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    Methods for thw determination of SO2 in the atmosphere

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    Methods for thw determination of SO2 in the atmosphere

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    © All Rights Reserved
    Download as PDF or read online from Scribd
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    13 views49 pages

    RPT 73 06

    Uploaded by

    CHRISTOS KALOUDIS
    Methods for thw determination of SO2 in the atmosphere

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    © All Rights Reserved
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    of 49
    Report Nr. 6/73 METHODS FOR THE DETERMINATION OF 80, IN THE ATMOSPHERE prepared by present and former members of CONCAWE's Special Task Force on the Study of Air Pollution, Sampling and Survey Techniques. The copyright of this document is vested in Stichting CONCAWE, The Hague. Recipients mst obtein the written authority of Stichting CONCAWE before reproducing the whole or any part of the contents. All rights reserved. Stichting CONCAWE The Hague September 1973 PRESENT AND FORMER MEMBERS OF CONCAWE'S SPECIAL TASK FORCE ON THE STUDY OF AIR POLLUTION, SAMPLING AND SURVEY TECHNIQUES J.H. Boddy (present Chairman) - MT. Westaway (former Chairman)- W. Bongers - A.J. Davies - H.Ch. Frohne - F. Gianni - J. Goldbach - J.R. Gordon 5 8.1. Hobkinson 5 F.H. Meppelder 5 R. Sarteur 5 P, Vercier - P.C. Blokker = Mobil O11 Co. BP Research Centre Shell Nederland Raffinaderij B.V. Ltd. Esso Research Centre VEBA-CHEMIE A.G. S.N.A.M. Progetti S.p.A. Esso A.G. Phillips-Imperial Petroleum Ltd. BP Research Centre Gulf Research Laboratoria B.V. Elf Union Compagnie Francaise de Raffinage Stichting CONCAWE 1.1.2 113 1.2 1.261 13 13.4 14 164e4 165 1.6 a 24 2.404 2162 2.2 CONTENTS STARY RECOMMENDATION INTRODUCTION QUANTITATIVE DISCONTINUOUS METHODS OF ANALYSIS DETERMINATION AFTER OXIDATION 10 SULPHATE ION BY HYDROGEN PEROXIDE Titration with Alkali ‘Titration with Barium Chloride Colorimetric with Methyl Thymol Blue (M.T.B.) DETERMINATION APIER REDUCTION TO HS Stratmann's Silica Process DIRECT COLORIMETRY West and Gaeke Procedure DEVERMINATION BASED ON PHYSICAL QUALITIES OR CHANGE Gas Chromatography and Flame Photometry ADDITIONAL METHODS ASSESSMENT OF DISCONTINUOUS METHODS QUANTITATIVE AUTOMATIC FIELD METHODS CONDUCTIMETRIC ANALYSIS Ultrages-3 (Messrs. Wosthoff) Picoflux (Messrs. Hartmann & Braun) pH SENSING Page 10 10 " ” 15 16 16 16 7 2.261 2.3 2.361 2.3.2 2.4 2401 2.4.2 24.3 2.4.4 2.5 2.541 2.5.2 2.5.3 2.564 2.6 2.7 2.7.1. 2.8 2.8.1 2.9 2.9.1. 2.9.2 2.9.3 2.9.4 ii S.F. (Soufre-Fumées = sulphur smoke) continuous recorder COULOMBTRIC ANALYSIS First type Second type COLORIMETRIC ANALYSTS Technicon Air Monitor IV Imcometer (Messrs. Bran & Lifbbe) ENRAF Nonius Atlas Colorimetric $0, or aldehyde analyzer FLAME PHOTOMETRY Bendix Tracor Meloy Total Sulphur monitor Bendix Total Sulphur Monitor Series 8300 ELECTROCHEMICAL METHODS USING A MEMBRANE SECOND DERIVATIVE U.V. SPECTROMETRY Spectrometrics of Florida Inc. CORRELATION SPECTROMETRY Cospect II (Barringer Research) ADDITIONAL INSTRUMENTS Conductimetric Method pH Recording Coulonetric Method Photometric Method Page 7 7 q7 18 19 19 20 20 20 20 at at 21 at 24 22 22 22 23 23 23 24 24 24 2.10 3.44 3.1.2 3.163 iid ASSESSMENT OF AUTOMATIC FIELD METHODS CALIBRATION, PREPARATION OF REFERENCE SAMPLES FOR THE STANDARD- TSATION OF SO, MEASURING APPARATUS IN AMBIENT ATR STATIC SYSTEMS Non-rigid receptacle Gravimetric Method Micro volumetric method DYNAMIC SYSTEMS Mixing of Gases by Double Dilution Impulse Injection Method Method by Permeation ASSESSMENT OF CALIBRATION MeTHODS FILTERS FOR IMPROVING SPECIFICITY REFERENCES ‘APPENDIX NOTE ‘The disconinuity of the page numbering is due to some blank pages that had been normally numbered in the original hard copy but left out of the scanned file in order to reduce the digital file size Page 25 eT eT 28 28 28 28 29 29 30 35 37 4% SUMMARY A description is given of the many methods which are used for the de- termination of S02 in the atmosphere. The report has the overall pur- pose of providing guidance for selecting the most appropriate analytical method for the work in hand. In order to facilitate this, methods are classified as discontinuous analysis methods or quantitative automatic field methods and descriptions of methods under these two classifications are grouped in two separate sectionmsof the report. Calibration is recog- nized as a vital part of any instrumentation and techniques for cali- brating the various instruments are described. Since many of the methods are non specific, a short review is given of selective filters. Methods are assessed mainly on the principles involved since it would be impracticable to give up-to-date objective assessments of all the in- struments in current use. Whilst recognizing the cost as an important part of the assessment of an instrument, cost data are given in French currency only and is intended as an approximate guide to relative prices. New methods are in the process of development and old ones are becoming obsolete or obsolescent. Minimal description is given to those methods which are obsolescent, though in many instances they are being usefully applied. In the case of new methods, the experience is very small and manufacturers! data often very limited. It may, therefore, be necessary ‘to add suppleaents to this report as new methods become better known. RECOMMENDATION The CONCAWE report 14/72 surveying air pollution arownd oil refineries listed six alternative objectives in studies of S02 in the environment. ‘The first three of these were: a) To check adherence to air quality standards. b) To observe pollution trends. c) To develop and evaluate abatement strategies. For many purposes associated with these objectives 24 hour averages will be adequate. In some countries legislative requirements are for 30 minute averages and must conform to air quality standards. For 24 hour averages ‘the West and Gaeke discontinuous procedure is recommended. To reduce man- power expenditure sequential sampling devices may be added and are commercially available at prices approximating to $1500. Where 30 minute averages are required manpower costs for the manual application of the West and Gacke method would be prohibitive if the study was to be extended beyond a few days. A normal recommendation for such requirements would be a well proven fully automatic instrument. A comprehensive selection of such instruments is given in section 2 of the report under the title "Quantitative Automatic Pield Methods". A further economy of manpower can be achieved by using an integrator to obtain the 4 hour averages from the automatic continuous recording inetruments. ‘The other three objectives listed in the report 14/72 include:~ 4) Assessment of health effect or plant damage. e) The development of a warning system. £) The development and test of diffusion models. These objectives are usually associated with determining peak levels and duration of levels so that continuous automatic methods are most appro- priate. 30 minute average may in some instances be adequate, but again would normally involve instrument methods. Such work programmes are usually of short duration in which accuracy, response time and portability are more important than reliability and low maintenance cost. Flame photo- metry methods may be considered for this work, however, individual cir- cumstances will best determine the specific instrument most suited to the ‘task. Where the development applies to warning systems it will be appre- ciated that robust limit sensing devices will ultimately be required and be quite different from the research type instruments used in develop- ment studies. INTRODUCTION Sulphur dioxide is a much measured pollutant and different methods have been used for its determination. The selection and evaluation of which analytical methods to use, depends to a great extent on the objectives envisaged which must include consideration of the concentration levels and range of levels to be measured. These objectives will determine the demands to be made on accuracy and specificity, the period of time during which measurement can be made, the overall time and facilities to be nade available for the analysis, and the desirability to automate the method. Quite often these factors are interdependent - for example, the need for greater specificity must involve a method of high complexity, and consequently be a determining factor in the facilities necessary. At times the orly interest is to observe changes