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Chemical Speciation and Bioavailability, (1999), 11(2)

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Single extractions versus sequential extraction for the estimation of heavy metal fractions in reduced and oxidised dredged sediments
Filip M.G. Tack* and Marc G. Verloo
Laboratory of Analytical Chemistry and Applied Ecochemistry, University of Gent, Coupure Links 653, B-9000 Gent, Belgium

ABSTRACT

Sequential extraction is applied to estimate the chemical association of trace elements in soils and sediments. An approach where the same information is gained from single extractions would be advantageous: sample preservation is critical only before and during one extraction, there is no risk for sample losses during consecutive steps and results can be obtained faster. The drawbacks are that more sample is needed and that sample heterogeneity may introduce errors. Five soil or sediment samples were subjected to sequential extraction according to Tessier et al. and to single extractions, using the reacting conditions of the sequential steps. Estimates of the acid extractable, reducible and residual fractions from single extractions generally agreed with these determined by sequential extraction. The oxidisable fraction should be determined by extraction of the residue of a hydroxylaminehydrochloride extraction. The differences observed between determined and estimated fractionation would not seriously affect interpretation of the results. To estimate metal fractions in soils and sediments, the use of single extractions rather than sequential extraction according to Tessier et al. could be justied for practical purposes. Keywords: Heavy metals, sequential extraction, single extraction, fractionation, speciation, sediment.

INTRODUCTION Sequential extraction is frequently applied for the fractionation of solid phase associated elements in soils and sediments (Pickering, 1981; Lund, 1990; Ure, 1990a; Tack and Verloo, 1995). Apart from conceptual problems associated with the use of sequential extraction (e.g., non-selectivity of the extractants, redistribution of trace element among phases during extraction), proper sample handling and preparation (e.g., freeze drying, oven drying) remains a major practical problem, because it critically inuences the results of a sequential extraction (Rapin et al., 1986). For anoxic sediments, the necessity of maintaining anoxic conditions during sampling, sample treatment and extraction has been clearly evidenced (Rapin et al., 1986; Wallmann et al., 1993).

An approach where the same information is gained from separate, single extractions can be advantageous: sample preservation is critical only before adding the reagent and during one extraction, there is no risk for sample losses during consecutive phase separations and washing steps, not all work is lost when something goes wrong during an extraction step, and nally, results can be obtained faster because the extractions can be carried out simultaneously. Drawbacks include that more sample is needed and that errors may be introduced due to sample heterogeneity. Gupta et al. (1990) developed a scheme consisting of several single extraction to substitute for sequential extraction of metals in sewage sludge by the procedure of Stover et al. (1976). They found a good agreement in the metal fractionation patterns, obtained by the two methods. Bendell-Young et al. (1992) compared a

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simultaneous extraction procedure for low carbonate sediments with the method of Tessier et al. (1979). We compared sequential extraction according to Tessier et al. (1979) of a high alkalinity reduced dredged sediment with the results, obtained from single extractions that used reacting conditions similar to these of the sequential steps (Tack et al., 1996). The estimates of the exchangeable, acid extractable and reducible fractions were in good agreement with the fractions obtained using sequential extraction, while the oxidisable fraction should be determined by extraction of the residue of a hydroxilamine-hydrochloride extraction. In this report, results are presented for one more reduced sediment and three oxidised dredged sediment derived surface soils, in order to support our previous ndings (Tack et al., 1996). MATERIALS AND METHODS Sampling and sample preparation Samples MG 1 and MG 2 were dredged material derived surface soils. These were sampled to a depth of 30 cm at conned disposal sites situated on the left bank of the deviation canal from the river Leie, at Meigem in Belgium. The site denoted as MG 1 is 10 years old. Experimental forestry plantations of ash tree (Fraxinus sp.), Canadian ea-bane (Erigeron canadensis L.), water-willow (Salix caprea L.), great bindweed (Calystegia sepium R.Br.), and poplar (Populus sp.) were growing at the sampled area. Disposal site MG 3 received sediments 3 years before our sampling and was densely covered by stinging nettle (Urtica dioica L.). Two samples, GH 1 and GH 2, were taken at the Geuzenhoek disposal site to a depth of 30 cm. Sediment GH 1 was disposed one year before our sampling. A supercial layer of approx. 3040 cm was partially dried and oxidised and sparingly covered with weeds. Sample GH 2 was from a compartment where the sediment still was covered with 3050 cm water and was in a reduced state. Sample K 1 was sampled during dredging operations from the Scheldt estuary. These results were presented in our previous study (Tack et al., 1996) and are included here for comparison. The reduced sediments (GH 2 and K 1) were stored in closed containers under water and kept at ambient temperature. The oxidised soils/sediments (MG 1, MG 3 and GH 1) were air dried during several days, hand-crushed using a mortar and sieved (2 mm). Selected physical and chemical properties of the sediments studied are presented in Table 1. Chemical analysis Sediment pH was measured potentiometrically in a suspension of 10 g sediment in 50 mL distilled water after 12 hrs. Carbonate content was determined by back titration of an excess of 0.5 mol L1 HCl added to 1 g

