An investigation of the origin and mobility of phosphorus in freshwater sediments from Bort-Les-Orgues Reservoir, France

In order to assess the origin and the potential mobility of phosphorus (P) in the sediment of the Bort-Les-Orgues Reservoir, France, two sequential extraction schemes, i.e., the SMT (modified Williams method) and the Golterman schemes, were compared. Finally, the potential mobility of P in this sediment was estimated from results of sequential extraction. The SMT method appeared to be more satisfactory than the Golterman method, which is in accordance with results from a study currently carried out in the framework of the European programme Standards, Measurements and Testing. Iron-bound P and organic P were the dominant forms of P in the sediment; these forms are likely to be released at the sediment/water interface in case of anoxia and could diffuse into the water column, thus increasing the risk of eutrophication in this sensitive reservoir. The P stock (330 +/- 66 t) is not negligible and should be taken into account in any restoration project of the reservoir. The SMT procedure seems promising and will provide, in the near future, a valuable tool for water managers in the field of lake restoration.     

Accelerated fractionation of heavy metals in contaminated soils and sediments using rotating coiled columns

A new approach to performing an accelerated sequential extraction of trace elements from solid samples has been proposed. It has been shown that rotating coiled columns (RCC) earlier used in counter-current chromatography can be successfully applied to the dynamic leaching of heavy metals from soils and sediments. A solid sample was retained in the rotating column as the stationary phase under the action of centrifugal forces while different eluents (aqueous solutions of complexing reagents, mineral salts and acids) were continuously pumped through. The procedure developed is time saving and requires only 4-5 h instead of the several days needed for traditional sequential extraction (TSE), complete automation being possible. Losses of solid sample are minimal. In most cases the recoveries of readily bioavailable and leachable forms of Pb, Zn, and Cd are higher, if a dynamic extraction in RCC is used. Since naturally occurring processes are always dynamic, continuous extraction in RCC may help to estimate the contents of leachable forms and their potential risk for the environment more correctly than batch TSE. The Kersten-Foerstner and McLaren-Crawford leaching schemes have been compared, the former has been found to be preferable.     

Comparison of three sequential extraction procedures for partitioning of heavy metals in car park dusts

The aim of this study was to elucidate the amount of metal released at each step by using different extractants in three sequential extraction schemes for the partitioning of metal contents of car park deposited dust samples. For this purpose, three different sequential extraction procedures (SEP) were employed for the metal fractionation in car park dust samples collected from the campus of Erciyes University, Kayseri, Turkey. While two of the sequential extraction procedures contain five steps the other, namely the BCR sequential extraction scheme, has three steps. The first two methods fractionate metals to be exchangeable, bound to carbonates, bound to Mn oxides, bound to Fe oxides and bound to organic matter, and the BCR protocol fractionates the metals as acid soluble and exchangeable, reducible, and oxidisable. Determination of the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn was performed by flame atomic absorption spectrometry (FAAS). The results obtained by the three methods were compared and showed that the amount of metal released at each step of the leaching procedure depended both on the type of reagents used and the sequence in which they were applied. The most mobile elements were Cd, Pb and Zn which are metals potentially toxic to the environment and are also known to originate from traffic. The calculated enrichment factors for Cd and Pb were substantially high (73.5-187 and 18.4-27.5, respectively) and somewhat lower for Zn (5.1-6.8). These results confirm that they are important metal pollutants for car parks. Detection limits and recoveries were found in the range of 0.01-1.39 microg ml(-1) and 68-126%, respectively, for the metals studied and the three sequential extraction procedures.     

Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials

The Standards, Measurements and Testing Programme (formerly BCR) of the European Commission proposed a three-step sequential extraction procedure for sediment analysis, following extensive expert consultations and two interlaboratory studies. This scheme was recently used to certify the extractable trace element contents of a sediment reference material (CRM 601). Although this procedure offers a means to ensure the comparability of data in this field, some difficulties concerning the interlaboratory reproducibility still remain, and a new project is currently being conducted to determine the causes of poor reproducibility in the extraction scheme. The final objective of the project is the certification of new sediment and soil reference materials for their extractable contents of Cd, Cr, Cu, Ni, Pb and Zn. This paper presents the results of a small-scale interlaboratory study, which aimed to test a revised version of the extraction schemes by comparing the original and the modified protocols using the CRM 601 sample. This work offers an improvement to the BCR sequential extraction procedure through intercomparison exercises. This improved procedure will allow the obtaining of CRMs to validate analytical data in the analysis of soils and sediments, and it will also facilitate comparability of data in the European Union.     

Speciation/fractionation of nickel in airborne particulate matter: improvements in the Zatka sequential leaching procedure

Modifications are reported to the sequential leaching analytical method for nickel speciation/fractionation specified by Zatka so that larger sample masses can be analyzed. Improvements have been made in the completeness of the sulfide/metallic separation during the peroxide-citrate leach step by use of a larger volume of leachant, a longer leach duration and an orbital shaker. Minimal extraction of metallic nickel in this prolonged sulfidic nickel extraction has been confirmed. An increase in the number of samples analyzed simultaneously using these modifications has resulted in substantial productivity improvements and concomitant lower costs. It is critical for practitioners of sequential leaching techniques to recognize potential limitations and to use professional judgment when interpreting results. For example, results obtained may not be biologically relevant in assessing health risks; the acts of sampling and storage may result in changes in fractionation with time; surface coatings/films may alter the ability of a leachant to react with the target compound; and leaching behaviours may be different for samples differing only in particle size distributions.     

Conventional, microwave, and ultrasound sequential extractions for the fractionation of metals in sediments within the Petrochemical Industry, Serbia

In this paper, the main objective was fractionation of Cd, Cu, Ni, Pb, Zn, Ca, Fe, and K in certificate material and sediment samples gathered from and around the Petrochemical Industry using the conventional, microwave and ultrasonic sequential extraction. Microwave oven and ultrasound bath were used as an energy source for achieving faster extraction. Additional heating and boiling of samples were avoided by using lower power and shorter time for microwave and ultrasound extraction. Precision and accuracy of procedure were evaluated by using certificate material (BCR701). Acceptable accuracy of metals (87.0–111.3 %) was achieved for all three-step sequential of conventional extraction protocol. An accuracy of the fourth step has been verified with two certificate materials: BCR143R and 146R. The range of total extracted metal concentrations from sediments was similar for all three extraction techniques. A significant high percentage of Cd, Cu, and Zn were obtained after extraction of the exchangeable and acid soluble sediment fraction. Principal component analysis of values obtained after determination of risk assessment code using conventional and ultrasound sequential extraction show similarity of these values. Accuracy, recovery, and risk assessment code values imply that ultrasound sequential extraction is a more suitable, accelerated sequential extraction procedure (30 min per extraction step) than microwave extraction in applied conditions.     

Speciation of heavy metals in biosolids of wastewater treatment plants at Mysore,Karnataka, India

Urban wastewater treatment leads to the generation of large quantities of biosolids. Accumulation of biosolids is a problem of environmental relevance due to the existence of heavy metals in the biosolids. Determination of total metal in biosolid provides information relating pollution levels. Determination of their mobilization capacity and behaviour in the environment is an important task. An experimental approach commonly used for studying the mobility, transport and bioavailability of metal in biosolids is the use of selective sequential extraction procedure. In the present study an attempt has been made to study the heavy metal properties in biosolid samples collected from urban wastewater treatment plants located at Mysore, Karnataka. Few heavy metals selected for the present study are cadmium, chromium, copper, iron, nickel and zinc. The concentration of these metals in biosolids and their partition in different fractions are studied. The speciation of metals based on the sequential extraction scheme was carried out. The concentration of heavy metals is lower than that established by European legislation. The residual fraction has the maximum percentage of heavy metals whereas, only a small fraction of heavy metals (Fe, Zn and Cd) are extracted in the most soluble fractions, exchangeable and carbonate fractions.     

