Wat. Res. Vol. 20, No. 1, pp. 21-26. 1986 Printed in Great Britain.

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0043-1354/86 $3.00 + 0.00 Copyright ~-~ 1986 Pergamon Press Ltd

BATCH METAL REMOVAL BY PEAT
KINETICS AND THERMODYNAMICS

THIERRY GOSSETI, JEAN-Luc TRANCARTI and DANIEL R. THI~VENOT 2'* ~Agence Financi6re de Bassin Seine-Normandie, C.R.E.A.T.E., 5,7,9, Boulevard Louis Seguin, 92700 Colombes and 2Laboratoire de Bio61ectrochimie et Analyse du Milieu, L.A. 329 du C.N.R.S., U.E.R. de Sciences, Universit6 Paris-Val de Marne, Avenue du G6n6ral de Gaulle, 94010 Cr6teil Cedex, France
(Received September 1984)

Abstract--Peat moss, a natural inexpensive material, is able to play an important rrle in treatment processes of metal-bearing industrial effluents since it adsorbs, complexes or exchanges various metal cations. This paper presents kinetics and thermodynamics of batch metal removal reactions by 50 g l(dry wt) eutrophic or oligotrophic peat particles using Cu 2+, Cd :÷, Zn 2÷ and Ni 2÷ concentrations ranging from 0.01 to 100raM. Metal cation removal reactions are moderately rapid in l0 mM metal unbuffered solutions: the forward kinetic constant ranges between 0.005 and 0.17 M-Is-~, and equilibrium is reached within about 1 h. Under these conditions of pH (2.2-4.2) and concentrations, apparent binding equilibrium constants were found to range between 2 and 3150 M -~ depending upon the peat origin and the metal cation. In 0-6.5 pH-buffered metal cation solutions, the four cations binding reactions behaved differently demonstrating that metal binding equilibrium constant decrease in the order Ni 2+ > Cu 2+ > Cd 2+ = Zn 2÷. When pH is higher than 6.7, more than 90% of a 10 mM metal cation solution is removed by 50 g 1-t peat particles and metal binding capacities equal 200 mmol kg- ~ dry wt, whatever the metal nature and the peat origin. Except for nickel cation which is very strongly bound to peat, all metal cations are completely released when pH is fixed below 1.5.
Key words--peat, heavy metals, ion exchange, complexation, kinetics, thermodynamics

INTRODUCTION Surface water is often polluted by the improper disposal of metal-bearing industrial effluents. Numerous approaches have been studied for the development of metal trapping materials. Besides the highly effective artificial chelating polymers containing, for example, thiol functions (Deratani and S6bille, 198l), cheap natural polymeric materials, such as humic substances or peat, have been extensively studied. They indeed strongly adsorb, exchange or complex various metal cations using their carboxylic, phenolic and hydroxylic functional groups (Smith et al., 1977; W o l f et al., 1977; Takamatsu et al., 1978; Sipos et al., 1978; Meisel et al., 1979; Bloom and McBride, 1979). Following Coupal and Lalancette (1976), it has been suggested by several research groups to use peat moss in beds or columns for metal-containing effluent treatment (Poots et al., 1978; Poots and McKay, 1980; Chaney and Hundemann, 1979; M c K a y 1980; Dissanayake and Weerasooriya, 1981). Before attempting to develop such a peat treatment process in columns, we decided to study the metal removal reactions in batch and determine their kinetics (Gosset et al., 1984) and thermodynamics. We present here results obtained *To whom all correspondence should be addressed. 21

with metals cations playing an important r61e in water quality, i.e. copper, cadmium, zinc and nickel.

MATERIALS AND METHODS

Peat and reagents Two types of peat were studied: an oligotrophic peat called "Floratorf" and an eutrophic one called "Heurteauville peat", both being commercially available in France for agricultural purposes. The metallic salts used were cupric nitrate, cadmium acetate, zinc and nickel chlorides dissolved in slightly acidified distilled water. All metallic salts and chemicals were of analytical grade (Prolabo P.A.). Peat treatment In order to homogenize peat samples and to clear them from metallic cations which they could have previously fixed, we pretreated peat in five steps:

