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.     

Determination of total and EDTA extractable metal distributions in the colloidal fraction of contaminated soils using SdFFF-ICP-HRMS

Newly developed methods involving an on-line combination of sedimentation field-flow fractionation-inductively coupled plasma-high resolution mass spectrometry (SdFFF-ICP-HRMS) have been used to study the distributions of extractable heavy metals in a soil which had been treated with sewage sludge contaminated with Cu or Pb. The relationship of these metals with other elements in the colloidal fraction was also investigated. The colloidal fraction from the soil was obtained by repeated gravitational sedimentation and extracted with 0.11 M acetic acid, 0.1 M hydroxylamine hydrochloride, 0.05 M ethylenediaminetetraacetic acid disodium salt (EDTA) or aqua regia to assess the potential availability of the metals Cu and Pb. Large proportions of the Cu and Pb were extracted by EDTA, approaching that removed by aqua regia, whereas < 10% of the aqua regia extractable metals were removed by acetic acid and hydroxylamine chloride. The distributions of the heavy metals, the major mineral forming element (Al) and the elements forming sesquioxides (Fe and Mn) within different size classes (0.05-1 microm) of the colloidal fraction were measured using SdFFF-ICP-HRMS before and after extraction with EDTA. This information provides an insight into the composition of the colloids and the distributions of metal contaminants. In the contaminated soil colloids, the concentration of Fe, Mn and Pb is greatest in the smaller particles (<0.2 microm). In contrast, the Cu concentration is constant over the size range studied. Iron oxide surface coatings probably play a significant role in Pb adsorption on soil particles, but may be less important for Cu. The combination of selective chemical extraction, SdFFF and ICP-HRMS provides a means of determining the distribution of potentially available heavy metals within the colloidal fraction of contaminated soils.     

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.     

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.     

Environmental risk assessment of heavy metal extractability in a biosludge from the biological wastewater treatment plant of a pulp and paper mill

A five-stage sequential extraction procedure was used to fractionate heavy metals (Cd, Cu, Pb, Cr, Zn, Fe, Mn, Ni, Co, As, V and Ba) in a biosludge from the biological wastewater treatment plant of Stora Enso Oyj Veitsiluoto Mills at Kemi, Northern Finland, into the following fractions: (1) water-soluble fraction, (2) exchangeable fraction, (3) easily reduced fraction, (4) oxidizable fraction, and (5) residual fraction. The biosludge investigated in this study is a combination of sludge from the primary and secondary clarifiers at the biological wastewater treatment plant. Extraction stages (2)–(4) follow the protocol proposed by the Measurements and Testing Program (formerly BCR Programme) of the European Commission, which is based on acetic acid extraction (stage 2), hydroxylamine hydrochloride extraction (stage 3), and hydrogen peroxide digestion following the ammonium acetate extraction (stage 4). The residual fraction (stage 5) was based on digestion of the residue from stage 4 in a mixture of HF + HNO₃ + HCl. Although metals were extractable in all fractions, the highest concentrations of most of the metals occurred in the residual fraction. From the environmental point of view, it was notable that the total heavy metal concentrations in the biosludge did not exceed the maximal allowable heavy metal concentrations for sewage sludge used in agriculture, set on the basis of environmental protection of soil by European Union Directive 86/278/EEC, and by the Finnish legislation. The Ca (98.6 g kg⁻¹; dry weight) and Mg (2.2 g kg⁻¹; dry weight) concentrations in the biosludge were 62 and 11 times higher than the typical values of 1.6 and of 0.2 g kg⁻¹ (dry weight), respectively, in arable land in Central Finland. The biosludge had a slightly alkaline pH (∼8.30), a high loss-on-ignition value (∼78%) and a liming effect of 10.3% expressed as Ca equivalents (dry weight). This indicates its potential as a soil conditioner and improvement agent, as well as a pH buffer.     

