properties. 47 Carcinogens. 158 Clarification. 212–14 air. 154 Chloride determination. 141. 67–74 Biological sensors. 29. 213 mechanical. 181 Cellulose acetate membranes. 107–9. 155–6 generation. 181–2 Chart recorders. 184–5 Coagulation. 52. 152 chemistry of. 59. 146 residual. 28. 146–7 Boiler feedwater treatment. 158 Chlorine. 165–6 . 119–23 ‘Breakpoint’ chlorination. 8–9. 144 Brine concentrate disposal. 144. 142 Carbon activated. 158 Chloroform. 142. 147–52 dioxide. 197 Chlorination. 213 automatic. 143 production. 79 Chloramines. 61 Chemical oxygen demand (COD). 146 Chlorite. 65. 158. 142. 149 forms of. 185 replacement. 142 Cleaning. 146. 158 Carman-Kozeny equation. 210 Bleaching powder.Index 190 Biological nitrification. 63–6. 113. 66 Coagulant recovery. 217 Chemical methods. 212 ultrasonic. 212 chemical. 28. 145. 143–54. 152–4. 155 history. 175. 47 Centrifuging. See Activated carbon total organic. 201 Carbonaceous adsorbents.

65. 33 DPD test. 90–106 multiple effect. 134 systems available. 194 Dichloramine. 191–7. 138–9 multi-stage flash distillation. 197–9 Disinfection. 157–60 mixed treatments. 214. 141–62 agents used in. 211 Control of Pollution Act 1974. 132 size. 141–2 by-products. 74 Denitrification. 157 Distillation processes. 210 Continuous distillation head. 149. 132 Emission spectroscopy. See Multi-stage flash (MSF) distillation Dosing systems. 135 principle of. 131–8 capacity installed. 131–6 polarity reversal. 160 Discrete analysers. fouling by. 202–4 Demineralisation. 201 Energy . 26 Compressibility index. 196 Cyanide determination. 160 Drying beds. 53 D’Arcy equation. 47. 106–31 Dialysis unit. 178–9 ‘Ducol’ process. 89–140 miscellaneous processes. 168 Cross-contamination. 135 costs. 216–17 processing. 202–4 logging. 122 Colour removal. 81–6 Desalination. 175 Data collection. 26 Colloids. 154 2. 158 relative costs. 90–106 reverse osmosis. 195 Cysticidal residuals. 176 Conductivity. 193. 33 Electrodialysis. 75–7. 92. 78 Dust control.4-D. 100 multi-stage flash. 64. 195 Continuous flow analysers. 136–8 description of process.Index 191 Colloidal material.



consumption, 94 recovery, 124 Enzyme mechanisms, 74 Ethyl cellulose membranes, 52 Evaporation, 179 Evaporator costs, 102–6 materials, 100–2 Faraday’s Law, 132 Feed pumps, 124 Ferrous hydroxide, 74 Filterability index, 23 Filter (s), 158, 165 backwashing, 20–1, 169 cleaning, 11 continuous screen, 123 control, 19 conventional, 4 ‘dry’ sand, 72–3 hydraulic control, 20 Immedium, 15–16 L’Eau Claire, 16–17 micron, 123 pilot-scale, 22 pressing, 180–1 radial flow, 17–18 rapid, 5–6 rotary vacuum, 179–80 slow, 3–5, 19 slow sand, 26, 28, 165 Tenten, 18 types of media, 13 upflow, 15–17 Filtration, 1–24, 142, 169–71, 176 applications, 2–3 attachment mechanisms, 8 conventional, 3 design methods, 21–3 dual and multi media beds, 13 effective use of bed capacity, 12–18 head loss during, 9 relationships, 14 hydraulics, 8–10 Filtr ation—con td. mathematical modelling, 10, 22 nature of suspension to be treated, 23 process details, 6–12 modifications, 18–19



solids removal, 10 transport mechanisms, 7 trends and developments, 12–23 Fish behaviour, 210 Fishmoor plant, 171 Flameless atomic absorption, 199 Flash chambers, 101–2 Flotation, 183–4 Fluidised bed MSF, 98–100 system, 71 Fluidised sand units, 81–6 Fouling colloids, by, 122 index test, 121 Freeze-thaw process, 182 Freezing processes, 91, 138–9, 182 Freundlich isotherm, 30 Gas chromatography with mass spectrometry (GCMS), 202 Granular carbon. See Activated carbon Groundwaters, 122 Heat-pumping, 138 Hewlett Packard Interface Bus, 203 High Test Hypochlorite, 146 Humic acids, 49 Hydrochloric acid, 145, 147 Hypochlorites, 146, 147 Hypochlorous acid, 145, 147 Immedium filters, 15–16 Immobilised enzymes, 74 Instrumentation, 191, 218 buses, 218–19 Iodine, 142 Ion exchange resins applications, 49 desalination, 91 evaluation methods, 48–9 nitrate removal, 75–81 nitrogen compounds, 61, 66–7 organics removal, 46–51 test results, 49 theory, 48 Ion selective electrodes, 208–9 Iron (III) thiocyanate, 197 Kozeny equation, 8