(a) 24h drying at 100°C; (b) dry sieving with a shaker (Prolabo) to 0.5-1.25 or 1.25-5 mm particle size; (c) acidification of the sieved samples, I0 g of dry peat being thoroughly shaken for 2 h with 100 ml of l M HCl; (d) washing with deionized water until filtrate reaches pH 4; (e) 24 h drying at 70°C. When the effect of acidification procedure of peat samples was studied, steps (c) and (d) were avoided. In particle size dependence studies, peat treatment procedure avoided steps (b), (c), (d) and (e).

e. " I n ~ ~ " 1 I 0 Time (h) I 1. i.e.kl/k: KINETICS OF METAL BINDING In order to optimize the residence time o f industrial waste water in peat columns. the simplest way to describe these metal removal reactions by peat is: P + M~. Thermo(Ivnamic constants determination Two grams of formerly acidified or non-acidified peat. using standard addition procedure and recording 2-3 polarograms per solution. including or omitting step (c) in peat treatment procedure.~-PM with K' where (P) = the concentration o f peat binding sites (M).45 iLm membrane filter (Millipore) before metal determination. pH dependence Two and half grams of natural peat.0 0. All samples were filtered through a 0. one should observe a 10 or 20 m M p r o t o n concentration increase and a pH shift from 3-4 to approx.~--C/° " _ . element per element. 1979.2 ml of 1 M perchloric acid..1100 mV/AgC1. the number o f p r o t o n released per metal cation b o u n d to peat is always lower than 0. Indeed if 1 or 2 p r o t o n s were released during each metal binding reaction on peat.7 4 0 and -420mV/AgCI respectively for copper. 1984). unsieved and non acidified.e. 0.25. it seems clear that. For determinations of free metal at lower concentrations. Cd 2+. pH was adjusted by addition of I M perchloric acid or of 1M sodium hydroxyde. Figure I shows the evolution of metal a m o u n t s bound to eutrophic peat.2 and 0 . we studied the kinetics of t 0 m M metal cation removal by 5 0 g l '~ peat particles in batch experiments. using 1 100 mM initial metal concentrations. ([Z) zinc and (A) nickel unbuffered solutions: final pH ranged from 2. under these conditions. complexing or adsorption reactions are more i m p o r t a n t than ion exchange reactions in metal removal processes by peat.2 ml samples were taken from the supernatant and added to 10 ml of deionized water formerly acidified with 0. in absence o f any metal. The initial concentrations of metallic cations were fixed to values ranging between 0. 5 g acidified (dry wt) 0. Bloom and McBride. i. Furthermore. Peat particles werc stirred for 3 h and centrifuged 5min at 12. Zn 2~ and NIX: peat suspensions were shaken during 2 h at room temperature and 1 ml samples were collected every 15 min and centrifuged during 5min at 12. ( + ) cadmium. pH was measured at the beginning of reactions and after 1 h of mixing and then readjusted if necessary. 1985). we used anodic stripping differential pulse polarography with a preconcentration step of 90 s at . 50 g l ~ (dry wt). 1.5 I 2 0 I 2 5 "0. i. Meisel et al. including or omitting step (c) and (d) in the peat treatment procedure. Aho and T u m m a v u o r i . i.000 rpm. solutions in contact with peat presented some pH variations: pH decreases were found to .e. The superimposed constant amplitude pulse was 50 mV and the mercury drop period fixed at 1 s. the pH variations observed when peat was suspended into 10mM initial metal ion solutions were similar to those observed when equal a m o u n t s o f peat were suspended in deionized water. Table 1 shows that H / M ratios. Concentration of metallic cations were determined by flame atomic absorption spectrophotometry on supernatants as previously mentioned. In absence o f stoichiometric data.e. were thoroughly mixed into 100ml of 10raM solution of one of the following metallic cations: Cu 2+. 6 p H units whatever the metal and the peat origin. the pH buffering capacity of peat weak acid groups.2. 1976. 1979. were thoroughly mixed into 40 ml metal solution during 2 h at room temperature. For high free metal concentrations. 200 -- ~ t60 -- .m e t a l cation interactions. Boyd et al. . range between 0. proton release when metal cations bind to peat (Bunzl et al. limiting possible pH variations related to previously mentioned proton release (Attal et al. Kinetic constants determination Five grams of formerly acidified or non-acidified peat. analysis procedure was direct differential pulse polarography.e.. were suspended in 50 mt of 10mM metal cation solutions. Metal determinations were performed by direct differential pulse polarography with initial potentials of + 140.__ ~ ~ o_ 80 40 a/ . All kinetic and thermodynamic batch experiments used the same concentration of peat particles.01 and 100 mM. Metal concentrations were calculated by averaging 3-5 determinations with the same solution and using calibration curves taking into account a blank and 3 standards. i. i.000 rpm. As these first experiments were made without buffering pH. i. Heavy metals were measured. zinc + nickel and cadmium and potential sweep rate fixed to . Although we do not intend in such experiments to identify the chemical or physical nature o f p e a t . 2. 1981): some ion exchange reactions.e. 1979.22 THIERRY GOSSET eta/.25 mm peat shaken in 100 ml 10 mM (ll) copper..5 1. Thus pH variations encountered when peat particles are mixed with metal cation solutions result probably from: the acidic properties of carboxylic and phenolic functional groups present in humic substances (Bloom and McBride. The analysis by acetylene-air flame atomic absorption spectrophotometry was performed with a Perkin-Elmer 2380 and single element hollow cathode lamps.. Kinetics of metal binding reactions on eutrophic peat. Supernatants were analysed using either differential pulse polarography or flame atomic absorption.5 mV s-~.5 Fig. (PM) (P)(M) . dried 24 h at 100 ('. The electrochemical assembly contained a static mercury drop electrode (EGG PAR 303) connected to a differential pulse polarograph (EGG PAR 364).2 to 4.