in air concentration levels when @ simple method is quite adequate for this purpose. Further factors that should be considered are sampling techniques, lapse time between sampling and analysis, and materials of construction of the equipment. Sulphur dioxide can be absorbed, catalytically transformed or undergo chemical reactions quite readily. On this basis it is con- sidered advisable that materials such as borosilicate glass and teflon should be used as much as possible, particularly with discontinuous procedures. ‘The report is divided into four chapters which review discontinuous methods of analysis, quantitative automatic field methods, techniques for calibration and, finally, give a short review of selective filters. In the first three chapters some assessment of the relative values of the procedures and techniques is made. The calibrating techniques require careful consideration as well as the chosen method, since accuracy in these will be a determining factor in the accuracy of test results. It is important to note that the assessment of the automatic field methods is, in fact, an assessment of the principles involved. Bven with the wide range of experience available within CONCAWE menber companies it would be impractical to give an up-to-date, complete assessment of all the instruments in current use. Instruments which may be subject to difficulties due to minor manufacturing faults could become outstanding in performance when such faults are corrected. Therefore, it could be misleading ta comment on individual instruments and the report becomes quickly outdated. One further point is that the capital cost of some of the instruments is extremely high and still higher costs may be involved if the instrument requires an integrator to give easily available 15 or 30 minute average readings. (Some instruments do not need integrators - the integration can be made conveniently by sampling for the required period, prior to analysis). Instrument cost will necessarily be a factor influencing the assessment of a company or individual to use the in- strunent and must be teken into account. Only limited cost data is for the reason that this will vary with time and location of purchase. The instrument selection given in the report is not based on an exhaustive comparison of all available equipment but on data or experience available within the CONCAWE member companies. Other commercial units may well match the performance of those listed. 144 QUANTITATIVE DISCONTINUOUS METHODS OF ANALYSIS The reactive nature of sulphur dioxide lends itself to analytical in- vestigation. For example it can: a. be oxidized to the sulphate ion b. be reduced to HS c. bring about colour changes in certain reagents a. undergo physical reactions or changes. These characteristics form the basis of the following subdivision of methods. Summaries of the methods are given in Table 1. BR OXIDATION 10 SULPHATE ION BY HYDROGEN PEROXIDE This family of methods depends on the absorption of S0, into dilute aqueous hydrogen peroxide via some sort of bubbler (ustially Drechsel dottle). About 1,5 litres of air per minute are passed through the solution. A filter paper (usually Whatman No. 1) is connected upstream to collect aerosols (1). The sampling period should preferably be several hours but is quite often 24 hours. Shorter sampling periods are possible by using an impinger instead of a wash bottle, enabling the air to be passed through 100 ml of absorption fluid at a rate of 35 litres/min. (2). The amount of sulphate ion produced can be determined ty various methods. Titration with Alkali (1,3) ‘This method assumes the sulphate ion to be present as sulphuric acid. Consequently, this method is not specific ~ any basic or acidic compounds will interfere strongly. A correction can be made for any interference from ammonia by a separate determination using Nessler's reagent. The lower detection limit is about 60yg of SO, in 100 ml of peroxide solution. An accuracy of approximately 10% for‘ the complete procedure is given for concentrations above 100 yg/m. The British Standards Institute assess the reproducibility as follow: 16102 to103 ~3- ue/n? of 80, Maximum deviation of replicate analyses up to 500 toug over 500 tap (3) Titration with Barium Chloride (4) There are many ways to determine trace amounts of sulphate in solution involving titrations with the barium ion. However, in the interests of standardisation the following technique recommended by the Comité Buropéen de Nomalisation for the determination of trace amounts of sulphate in hydrogen peroxide solution, should be used. The sulphate solution is titrated automatically with N/1600 barium chloride. The end-point is detected by the change in conductivity when all the sulphate ion has precipitated. The lower limit of detection is 20 ug SO, in 50 ml of peroxide solution (i.e. 1 ml of titrant). Heavy metals afid phosphates interfere. Colorimetric with Methyl Thymol Blue (M.T.B.) (5) Manual sampling is not practical with this method, thus it is necessary to use equipment such as the Technicon Auto-Analyzer. The sample is mixed with a reagent containing equi-molar amounts of BaCl, and MIB in an acid solution. Barium sulphate precipitates. The sclution“is adjusted to pH 12, allowing the Ba-MIB complex to be formed. The excess MTB is equivalent to the amount of sulphate present in the original sample. The concentration of excess MIB is measured at 420 nm. Any interfering cations are removed by pumping the sample through 2 small cation exchange resin prior to mixing with the reagent. Anions such as phosphate would interfere, but are unlikely to be present. The repro- ducibility is within 0.1 ppm at the 5 ppm sulphate level. The range of the method is 0.5-5 ppm sulphate (this analysis is usually undertaken on a 2 ml aliquot from the total sample of 100 ml of peroxide solution), Thus the lower limit of detection is 0.3/ug S0, per ml of peroxide solution, 1.2 46261 163 UBTERMINATION AFTER REDUCTION TO HS Stratmann's Silica Process (1, 6, 7) The atmosphere is sampled by bubbling through phosphoric acid to remove Gust and most sulphuric acid and then through a small silica tube packed with specially prepared silica gel. The 80) is adsorbed on the silica gel. The tube is then sealed and removed to the laboratory. The samples can be stored for up to three days at this stage. The adsorbed 802 is desorbed by heating at 500°C. It is then reduced to HpS by passing it’with hydrogen over a platinum wire catalyst at 600°C. The HoS is ab- sorbed in 5 ml ammonium molybdate to form molybdenum blue. The intensity of the resulting colour is measured at 570 nm. Sampling time required is 5 to 50 minutes. Sample volume is 10-30 litres. The upper limit must not be exceeded or too much moisture is adsorbed and S02 is displaced or not adsorbed. Some interference by sulphates can occur. HS and mercaptans interfere positively but can be removed by the use of a filter. It is claimed also that difficulties can arise in the desorption of S02 when other pollutants are present. It is extremely important that the silica gel be prepared correctly (1, 8) and that regular checks of adsorption/desorption efficiencies are made. (The gel is available from Macherey, Nagel and Co., 516 Diiren, Germany, P.0.B. 307, under the trade name Kieselgel fiir $0j-Bestimmng Nach VDI 2451). ‘The lower limit of detection of this procedure is 0.5 ye S02 per 5 ml of ammonium molybdate solution. At about 500 ug S02 per m) the standard deviation is + 30 ug S02 per m3, DIRECT COLORIMETRY West and Gaeke Procedure (1, 9, 10, 11, 63) ‘The S02 is absorbed in 0.1 M sodium tetrachloromercurate (TOM) forming non-volatile dichlorosulphitomercurate. This complex is not oxidized by air. In an acidic medium the complex reacts with formaldehyde and p- rosaniline to form red-violet methylsulphonic acid. The intensity of the colour formed is measured between 540 nm and 575 nm depending on the variation of technique used (1, 9, 10, 11, 12, 63). The method is extremely sensitive and selective. Only NOp, heavy metals and ogone interfere. The interference of ozone is of little consequence however. The effect of NOp can be avoided by the addition of sulphamic acid to the absorbent (13) or to the sample during development of colour (14). Heavy metal contamination can be avoided by including a filter in the sampling train but some loss of S02 occurs. Alternatively this inter- ference can be eliminated by complexing the metals with EDTA (Complexon) (13). 