Certified reference material for the quality control of EDTA- and DTPA-extractable trace metal contents in calcareous soil (CRM 600)

Single extraction tests are commonly used to study the eco-toxicity and mobility of metals in soils, e.g. to assess the bioavailable metal fraction (and thus to estimate the related phyto-toxic and nutritional deficiency effects) and the environmentally accessible trace metals upon disposal of e.g. sediment on to a soil (e.g. contamination of ground waters). However, the lack of uniformity in the different procedures does not allow the results to be compared worldwide nor the procedures to be validated. This paper describes the interlaboratory testing of EDTA- and DTPA-extraction procedures for soil analysis, followed by the preparation of a calcareous soil reference material (CRM 600), the homogeneity and stability studies and the analytical work performed for the certification of the EDTA- and DTPA- extractable contents of some trace metals (following the standardized extraction procedures). Received: 21 May 1997 / Revised: 4 July 1997 / Accepted: 9 July 1997     

Certified reference material for the quality control of EDTA- and DTPA-extractable trace metal contents in calcareous soil (CRM 600)

Single extraction tests are commonly used to study the eco-toxicity and mobility of metals in soils, e.g. to assess the bioavailable metal fraction (and thus to estimate the related phyto-toxic and nutritional deficiency effects) and the environmentally accessible trace metals upon disposal of e.g. sediment on to a soil (e.g. contamination of ground waters). However, the lack of uniformity in the different procedures does not allow the results to be compared worldwide nor the procedures to be validated. This paper describes the interlaboratory testing of EDTA- and DTPA-extraction procedures for soil analysis, followed by the preparation of a calcareous soil reference material (CRM 600), the homogeneity and stability studies and the analytical work performed for the certification of the EDTA- and DTPA- extractable contents of some trace metals (following the standardized extraction procedures). Received: 21 May 1997 / Revised: 4 July 1997 / Accepted: 9 July 1997     

Single and Sequential Extraction in Sediments and Soils

Abstract

The determination of extractable trace metal contents in soils and sediments is currently performed in many laboratories to assess the bioavailable metal fraction (and related potential phyto-toxic effects) and the importance and possibility of mobilization of trace metals from polluted soil, sludge and sediment upon landfill application. Single and sequential extraction schemes are used for the assessment of the different “forms” of trace metals (e.g. “mobile/bioavailable”, “carbonate-bound” etc.). The lack of uniformity in the different extraction procedures used throughout the world does not allow the results to be compared or the procedures to be validated which has led to many criticisms in the past few years. Moreover, the lack of suitable reference materials for this type of operationally defined determinations did not enable the quality of the measurements to be controlled. Owing to the need for establishing common schemes for single and sequential extractions as well as for the improvement of the quality of extractable trace metal determinations in soil and sediments, the Community Bureau of Reference (BCR) has organised a project which results along with the state of the art of extractable trace metal determinations, use and applicability of extraction schemes and analytical limitations were decided to be thoroughly discussed in a workshop. This paper presents its main conclusions.     

Improvement of Analytical Measurements within the BCR-Programme: Single and Sequential Extraction Procedures Applied to Soil and Sediment Analysis

Abstract

The determination of extractable trace metal contents in soil and sediment, using respectively single and sequential extraction procedures, is currently performed in many laboratories to assess the bioavailable metal fraction (and related phyto-toxic effects) and the accessability to the environment (e.g. contamination of ground waters).

Owing to the need for validation of the extraction schemes used and of the analytical techniques, the Community Bureau of Reference (BCR) decided to organize a project for the improvement of the quality of determinations of extractable trace metal contents in soil and sediment. The implementation of this project follows a stepwise approach involving feasibility studies, intercomparisons to detect and remove sources of errors in the application of the analytical methods, and the certification of the extractable compounds. This paper describes the organization of the work completed so far (feasibility studies and first intercomparison) and discusses its further development.     

Extraction procedures for the determination of heavy metals in contaminated soil and sediment

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 certified reference materials for extractable heavy metal contents.     