p e a t . On the few examples tested. (P)in metal binding capacitiesestimated by batch metal binding experiments using 100 mM metal cation solutions bufferedat pH equal to final pH in this table (Gangneux et al.5-1.. eutr. Using these values for k~ and K'. respectively.0 0.026 5.(PM).013 3.8 Eo4 0.25 Ni 0. 0.25 Ni 0.(PM) I n . olig.' exp ([(M).2 E-3 0. K' (mM) (M -I) pH (final) 23 Metal H/M ac. olig.005 1. 100 m M . Slopes o f these straight lines.6 E-3 0.5-1.) oligotrophic. Lines were obtained by least square regression: slopes of these lines and correlation coefficients are given in Table 1. .118 3.63 7. These metal binding capacities (P)~. 0.01 ac.25 ac. (olig.25 Zn 0.. (M) = the concentration o f free metal in solution (M). in solutions whose p H was buffered between 0 and 6 (Gangneux et al.5 E-4 0. A p p a r e n t conditional stability constants K ' were calculated taking into account equilibrium concentrations o f free (M) and b o u n d (PM) metal and the a m o u n t (P)m o f metal binding sites on peat.~m]" k. 2. (M)~.~.004 (eutr.2 0.25 Cu 0.~ . nat.) acidified and (nat. Whereas k~ was found to range between 0.75 27 30 3.98 483 27 3. 1. the highest values being obtained for copper removal by eutrophic peat (Table 1). olig.1 E-3 0.0005 ac. W h e n other 25 I Fig.n .Batch metal removal by peat Table 1. Binding kinetic c o n s t a n t k~ was obtained assuming that: reverse reaction 2 was negligible.) eutrophic. This result may be interpreted as a structure modification o f this natural matter when acid pretreated.5 1.6 0.98 3150 20 4. eutr.98 34 52 ac.1 (M)i.03 ac.) unsieved and unacidified peat.25 Cu 0.6 30 ac. we c o m p a r e d the experimental evolution o f b o u n d metal (PM) and c o r r e s p o n d i n g calculated curves (where reverse reactions were neglected): (PM) = exp([(M)~. . 1. we were not able to obtain such good fit o f experimental data.050 1. eutr.5 20 where (PM) and (PM)lim are the variable and equilibrium b o u n d metal concentrations (M). ) unsieved and unacidified or acidified ( + ) 0.6 49 0. were estimated from b o u n d metal amounts.m e t a l cation stoichiometry was c o n s t a n t for all experimental conditions and equal to one metal cation per peat binding site.03 ac.74 2. 0." t) .041 1.25 5 Cu 0. 2 ~ .(M)i n (PM)lim (M)~. Kinetic plots similar to those presented on Fig..e.1 39 2.170 0.5 1. unsieved and n o n acidified oligotrophic or eutrophic peat samples seemed to bind copper more rapidly and efficiently than sieved and acidified ones. (M)in .(PM)lim ." • / / ~.im 1250 1ooo 750 5OO i + .25 mm or (A) 1.0 eutr. is the initial free metal concentration (M). eutr.(PM)..96 355 25 2. 2 were found to range between 2 and 3150 M .t s ~) and k2(s ~) are the forward and reverse kinetic constant. giving k~.3 E-4 0.01 s -~. 2 were f o u n d to be linear with correlation coefficients higher than 0. .036 4.31 5. 1985).7 on 9 curves over 12. (ac.5-1. nat.061 1. eutr. allowed us to calculate the reverse kinetic c o n s t a n t k2 using previously mentioned a p p a r e n t stability c o n s t a n t K ' (Table 1).74 41 55 2. Metal binding kinetics and equilibrium constants using 50 g 1-I peat in unbuffered 10 mM metal cation solutions Peat type Particle size (ram) kt (M Is i) kz (s i) Cor.1 (PM).25 Cd 0. i. A p p a r e n t binding constants at p H 2 . and by plotting calculated kt " t assumptions than those listed above were tested. k l ( M . olig 0.17 M .2 0.5 ac. 1985).5-1.6 E-2 0. i / / (M)i n (PM)lim .0 Time (h) 1.60 28 30 3.2 E°4 0. (H/M) proton/metal exchange ratios.8 0.7 E-3 0.5 1. overall reaction kinetic was limited by the binding reaction itself and not by diffusion o f species. coeff. . 0. k 2 values were always smaller than 0.0 olig.8 46 4.005 and 0. Eutrophic peat pretreatment and size dependence of copper binding reaction kinetics: determination of forward kinetic constant k I .23 ac. (PM) = the concentration o f metal b o u n d to peat (M) K ' = the a p p a r e n t conditional stability c o n s t a n t at experimental p H (M ~). olig.25-5 Cu 0.2 0.25 Zn 0.7 E-3 0. using higher metal cation concentrations. Cu 0. 5 g dry wt ( .(PM) vs time l 25O 0 O0 05 1.7 E-4 0. 0. -.~ s . with the highest values for copper removal by eutrophic peat. (r 2) (P)i.~m] "k.3 E-4 0.5-1. 0.060 1.77 5. . 0.85 41 26 2.03 10. "t) . Cu 0.055 9.25-5 mm peat suspended in 100 ml l0 mM copper unbuffered solutions.5-1.25 Cd 0.

