Wat. Res. Vol. 20, No. I1, pp. 1397-1406, 1986 Printed in Great Britain.

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

A N O D I C STRIPPING VOLTAMMETRIC STUDY OF THE LABILITY OF Cd, Pb, Cu IONS SORBED ON H U M I C ACID PARTICLES
T. U. AUALIITIAand W. F. PICKERING Chemistry Department, University of Newcastle, N.S.W. 2308, Australia (Received July 1985) Abstract--The sorption of Cd, Pb and Cu by humic acid particles has been studied at #g 1-t levels using A.S.V. on a Hg film electrode as the measuring technique. The variables examined included amount of solid present (0.01--0.2% w/v), initial metal ion concn (10--100#g l-l), systems pH (5.3, 6.35, 8.15) and base electrolyte composition. The calculated capacity for specific adsorption of the metal ions was a few mmol M 2+ kg -~, or less. The apparent lability of part of the sorbed material was examined by analysing the base solution before and after filtering, and by adding Chelex 100 particles to the suspension. Some sorbed Cd2+ was A.S.V. labile, another fraction transferred to the resin. The effect of solution reactions on uptake was studied by making the 1 M CH3COONa base solution 0.2 M in a range of Na + salts (8 different anions), or in carboxylic acid content (5 acids) or in compounds having S-type bonding groups. Formation of complex ions in solution altered the extent of metal ion uptake, and in the case ofCu A.S.V. peak size, shape and position were varied. It is suggested that natural waters containing suspended matter should be analysed by A.S.V. "as received", as well as after filtration since response differences provide guidance in respect to the lability of sorbed ions. Key words--voltametry, anodic stripping, A.S.V., colloid effects, heavy metal-colloid sorption, humic acid-metal sorption, fulvic acid-metal sorption

INTRODUCTION

Colloidal particles contribute greatly to the movement and distribution of metal ions within a waterway system with up to 95% of the heavy metals transported by fresh waters from land to sea possibly being associated with particulate matter (Martin and Meybeck, 1979). During migration, sorbed species may be continuously re-distributed between the aqueous and solid phases, until finally incorporated in bed sediments following flocculation (e.g. in estuaries) and particle settling (Hart, 1981). The complexity of natural systems and limited understanding of many of the chemical processes involved has hindered rigorous evaluation of the particulate role. Distribution patterns are usually discerned on the basis of an analysis of metal content of >45/~m particles and aqueous phases separately, but this approach ignores the possibility that some of the sorbed ion may be quite labile (i.e. loosely bound and mobile under the influence of an applied chemical or electrical potential), and thus available for transfer (e.g. to biological systems). Several more complex schemes have been devised, and these allocate the different species present into more specific categories. The results demonstrate, inter alia that a significant fraction of the total metal content can be associated with colloidal organic matter (Gardiner, 1974; Batley and Florence, 1976; Turekian, 1977; Batley and Gardiner, 1978; Florence and Batley, 1977, 1980).

When using anodic stripping voltammetry (A.S.V.) as the measuring technique, adding humic acid to dilute metal ion solutions and synthetic seawater has been found to alter the magnitude of the peak currents (ip) and occasionally the peak potential (Ep) positions (thereby signifying formation of a new chemical species), with the magnitude of the effect varying with pH (Ernst et al., 1975; Sagberg and Lund, 1982; Ugapo and Pickering, 1985). Bonding between metal ions and humic acids itself varies with pH, relative concentrations and type of functional groups involved (Zurino et al., 1975; Stevenson, 1977). These parameters also influence the amount of metal ion that can be sorbed by the solids (Farrah and Picketing, 1978). Extraction studies using solids loaded with > 100 mmol M 2+ per kg humic acid, indicate that a high proportion of the M 2+ is ion-exchangeable, and may thus be A.S.V. labile (Slavek et al., 1982). This prediction was partly substantiated when suspensions of humic acid containing /agl -I amounts of Me 2+ were analysed before and after filtration (Ugapo and Pickering, 1985). A voltammetric study of Pb(II) solutions containing hydrous oxide suspensions, however, supports the theoretical viewpoint that metal ions adsorbed on particle surfaces are essentially nonlabile (Goncalves et al., 1985). In view of the important role that suspended organic matter may play in metal ion transport, a study has been made of metal sorption, and factors influencing uptake and lability, using initial M 2+

