Wa Se Tech. Vel.27.No. 1 pp. 1-20. 198% 0273122399 $2400 Pied Grou Britain All igs served CCopsnght © 1988 AW. CONTROL OF ORGANIC MATTER BY COAGULATION AND FLOC SEPARATION Menahem Rebhun and Michael Lurie Environmental and Water Resouces Enyincering Technion, Israet lastitute of Technados. Hasfe. 22000, svat KEYWORDS ‘Coagulation, flocculation, aqueous organics. humic substances, coagulation mechanisms, floc properties INTRODUCTION Jn the last decade and 4 half, “organies” have been the majoe topic in water quality research and in the developmen of weatmentprocestes ‘The effecisof gan raion sad hit atin coagulation and separation are a dominant facior in deating with these processes. Of the four main objectives of ‘coagulation: flocculation, offen cited as reduction of (1) Turbidity, (2) Color, (3) THM and TOX Precursors and (4) Microorganisms, three are related to organic material, particularly of the type of macromolecular natural organic matter. These organics are « dominant factor affecting colloid stability and coagulation. CLASSIFICATION OF ORGANIC MATTER RELEVANT TO COAGULATION Dissolved organic matter (DOM) (Organic macromolecukes) Humic substances “Humic acid (humates) Fulvic acid ¢fulvates) Proteins Polysaccharides ‘Microorganisms - Particulate Organics Living Cells Cell Fragments Particles Coated by Organic Macromolecules Mineral Particles in DOM "solution’. Organic particulates in DOM “solution”. Oi Emulsions HUMIC SUBSTANCES Humie substances are the main group of organic mater affecting coagulation in water treatment operations andthe main target related fo reament objetves by coagulon, The importance of humic sbstanoes in the global carbon cycle and balance can be seen in Fig.l and in Table 1. taken from Aiken et al (1985)M, REBHUN and M, LURIB, sian, DUCE SOC Go eeme saat) 296, (50% nme Ce saat Terrestrial ecosystems Marine ecosystems Fig. 1. Diagram of the global carbon cycle, indicating the importance of hut substances (Aiken, et al, 1985) TABLE 1 Estimated Size of Major Pools of Carbon in the ‘World Carbon Budget (Aiken ef al., 1985) x 1015 g. c ‘imosphere 638-702 Land Biota (plants) a7 Soil humus 700 - 3,000 Oceans Biota 2 Organic (50% humic substances) 1,700 Inorganic 38,600 Fossil Fuels 10.000 Source: Woodwell and Houghton (1977) and Woodell et al. (1978) Humies constivute 25 percent of total world organic carbon budget and $0 percent of organic carbon in ‘oceans and fresh waters, Humics as a gsoup were recognised 200 years ago by Achard (1786), extracting procedures were developed by Berzelius (1839) {In the last 30-40 years progress has heen made in understanding the properties and behaviour of aqueous humic substances. Aqueous humics are a major part of what is nowadays defined as Natural Organic Matter (NOM) or Dissolved Organic Matter (DOM). While in the 19505 they were still described as "Yellow ‘Acids" by Shapiro, modem more advanced snudics of their composition, functional groups, structures an reactivities, tc. were contributed by Christman, Gjessing, Wershaw, Schnitzer, Marinsky and Buffle, Based on their solubilities, humic substances are often divided into Humic, Fulvic and Hymathomelanic ‘acids and their salts. Molecular weights ascribed to Humic Acids are in the range of S x 10° to 10° while Fulvic Acids are in the range of 500 to 5 x 10°, Table 2 gives a compilation of findings of several investigators.Coagulation and floc separation TABLE 2 Molecular weight range of major part of humic substances in various waters and in secondary efftuent (Manka et al., 1974) Source of humic Molecular weight range of ‘compound and reference ‘major part of humic compounds. Take water (Shapiro, 1966) ‘Over 10,000 Nanral waters Cucens) (Ghassemi, 1968) 700 ~ 10,000 ‘Moorland water (Gjessing, 1963) 100,000 - 200,000 and'< 10,000 River water (Rashid, 1972) 700 - 5000 ‘Secondary effluents (our findings) 11000 - 5000 ‘Typical chemical structures proposed for aquatic humacs are shown