Geoderma 133 (2006) 151 159 www.elsevier.

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Competitive adsorption and desorption of copper and zinc in acid soils

M. Arias *, C. Perez-Novo, E. Lopez, B. Soto
Area de Edafoloxa e Qumica Agrcola, Departamento de Bioloxa Vexetal e Ciencias do Solo, Universidade de Vigo, Facultade de Ciencias, Ourense, 32004 Ourense, Spain Received 17 September 2004; received in revised form 30 June 2005; accepted 5 July 2005 Available online 15 August 2005

Abstract As an aid to evaluating the environmental threat posed by Cu and Zn when both are present in acid soils, competitive and noncompetitive adsorption of Cu and Zn onto samples of the surface horizon of eight such soils was measured in batch experiments carried out at pH 5 with 0.01 M NaNO3 as background electrolyte. Noncompetitive adsorption of Cu exceeded that of Zn, especially in the soils with greatest organic matter contents. These data were better fitted by the Freundlich equation than by the Langmuir equation, possibly due to the heterogeneity of the adsorbent surfaces. The Langmuir Freundlich equation was not appropriate for these data: it could not be fitted to the Zn data, and when fitted to the Cu data the uncertainty in the values of its parameters was too large for them to be useful. Total metal adsorption from solutions containing Cu and Zn in 1 : 1 mole ratio was intermediate between adsorption from Zn and Cu solutions of the same total concentration, indicating competition between the two metals. Adsorption of Zn was severely depressed (in some soils almost completely) by the presence of increasing concentrations of Cu in the adsorption solution, but adsorption of Cu was depressed by at most 31% by the presence of increasing concentrations of Zn. Adsorption of Zn from solutions containing both Zn and Cu was modelled well by Murali and Aylmores generalization of the Freundlich equation, but this equation reduced to the Freundlich equation itself when it was fitted to data for the adsorption of Cu from mixed solutions. Desorption of Cu into NaNO3 solution from previously Cu-loaded soils in no case exceeded 11% of the Cu previously adsorbed, whereas analogous desorption of Zn was in all cases greater and ranged from 9% to 32%. Desorption of both Cu and Zn was greater when Cu was desorbed into Zn(NO3)2 and Zn into Cu(NO3)2. D 2005 Elsevier B.V. All rights reserved.
Keywords: Competitive adsorption; Noncompetitive adsortion; Copper; Zinc; Desorption

1. Introduction In recent decades there has been an increase in Cu and Zn concentrations in certain agricultural soils as the result of the use of pesticides and of

* Corresponding author. Tel.: +34988387070; fax: +34988387001. E-mail address: mastevez@uvigo.es (M. Arias). 0016-7061/$ - see front matter D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.geoderma.2005.07.002

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organic and inorganic fertilizers, together with deposition of industrial emissions (Kabata-Pendias and Pendias, 2001). The phytotoxic threat of both these metals, and the risk of their contaminating surface or ground water, depend on the sorption equilibria that govern their exchange between soil particulate matter and the solution with which it is in contact. Studies of their adsorption onto soils of various kinds (and onto certain individual soil fractions and other substrates; see Spark et al., 1995; Lopez et al., 1998; Kardivelu et al., 2001) have shown that the main physical and chemical factors governing these processes are pH and the presence of organic and/or inorganic colloids (McBride et al., 1997). Copper and Zinc are individually more soluble in acid soils than in calcareous soils, and their marked sorption hysteresis is most marked in the case of sorption by organic soil components (McLaren et al., 1983; Barrow et al., 1989; Wu et al., 1999). In the absence of other metals, copper is generally considered to be adsorbed in greater quantities than is zinc (Elliott et al., 1986), although they behave more similarly in soils with low organic matter content (Karathanasis, 1999). For proper evaluation of the environmental threat posed by Cu and Zn, or of their availability, it is necessary to supplement the individual sorption characteristics summarized above with information on their adsorption from solutions in which both are present, especially since Cu and Zn can be introduced into the soil together through the application of inorganic fertilizer, organic manure or pesticides. It is well documented that adsorption is reduced by the presence of a second adsorbate. The competitive adsorption has mainly been studied using clay minerals or isolated organic soil components as adsorbents rather than whole soil (Pinheiro et al., 1999; Arias et al., 2002; Saha et al., 2002). Selective adsorption of Cu and Zn has been related to their susceptibility to hydration, their charge / radius ratio, their electronegativity and their Misono softness (McBride, 1989). Studies of adsorption of heavy metals from mixed solutions onto the more heterogeneous surfaces of whole soil or soil horizons (Miller et al., 1983; Agbenin and Olojo, 2004; Serrano et al., 2005) have not totally coincided with those obtained in the studies that have used simpler, semisynthetic