1397

1398

T . U . AUALIITIAand W. F. PICKERING of limited solubility in restricted pH regions (Slavek and Pickering, 1981). To study competition between the Chelex-100 resin (CR) and humic acids for metal ions, mixed additions were also made e.g. 2 mg HA plus varying amounts of CR. In another series, the amount of solid present was kept constant (e.g. 2 mg HA, or 2 mg HA + 2 mg CR) and the concentration of metal ion was varied between 10 and 100 ,ug 1-~. To examine the effect of any interaction of the M 2+ ions with different inorganic anions, acetate base solutions (pH 5.3) were made 0.2 M in respect to many Na + salts (e.g. F-, CI-, Br , I - , NO3-, CNS-, H2PO4, CO~- and SO~-). Competition effects from added organic ligands was studied by including in the base solutions either diverse acid species (e.g. benzoic, nicotinic, glutaric, salicylic and tartaric acids) or compounds containing S and/or N functional groups (e.g. L-cysteine, thioacetamide, thiomalic acid, thiodiglycerol).

c o n c e n t r a t i o n s of the order encountered in mildly polluted waters (i.e. 1 0 - 1 0 0 # g l 1).

EXPERIMENTAL

The ESA Model 2014 Anodic Stripping Analyser uses thin ( ~ 150 nm) Hg films deposited on wax-saturated graphite rods. The 4 #mol of Hg coatings were renewed regularly, and with different films the reproducibility of Cd or Pb peak currents (100 # g l -I) was usually + 2 ~ , % R.S.D. As small differences in cell geometry contribute to peak current variance, in comparison studies one film (and cell) was used for each limited test sequence. A nitrogen stream ( ~ 40 cm 3 min-~) both deoxygenated and stirred the 5.0 cm 3 of assay solution held by the individual Analyser cells. The nominated supporting electrolyte solutions (usually 1 M CH3COONa, 0.2 M in C H 3 COOH, or NaC1, or other salts, pH ~ 5) were purified by electrolysis using an ESA Model 2014 P Reagent Cleaning System. The standard metal ion solutions were prepared from A.R. salts and de-ionized distilled water (Elga Model B116 Cartridge Deionizer). After dilution with supporting electrolyte solution, the comparison test solutions contained up to 100 #g 1 - t of Pb and Cd, or of Cu. The A.S.V. operating parameters used were: 5 min deaeration of suspensions in sample vials remote from the cell system; then when transferred to the electrode area, metal was deposited for 10min using an applied potential of - 6 0 0 mV (for Cu studies) or - 9 0 0 mV (Cd and for Pb); followed by stripping at a scan speed of 50 mV s-t to a cut-off potential of - 50 mV. Five analytical cycles were run on each test solution, and the A.S.V. traces were recorded on a fast response Richadenki Chart Recorder (Model B-181H) (chart speed, 30cmmin-I). With standard 100 #g I ~ solutions, the calculated precision of the successive deposition/stripping cycle results was generally < + 4% R.S.D. for Cd and Pb peaks, and < + 12% R.S.D. for Cu peaks. This poor result for Cu arose from peak growth in each successive cycle, a pattern of behaviour noted in other thin film, A.S.V. studies. (Schonberger and Pickering, 1980; Beveridge and Pickering, 1984; Ugapo and Pickering, 1985). Cu peaks change shape when deposition potentials < - 6 0 0 m V are used, and distortion also occurs if suspensions are in contact with the Hg film for prolonged periods prior to the analytical cycle (e.g. during deaeration). Pre-analysis film abrasion by particles causes enhancement of Cd and Pb peak currents (Ugapo and Picketing, 1985). To examine the effect of particle density on A.S.V. response, varying amounts of solid (0.5-10 mg per 5 cm 3) were added to clean vials containing supporting electrolyte solution loaded with either 100 #g I-t of both Cd and Pb or with 100~gl-~Cu. The vials were capped and shaken overnight on a sample agitator to ensure equilibration between phases. Besides weight of solid present, other experimental parameters were varied, including particle type, pH, electrolyte composition, and deposition potential. In some experiments the test solutions were subjected to A.S.V. analysis before and after filtration through an 0.45/~m membrane. Some comparison studies were also made with a membrane film interspersed between the Hg film and colloid suspension (a procedure recently described by Smart and Stewart, 1985). The solids added were two humic acids {supplied by Fluka A. G. [HA(F)] and Aldrich [HA(A)]}, a fulvic acid (FA) [supplied by Contech Ltd, Ottowa] and Na+-form Chelex 100 resin beads (200-400 mesh) [supplied by BioRad. Laboratories]. The humic acids were technical grade products whose adsorptive behaviour in the presence of mg 1-~ concentrations of M 2+ had been studied previously (Beveridge and Pickering, 1980). The fulvic acid has a mol. wt < 1000, and has been observed to form metal complexes