The utilization of modified BCR three-step sequential extraction procedure for the fractionation of Cd, Cr, Cu, Ni, Pb and Zn in soil reference materials of different origins

A modified three-step sequential extraction procedure for the fractionation of heavy metals, proposed by the Commission of the European Communities Bureau of Reference (BCR) has been applied to the Slovak reference materials of soils (soil orthic luvisols, soil rendzina and soil eutric cambisol), which represent pedologically different types of soils in Slovakia. Analyses were carried out by flame or electrothermal atomic absorption spectrometry (FAAS or ETAAS). The fractions extracted were: exchangeable (extraction step 1), reducible-iron/manganese oxides (extraction step 2), oxidizable-organic matter and sulfides (extraction step 3). The sum of the element contents in the three fractions plus aqua-regia extractable content of the residue was compared to the aqua-regia extractable content of the elements in the origin soils. The accuracy obtained by comparing the determined contents of the elements with certified values, using BCR CRM 701, certified for the extractable contents (mass fractions) of Cd, Cr, Cu, Ni, Pb and Zn in sediment following a modified BCR-three step sequential extraction procedure, was found to be satisfactory.     

Operationally defined extraction procedures for soil and sediment analysis: II. Certified reference materials

Single or sequential extraction procedures are often used for soil and sediment studies to determine forms or phases of elements (e.g. ‘bioavailable' forms of elements). The significance of the analytical results is highly dependent on the extraction procedures used, owing to the ‘operationally defined' character of these schemes which requires the adoption of standardized protocols. The first part of the present review discusses the aspects of standardization of leaching and extraction schemes as applied to environmental analysis. This second part focuses on the validation aspects of such procedures and describes the preparation and certification of soil and sediment reference materials certified for their extractable trace element contents, following standardized single and sequential extraction procedures.     

NH4NO3 extractable trace element contents of soil samples prepared for proficiency testing--a stability study.

In view of its intended use as a sample for proficiency testing or as a reference material the stability of the extractable trace element contents of a soil from an irrigation field was tested using the extraction with 1 mol/L ammonium nitrate solution according to DIN 19730. Therefore, changes of the extractability of sterilized and non sterilized soil samples stored at different temperatures were evaluated over a period of 18 months. Sets of bottles were kept at -20 degrees C, +4 degrees C, about +20 degrees C and +40 degrees C, respectively. The NH4NO3 extractable contents of Cd, Cr, Cu, Ni, Pb and Zn were determined immediately after bottling and then after 3, 6, 12 and 18 months with ICP-AES or ETAAS. Appropriate storage conditions are of utmost importance to prevent deterioration of soil samples prepared for the determination of NH4NO3 extractable trace element contents. Temperatures above +20 degrees C must be avoided. The observed changes in the extractability of the metals (especially for Cr and Cu) most likely could be related to thermal degradation of the organic matter of the soil. There is no need to sterilize dry soil samples, because microbiological activity in soils with a low moisture content appears to be negligible with regard to trace element mobilization.     

Speciation of Heavy Metals in Soils and Sediments. An Account of the Improvement and Harmonization of Extraction Techniques Undertaken Under the Auspices of the BCR of the Commission of the European Communities

Abstract

An account is presented of a series of investigations and collaborative studies, initiated by BCR, on current methods of metal speciation by extraction of soils and sediments with chemical reagents. It was established by extensive consultation with European experts that the diverse procedures used could be harmonized into agreed methods. These methods, including both single extractant and sequential extraction procedures were subjected to collaborative, interlaboratory trials and the results, presented briefly here, showed that it was both possible and desirable that reference soils and sediments, characterised by certified values for extractable contents, be prepared. As a consequence of these studies two soils have been prepared and will shortly be the subject of interlaboratory analysis with a view to certification of their EDTA and acetic acid extractable contents of some heavy metals. Following this workshop a feasibility study of the agreed sequential extraction procedure will, it is believed, shortly lead to certification of sediments for contents extractable by a defined sequential extraction procedure.     