adsorbents. Given the differences among different soils as regards their adsorbent surfaces, this variability indicates a need for further research to characterize the adsorption of particular adsorbates from mixed solutions onto different soil types. In the work described here we therefore characterized the sorption dynamics of Cu and Zn when added, separately or together, to acid soils of the kind that prevail in our region (Galicia, N.W. Spain), the predominant features of which are their high organic matter and iron oxides contents. Our experimental results were analysed by fitting the Langmuir, Freundlich and LangmuirFreundlich isotherms.

2. Materials and methods 2.1. Soil samples used in the study Samples of the top 20 cm of eight acid soils were taken with an Edelman auger in the provinces of A Coruna and Ourense (Galicia, NW Spain). Four of these soils had developed over granite and were classified as Typic Haplumbrepts, and the other four had developed over amphibolites and were classified as Andic Haplumbrepts. Four of the samples (two Typic Haplumbrepts and two Andic Haplumbrepts) were taken from maize fields, and four (two of each soil type) from pinewood. All samples were dried at room temperature, passed through a 2 mm sieve, homogenized, and stored pending analysis. 2.2. Analytical methods Soil pH was measured in H2O, 0.1 M KCl and 1.2 M NaF (in the latter to allow detection of noncrystalline aluminosilicates; see Results and Discussion) using a 1 : 50 soil : solution mixture in this last case and 1 : 2.5 mixtures in the others. In all cases a combined glass electrode was employed. Organic carbon, nitrogen and sulphur contents were measured by elemental analysis. Percentages of sand (20.05 mm), silt (0.050.002 mm) and clay (b 0.002 mm) were determined by the wet sieving method and the pipette method. Exchangeable cations were extracted with 0.2M NH4Cl (Summer and Miller, 1996) and were measured by atomic absorption spectrophotometry (Ca

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and Mg) and flame emission spectrophotometry (Na and K). Exchangeable Al was determined by displacement with 1M KCl followed by atomic absorption spectrophotometry. Selective extraction of Al (Als) and Fe (Fed) compounds was carried out using NaOH (Boggaard, 1985) and dithionitecitrate (Holmgren, 1967), respectively. All analyses were performed in duplicate, and the results presented are the means of the two determinations. 2.3. Adsorption of Cu and Zn individually Soil samples (1 g) were equilibrated for 24 h at room temperature (22 F 2 8C) with various solutions (20 mL) of Cu or Zn nitrates in the concentration range 153150 Amol L 1, with 0.01 M NaNO3 as background electrolyte (initial pH 5.0). After equilibration between soil and solution, the Cu solutions were at pH 4.9 F 0.2 and the Zn solutions at pH 5.0 F 0.1. Theoretical calculations using MINTEQA2 v. 4.0 (USEPA, 1999) indicated that under these pH conditions all initial solutions were unsaturated with respect to each metal nitrate and hydroxide, and that the predominant forms were Cu2+ (N97.5% of all Cu) and Zn2+ (N 98.0% of all Zn). The equilibrated suspensions were centrifuged at 1500 g for 15 min, the supernatant was drawn off and filtered through Whatman 540 paper, and its Cu or Zn content was measured using atomic absorption spectrophotometry. Adsorbed Cu or Zn was calculated as the difference between the amount added initially and the amount remaining in solution after equilibration. All measurements were made in triplicate. 2.4. Adsorption from mixed solutions Adsorption from mixed solutions was evaluated like individual adsorptions (see above), except that in one series of experiments 1 g of soil was mixed with 20 mL of a solution containing copper and zinc in 1 : 1 mole ratio (total concentration range 751575 Amol L 1, and in a second series the concentration of one metal was fixed (1575 Amol L 1) while that of the other was varied between 150 and 3150 Amol L 1.

