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.     

Application of sequential leaching, risk indices and multivariate statistics to evaluate heavy metal contamination of estuarine sediments: Dhamara Estuary, East Coast of India

In the present study, concentration of some selected trace metals (Fe, Mn, Ni, Co, Pb, Zn, Cu, Cr and Cd) are measured in Brahmani, Baitarani river complex along with Dhamara estuary and its near shore. Chemical partitioning has been made to establish association of metals into different geochemical phases. The exchangeable fraction is having high environmental risk among non-lithogeneous phases due to greater potential for mobility into pore water. The metals with highest bio-availability being Cd, Zn and Cr. The metals like Mn, Zn, Cd and Cu represent an appreciable portion in carbonate phase. Fe–Mn oxides act as efficient scavenger for most of the metals playing a prime role in controlling their fate and transport. Among non-lithogeneous phases apart from reducible, Cr showed a significant enrichment in organic phase. Risk assessment code values indicate that all metals except Fe fall under medium-risk zone. In estuarine zone Cd, Zn, Pb and Cr are released to 32.43, 26.10, 21.81 and 20 %, respectively, indicating their significant bio-availability pose high ecological risk. A quantitative approach has been made through the use of different risk indices like enrichment factor, geo-accumulation index and pollution load index. Factor analysis indicates that in riverine zone, Fe–Mn oxides/hydroxides seem to play an important role in scavenging metals, in estuarine zone, organic precipitation and adsorption to the fine silt and clay particles while in coastal zone, co-precipitation with Fe could be the mechanism for the same. Canonical discriminant function indicates that it is highly successful in discriminating the groups as predicted.     

Trace metal speciation and contamination in an intertidal estuary

An analysis of the geochemical distribution of selected trace metals among various geochemical phases of the sediments in the Tees estuary was carried out using a sequential extraction technique and Differential Stripping Voltammetry. The sediments of the estuary are mainly organic rich clay silts and metal concentrations exceed those in the water column. Speciation results show that contamination of the estuary is mainly from anthropogenic sources. Pb and Zn are associated with the reducible, residual and oxidisable fractions. The speciation pattern of Cd was similar to those of lead and zinc. However there were also some exchangeable and bound to carbonate fractions although these were less significant. Cu is largely associated with the oxidisable and residual fractions, with insignificant bound to carbonate, exchangeable and reducible fractions. The most bioavailable forms of the metals are the free inorganic ions. Total metal concentrations in the estuary display a downward trend since the 1970s.     

Speciation of Trace Metals in Coastal Sediments of El-Mex Bay South Mediterranean Sea–West of Alexandria (Egypt)

Sediments of El-Mex Bay estuary on the southern Mediterranean Sea have been analyzed for trace metals after sediment fractionation by sequential leaching. A sequential extraction procedure was applied to identify forms of Mn, Cu, Cd, Cr, Zn and Fe. The five steps of the sequential extraction procedure partitioned metals into: CH₃COONH₄ extractable (F1); NaOAC carbonate extractable (F2); NH₂OH.HCl/CH₃COOH reducible extractable (F3); H₂O₂–HNO₃ organic extractable (F4) and NHO₃/HClO₄/HF acid soluble residue (F5). Extracted concentrations of trace metals analyzed after all five steps, were found to be (μg/g) for Mn: 1930.2, Cu: 165.3, Cd: 60.9, Cr: 386.3, Zn: 2351.3 and Fe: 10895. Most of elements were found in reducible fraction except Fe found in acid soluble residue, characterizing stable compounds in sediments. Labile (non-residual) fractions of trace elements (sum of the first four fractions) were analyzed because they are more bioavailable than the residual amount. Correlation analysis was used to understand and visualize the associations between the labile fractions of trace metals and certain forms, since Fe-and Mn-oxides play an important role in trace metals sorption within aquatic systems, especially within El-Mex Bay sediments that characterized by varying metal bioavailability.     

Trace metal fractionation in the Pichavaram mangrove–estuarine sediments in southeast India after the tsunami of 2004

The geochemistry of coastal sediments of southern India was altered after the tsunami in 2004. A five-step sequential extraction procedure was applied to assess the effects of tsunami on mobility and redistribution of selected elements (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn). Ten surface sediments and three cores were analyzed for different metal fractions (exchangeable, carbonate, reduced, oxidized, and residual). Total metal concentrations increased in mangrove sediments after the tsunami, but their spatial distribution did not show significant variation (except Mn). The sediments were mixed by the tsunami, and there was lack of variation in metal concentrations in different fractions with depth (except Pb and Mn). High concentrations of Pb and Zn occurred in the oxide fractions, whereas Cu, Cr, Cd, and Ni were high in the organic and sulfide-rich fractions. Metals in the residual fraction (lattice bound) had the highest concentration suggesting their non-availability and limited biological uptake in the system. Most of the metals (except Mn) do not constitute a risk based on the different geochemical indices.     

