An ultrasound accelerated sequential extraction method and its application for element partitioning studies in compost from mixed waste streams

A rapid ultrasound accelerated sequential extraction procedure is presented which is modified from the standard BCR protocol and validated using the BCR 601 reference material. The method is accelerated at the extraction steps: for example, in the standard method each extraction step takes 16 h whereas with the ultrasonic extraction method developed in this work each step took 15 min. This means a further step can be included in the protocol without greatly increasing the experimental time. An extraction with pyrophosphate solution was therefore included to provide more information about the interaction between the elements and humic substances during the composting process. The new method has been applied to monitoring the metal partitioning behaviours in a composting process involving mixed waste streams. The metal partitioning profiles obtained from this new method show that in many cases composting tends to redistribute the metals from more labile forms to combined forms, especially to forms combined with humic substances.     

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.     

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.     

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.     

Addressing the challenges of tetracycline analysis in soil: extraction, clean-up, and matrix effects in LC-MS

An optimized extraction and clean-up method for the analysis of chlortetracycline, doxycycline, oxytetracycline, and tetracycline antibiotics in soil is presented in this work. Soil extraction using different solvents was performed, but the use of a 50 : 50 (v/v) methanol : acetate buffer (pH 8) solvent mixture in a pressurized liquid extraction (PLE) system proved to give the best extraction efficiency and reproducibility. The effect of soil composition on the PLE extraction efficiency was also examined, and results indicated that recovery data for one soil is not necessarily consistent with other soil types containing different compositions of clay and organic matter content. The percent recoveries of the optimized PLE method varied between the soils and ranged from 22-99%, depending on soil type, and more specifically clay content. In addition, the extent of ionization suppression caused by co-extracted humic acids was examined in an ion trap mass spectrometer (MS), and a single quadrupole MS. It was found that under positive electrospray ionization, the single quadrupole MS was less susceptible to ionization suppression than the ion trap MS. Therefore, various sample clean-up procedures were evaluated to selectively reduce the amount of co-extracted humic acids in the soil extracts. The most effective clean-up was obtained from the use of StrataX sorbent in combination with a strong anion exchange cartridge.     

Fractionation of traffic-emitted Ce, La and Zr in road dusts

The introduction of catalytic converters has led to a new environmental problem since catalysts emit platinum group elements (PGEs) which are among the least distributed elements in nature. Along with PGEs the vehicle exhaust catalysts contain also a number of stabilizers, commonly oxides of rare earth elements and alkaline earth elements such as Ce, La and Zr. Since vehicular emission of these elements has received little attention so far this work attempts to offer insight into their distribution and fate in the environment by measuring their speciation in road dust samples collected along several highways in Germany and a city centre (Saarbrücken). Speciation of the elements (fractionation into associated mineralogical phases) was carried out via a conventional sequential extraction protocol and the complexing abilities of humic substances in the organic matter were investigated by selective extraction methods in combination with size segregation. For evaluation purposes soil samples spiked with catalytic converter material were analyzed, showing a much lower fraction of Ce, La and Zr mobilized in comparison to the road dust samples. It was found that the elements were effectively bound to humic substances in road dust with a preference for complexation with low molecular weight compounds (<1600 Da).     

Development and application of microwave assisted extraction (MAE) for the extraction of five polycyclic aromatic hydrocarbons in sediment samples in Johannesburg area, South Africa

A microwave-assisted extraction (MAE) method was verified and applied for the extraction of polycyclic aromatic hydrocarbons (PAHs) in sediment samples. Soxhlet extraction was used as the reference method. The optimum MAE was carried out with 20 mL of hexane/acetone (1:1, v/v) mixture in a 1-g sample at 250 W for 20 min. Soxhlet extraction was carried out with 250 mL of dichloromethane:hexane (1:1, v/v) mixture in a 15-g sample for 24 h in a water bath maintained at 60 °C. The collected extracts were both cleaned up, reduced to 1 mL under nitrogen and then injected into an HPLC fluorescence. To increase the sample throughput, simultaneous MAE was performed. The obtained percentage recoveries ranged from 61 to 93 and 88–98 for MAE and SE, respectively. The optimised MAE method was validated using certified reference material. It was then applied to real sediment samples from in and around the greater Johannesburg area. The sediments from Jukskei River were found to be the most polluted while Hartbeespoort Dam sediments were found to be least polluted. The overall order of concentrations for the studied PAHs per site was as follows: Jukskei River?>?Kempton Park?>?Centurion Dams?>?Natalspruit River (PIT)?>?Hartbeespoort Dam.     