In re zr oO "oO Tee ot. Sow HO’ 4 Oe fin on Bon ko Oy 0H Ho- OH HO ‘Ot OH Ho-¢ G0 ose Ho O O ‘OH 2 Go OH oH 50 oH On CH, — CH, —Ct yn ey 2 eS Hoc, H CH Hooc™ (ay Bd hetical structures of humic substances from freshwater and from eaPated a age ystems: (a) from Gamble and Schnitzer (1974); (6) from Bergmann (1978) (Adopted from Steinberg and Muenster, 1985)M. REBHUN and Mi, LURIE They are polyaromatic compounds with phenolic and carboxylic functional groups. The functional groups may be protonated-deprotonated depending on pH. Carborytie~ COOH 7? -COO™ +I Phenolic - OH =O 41% e In most waters they ate, at least, partly deprotonated, thus in anionic form and can be tegarded as potyanions. This is relevant to coagulation processes. Typical charge densities by carboxylic and phenolic ‘groups on some fulvie acids and titration curve are shown in Fig. % The charge densities represent their jon exchange capacities and some measure of metal ion’scomplexing properties Phenoic-OH and -COOH Groups ia Hume nd Fale teeth, Fig. 3. Potentiometric Gitration curve of fulvic and hmmie acids (Narkis & Rebhun, An important parameter characterizing aqueous humics and DOM. in general, is their UV absorbance (260 nm), The UV absorbing DOM and humics are of special water quality significance. UV absorbance, {otal and specific (per mass of DOM),and the ratio of UV absorbing to nowrabsorbing DOM were proposed as quality parameters in general and for DOM separation in particular ¢ Tambo, 19%). Humic substances account for 40 10 60 percent of DOM in natural fresh surface waters (Vik and Eikebrokk, 1989). Also close to 50 percent of DOM in secondary effluent was defined as humic substances (Manka ct al.,1974), see Table 3. TABLE 3 Distribution of Organic Groupings in Secondary EMuents - Mean Values (Manka et al., 1974). ‘Municipal wastewater: Municipal Domestic ‘Organic groupings high rate tickling wastewater: wastewater: and fractions: filter stabilization extended aeration pond activated sludge Proteins 216 24 2. Carbohydrates 59 78 46 Tannins and lignins 13 2a 1.0 ‘Anionic detergents 16.6 122 160 Ether extractables 14 9 163 Falvic acid 254 26.6 240 Humic acid 125 147 61 Hymathomelanic acid 17 67 48‘Cexugulation and floe separauon 5 “The significance of humic substances to water quality can be summarized as follows: Colour THM Precursors Precursors of other haloorganic DBP. Fouling of resins, raembranes, equipment. Interference with water teamment Binding. complexing of ssvrganic and organie miccopollutants and facilitate transport of ‘contaminants, COAGULATION-FLOCCULATION Major Topics in Coagulation of DOM (Humes): Coagulation of Hunaie Substances Alone Coagulation of Mineral Particles ii Presence of Free Humics andl Adsorbed on Particles, Coagulation of Microorganins Coagulants: AKI, Fe(TIl, Polyeketrolytes, Etfects of Ozonation Mechanisms and Stoichiometry Flac Properties Separation Processes Following Flu: Formation Settling (Sedireetation) Dissolved Air Flotation Filuation ‘The important floc properties relevant 6 thase pmicesses are: Size, Density, Volume, auxi Suenger ‘The chemical characteristics of hurnics relevant ty coagulation can be summarized as follows: High toolecutar weight polyanions Polyaromatic polyhydroxy-mettioxy carboxylic acids ‘Total charge and charge deuisity are pH dependent Comnplexing properties In waters containing DOM, the organic matter (Humics) is the dominant factor affecting the coagulation process. This és a result of their reactivity and of the particle number concentration (reacting units concentrations) of DOM as compared to number concentrations of mineral particles at commonly encountered mass concentrations. Table 4 shows typicat mass, ntmber and volume concentrations of dispersed matter in various waters and wastewaters. TABLE 4 Types and concentration ranges of dispersions in water technology a “Metal hydroxides, organic High M.wt, organics Minerals pariculates, debris, hhurmies, proteins, ‘wastewater solids polymeric c N wet vol/vol, sgl O05 108 10 sludges 10° high turbidity 10°10" sludge blanker wastewater 1010! 