oven dried and 2-mm sieved sample with 0.5 mol L1 NaOH (Nelson, 1982). Organic carbon was estimated by the Walkley-Black method (Nelson and Sommers, 1982). Particle size fractionation was performed with dry and wet sieving techniques (Gee and Bauder, 1986). Sequential extraction The sediments were sequentially extracted according to the Tessier method (Tessier et al., 1979). The residual fraction was determined after aqua regia destruction (Ure, 1990b). Aliquots of the sample were subjected to single extractions using similar reacting conditions as the steps of the sequential extraction. The extracting conditions applied are outlined in Table 2. The extractions were performed on the equivalent of 3.00 g sediment dry matter in 250 mL polyethylene centrifuge tubes. The sediment dry weight was determined on a separate portion by drying at 120C until constant weight. To prevent oxidation during extraction of the reduced sediments, the tube was sealed with laboratory lm after ushing the head space with N2-gas. This precaution was taken during the rst three steps of the sequential extraction procedure only. After each extraction step, the suspension was centrifuged (1,500 g during 20 min) and the supernatant solution removed using a syringe. The remaining solids were suspended in 24 mL deionised water, that was separated in a similar way and discarded. Metal concentrations in the supernatant solution were determined with ame atomic absorption (Varian AA-1475 or SPECTRAA-10). Calcium was measured with ame emission (Eppendorf ELEX 631). For each extract, external standards, prepared in the corresponding extraction solution, were used for calibration. The exact volume of the extract after each extraction step was determined by weighing the centrifuge tube just before sampling the supernatant liquid. Extractions were replicated three times for the oxidised sediments MG 1, MG 3 and GH 1, and repeated four times for GH 1 and K 1. RESULTS AND DISCUSSION According to the fractionation scheme of Tessier et al. (1979), metals are categorised as exchangeable, bound to carbonates, bound to iron and manganese oxides, bound to organic matter and residual. The extractions, however, are not so specic as previously stated (Tack and Verloo, 1995). The corresponding fractions will therefore be referred to as exchangeable, acid extractable, reducible, oxidisable and residual, respectively. Exchangeable fraction The exchangeable fraction consists of metals that are readily leached by a neutral salt. In soils and sediments,

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Table 1 Characteristics of the sediments studied GH 1 Granulometry (%) 0-2 m 2-50 m > 50 m pH-H2O (1:5) Organic carbon (%) CaCO3 (%)
Mean