Lamella sedimentation, 184 LaMotte test kit, 161 Langelier Index, 120 L’Eau Claire filter, 16–17 Lindane, 53 Membrane(s) composite, 109 configuration, 54, 109 hollow fibre, 112 materials, 52–3 performance characteristics, 111 processes, 106, 131 product flux, 112 types, 107, 109–15 Metal analysis, 199–201 detection limits, 201 Methaemoglobinaemia, 59 Methanol, 83, 84, 86 Microstrainers, 165 Monitoring, 189–222 automatic, 204–5 real time, 214–15 station design, 213 Monitors basic types, 205 design considerations, 205 submersible, 205–7 Monochloramine, 145, 146, 160 Monochromator, 201 Multiple effect distillation, 92, 100 Multi-stage flash (MSF) distillation, 90–106 evaporator costs, 102–6 fluidised bed, 98–100 Nitrate, 59–61 removal, 74–86 biological denitrification, 75–7, 81–6 ion exchange, resins, 75–81 possible methods, 74–7 Nitrification, 67–74 Nitrogen, 65 compounds, 59–88 trichloride, 64, 65, 149, 160 Nitrosamines, 59 Odorous substances, 30 Ohm’s Law, 132 Organic compounds, 25–7 health effects, 26



objectives or removal, 26 oxidative processes, 29 removal by conventional processes, 26 water, in, 25–6 Organic contaminant monitoring, 201–2 Oxidation-reduction potential (ORP), 209 Oxidative processes, 29 Oxidising agents, 29 Oxygen, dissolved, 207–8 Ozone, 29, 142, 156–8 application, 156–7 applied doses, 157 generation, 156–7 history, 156 Permanganate Value (PV), 28 Permasep polyamide, 118 Pesticides, 28, 53 pH effects chlorination, 148, 153 chlorine dioxide disinfection, 156 desalination, 123 monitoring, 208 phenol uptake, 49 residual chlorine, 152 reverse osmosis, 52 Phenol determination, 195 uptake, 49 Phosphoric acid, 195 Physico-chemical methods, 61, 66–7 Plasma emission spectroscopy, 214 Pollution, 207, 211 Polyamide, 107, 114, 118 Polyelectrolytes, 170, 172, 173, 181, 182, 185 Polymeric resins, 47 Polynuclear aromatic hydrocarbons (PAH), 28, 52 Polysulphone (TFC), 107, 111, 113, 115 Potassium iodide, 145 permanganate, 29 Precipitation, 28 softening, 166 Rate constant, 70 Real time, 214–15 Redox potential, 209 Reference electrodes, 209 Reverse osmosis, 51–4 basic principles, 107 costs, 131

186–7 optimisation process. 78 sulphite. 165–6 iron and manganese removal plants. 164 waterworks. 186 lime addition. 91 Solar energy. 121 Sirotherm ion exchange process. 126 systems design. 163–88 coagulant-based. 90. 183–6 types of. 166 produced from chemical treatment process. 168–70 Sodium bisulphite. 28. 175–8 estimation of. 207 Sand-washing plants. 184 Sensors. 210 Silting Density Index (SDI). 213 Stocks plant. 170–5 treatment operational aspects. 165 Scale control. 106–31 disposal of brine concentrate. 168–70 capital costs. 126 nitrogen compounds. 204. 51–4 plant developments and installations. 165 thickening. 210 Samplers. 96–8. 138 Specific resistance. 127–31 post-treatment of product water. 176 Sterilisation. 153 thiosulphate. 138 Sludge. 173 . 164–5 use of term. 124 instrumentation. 166 precipitation softening. 61 organic compounds. 153 Solar distillation.Index 196 desalination. 119 Sedimentation. 181 conditioning. 165–6 produced without chemical treatment. 168 further methods. 178 dewatering. 126 feed pumps. 178–82 theory. 123–7 Ring-type electrodes. 165 produced by coagulation. 153 chloride. 142. 181 primary sedimentation. 171.

142 Vapour compression (VC) processes. 160 Trace analysis. 7 Trihalomethanes (THM). 54 Ultraviolet radiation. 178 Zeta potential. 78 Sulphur dioxide. 209–10 Telemetry. 101 Water Research Centre.Index 197 Styrene-divinylbenzene resins. 18 Tintometer Lovibond test kit. 175 ‘Wedge-wire’. 92 Viewdata. 211–12 Tenten filter. 122 . 219–20 Wastewater recycling. 153 Suspended solids. 65–6 Ultrafiltration. 191 Transport mechanisms. 164 Water-boxes. 215 Temperature measurement.

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