104 medium turbidity 107 102 flocs (Al,Fe) 10"? precursors effluents colour 101 10! 1G5 tow tsladiey 10? 103 106 so 10 10° 105M.REBHUN and M. LURIE Ttcan be seen that in natural waters for the same mass concentrations of mineral particles and DOM (such 25 fulvic acid), the number concentration of the DOM fulvies is 410 6 orders of magnitude higher than that ‘of mineral particles. This means comespondingly higher concentrations of charges, surfaces and reaction 3s. Also, kinetically the DOM ean easily outcompete the mineral particles. I seems that this great difference in reacting units cocentrations’is a key factor explaining the strong effects of DOM in ‘coagulation. COAGULATION WITH AL(II) Aluminium and Ferric Salts are the most commonly used coagulants-flocculants, particularly when DOM is present and DOM removal is the objective of the treatment process. The chemistry of AICI) as a coagulant-floccufant can be summarized in a very simplified and very short manner as follows: (ALGO TAI HOSOHY? 3, (Als OF fap [Als (OH fy pH4to7 ~>[AL (O83 20)31, OF (ALOHA) ~ alkaline pH ‘The positively charged polyhydroxa-complexes such 2s[Al,(OH)aq]", in the pH range between 4 and 7, are the effective floceutants. Oversanuration and fomtation of amorphous hydroxide precipitate (Al(OH), (H,0),)¢g enmeshes colloidal particle in a “sweep floc”. Many other monomeric and polymeric species have been reported and listed below: ‘Monomers; [Al (OHD]"*, [Al (OH,)I* (Al, (OFD,J*, [Al OH) Polymers: [Al (OH), <]°*, [Al, (OH) 91, [ly (OH) oo), {Alyy (,COH),91"*, (Al, sOH) 1. Reaction (formation) rates of the different species, examples are listed in Table 5, play an important role in specific mechanisms. Several mechanisms (reactions) are possible simultaneously, as kinetically ‘competing reactions. TABLE $ Kinetics of Al (III) Reactions (t,,.) Compound ta Formation of monomeric hydroxo 104s Formation of dimers ts Formation of Al, Polymers minutes AN OH)(9) (am) precipitation Isto years ANOH), (9) crystalize ‘months to years Rates depend on pH and types of ions present. Transformation from polymeric Al 0 Al (OH), (8) is slow Anhibited) in absence of sulfate, In presence of sulfate tansformation and precipitation are fast ‘The accumulated evidence and proposed mechanisms of coagulation-flocculation of hamics with AICI) and Fe(M) could be surnarized as follows: Chae cewal ization and precipitation of humics with hydrolyzed monomeric and polymeric alurno Possible complex formation of HA-Alumo precipitates. i ‘Adsorption and surface precipitation on alumino hydroxide solid precipitate. Mechanisms are pH dependent Stoichiometry is observed and is pH dependent,CCoagulmion and floc separation Precipia Hf + Monomeric Al [24 Monomeric at] (s) pH =40--5.0 Bh + Polymeric Al [28 Polymeric A! ]«s) pHS0-66 Adsorpiion (QH >7) Ef + aL cOi)s (=) Adsorption a [EA Polymeric ai] + At (OH); (=) Adsorption ‘The many mechanisms postulated for coagulation of humics and DOM by AICI) are a result of the many hydrolysis and polymeric species involved and the final appearance of the solid Al(OH)(8) precipitate, the ler being the most frequent constient of alum floes in most water treatment sieuaions. The mechanisms and the reaction pathways depend on kinetics and relative rates of the possible reactions. The dominant presence of the aluminohydroxide precipitace in the final flac product should not imply. in our view, that tte main reaction mechanism isthe interaction of TA with solid AKOH),(s) ‘The reaction of HA with a monomeric or polymeric AI(IID hydroxo species is kinetically faster than the precipitation of aluminium hydroxide. Thus, the formation of Alumo-HA complexes precipitates which in tum may adsorb on solid Al(OH4(s), consequently formed, may be a plausible mechani In waters rich in DOM in the absence