RESULTS AND DISCUSSION

Specific sorption of metal ions

The test solutions c o n t a i n e d > 1 mol 1 ~N a +, a n d acetate levels t h a t ensured conversion of metal ions into aceto-complexes, a n d these conditions should have minimized metal ion retention a t t r i b u t a b l e to simple ion exchange processes. F o r m a t i o n of a mixed complex involving acetate, metal ion a n d humic substance is a possibility, but in order to explain the change in A.S.V. peak size observed in the presence o f humic acids the metal species must be strongly b o u n d to the solid (i.e. equivalent to specific adsorption). The high lability of aceto-complexes facilitates electro-reduction processes, a n d presumably any specific b o n d i n g process. In an earlier study ( U g a p o a n d Pickering, 1985) e n h a n c e d u p t a k e attributable to a second retention m e c h a n i s m only became a p p a r e n t when the base solutions c o n t a i n e d <0.2 M CH3COONa. The a m o u n t of metal ion retained (or converted into a labile complex) varied with the weight of solid present (i.e. 0.02-0.1 w / v % ) as shown o n Fig. 1. Each plot s h o w n represents m e a n values o f triplicate analyses o n five different weights ( R . S . D . < + 6 % ) . The N a + - f o r m humic acid [HA(F)] retained m o r e per unit weight t h a n the p r e d o m i n a n t l y Ca2+-form solid [HA(A)], and uptakes by b o t h increased with increasing p H (cf. curves A', A", A " or F', F", F " c o r r e s p o n d i n g to p H 5.3, 6.35 a n d 8.15 respectively). Cu A.S.V. peaks were n o t discernible at p H > 5.3, a n d P b peaks split at pH 8.15 except at higher solid densities [cf. Fig. l(b)] where the two segments coalesced into a single b r o a d peak (the anodic segment was attributed to metal hydroxy species). The a m o u n t s retained, using any selected experimental conditions, decreased along the sequence Cu >>P b > Cd. W i t h increasing solid densities uptake levelled off, a trend indicative of some complicating factor. Specific s o r p t i o n m a y become negligible below some critical equilibrium solution level. Alternatively, the plateau could respond to the solubility o f the metal h u m a t e species formed at the surface. For-

(a)
tO 0 ~ , -

,4:F" ~.-----F~..--~A

'

~+_. . , . . . . _ . ~ ~ A

420

10 i

Copper

//

o. m 1 0 0o o
80
I

IF

I'

Lead
/

FC~An
AC~Zln

60

//

40

o.
o

20 0

~
//~,4,,/ ~ F ' " /~"~....---F'
/ -..-- .._.__~'
, 2 , 3 , 4 , 5

/ ~

F,4"
FA'

g 80 I -~ 60[4o

Cadmium

F,4'"

o r , 0

Weight of organic particulate (mg / 5 cm 3 )

2 (b)

!!