GH2 15 31 54 7.5 3.9 0.3 11.0 0.1

K1 34 57 9 7.3 5.4 0.1 15.3 0.3

MG 1 37 50 13 7.4 3.7 0.4 9.1 0.5

MG 2 47 51 2 7.2 4.9 0.4 7.7 0.6

29 57 14 7.3 5.0 0.3 10.7 0.7

SD of 3 replicates

Table 2 Experimental extraction conditions used per gram reduced sediment MgCl2-extraction NaOAc-extraction NH2OH.HCl-extraction H2O2-extraction Aqua regia destruction 8 mL 1 mol L1 MgCl2 (pH 7), 1 h, room temperature, continuous shaking 8 mL 1 mol L1 NaOAc + HOAc (pH 5), 5 h, room temperature, continuous shaking 20 mL 0.04 mol L1 NH2OH.HCl in 25% HOAc, 6 h, 95C, intermittent shaking 3 mL 0.02 HNO3 + 2 mL 30% H2O2 (pH 2), 2 h, 85C, intermittent shaking; 3 mL 30% H2O2 (pH 2), 3 h, 85C, intermittent shaking; 5 mL 3.2 mol L1 NH4OAc in 20% HNO3 + 7 mL H2O, 30 min, room temperature 7.5 mL 37% HCl + 2.5 mL 65% HNO3, overnight at room temperature, 2 h heating under reux

this metal fraction is usually low and for many metals, concentrations in the extracts were below the detection limit of ame atomic absorption (Table 3). In the oxidised sediments GH 1, MG 1 and MG 2, as opposed to the reduced sediments, the exchangeable fractions of Cd, Ni, and Zn were signicant, illustrating that metals tend to be mobilised when sediments are brought in upland conditions (Gambrell, 1994).Acid extractable fraction The acid extractable fraction is obtained by extracting the soil or sediment in an acetic acid/acetate buffer at pH 5 (NaOAc-extraction). In principle, this step should selectively dissolve carbonates and thereby release associated metals (Tessier et al., 1979). Metals released in that step may also include species that are more strongly adsorbed on different solid phases of the system and hence were not released at pH 7 during the previous step (Kim and Fergusson, 1991). When single NaOAc-extraction is applied to a soil or sediment, reaction conditions are such that metals of

the exchangeable fraction will also be released. The acid extractable fraction hence can be estimated from the difference between NaOAc-extraction and MgCl2extraction. This is supported by the overall good agreement between the acid extractable fraction determined by sequential extraction and that, estimated from single extractions (Table 4). For MG 1 and MG 2, standard errors of the estimation of acid extractable Cd were large compared to that of its determination. The standard error of the exchangeable fraction in these sediments (Table 3) affected the precision of the estimate of the relative small acid extractable fraction from single extractions. In sediment GH 1, acid extractable Pb determined by sequential extraction was only half the amount estimated by single extractions (Table 4). This was perhaps related to the sediment being only partially oxidised. Iron hydroxides may have formed during the MgCl2extraction. Lead can then sorb onto these hydroxides

Table 3 Exchangeable fraction determined by MgCl2-extraction (mg kg1 dry matter SD) Metal Ca Cd Co Cu Fe Mn Ni Pb Zn GH 1 5200 140 2.5 0.4 3.1 0.2 < 0.2 18 8 111 18 1.6 0.3 3.5 0.2 37 4 GH 2 3258 190 < 0.07 < 0.3 < 0.2 370 15 138 15 < 0.3 < 0.6 < 0.04 K1 4140 150 < 0.07 < 0.3 < 0.2 10 1.5 37 1 < 0.3 < 0.6 < 0.04 MG 1 5100 360 4.6 1.3 < 0.3 < 0.2 95 61 2.2 0.3 < 0.6 25 2 MG 2 10300 690 7.2 1.8 < 0.3 < 0.2 11 7 73 3.5 0.7 < 0.6 30 4

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Table 4 Acid extractable fraction determined (D) by sequential extraction and estimated (E) by subtraction of NaOAc-extractable and MgCl2-extractable amounts (mg kg1 dry matter SD) Metal Ca Cd Co Cu Fe Mn Ni Pb Zn D E D E D E D E D E D E D E D E D E GH 1 31,500 860 34,400 1,400 5.2 0.3 5.4 0.6 6.5 0.4** 3.3 0.6 7.0 2.5 7.7 0.5 33 1 31 9 260 4 260 26 9.3 0.6 8.8 0.9 17 2** 28 2 740 27 725 33 GH 2 21,900 2,400 24,500 2,100 < 0.7 <1 2.4 0.5 2.2 0.4 < 0.2 < 0.3 7,100 80 7,400 440 890 99 800 71 5.6 0.6* 7.1 0.8 < 0.6 < 0.9 160 23* 200 17 K1 37,000 4,600 33,100 2,500 < 0.7 <1 4.2 0.3* 3.4 0.2 < 0.2 < 0.3 4,970 1,100 3,400 720 510 45 460 31 6.8 0.6 7.4 0.5 11 2 13 2 50 15 55 9 MG 1 30,100 480 31,100 1,700 3 0.9 1.7 3.0 2.1 0.1 31 12.0 0.7 12.6 2.4 21 2 16 6 97 1 100 6 4.9 0.5 4.4 2.1 15 2 13 4 410 3* 340 36 MG 2 26,900 240 28,200 2,000 2.8 0.1 1.7 2.9 2.9 0.2 3.6 1 23.8 0.7** 27.5 1.4 32 2 31 9 118 1* 89 9 16.9 0.4 14.1 2.0 20 2 20 2 580 16 510 38