1.4 1.401 “10- Objections to this method are: a. Mercury salts are poisonous b. Colour development takes rather long (30 minutes) c. The variable purity of the p-rosaniline d. The stability of the complex is in doubt so that sampling should be limited to 6 hours. Exposed samples should be analysed within 48 hours (1) or kept below 5 C°(15). Sunlight or UV light should be excluded during sampling and analysis. Normal sampling period - 30 minutes Sampling rate - 2.5 litres/minute Limit of detection is between 0.2 ug 80, and 0.8 yg 80, per 10 ml of absorbent depending on the variation uséd. Accuracy at“low concentrations is 10%. DETERMINATION BASED ON PHYSICAL QUALITIES OR CHANGE Gas Chromatography and Flame Photometry The development of a flame photometric detector (FPD) for sulphur com- pounds provides a very rapid and direct technique (16). The FPD fitted with a 394 nm optical filter will detect the total sulphur concentration in the atmosphere without prior concentration. The linking of the FPD with gas chromatography has resulted in a very specific and sensitive nethod for S0,. The 80, is separated from other sulphur compounds by phosphoric acfd-polyphényl ether held on teflon and packed in fluorinated ethylene-propylene copolymer tube. The materials of construction of this apparatus are extremely important - such small volumes of air are taken that any loss through adsorption would be critical. The effluent from the column is combusted in a hydrogen-rich atmosphere. The excited S, species is formed giving rise to the emission of charac- teristic radiation. This omission of light is detected by a photo- multiplier and the response fed to a recorder. Concentrations as low as 15 @/m? $0, have been determined (16) using this GC/FPD technique. 4.5 1.6 atte ADDITIONAL METHODS Additional methods given in Table 2 have been used, but in the experience of the Committee, are not readily applicable or so well suited as those mentioned in the previous sections. Nevertheless where objectives are unusual, they may be applicable and where the methods suggested in Table 1 do not readily apply, a review of these additional methods may be worth- while. ASSESSMENT OF DISCONTINUOUS METHODS The CONCAWE report on "Surveying Air Pollution around Oil Refineries" gives a breakdown of the types of objective held by air pollution monitoring programmes. The needs can be quite diverse. Similarly, the nethods tabulated in Table 1 offer a wide range of applications. Where 24-hour average results suffice, the group of methods based on oxidation with hydrogen peroxide is well suited. The choice of which method within this group depends on what other interferences are present and how many analyses are required. The automatic conductimetric titration with BaCl, is the most sensitive but the automatic colour measurement with MB Gould handle samples moze rapidly and conveniently. On the other hand, the acid-base titration is extremely cheap and simple. As a group, these methods based on oxidation with hydrogen peroxide are relatively insensitive and of little use where short-term averages of, say, 30 minutes are required. The methods that are currently used for the short-term averages are the West and Gaeke, and Stratmann procedures. Both have drawbacks. The Stratmann process involves a lot of transfer stages and needs considerable operator ability. The silica gel is difficult to prepare, but is available commercially. The adsorption of SO, onto the silica gel is not straight forward. Other pollutants and in particular water vapour can compete for the adsorption sites and 80> adsorption is reduced. Hydrogen sulphide and mercaptans interfere. The West and Gaeke procedure is extremely widely used in its many variations. It should, for this reason alone, be considered’ very seriously when choosing the method of analysis. The method is also very specific with its various improvements. However, it is still necessary to control very carefully the pH of the final solution, purity of reagents and to avoid any stray light. Methods based on the flame photometric detector (FFD) have the distinct advantage of not needing any concentration or extraction stage. The FPD can be used on the atmosphere directly or, in the case where other sulphur compounds are present, as a detector for a gas chronatogranh. This latter procedure provides the most selective and convenient method yet devised. It requires ten millilitres of sample. 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If the analysis is to be made by sensing a sample over a time period of less than 30 minutes it will be a practical necessity for the sampling to be automatic. This section is concerned with automatic sampling methods and analysis methods used with then. dn example of automatic sampling with manual analysis for 80, measurement ig the method developed by Huygen (34). By this method, the dir is aspirated at pre-set intervals through a strip of filter paper impregnated with a solution of KOH and glycerol and mounted in the AISI (American Iron and Steel Institute) automatic smoke sampler. In the laboratory the pieces of filter paper belonging to the pre-set sampling period are eluted and, after acidifying, the 80, content is determined with the p-rosaniline method. In practice, however, thé method does not seem to be wholly satisfactory, one of the reasons being the insufficient 80, absorption at relative humidities below 25% (35). Sampling with memBrane filters impregnated with potassium bicarbonate is also used (36). More than 95% of the $0, is captured, Nearly always, however, the sampling is combined with continuous analysis and recording in order to save the high cost of many analyses carried out in the laboratory. The necessary instrumentation is, however, rather complex and expensive, and mainly in the initial period of development of such instruments, failures were frequent because of air bubbles and deposits of dust, fungi, algae, etc., in the feeder tubes of the liquid piping and cocks. This necessitated constant supervision and cleaning by technically skilled and therefore expensive staff. The regular checks on the accuracy of the recorded concentrations were also a problem. Meanwhile, automatic instrumentation has been improved substantially but evaluation of the long-term reliability is particularly difficult and certainly not within our capabilities. The answers to these problems can only be expected to come from practical use or from a sort of consumer's service. Therefore, we shall Limit ourselves to some remarks on the principles applied, aost of which have already been described in evaluating the discontinuous methods. A field evaluation of sulphur dioxide monitoring inetruments has been carried out by Stevens of the H.P.A. with Ballard and Decker of the Research Triangle Institute (37). This paper makes a comparison of S09 monitoring principles when used in the Ios Angeles area. It concludes that conductimetric and coulometric methods give higher values than the West and Gacke, flame photometric and chromatographic - FPD analysers. However, it is not certain that this conclusion is correct for other areas because it may be that any order can be obtained depending on the presence of interfering gaseous pollutants other than S05. 24 anil 2.1.2 ~16- CONDUCLINETRIC ANALYSIS The 80, is absorbed in a weak acidic solution containing hydrogen per- oxide And the increase in conductivity is measured. This method is not very specific, and this may be improved by filters but these are not always used. Near the sea, interference by salt mist can be very serious in stormy weather. The objection to filters is often that they become wet and thereby retain 80,. Well kmown and commercially available instruments are: Ultragas-3 (Messrs. Wisthoff) (38) Gas and liquid flow is controlled by means of plunger and diaphregn pumpo. The apparatus is sensitive to HCl, Clo» S0,, MH, and NO,. A filter clement filled with silver wool or fuged sflica*wool infregnated with KHSO, and Ag,S0, may be used to filter out the majority of these interfeniits oybstineds. Hovever, intexference from Cl» and NO, will remain, (I ng/n? of Cl, will cause an erzor of shogt 0.5 mg $05/m> and 1 mg/n3 NO, will cauge an error of 0.07 mg S0,/1 The instrufient does not include constant Le control and appears to suffer zero shift. The reagent solutions have to be renewed at least once per week and a check with calibration gas is necessary at least once every two weeks. Picoflux (Messrs. Hartmann & Braun) (39) Dosing of gas and liquids is carried out by means of a pump and capillaries. This instrument is also sensitive to HCL, NH,, and, to some extent, Cl, (1 mg/a3 causes an error of 0.03 mg S0p/m? )%and NO, (0.04 mg 50, /a3).2 Even with the filter element mentioned“above under *Ultragas', the interference by NO, still remains. The device is kept at a constant temperature. However, this nstrument also appears to suffer zero shift. The reagent solutions must be renewed once a week (or more frequently in the event of algae or fungi formation). It is also necessary to recalibrate the instrument at weekly intervals. 