Operationally defined extraction procedures for soil and sediment analysis: II. Certified reference materials

Single or sequential extraction procedures are often used for soil and sediment studies to determine forms or phases of elements (e.g. `bioavailable' forms of elements). The significance of the analytical results is highly dependent on the extraction procedures used, owing to the `operationally defined' character of these schemes which requires the adoption of standardized protocols. The first part of the present review discusses the aspects of standardization of leaching and extraction schemes as applied to environmental analysis. This second part focuses on the validation aspects of such procedures and describes the preparation and certification of soil and sediment reference materials certified for their extractable trace element contents, following standardized single and sequential extraction procedures.     

Environmental cadmium, lead and nickel contamination: possible relationship between soil and vegetable content

Summary The cadmium, lead and nickel content of soils of four agricultural areas exposed to different degrees of environmental pollution and vegetables grown there were measured by Atomic Absorption Spectrophotometry (AAS). In order to ascertain the possible relationship between the heavy metal content of soils (total and extractable) and of vegetables grown in them, the correlation between the two was calculated. The highest correlation values between metal content of soil and vegetables are these corresponding to nickel: the total metal content in soils and leaves-stems are linear (p<0.01). The extractable metal content of soils and leaves-stems are linear (p<0.1). Therefore, soil seems to be the main contributor to nickel content of plants (leaves-stems). In the case of cadmium a statistically significant linear correlation (p<0.01) was observed between total metal content in soil and in leaves-stems and a negative one between extractable metal content of soils and that of roots-bulbs. For lead a negative correlation was found between extractable metal content of soils and leaves-stems. In any case, the lead content of soils is not the main factor that influences the lead content of vegetables. Anthropogenic and environmental factors play a more important role than the lead in soils in the lead content of vegetables.     

Anodic stripping voltammetric determination of lead and cadmium in soil extracts

Two single-step extraction procedures validated by BCR, extraction with 0.43 mol dm⁻³ acetic acid and 0.05 mol dm⁻³ EDTA, are used for assessing bioavailable species of Pb and Cd in soils. After an extensive study of interferences of humic substances and using standard additions procedures, the extractable contents of Pb and Cd have been determined by DPASV directly in soil extracts with a good reproducibility (RSD varied from 1.0 to 7.9 %). Pb(II) and Cd(II) were released from complex in EDTA extracts by pH adjustment to 1 with 1 mol dm⁻³ HCl. The results were compared with those obtained with atomic absorption spectrometry and indicated reasonable agreement of both methods. Exchangeable forms represented 0.2 to 3.3 % and 13.0 to 63.6 % of total content of Pb and Cd in soils, respectively. EDTA extraction released from soils 7.9 to 29.9 % and 33.5 to 59.6 % of total content of Pb and Cd, respectively.     

Influence of the physical properties and handling of silica gel modified carbon paste electrodes on the phase transfer of solved Cu(II) ions

EDTA, a powerful chelating agent, is used extensively in soil sciences to determine the bioavailability of trace metals and their possible decontamination from polluted soils. Because of its non-selective nature, the co-dissolution of major elements also occurs, in addition to the extraction of trace metal ions.In this work, the reactivity of trace and major elements (Pb, Cu, Cd, Al, Fe, Ca and Mg) with different concentrations of EDTA was studied in eight soil samples (Burgundy, France). The limit between lack and excess of EDTA with respect to total metal extracted, determined after 24 h of reaction for different types of soil varied from 0.002 to 0.05 M, respectively.For calcareous samples the amount of Pb, Cu and Cd extracted by EDTA was reduced to 50% of that extracted in non-calcareous soils.From the kinetic point of view, the extraction behavior of major elements seemed to depend heavily on excess or lack of EDTA and the soil Ca content. For a lack of EDTA, different competitive behaviors were revealed for the major elements (Al, Ca, Fe and Mg) towards the reagent, depending on the soil matrix.According to these experimental results, the mass balance between the reagent and cations in any EDTA-soil media is strongly controlled by major metal extraction. When choosing the reagent concentration needed to extract the trace metals efficiently, all the extractable metal present in the concerned sample must be taken into account.     