The signicance of the difference between determined and estimated amounts was evaluated using an independent sample T test at the 95% (*) or the 99% (**) signicance level.

and be released less effectively by NaOAc during sequential extraction. This may be supported by comparing Fe and Mn concentrations in the exchangeable fraction of reduced and oxidised sediments (Table 3). While Mn in the exchangeable fraction was two to threefold higher than in the fully oxidised sediments MG 1 and MG 2, Fe was in the same range. On the other hand, both Fe and Mn were high in the reduced sediments GH 2 and K 1. Reducible fraction The reducible fraction is determined after extraction with acidic NH2OH.HCl. Conceptually, this reagent is designed to release amorphous ironmanganese oxides and associated metals (Tessier et al., 1979). If applied as a single reagent, it will, because of the low reagent pH, release adsorbed and carbonate associated metals as well. The reducible fraction hence could be estimated by the difference of the NH2OH.HCl-extractable and the NaOAc-extractable amounts (Table 5). Estimates of the reducible fraction agreed in most cases with the determination using sequential extraction. Signicant differences occurred primarily for the soils MG 1 and MG 2. These have the highest clay content among the sediments studied (Table 1). If Ca is considered indicative for the amounts of carbonates dissolved, then it may be concluded that similar amounts of carbonates were released by sequential extraction compared to the single approach. Differences in dissolved Fe between the reducible fraction determined by sequential extraction and that estimated from single extractions indicate that the extrac-

tion efficiency of iron oxides was affected by the procedure used. For soils MG 1 and MG 2, signicantly more Fe was released in the reducible fraction of sequential extraction than estimated from single extractions. For K 1, on the other hand, Fe was signicantly lower, while differences in Fe were not signicant for sediments GH 1 and GH 2. This behaviour is not readily explained as several factors may inuence the extraction efficiency of iron oxides. The nal pH during single NH2OH.HClextraction will usually be higher than in sequential NH2OH.HCl-extraction because more acid is needed to dissolve carbonates that, in the sequential approach, have been dissolved during the preceding NaOAcextraction. The nal pH of the single extraction with NH2OH.HCl was 2.81 and 2.72 for soils MG 1 and MG 2, respectively, as compared to 2.39 and 2.43 for the reducible step in sequential extraction. During single extraction, an undisturbed sediment matrix is contacted with NH2OH.HCl. Iron oxides may, for example, be coated by carbonate phases and hence be dissolved more slowly than in sequential extraction. These factors may result in a lower extractability of Fe during single extraction than during sequential extraction. On the other hand, effects of oxidation during sequential extraction of reduced sediments may result in a lower Fe extractability during the reducible step of sequential extraction compared to that estimated from single extractions. In particular for strongly reduced sediments such as K 1, much stricter precautions than those we took may be required to prevent any oxidation from occurring during the subse-