or of very low minerai particulate content, the products of HA-AT monomeric and HA-Al polymeric precipitates are poorly separable (or nonseparable). In such cases, it becomes necessary to werk in the "sweep" AKOHD,(s) region. The HA-AL monomeric or polymeric products adsorb or interact otherwise with the AIKQH),(s) sweep floc. ‘As mentioned before, two major mechanisms are being considered in the last years: precipitation and adsorption, each one being proposed for a separue pH range. An example of explaining flocculation-filtration results in this manner can be seen in the work of Vik and Eikebrokk (1989). Showing two pH ranges of effective flocculation, the low pH range is explained as precipitation while the higher PH range ( 6.5) as adsorption. ‘A different presentation, but in principle, similar in its implication to the above regarding two mechanisms depending on pH, can be scen in the excellent series of ‘by Dempsey er al. (1984, 1985), Dempsey. (1989), and O'Melia (1991). Two domains of effective formation of fulvic acid are shown (Fig, 4), -35 -40 LOG Aly tmotes/L) LOG Aly (moles/L) Fig. 4. Aluminium doses and pH values that permit removal of fulvic acid from water when (a) alum or (6) polyalumunium chloride is the coagulant (Dempsey, 1989)IM. REBHUN and M.LURIE, Zone 11 at low pH represents precipitation reaction while zone I represents supposedly adsorption on Al(OH), (6) at higher pH vatues. These two 2ones represent formation of separable flocs, However, {interaction products of AICIID) and FA were formed within the whole boundary of the contoured part of the ‘master diagram. Those formed outside the black areas showing zones I and Il were not separable by the 0.4 um membrane filter used by Dempsey. If @ membrane of a lower cutoff would be used, such as ultrafiltration membrane, these formation products could be detected and determined. Indeed, UF ‘membranes should be used in studies of reaction products in coagulation reaction of fulvic acids and DOM in general. The fact that reaction products of coagutants with fulvics are formed in ail domtiains, though in some domains very colloidal and not as separable flocs, may indicate the fast rate of cheir formation and that these reactions between FA and monomeric and polymeric AI(TID) species are always an intermediate step in any mechanism, Edwards and Amirtharajah (1985) explained their findings of linear stoichiometry at pli=5 as ‘neutralization precipitation while non-lincar stoichiometry (defined by them as non-stoichiometry) at pH=7 188.2 proof of adsorption on AKOH),(s). Dempsey (1989) showed a stoichiomearic relationship between the required Al dosage and the initial fulvic acid concemtration at pH1=7.2. Also, the ion activity product indicated AI(OH),(5) precipitation ancl was essentially identical in presence and absence of FA and at all dosages of AIAID applied. which was used as proof thal adsorption was the mechanism at shis pH. Adsorption isotherms of Langmuir type were reported by Jekcl (1986) in his interesting study of surface complexation of FA on AIOH}s(3). Proposed pathways for alum coagulation of humic substances by Eizwald(1986) is shown in fig. 5. Ah 0)f7 SE ease arcmart me Small al Polymers TOF eee davon ereter AE Cause, gtOHNSe) LOMs Wepends on 855.0%) Fig. 5. Proposed mechanisms for alum coagulation of humic substances. Pathways at top resulting in Ai-humate precipitation favored by low TOC and pH < 6. Pathway resulting in Al (OH), precipitati by high TOC or pH above approximately 6 (Edzwald, 1986) Dempsey et al. (1984) summarized in Table 6 the hypothesized mechanisms at the various pH ranges, TABLE 6 Effect of the complexing ability of fulvic acid on the coagulant dosage of alum required for the removal of fulvic acid by settling (Dempsey et al., 1984) Removal zone pH Hypothesized renotion Effect on coagutant dosage ‘mechanism 1 45-50 Precipitaion of FA by Strong complexers of Ca require monomers of Al less Aly for removal. 