2.5. Isotherm fitting The experimental adsorption data were fitted with Langmuir, Freundlich and LangmuirFreundlich isotherms (Eqs. (1) (2) and (3), respectively): KL Xm C 1 KL C

X KF C n KLF Xm C n 1 KLF C n

where X is the adsorbed metal concentration (Amol g 1), C is the concentration of the metal in solution at equilibrium (AM), X m is the maximum adsorbed metal concentration (Amol g 1), and n (dimensionless), K L (L Amol 1), K F ([L g 1]n ) and K LF ([L g 1]n ) are constants (K L and K LF are related to the energy of adsorption) The LangmuirFreundlich equation reduces to the Langmuir equation for homogeneous adsorbent surfaces (n = 1), and to the Freundlich equation for low adsorbate concentrations. 2.6. Desorption of Cu and Zn Immediately following adsorption of Cu or Zn from solutions with initial concentrations of 785, 1180, 1575, 2360 or 3150 Amol L 1, the centrifuged residues were weighed to determine the amount of occluded solution, resuspended in 20 mL of fresh Cuand Zn-free 0.01M NaNO3, and left to equilibrate for 24 h before centrifugation of the suspension and removal and filtration of the supernatant. This sequence of operations (weighing, suspension, equilibration, centrifugation, separation) was repeated a total of five times, and the Cu and Zn concentrations in each supernatant were measured as described above. In a second series of desorption experiments, Cu was adsorbed from a 1575 Amol L 1 solution and desorbed into 0.005 M Zn(NO3)2 solution, and Zn was adsorbed from a 1575 Amol L 1 solution and desorbed into 0.005 M Cu(NO3)2 solution.

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3. Results and discussion 3.1. Soil characteristics Table 1 lists the characteristics of the soils used. All are sandy loams or sandy clay loams with acid pH (pHH2O 4.25.2) and organic carbon contents of 3 10%. The soils developed over amphibolites generally have higher levels of Fe and Al oxides than those developed over granite, the exception being the relatively low Al oxide levels of soils 5 and 7. The exchangeable cation spectrum is dominated by Ca in the samples of cultivated soils and by Al in samples of forest soils over granite; Ca and Al are present in similar amounts in forest soils developed over amphibolites. Both Cu and Zn contents were high, although lower in granite than in amphibolite soils: 211 as against 56110 mg kg 1 for Cu, and 2763 as against 80102 mg kg 1 for Zn. However, Cu and Zn soluble in 0.01 M NaNO3 was in all soils less than 0.0016 Amol g 1. 3.2. Adsorption of Cu and Zn individually In all the soils used, more copper was adsorbed than zinc, the difference being most marked in soils 3, 6 and 8; these are the soils with the highest organic matter contents and with pHNaF values higher than 10, which are indicative of the presence of amorphous aluminosilicates (Fieldes and Perrot, 1966). Cu and Zn adsorption levels were most similar in soils 2 and 4, which have the lowest pHNaF values (8.1 in both

cases). Fig. 1a and b shown the results for sample 1 (Granite) and for sample 8 (Amphibolite). The affinity of copper for organic matter, especially under acid conditions, has been stressed by several authors (McLaren et al., 1983; Elliott et al., 1986; McBride et al., 1998); in particular, copper has strong affinity for fulvic and humic acids (Senesi et al., 1989; Arias et al., 2002). The Cu and Zn adsorption data, the former especially, are better fitted by the empirical Freundlich equation (R 2 between 0.9600.994 for Cu and between 0.9390.994 for Zn), than by the Langmuir equation (R 2 0.8660.949 for Cu and 0.8940.961 for Zn) although both equations accounted for a statistically significant proportion of variance ( p b 0.01). The Freundlich equation often provides a good description of adsorption onto heterogeneous solid surfaces (Stum and Morgan, 1981). The copper adsorption data were also fitted well by the LangmuirFreundlich equation (R 2 N 0.983), but with such large uncertainties in the estimated values of the parameters as to make these fits useless for interpretation of the data. Both the good fit and the large uncertainties are attributable to the LangmuirFreundlich equation having one more adjustable parameter than either the Langmuir or the Freundlich equation. Furthermore, attempts to fit the LangmuirFreundlich equation to the zinc adsorption data failed completely (the algorithm failed to converge); this is attributed to low saturation of the adsorbent surfaces of the soil, i.e., to the segment of the adsorption curve that was sampled