76 • / / -75 -85 I -5 [ -4 I -3 I -2 I -4 I 0 log ( M ) ( m o l t-1) Fig. may vary due to unbuffered conditions. this seems to indicate that the peat-metal complex stoichiometry and thermodynamic are probably dependent on the free metal concentration and on pH which. THIERRY GOSSET('t al. taking into account kinetic constants values presented in Table 1.b) and Bunzl e t al. Furthermore. no sorption or binding saturation was observed in these unbuffered solutions. 2 g (dry wt) acidified 0. . slopes ranging between 0.5-1. especially for oligotrophic peat.5-1.1 M in 50 g l ' peat suspensions. Lines correspond to calculated fixed copper amounts. This result is of extreme importance if one thinks of the possible applications of peat columns in waste water treatment: metal binding functions should not dissolve into the flowing -25 I -35 ~ -45 E -5 5 n ~ -65 • .2-0. Kinetics of metal ion binding by peat has been previously studied by Bunzl (1974a. and before each experiment 0. total soluble concentrations. in these experiments. free and labile species. that the bound to free metal ratio (PM)/(M) was maximum for total metal concentrations in the 0. METAL REMOVAL THERMODYNAMICS In order to use peat for environmental applications.e. As shown on Fig.01-100ram initial concentration range• Same symbols as Figs 1 and 4.5 or 5 g I t (wet wt) peat particles were allowed to establish swelling equilibrium in well-stirred deionized water for several hours. Metal binding isotherms on eutrophic peat in unbuffered solutions. Same symbols as Fig. 3 where such a comparison is presented.. reaction half-times ranging between 5 and 15 s (instead of 15-30 min in this paper). we found it necessary to determine the peat metal cation binding isotherms for different unbuffered metal solutions equilibrated with two types of peat samples (Figs 4 and 5). even when total metal concentration reached 0. (1976) using either continuous or discrete metal cation addition to preacidified sphagnum peat in batch experiments. Fig.24 200 . 5. i. Such a difference of magnitude in kinetic constants may be related to the large differences in experimental conditions: Bunzl used to shred and sieve peat samples in water to a particle size of 0. 4. . Such agreement supports our set of assumptions concerning these kinetics and especially the assumption of a chemical rate limiting step: flow-through experiments in columns should be used to confirm such kinetic behaviour.45/~m filtration. Differences were generally within the range of reproductibility of such heterogeneous experiments. 3. . J L t I -6 -5 -4 -3 -2 -1 0 Time ( h ) log ( M } ( m o l [-~) Fig.~ _J ..5 " o E ~° i2 o O0 .01 lOOmM initial concentration range.e. 2 for experimental data.25 mm peat equilibrated with 40ml deionized water containing metal cations in the 0. such isotherms were drawn using either polarographic data..25 mm peat equilibrated with 40 ml deionized water containing metal cations in the 0. 1. differences between experimental and calculated data being usually smaller than 6%.0 l 25 -8 ! 5 L . Same symbols as Fig.5 and 2. Our 24 h drying procedure of non-shredded peat samples may have significantly decreased swelling and metal binding kinetics of much more concentrated peat suspensions (50 g I ' dry wt). 2 g (dry wt) acidified 0. : -7: 160 ~ 12o .. . indicating the negligible importance of soluble humic metal complexes under our experimental conditions. none of these curves is linear. We frequently observed.. i.1-1 mM range: such a concentration range should correspond to the maximum efficiency of a waste water treatment process using peat columns or batches.e. In order to evaluate the occurrence of soluble forms of complexed metal. . agreement is generally good. i.0.7 mm. Whatever the peat origin and the metal cation.>/ .' / I 05 i t 0 I ]5 1 2. Metal binding isotherms on oligotrophic peat in unbuffered solutions. about 5%. or atomic absorption data after 0.. Calculated and experimental evolution of copper fixed on peat: eutrophic peat pretreatment and size dependence... . Reaction kinetics were much more rapid.