-E
E
0

I/' , / /

///
,'/

Humic acid present ( mg/5 cm 3 )

Fig. !. (a) Diagram sJaowing the effect of solid density (mg/5 cm 3) on the amount of metal ion sorbed or converted to non-labile metal complex. Letters A and F define the humic acid samples studied, FA represents a fulvic acid sample. Primes (', ", ") denote system pH's of 5.3, 6.35 and 8.15 respectively. The supporting electrolyte solution for most studies was l M CH3COONa, 0.2 M CH3COOH; superscripts c and n indicate base solutions where NaC1 was substituted for CH3 COOH or CH 3COONI-I4 replaced the Na + salt. Each curve was defined by a minimum of five experimental points; (b) Lead stripping peaks at pH 8.15. a and c indicate the anodic and cathodic peak segments respectively in the presence o f humic acids HA(A) and HA(F). 1399

1400

T.U. AUALIITIA and W. F. PICKERING

..!io,
y ~ b

/p

]~/x\~ (c)
/,-

~.._~

(f)

/ l,o,f
(el
I
- 900 -617

, f
I
-617

1
-333

L
-333

I
-50

Ep (mY)

Fig. 2. Voltammograms of solutions containing 100 #gl ~of Cd, Pb and Cu ions in 1 M CH3COONa, 0.2 M CH3COOH support solution. Dotted lines indicate response on adding 2 mg HA(F) particles/5 cmk (a) pH 5.3; (b) pH 8.15; (c) l mmol L-cysteineadded; (d) 1 mmol thiocyanate ion present; (e) 1 mmol thioacetamide added; (f) l mmol thiomalic acid; (g) 1 mmol thiodiglycerol.

mation of a non-labile soluble complex would also result in reduced peak values. Both of these alternatives could promote peak shifts such as observed in Cu systems (cf. Table 2), and to a much lesser extent, noted with Pb and Cd at pH 6.35 and 8.15. Figure 2 (curves a, b) indicates how pH and the addition of humic acid altered the shape of the A.S.V. stripping curves at pH 5.3 and 8.15 respectively. The dominant role of sorption was confirmed by isolating the suspended particles on a 0.45 #m membrane filter disk, prior to analysing for residual M 2+ in solution using both A.S.V. and A.A.S. For Cd 2+ determinations, carbon cup A.A.S. values were

similar to A.S.V. figures; with Cu 2+ modified flame A.A.S. procedures also yielded data consistent with the A.S.V. analyses. (The acetate matrix interferred with Pb determination by carbon cup A.A.S.). It was concluded that with the conditions used (2 mg solid) formation of non-labile soluble complexes was minimal. The data recorded on Fig. 1 were accordingly substituted into the graphical forms of both the Freundlich and Langmuir adsorption isotherm relationships. The latter approach yielded curves similar to the plots reported (Harmsen, 1977) for a relationship such as:

Metal sorption on humic acids Table 1. Adsorption isotherm parameters for specific sorption of Cd2+ and Pb2 on humic acids (in 1M CH3COONa solution) Adsorption Bonding capacity (mmolkg-]) constant (1061mol L) Freundlichpower term(s) Adsorbent Cd Pb Cd Pb Cd Pb HA(A) pH 5.3 0.3 0.5 2.8 7 0.28 0.76 6.35 1.4 4.0 2 2 0.59 2.1 8.15 1.8 * 5 * 1.45 * HA(F) pH 5.3 0.4 1.0 9 5 0.32 1.I 6.35 1.5 5.0 3 2 1.9 2.1 8.15 2.0 * 10 * 1.5 * Fulvicacid pH 6.35 0.4 2 3 1.5 0.5 1.5 8.15 0.7 * 5 7.0 1,0 * *Split peak.