Table 1 Characteristics of the soils used Soil PM Use (%)a Clay 1 2 3 4 5 6 7 8 G G G G A A A A C C W W C C W W 14 10 13 11 17 28 20 26 Silt 17 16 15 18 28 48 30 43 Sand 69 74 72 71 55 24 50 31 pHb H2 O 4.7 4.4 4.5 4.2 5.2 4.8 4.6 4.5 KCl 4.1 3.7 3.9 3.6 4.7 4.5 4.1 4.2 NaF 8.9 8.1 10.3 8.1 9.0 10.8 9.7 11.0 (%)b C 4.1 3.0 6.2 2.6 3.2 6.5 3.1 10.5 N 0.61 0.19 0.48 0.26 0.41 0.68 0.34 1.07 S 0.02 0.01 0.03 0.01 0.04 0.05 0.04 0.06 Exchangeable cationsb (cmol(c)kg 1) Na 0.4 0.3 0.2 0.2 0.3 0.6 0.2 0.2 K 0.4 0.6 0.4 0.5 0.4 0.3 0.5 0.4 Mg 0.6 0.5 0.3 0.4 0.1 0.9 0.6 0.5 Ca 2.5 2.2 1.0 1.5 3.1 4.7 1.7 1.5 Al 0.7 0.8 3.9 2.9 0.2 0.1 1.7 1.7 CEC 4.4 4.4 5.8 5.3 4.1 6.6 4.7 4.3
b

mg kg 1 Als 5 2 8 3 6 23 8 26 Cut 11 2 3 5 57 110 56 81 Znt 63 52 27 37 102 92 80 90

Fed 3 2 6 2 34 60 42 48

Fed, dithionitecitrate-extractable iron; Als, NaOH-extractable aluminium; Cut, total copper content; Znt, total zinc content; PM, parent material. G, granite; A, amphibolite; C, cultivated; W, woodland. a Coefficients of variation were less than 10%. b Coefficients of variation were less than 5%.

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155

50,0 40,0

a)
mol g-1

50,0 40,0 30,0 20,0 10,0 0,0

b)

mol g-1

30,0 20,0 10,0 0,0 0 500 1000 1500 2000 2500

500

1000 1500 2000 2500

mol
25,0 20,0

L-1
25,0

mol L-1

c)
mol g-1

d)

20,0 15,0 10,0 5,0 0,0

mol g-1

15,0 10,0 5,0 0,0 0 250 500 750 1000

250

500

750

1000

mol
15,0

L-1

mol

L-1

e)
15,0

f)
mol g-1
10,0 5,0 0,0

mol g-1

10,0 5,0 0,0 0 1000 2000 3000 4000

1000

2000

3000

4000

mol L-1 (Cu or Zn)

mol L-1 (Cu or Zn)

Fig. 1. a) Soil 1 and b) Soil 8: Adsorption of Cu (n) and Zn (E) from solutions of the same metal (1503150 Amol L 1), plotted against the concentration in solution at equilibrium. c) Soil 1 and d) Soil 8: Adsorption of Cu (n) and Zn (E) from solutions of both metals in 1:1 mole ratio, plotted against the concentrations in solution at equilibrium. e) Soil 1 and f) Soil 8: Adsorption of Cu (n) from 1575 Amol L 1 Cu solutions containing various initial concentrations of Zn, and of Zn (E) from 1575 Amol L 1 Zn solutions containing various initial concentrations of Cu. Vertical bars indicate F1 standard deviation (where not shown, the symbol height is less than 2 standard deviations).