1 5-6 Precipitation of FA by Strong ecmplexers of Ca inhibit polymers of Al the formation of aluminiumpolymers: a higher dosage of Aly is required. 1 o7 Adsorption of FA on Strong complexers of Ca inhibit the AKOH),(8) formation of AMOH),(s): a higher dosage of Al; is required.‘Coagadn and te eperadon Tr should be remembered that in both Dempsey et al. (1984) and Jeke’s (1986) studies good adsorption ‘was obiained only on AV(OH)3() precipitated “in stu". Demptey et al. (1984) compares nicely adsorption on gibbsite, pre-precipitated and “in siu® formed hydroxide. 100 hundred) imes more was adsorbed on “nesita than on pre-preciitated hydroxide. The low adsorption effectiveness of pre-precipitaed hydroxides is known w sclentists working inthis arc. Imray be explained by lower available surface area fcr ste inactivation ofthe pre-precipsted product ‘The simplest well Based explanation seems be that since the fastest reactions are: ‘FA or HA + Al monomers FAorHA + Al polymers their reaction product ae the first intermediates which in turn ae being adsorbed ard “sweeped” by the precipitating ALOH).(6) It would be nice if scientists working in the field could devise experiments to rove or disprove these pashwvays. Dempsey (1989) in his concluding remarks indeed writes tha the presence of precipitates of AU(OH),(6).even massive ones, doesnot exclude simultaneous mechanisms ‘with monomeric and polymere species. We would adé "and consecutive reactions”. Prepolymerized ANI) as Coagulane Prcpomesiaed AME boca poplar inst years, Some of is charserisis ae sunmasized below: Supposed polymer type is (Al, 0, (OH: To minimize presence of AIOH),0), the desirable [OM] {AN} = LS t02.0atpi 106; Polyalyminium eblorie (PACY is more effeive: "For organic color cougulaton Eo high organi couteat Fares coring pclae sos InFig. 4 shown above, PACI ws found effexive in a wide range of pH. is effective lo formation were explained by ts fact srwctre (Bottero and Berillon, 1989) ‘Ac neural ard higher pH. alum is sometimes more effective de o formation of AKOBD.(S) {tis caine that PACLs efiiont at lower A doses than alan sisimizes sludge reduction and may be preferable for direct FA filtration. It socms to us that studies wih PACI may be niprtant for Understanding coagulation mechanisms widh ANI) salts in general. COAGULATION-FLOCCULATION WITH CATIONIC POLYELECTROLYTES Ara ep pes ny ec ype ia a-axis foes pete ees ea somes alo sete ett aPelues tac Sark flocculation diagram is given in Fig, 6, The coagulation -floceviaton mechanism, based on these Sova (Cars neualization-itraction of polylecalys of opps charge. ‘Strong association complexes ae formed leading wo precipitation. ‘At low coagulat to uric ratios an excess of negative charges exists, only pail preciphation takes place and the precipitates are highly colloidal, non-separable, causing aa increase in turbidity. trate eas to complete char neal, the rece cetnfgable, ddionl lrslan dost ssl pint yes god Noclation fomang stkeabe foc ‘Overdasing brings about charge reversal and restabl ‘Recast of bari fly scheme end canbe comelted wih the funcuonal group ‘concentration. A sioichioneary was observed by Katchalsky and Spitnik (1954) 40 years ago in tiation of. pelygnine (aden) by plymethacrie (none)0 IM. REBUN nt M, LURE Fig. 6. Effect of cationic polyelectrolyte on Fig. 7. Optimal dose of cationie Nachumate solution 10 mg/l humic poly-clectrolyte required acid, pil of 8.0 a5 8 function of Ne-fulvate GMarkis & Rebhun, 1977) and Na-humate solutions pits8.0 (Narkis & Rebhun,t977) caso Terre AcaANES 6 SG ASSOCIATION comes [Sf TAS ake Font own 0st Fig. 8Schematie description of the effect of cationic polyelectrolyte om humate solutionCoaguiion an fe spaaon L MINERAL PARTICULATES IN HUMIC SUBSTANCES SOLUTIONS. EFFECT ON STABILITY Four situations canbe considered as showin fig. 9 "Bare" mineral particles "Bare" mineral partes in Free Humic Solution ‘Mineral parle coated