1401

x / m = (x/m)m~K(C~pp - Cm)/{ 1 + K(C~pp - C,.)}

where Cin represents a constant concentration of inactive form, present in the apparent concentration C, pp. If one considers only the 4 to 5 points corresponding to solid densities of < 3 mg added per 5 cm 3, the Langmuir plots were linear (r > 0.98) with slopes corresponding to (x/rn)m,x values of 0.5-2mmol Cd kg -I HA, or 1-6 mmol Pb kg -l HA. In another series of experiments, the weight of solid added was fixed (2 mg) and the initial M s+ concentration varied. The data obtained for Cd and Pb conformed to a Langmuir plot and the derived parameters are summarized on Table 1. Values for Cu, and Pb at pH 8.15 are not included, because of the tendency of the peaks to be distorted in shape (i.e. overlapping unresolved dual peaks). The Cd and Pb capacity values obtained were similar to those derived from the variable weight studies. The affinity of Cu for the humic acids was higher, with > 90% of added Cu 2 being retained. The derived specific adsorption capacities are very much smaller than the total adsorptive capacities determined in lower ionic strength solutions, using ~ 1 0 - 4 M M 2+ solutions. Under these conditions, (x/m)m,x values at p H 5 ranged from around 250mmol Cd 2+kg -1 HA(A) to l m o l Pb 2+kg -1 HA(F), with bonding constants of approx. 2 x 10 -5 i mol -~ (Beveridge and Pickering, 1980). Changes in interaction behaviour as solid to adsorbate ratios are varied (e.g. decreasing x / m values as solid density increases) have been attributed (Benjamin and Leckie, 1981) to three possible causes, viz. (i) decreasing coulombic attraction due to sorption increasing (positively) the net surface charge; (ii) unfavorable chemical interactions between adjacent adsorbed ions; and (iii) existence on the surface of a variety of site types, each having a different bonding strength. Explanation (iii) applies to the humic acid studies (cf. difference between specific and total adsorption capacities), and it is proposed that the specific bonding segment most probably involves - - S H sites present in the organic matrices (% organic S in

HA(A) and HA(F) was 3.3 and 2.9%, respectively). Present in much higher proportions are ---COOH, and ---OH groups and metal binding by humic acids is usually attributed to interaction with these sites. The strong bonding that can develop between metal ions and S ligand groups is indicated by the A.S.V. curves recorded in the presence of excess S, or N donor compounds (Fig. 2, curves c-g). It can also be noted from Fig. 1, that the addition of a lower molecular weight and more soluble solid, fulvic acid (curves symbol FA) changed A.S.V. response in a manner similar to humic acids, except that the reduction in peak size was smaller.
Lability studies

Metal ions specifically sorbed to humic acids should not be A.S.V. labile, but other retained ions might migrate under the influence of an applied potential, particularly if stirring (e.g. by N2) ensures occasional contact between particles and the Hg film. Filtration of the equilibrated systems prior to A.S.V. analysis did not result in any significant change in the size of Pb or Cu peaks, which suggests that little (if any) of the sorbed metal ion was A.S.V. labile. Detracting from the validity of this conclusion is the observation that making the deposition potential more negative results in the release of more Pb (approx. 10-15% increase in peak size per 100mV). With Cu, deposition potentials < - 6 0 0 mV causes more peak distortion due to a secondary electrontransfer process. With Cd, peak currents decreased further on filtration, which strongly suggests that part of the sorbed Cd 2+ species was A.S.V. labile. As shown on Fig. 3, up to 12% of the total Cd ~* sorbed on humic acids fell into this category. This percentage decreased with increasing weight of solid present, and varied with solid type, system pH and deposition potential used. The results obtained using a membrane film between colloid and Hg film were essentially similar to those obtained after solid removal by filtration, hence the observed parameter changes do not arise from colloid/Hg film interaction.

1402

T.U. AUALIITIA and W. F. PICKERING

12

tO

6t
_J

'r

Weight

of humic

acid present

( m e / 5 crn ~ )

Fig. 3. Factors influencing the A.S.V. lability of Cd 2+ sorbed on humic acids. Humic acid HA(A): (A) pH5.3, Ed~p--900mV; (B) pH6.35, Edep--900mV; (E) pH5.3, Edep--1000mV; (F) pH5.3, Eoep-ll00mV; (G) pH5.3; Edep-1200mV. HA(F), (C) pH5.3; Ed,p--900mV; (D) pH6.35, Ed~ p -- 900 inV.

