Talanta 46 (1998) 449 455

Extraction procedures for the determination of heavy metals in contaminated soil and sediment
Gemma Rauret
Dept. Qu mica Anal tica, Uni6ersitat de Barcelona, Barcelona, Spain Received 25 May 1997; accepted 14 October 1997

Abstract Extraction tests are commonly used to study the mobility of metals in soils and sediments by mimicking different environmental conditions or dramatic changes on them. The results obtained by determining the extractable elements are dependent on the extraction procedure applied. The paper summarises state of the art extraction procedures used for heavy metal determination in contaminated soil and sediments. Two types of extraction are considered: single and sequential. Special attention is paid to the Standard, Measurement and Testing projects from the European Commission which focused on the harmonisation of the extraction procedures and on preparing soil and sediment certied reference materials for extractable heavy metal contents. 1998 Elsevier Science B.V. All rights reserved. Keywords: Extraction procedures; Heavy metals; Contaminated soil; Sediment; Certied reference materials

1. Introduction Trace metals in soils and sediments may exist in different chemical forms or ways of binding. In unpolluted soils or sediments trace metals are mainly bound to silicates and primary minerals forming relatively immobile species, whereas in polluted ones trace metals are generally more mobile and bound to other soil or sediments phases. In environmental studies the determination of the different ways of binding gives more information on trace metal mobility, as well as on their availability or toxicity, in comparison with the total element content. However, the determination of the different ways of binding is difcult and often impossible. Different approaches are used for soil and sediment analysis, many of them

focused on pollutant desorption from the solid phase; others are focused on the pollutant adsorption from a solution by the solid phase. Among those approaches based on desorption, leaching procedures are the most widely accepted and used. Extraction procedures by means of a single extractant are widely used in soil science. These procedures are designed to dissolve a phase whose element content is correlated with the availability of the element to the plants. This approach is well established for major elements and nutrients and it is commonly applied in studies of fertility and quality of crops, for predicting the uptake of essential elements, for diagnosis of deciency or excess of one element in a soil, in studies of the physical-chemical behaviour of elements in soils

0039-9140/98/$19.00 1998 Elsevier Science B.V. All rights reserved. PII S 0 0 3 9 - 9 1 4 0 ( 9 7 ) 0 0 4 0 6 - 2

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and for survey purposes. To a lesser extent they are applied to elements considered as pollutants such as heavy metals. The application of extraction procedures to polluted or naturally contaminated soils is mainly focused to ascertain the potential availability and mobility of pollutants which is related to soil-plant transfer of pollutants and to study its migration in a soil prole which is usually connected with groundwater problems [1]. For sediment analysis, extraction is used to asses long term emission potential of pollutants and to study the distribution of pollutants among the geochemical phases. As far as heavy metals are concerned sediments are usually a sink but may also become a source under certain conditions, especially in heavily contaminated areas or in drastically changing environments. Chemical extraction of sediments has proven to be adequate for determining the metal associated with source constituents in sedimentary deposits [2], but the general aim of many studies involving chemical extraction is the determination of element distribution among different phases of a sediment. Single extractants are usually chosen to evaluate a particular release controlling mechanism such as desorption by increasing salinity or complexing by competing organic agents. Generally, fractions can be isolated more specically by using sequential extraction schemes. For sediments these procedures are frequently used and are designed in relation to the problems arising from disposal of dredged materials. Extraction tests, either in soils and sediments, are always restricted to a reduced group of elements and as far as soil is concerned they are applied to a particular type of soil; silicious, carbonated or organic. In a regulatory context, two applications for leaching tests can be recognised: the assessment or prediction of the environmental effects of a pollutant concentration in the environment and the promulgation of guidelines or objectives for soil quality as for example for land application of sewage sludge or dredge sediments. The data obtained when applying these tests are used for decision makers in topics such as land use of soil or in countermeasures application.

2. Commonly used extraction procedures in soils During the last decades several extraction procedures for extractable heavy metals in soils have been developed and modied. In this respect, two groups of tests must be considered: the single reagent extraction test, one extraction solution and one soil sample, and in the sequential extraction procedures, several extraction solutions are used sequentially to the same sample although this last type of extraction is still in development for soils. Both types of extraction are applied using not only different extracting schemes but also different laboratory conditions. This leads to the use of a great deal of extraction procedures. In Table 1 a summary of the most common leaching test are given.
Table 1 Most common single extraction tests Group Acid extraction Type and solution strength HNO3 0.43 2 mol l1 Aqua regia HCl 0.1 1 mol l1 CH3COOH 0.1 mol l1 Melich 1: HCl 0.05 mol l1+H2SO4 0.0125 mol l1 Reference [3] [4] [3] [5] [6]