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Table 5 Reducible fraction determined (D) by sequential extraction and estimated (E) by subtraction of NH2OH.HCl-extractable and NaOAc-extractable amounts (mg kg1 dry matter SD) Metal Ca Cd Co Cu Fe Mn Ni Pb Zn D E D E D E D E D E D E D E D E D E GH 1 6,750 190 4,600 1,500 3.3 0.5 2.7 0.6 5.8 0.7** 10.7 1.1 < 0.5 0 0.9 7,700 100 7,330 250 306 10* 378 21 17.6 0.8 15.7 1.1 50 4 44 5 670 13 670 42 GH 2 13,440 2,300 10,100 4,600 3.7 0.3* 4.3 0.3 < 0.9 1.2 0.7 < 0.5 < 0.5 7,400 1,300 9,800 7,900 600 62 940 360 9.3 0.4 9.7 2.2 62 6 55 6 1,400 49 1,480 150 K1 10,700 3,000 14,800 3,600 9.6 0.3 10.1 0.4 8.2 0.8 7.6 1.1 21.6 1.3** 11.6 0.6 13,600 930** 19,600 720 366 36 376 450 9.9 0.8 11.0 0.7 64 8* 79 2 435 26 440 15 MG 1 5,100 42 2,380 1,800 4.5 1.3 6.5 2.9 5.5 0.1 11.0 3.8 17.4 2.3* 1.4 4.3 7,860 200** 5,800 44 527 14** 166 42 16.9 1.0 15.1 2.3 47 4 52 6 760 20 770 120 MG 2 4,904 67* < 2,000 3.4 0.2 2.7 2.3 4.6 0.1* 12.0 2.4 14.8 2.5** 0 1.8 9,500 320** 6,800 470 483 16** 157 62 45.5 3.0 41.9 3.8 40 4 49 5 895 9 820 120

The signicance of the difference between determined and estimated amounts was evaluated using an independent sample T test at the 95% (*) or the 99% (**) signicance level.

quent extraction and washing steps of the sequential procedure. For the other metals there generally was no signicant difference between the determined reducible fraction and that, estimated from single extractions. A difference in Pb for sample K 1 was slightly signicant. For Cu, amounts extracted during sequential extraction were signicantly higher. However, the amounts released in that fraction are low compared to the amount associated with the subsequent, oxidisable fraction and will therefore not inuence the overall distribution pattern of Cu. Oxidisable fraction The oxidisable fraction is determined after destruction of organic matter with hydrogen peroxide at pH 2 (Table 6). Because of the acidity, adsorbed metals and carbonate associated metals can be expected to be released when H2O2-extraction is applied to the fresh sediment (Table 7). A comparison of Ca extracted with H2O2 and acid extractable Ca (Table 4) suggests that the efficiency in releasing carbonates was at least similar to NaOAc-extraction. Because reacting conditions are oxidising rather than reducing, only approx. 10% of iron that may be released with NH2OH.HCl is dissolved by single H2O2extraction (Table 7). Sediment K 1, which was strongly reducing, was an exception. Iron sulphides present may explain the high levels of Fe extracted by H2O2 (Tessier et al., 1979; Shanon and White, 1991). Metals are extracted with a varying efficiency and may be as low as the sum of the exchangeable and acid extractable

fractions (e.g. Zn in GH 1), or higher than the sum of the exchangeable , acid extractable and reducible fractions (e.g. Pb in K 1). For example, single H2O2-extraction is able to efficiently release metal sulphides including the portion that may also be released by NH2OH.HCl (Shanon and White, 1991). In contrast, metals bound by iron oxides are not released by single H2O2-extraction, although they are efficiently released by NH2OH.HCl. Estimation of the oxidisable step from single extractions is therefore not possible. The oxidisable fraction may, however, be determined on the residue of the hydroxylamine hydrochloride extraction. Residual fraction The residual fraction may be estimated by subtracting the NH2OH.HCl-extractable amounts and the oxidisable fraction from the total content (Table 8). In most cases, there was no signicant difference between the determined residual content and the contents evaluated by difference. The standard deviations of the estimates by single extraction moreover were in the range of the standard deviations of the sequential extraction. For Zn, larger standard deviations on the estimates resulted from the standard deviations on the high acid extractable and reducible fractions. Metal fractionation The fractionations of selected metals, determined using sequential extraction and estimated from single extractions, are compared in Figure 1. Determined and estimated fractionation agreed fairly. Although differences were in several occasions statistically signicant, these