Chemical sequential extraction for metal partitioning in environmental solid samples

A comprehensive review of the sequential extraction schemes for metal fractionation in environmental samples (ie., sediment, soil, sewage sludge, fly ash, etc.) is presented. The review contains more than 400 references and covers principally the literature published over the last decade. The use of each reagent involved in these schemes is looked at critically, and guidelines for their selectivity and extraction capacity are given. The operational character of these schemes is emphasised. Topics such as comparability between sequential extraction schemes of widespread use, harmonisation, acceleration, validation, etc. are addressed and future developments outlined.     

Analytical approaches to the determination of phosphorus partitioning patterns in sediments

Three methods for phosphorus fractionation in sediments based on chemical extractions have been applied to fourteen aquatic sediment samples of different origin and characteristics. Two of the methods used different approaches to obtain the inorganic fractions. The Hieltjes and Lijklema procedure (HL) uses strong acids or bases, whereas the Golterman procedure (G) uses chelating reagents. The third one, the Standards, Measurements and Testing (SMT) protocol, was proposed in the frame of the SMT Programme (European Commission) which aimed to provide harmonisation and the validation of such methodologies. This harmonised procedure was also used for the certification of the extractable phosphorus contents in a sediment certified reference material (CRM BCR 684). Principal component analysis (PCA) was used to group sediments according to their composition and the three extraction methods were applied to the samples including CRM BCR 684. The data obtained show that there is some correlation between the results from the three methods when considering the organic and the residual fractions together. The SMT and the HL methods are the most comparable, whereas the G method, using a different type of reagent, yields different distribution patterns depending on sample composition. In relation to the inorganic phosphorus, the three methods give similar information, although the distribution between non-apatite and apatite fractions can be different.     

A new organic-rich soil reference material certified for its EDTA- and acetic acid- extractable contents of Cd, Cr, Cu, Ni, Pb and Zn, following collaboratively tested and harmonised procedures

There is an increasing requirement for assessment of the bioavailable metal fraction and the mobility of trace elements in soils upon disposal. One of the approaches is the use of leaching procedures, but the results obtained are operationally defined; therefore, their significance is highly dependent on the extraction protocol performed. So, for this type of study, there is a need for reference materials that allow the quality of measurements to be controlled. This paper describes the steps involved in the certification of an organic-rich soil reference material, BCR-700, for the EDTA- and acetic acid-extractable contents of some trace elements, following collaboratively tested and harmonised extraction procedures. Details are given for the preparation of the soil, homogeneity and stability testing, analytical procedures and the statistical selection of data to be included in the certification.     

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.     

Effect of ultrasonic agitation on the release of copper, iron, manganese and zinc from soil and sediment using the BCR three-stage sequential extraction

An ultrasonic bath and an ultrasonic probe have been used to develop rapid versions of the three-stage Community Bureau of Reference (BCR, now the Standards, Measurement and Testing Programme) sequential extraction procedure. The effect of the ultrasonic treatments on the extraction of copper, iron, manganese and zinc from a sewage sludge-amended soil has been assessed. Recoveries similar to those of conventional shaking (i.e., conventional value, +/- 30%) could generally be obtained for copper, manganese and zinc, but not for the important matrix element iron. With the use of compromise sonication conditions, steps 1, 2 and 3 of the sequential extraction (excluding the hydrogen peroxide digestion in step 3, which was not performed with sonication) could be completed in 3, 5 and 1 min, respectively, using the ultrasonic probe, and in 3, 1 and 1 h, respectively, using the bath. The extraction procedures developed using the soil performed well when applied to lake sediment BCR CRM 601. Analyte partitioning was generally similar to that obtained with mechanical shaking, and overall metal recoveries were 84-98% of those obtained with the conventional BCR protocol, except for copper extracted with the probe (74%). Poorer performance (analyte recoveries, 58-104%) was obtained when the methods were applied to an intertidal sediment. This highlights the difficulty of developing a version of the BCR extraction, with ultrasonic assistance, which gives a performance equivalent to conventional shaking when applied to different substrates.     