Moderately labile sorbed ions The deposition potential effect implies that some sorbed ions are "moderately labile" (i.e. migrate under the influence of an enhanced attractive force) and confirmation was sought by equilibrating dilute metal ion solutions with mixtures of humic acid and Chelex resin particles. The resultant ip changes were converted to nmol of metal ion lost from solution, and the results for Cd and Pb systems are summarized on Fig. 4. [This mixed solid approach was not informative in Cu systems, due to both solids being capable of sorbing most of the 0.5 ~g of Cu(II) present in the original solution.] If one postulates that both labile and moderately labile sorbed ions transfer to the imino-diacetate bonding group on the resin, then the difference between the amount retained by the mixture of solids and uptake by resin alone [at specified equilibrium M(II) values] provides a measure of the amount specifically sorbed by the humic acid. Comparison of these "specific" values against uptake readings obtained using HA alone indicated the extent of "moderately labile bonding". The data shown on Fig. 4 suggests that up to 25% of the Cd(II) sorbed by HA(F), and nearly all that normally retained by HA(A), could be transformed to the resin. The percentage transfer on HA(F) varied with the equilibrium concentration (i.e. was sensitive to the initial

metal ion concentration and amount of solid added). Using equal amounts of HA(F) and CR, in combinations weighing from 1 to 5 mg, the percent of Cd preferentially sorbed by the resin increased with increasing total weight. At pH 6.3, resin sorption predominated, i.e. transfer from both HA(A) and HA(F) was near total. The apparent mobility of Cd associated with organic matter present in natural waters has been noted previously (Duinker and Kramer, 1977; Florence and Batley, 1980; Figura and McDuffie, 1980; Laxen and Harrison, 1981). The lability was found to be a function of several factors, including the complexing power of the metal, the binding affinities of the particulates present and experimental conditions (e.g. pH and deposition potential). On a weight for weight basis, the affinity of the humic acids for Pb ions exceeded that for the resin (cf. Fig. 4), and in this case the combined solid data implies that the resin may contain up to 8% [with HA(F)] or 12% [with HA(A)] less metal ion than predicted from the Chelex line at particular equilibrium concentrations. As with Cd, the percentage change depended on the initial concentration involved, and on the weight of mixed solids present. Increasing the mixture weight from 1 to 5mg changed the distribution in favour of HA(A) from 15 to 30% (pH5.3) or 17 to 45% (pH6.35). With

Metal sorption on humic acids

7R=CR( A): CR(F) at pH 635

1403

/o CR(F) / ~CR= CR(A)

'1

/'/~

/ /i l
.

HA(F)

O I~'~"T

"G 2 ~

I I I I I I 2 3 4 5 6 7 ASV labile Cd2+concentralion (10-7M)

--~

C~'(F) /o eCRXA) Lead (pH53) el/d i /oH,4(F) ~it/ /b iiHA(A) I / . o"~ cJ I~cR

I I

I 2

I 3

ASV lebile pb2+concenlrafion {10-ZM)

Fig. 4. Adsorption plots for Cd and Pb in the presence of suspended particles, pH 5.3, (a) HA(A) 2 rag; (b) HA(F), 2 mg; (c) Chelex resin, 2 nag; (d) HA(A) 2 rag, CR 2 mg; (e) HA(F) 2mg, CR 2mg; (f) pH6.35, 2mg CR; or 2mg CR + 2 mg HA(A) or HA(F).

HA(F), at pH 6.35 the percent nominally transferred ranged from 20 to 6 0 * . Such calculations merely confirmed that in terms of transfer to a nominated alternative adsorbent, Pb sorbed on humic acids was essentially non-labile. It was concluded that the mixed adsorbent approach had limited value, due to the marked influence of experimental parameters on the behaviour observed. The limitations were equally apparent when base composition was varied.