2 to 4. 50 and 90% extraction and maximum capacities observed Eutrophic peat Oligotrophic peat pH values for Metal cation Cu .0 0 50% extr. pH dependence of the metal uptake of eutrophic peat. 1979.. .0 Maximum 90% capacity extr. 1986).3/"/ I/% I 1 2 o 0 I 3 I 4 I 5 I 6 I 7 pH Fig. 1oo . We found that such experiments need several p H adjustments with small additions of strong acid or base: indeed several hours are necessary to obtain a stable p H in a solution in contact with peat (Attal et aL.5 0 3.t ) 3. 6..2 50% extr. It demonstrates that metal-peat interactions present the same stoichiometries and that the available binding capacities are similar for eutrophic and oligotrophic peat. .//// /. 2. The same pH dependence of metal distribution coefficient was demonstrated by A h o and Tummavuori (1984) Table 2.7 200 4. 2.2 and 4. 7. This study was performed at p H lower than 6.~. 1984).-/ /°° ~.6 180 6. 1.. Although these experiments enable the comparison of the respective metal-peat binding energetics. even in very acidic media.3 1. cadmium and zinc present a similar p H dependence and are less strongly fixed than the two other cations. (retoolkg. the addition of metal cations and/or strong acid or base does not seem to decrease significantly the time which is necessary for peat to equilibrate its acido-basic functions.8 2. unsieved and unacidified peat equilibrated with 10 mM metal cation solutions: pH values for 10. .6 190 4.i ) 4. Taking into account pH values for 50% metal binding capacities. pH dependence of the metal uptake of oligotrophic peat.0 2.2 in the previously mentioned unbuffered solutions (Table 1).6-2. 1976. 6. pH values for Maximum 90% capacity extr. equilibrium constants may be compared: Ni 2+ > Cu 2+ > Zn 2+ = Cd 2+. Competition between proton and metal ion exchange or complexation is an indirect method to compare their energetics (Stumm and M o r g a n 1981).7 200 4.3 3.0 200 10% extr.2-1. We have observed that p H presents a strong influence on metal ion binding equilibria when the total concentration of metal cation equals 1 0 m M . 0. Giesy.5 3. ~o40 2o As equilibrium p H in 50 g 1-I peat suspensions had been found to range between 2. -. varies from 0 to almost 100% within 4-5 p H units (Figs 6 and 7 in Table 2). (I-1) zinc or (A) nickel solutions. 2. we decided to study more precisely the pH dependence of metal removal thermodynamics. these results are in good agreement with metal-humic substances previous results (Bunzl et al.1 3.2 Cd Zn Ni 1. (mmolk g . Except for nickel and copper respective positions.. above pH 3 copper binding is very similar to nickel. A _ 25 o 100 80- pH DEPENDENCE OF THE METAL REMOVAL T H E R M O D Y N A M I C S ////o . pH dependence of metal removal by 50 g l i dried. . Indeed the percentage of metal extraction. they also show clearly that the maximum binding capacities in 10 m M metal cation solutions are very similar for the different metals and peats: all values range between 180 and 200 mmol kg -~ dry wt (Table 2). 1983).1 1.5 g unsieved and unacidified peat equilibrated with 50 ml 10 mM metal cation solutions either acidified by 1 M perchloric acid or alcalinised by I M sodium hydroxide: (ll) copper.5 190 10% extr.e. (+) cadmium. (PM)/[(PM) + (M)] ratio.7 170 4.Batch metal removal by peat through solutions (Chaney and Hundemann.5 in order to prevent precipitation o f metal hydroxides.-~ eo _ . but below pH 3 copper may be completely released from peat.0 190 5. Such a result is not obvious when metal binding experiments are achieved in unbuffered media of pH ranging from 2.5 1. i. Same symbols as Fig.6 .e~. Independently of peat origin three important results were obtained in relation to metal cation: nickel is the most strongly fixed. Aho and Tummavuori./o / 4o • ~ 20 o 0 I 1 I 2 I 3 I 4 I 5 I 6 I 7 DH Fig.2 (Figs 1-5).