having been too small to allow the three-parameter equation to be fitted. Examination of the parameters of the best-fitting equation shows that for copper K F ranges from 1.3 to 8.7, whereas for zinc its values are between 6 and 88 times smaller (ranged from b01 to 1.4), with only soil 6 having a value greater than unity. For both metals, however, K F is on average smaller for soils developed over granite (2.3 for Cu and 0.1 for Zn) than for those developed over amphibolites (5.1 for Cu and 0.6 for Zn), which have higher iron oxide contents. The value of n is greater for zinc (average 0.6) than for copper (average 0.3),

reflecting the more linear adsorption profiles of zinc (Fig. 1a, b). 3.3. Adsorption from mixed solutions 3.3.1. 1 : 1 mole ratio Fig. 1c and d for samples 1 and 8, respectively show the results obtained when Cu and Zn were added to the soils simultaneously in 1 : 1 mole ratio. The general pattern is the same as when the metals were added separately, adsorption of Cu being in all cases greater than adsorption of Zn and the greatest differences between the two being found in

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M. Arias et al. / Geoderma 133 (2006) 151159 Table 2 Results of fitting the equations of Murali and Aylmore (1983) to data for adsorption of Cu (component 1 in Eqs.(5) and (6)) and Zn (component 2) from 1 : 1 solutions of the two, when adsorbed metal concentrations are measured in Amol g 1 and equilibrium metal concentrations in solution in Amol L 1 Soil 1 2 3 4 5 6 7 8 a 12 0.2 F 0.0 0.6 F 0.1 0.3 F 0.0 0.7 F 0.1 0.1 F 0.0 0.1 F 0.0 0.2 F 0.0 0.1 F 0.0 R2 0.884** 0.637* 0.917** 0.612* 0.778** 0.731* 0.878** 0.922** a 21 2.6 F 0.4 1.8 F 0.2 1.0 F 0.3 1.1 F 0.2 0.4 F 0.2 14.7 F 2.0 2.6 F 0.3 7.3 F 0.9 R2 0.769** 0.730* 0.806** 0.831** 0.781** 0.739* 0.780** 0.816**

the soils with the highest organic matter contents. This confirms that Cu has greater affinity for the binding sites of soil organic matter than Zn. It has been reported, moreover, that Cu binds more selectively than Zn to organic matter, since adsorption of Cu is less strongly reduced by prior extraction of Fe and Al oxides than is adsorption of Zn (Cavallaro and McBride, 1984). Fitting the data for total metal adsorption with the Freundlich equation, which in this case adopts the form n X Cu X Zn K C Cu C Cd
2

*p b 0.05; **p b 0.01.

afforded satisfactory R values in all cases (0.933 0.999). K F was in all cases following the sequence K Cu N K CuZn N K Zn, and the same was true for n but in the reverse direction. This behaviour is reflected in Fig. 2, which compares the amounts of metal bound when the soils were treated with Cu alone at a concentration of 1574 Amol L 1, with Zn alone at the same concentration, and with a solution of Cu and Zn at concentrations of 787 Amol L 1 each. It shows that Cu and Zn do indeed compete for bind-

ing sites rather than binding to Cu-specific and Znspecific sites, respectively in which case total adsorption from the mixture would be simply the sum of adsorption of Cu from a 787 Amol L 1 of Cu and adsorption of Zn from a 787 Amol L 1 of Zn, which would in all cases exceed the observed total adsorption. Similar behaviour has been observed when Cu competes with Cd for binding sites on kaolin (Arias et al., 2002). Several models have been put forward to describe the adsorption of individual adsorbates from multiadsorbate solutions when all these adsorbates comply with Freundlich equations in the absence of competitors (LeVan and Vermeulen, 1981; Murali and Aylmore, 1983; Koopal et al., 1994). In this

100 80

Reduction (%)

60 40 20 0 0 1000 2000 3000 4000

Fig. 2. Adsorption of Cu from a 1575 Amol L 1 Cu solution (unshaded bars), adsorption of Zn from a 1575 Amol L 1 Zn solution (hatched bars), and total adsorption of Cu and Zn from a solution in which both had a concentration of 785 Amol L1 (bars with solid shading).

M (Cu or Zn)
Fig. 3. Percentage reductions in adsorption of Cu (n) and Zn (E) from 1575 Amol L 1 solutions of these metals containing various initial concentrations of the other (averages of the eight soils, with ranges indicated by vertical bars).