Total concentrations, fractionation and mobility of heavy metals in soils of urban area of Guwahati, India

This work describes the results of assessment of the heavy metals, Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn in urban soil of Guwahati City, India from 31 sites of five different land use types covering residential, commercial, industrial, public utilities, and roadside. Sequential extraction procedure was used to evaluate the relative distribution of the eight metals in exchangeable, carbonate, reducible (Fe?CMn oxide), organic and sulfide, and residual fractions. Of the eight metals, Cd and Co occur in lower concentrations (Cd <?< Co) in all types of land, and concentration variation from one type of land use to another is not much significant for both the metals. Ni presence is more than Co, and the concentrations show some variation depending on land use status. Average Cr and Cu concentrations are ??100?mg/kg, but Cr has a significantly higher presence in industrial land use. The results are similar in case of Pb. The two metals, Mn and Zn have domination over the other metals, and the values are ??300?mg/kg. Industrial and roadside soil contains much more Mn, while commercial soil is most enriched with Zn. Of the metals, Ni has the largest proportion (~42%) bound to the exchangeable fraction and Co, Cr, and Pb also have appreciable proportion bound to the same fraction. A significant amount of Co is associated with carbonates. The reducible fraction has bound considerable quantity of Mn and Zn, while most of Cu is associated with the organic and sulfide fraction. Both Cd and Pb are dominantly associated with the residual fraction. Computation of the mobility factor of the metals indicates Mn to be the most mobile metal present in the soil samples.     

Vertical distribution of heavy metals in soil profile in a seasonally waterlogging agriculture field in Eastern Ganges Basin

The accumulation of heavy metals in soil and water is a serious concern due to their persistence and toxicity. This study investigated the vertical distribution of heavy metals, possible sources and their relation with soil texture in a soil profile from seasonally waterlogged agriculture fields of Eastern Ganges basin. Fifteen samples were collected at ～0.90-m interval during drilling of 13.11 mbgl and analysed for physical parameters (moisture content and grain size parameters: sand, silt, clay ratio) and heavy metals (Fe, Mn, Cr, Cu, Pb, Zn, Co, Ni and Cd). The average metal content was in the decreasing order of Fe?>?Mn?>?Cr?>?Zn?>?Ni?>?Cu?>?Co?>?Pb?>?Cd. Vertical distribution of Fe, Mn, Zn and Ni shows more or less similar trends, and clay zone records high concentration of heavy metals. The enrichment of heavy metals in clay zone with alkaline pH strongly implies that the heavy metal distributions in the study site are effectively regulated by soil texture and reductive dissolution of Fe and Mn oxy-hydroxides. Correlation coefficient analysis indicates that most of the metals correlate with Fe, Mn and soil texture (clay and silt). Soil quality assessment was carried out using geoaccumulation index (I _geo), enrichment factor (EF) and contamination factor (CF). The enrichment factor values were ranged between 0.66 (Mn) and 2.34 (Co) for the studied metals, and the contamination factor values varied between 0.79 (Mn) and 2.55 (Co). Results suggest that the elements such as Cu and Co are categorized as moderate to moderately severe contamination, which are further confirmed by I _geo values (0.69 for Cu and 0.78 for Co). The concentration of Ni exceeded the effects-range median values, and the biological adverse effect of this metal is 87 %. The average concentration of heavy metals was compared with published data such as concentration of heavy metals in Ganga River sediments, Ganga Delta sediments and upper continental crust (UCC), which apparently revealed that heavy metals such as Fe, Mn, Cr, Pb, Zn and Cd are influenced by the dynamic nature of flood plain deposits. Agricultural practice and domestic sewage are also influenced on the heavy metal content in the study area.     