Chelating agents

EDTA 0.01 0.05 mols l1 [3] at different pH DTPA 0.005 mol l1+TEA [7] 0.1 mol l1 CaCl2 0.01 mol l1 Melich 3: [8] CH3COOH 0.02 mol l1 NH4F 0.015 mol l1 HNO3 0.013 mol l1 EDTA 0.001 mol l1 NH4 acetate, acetic acid buffer pH = 7; 1 mol l1 NH4 acetate, acetic acid buffer pH = 4.8; 1 mol l1 [9] [3] [3] [3] [3] [10] [3] [11] [12]

Buffered salt solution

Unbuffered salt CaCl2 0.1 mol l1 solution CaCl2 0.05 mol l1 CaCl2 0.01 mol l1 NaNO3 0.1 mol l1 NH4NO3 1 mol l1 AlCl3 0.3 mol l1 BaCl2 0.1 mol l1

G. Rauret / Talanta 46 (1998) 449455 Table 2 Extraction methods proposed for standardisation or standardised in some European countries Country Germany France Method 1 mol l1 NH4NO3 0.01 mol l1 Na2 EDTA+1 mol l1 CH3COONH4 at pH = 7 DTPA 0.005 mol l1+TEA 0.1 mol l1+ CaCl2 0.01 mol l1 at pH = 7.3 0.02 mol l1 EDTA+0.5 mol l1 CH3COONH4 at pH = 4.6 DTPA 0.005 mol l1+TEA 0.1 mol l1+ CaCl2 0.01 mol l1 at pH = 7.3 CaCl2 0.1 mol l1 NaNO3 0.1 mol l1 Method Mobile trace element determination Reference [15]

451

Available Cu, Zn and Mn evaluation for fer- [16] tilisation purposes

Italy

Available Cu, Zn, Fe and Mn evaluation in acidic soils

[17]

Netherlands Switzerland

Availability and mobility of heavy metals in polluted soils evaluation

[18]

Soluble heavy metal (Cu, Zn, Cd, Pb and [19] Ni) determination and ecotoxicity risk evaluation Cu availability evaluation [20]

United Kingdom

EDTA 0.05 mol l1 at pH = 4

From Table 1 it can be observed that a single extraction including a large spectra of extractants are used. It ranges from very strong acids, such as aqua regia, nitric acid or hydrochloric acid, to neutral unbuffered salt solutions, mainly CaCl2 or NaNO3. Other extractants such as buffered salt solutions or complexing agents are frequently applied, because of their ability to form very stable water soluble complexes with a wide range of cations. Hot water is also used for the extraction of boron. Basic extraction by using sodium hydroxide is used to assess the inuence of the dissolved organic carbon in the release of heavy metals from soils. A large number of extractants are reviewed by Pickering [13] and Lebourg [14]. The increasing performance of the analytical techniques used for element determination in an extract, together with the increasing evidence that exchangeable metals better correlate with plant uptake, has lead extraction methods to evolve towards the use of less and less aggressive solutions [10]. These solutions are sometimes called soft extractants and are based on non buffered salt solutions although diluted acids and complexant agents are also included in the group. Neutral salts dissolve mainly the cation exchangeable fraction although in some cases the complexing ability

of the anion can play a certain role. Diluted acids dissolve partially trace elements associated to different fractions such as exchangeable, carbonates, iron and manganese oxides and organic matter. Complexing agents dissolve not only exchangeable element fraction but also the element fraction forming organic matter complexes and the element fraction xed on the soil hydroxides. Nowadays it is generally accepted that extractants are not selective and that minor variations in analytical procedures have signicant effects on the results. Some leaching procedures for soils have been adopted ofcially or its adoption is under study in different countries with different objectives [14]. An account of these methods are given on Table 2.

3. Commonly used extraction procedures in sediments As for soils, exchangeable metal in sediments are selectively displaced by soft extractants. Other extractants used are less selective and they co-extract the exchangeable fraction together with metals bound to different sediment phases more