M. Arias et al. / Geoderma 133 (2006) 151159 Table 3 Results of fitting the second equation of Murali and Aylmore (1983) to data for adsorption of Zn (component 2 in Eq. (6)) from solutions with an initial Zn concentration of 1574 Amol L 1 and various initial Cu concentrations, when adsorbed metal concentrations are measured in Amol g 1 and equilibrium metal concentrations in solution in Amol L 1 Soil 1 2 3 4 5 6 7 8 **p b 0.01. a 21 2.5 F 0.4 1.6 F 0.4 2.8 F 1.3 4.3 F 1.2 2.7 F 0.4 2.2 F 0.5 3.7 F 0.6 6.8 F 1.4 R 2** 0.986 0.957 0.896 0.906 0.991 0.973 0.978 0.957

157

tional parameters that account for competition between the two species. In all cases, fit was poorer than for the Freundlich equations fitted to the data from the single-metal experiments, but was nevertheless statistically significant at the p b 0.05 level or better (Table 2). The parameter a 21 is in all cases greater than a 12, showing that adsorption of zinc is reduced more by the presence of copper than adsorption of copper by the presence of zinc. The difference is especially marked for two of the soils with highest organic matter contents (6 and 8, both developed over amphibolites), suggesting that in these soils copper dominates binding to this component whereas the high-organic-matter soil developed over granite has one of the lowest a 21 / a 12 ratios. 3.3.2. Variable mole ratios Increasing the initial concentration of Cu in solution from 0 to 3150 Amol L 1 while maintaining the initial Zn concentration at a constant 1574 Amol L 1 resulted in adsorption of Zn falling practically to zero in all the soils studied, whereas inverting the roles of Cu and Zn brought about reductions in adsorption of Cu of only 731% (Figs. 1ef and 3). The blockade of Zn adsorption is modelled well by Eq. (6), with a 21 values of 1.66.8 indicative of strong competition from Cu (Table 3), but fitting Eq. (5) afforded values of a 12 that did not differ significantly from zero.

study, best fit was afforded by the MuraliAylmore equations: X1

n K1 C1 1 1 C1 a12 C2 n K2 C2 2 1 C2 a21 C1

X2

where C 1 and C 2 are again concentrations in solution at equilibrium, K 1, K 2, n 1 and n 2 are the Freundlich parameters for adsorption of species 1 and 2 in the absence of competitors, and a 12 and a 21 are addi-

Table 4 Desorption (Amol g 1) of Cu and Zn into NaNO3 solution from soils previously loaded by equilibration in solutions with various concentrations of the corresponding metal (Amol L 1) Soil Initial concentration of metal in loading solution (Amol L 1) 785 Cu Amol g 1 1 2 3 4 5 6 7 8 0.4 F 0.02 0.6 F 0.05 0.5 F 0.02 0.4 F 0.01 0.3 F 0.02 0.1 F 0.00 0.7 F 0.02 0.5 F 0.02 1.2 F 0.04 1.1 F 0.01 1.2 F 0.04 1.1 F 0.03 1.3 F 0.04 1.1 F 0.02 1.9 F 0.03 1.8 F 0.01 0.3 F 0.04 0.7 F 0.02 0.6 F 0.01 0.5 F 0.00 0.6 F 0.01 0.2 F 0.01 1.0 F 0.04 1.1 F 0.01 1.8 F 0.02 1.7 F 0.05 1.8 F 0.05 1.9 F 0.04 1.8 F 0.01 2.0 F 0.01 2.2 F 0.02 3.0 F 0.04 0.6 F 0.03 0.6 F 0.03 1.2 F 0.01 0.7 F 0.02 0.9 F 0.03 0.4 F 0.01 1.8 F 0.04 1.1 F 0.03 2.1 F 0.03 1.8 F 0.02 2.1 F 0.00 1.8 F 0.04 2.3 F 0.00 2.6 F 0.00 2.3 F 0.05 3.4 F 0.06 0.6 F 0.04 nd 1.3 F 0.03 0.6 F 0.02 0.8 F 0.03 0.9 F 0.01 1.5 F 0.03 2.0 F 0.02 2.7 F 0.04 2.1 F 0.04 1.8 F 0.05 2.7 F 0.04 2.8 F 0.04 3.6 F 0.01 2.9 F 0.04 4.1 F 0.01 nd nd 1.3 F 0.03 0.8 F 0.02 0.8 F 0.02 1.8 F 0.03 1.4 F 0.03 4.6 F 0.06 3.0 F 0.02 2.2 F 0.04 3.3 F 0.03 2.5 F 0.03 3.2 F 0.04 4.2 F 0.00 3.1 F 0.01 4.7 F 0.04 Zn 1180 Cu Zn 1575 Cu Zn 2360 Cu Zn 3150 Cu Zn