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Table 6 Oxidisable fraction determined by H2O2-extraction (mg kg1 dry matter SD) Metal Ca Cd Co Cu Fe Mn Ni Pb Zn GH 1 353 10 < 0.2 < 0.9 105 5 950 28 43 2 9.3 0.4 21 4 154 3 GH 2 1375 220 < 0.2 < 0.9 51 4 80 20 58 5 < 0.8 28 4 205 8 K1 670 51 < 0.2 10 0.1 115 3 9500 1200 49 1 14.7 0.3 92 10 90 2 MG 1 459 48 < 0.2 < 0.9 67 1 1300 63 35 2 6.0 0.3 10 1 121 12 MG 2 399 48 < 0.2 < 0.9 114 3 1760 44 38 2 14.0 0.2 < 1.4 143 9

Table 7 Metals released during single reagent extraction with H2O2 (mg kg1 dry matter SD) Metal Ca Cd Co Cu Fe Mn Ni Pb Zn GH 1 31,200 990 < 0.2 5.3 0.2 59 4 120 6 489 16 11.6 0.5 17 1 840 28 GH 2 30,000 860 < 0.2 < 0.9 32 1 68 10 942 54 9.3 0.5 27 1 1,150 25 K1 53,900 720 11.0 0.3 15.0 0.1 104 1 24,000 280 940 4 18.5 1.7 165 1 505 5 MG 1 27,800 660 7.1 0.7 5.9 0.5 49 2 131 13 182 58 9.4 0.5 19 3 470 50 MG 2 26,000 550 8.0 1.2 7.2 0.1 87 1 132 10 144 8 20.9 0.6 18 2 620 60

Table 8 Residual fraction determined (D) by sequential extraction and estimated (E) by subtraction of NH2OH.HCl-extractable amounts and the oxidisable fraction from aqua regia extractable amounts (mg kg1 dry matter SD) Metal Ca Cd Co Cu Fe Mn Ni Pb Zn D E D E D E D E D E D E D E D E D E GH 1 274 13 < 2000 < 0.9 < 1.2 5.7 0.5* 2.4 0.9 44 3 54 5 24,900 1,100 22,700 1,600 83 2** < 16 19 1** 11 1 245 11 245 8 76 5* < 35 GH 2 261 34 < 4000 < 0.9 1.1 1.1 <4 6.0 1.1 23 4 23 5 23,400 8,100 15,800 7,900 150 44 < 370 12 3 13 2 420 33 380 36 100 32 190 160 K1 328 10 < 3000 < 0.9 < 0.4 11.3 1.3** 4.0 1.5 27 1** < 5.0 30,700 680* 26,500 2,600 103 4 150 440 28 3* 19 3 23 1* < 10 66 2 45 17 MG 1 249 43 < 3000 < 0.9 < 1.1 7.6 3.1 7.1 5.6 47 8 57 10 3,750 2,500* 25,000 6,700 82 6 80 82 22 3 20 4 169 2 180 19 166 42 < 160 MG 2 269 47 < 2500 < 0.9 < 1.4 12.4 2.1 9.5 5.2 66 6 95 17 41,000 3,000 28,200 10,000 84 4 120 64 26 5 22 9 190 21 200 18 146 26 30 190

The signicance of the difference between determined and estimated amounts was evaluated using an independent sample T test at the 95% (*) or the 99% (**) signicance level.

would not seriously affect interpretation of the results. As discussed before, most of these differences were related to the propagation of errors in the fraction estimates rather than to systematic differences in extraction efficiency between the sequential and the single extraction approach.

CONCLUSIONS The data conrmed that the estimation of the exchangeable, acid extractable, reducible and residual fractions from single extractions on separate subsamples was in general equivalent to their determination using

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Figure 1 Metal fractionation of Cd, Co, Cu. Ni, Pb and Zn as a percent of total metal content, determined by sequential extraction (D) and estimated by single extractions (E).

sequential extraction for both reduced and oxidised sediments containing high levels of carbonates and organic carbon. The oxidisable fraction should be estimated from a H2O2-extraction on the residue of the NH2OH.HCl-extract.