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or less extensively. The phases considered relevant in heavy metals adsorption in sediments are oxides, sulphides and organic matter. Fractionation is usually performed by using sequential extraction schemes. The fractions obtained, when applying these schemes, are related to exchangeable metals, metals mainly bound to carbonates, metals released in reducible conditions such as those bound to hydrous oxides of Fe and Mn, metals bonded to oxidable components such as organic matter and sulphides and residual fraction. The extractants more commonly used in sequential extraction schemes are generally applied according to the following order: unbuffered salts, weak acids, reducing agents, oxidising agents and strong acids. In Table 3 the extractants most commonly used to isolate each fraction are given [21]. The water soluble fraction may be obtained by two ways, by sampling sediment pore solution using in situ ltration, dialysis tubes or bags, or by a leaching procedure in the laboratory. When this procedure is used the pH may be indeterminate because of
Table 3 Most common extractants used in sequential extraction schemes Group Water soluble fraction Exchangeable and weakly adsorbed fraction Type and solution strenght H2O NaNO3 0.1 mol l1 KNO3 0.1 mol l1 MgCl2 1 mol l1 CaCl2 0.05 mol l1 Ca(NO3)2 0.1 mol l1 NH4OAc 1 mol l1 pH = 7 Carbonate bound fraction HOAc 0.5 mol l1 HOAc/NaOAc 1 mol l1 pH = 5 NH2OH.HCl 0.04 mol l1 in acetic or nitric acid NH4Ox Sodium ditionite, sodium citrate, sodium bicarbonate (DCB) H2O2 NaOCl

the low buffering capacity of the extractant and problems with readsorption occurs. Exchangeable fraction uses an electrolyte such as salts of strong acids and bases or salts of weak acids and bases at pH 7 to prevent oxyhydroxy phases precipitation. The carbonate bound fraction generally uses an acid such as acetic or a buffer solution acetic acid-sodium acetate at pH 5. These reagents are not able to attack all the carbonate content, as for example dolomitic carbonates, neither to attack carbonate selectively as they also remove partially organically bound trace metals. The fraction obtained when a reducing solution is used as extractant is mainly related to metals bound to iron and manganese oxides. Hydroxylamine in acid solution is the reducing agent most widely used to solubilise these oxides although iron oxide is not completely dissolved. Ammonium oxalate seems to be most effective when used in the dark, although some problems in heavy metals oxalate phase precipitation may occur even at low pH. The sodium dithionite/citrate/carbonate reagent dissolves the oxide and hydroxyoxides but can attack iron rich silicates. So reducing extractants are neither selective nor completely effective for iron and manganese oxides. Other group of extractants used sequentially includes oxidising reagents which destroy organic matter and also oxidises sulphides to sulphates. The extractants most widely used in this group are H2O2 and NaOCl. Hydrogen peroxide seems to be more efcient if used after the oxide extraction step. The most widely used extraction scheme is the one proposed by Tessier [22] which has been modied by several authors [2325]. Many of these modications make more specic the isolation of the iron and manganese oxide and hydroxide phases. The Tessier procedure is schematised in Table 4 together with the modied procedures of Fo rstner [26] and of Meguelatti [24].

Fractions bound to hydrous oxides of Fe and Mn

4. Harmonisation and method validation Owing to the need of establishing common schemes in Europe for extractable trace metals in soils and sediments the EC Standards, Measurement and Testing Programme, formerly BCR (Bu-

Organically bound fraction

G. Rauret / Talanta 46 (1998) 449455 Table 4 Sequential extraction schemes Method Tessier et al. 1 MgCl2 mol l1 pH 7 exchangeable Fo rstner NaOAc 1 mol l1 pH 5 exchan+carb 2 NaOAc 1mol l1 pH 5 carbonate NH2OH.HCl 0.1 mol l1 easily reducible 3 4 5 HF/HClO4 residual silicate phase HNO3 residual silicate phase ashing + HF/HCl residual silicate phase

453

NH2OH.HCl 0.04 mol H2O2 8.8 mol l1 l1 25% HOAc HNO3/NH4OAc Fe/Mn oxides organic matter+sulphide NH4Ox/HOx 0.1 mol l1 pH 3 in dark moderately reducible NaOAc 1 mol l1 pH 5 carbonate H2O2 8.8 mol l1 pH 7 NH4OAc organic matter+sulphide NH2OH.HCl 0.1 mol l 1 25%HOAc Fe/Mn oxides

Meguellati

BaCl2 1 mol l1 H2O2 8.8 mol l1+ HNO3 pH 7 exchangeable organic matter+sulphide

reau Community of Reference), has sponsored from 1987 several projects focused on single extraction for soils and sequential extraction for soils and sediments. The project started with the intercomparison of existing procedures tested in an interlaboratory exercise [27]. The next step was to adopt common procedures for single extraction of trace metals from mineral soils. The second step was to adopt a common procedure for sequential extraction of sediment. As a conclusion of the rst step, single extraction procedures using acetic acid, 0.43 mol l 1, and EDTA, 0.005 mol l 1 for mineral soils and a mixture of DTPA, 0.005 mol l 1 diethylenetriamine pentaacetic acid, 0.01 mol l 1 CaCl2 and 0.1 mol l 1 triethanolamine for calcareous soils were adopted for extractable Cd, Cr, Cu, Ni, Pb and Zn. In order to improve the quality of the determination of extractable metal content in different types of soil using the procedures previously adopted, the extraction procedures were validated by means of intercomparison exercises [28,29]. Moreover the lack of suitable certied reference materials for this type of studies did not enable the quality of the measurements to be controlled. With the purpose to overcome this problem three certied reference materials: a terra rossa soil, a sewage amended soil and a calcareous soil have been