2.2 2.2.4 2.3 2.3.1 “Te pH SENSING S.F. (Soufre-Fumées = sulphur smoke) continuous recorder (40, 41) In this instrument S0, is oxidized to sulphuric acid in a solution of hydrogen peroxide. The pH is measured and automatically kept constant at 4.5 by electrometric titration with sodium tetraborates. ‘The dis- placement of the liquid is recorded as an average over a fixed period (usually 15 minutes). The instrument is equipped with a filter and an automatic device for compensating evaporation of the solution. COULOMETRIC ANALYSIS ‘The principle is that the captured 90, reduces electrolytically formed ‘bromine or iodine and that the current which is necessary to bring this electrolysis to a fixed level is recorded. Two designs based on this principle are known in commercial instruments. First type At an anode placed in a solution containing very little free halogen, new halogen is only formed by electrolysis after 50, has renoved the free halogen. This is controlled ty the potential of an oxidation/ reduction electrode, and so this is really en application of electrometric titration. Examples are the Philips SO, meter and the Titrolog. The following data are available: Philips SO, meter (42) Lower detection Limit : less then 10 ug S0,/n? Electrolyte : Potassium bromide and H,S0, is regenerated and renewal of the electrolyte 4s therefore not necessary. Calibration : By means of a S0, source, consisting of a glass vessel containing S0, + air from which 80, diffuses continuously via a sflicon rubber diaphragm. Automatic daily checks. Filters: Aerosol filter, dust filter and silver gauze (at a temperature of 120°C) for removing ozone, H,S and HCL) e 2.3.2 ~18- Source of Water A Peltier cooler which condenses evaporated water as soon as the water level drops below a set level. Zero Current Automatic daily check. Shift cusller than 0.03 me/m3/day. Selectivity + Interfergnees caused by 1 ng/n?, expressed in mg 80,/m?, NO, + ~ 0,05 Methyl mercaptan : + 1.8 Stevens of the National Air Pollution Control Administration of the U.S. Dept., of HEW gives a highly favourable report on the instrument (43). @itrilog (Electrolysis 802 Analyzer: Process Analysers Incorporated, ~~" Houston, Texas) (44, 45, 46) Lower detection limit : 30 ug 80,/0° Electrolyte Potassium bromide and 11,50, Calibration + Non-automatic Filters 3 None Zero Current + Non-automatic Selectivity Sensitive to 80,5 HLS, mercaptans, chlorine, NO, and ozone. Second type Halogen continuously formed at an anode by a constant current is removed ty reduction at the cathode placed in the same liquid. The entering current (at the anode) and the outgoing current (at the cathode) are then equal to each other. If $0, is present, free halogen is taken away, thus leaving less halogen available to be reduced at the cathode. This causes a decrease in the outgoing current which is compensated by a current at a reference electrode of activated charcoal placed in the same liquid. The differential in current intensity between anode and cathode which equals the outgoing current at the reference electrode and which is recorded is proportional to the quantity of 80,. This system is used in the Beckuann 906 50, analyser. 2.4 2edet “19+ Beckmann 906A 50, Analyser (47) Lower detection Limit + 55 yg 50,/u” Electrolyte : Potassium iodide in potassium bromide solution. The electrolyte is regenerated and electrolyte renewal is therefore not necessary. Calibration : Non-automatic Filters : Silver grains treated with a small amount of sulphur. Zero current Non-automatic, to be adjusted once a week. Selectivity : Interference caused by 1 mg/n?, expressed in mg 50,/n> = ozone = 0.15 Hes 0.20 Mercaptans 0.15 Chlorine - 1.0 WO, 0.05 Source of water + Automatic non-continuous replenishnent from a reservoir. COLORIMETRIC ANALYSIS ‘The colour reactions applied in most automatic recording instruments are those using para-rosmiline,(for sulphate formed by oxidation of 80). The following instruments are Imown to ust Technicon Air Monitor IV The Technicon Analyser which was developed for S03 (48, 49) is based on the p-rosaniline method, adapted to suit the instrument by Welch and Terry (50). Technicon have put on the market an instrument specially designed for field analyses. This is named MONITOR IV which takes the place of MONITOR II. Its most selective range is 0-300 ug/m3 and its maximum sensitivity 6 ug/m3 (51). The originality of the instrument is that absorption, colour formation and detection are performed in a continuous flow system. The instrument can automatically set itself back to standard, once or twice a day by means of a metabisulphite solution. Once a week the reagent containers are refilled and standardization is checked. 2.4.2 2.4.3 2.44 2.5 -20- Imcometer (Messrs. Bran & Litbbe) (52, 53) This is another instrument based on the p-rosaniline method. It gives values for the average concentration with collection and measuring periods of 15 or 30 minutes depgndant on preferance. The lower detection limit is about 20 ug $02/m?. The instrument is provided with zero compensation and calibration. The interference of N02 is avoided by adding aminosulphonic acid to the reagent. The most sensitive range is 0-750 ug/m. The instrument will continue operating satisfactorily without attention for 14 days. ENRAF Wonius (54) This instrument is based on the colour reaction with N-N-diethylaminoaniline. It gives values for the average concgntration for 30 or 15 minutes. The lower detection limit is about 20 yg S02/m?. The instrument has automatic zero compensation and provision for static calibration check. Interference by NO2 and 03 amounts to less than 2% of the ambient concentrations of these pollutants. Atlas Colorimetric 80, or aldehyde analyzer This instrument is based on a colour reaction with m-(p-aminophenyl-azo) benzene sulfonic acid (Schulze reagent). The lower limit of detection is 6 we S02/m>, The instrument is provided with automatic zero compensation and calibration. No interferences of other gases claimed. FLAME PHOTOMETRY The operating principle of flame photometric detection uses the detection of the 394 nm centered band emitted by sulphur containing compounds in a hydrogen rich flame (16). Its specificity arises from a geometric device that optically shields the photomultiplier tube from the primary flame and the use of a narrow band-pass interference filter - the detector responds as a veal time analyser. It detects all sulphur compounds and selection filters mst be used for specific compounds. There are two ways of analysing $0, using this principle: 1. Linking the detection to a gaschromatography system (as explained in 1.4.1 above) 2. Filtering the air before detection with a chemical scrubber or silver gauge for trapping other sulphur compounds. 2.564 2.5.2 2.563 25d 2.6 -21- Limit of detection is better than 15 ue S0/m>. Good quantitative results up to 30 mg/m? can be obteined. Upper con- centration limit may be extended by dilution of the incoming gas. Various suppliers market Hp generators for use with this type of in- strument in field applications. Bendix The 8700 chromatograph separates HpS, S0p and analyses total sulphur. It works on a sequential acheme with cycle times of several minutes. Maintenance is reduced to one check per week. Tracor Tracor is also supplying an instrament based on the same principle as the Bendix 8700 and is designated TRACOR 250H. The performance is similar to the Bendix instruments. Meloy Total Sulphur monitor This instrament measures total sulphur but can be linked with a gas- chromatography system which either gives total sulphur, S02 and H,8 or nereaptans, SO and HyS. A new version is the Diffusatron which uses a selective membrane through which only 802 diffuses. Bendix Total Sulphur Monitor Series 8300 A similar instrument to the Meloy, but only measuring total sulphur. In most cases this will be sufficient to measure S02 in ambient at- mosphere because other sulphur compounds are mostly only present in minor concentrations. ELECTROCHEMICAL METHODS USING A MEMBRANE Methods using an electrochemical cell having a thin membrane on its outer surface, through which the gas has to permeate to activate the response, have been developed. By suitable choice of electrolyte the cell can detect NO, N02, S02 and HoS. 2.7 2.7.1 2.8 2 Detection ranges can be chosen between 0 - 0.2 ppm and 0 - 5000 ppm or higher. Following three manufacturers make instruments based on this principle. Little experience is available. 