Investigation of trace elements in agricultural soils by BCR sequential extraction method and its transfer to wheat plants

In this study, soil samples were collected from Edirne, Turkey in both summer and winter seasons and subjected to the modified Community Bureau of Reference (BCR) sequential extraction procedure in order to investigate the chemical partitioning of metals in soils and to predict heavy metals uptake by wheat grains which grown at the same soils. The samples were subjected to a three stage extraction procedure proposed by the BCR. The three phases that were separated out in the following order: (1) carbonate, exchangeable, (2) Fe?CMn oxides, and (3) organic matter. Metal concentrations of soil fractions and grain samples were determined by inductively coupled plasma atomic emission spectroscopy. The wheat samples were prepared to analysis using microwave acid digestion procedure. The pseudo-total concentrations of metals were determined after aqua regia digestion. The analytical accuracy of the method was evaluated by using the Standard Reference Materials (BCR 142R Light Sandy Soil, NIST 2711 Montana Soil, and NIST 2704 Buffalo River Sediment). The sum of the metal contents obtained from the modified BCR sequential extraction procedure and pseudo-total metal contents for soil samples were used to calculate recovery values. In order to evaluate the bioavailability of metals, the relationships between the wheat-metal and soil-extractable metal concentrations were compared.     

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.     

A field screening test for the assessment of concentrations and mobility of potentially toxic elements in soils: a case study on urban soils from Rome and Novi Sad

The increasing demand for environmental pollution control results in the development and use of new procedures for the determination of dangerous chemicals. Simple screening methods, which can be used directly in the field for a preliminary assessment of soil contamination, seem to be extremely advantageous. In our laboratory, we developed and optimized a rapid test for a preliminary evaluation of both the concentration and the mobility of some potentially toxic metals in soils. This screening test consists of a single extraction of the soil sample with a buffer solution, followed by the titration of the extracted solution with dithizone to determine the contents of bi-valent heavy metals (such as Pb, Cu, Zn, and Cd). This screening method was then directly applied in the field during the sampling campaign in the framework of an Italian–Serbian collaborative project, finalized in the study of metal availability in soils. The results obtained in the field with the rapid test were compared with those obtained in the laboratory following the conventional procedure commonly used to evaluate metal bioavailability (diethylenetriaminepentaacetic extraction). Moreover, selected samples were analyzed sequentially in the laboratory using the standardized BCR three-step sequential extraction procedure. The screening test gave results conceptually in good agreement with those obtained via the BCR procedure. These preliminary data show that the proposed screening test is a reliable method for the preliminary rapid evaluation of metal total concentrations and of potential metal mobility in soils, supporting sampling activities directly in the field.     

Continuous-flow fractionation of trace metals in environmental solids using rotating coiled columns. Some kinetic aspects and applicability of three-step BCR leaching schemes

The applicability of the three-step BCR leaching scheme to the continuous-flow fractionation of trace metals (TM) using rotating coiled columns (RCC) has been investigated taking soil and sediment reference samples (SRM-2710, CRM-601, BCR-701) as examples. A particulate sample was retained in the rotating column as the stationary phase under the action of centrifugal forces while different eluents, used according to the original and optimised BCR protocols, were continuously pumped through. The whole procedure required 3-4 h instead of at least 50 h needed for the traditional sequential extraction. It has been shown that in comparison with batch sequential extraction procedures (SEP), the recoveries of Cd, Zn, Cu, and Pb at the first stage (most mobile and potentially dangerous acid soluble forms) are somewhat higher, if a dynamic extraction in RCC is used. Nevertheless, the distribution patterns for TM in the first two leachable fractions (acid soluble and reducible forms) are similar in most cases. Since no heating is used in RCC, the recoveries of TM at the third stage (when hydrogen peroxide is applied to oxidize the organic matter) may be incomplete and matrix-dependent. The effect of eluent volume and flow rate on the recovery of TM in different forms has been investigated. It has been shown that the kinetics of heavy metal leaching vary significantly with samples. Hence, investigating the elution profiles can provide additional important information for risk assessment of TM mobilization.     