Solution equilibria effects

It can be seen from Fig. 1, that the presence of C1(superscript c) or N H ; (superscript n) reduced the percentage of Cu or Cd retained by the humic acids at pH 5.3. Figure 2 (curves c-g) shows the effect of added L-cysteine, thiocyanate, thioacetamide, thiomalic acid or thiodiglycerol, on ASV traces. It can be seen that the S or N donor ligands influenced the position, size and shape of the ASV peaks for Cd, Pb and Cu, and minimized interaction with added humic acids. The Pb and Cd complexes formed were moderately labile, as shown by the two- or fourfoldincreases in current (in the presence of the latter three organic ligands) when deposition potentials were made 200 mV more negative. Figure 5 summarizes the changes observed in the amount of metal ion sorbed by particulates when the

acetate base solution was made 0.2 M in respect to a series of sodium salts or different carboxylic acids. With Cu systems changes in peak size were accompanied by significant changes in peak position (cf. Table 2), indicating some stable complex formation. No peak shifts were observed using Cd systems; with Pb only occasional small shifts ( < 1 0 m V ) were detected. No simple link between the peak effects noted in the presence of the different carboxylic acids and published metal complex stability values was discerned. Both tartaric and salicylic acids, for example, should have displaced acetate ions from the coordination sphere. The addition of tartrate reduced the amount of metal ion retained by the solids added; but salicylic acid had the opposite effect on Pb and Cd uptakes. Such diverse behaviour serves to emphasize that A.S.V. response reflects both the stability and lability of solution and surface complexes. Interpretation of the effect of high levels (0.2 M) of inorganic anions proved equally difficult. All the added salts changed the ionic strength, and thus promoted some changes in aceto-complex distribution patterns. Some of the anions react with metal ions to form sparingly soluble salts (e.g. Pb 2+ with F - , I - , CO~-, SO~-, H2PO4) but calculations indicated that in the presence of excess CH3COO- , solubility products were unlikely to be exceeded. Other anions form stable Cu(I) species. The peak split and decrease in size observed in the presence of CI- has been attributed (Pinchin and Newham, 1977) to simultaneous occurrence of one and two electron transfer processes during dissolution of deposited Cu(e.g. Cu + 2Ci- ~ CuCIf + e; and Cu + 3C1- ~ CuCIf + 2e). The amount of metal ion retained by the solids decreased along the halide sequence F - , CI-, Br-, I (cf. Fig. 5). In the absence of solids, Cu peak movement also changed from an Ep value of - 9 7 mV vs the S.R.E. with acetate solutions, to - 1 1 5 mV (F-), - 182 mV (CI-), - 245 mV(Br-) or - 4 1 1 mV (I-). It was concluded that while adsorption decreased with increasing stability of the complex ion formed, lability of the solution species seemed to increase along the sequence. Solution equilibria changes appeared to have the same general effect on both humic acids and Chelex resin, but using mixtures of adsorbents, peak size changes were only occasionally additive or proportional to relative affinities. This has been attributed to added salts promoting displacement of many of the diverse counter-ions normally associated with technical quality humic acids (e.g. Ca 2+, Fe 3+, A13+). These cations would be sorbed by the resin, and the net result may be creation of more metal-retentive sites on the humic acids. Apportioning individual contributions using the procedure outlined for Cd in the preceding section (cf. Fig. 4) led to the conclusion that little Cd 2+ was retained by HA(A) in the

1404
I00

T.U. AUALIITIAand W. F.

PICKERING

>''--'~ L=
80

60

/
Copper

40

20

Q~ J~ 0

80 / 60 ~A ~ \ ' \ Lead . . . .

0 c

E 40
Q~

20
C

+.

o~

60
.

40

20

A~

c~

B,

co; No; Po; so;

Anions

sA

NA

GA

SA

rA

Fig. 5, Diagram showing the effect of 0.2 M additions of different Na 4 salts or organic acids to 1 M CHsCOONa (pH 5.3) base solution, on the percentage change in peak height in presence of 2 mg solid particles (4 mg mixtures). Acid code: BA, benzoic acid; NA, nicotinic acid; GA, glutaric acid; SA, salicylic acid; TA, tartaric acid. Particulate code: - HA(A); . . . . . HA(F); & Chelex resin (CR); CR + HA(A); * CR + HA(F).

presence of resin, using base solutions containing excess F - , CI-, I - of CO~-. With Br- or glutaric acid present, the moderately labile fraction was ~ 4 0 or 20% respectively. Using HA(F) the transferable to resin fraction varied, e.g. 100% (NOj-), ~ 70% (glutaric and nicotinic acid systems) and 45% (CI-). There were some systems (e.g. C1- or C O l - ) where part of sorbed Pb may have been moderately labile, but in most cases uptake by mixtures exceeded predictions.