with Humies-Organo-Minera complen ‘Coated parle (Organo-Mineral Complex) dispersed in solution of Free Huis Fig. 9. Schematic description of mutual relations between mineral clay particles ‘and organic’ molecules, ‘The trong sift fed is okserved in electrophoretic mobility potential as result of “coting” of the parles by humics (Naki ta, 1968) {nan inersing soy, Sokel (1986) has shown the effet of adsobo eves huis om the colloidal stability of kaolin, Fig. 10. pie erecta os Fig. 10. Correlation of stabilization with coverage of kaolinite particles with (wo humic acids (Jekel, 1986)1M, REBHUN sm M, LURIE COAGULATION - FLOCCULATION OF MINERAL AND HUMIC DISPERSIONS. {In systems containing mineral particles and dissolved humics, dhe coagulation flocculation process is deveined aeneme ‘absences Typiclcongulston behaviours shown in Figures 11 and 12 (Nakis ue Fi rae 48 img Fig. 11, Floceutation of montmorillonite M-20 suspensions, at various sonatas of interactions with flv acs with PuriMoe C31 (Narkis un, ‘Tre cationic polyeleculyte reacts fist withthe free humics and only when this reaction is completed and the coagulant demand was sanfied,can the coaguluat interact with the particulate mater, “Therefore the coagulant demand is desenined essentially bythe humic substances which can be aso seen in Fig. 13.Residual, Fuscoulent ug/L orgsrohay-Cmpiex Suspension fest eritacantae Overdose . seat Chay suepeston se suermie bemrens Rents stati PRGERES Pana Ho Visihne mumate Solution fo teeta PES ce Fig. 12. ‘Coagulation and floc separacion Organo-Clay-Cooplex Suspension Gs Hunste colution vissoe |, rocraased Goa erdose ‘Reaction Turbidity, larsricatien| overdo Renova, Minered Clay Suspension = 26 3B = Flecewlant Dose - ws/2 Residual radioactively labelled cationic polyelectrolyte, PYMPI, in supernatant after flocculation of montmorillonite suspensions at various conditions of interaction with humic acids (Narkis & Rebbun, 4975) BM.REBHUN and M, LORIE RESIOUAL FULVIC ACIDS mgr) ‘rus ruRpapery FULVIC ACIDE (mpi) OPTICAL SenSiTY PURIFLOG €-31 DOSE (mgiL) Fig. 13, Flocculation of montmorillonite M-20 chay suspension dispersed in various concentrations of falvic acids solutions with purifloc C-31 (Narkis & Rebhun, 1990) Unlike in “pure” mineral suspensions, in presence of humics, the optimum coagulant dose coinciges with the isoelectric point, due to the charge nemtralization involved in humic-coagulant interaction. The dorninant influence of humic substances is also observed in flocculation of mineral humic disperstons by ‘ATID and Fe(II) salts (Narkis and Rebhun, 1990). The dominance of humic substance in determining the coagulation - flocculation behaviour should not be surprising, We showed in one of the previous paragraphs that the number concentration of humic interacting units is 4 6 orders of magnitudes higher than of mineral panicles of the same mass concentration, Dente! (1988) calculated that the equivalent radius of a single FA molecule was found to be 14x10"? em, with a maximum possible charge density of 14 yCfeny?, The 3.5 mg/l. FA system used provides approximately the same surface area as 1700 mg/L of silica Min-U-Sil 5. ‘While the humies dominate the behaviour of the coagulation process, the presence of mineral particulates iaproves greatly floc formation and results in a auch stronger and denser floc. This is well known from practical experience in treatment works. A nice schematic picture (Fig, 14) by Tambo (1990) explains very Well the vatious interactions of AKI with humics, subsequent reaction with precipitated hydroxide and finally the interaction, even bridging, with mineral particles. ‘There is experimental evidence that natural DOM and effluent DOM promote floc formation of mineral patticulates and vice versa when flocculant demand is determined by the DOM (Rebhun et al. 1969). ‘Knother schematic diagram by Berahardt etal. (1985), Fig. 15 explains how exiracelluar DOM (probably high