Evaluation of performance of time-saving extraction devices in the BCR three-step sequential extraction procedure

Two alternative extraction methods--a routine ultrasonic bath and a microwave oven--were developed and optimized for their eventual exploitation in the three-stage sequential extraction procedure proposed by the European Standards, Measurements and Testing (S, M & T) Programme, formerly Bureau Communitaire de Reference (BCR), for the operationally defined speciation of Cd, Cr, Cu, Ni and Zn. The conventional BCR three-stage sequential extraction procedure was modified at each stage, applying ultrasonic or microwave devices in order to shorten the required 16 h of shaking in all three steps. The experimental tests and the optimization of the operating parameters were carried out on a highly homogenized estuarine sediment reference material (RM S7) prepared by the Joint Research Centre (JRC) of ISPRA. Extractable metal contents were measured by inductively coupled plasma-mass spectrometry (ICP-MS) and the results obtained in each fraction by all three methods were statistically compared for all the studied elements. The conventional and newly developed alternative extraction methods were finally compared by the analysis of BCR 601, which is certified for the three-step BCR sequential extraction procedure. According to the statistical evaluation of the results, the proposed accelerated sequential extraction methods are valid alternatives to conventional shaking, with much shorter extraction times.     

Chemical techniques for assessing bioavailability of sediment-associated contaminants: SPME versus Tenax extraction

The traditional approach for predicting the risk of hydrophobic organic contaminants (HOCs) in sediment is to relate organic carbon normalized sediment concentrations to body residues or toxic effects to organisms. However, due to the multiple variables controlling bioavailability, this method has limitations. A matrix independent method of predicting bioavailability needs to be used in order to be universally applicable. Both chemical activity (freely dissolved chemical concentrations) measured by solid-phase microextraction (SPME) and bioaccessibility (rapidly desorbing fraction) estimated by Tenax extraction have been developed to predict bioavailability of sediment-associated HOCs. The objectives of this review are to summarize a number of studies using matrix-SPME or Tenax extraction to estimate bioavailability and/or toxicity of different classes of HOCs and evaluate the strengths and weakness of these two techniques. Although the two chemical techniques assess different components of the matrix, estimates obtained from both techniques have been correlated to organism body residues. The advantages of SPME fibers are their applicability for use in situ and their potential usage for a wide array of contaminants by selection of appropriate coatings. Single time-point Tenax extraction, however, is more time- and labor-effective. Tenax extraction also has lower detection limits, making it more applicable for highly toxic contaminants. This review also calls for additional research to evaluate the role of sequestrated contaminants and ingestion of sediment particles by organisms on HOC bioavailability. The use of performance reference compounds to reduce SPME sampling time and linking chemical based bioavailability estimates to toxicological endpoints are essential to expand the applications of these methods.     

Risk assessment of trace metals in an extreme environment sediment: shallow,hypersaline, alkaline,and industrial Lake Acıgöl,Denizli, Turkey

The major and trace element component of 48 recent sediment samples in three distinct intervals (0–10, 10–20, and 20–30 cm) from Lake Ac?göl is described to present the current contamination levels and grift structure of detrital and evaporate mineral patterns of these sediments in this extreme saline environment. The spatial and vertical concentrations of major oxides were not uniform in the each subsurface interval. However, similar spatial distribution patterns were observed for some major element couples, due mainly to the detrital and evaporate origin of these elements. A sequential extraction procedure including five distinct steps was also performed to determine the different bonds of trace elements in the <?60-μ particulate size of recent sediments. Eleven trace elements (Ni, Fe, Cd, Pb, Cu, Zn, As, Co, Cr, Al and Mn) in nine surface and subsurface sediment samples were analyzed with chemical partitioning procedures to determine the trace element percentage loads in these different sequential extraction phases. The obtained accuracy values via comparison of the bulk trace metal loads with the total loads of five extraction steps were satisfying for the Ni, Fe, Cd, Zn, and Co. While, bulk analysis results of the Cu, Ni, and V elements have good correlation with total organic matter, organic fraction of sequential extraction characterized by Cu, As, Cd, and Pb. Shallow Lake Ac?göl sediment is characteristic with two different redox layer a) oxic upper level sediments, where trace metals are mobilized, b) reduced subsurface level, where the trace metals are precipitated.     