1. Dymasciences 2. Theta - NO,/S0p Monitor (55) 3. Environmetrics (56) SECOND DERIVATIVE U, SPECTROMETRY In the second derivative (42) spectrometry the sensitivity of UV ab- sorption measurenent is increased by two to three orders of magitude with respect to direct UV absorption, by processing electro-mechanically the second derivative of the ordinary UV transmission versus wavelength curves. Absorption changes as small as 0.05% are readily resolved. By using 2 20 m cell, 9 ug sensitivity for S03 can be obtained in a quas: real time measurement by seaming over the 211 nm S0p absorption band. Spectrometrics of Florida Inc. ‘This company has commercialised an analyser for S02, NO, NOg and 05 based on this principle. CORRELATION SPECTROMETRY This method is used for measuring the burden of 80 in the atmosphere over long distances. Apparatuses using this principle contain two telescopes to collect light from a distant source, a 2-grating spectzo- meter for dispersion of the incoming light, a disc-shaped exit nask or correlator and an electronics system. The correlator functions as a high contrast reference spectrum for matching against the incoming spectra and is comprised of arrays designed to correlate sequentially in positive and negative sense with absorption bands of the target gas vy rotation of the disc in the exit plane. The light modulations are detected by photo-multiplier tubes and processed in the electronics to produce a voltage output which is proportional to the optical depth or burden (ppm-meters) of the gas cloud under observation. The system automatically compensates for changes in average source light intensity in each channel. 2.6.1 2.9 2.961 Cospec II (Barringer Research) ‘This is a portable instrument intended for the quantitative measurement of nitrogen dioxide (NO,) and sulphur dioxide (SO,) in an optical path between a suitable sourée of visible and ultra-vidlet (UV) radiant energy. The sensor is designed for maximum versatility in the remote measurement of gas clouds using scattered skylight as the light source. It may also ve used with artificial sources such as quartz-iodine or high pressure Xenon arc lamps. The instrument is intended for fixed ground station, ground mobile or airborne installations. ADDITIONAL INSTRUMENTS Under this section instruments are mentioned which are little known in Europe, ill fitted to the problem under study, or obsolete. They are described in order to make the report complete in defining instruments less likely to be suitable and to provide possible assistance in unusual circumstances where they could be applied. Conductimetric Method (57, 58) 1, Thomas-Autometer (59) ‘he oldest used in Burope 2. Acidity Analyser - type P2 L (Licensed Sté 1'Air Liquide) The principle is as follows: The air to be analysed can first of all be pumped at a known rate through a paper filter on which the solid particles are retained. These can then be quantitatively measured by reflectometry. 4n air input at a determined flow rate then passes continuously through a gas-liquid interface (Air Liquide Patent) in which S0,, characteristic of strong air acidity, is totally oxidized and hydroliséd by a hydrogen Peroxide solution, to form an H,50, solution. The measure of the acid concentration of this solution is the electric conductivity. 2.9.2 2.9.3 2.9.4 -24- pH Recording 1, Taricum IT (60) This instrument does not record the increase in conductivity but the decrease in pH. It is less sensitive then the conductimetric instruments. When the air sample is conducted through the instrument for a period of 10 minutes at a flow velocity of 0.85 1./min., a pH decrease of 0.1 is obtained for a concentration of 0.3 mg S0,/m: Coulometric Method 1, Atlas Electric Devices Co. 80, Analyser N 210 (61) This instrument is different from those described above insofar as the measuroment is based on the fact that potassium iodide solution is non-conducting at a low voltage (about 0.18 V) because of polarization of the electrodes, while iodine, because of its depolarizing effect, generates a current proportional to the iodine concentration. The decrease in current intensity in a potassium iodide solution containing iodine, which is a consequence of the decrease in iodine concentration caused by the regetion with $0, is recorded. The lower detection Limit is 30 ug 80,/m?. Interference by ozone is avoided by installing a filter containing granular FeS04. 7H20. NOz has little influence. Calibration is carried out using iodine set free by cleaned air. Photometric Method 1. Waco Air analyser (Wilkens-Anderson Co.) (62) This instrument is also based on the p-rosaniline method. One special feature is that it is possible to dispense with the sodium tetrachloro mercurate normally used. We have no other details regarding accuracy, ete. 2. Staatsmijnen, Centraal Laboratorium Bokhoven and Niessen (32) have developed a continuous recorder for S0,. The instrument is provided with a filter for preventing interference by NO, and ozone (see 3.3.1). This instrument is not commercially available. 3. Buroglass, Delft This manufacturer also markets an instrument based on the decolourizing effect of 802 on starch iodide. The instrument was developed by the Health Research Department of the Central Organisation for Applied Scientific Research at Delft (64). Values are recorded every half hour. 2.10 4. C.E.R-L., Evans Electroselenium (31, 65) Wo longer on the market. The method of operation is based on the discolouring of starch- iodide by S0p. The lower detection limit is 30 ug/m) of S02. ASSESSMENT OF AUTOMATIC FIELD METHODS Table 3 gives a summary qualitative assessment of principal advantages and disadvantages of the methods described. Manufacturers’ specification data are given in Appendix 1. -26- ‘TABLE 5 QUALITATIVE ASSESSMENT OF PRINCIPAL ADVANTAGES AND DISADVANTAGES OF MEASURING APPARATUS ACCORDING TO THEIR PRINCIPLES Principles Aavantoges Disadvantages comucramiee Patmy good aeneitivity not apecific = too many filters needed, Gee2-1) rather sinple manufacturing Interferences by acids, bavesy oxi: or retucing naterials, and seit. Froquent inaintensnce operations once ® week at Least. 4 sam Lainly good seneitivity reasonably specific, interference by aclis eee 2.2), low cost and basen necessary accumation omen no ceneitivity to asid cr tasie | - sensitive to oxidising or reducing satertales (eee 2:3), materials Beagonable specificity casy maintenance oving +o axto- | ~ S00! provision in nartiscturtrg. Satie segeneration of solutions good sensitivity af cone typee coueRnimRY (eee 24) a based on very opectt expensive (advanced precision in mamfacturing) pprorend2ine ny sensitive ong. response tine based on Sotine Souplenee formes nave Linited ceabtiity igh parity of perosantline requined advanced precteten {1 minufactunine requives interference ly nay autdizing or seducing pollutants. Rolanate sonaitivity. Meee typee of apvaretae axe, however, either obsolete or hardly mukoted Fane oTONETEY eee 2-5), a, Total sulpiur b, Detailed sulphur ‘need no liquid reagent only one filter Tittie maintenance vyony apecific, no inter ves SOzy MyS and total Shiphar 3¢ the enna tine faizly expensive fail BLBCTROGIERICAL. WITH RA (eee 2.5) vory low interferences Sladnes Ifttle mointenance duet Pitter equized Little experience up to 204 sconD oeRIvArTvR ‘er. SeRoTCeaTEY (eee 217) ‘very specific igh sense tivity Little emenionse up to now expensive ‘oma zc eee he enmpling wvexy epectite high seneitivity Little experiance up to now 31 2h CALIBRATION, PREPARATION OF REFERENCE SAMPLES FOR THE STANDARDIZATION OF SO, MEASURING APPARATUS IN AMBIENT ATR In order to judge satisfactorily the performance of 80, measuring apparatus in air and to compare their respective merits, it is necessary to produce atmospheres of precise composition for utilization either in the laboratory or in the field. These methods can be used equally well for calibrating discontinuous as well as automatic quantitative analysis equipment. In this chapter the choice of methods is presented to establish those more suited to the objective (i.e. simple to operate, precise, absence of interaction, versatility, minimum maintenance) and to show the advantages and disadvantages. Controlled atmospheres can be created in both static and dynamic systems: STAPIC SYSTEMS These are usable at all pressures. Generally they are applicable to small volumes and their use is particularly recommended for tne calibration of static instruments. They are sufficiently portable for transporting in small vehicles. Non-rigid receptacle (66) ‘This is a bag of plastic material which is flattened to expel air or to be evacuated by a pump. The bag is then connected to the source of gas which penetrates slowly into the bag through a rotameter. S02 is injected into the gas by a syringe either during the filling of the bag or when it is full. This method gives advantages over other static systems, e.g., sample removal does not cause dilution or variation in pressure within the container; the plastic bag can be removed from the apparatus for calibration; bags are light, compact and readily portable. The principle fault is diffusion through the walls of the bag (67). This can be minimized with the aid of aluminised coating (68). There remains, however, the problem of absorption into the walls; thus a bag of 120 litres with en initial $02 concentration of 1 ppm will fall to 70 of its initial value in seven days and a bag of 25 litres will fall to 20% in the same time (69). This effect must be minimized by conditioning the bag with a sample of the product. It is also recommended that samples aust be used as soon as possible after preparation. The method requires small sampling volumes over short tine periods. 