Environmentally safe sewage sludge disposal: the impact of liming on the behaviour of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn

Dewatered sewage sludge containing relatively high total concentrations of Cr (945 micrograms ml-1), Cu (523 micrograms ml-1), Ni (1186 micrograms ml-1) and Zn (2950 micrograms ml-1) was treated with quicklime and sawdust for sludge disinfection and post-stabilisation. The mobility of the heavy metals in the sludge samples was assessed by applying a modified five-step Tessier sequential extraction procedure. Water was added as a first step for estimation of the proportion of the easily soluble metal fractions. To check the precision of the analytical work the concentrations of heavy metals in steps 1-6 of the extraction procedure were summed and compared to the total metal concentrations. The mass balance agreed within +/- 3% for Cd, Cu, Cr, and Zn and within +/- 5% for Ni, Pb, Fe and Mn. Data from the partitioning study indicate that in the lime-treated sludge at a pH of 12 the mobility of Cu and Ni notably increased with the solubilisation of these metals from their organic and/or carbonate and Fe and Mn oxide and hydroxide fractions, respectively. Liming slightly decreased the proportion of other heavy metals in the easily soluble fractions while its impact on the partitioning between other sludge phases was almost insignificant. Due to the increased solubility of Ni and Cu as well as potential Cr oxidation at high pH, liming cannot be recommended for sludge disinfection. Addition of sawdust did not change the heavy metal partitioning.     

Factors affecting metal concentrations in the upper sediment layer of intertidal reedbeds along the river Scheldt

Factors that play a role in determining metal accumulation in sediments of 26 intertidal marshes which are mainly vegetated by reed plants (Phragmites australis) were assessed along the Scheldt estuary (Belgium and The Netherlands). In the upper 20 cm sediment layer, several physico-chemical properties (clay, silt and sand content, organic matter, carbonate and chloride content, pH and conductivity) and aqua regia extractable metals (Cd, Cr, Cu, Ni, Pb, Zn) were determined. The sediments were significantly contaminated with trace metals. The Cd concentrations often exceeded the Flemish soil remediation thresholds for nature areas, whereas Cr, Cu and Zn levels indicated moderate contamination. Pb concentrations occasionally were high, whereas Ni concentrations leaned towards background values. Organic matter was the single most important predictor variable for total metal contents in regression models, except for Cr. Additional significant predictor variables were clay or chloride content, depending on the metal. Observed metal concentrations at sites within a range of a few km from specific point-sources of metals (e.g. shipyards, industrial areas with metallurgic activities, affluents, major motorways) were somewhat higher than predicted by the models, whereas they were lower than predicted at sites which are regularly subjected to flooding by water of high salinity. The ratio between observed and predicted concentrations seems to be a valuable tool for the identification of areas which are specifically impacted by point sources.     

Distribution and accumulation of heavy metals in the sediments of Akkaya Dam,Nigde, Turkey

Twenty-one surface sediment samples were collected from Akkaya Dam. Heavy metal concentrations (Mo, Cu, Pb, Zn, Ni, Co, Mn, Fe, Cr, As, V and Cd), grain size, organic carbon and carbonate contents were studied in order to assess the extent of environmental pollution and to discuss the origin of these contaminants in sediments of dam. The sediments in the study area are mostly very fine sands. However, mud was observed in the northeast of the dam. Sediment pollution assessment was carried out using enrichment factor. The calculation of enrichment factors showed that Mo is depleted by 1.0 whereas Cu, Pb, Zn, Ni, Co, Mn, As, V, Cr and Cd are enriched by 3, 5.4, 7, 2.7, 2.2, 3.4, 42.3, 2.1, 1.8 and 7.2, respectively. Relatively high concentrations heavy metals occurred in north (textile industry area) and east (Karasu River) due to enrichment controlled by anthropogenic wastes. The results of correlation analysis show low–medium positive and negative correlations among metals, grain size, carbonate contents and organic carbon and indicate that heavy metals in sediments of the Akkaya Dam have different anthropogenic sources.     

Mobility and ecological risk assessment of trace metals in polluted estuarine sediments using a sequential extraction scheme

The three-stage sequential extraction procedure for the fractionation of Cd, Cr, Cu, Ni, Pb, and Zn, proposed by the Commission of the European Communities Bureau of Reference, was applied to sediment five samples collected from the Sal estuary, Sergipe State, northeast Brazil, in September 2009. The method showed satisfactory recoveries, detection limits, and standard deviations for determinations of trace metals in the sediments. Cd and Pb were the metals most prevalent in the bioavailable fractions (carbonates, Fe and Mn oxides, organic matter, and sulfides), while Ni, Zn, Cu, and Cr showed higher percentages in the inert fraction. The order of mobility of the metals was Cd (66 %) > Pb (65 %) > Zn (59 %) > Ni (57 %) = Cr (57 %) > Cu (56 %). Possible toxicity related to these metals was examined using the risk assessment code, and by comparing the chemical data with sediment quality guideline ERL-ERM values. Results obtained using the two methods were in agreement, and showed low to medium risk for all metals, indicating that adverse effects on aquatic biota should rarely occur.     