Sequential extractions of selenium soils from Stewart Lake: total selenium and speciation measurements with ICP-MS detection

Different techniques have been employed in order to evaluate the most efficient procedure for the extraction of selenium from soil as required for speciation. Selenium contaminated sediments from Stewart Lake Wetland, California were used. A strong acid mineralization of the samples gives quantitative total selenium, which is then used to estimate recoveries for the milder extraction methods. The different extraction methodologies involve the sequential use of water, buffer (phosphate, pH 7) and either acid solution (e.g. HNO3 or HCl) or basic solutions (e.g. ammonium acetate, NaOH or TMAH). Pyrophosphate extraction was also evaluated and showed that selenium was not associated with humic acids. The extractants were subsequently analyzed by size exclusion chromatography (SEC) with UV (254 and 400 nm) and on-line ICP-MS detection; anion exchange chromatography, and ion-pair reversed phase chromatography with ICP-MS detection. For sequential extractions the extraction efficiencies showed that the basic extractions were more efficient than the acidic. The difference between the acidic and the basic extraction efficiency is carried to the sulfite extraction, suggesting that whatever is not extracted by the acid is subsequently extracted by the sulfite. The species identified with the different chromatographies were selenate, selenite, elemental selenium and some organic selenium.     

Development of an Overall Index of Pollution for Surface Water Based on a General Classification Scheme in Indian Context

Various National and International Agencies involved in water quality assessment and pollution control have defined water quality criteria for different uses of water considering different indicator parameters. Classification schemes for water quality criteria/standards developed by these agencies differ inaddition to terminologies used such as Action level, Guide level etc. in defining the concentration values in these classes. In the present article a general classification scheme viz. Excellent,Acceptable, Slightly Polluted, Polluted and Heavily Polluted water is proposed for surface water quality assessment. The concentration ranges in these classes are defined in Indianscenario considering Indian Standards and CPCB criteria. Standardsby the European Community (EC), WHO etc. and the reported factsabout the pollution effects of important water quality indicatorparameters on the surrounding were also taken into account. Themathematical equations to transform the actual concentrationvalues into pollution indices are formulated and correspondingvalue function curves are plotted. Based on the individual indexvalues, an `Overall Index of Pollution' (OIP) is estimated. Theapplication of OIP is demonstrated at a few sampling stations onriver Yamuna based on observed water quality data. The general classification scheme along with concentrationranges defined in these classes will be of immense use fordetermining the surface water quality status with reference tospecific individual parameter, and the OIP for assessing theoverall water quality status in Indian context.     

Selection and evaluation of sequential extraction procedures for the determination of phosphorus forms in lake sediment

In order to achieve comparable measurements in the determination of phosphate forms in freshwater sediments, the Standards, Measurements and Testing Programme (formerly BCR) of the European Commission has launched a project the first step of which was to select and evaluate collaboratively existing extraction procedures. This was carried out through expert consultations and a literature survey, and was followed by the organisation of a first interlaboratory study for the evaluation of four sequential extraction schemes, one of which was selected as the most promising method for achieving comparability. This scheme, a modified version of the Williams protocol, was further tested in a second interlaboratory study. The so-called SMT extraction scheme seems promising and will provide, in the near future, a valuable tool for water managers in the field of lake restoration. It will be particularly helpful in estimating the stock of P potentially available, hence the risk of eutrophication due to internal P release.     

