Experimental photochemical release of organically bound aluminum and iron in three streams in Maine, USA

In the present study, the BCR (Community Bureau of Reference) sequential procedure has been applied to determine the zinc partition in sediments taken from a river situated in the Southwest of Romania, in a region subject of intense mining activities. The sampling was performed during three sampling expeditions, organized in the spring, summer, and autumn, 2007. The zinc concentration in different fractions was normalized, its concentration being related to the concentrations of some metals (such as Al or Fe) that are naturally present in sediments. The zinc-contaminated sediments from the investigated area have been evaluated by means of combining the analysis data from the BCR sequential extraction with the normalization to the Al content. The most important zinc collector in the samples taken during the three sampling expeditions is the easily soluble fraction, next being amorphous iron and manganese hydrated oxides fraction, followed by organic matter fraction.     

Pollution and potential mobility of Cd, Ni and Pb in the sediments of a wastewater-receiving river in Hanoi, Vietnam

Large quantities of untreated industrial and domestic wastewater are discharged from the city of Hanoi into urban rivers. Sediment samples from three sites in the To Lich River in Hanoi were assessed with respect to the concentrations and potential mobility of cadmium (Cd), nickel (Ni) and lead (Pb). Due to very high Cd concentrations up to 700 mg kg^?1 at one site, the sediment was considered highly unsuitable for any types of land use if dredged and disposed of on land. Chemical sequential extractions of wet and anoxic sediment samples showed that Cd and Pb were largely associated with the redox-sensitive fractions and could thus be mobilised following measures such as resuspension or dredging. To assess the potential mobilisation of heavy metals from the anoxic sediment due to oxidation, the samples were exposed to different oxidants (i.e. atmospheric air and hydrogen peroxide) and afterwards submitted to a leaching test. These experiments showed that although oxidation may increase the equilibrium pore water concentrations of heavy metals in the sediments, other sediment mineral fractions seem to effectively immobilise heavy metals potentially released from the oxidisable fraction.     

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.     

Statistical comparison of heavy metal concentrations in various louisiana sediments

The use of statistical t tests were used to determine lead, zinc, and cadmium enrichment in various Louisiana sediments. Both absolute metal concentrations and trace metal/conservative metal concentration ratios were used in comparing sampled sites to a 110 m deep background core taken just off the mouth of the Mississippi River. Concentration ratios were used to reduce the effects of certain chemical and physical sediment characteristics on the quantity of metal contained in a given sediment.Results from the comparison of sample sites to the background reveal metal enrichment at several sites. The University Lake sampling sites exhibit both lead and zinc enrichment when using both the concentration alone and ratio methods of comparison. Additionally, cadmium enrichment is indicated in the sediments of University Lake when using only the ratio method of comparison. Several sampled sediments in and around the New Orleans metropolitan area exhibited lead and cadmium enrichment.     

Heavy metal concentrations in water and sediments in Tasik Chini, a freshwater lake, Malaysia

The purpose of this paper are to determine the concentration of heavy metals namely cadmium (Cd), copper (Cu) and lead (Pb) in water and sediment; and to investigate the effect of sediment pH and sediment organic matter on concentration of cadmium, copper and lead in sediment at oxidation fraction. For this purpose the concentration of heavy metals were measured in water and sediments at 15 sites from Tasik Chini, Peninsular Malaysia. The sequential extraction procedure used in this study was based on defined fractions: exchangeable, acid reduction, oxidation, and residual. The concentration of heavy metals in residual fraction was higher than the other fractions. Among the non-residual fractions, the concentration of heavy metals in organic matter fraction was much higher than other fractions collected from all sampling sites. The pH of the sediment in all sites was acidic. The mean pH ranges from 4.8 to 5.5 with the higher value observed at site 15. Results of organic matter analysis showed that the percentage of organic matter present in sediment samples varies throughout the lake and all sites of sediments were relatively rich in organic matter ranging from 13.0% to 34.2%. The highest mean percentage of organic matter was measured at sampling site 15, with value of 31.78%.     