prepared and their extractable trace metal contents were certied (CRM 483, CRM 484 and CRM 600) [30,31]. The second step of the EC, Standards, Measurement and Testing was focused on a feasibility study on the adoption and validation of a sequential extraction scheme for sediment samples. In a workshop held in 1992 in Sitges (Spain) a sequential extraction scheme was proposed which includes three steps: acetic acid, hydroxylamine hydrochloride or a reducing reagent and hydrogen peroxide or an oxidising reagent. This procedure is schematised in Table 5. Moreover in this workshop the main analytical limitations in sequential extraction of trace metals in sediments were thoroughly discussed and practical recommendations were given [32,33]. These recommendations deal with sampling and sample pre-treatment, practical experiences with reagents and matrices and analytical problems after extraction. Once the scheme was designed, it was tested through two round robin exercises using two different type of sediment, silicious and calcareous [34]. In these exercises some critical parameters in the protocol were identied such as the type and the speed of the shaking and the need of an optimal separation of the liquidsolid phases after the extraction. It was stated that the sediment

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should be continually in suspension during the extraction. In these intercomparison exercises an important decrease was noted on the acceptable set of values for concentration in the extract lower than 10 mg l 1, which illustrates the difculties experienced by a number of laboratories in the determination of such concentration levels in these matrices. It was concluded that when electrothermal atomic absorption spectrometry is used for the nal determination, the method of standard additions is strongly recommended for calibration. The results obtained in the round robin exercises encouraged to proceed with the organisation of a certication campaign in order to produce a sediment reference material following the sequential extraction scheme adopted. So the next step of the project was the preparation of a sediment certied reference material for the extractable contents of Cd, Cr, Cu, Ni. Pb and Zn, following the three-step sequential extraction procedure. A silicious type sediment with rather high trace metal content was chosen for this purpose. This material has been recently certied for ve metals, Cd, Cr, Ni, Pb and Zn in the rst step, Cd, Ni and Zn in the second step and Cd, Ni and Pb in the third step [35]. Not all the elements
Table 5 EC Standard, Measurements and Testing procedure Step 1 Conditions 0.11 mol l1 HOAc, V m1 40 ml g1 temp. 20oC, shaking overnight 0.1 mol l1 NH2OH.HCl (pH = 2 with HNO3) V m1 40 ml.g1 temp. 20oC shaking overnight 8.8 mol l1 H2O2 (pH = 23 with HNO3) V m1 = 10 ml g1 room temperature 1h. New addition 10 ml g1 85oC for 1h. reduce volume to few ml. 1 mol l1 NH4Oac (pH = 2 with HNO3) V m1 = 50 ml g1 20oC shaking overnight

were certied because the lack of reproducibility atributable to non adherence to the protocol, in the acceptance of too large tolerances in the conditions specied in it or in the existence of critical aspects in the procedure referred mainly to the second step. These aspects were mainly pH, redox conditions and possible losses of sediment in the transfer. The results obtained in the certication exercise recommended to continue the development of the extraction protocol in order to increase reproducibility. Consequently the causes of non reproducibility are now under study in a new SMT project. 5. Conclusions The advantages of a differential analysis over investigations of total metal contents and about the usefulness of single and sequential chemical extraction for predicting long-term adverse effects of heavy metals from polluted solid material, soils and sediments, is beyond any doubt. The advances in this eld, especially to make available soil and sediment certied reference materials for extractable element contents by using harmonised procedures, is going to increase the quality of the results due to the possibility of verifying the analytical quality control. Nevertheless some problems need to be solved with these procedures for example: (1) reactions are not selective and are inuenced by the experimental conditions so it is necessary to identify the main variables which involves a lack of reproducibility when applying a procedure, to write very well dened protocols and to validate them; (2) labile fractions could be transformed during sample preparation and during sequential extraction schemes application so problems encountered when preparing certied reference materials are not representing all the problems to be found when working with environmental samples such as wet sediments, some work in this area is needed; (3) analytical problems due to the low level of metals to be measured in the different fractions especially when using soft extractants; and (4) the procedures need to be optimised and validated for different type of soils, including organic soils and sediments.

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