Sequential element extraction of soils from abandoned farms: an investigation of the partitioning of anthropogenic element inputs from historic land use

Enhanced soil element concentrations may serve as indicators not only of modern pollution, but also of former historic and/or pre-historic human activity. However, there is little consensus over the most appropriate means of extraction for identifying chemical signatures of modern and archaeological pollution. This study addressed this question by using a 5-step sequential extraction to examine the partitioning of elements within the soil. Samples were taken from known functional areas (hearth, house, byre, arable, and grazing areas) on a 19th century abandoned croft (small farm). A hot nitric acid digest and five-stage sequential extraction method were used to examine the partitioning of elements in soil and identify the current elemental distribution of anthropogenic contamination. The results indicate that although a significant proportion of Ca tends to be bound with exchangeable and weak acid soluble fractions, in the hearth and house areas there is also a significant proportion held within the recalcitrant residue. Pb concentrations tend to be associated with organic matter, ammonium oxalate extractable fractions and the residue, whilst Zn generally has a more even partitioning between the six soil fractions. The implications of this for extraction methodology are element and soil specific. However, the presence of a significant proportion of anthropogenically significant elements (including Ca, Pb, Zn, Sr, and Ba) within the resistant residue suggests the use of only a weak acid or an exchangeable fraction extraction would result in the loss of information from contamination resulting from former human activity. Hence, a total or pseudo-total extraction method is recommended for this type of study.     

Application of a modified BCR sequential extraction (three-step) procedure for the determination of extractable trace metal contents in a sewage sludge amended soil reference material (CRM 483), complemented by a three-year stability study of acetic acid and EDTA extractable metal content

This paper provides additional data on a sewage sludge amended soil certified reference material, CRM 483, which was certified in 1997 for its EDTA and acetic acid extractable contents of some trace metals, following standardised extraction procedures. The additional work aimed to test the long-term stability of the material and the applicability of an improved version of the BCR three-step sequential extraction procedure on the sewage sludge amended soil (CRM 483). The paper demonstrates the CRM 483 long-term stability for EDTA and acetic acid extractable contents of Cd, Cr, Cu, Ni, Pb and Zn and gives the results (obtained in the framework of an interlaboratory study) for the extractable contents of the same elements in the CRM 483, following the BCR three-step sequential extraction scheme. The aqua regia extractable contents following the ISO 11466 Standard are also given. The data are given as indicative (not certified) values.     

Fractionation and ecotoxicological implication of potentially toxic metals in sediments of three urban rivers and the Lagos Lagoon,Nigeria, West Africa

The potential environmental impact of sediment-bound Cd, Cr, Cu, Pb and Zn in three trans-urban rivers in Lagos state and in the Lagos Lagoon was assessed by use of the modified Community Bureau of Reference (BCR) sequential extraction. The quality of the data was checked using BCR CRM 143R and BCR CRM 701. Good agreement was obtained between found and certified/indicative values. Of the rivers, the Odo-Iyaalaro, was generally the most contaminated and the Ibeshe the least. Higher concentrations of metals were generally found in the dry season compared to the wet season. Cadmium and Zn were released mostly in the acid exchangeable step of the sequential extraction, indicating that they have the greatest potential mobility and bioavailability of the analytes studied. Chromium and Cu were associated mainly with the reducible and oxidisable fractions, and Pb predominantly with the reducible and residual fractions. Sediments with the highest pseudototal analyte concentrations also released higher proportions of analytes earlier in the sequential extraction procedure. The study suggests that, during the dry season, potentially toxic metals (PTM) may accumulate in sediments in relatively labile forms that are released and can potentially be transported or bioaccumulate in the rainy season. Application of risk assessment codes and Hankanson potential risk indices indicated that Cd was the element of greatest concern in the Lagos Lagoon system. The study indicated that there is a need to strengthen environmental management and pollution control measures to reduce risk from PTM, but that even relatively simple strategies, such as seasonal restrictions on dredging and fishing, could be beneficial.     