A complex investigation of the extent of pollution in sediments of the Sava River. Part 1: Selected elements

The Sava River is the biggest tributary to the Danube River. As a part of the 6th FW EU project, Sava River Basin: Sustainable Use, Management and Protection of Resources (SARIB), ecological status of sediments was investigated. In order to assess the geographical distribution in sediment contamination of the Sava River, inorganic and persistent organic pollutants were analyzed in sediments at 20 selected sampling sites along the Sava River from its spring to its outfall into the Danube River. For comparability of data to other river basins the sediment fraction below 63 μm was studied. Due to complexity of the work performed, the results are published separately (“Part I: Selected elements” and “Part II: Persistent organic pollutants”). In the present study, the extent of pollution was estimated by determination of the total element concentrations and by the identification of the most hazardous highly mobile element fractions and anthropogenic inputs of elements to sediments. To assess the mobile metal fraction extraction in 0.11 mol L^???1, acetic acid was performed (first step of the Community Bureau of Reference extraction procedure), while anthropogenic inputs of elements were estimated on the basis of normalization to aluminum (Al) concentration. According to the Water Framework Directive, the following elements were investigated in sediments: cadmium (Cd), lead (Pb), nickel (Ni), and mercury (Hg). Furthermore, copper (Cu), zinc (Zn), chromium (Cr), arsenic (As), and phosphorous (P) were determined. The analyses of sediments demonstrated slightly elevated values for Hg, Cr, and Ni in industrially exposed sites (concentrations up to 0.6, 380, and 210 mg kg^???1, respectively). However, the latter two elements exist in sparingly soluble forms and therefore do not represent an environmental burden. P concentrations were found in elevated concentrations at agricultural areas and big cities (up to 1,000 mg kg^???1).     

Groundwater environmental capacity and its evaluation index

At present, anthropogenic contribution of heavy metals far exceeds natural input in some aquatic sediment, but the proportions are difficult to differentiate due to the changes in sediment characters. In this paper, the metal (Al, Fe, K, Mg, Ca, Cr, Cu, Ni, and Zn) concentrations, grain size, and total organic carbon (TOC) content in the surface and core sediments of Nansihu Lake Catchment (the open lake and six inflow rivers) were determined. The chemical speciations of the metals (Al, Fe, Cr, Cu, Ni, and Zn) in the surface sediments were also analyzed. Approaches of factor analysis, normalized enrichment factor (EF) and the new non-residual fractions enrichment factor (K_NRF) were used to differentiate the sources of the metals in the sediments, from detrital clastic debris or anthropogenic input, and to quantify the anthropogenic contamination. The results indicate that natural processes were more dominant in concentrating the metals in the surface and core sediments of the open lake. High concentration of Ca and deficiency of other metals in the upper layers of the sediment core were attributed to the input of carbonate minerals in the catchment with increasing human activities since 1980s. High TOC content magnified the deficiency of the metals. Nevertheless, the EF and K_NRF both reveal moderate to significant anthropogenic contamination of Cr, Cu, Ni, and Zn in the surface sediments of Laoyun River and the estuary and Cr in the surface sediments of Baima River. The proportion of non-residual fractions (acid soluble, reducible, and oxidizable fractions) of Cr, Cu, Ni, and Zn in the contaminated sediments increased to 37–99% from the background levels less than 30%.     

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.     

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.     

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.     

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.     

Trace elements as tracers of environmental pollution in the canal sediments (alluvial formation of the Danube River, Serbia)

The purpose of this study was to examine the levels of trace elements and to discuss the origin and mobility of these contaminants in the canal sediments (alluvial formation of the Danube River). The most significant fractions binding all of the studied elements were oxides and silicates. The high proportion of elements in the residual fraction and the generally low contents of extractable elements reflected the background geochemical conditions. The contents of trace elements (except Hg and As) were dominantly controlled by the presence of Fe and Mn oxides as well as by the grain size and the geochemical composition of the sediment. The studied alluvial sediments were not heavily contaminated; there were only few sites where an anthropogenic influence on the concentrations of some metals (Cu, Cd, Zn, and Pb) was noticed. The results from this study show that impact of Pan?evo industrial zone on the quality of the Danube River and its contamination with trace element is minor.     