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.     

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.     

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.     

Comparison of SFE with Soxhlet in the analyses of PCDD/PCDFs and PCBs in sediment

The efficiency of supercritical fluid extraction (SFE) for the isolation of polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) from sediments was investigated by comparing SFE with Soxhlet. Five sediments obtained from an international interlaboratory study were used as a test material. SFE was performed with an automatic system where extracted analytes were collected by solid-phase trapping using carbon mixed with Celite as an adsorbent. For the first time, SFE of the most toxic PCBs, coplanar PCBs, was studied with real sediment samples. The majority of PCBs investigated, a total of 38 congeners from tri- to decachlorinated, were quantitatively extracted from sediment by SFE with pure CO2 at pressure 400 atm and temperature 100 degrees C. Under these conditions a successful extraction was obtained also for PCDD/PCDFs except for hepta- and octachlorinated congeners. Copper powder added to the sediment efficiently prevented the transfer of sulfur from the sample during SFE. The TEQs of both PCDD/PCDFs and PCBs obtained by SFE corresponded well with those obtained by the Soxhlet-based method. The reproducibility of SFE was high for both groups.     

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.     

Uranium speciation in moorland river water samples: a comparison of experimental results and computer model predictions

An on-line method has been developed for separating inorganic and organic bound uranium species present in river water samples. The method utilised a small chelating resin (Hyphan) column incorporated into the sample introduction manifold of an ICP-MS instrument. The method was evaluated for samples from rivers on Dartmoor (Devon, UK), an area of granite overlain with peat bogs. The results indicate that organic-uranium species form a major proportion (80%) of the total dissolved uranium present. Further work with synthetic water samples indicated that the level of dissolved organic carbon played a greater role in determining the level of organic-uranium species than did sample pH. Computer models for the water samples were constructed using the WHAM program (incorporating uranium data from the Nuclear Energy Agency Thermochemical Database project) in order to predict the levels of organic-uranium species that would form. By varying the proportion of humic and fulvic acids used in the humic component, predictions within 10% of the experimental results were obtained. The program did exhibit a low bias at higher pH values (7.5) and low organic carbon concentrations (0.5 microg ml(-1)), but under the natural conditions prevalent in the Dartmoor water samples, the model predictions were successful.     

Optimization of a multielement sequential extraction method employing an experimental design approach for metal partitioning in soils and sediments

The optimisation of a simple multielement extraction method employing an experimental design approach is described. The method uses centrifugation to pass one extractant solution at varying pH through a contaminated soil sample. The nature and concentration of the acid, rate of centrifugation and time, number of sequential leachates and the ratio of extractant volume: sample weight have been studied in order to obtain the optimum conditions for extraction. A fractional factorial experimental design was performed, and the results were used to identify significance which was then evaluated by carrying out a central composite experimental approach. Once optimum conditions had been obtained, sequential leaches were analysed by ICP-AES and chemometrics were employed to identify the composition of each component. Comparisons have been made with previous studies and tentative assignments, based on well defined separated fractions and percentage compositions for individual elements, used to identify the different physico-chemical components in the sample.     

Copper and other trace elements strongly bound to humic acids along sediment cores in the Ross Sea, Antarctica

Marine sediment cores sampled in three different areas, during the 1997/98 Italian Antarctic Expedition, were studied. The cores (40 cm) were immediately subdivided into 13 or 14 layers (2-4 cm) in order to obtain a high-depth resolution in the metal content and humic substance analyses. The results obtained for the amount of metals strongly bound to humic acids showed the following order: Cu > Zn > Co > As >or= Mn. The fraction of Cu, Zn and As bound to humic acid (microg g(-1) of HA) increases in the first 10-12 cm of cores, then a decrease is observed. This observation could be related both to the presence of a mobile fraction of metals in sediments successively bound to humic acids and to different structural features showed by humic acids along the cores, due to transformation processes. For the other metals a variable pattern along the cores was found.     