Certification of the extractable contents of Cd, Cr, Cu, Ni, Pb and Zn in a freshwater sediment following a collaboratively tested and optimised three-step sequential extraction procedure

Sequential extraction procedures have been used during the last decades to study and determine trace element mobility in aquatic sediments. However, the results obtained are operationally defined and, therefore, the significance of the analytical results is related to the extraction scheme used. So, there is a need for suitable reference materials for this type of study to enable the validation of the methodologies and to control the quality of the measurements. This paper describes the preparation of a sediment reference material, BCR-701, the homogeneity and stability studies and the analytical work performed for the certification of the extractable contents of some trace elements, following a collaboratively tested and optimised sequential (three-step) extraction procedure. The paper contains all the results and gives the methods used to certify the extractable contents (mass fractions expressed as mg kg-1 on a dry matter basis) of Cd, Cr, Cu, Ni, Pb and Zn in all steps. Moreover, indicative values are given for the aqua regia extractable contents of the six elements in the sediment and the residue obtained after sequential extraction.     

Leaching Characteristics of Heavy Metals and As from Two Urban Roadside Soils

The leaching tests, including the Toxicity Characteristic Leaching Procedure (TCLP), EDTA extraction and BCR sequential extractions before and after EDTA treatments, were performed on two specific soils to elucidate heavy metal-associated mineral fractions and general leachability. The TCLP illustrated the low leachability of heavy metals in soils from two sites. EDTA is a strong chelator and therefore had higher extraction efficiency compared to that of TCLP. The lower extraction percentages by EDTA for As and Sb were found compared to the other heavy metals derived from anthropogenic sources. Sequential extractions showed that the importance of acid-extractable, organically-bound and Fe–Mn oxide fractions was identified for anthropogenic heavy metals with the exception of As and Ni while the importance of residual fraction was identified for endogenous metals. Changes in sequential fractions of heavy metals after leaching with EDTA are very complex and it is difficult to generalize on which fraction was more mobile than the others. These combined results are helpful in elucidating the association of heavy metals to soil fractions and the mobility characteristics of heavy metals under certain environmental conditions.     

SMT法测定沉积物标准样品有机磷形态分析方法探究

目前水体沉积物中磷的分级提取没有统一的方法,不同的提取方法分析沉积物中的磷形态结果可能会有很大差异。SMT法因操作简单、重复性好而被广泛应用于沉积物磷形态分析,但是在实际操作中连续提取过程比较复杂,尤其是有机磷(OP)提取步骤比较繁琐,中间转移过程较多,分析人员人为操作等因素都会导致实验出现较大误差,通过多次实验研究发现,在此基础上还存在另外一种改进的OP提取方法。为了验证改进法是否具有合理可行性,以水系沉积物标准样品GSD-9和GSD-12为标样,同时以野外采集的沉积物样品为实际样品,采用标准SMT法和改进法重复测定(n=30)沉积物中OP含量。结果表明:标准SMT法提取沉积物标准样品GSD-9和GSD-12测得的OP含量分别占其总磷(TP)含量的9.33%和23.03%;改进法测得的OP含量分别占其TP含量的10.44%和23.13%,两种OP提取方法测得结果有着极高的相似性。结果表明,改进的OP提取方法具有可行性,对于沉积物OP分析提取方法的合理选择具有指导意义。     

Distribution and partitioning of iron, zinc, and arsenic in surface sediments in the Grande River mouth to Cuitzeo Lake, Mexico

Cuitzeo Lake is one of the largest and most important lakes in Mexico. It receives different types of pollutants through its main tributary, the Grande River of Morelia. The aim of this work was to determine if high concentrations of iron, zinc, and arsenic are present in sediments in an area near the river mouth to the lake, as well as to estimate the partitioning of these metals using a sequential extraction procedure in order to obtain information of their potential bioavailability. Sediment samples were collected from three different sites in Cuitzeo Lake and two sites in Grande River in both dry and wet seasons. A sequential extraction procedure was carried out to determine the concentrations of these elements in different geochemical phases of the sediments. Total metal concentrations were evaluated by using the enrichment factor and the geoaccumulation index. A comparison with sediment quality guidelines and shale values has also been made. The results indicate that sediments are considered unpolluted by iron and moderately polluted by zinc and arsenic. However, fractionation studies showed that significant amounts of Zn and As could be released to the lake ecosystem depending on the environmental conditions, representing a medium risk potential of bioavailability to the biota.