organic-rich waters. 25. 1241-1242. Previously. REFERENCES Aho M. hung. A 6. Giesy J. Soc. 53. 1071-1076.. P. (19803 Flow characteristics and parameters relating to use of peat and wood as cheap adsorbent materials for waste water purification. Peat as a metal-trapping material in the purification of industrial effluents. who worked with peat columns: they found copper binding capacities ranging between 200 and 300 m m o l kg ' using 0. R. Chemosphere 5. 68-73. Soc. was equal to the a m o u n t of metal released during the acidification step. Bunzl K. Boyd S. V. (1981) Aquatic Chemistry. Cu 2+ . (2) The metal removal efficiency in unbuffered solutions is significant in a very large c o n c e n t r a t i o n range. 51. Am.1 3 0 0 m m o l Cd 2+. MacCarthy P. (1979) Biopolymer-metal complex systems--VII. 207-213. (19783 Biopolymer metal complex systems-I1. and S6bille B. Cd -'~ and Zn 2~ by humic substances. A 6. (19783 Basic dye adsorption on peat. (19833 Metal binding capacity of soft. peat columns have been constructed a n d their h y d r o d y n a m i c a n d chemical properties and characteristics are u n d e r investigation. J. Lalancette J. 25. a d s o r p t i o n or ionexchange. 125. J. very thin peat layers or beds as proposed by Lalancette in its F r e n c h patent of 1972 seem very unlikely to achieve a complete metal removal by complexation.e.e. Brevet franqais No. Wolf A. (1974a) Kinetics of ion exchange in soil organic matter--ll. Deer A. and Mark H. Fed. Chaney R.. Attal A. (1981) Research Report. J. Cr6teit. 119773 Effects of Ca 2' ions on the absorption of Pb 2'. Schmidt W. All these metal binding capacities are s o m e w h a t smaller than those o b t a i n e d recently by G a n g n e u x et al. Deratani A. acid. R. B. R. Differential ion exchange reactions of pb2+-ions to humic acid and peat.5 m M metal solutions. CONCLUSION F o u r m a j o r results were found d u r i n g these batch experiments with eutrophic a n d oligotrophic peat: (l) Peat is able to strongly bind copper. Pollut.. 343-356. Toxic. Sommers L. P. McKay G. (19803 Peat--an adsorbent filtration medium for waste water treatment. 31 42. Bloom P. (4) Except for nickel cation which seems so strongly complexed on peat that at pH 1. Finally. 28.. 233-238. Bunzl et al. 27. a b o u t 5%. P. and McBride M. Bunzl K. L. Wat. (1979) Metal ion binding and exchange with hydrogen ions in acid-washed peat. 6 0 0 C d 2+ and 6 5 0 C u 2~ using 0. zinc and nickel cations in solution. and Nelson D. Meisel J. Communication to the Second International Conference on Humic Suhstances. Dietl F. F. 47 53. Dissanayake C. a n 2~ and Ca 2+. and Hundemann P. L. J. (1985) using 100 m M metal cation buffered solutions and 50 g l t dry wt eutrophic a n d oligotrophic peat suspensions: 6 5 0 . W. and Th+venot D. J. c a d m i u m and zinc may be easily removed from peat during an acid treatment. 407441. Soil Sci. J. envir. a m a x i m u m capacity of a b o u t 200 m m o l k g ~ dry wt being obtained at pH larger t h a n 6. 2nd edition. Suo 35. L. i. Z n 2+ or Ni 2+ kg t. S!pos S.2--2 h a l f of the m a x i m u m capacity is attained.7 8 0 m m o l C u Z + g ~ dry wt a n d 1 0 0 0 . copper. Soc. B. as estimated from the metal removal in solution.1-1 m M range. 