Influence of solvent and soil type on the pressurised fluid extraction of PAHs

Pressurised fluid extraction (PFE) of polycyclic aromatic hydrocarbons (PAHs) from a certified reference material (CRM) 524 has been firstly optimised following a central composite design. The instrumental parameters of the PFE (pressure, temperature, extraction time and number of solvent cycles) were studied in order to obtain maximum extraction yields. Neither pressure nor extraction time or temperature seemed to have any significant effect on the extraction yield, therefore one extraction cycle was enough to exhaustively extract all the PAHs from CRM 524. Once the instrumental conditions were established, the extraction yields obtained with eight different solvents or solvent mixtures [acetone, dichloromethane, acetonitrile, acetone-dichloromethane (1 + 1 v/v), acetone-isohexane (1 + 1 v/v), isohexane, methanol and toluene] from the CRM 524 were compared and showed that the best recoveries were obtained with acetone-isohexane (1 + 1 v/v). Finally, the effect of sand, silt, clay and the organic matter content of soil was investigated with respect to recovery of PAHs by PFE with different solvents or solvent mixtures for aged soil samples. In this case, eight soils with different sand, silt, clay and organic matter contents were slurry spiked with PAHs and aged for 19 days. Three aliquots of each slurry spiked soil were extracted with the previously mentioned solvents and the results were studied by means of principal component analysis (PCA) of the whole data set (soil composition, solubility parameter of the solvent and recoveries of all PAHs) and partial least squares (PLS). Clay and organic matter content and the squared solubility parameter have the highest correlation with the recovery of PAHs from soil samples.     

Comparison of three sequential extraction protocols for the fractionation of potentially toxic metals in coastal sediments

In the determination of the best sequential extraction procedures (SEP) for the speciation of metals in sediment samples from the Lagos lagoon system, three sequential extraction procedures were compared for the fractionation of Cd, Cr, Cu, Pb, and Zn. The SEP compared included a modified Tessier??s procedure carried out in five steps, while the two other procedures were the three-step original Community Bureau of Reference (BCR) and the modified BCR techniques (four steps). Quantification of the metal concentration was achieved with a flame atomic absorption spectrophotometer. The results obtained by the three methods were compared, and the modified BCR and Tessier SEP were found to extract more Cu, Cr, Pb, and Zn in the reducible phase and therefore a decrease in the oxidizable phase than the original BCR SEP. The most mobile elements were found to be Cd, Pb, and Zn. These are of environmental concern, as these potentially toxic metals could be easily released into the aquatic environment with consequent ingestion by aquatic organisms, thereby entering the food chain. The mass balance (percent recovery) was found to be between 85% and 115% in most cases. Prior to the comparison, the analytical performance of the laboratory was tested using a secondary reference material, GLAURM, using the three-step modified BCR procedure. The results showed high reliability of the analytical performance of the laboratory for all the metals considered.     

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.     

An assessment of the bioavailability of persistent organic pollutants from contaminated soil

A procedure to assess the bioavailability of persistent organic pollutants (POPs) from soil samples has been developed. The procedure is based on the use of simulated in vitro gastrointestinal extraction to remove POPs from soil matrices. The level of recovery, using this approach, is assessed following liquid-liquid extraction (LLE) and analysis by gas chromatography-mass selective detection (GC-MSD). The remaining soil residue is then extracted using pressurised fluid extraction (PFE) followed by GC-MSD analysis to assess the residual fraction. The residual fraction is monitored to determine the unavailable fraction i.e. not available for absorption in the gastrointestinal tract of humans. The procedure was applied to four soil samples i.e. an aged, spiked soil and three certified reference materials (CRMs) contaminated with POPs. Recoveries of pesticides (lindane, endosulfan I, endrin, DDE, DDD and endosulfan II), phenols (cresol, TCP and PCP), and base neutral compounds (hexachloroethane, acenaphthene, dibenzofuran, fluorene and hexachlorobenzene) from aged, spiked soil following extraction with gastric fluid ranged from 0.8 to 8.3% while following intestinal extraction ranged from 5.5 to 13.5%, irrespective of POP. Recoveries of pesticides (lindane, endosulfan I, endrin, DDE, DDD and endosulfan II) from CRM 805-050 following extraction with gastric fluid were below the limit of detection while following intestinal extraction ranged from 5.3 to 12.8%. Recoveries of phenols (cresol, TCP and PCP) from CRM 401-225 following extraction with gastric fluid ranged from 1.6 to 2.0% while following intestinal extraction ranged from 4.1 to 5.4%. Recoveries of base neutral acid analytes (hexachloroethane, acenaphthene, dibenzofuran, fluorene and hexachlorobenzene) from CRM 107-100 following extraction with gastric fluid ranged from 1.4 to 4.0% while following intestinal extraction ranged from 6.6 to 12.7%. It has been found that the majority of POPs present i.e. >75%, would be excreted if consumed and not be absorbed in the gastrointestinal tract of humans.     