Fractions estimated from single extractions agreed in most cases with these determined using sequential extraction. Signicant differences that were observed in some cases would not seriously affect interpretation of the results. The use of single extractions instead of

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Single extractions versus sequential extraction for the estimation of heavy metal fractions Analysis, Part 2. Chemical and Microbiological Properties, pp. 181-197. ASA, Madison, Wisconsin. Pickering, W.F. 1981. Selective chemical extraction of soil components and bound metal species. Crit. Rev. Anal. Chem., 12, 233-266. Rapin, F., Tessier, A., Campbell, P.G.C. and Carignan, R. 1986. Potential artifacts in the determination of metal partitioning in sediments by a sequential extraction procedure. Environ. Sci. Technol., 20, 836-840. Shannon, R.D. and White, J.R. 1991. The selectivity of a sequential extraction procedure for the determination of iron oxyhydroxides and iron suldes in lake sediments. Biogeochemistry, 14, 193-208. Stover, R.C., Sommers, L.E. and Silviera, D.J. 1976. Evaluation of metals in wastewater sludge. J. Water Pollut. Control Fed., 48, 2165-2175. Tack, F.M. and Verloo, M.G. 1995. Chemical speciation and fractionation in soil and sediment heavy metal analysis: a review. Intern. J. Environ. Anal. Chem., 59, 225-238. Tack, F.M.G., Vossius, H.A.H., Verloo, M.G. 1996. A comparison between sediment metal fractions, obtained from sequential extraction and estimated from single extractions. Intern. J. Environ. Anal. Chem., 63, 61-66. Tessier, A., Campbell, P.G.C. and Bisson, M. 1979. Sequential extraction procedure for the speciation of particulate trace metals. Anal. Chem., 51, 844-851. Ure, A.M. 1990a. Trace elements in soil: their determination and speciation. Fresenius J. Anal. Chem., 337, 577-581. Ure, A.M. 1990b. Methods of analysis for heavy metals in soils. In: Alloway, B.J. (ed.), Heavy Metals in Soils, pp. 40-73. Blackie and Son, Glasgow. Wallmann, K., Kersten, M., Gruber, J., Frstner, U. 1993. Artifacts in the determination of trace metal binding forms in anoxic sediments by sequential extraction. Intern. J. Environ. Anal. Chem., 51, 187-200. Paper received: 12 August 1997; accepted 22 September 1997.

sequential extraction to estimate metal fractions in soils and sediments hence can be justied for practical purposes. ACKNOWLEDGMENTS We wish to thank Herwig Vossius and Nico THooft for their valuable contributions to the experimental work and for the clarifying discussions. REFERENCES
Bendell-Young, L., Dutton, M. and Pick, F.R. 1992. Contrasting two methods for determining trace metal partitioning in oxidized lake sediments. Biogeochemistry, 17, 205219. Gambrell, R.P. 1994. Trace and toxic metals in wetlands a review. J. Environ. Qual., 23, 883-891. Gee, G.W. and Bauder, J.W. 1986. Particle-size analysis. In: Klute, A. (ed.), Methods of soil Analysis, Part 1. Physical and Mineralogical Methods, pp.377-382. ASA, Madison, Wisconsin. Gupta, S., Mehrotra, I. and Singh, O.V. 1990. Simultaneous extraction scheme: a method to characterize metal forms in sewage sludge. Environ. Technol., 11, 229-238. Kim, N.D. and Fergusson, J.E. 1991. Effectiveness of a commonly used sequential extraction technique in determining the speciation of cadmium in soils. Sci. Total Environ., 105, 191-209. Lund, W. 1990. Speciation analysis why and how? Fresenius J. Anal. Chem., 337, 557-564. Nelson, D.W. and Sommers, L.E. 1982. Total carbon, organic carbon, and organic matter. In: Page, A.L., Miller, R.H. and Keeney, D.R. (ed.), Methods of Soil Analysis, Part 2. Chemical and Microbiological Properties, pp.539-579. ASA, Madison, Wisconsin. Nelson, R.E. 1982. Carbonate and gypsum. In: Page, A.L., Miller, R.H. and Keeney, D.R. (ed.), Methods of Soil