687-692. and Th6venot D.. Bunzl K. the m a x i m u m extraction ratios being o b t a i n e d in the 0.01 to 1 0 0 m M . 32 4l. 142tter Serv. 633. Soc. Jr (1977) Sulfuric acid treatment of peat for cation exchange. Gangneux J. Control Fed... Duhl. and Weerasooriya S. 1972. hung. p. (19853 Research report. (1976) The treatment of waste waters with peat moss. R. (19843 Preliminary report on kinetics of batch metal complexation by peat. 49. (3) Batch reaction rates are such that a residence time seems necessary for a complete t r e a t m e n t of solutions on columns. J. Study of ion exchange and redox capacity of peat humic substances. Stumm W. Trancart J. Gosset T. (19783 Determination of stability constants of metal humic acid complexes by potentiometric titration and ion-selective electrodes. Scient.--638. C d : ' . 8 D6c. (19843 On the ion-exchange properties of peat--IV. c a d m i u m . Pollut. Control. . 84. 1742 1746. Proc. Am. 43. the a m o u n t of metal fixed on peat. and McKay G. and Th6venot D. Physical properties of humic substances and their metal complexes. 357-359. C. J. 625.01 to 0. Acta agron. Water Res. 401. (1974b) Kinetics of ion exchange in soil organic matter--Ill. and Mady G.26 THIERRY GOSSET el al.7 when the initial metal c o n c e n t r a t i o n s equal 10 m M . R. Comptexation en batch de cations m&alliques par la tourbe fi pH fix& Universit6 Paris-Val de Marne. Submitted for publication. Lakatos B. thus. The effect of experimental conditions on ion exchange properties of sphagnum peat. 72. Cu 2~. New York. B. some metal removal and recovery experiments were performed with copper solutions: within the experimental range o f error. France. Ser. and Yoshida T. McKay G. England. Dekany I. (1981) Copper (II) and iron (III) complexation by the carboxylate group of humic acid. J. M. Takamatsu T. Proc.. from 0. Gosset T. (19793 Use of peat moss columns to remove cadmium from waste waters. Chem. Soil Sci. (1976) Kinetics of ion exchange in soil organic matter--IV. (1972) Proc6d6 d'6puration d'eau pollute par un 616ment m&allique et de r6cup6ration dudit 616ment. 377 386. and Schmidt W. Soil Sci. Poots V. (19863 Caract6risation physico-chimique des tourbes utilis6es en epuration des eaux domestiques. M. 17-21. Ion exchange during continuous addition of pb2+-ions to humic acid and peat. Gosset T. Yu T. Acta agron. E. Wiley. Sipos E. and Sansoni B. 10.. Coupal B.43798. (1976) had f o u n d a p p a r e n t ion exchange capacities o f s p h a g n u m peat at pH 4 equal to 5 0 0 m m o l Z w ' * kg ~ dry wt. Taking into account the data o b t a i n e d d u r i n g these batch experiments. Smith E. 517-532.. T. and Healy J. 45. and Morgan J.. War. 203 224. 75-83..0025 m M Cu 2+ solutions. Meisel J. E. Dubl. J. J. R. Poots V. and Lakatos B. Soil Sci. i. Analvt. 6. and Lalancette J. R.. Scr. Stud. 61-76. Chem. J. Soil Sci.. (1981) Metal ion extraction with a thiol hydrophilic resin. 27. F. Scient. Bunzl K. Soil Sci. Adsorption and desorption o f P b -'+ . Birmingham.. abstract pp. envir. 17. and Tummavuori J.

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