Distribution and speciation of selected metals in surface sediments, from the tropical Zuari estuary, central west coast of India

Estuarine sediments are major reservoirs for the metals. Distribution and mobility of metals within estuaries depends strongly on their specific chemical form. In the present study, surface sediments from Zuari estuary, Goa were analysed by a sequential procedure for Fe, Mn, Cu, Zn, Cr and Co to determine their distribution in five geochemical phases (Exchangeable, carbonate, Fe-Mn oxide (reducible) organic bound (oxidisable) and residual). The total metal content, sand, silt, clay and organic carbon were also determined of the surface sediments. The total metal contents were found to be greater than the background concentrations of average shale values as well as to that of earlier studies indicating enrichment probably due to the anthropogenic origin of metals. The results obtained from sequential procedure showed that among the studied elements, Mn and Co are potentially available in the bioavailable fractions (exchangeable, carbonate and Fe-Mn oxide bound fractions) indicating their importance in toxicity whereas rest of the metals viz. Fe, Cu, Zn and to some extent Cr are largely available in residual phase although they are available in other fractions. The main source of metals to the estuary is mining and its associated activities in the study area. Chemical speciation by sequential extraction procedure has helped in assessing the mobility, bioavailability, diagenesis and toxicity of metals and hence giving a better insight into the ultimate fate of pollutants, which are introduced into the estuarine environment. To understand the risk of the metals to the sediment dwelling organisms the data were compared with the Sediment Quality Values (SQV) using SQUIRT. Also, correlation and Factor analysis were carried out to understand the associations of metals in the different fractions with sand, silt, clay, organic carbon and with other metals.     

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.     

Trace metals in the shells of blue mussels (Mytilus edulis) from the Poland coast of Baltic sea

The Odiel salt marshes (Marismas del Odiel) are an important nature area declared a Biosphere Reserve, but they are greatly affected by pollution from the Odiel River. Surface sediments from this area were analysed using the latest version of the BCR sequential extraction procedure to determine the fractionation of As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn among four geochemical phases (acid-soluble, reducible, oxidisable and residual). The total content of each of the metals and As was also determined. The results showed high concentrations of As, Cd, Cu, Pb and Zn, with maximums of 791 mg kg⁻¹ of As, 8.5 mg kg⁻¹ of Cd, 2,740 mg kg⁻¹ of Cu, 1,580 mg kg⁻¹ of Pb and 3,920 mg kg⁻¹ of Zn. The concentrations of Cr, Mn and Ni were low since there are no sources of pollution by them in the area. A comparison of the metal and As levels with the sediment quality guidelines showed that the pollution is sufficient to produce noxious effects in aquatic organisms in most of the Odiel salt marshes. Based on the chemical distribution of the elements, it was found that Cd and Zn were the most mobile (i.e., elements that can pass easily into the water under changing environmental conditions). However, Cr, Fe, Ni and As were present in the greatest percentages in the residual fraction, which implies that these elements are strongly linked to the sediments.     

Heavy metals partitioning in sediments of the Kabini River in South India

Cu, Cr, Fe, Mn, Ni, Pb, and Zn in the sediments of the Kabini River, Karnataka, India was studied to determine the association of metal with various geochemical phases by sequential extraction. The variations of heavy metal concentration depend on the lithology of the river basin and partly on anthropogenic activities. The Kabini River sediments are dominated by Sargur supracrustals with amphibolites, gneisses, carbonates, and ultrabasic rocks weathering into gneissic and serpentine soils carrying a natural load of cationic heavy metals. The source of heavy metals in the Kabini riverbed sediments is normally envisaged as additional inputs from anthropogenic over and above natural and lithogenic sources. Geochemical study indicates the metals under study were present mostly in the least mobilizable fraction in the overlying water and it is concluded that heavy metals in these sediments are to a great extent derived from multisource anthropogenic inputs besides geochemical background contributions The results show that lead and chromium have higher potential for mobilization from the sediment due to higher concentration at the exchangeable ion and sulfide ion bounded, also Cu and Pb have the greatest percentage of carbonate fraction, it means that the study area received inputs from urban and industrial effluents. Association of the Fe with organic matter fraction can be explained by the high affinity of these elements for the humic substances. Further, Zn and Ni reveal a significant enrichment in sediment and it is due to release of industrial wastewater into the river. These trace metals are possible contaminants to enter into aquatic and food chain.     

The effect of humic acids on the sequential extraction of metals in soils and sediments using ICP-AES and chemometric analysis

The effect of humic acids on the sequential extraction of metals from various soils and sediments has been studied. A new multi-element extraction method optimised via experimental design has been employed. The method uses centrifugation to pass the extractant solution, at varying pH, through the sediment sample. The sequential leaches were collected and analysed by ICP-AES. Chemometric data processing was utilised to identify the composition of the physico-chemical components in order to characterise the sample. A sediment sample collected from Carnon River (Cornwall, UK) and a reference material (NIST 2711 agricultural soil) were spiked with humic acids and the sequential extraction scheme was used to monitor the changes in metal distribution. The method has proved a quick and reliable way to evaluate different sediment samples, and has potential as a new tool for environmental geochemistry analysis.     