Plants as biomarkers for monitoring heavy metal contaminants on landfill sites using sequential extraction and inductively coupled plasma atomic emission spectrophotometry (ICP-AES)

There have been a number of studies investigating metal uptake in plants on contaminated landfill sites, but little on their role as biomarkers to identify metal mobility for continuous monitoring purposes. Vegetation can be used as a biomonitor of site pollution, by identifying the mobilisation of heavy metals and by providing an understanding of their bioavailability. Plants selected were the common nettle (Uritica Dioica), bramble (Rubus Fruticosa) and sycamore (Acer Pseudoplatanus). A study of the soil fractionation was made to investigate the soil properties that are likely to influence metal mobility and a correlation exercise was undertaken to investigate if variations in concentration of metals in vegetation can reflect variations in concentration of the metals in soil. The soil was digested using aqua regia in a microwave closed vessel. The vegetation was digested using both microwave and a hydrogen peroxide-nitric acid mixture, refluxed on a heating block and a comparison made. The certified reference materials (CRMs) used were Standard Reference Material (SRM) 1547, peach leaves for vegetation (NIST) and for soil CRM 143R, sewage sludge-amended soil (BCR). The relative standard deviations (RSDs) were 2-6% for the analyses. Our findings show evidence of phytoextraction by some plants, (especially bramble and nettle), with certain plants, (sycamore) exhibiting signs of phytostabilisation. The evidence suggests that there is a degree of selectivity in metal uptake and partitioning within the plant compartments. It was also possible to correlate mobility phases of certain metals (Pb, Cu and Zn) using the soil and plant record. Zn and Cu exhibited the greatest potential to migrate from the roots to the leaves, with Pb found principally in the roots of ground vegetation. Our results suggest that analysis of bramble leaves, nettle leaves and roots can be used to monitor the mobility of Pb in the soil with nettle, bramble and sycamore leaves to monitor Cu and Zn.     

Comparison of unmodified and modified BCR sequential extraction schemes for the fractionation of heavy metals in shrimp aquaculture sludge from Selangor, Malaysia

A study was carried out to investigate the fractionation of Cd, Cr, Cu, Fe, Mn, Pb, and Zn in shrimp aquaculture sludge from Selangor, Malaysia, using original (unmodified) and modified four-steps BCR (European Community Bureau of Reference, now known as the Standards Measurements and Testing Program) sequential extraction scheme. Step 2 of the unmodified BCR procedure (subsequently called Method A) involves treatment with 0.1 M hydroxylammonium chloride at pH 2, whereas 0.5 M hydroxylammonium chloride at pH 1.5 was used in the modified BCR procedure (subsequently called Method B). Metal analyses were carried out by flame atomic absorption spectrometry. A pseudo-total aqua-regia digest of BCR CRM 701 has also been undertaken for quality assurance purposes. The recovery of Method A for all metals studied ranges from 96.14% to 105.26%, while the recovery for Method B ranges from 95.94% to 122.40%. Our results reveal that Method A underestimated the proportion of metals bound to the easily reducible fraction except for copper. Therefore, the potential mobility of these elements is higher than others. Thus, to use this sludge as a fertilizer we have to first find a remediation for reduction of heavy metal contamination.