3.2 3.2.1 28 Gravimetric Method (70, 71) A pressure vessel is used, made from a metal with low adsorptivity. To meet the requirements of pollution measurement, it is necessary to first establish initial dilution by weighing a known quantity in the receptacle using a high precision balance which is able to measure large weights. (The vessel should have been conditioned previously with S0,) A part of the concentrated mixture is then transferred into a second’ bottle which will be diluted again. Alternatively, a glass ampoule of liquid S05 is weighed and released into the vessel. This method is very precise and exact. It also has the advantage of enabling one to prepare substantial quantities of calibrating gas. However, it is expensive because it requires a special balance unless ampoules are used and costly metal bottles, or the loss of 50, becomes a problem. Micro volumetric method (72) For low concentrations a proposed technique consists of encapsulating, measuring and storing a very small quantity of pure pollution gas as a nicro-bubble in a capillary and then, at the time of analysis, mixing the pollutant gas with e known large quantity of clean diluent gas. The mixing operation is carried out in a separate, passivated diluent cylinder. DYNAMIC SYSTEMS The dynamic method for creating controlled atmospheres needs a constant and uninterrupted mixture of compounds over a specific period of time. There are many advantages of this method, notably that which concerns reactive gases, where the results of the adsorption become negligible compared with equilibrium. It is possible to produce large quantities of gas over a long period of time ranging in concentration from 50% to 1 ppm. The composition can algo be modified continuously in a simple way. Mixing of Gases by Double Dilution (73) The principle consists of diluting the contaminating gas, passing it continuously and in known quantity through the diluent, which is also of known composition. Single dilution, however, is not practical for maintaining levels below 1 ppm. For lower concentrations secondary dilution mst be used. 3.2.2 5.263 Part of the mixture from the first operation is extracted and, into the remainder, which is metered ty a rotameter, there is added another very precisely measured diluent. It is necessary to avoid triple dilution as this creates too many problems. ‘The advantages of this method are that it is possible to cover a wide range of concentrations which can be changed fairly quickly, and the apparatus is not expensive. However, accurary is not assured and the loss of gas is considerable. The system is, perhaps, clumsy for trans- porting out of doors. Impulse Injection Method (74, 75, 76, 77) ‘The contaminating gas passes through a rotating valve, the internal volume of which is known. When the tap is tumed through 90° the dilution gas scavenges the valve and the two gases are mixed in a special chamber. After the purging operation the valve returns to its initial position. Any undue disturbance to the concentration is prevented by a suitable design of the mixing chamber. In order to reach the low levels, two or more units of dilution may be necessary. The commercial version of this apparatus would suit S02 well because it is made from borosilicate glass and teflon. A flow scheme of the principle is shown in Fig. 1. This method is practical for the preparation of analytical standards for instruments which measure the concentration in $02 continuously. The price is fairly high and several hours must pass before attaining equilibrium. Kethod by Permeation (63, 78 19, 80) The Liquified gas is enclosed in a plastic ampoule. The gas permeates from this ampoule into a surrounding tube in which mixing takes place with dilution gas. As a first approximation the speed of permeation varies only with the temperature of the ampoule. ‘The measurement of the permeation rate is made by gravimetric means. After equilibrium has been established the ampoule is weighed and is then stored in a dessicator for a period of several days before being weighed again to establish the rate of permeation. This system is very simple and easily handles concentrations ranging from 0.2 to 200 ppm, a sufficient range to cover the calibration of instruments in the field. The laboratory primary calibration device is shown in Fig. 2. (63). The latest version for field checking, as suggested by ASTM is shown in Pig. 3. (81). 30. A precision of + 1% is maintained with good control of the temperature. It is easy to change the concentration by varying the carrier gas flow rate. It is not advised to change temperature since it takes several days to re-establish equilibrium. Temperature control is very delicate because a 0.1°C change causes a variation in the final concentration of 1%, It is essential, therefore, to use very high precision thermostats, and these can be very expensive. ‘This method is recommended for the calibration of S02 analysis by the American Authorities of the Environment Protection Agency (82). If very precise concentrations are needed one could use the apparatus designed by TNO (82a) in which a glass ampoule is used with a tip of plastic (polytetrafluorethylene). In an upright position there is only gas phase pemeation, in an inverted position one obtains liquid phase permeation. ‘The permeation rates in both positions did not depend on the respective quantities of gas and liquid, but the rate of permeation with the liquid phase was 2.3% higher than with the gas phase. ASSESSMENT OF CALIBRATION METHODS The methods described and other methods are sumarized in Table 4. te Wee ae eT Pay | eadeer jo Arnab ” os a spa Soe e ee er uorysees qeoreaye | ow 1 vom 5 t stove wera Aron] os 99 BE 0 orgerogeas zs | ow ogy | cure aun . ae very fron | ld ong ot 10 corenssTe 8 oe w supa $> " t 5 very Aron We 04 0 tte om nosy | cura y> 1 ‘ “ ery Aron eo oe | remne ou merw | com> 1 . “ : sito 04 One rq ou wow | cam y> 1 te a Too os] to on we awe ss0urzh geno 16 06 60 o 1 souasee 1 uc eb #05 oF BE oo rants erdurs fy contd Jo SUT aaaat Sra 62 tha t90 on 8 sn 5 « a sio6 04 m8 oot ornsaom, So tho on " sue " x | oot ELS or 1 St0| 9 mor 08 aE mas © seraunto} eo | soe 1 —— 1 x" b scuton . we | se 7 ae oF 1 ¥ t stoendoaar 30 301 6 09 Bat ob orowatooar orsurg BREE onnS SD SO popu ad oe ou net ues e wera 2 a6 06 worqpoured y poman a a sxnou, uc erm bron] yata on ade vio | gomoe eorsootur ote spuasoe a ou wos ‘anes uc ous sh oe ca uosyntyo etanop (6g soot) 0 Suse aes aE oe 5 5 - - - pownse orsyeurtonoaors ou 1 mo ost ot Tovetg oT 4) doe oy oft a2 © spounee oraaosratsy ou 1 “7 O47 ‘ « 901 oF 4 6 oat 4 oroendoses pre-e SEE oS orem “sympanne oa Soa mara | seeroace | op popes peseoart axes coms semzozoy | uovantre | arora oes Eye yo 20mg, orseriusatg omen HOLGTSOANOO SSLOMIA 40 SHUTHASOMLY TONCOUA OL SCOMMAT HHL AO SOTLSTURLOVEVEO FIG. 1 PRINCIPLE OF PREPARING STANDARD CONCENTRATIONS OF SULFUR DIOXIDE BY THE IMPULSE INJECTION METHOD (77) air D Dosing device M, Mixing container 300 ml D, Dosing clock M, ‘Mixing container 160 ml Dy Gas stream indicator M-M, Absorption vessel D, By-pass valve Po“ Fomvarding pune for carrier 8 Suitch impulse treneniesion ‘The flow scheme shows the pure S02 gas A injected into the fixed-flow air stream B. The first-cut dilution C is then mixed with an airstream E, If higher dilutions are needed, the diluted stream F can be used as an injection stream to a second identical gas injector. FIG. 2 GAS DILUTION SYSTEM YOR PREPARATION OF STANDARD CONCENTRATIONS OF SULFUR DIOXIDE FOR LABORATORY USE BY THE PERMEATION TUBE METHOD (63) row ueren ve ‘WEEDLE VALVE DRY TEST NE valve Wen (Recon an O iow werer Slenmeat one L camicat omfice a Fain cane ut romeo _ SHE ——P 4 on srstew wireocex waree nour waste FIG. 3 DYNAMIC PERMEATION TEST DEVICE FOR FIELD CALIBRATION (81) ne cure Seti | Poe curd =35- PILPERS FOR IMPROVING SPECIFICITY Filters may be used for improving the specificity of test methods. This section gives a brief reference to a range of filters which have been found specially useful for measuring S02. As a rule solid sorbents are preferable as liquids are more likely to absorb small quantities of S02. Nevertheless the use of solid filters does not exclude the possibility of losses. The available descriptions of automatic instruments do not usually contain information on the type of filter used. The sorbents to which reference is made in the literature are listed as follows: For the removal of: ‘type of filter: Solid particles and aerosols Whatman No. 1 filter paper or equivalent. (1) Menbrane filters. Glass fibre paper. Glass wool. Ammonia. 