mr. polymers)aids flocculationby bridging at appropriate surface coverage,‘Coagulation and foc separation Is Precipitated Aluminium Highly charged ‘Aluminium polymer Fiumies highly charged (bMutuat Coagulation Aluminium Futvics Precipitated Aluminium Précipitated Highly charged ‘Aluminium Aluminium polymer {a}Bridging Coagulation (e)Adsorptive Coagulation Fig. 14, Schematic of floc formation (Tambo et al., 1989) 15. Effect of the EOM as a flocculation aid. The ratio EOM concentration te the particle surface concentration is low (-75 mg/m*) (Bernhardt et al, 1985)6 M, REBITUN and M. LURIE, ‘Studies on coagulation flocculation of secondary effluents (Rebhun et al., 1969, Narkis & Rebhun, 1983) [that the DOM in the effluent is the main factor determining flocculation behaviour. This is in accordance with the findings in table 2 showing that a major part of the DOM in effluents are hurnic substances of nature simifar to those in natural fresh water. Lime flocculation has been used for tertiary treatment and is very popular in Scandinavian countries for Faw wastewater treaiment. Lime flocculation studies by Leentvaar and Rebhun (1982) indicated that CaCO,(s) could act as a "sweep" flocculant for particulate matter including organic particles, but colloidal organics and DOM were affected only when lime doses were used into the range of Mg(OH),(S) precipitation, i. pH > 10.5. The necessity of Mg(OH),(s) was proven when waters without Mg content did not floccuiate smali colloidal matter and DOM, even at high pH. The interaction of DOM with ‘Mg(OFT)2(8) could be described by an adsorption isotherm. Itis known that Mg(OH),(3) carries a positive charge and is characterized by an amorphous structure and high specific surface area, factors favouring adsorptive coagulation. Te might be assumed that the MgOH™*,, complex reacts with DOM and the product adsorbs on the Mg(OH),(s). While Mg(OH),(s) coagulates-flocculaies DOM, the DOM was found te ‘inhibit the formation of separable Mg(OH).(s) precipitate and a higher ion activity product is required to ‘obtain a ipitate in presence of DOM as compared to organic free water. This is similar vo reported pepucatn otal um hydroxide by fulvic acid at cenainratos of FA to Al Flocculation of microalgae rom wastewater oxidation ponds by time could be accomplished only in the Mg(OH),(s) precipitation range (Folkman & Wachs,1973) Fons proparsory pag, bef ‘Alpcculation and particularly before ulation-fitration Ozonation as a stage, before flocet vularly contact coagulation-f has been recelving a lor of atetion inthe lst decade tn research and development. Many fallseale trearens plans have installed ozonation as a preliminary stage, the recent and largest being the Los ‘Angeles 600 mgd high rate water treatment plant. However the mechanisms of ozone's effect on coagulation have not been clarified up to now. Some scientists and engineers still question whether there is any effect at all or itis an artifact. Two possible mechanisms of ozone's effect on coagulation are proposed: (a) oxidation of adsorbed ‘organics, their hydrophilization and eventual desorption leading to destabilization of the particles such as shown in work of Jekel (1986); (b) catalyzed polymerization of DOM and subsequent adsorption bridging ‘ iat neah aes arding should be asked: how does it effect DOM removal in A very important question regarding preozonation should be asked: how does it effect ‘subsequent coagulation-separation processes. If ozonation oxidizes, breaks down and. ises DOM. then one would expect poorer removals of DOM by coagulation after peeozonation. is & Benjamin (1992) indeed had shown the formation of low organic acids by ozonation. Results by Jekel (1986) (Fig. 16) definitely indicate much poorer DOC removal by alum following preozonation. Therefore, ‘treaiment of preozonated water, without bioactivity in filters or in activated carbon contactors, will result poorer removal of DOM than