Extraction of soil organic phosphorus

Organic phosphorus is an important component of soil biogeochemical cycles, but must be extracted from soil prior to analysis. Here we critically review the extraction of soil organic phosphorus, including procedures for quantification, speciation, and assessment of biological availability. Quantitative extraction conventionally requires strong acids and bases, which inevitably alter chemical structure. However, a single-step procedure involving sodium hydroxide and EDTA (ethylenediaminetetraacetate) is suitable for most soils and facilitates subsequent speciation by nuclear magnetic resonance spectroscopy. Analysis of extracts by molybdate colorimetry is a potential source of error in all procedures, because organic phosphorus is overestimated in the presence of inorganic polyphosphates or complexes between inorganic phosphate and humic substances. Sequential extraction schemes fractionate organic phosphorus based on chemical solubility, but the link to potential bioavailability is misleading. Research should be directed urgently towards establishing extractable pools of soil organic phosphorus with ecological relevance.     

Evaluation of a sequential extraction procedure for the determination of extractable trace metal contents in sediments

The determination of extractable trace metals in sediments using sequential extraction procedures has been performed in many laboratories within the last ten years in order to study environmental pathways (e.g. mobility of metals, bounding states). However, the results obtained by different laboratories could hardly be compared due to lack of harmonized schemes. Owing to the need for standardization and subsequent validation of extraction schemes for sediment analysis, the Measurements and Testing Programme (formerly BCR Programme) of the European Commission has organized a project to adopt a sequential extraction procedure that could be used as a mean of comparison of data of extractable trace metals in sediments. A scheme was designed after a series of investigations on existing schemes and tested in interlaboratory studies. This paper presents the results of two round-robin exercises on extractable trace metals using this sequential extraction protocol and describes the final version of the extraction procedure amended according to the most recent improvements.     

Certified reference materials for the quality control of EDTA- and acetic acid-extractable contents of trace elements in sewage sludge amended soils (CRMs 483 and 484)

 The ecotoxicity and mobility of trace elements in soils are often evaluated through analytical results resulting from operationally-defined determinations (single and sequential extractions), e.g. based on EDTA, acetic acid etc. extractions. The significance and comparability of these results is highly dependent on the procedures used (standardized protocols or standards adopted by international bodies) and their quality control relies on the availability of reference materials certified following these strictly applied procedures. Recognizing the need to harmonize some of the extraction schemes currently used for soil analysis, the Measurements and Testing Programme (formerly BCR) has organized a series of interlaboratory studies, the first aim of which was to evaluate EDTA- and acetic acid-extraction procedures and the second objective was to certify reference materials for their extractable trace element contents. Two sewage amended soils have been prepared for this purpose, originating respectively from Scotland and Catalonia. This paper describes the preparation, homogeneity and stability studies, and gives an overview of the certification campaign. Received: 6 May 1996/Revised: 14 June 1996/Accepted: 27 June 1996     

Persistence of Metal Residues in Sewage Sludge Treated Soils Over Seventeen Years

Abstract

Results from two long-term sewage sludge experiments conducted on different soil types are presented. Sewage sludges highly contaminated with Cr, Cu, Ni or Zn and a relatively uncontaminated sludge were applied at both sites at the same rates and metal contents in 1968. The Cr-rich sludge also had a high Cd content. Plot soils were sampled in 1972, 1976 or 1977, 1981 and 1985 and total and extractable metal contents determined. Metals added in sewage sludge may change their form but persist in soils in an extractable and plant available form for many years. There is little difference in soil extractable contents or plant uptake of Cu and Zn whether sludge is applied as one single application or as its equivalent in four separate annual applications of one quarter the amount. The percentages of the total chromium contents extractable by both EDTA and acetic acid were small and this was reflected in a low uptake of this element by pasture herbage species (<0.3 mg Cr/kg DM).     