Distribution and availability of trace elements in municipal solid waste composts

Trace element contamination is one of the main problems linked to the quality of compost, especially when it is produced from urban wastes, which can lead to high levels of some potentially toxic elements such as Cu, Pb or Zn. In this work, the distribution and bioavailability of five elements (Cu, Zn, Pb, Cr and Ni) were studied in five Spanish composts obtained from different feedstocks (municipal solid waste, garden trimmings, sewage sludge and mixed manure). The five composts showed high total concentrations of these elements, which in some cases limited their commercialization due to legal imperatives. First, a physical fractionation of the composts was performed, and the five elements were determined in each size fraction. Their availability was assessed by several methods of extraction (water, CaCl(2)-DTPA, the PBET extract, the TCLP extract, and sodium pyrophosphate), and their chemical distribution was assessed using the BCR sequential extraction procedure. The results showed that the finer fractions were enriched with the elements studied, and that Cu, Pb and Zn were the most potentially problematic ones, due to both their high total concentrations and availability. The partition into the BCR fractions was different for each element, but the differences between composts were scarce. Pb was evenly distributed among the four fractions defined in the BCR (soluble, oxidizable, reducible and residual); Cu was mainly found in the oxidizable fraction, linked to organic matter, and Zn was mainly associated to the reducible fraction (iron oxides), while Ni and Cr were mainly present almost exclusively in the residual fraction. It was not possible to establish a univocal relation between trace elements availability and their BCR fractionation. Given the differences existing for the availability and distribution of these elements, which not always were related to their total concentrations, we think that legal limits should consider availability, in order to achieve a more realistic assessment of the risks linked to compost use.     

Accumulation and remobilization of metals in superficial sediments in Tianjin, China

The concentrations of Cr, Ni, Cu, Zn, Cd, and Pb in superficial sediment samples collected from three representative sites (Yuqiao Reservoir, Haihe River, and Haihe River Estuary) in Tianjin, North China, were analyzed using various single extraction and sequential extraction procedures to determine their remobilization, extractability, and distribution patterns. Sediments from the Haihe River had higher metal concentrations and geo-accumulation indices, especially for Cd and Zn, than sediments from the other two sites, suggesting that the Haihe River has been heavily influenced by anthropogenic activities. In addition, over 31% and 28.2% of the total Cd in the Haihe River and the Yuqiao Reservoir, respectively, and 18.2% of the total Zn in the Haihe River were found to be associated with the exchangeable form, indicating the significant remobilization of Cd and Zn when compared with Cr and Ni. However, over 98% of the Ni and 78% of the Cr were most closely associated with the residue and oxidizable fractions, which resulted in their becoming environmentally immobile. Based on the Environmental Protection Agency method 3050B, Cd and Zn had the greatest extraction efficiency when a single extraction procedure using 0.5-mol L^???1 HCl, 0.43-mol L^???1 HAcO, and 0.05-mol L^???1 ethylene-diamine-tetra-acetic acid was conducted, with extraction yields of up to 72%, 68%, and 56% for Cd and 50%, 49%, and 29% for Zn, respectively, being obtained for the Haihe River sediments. This was followed by the yields of Cu and Pb and, finally, those of unpolluted metals such as Cr and Ni. HCl and acetic acid extraction provided equivalent information for predicting Cd and Zn mobility in the sediments studied and produced suitable results for quick screening.     

天津滨海新区黑潴河下游沉积物多环芳烃风险评价及环境基准值的比较

对黑潴河下游表层沉积物中16种多环芳烃(PAHs)的污染现状进行了调查研究。结果表明,表层沉积物中PAHs总量变化范围为41.2～129.3ng/g(平均值为83.7ng/g),PAHs的组成以5～6环PAHs组分为主。黑潴河下游沉积物中PAHs主要来源于周边地区化石燃料的高温燃烧。比较了基于不同方法建立的沉积物中PAHs环境基准值的差异,分析产生差异的原因,选择生态效应区间法对黑潴河沉积物中的PAHs进行了生态风险评价。黑潴河下游PAHs生态风险较小,属PAHs低生态风险河道。