Environmental and analytical implications

This investigation has confirmed that humic and fulvic acids, if present in waters, effectively abstract Cd, Pb and Cu ions, even when initial metal ion levels are in the/~g 1-1 range. Most of the uptake from such dilute solutions is specifically sorbed (i.e. very firmly bound), but a small fraction of retained Cd(II) remains relatively mobile and available for transfer to other adsorbent species. The a m o u n t sorbed varies with the nature and concentration of electrolytes

Metal sorption on humic acids

1405

Table 2. Observed ASV peak shifts in I M CH3COONa (pH 5.3) base solutions containing diverse inorganic and organic anions (0.2 M) and organic particulates (2 rag/5 em3) Peak shifts (AEp), mV ~ Solid Pb Cu Base plus ~ HA(A) HA(F) CR CR+ HA(A) CR + HA(F) HA(A) HA(F) CR CR + HA(A) CR + HA(F) OAcnc nc nc nc nc 50 79 99 100 100 F/ nc 4 3 4 51 56 67 69 62 CI 4 5 3 6 8 34 54 63 68 78 Br5 7 5 8 9 24 37 39 49 49 I5 3 nc nc 5 25 20 12 21 20 CO~nc -3 -3 -2 -2 35 40 39 49 59 NO~ 3 2 nc nc -3 30 55 49 49 49 PO~ -4 - 1 -2 nc nc 29 34 29 34 44 SO~I nc nc nc nc 23 39 44 44 49 BA 5 5 nc nc . nc 45 54 59 59 56 NA nc nc -5 nc -1 10 29 24 29 34 GA 2 2 nc nc nc 25 39 44 61 84 SA 4 5 8 nc 4 24 48 68 78 92 TA 10 10 5 10 14 20 24 30 44 54 No significant peak shift detected with Cd: HA(A) and HA(F), humic acids; CR, Chelex 100 resin; nc, no change noted.

present, a n d the process is sensitive to soluble complex formation. T h e chemical structure o f h u m i c acids varies with source a n d the salt c o n t e n t o f waterways r a n g e f r o m low values in m o u n t a i n streams to the 3 % (w/v) c o n t e n t o f seawaters. Accordingly, a d s o r p t i o n values in n a t u r a l systems are predicted to differ f r o m those reported in this paper. C o n t r i b u t i n g to such variations is the polyelectrolyte n a t u r e of h u m i c substances since this causes the size a n d shape o f suspended particles to be influenced by v a r i a t i o n s in the c o n c e n t r a t i o n o f electrolyte present. W h e r e m a j o r variations in aqueous c o m p o s i t i o n occur (e.g. fresh waters c o m i n g in c o n t a c t with industrial effluents or b r a c k i s h waters in estuaries), significant changes in phase distribution values should follow. The gross d i s t r i b u t i o n effect is currently m e a s u r e d by separating the solid a n d a q u e o u s phase, with i n d e p e n d e n t analysis of each segment. U n f o r t u n a t e l y this a p p r o a c h does n o t identify any loosely-bound fraction of metal ion, t h a t is, material which m a y transfer readily o n c o n t a c t with a n o t h e r retentive surface (e.g. filter feeding mussels). A.S.V. analysis o f b o t h the initial suspension a n d isolated a q u e o u s p h a s e has been d e m o n s t r a t e d in this study to provide access to this additional sub-category. By altering the ionic strength a n d chemical n a t u r e o f the s u p p o r t i n g aqueous p h a s e ( a n d / o r by altering the applied potential used in the electrodeposition stage) one c a n also o b t a i n a n estimate o f the relative b o n d i n g strength o f m e t a l i o n - s o l i d substrate couples. The wider applicability o f this a p p r o a c h is currently u n d e r investigation.
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