Utilization of optimized BCR three-step sequential and dilute HCl single extraction procedures for soil-plant metal transfer predictions in contaminated lands

The prediction of soil metal phytoavailability using the chemical extractions is a conventional approach routinely used in soil testing. The adequacy of such soil tests for this purpose is commonly assessed through a comparison of extraction results with metal contents in relevant plants. In this work, the fractions of selected risk metals (Al, As, Cd, Cu, Fe, Mn, Ni, Pb, Zn) that can be taken up by various plants were obtained by optimized BCR (Community Bureau of Reference) three-step sequential extraction procedure (SEP) and by single 0.5 mol L(-1) HCl extraction. These procedures were validated using five soil and sediment reference materials (SRM 2710, SRM 2711, CRM 483, CRM 701, SRM RTH 912) and applied to significantly different acidified soils for the fractionation of studied metals. The new indicative values of Al, Cd, Cu, Fe, Mn, P, Pb and Zn fractional concentrations for these reference materials were obtained by the dilute HCl single extraction. The influence of various soil genesis, content of essential elements (Ca, Mg, K, P) and different anthropogenic sources of acidification on extraction yields of individual risk metal fractions was investigated. The concentrations of studied elements were determined by atomic spectrometry methods (flame, graphite furnace and hydride generation atomic absorption spectrometry and inductively coupled plasma optical emission spectrometry). It can be concluded that the data of extraction yields from first BCR SEP acid extractable step and soil-plant transfer coefficients can be applied to the prediction of qualitative mobility of selected risk metals in different soil systems.     

NH4NO3 extractable trace element contents of soil samples prepared for proficiency testing – a stability study

In view of its intended use as a sample for proficiency testing or as a reference material the stability of the extractable trace element contents of a soil from an irrigation field was tested using the extraction with 1 mol/L ammonium nitrate solution according to DIN 19730. Therefore, changes of the extractability of sterilized and non sterilized soil samples stored at different temperatures were evaluated over a period of 18 months. Sets of bottles were kept at –20?°C, +4?°C, about +20?°C and +40?°C, respectively. The NH₄NO₃ extractable contents of Cd, Cr, Cu, Ni, Pb and Zn were determined immediately after bottling and then after 3, 6, 12 and 18 months with ICP-AES or ETAAS. Appropriate storage conditions are of utmost importance to prevent deterioration of soil samples prepared for the determination of NH₄NO₃ extractable trace element contents. Temperatures above +20?°C must be avoided. The observed changes in the extractability of the metals (especially for Cr and Cu) most likely could be related to thermal degradation of the organic matter of the soil. There is no need to sterilize dry soil samples, because microbiological activity in soils with a low moisture content appears to be negligible with regard to trace element mobilization.     

Trace elements in soil: Their determination and speciation

Summary The different types of soil analysis are reviewed in-outline and some recent developments and methodologies are discussed.For the determination of the total trace element content of soils, conventional, multi-element, solid sample methods including d.c. arc optical emission and spark source mass spectrometric procedures are briefly considered together with the potential of current X-ray fluorescence, solid sample graphite furnace atomic absorption and glow discharge mass spectrometry.The use of strong acid digestion, with for example aqua regia, for the determination of pseudo-total concentrations of heavy or toxic metal accumulations in soil is described.The limitations of solution methods for multi-element analysis of soils are outlined together with the prospects for the use of soil slurries to eliminate the sample preparation and dilution problems associated with the dissolution of soils. The difficulties in taking reproducible and representative samples of inhomogeneous materials such as soils are highlighted.Trace element speciation can be defined as the identification and quantification of the different forms or phases in which they occur in soils. Some examples of such procedures and extractants for both essential and toxic elements in soils are presented. The difficulties of trace element speciation in soils as distinct from soil extracts or soil solutions are illustrated briefly.