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。     

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.     

Strong correlations between metal in mollusk soft tissue and nonresistant sediment fraction: a tool for biomonitoring intertidal zone of the Persian Gulf,Iran

Cadmium (Cd) and lead (Pb) were determined in three species of mollusks and associated sediment. Samples were collected from two locations along the intertidal zone of the Persian Gulf near Bandar Abbas. The study was conducted during the spring of 2011, 10 sediment samples and 15 mollusks from each of the following species: Saccostrea cucullata, Solen brevis, and Callista umbonella, were simultaneously collected. Soft tissue, shell, and sediment were tested for metals using an atomic absorption spectrophotometer. Geochemical fractions of the sediment were examined for metals using a sequential extraction technique. Our results indicate that over half of Cd and Pb in the sediment had natural origins. Independent sample t test showed statistically significant (p?<?0.05) inter-tissue differences in accumulation of Cd and Pb. Soft tissue of C. umbonella contained highest levels of Cd. Pb accumulation was highest in S. brevis shell. Significant correlations (p?<?0.05) were found between Cd in the soft tissue of C. umbonella and its levels in the geochemical fractions of the sediment. Lead levels in the resistant geochemical fractions of the sediment and S. brevis shell were significantly correlated. Our results suggest that soft tissue of C. umbonella and shell of S. brevis are reliable biomonitoring tools for Cd and Pb, respectively.     

Determination of metal and organometal trophic bioaccumulation in the benthic macrofauna of the Adour estuary coastal zone (SW France, Bay of Biscay)

A multidisciplinary approach has been adopted in order to investigate the bioaccumulation of metals and organometals in macrobenthic populations. A complete method coupling a sampling strategy and classification of benthic organisms with a performant analytical procedure for the analysis of both metals and organometals has been developed. A single sample preparation method using a TMAH extraction and species specific isotope dilution makes it possible to analyse metals and organometals in the same extract, which is especially interesting for situations where only a limited amount of sample is available. Low detection limits have been obtained in the range of 12-250 pg g(-1) for mercury and butyltin compounds and 0.4-50 ng g(-1) for metals with good precision (1-10% RSD) even for a very low mass of sample (0.02 g). This method has been applied for monitoring contamination and bioaccumulation of metals and organometals as well as the biodiversity and trophic structure of the macrobenthic population of the Adour Estuary (South-West, France). The benthic macrofauna diversity indicates that inner estuarine stations are moderately polluted whereas outer estuarine stations are less impacted. However, metals concentrations in both sediment and benthic biomass do not change drastically between stations. Moreover, the bioaccumulation has been determined in relation to the feeding guild of benthic organisms. The results demonstrate that higher bioaccumulation is generally observed for deposit feeders directly impacted by sediment contamination compared to suspensive feeders and predators. Biomagnification along the trophic levels was highlighted for MMHg but no significant trend was observed for the other metallic compounds.     

Speciation of selected heavy metals geochemistry in surface sediments from Tirumalairajan river estuary, east coast of India

Surface sediment samples from the Tirumalairajan river estuary were studied for grain size pattern, organic matter, and heavy metals (Fe, Mn, Zn, and Pb) using the sequential and bulk metal extraction methods to evaluate metal behavior. Ten surface sediment samples were collected during the monsoon and summer seasons of the year 2009. The observed orders of concentrations of heavy metals in the sediments were as follows: Fe?>?Mn?>?Zn?>?Pb. The results obtained from sequential extraction showed that, among the metals studied, a larger portion of the metals were associated with the residual phase, although they are available in other fractions. The low concentration of metals available in bioavailable phases indicated that the sediments of Tirumalairajan river estuary were relatively unpolluted. Correlation analysis was also carried out to understand the associations of metals in different phases with sand, silt, clay, and organic matter. To understand the risk of heavy metals to sediment-dwelling organisms, the data were compared with risk assessment code and sediment quality values using the screening quick reference table. The main source of metals to the estuary is from the irrigation field and its associated activities in the study area.