40% phosphoric acid. (7) Filter element with silver wool or fused silica wool, impregnated with HHSO, and Ag,S0,. @ Hydrogen sulphide and Dry membrane filters, impregnated with mercaptans AgilOz, boric acid and tartaric acid. (94, Filtér element with KHS04/Ag2S0, (see ammonia). Silver gauze or silver grains. Heated silver gauze. Ozone Heated platinum catalyst. Heated silver gauze. Solid Fe80,. 7H,0. nO, Heated platinum catalyst. HCL Heated silver gauze. (42: Filter element with IS0,/ag,S0, (see amonia). REFERENCES 4 5. 10. We 12. 13. 14, 15. OECD, Working Party on methods of measuring air pollution and survey techniques, "Methods of measuring air pollution", Paris, 1964. Greenburg, L, "The Greenburg-Smith impinger sampling apparatus for dusts, fumes and gases", Am. J. Public Health 22 (1932) 1077. British Standard 1747, part 3 1969, "Methods for the measurement of air pollution". C.E.N. Unification Document 72-52609, August, 1972. Lazrus, A.L.; Hill, K.C.; Lodge, J.P."A new colorimetric micro- determination of the sulfate ion". Presented at the Technicon Symposium - "Automation in Analytical Chemistry", New York 1965. Stratmann, H. "Eine mikroanalytische Methode aur Bestimmung von Schwefeldioxid in der Atmosphare". Mikrochim.Acta 6 (1954) 668-678. V.D.T. Guideline No. 2451, Blatt 1. Hartkamp, H.; Gies, H.; Marenbach, 8. "Reinigung und Aktivierung von Kieselgel fiir die Schwefeldioxid - Bestimmung nach STRATMANN". Volume 14 LIB series of publications. Hochheiser, S. sulphur dioxide’ AP-6 (1964). lethods of measuring and monitoring atmospheric Publ. Health Serv., U.S. Dept. of HEW, No. 999- West, P.W.g Gaeke, G.C. "Fixation of sulfur dioxide as disulfito- mereurate (II) and subsequent colorimetric estimation". Anal. Chem. 28 (1956) 1816 - 1819. V.D.I. Guideline No. 2451, Blatt 3. Intersociety Committee Methods for Ambient Air Sampling and Analysis. Health Laboratory Science - supplement to January 1970 issue. West, P.W.; Ordoveza, FP. "Elimination of nitrogen dioxide inter- ference in the determination of sulfur dioxide". Anal. Chem. 34 (1962), 1324 - 1325. Pate, J.B.; Ammono, B.E.; Swanson, G.A.; Lodge, J.P. "Nitrogen Dioxide interference in the colorimetric determination of atmos- pheric sulfur dioxide". Anal. Chem. 37 (1965) 942 - 945. Scaringelli, F.P.; Elfers, L.; Norris, D; Hochheiser, S. "Enhanced Stability of S0p in Solution". Anal. Chem. 42 (1970) 1818. 16. ike 18, 19. at, 22. 23. 24. 256 26. 27. 28. 29. 31. Stevens, R.K.; O'Keefe. "Modern Aspects of Air Pollution Monitoring" Amal. Chen. 42 (1970) 143A - 149A. Leclerc, E. "A propos de la determination du degré de pollution de lfatmosphare des villes. Discussion de quelques résultats obtenus.” Revue Universelle des Mines 9th Series, Vol. 9, No. 12 (1953). "Evaluation of total sulfation in atmosphere by the lead peroxide candle", ASTM D2010. ‘Thomas, F.W.; Davidson, C.L.M. "Monitoring sulfur dioxide with lead peroxide cylinders", J.A.P.C.A. 11 (1961) 24 - 27. WA. Huey. The lead dioxide estimation of sulfur dioxide pollution. J. Air Pollution Control Association. 18 610 - 611 (1968). Fritz, J.S.; Yamamura, S.S. “Rapid Microtitration of Sulphate". Anal. Chem. 27 (1955) 1461. Menis, 0.; Manning, D.L.; Ball, R.G. "Automatic spectrophotometric titration of fluoride, sulfate, uranium and thorium". Anal. 30 (1958) 1772 - 1776. Kindig, S. "Beitrag cur Schwefeldioxidbestimmmg". Chen. Rasch. (Solothum) 18 No. 5 (1965). Kanno, S. "The colorimetric determination of sulfur oxides in the atmosphere". Int. J. Air Poll. 1 (1959) 231 - 233. Zinnermann, H. "Bestimmung von Schwefelspuren in kleinen Luft- mengen", Angew. Chem. 71 (1959) 336 - 339. Urone, P-F.; Boggs, WE. “Acid bleached fuchsin in the determination of sulfur dioxide in the atmosphere", Anal. Chem. 22 (1950) 493. American Conference of Governmental Industrial Hygienists, Methods Manual: "Determination of sulfur dioxide in air, Fuchsin-formaldehydée method", Cincinatti, Ohio, 1958. Stephens, B.G.; Lindstrom, F. "Spectrophotometric determination of sulfur dioxide suitable for atmospheric analysis". Anal. Chem. 36 (1964). Bourbon, P.; Malbose, R. et al. "Contribution & la détermination spécifique dans l'atmosph’re du dioxyde de soufre". Pollution Atmosphérique 52 (1971). 271 = 275. Terroglio, P.T.; Manganelli, R.M. "Evaluation of 502 methods and ‘the influence of ozone/oxides of nitrogen mixtures", Anal. Chem. 34 (1962) 675 - 67. Cumnings, W.; Redfearn, M. "Instruments for measuring small quantities of sulfur dioxide in the atmosphere". J. Inst. Fuel (London) 30 (1957) 628 - 635. 32. 3B. 35. 36. 31 38. 39 40. at. 42. Be 46. 47. 48. Bokhoven, C.; Niessen, H.L.J. "The continuous monitoring of traces of S0p in air on the basis of discoloration of the starch-iodine reaction with prior elimination of interfering compounds". Air and Water Poll. Int. J. 10 (1966) 233 - 234. Bersin, RL. et al. "Monitoring atmospheric S02 employing inverse vadioactive tracers". J.A.P.C.A. 12 (1962) 129 - 137. Huygon, C. "The sampling of sulfur dioxide in air with impregnated filter paper". Anal. Chim. Acta 28 (1963) 349 - 360. Commission Measuring Methods S02 of the Dutch Health Council. Pate, J.B.; Lodge, J.P.3 Neary, M.P. "The use of impregnated filters to collect traces of gases in the atmosphere. IT: Collection of S02 on membrane filters". Anal. Chim. Acta 28 (1963) 341 - 348. Stevens; Ballard; Decker. "Field Evaluation of Sulphur Dioxide Monitoring Instruments". EPA Air Pollution Control Office 1971. VDI Guideline No. 2451, Blatt 2 with references. VDI Guideline No. 2451, Blatt 4. Debrun, G. "Appareil S.F. (Soufre-fumées) enregistreur en continu", Pollution Atmosphérique 10 No. 38 (1968), 81 - 87. ABNOR, "Mesure de l'acidité forte dans l'air". NF - X43 - 005, 1966. Hietbrink, H.H., "An automated air pollution network". IUPAC Symposium of the Control of the Human Environment. Jaly, 1969, Johannesburg, S.A. Stevens, R.K. "Review of analytical methods for the measurement of sulfur compounds in the atmosphere". Presented at 1ith Conf. on Methods in Air Pollution and Industrial Hygiene Studies, Calif. State Dept. of Public Health, March 30 - April 1, 1970. ASIM D 1355, Continuous analysis and automatic recording of the sulfur dioxide content of the atmosphere; Method B Electrolysis method. Nader, J:8.; Dolphin, J.L. "Improved Titrolog Sensitivity" JsAP.C.A. 8 (1959), 336 - 337. McKee, A.C.; Rollwitz, W.L., “Improved Titrolog sefisitivity ptII. Field performance and evaluation". J.A.P.C.A. & (1959), 338 - 340. Beckmann Bulletin 4097A. Ingran, W.T. Technicon 25th Anniversary International Symposiua on automated analytical chemistry, Sept. 16, 1964. =40- 49. Zaleiko, N.S., "automation of colorimetric chemical procedures as applied to analytical requirenents in air pollution programs". TeAsP.C.A. 13 (1963), 531 - 534. 50. Welch, A.F.; Terry, J.P., "Development in the measurenent of atmospheric sulfur dioxide". J. Am. Ind. yg. Ass. 21 (1960), 316 = 521. 51. Technicon Monitor IV. Manufacturers' pamphlet. VDI Guideline 2451, Blatt 3. 53. Puhrmann, H., "Die registrierende Messung gasférmiger Inmmissions— Konzentrationen mit einem neuen Analysengerat". Staub 25 (1965), 266 = 270. 54. ENRAF Nonius, Manufacturers’ pamphlet. 55. Morrow, N.L.; Brief, R.S. and Bertrand, R.R., "Sampling and Analyzing Air pollution sources". Chem. Eng. January 2th, 1972. 84 - 98. 56. Chand, Cunningham. "Characterisation of Organic Solvents for Electrochemical Pollution Sensors". I.E.E.E. Transactions on Geoscience electronics. Vol. GE-8 No. 3 July 1970. 