Values shown are means F standard deviations. nd: not determined.

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3.4. Desorption Depending on the concentrations of the solutions from which initial adsorption had occurred, desorption into NaNO3 solution ranged from 0.1 to 4.6 Amol g 1 for Cu and from 1.1 to 4.7 Amol g 1 for Zn, and for a given concentration of the initial adsorption solution was always greater for Zn than for Cu (Table 4). In terms of the quantities initially adsorbed, desorption was always less than 11% for Cu and ranged between 9% and 32% for Zn, i.e., sorption hysteresis was greater for Cu. These results are in keeping with reports of very low desorption of copper from humic acids and soil oxides (McLaren et al., 1983; Wu et al., 1999), and with Miller et al. (1983) observation of preferential adsorption of Cu and Pb with respect to Cd and Zn. That Cu has greater specific binding affinity than Zn is also in keeping with the differences between these metals as regards other physical and chemical characteristics, such as capacity for hydroxylation, ionic potential, electronegativity, softness, and position in the IrvingWilliams series (Brummer, 1986; McBride, 1989). The slight increase in desorption with the concentration of the initial adsorption solution that was observed in this study is attributable to the increased occupancy of binding sites, which reduces binding energy.

Percentage desorption into 0.005 M Zn(NO3)2 solution (for Cu) or 0.005 M Cu(NO3)2 solution (for Zn) was greater than into NaNO3 solution, although desorption of Cu, which in no case exceeded 50%, was again always less than desorption of Zn, which ranged from about 45% to nearly 80% (Fig. 4).

4. Conclusions In this study, adsorption of Cu from Cu solutions by eight acid soils was greater than adsorption of Zn from Zn solutions of the same initial concentrations, especially for the soils with the highest organic matter contents. The experimental data were better fitted by Freundlich equations than by Langmuir or LangmuirFreundlich isotherms. Total metal adsorption from solutions containing Cu and Zn in 1 : 1 mole ratio was intermediate between the levels of adsorption of Zn and Cu from single-metal solutions of the same total concentrations. Adsorption of Zn from solutions containing a fixed Zn concentration was severely depressed by increasing the concentration of Cu in the solution, but inverting the roles of Cu and Zn caused only a relatively minor reduction in adsorption of Cu. The adsorption of Zn in the presence of Cu was satisfactorily modelled by Murali and Aylmore (1983) generalization of the Freundlich equation. In keeping with these findings indicative of greater affinity of these soils for Cu than for Zn, desorption of Cu into NaNO3 solution occurred much less readily than desorption of Zn. The presence of Zn in the desorption solution increased desorption of Cu, but for most soils the presence of Cu in the desorption solution caused an even greater increase in the desorption of Zn. The observed influence of Cu and Zn on the adsorption and desorption of the other onto and from acid soils must be taken into account when calculating their availability or, at higher levels, their phytotoxic potential.

100 90 80

Cu, NaNO3 Cu, Zn(NO3)2

Zn, NaNO3 Zn, Cu(NO3)2

Desorption (%)

70 60 50 40 30 20 10 0 1 2 3 4 5 6 7 8

Acknowledgement This work was partially financed by an MCYT bRamon and CajalQ contract to Manuel Arias Estevez, cofinanced by the University of Vigo.

Soil
Fig. 4. Percentage desorption of Cu into NaNO3 and Zn(NO3)2, and of Zn into NaNO3 and Cu(NO3)2, following adsorption from singlemetal 1575 Amol L 1 solutions.

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