without preozonation. If ozonation is to be widely considered as a pretreatment, these implications of DOM fate in coagulation should be seriously taken into account. ” 3° 3 ps ae + + * i ieee « SO “SByy 900 jo 3 18h 80 i ‘ong 006 » me Q 40 e6aed, mot mn? Fig. 16. Removal of DOC and aluminium with Hohloh-humic acid before and after ozonation (Jekel, 1936)Congulation and Noe separation v PROPERTIES OF FLOCS WITH ORGANIC MATTER Alumo-humate (DOM) flocs are fluffy, more voluminous and fragile when compared to alumo-mineral articles flocs. Floc density ts known to increase with increase in rainerai particle content, Density and strength of flocs or agglomerates affects both the flocculation-setding process and the contact coagulation filtration process. Poorer settling of flocs formed in highly colored low turbidity waters and early ‘breakthroughs and short runs in filtration of such waters are known to treatment plant operators. ‘Quantitative parameters of floc and filter deposit strength in terms of floc breakup constants K, and filter deposit detachment constants Kp, were studied and reported by Rebhun, et al. (1984) and Rebhun (1990) and shown in Table 7. TABLE 7 loc formation and breakup constants in flocculation attachment and detachment constants in filtration (Rebhun, 1990) Disperson + Flocculant Floceulation Filtration Kpx1o4 Kg x to? K,yxl03 Kx 103 Glay and alum a1 637 36 ae Clay and polymer 193 0.56 438 25 ‘Humics and alum 2a 140 34 700 (Ke Floc formation constant, K, - Floe attachment constant) “The floc breakup constant for alum humic floc was two times higher then for alumo-clay mineral floc and the filter detachment constant was 15 times higher for alumo humate deposit than for alumo-clay mineral deposit (Bratby, 1980) reported that breakup constant for alum + humic flocs were 10 times higher than foralum + kaolinite flocs. ‘Densities of alumo-humate flocs can be detived from Tambo and Watanabe (1979; (Fig. 17) floc density plots and for alumo-humate filter deposits from Rebhun, et al. (1984). In both cases the alumo-humate agglomerates were of much lower densities than alumo-mineral agglomerates under similar conditions. ‘There are significant engineering and cost implications related to the strength and densities of these agglomerates, AT 18g, s10% ene ge 77 woe Sse BAo 10 me : : é Flee siomeree, 10% Fig. 17. Plots of floc density function of color-aluminium (2) and color-PACI (®) flocs (Tambo & Watanab, 1979)18 M, REBHUN ap? M, LURIE LARGE AQUATIC ORGANISMS IN FLOC FORMATION Up wo this point our discussions and deliberations dealt with macromolecules 2 to 20 nm, colloidal submicron and micron size particulates, In real surface water situation, we also encounter organic *paticles” of entirely different type,mnultimicron in size (10,000-20,000 am)living and motile (moving), such as lage algae, agli, oc. Berard Chasen (1991) desrlbed acculation suds wit such panicles (Fig, 18). Some of these organisms affect floc properties by moving, escaping from being ‘entrapped in the floc, such as the flagglclate in the last figure. Wat fascinating, such floc behaviour may be aa \ fs earners i iy. ui” zed a, i. : Ble, as Creer eee baw tpmlne ove Stall SI Feet inate en 6) petit nebo mt sete eedcek stasis tye er iceman Stemaann f 4 2} Pages Crypsomanas eoua ie Mhasdorona Fig. 18. Large microorganisms in the flocculation process (Bernhardt & 6 Chasen, 3) ” CONCLUDING REMARKS Congulation-Flocculation is a fascinating area. Organic matter in water became a major topic in water technology and in the management of the aquatic environment, Reading the papers of the many scientists, reviewed in this work and utilizing their tindings in my owa way was enlightening and an intellectual ‘experience. Thanks to all of them and to participants of the Joint Specialized Conference. REFERENCES Achard, F.K. (1786). Chemische Utersuchung des Torfts. Crell's Chem. 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