57. Thomas, M.D.; Ivie, J.0.; Fitt, T.C., "Automatic apparatus for determination of small concentrations of sulfur dioxide in air". Ind. Eng. Chem. Anal. Hd. 18 (1946), 383. 58. ASTM D 1355, "Continuous analysis and automatic recording of the sulfur dioxide content of the atmosphere", Method A, Conductivity method. 59. Kuczynski, B.R., "Effects of gaseous air pollutants on the response of the Thomas S0j Autometer". Env. Sc. and Technol. 1 (1967), 68 ~ 73. 60. Kundig, S.; Hvgger, D., “Turicum II, ein einfacher Apparat zur Registrierung der Schwefeldioxydkonzentration in der Atmosphére". Staub 24 (1964) 408 - 409. 61. Schulze, F. analyzer" "Versatile combination ozone and sulfur dioxide Anal. Chem. 38 (1966), 748 - 752. 62. Lyshkow, N.A. "The continuous analysis of sulphur dioxide in gaseous samples". J.A.P.C.A. 17 (1967) 687 - 689. 63. ASIM D2914-701. Sulphurdioxide content of the atmosphere (West- Gaeke method). 64. Natan, F.J.M. "Registrerende meting van S02 in de atmosfee: T.N.O. Nieuws 19 (1964) 721. 65. 66. 61. 68. 6. 70. mM 12. ‘13. 14. 16. TT. 78. 19. 80. -41- Basset, P.M.; Davies, J., "A portable sulphur dioxide recorde: Air and Water Pollution Int. J. 10 (1966), 633 - 635. Nelson, Controlled test atmospheres, Ann. Arbor Science Publishers, Inc., Ann. Arbor, Mich. (1971). Baker, R.A.; Diérr, R.C., "Methods of Sampling and Storage of Air containing Vapors end Gases", Int. J. Air Poll. 2 (1959) 142 - 158. Lodge, J.P., "Production of Controlled Test Atmospheres" in "Air Pollution", A.C, Stem Ed., New York, Academic Press, 1962. Comer, W.D.; Nader, J.S., "Air sampling with plastic bags". 4m. Ind. Hyg. Ass. J. 25 (1964) 291 ~ 297. Collins, "A gravimetric standard for primary gas flow measurement" report no. K-L-6181, Oak Ridge National Laboratory, Oak Ridge, Tenn., 1967. AFNOR, "Préparation de mélanges de gaz pour étalomage." Néthodes pondérales NF X 20 - 202. Paule, R.C., "Low level calibration mixtures for gaseous pollutants". Anal. Chem. Vol. 44 No. 8 (1972) 1537 - 1538. Schnelle, P.C., "A precision gasmixer for calibrating analyzers". Instr. Soc. Am. J. 4 (1957) 128 = 133. Axelrod, H.D.; Carey, J-H.; Bonelli, J.B.; Lodge, J.P., "Fluorescence determination of sub-parts per billion hydrogen sulfide in the atmosphere" Anal. Chem. 41 (1969) 1856 - 1658. Axelrod, E.D.; Pate, J.B.; Barchet, W.R.; Lodge, J.P., "Dynamic trace- gas dilution systems". Atm. Environm. 4 (1970) 209 - 212. Brochure, Calibrated Instruments, Inc., New York, N.Y. AFNOR, "Préparation de mélanges de gaz pour étalomage" Méthode volumétrique par injections périodiques. NF X 20 - 205 (1972). Stevens, R.K.; O'Keeffe, A.E.; Ortman, G.C., "Absolute calibration of @ flame photonetric detector to volatile sulfur compounds at sub-part per million levels." Env. Sci. Techn. 3 (1969) 652 - 655. Scaringelli, P.P.; Frey, S.A.; Salteman, B.E., "Evaluation of Teflon permeation tubes for use with sulfur di¢xide". Am. Ind, Hyg. Ass. J. 28 (1967) 260 ~ 266, Scaringelli, F.P.; O'Keeffe, A.B.; Rosenberg, E.; Bell, J.P., "Preparation of known concentrations of gases and vapors with permeation devices calibrated gravimetrically. Anal. Chen. 42 (1970) 871 - 876. 81. ASIM. Dynamic permeation test device for field calibration. ASTM Materials, Research and standards, February 1972, p. 43. 82, U.S. Federal Register, Vol. 36, No. 84, page 6186 April 1971. 82a Lindqvist, F. and Lanting, R.W., "A modified permeation device for the preparation of trace gas mixtures". Atm. Env. 6 (1972) 943 - 946. 83. Apol, A.G.; Cook, W.A.; Lawrence, E.P., “Plastic bags for calibration of air sampling devices - Determination of precision of method. Am. Ind. Hyg. Ass. J. 27 (1966) 149 - 153. 684. AFNOR, "Préparation de mélanges de gaz pour étalonnage", Méthode volunétrique (statistiques). NF X 20 - 203. 85. Opler, A; Smith, B.S., "Device for preparing gas mixtures for calibration." Anal. Chem. 25 (1953) 686. 86. Rubis, "An apparatus for the preparation of standard gas mixtures containing trace level components", report no. RFP-358, Dow Chemical Co., Rocky Flats, Col. 1964. 87. Zérojewski, A.; Monknan, J.L., "A simple gas dilution apparatus". Am. Ind. Hyg. Ass. J. 30 (1969) 650 - 653. 88. Hughes, E.E.; Dorko, W.D., "Accurate mass spectrometric determination of low concentrations of carbon dioxide in nitrogen". Anal. Chem. 40 (1968) 750 - 755. 89. Kusnetz, H.L.; Saltzman, B.E.; Lanier, M.B., "Calibration and evaluation of gas detecting tubes". Am. Ind. Hyg. Ass. J. 21 (4960) 361 = 373. 90. Caplan, "Calibration of air sampling instruments", in "Air sampling instruments for evaluation of atmospheric contaminants", American Conference of Governmental Industrial Hygienists, Cincimati, Ohio, 1966. 91. Brochure, Matheson Company Inc., Cucamonga, Calif. 92, Mo Kelvey, J.M.;Hoescher, H.B., "Apparatus for preparation of very dilute gas-mixtures". Anal. Chem. 29 (1957) 123. 93. Hersch, P.A., "Controlled addition of experimental pollutants to air", JsA.P.C.A. 19 (1969) 164 - 172. 94. Adans, D.F.; Bamesberger, W.L.; Robertson .J., “Analysis of sulphur containing gases in the ambient air using selective pre-filters and a micro-coulometric detector". J.A.P.C.A. 18 (1968) 145 = 148. 95. Hersch, P.A.; Deuringer, R., "Galvanic-coulometric monitoring of S0j in air" 149th meeting Am. Chem. Soc. Detroit. April 1965. =43- APPENDIX MANUFACTURERS’ SPECIFICATION DATA OF AUTOMATIC FIELD INSTRUMENTS CONDUCTIMETRIC INSTRUMENTS (see 2.1) WoomIORF (untzagas.4 K) HagonuoN uRAUN (Picoftax 80,) between 0,4 and 0,75 me/nd Range in e/a? 9 = 1000 10005 02000 + 0 = 50005 ‘-10000 operating temperature o- 0% = 390 t0, 51°C varios <1 0,596 for aash 40% envizonnent variation Response time start start +6 te 10 2. at 9081 120 8. at 906 = 30 5. to 300 a. ascuracy Reprodue ibi2: Reproducibility obtained: 2 Yon tine intervals of 30 min. on S0, concentration sana tivity bout 30 sa/a? Fron 15 to 50 e/a? Spocstiesty Without Piter With Filter Without Piiter with #itter for 1 ae/a? ea 0,840 ° cos + Oya ° interfering agent ae ole 8,148 ie ovoz7 0,005, x ng Bla/avare re o rs to o o detected oe 2,08, 5,067 Woe Syog2 2,035 505 ors 505 1034 mS = 1800 % = 1300 ES 8 i = 0435) © ies 0,06 ° ot o 6 oe ofot 6,01 oe 5.10 2 os c e in a é ae = 0,08 np 25.10) Be if if Masneenance reagent souutions 10 Additional details sore arist 216 por 24 hours Sensitivity drift 228 por 24 h Bower 1 60 watt sero drift § 16/2) per 24 noure <15 e/a per week onsitivity drift ase ose socaosy ee typ of fat sca Siang SOS “e 2% range 0750 otter than 10 ya/a? better than 30 y e/a? beter than 55 y/o? spectttetty wituoat ster shout the saue as for sonovea every © nonthe Blectrolyte to be ‘changed once a years oye oe Baliye wtime'tite, |g oy . 2 ce a hoaae swe, | a2 2 tort mgs? intae | rs aiyee totm mayne, | ess 0.z0 acing Seagt for toe ativan gate | aot, ons add Por 8: he net ays 80 Syetds ma | age 0105 wetene | OS 7 4 Taintenance reagent solution to be | vany feaguent shosting. | seagunt cclution to be checked ‘noe a ponth ‘ational detaiie azitt of goro olga <26 ve/a> 02 per day Filter fem 03, a8, Che Incorporated. Involve ited sitanstio standards Shecton. Powest 130 sae? plsion can be provide ALRZieALt to obtain aqare parte, Jactisioss saintes fe: Geist outa he ‘Teanenission can be providea| 46 of fui scale (Geax 0 rea) Tranentocton can be provided fon Prices (without taxes) 29,000 P. (Kareh 1972) 19.591 Ps (anon 1972) Nomsfactaners" Saeresnes ue. muipe Solgctifie dnatytioat Bytpaant Depts, Glvektaapen fabbiskeny Process Analyssrs Ino. Houston, Teste, UeSeh. BoOKAN STAM, Tse. Process Inatrusente Dives Ostifomia 92634, U.S.A. =46- agop mr oor ony Poanasnsen Sf i ‘oednog e800 burton / a3T2¢ sooai 9 E ‘es0009 enh senor SEO ‘Paprioy SeRESoO (om on) : (cues eee) a 206"18 Some Tame ois sear eu yp once sonien ermount sve ogg #50801 se on snag “sre usenoa gsto Gest nol f boone tyeoenonee yrs yuo sopyseundany 80g e Ge siowrorsse Bervaang | “aay 02 Sod sevog es exes oryamuadaco suck ¢ ay ge tonie goasme | ssu'ye aed geet aT ret er “euowe © foun ported aq o4 snqate dont soon = os Ednouar Si oy uotanvoe susbvor | cqquoe ¢ £5650 pensuas on op toranron auA¥or poses = 11 APT genes wigenn e'soue | sosmrerey motes ee oe Soro 10% (sorts ov) 6-0 Hg que Sur: ssouara3sa3z7 of ‘pros ovomafree 30 supa 4 poguoaand SoursOIA40F “OR fyrorstoade eres $/9" ce sedies op SUTIMOODE co: 2,5 1074 ue: 1,5.1074 15.10 NO + 2,5.10 Ip # 255.1071 Noy + 3.107? 8 2 4.10 Maintenance Cell to be changed every six months Additional 1. no solid or liquid particles over details 100 ug 2. relative humidity 50%

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