Chemometric study on the trace metal accumulation in the sediments of the Cochin Estuary―Southwest coast of India

The distribution and accumulation of trace metals in the sediments of the Cochin estuary during the pre-monsoon, monsoon and post-monsoon periods were investigated. Sediment samples from 14 locations were collected and analysed for the metal contents (Mg, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb), organic carbon, total nitrogen, total sulphur and grain size. The data were processed using statistical tools like correlation, factor and cluster analysis. The study revealed an enrichment of Cd and Zn in the study area particularly at station 2, which is confirmed by enrichment factor, contamination factor and geoaccumulation index. The factor analysis revealed that the source of Cd and Zn may be same. The study indicated that the spatial variation for the metals like Mg, Cr, Fe, Co, Ni, Cu, Zn, Cd and Pb were predominant unlike Mn which shows a temporal variation. The strong association of trace metals with Fe and Mn hydroxides and oxides are prominent along the Cochin estuary. The anthropogenic inputs of industrial effluents mainly control the trace metals enrichment in the Cochin estuary.     

An assessment of heavy metal contamination in soils of fresh water aquifer system and evaluation of eco-toxicity by lithogenic implications

The chemistry of heavy metals in sediments with respect to bio-availability and chemical reactivity is regulated by pH, texture, and organic matter contents of the sediments and specific binding form and coupled reactivity of the metals within. To focus on the metal distribution (Fe, Mn, Pb, Cd, Zn, Co, Cu, and Cr) and behavior in a fresh water aquifer system along with the ecological toxicity parameters, a four-step sequential extraction method was applied on 18 Eastern Ghats’ type sediments from fluorosis-hit Nayagarh district, India. Geo-accumulation index of metals in the sediments indicates that they are practically uncontaminated and/or less contaminated with and Fe, Mn, and Cu; contaminated to moderately contaminated with Pb, Zn, and Cr; and strongly contaminated with Cd. Rather, more than 80 % recovered Cd metal concentration in sediments constitute the labile fractions. Temporal clustering of metal fractions indicates transition metal fraction distribution claiming the sediment pH regulation. Similarly, base metal distribution accounts for organic carbon and soil conductivity due to their greater availability in exchangeable and sulfide fractions. Correlation analysis and factor analysis scores demonstrate lack of inter-relationship between transition group and base metal fractions. High fluoride concentration in ground water is associated with high sodium-bicarbonate-iron affinity with elevated pH values (i.e., >7.0) and high positive factor score with the total iron concentration in ground water.     

Study of Geochemical Association of Some Trace Metals in the Sediments of Chilika Lake: A Multivariate Statistical Approach

In order to establish the natural processes and geochemical factors responsible for enrichment of trace metal ions (Cu, Co, Ni, Zn and Cr) with respect to textural parameters (sand, silt and clay weight percentages) along with depth, multivariate statistical approach has been carried out for sediments in different water zones of Chilika lake, the largest brackish water lagoon in Asia. The rotated varimax factor results reveal that Cobalt enrichment is controlled by both textural parameters as well as adsorption mechanism. In fresh and saline water region, textural parameters and in mixed water, adsorption phenomenon predominates. Zn in fresh water is related to clay, whereas it is in adsorbed state in mixed water. Cu in fresh water sediments is in absorbed state and in mixed water it is related to depth and Co concentration. Cr does not show any specific association in fresh water, but in both mixed and saline water it is associated with clay minerals. Although both textural parameters and adsorption mechanism play an important role for the enrichment of trace metal ions in these lagoonal sediments, their relative importance varies with specific metal ions as well as the water quality. Sequential extraction technique was used to characterize the various forms of metals in the < 63μ size sediments of Chilika lake. The concentrations determined indicated selective accumulation of the various metals in the different phases with spatial variability in different water zones. Slightly higher availability of Co and Zn near Balugaon township in exchangeable phase may be related to anthropogenic activities. Among the non-lithogenous (NL) phases, reducible phase associated with higher concentration of Ni, Cu and Cr. Organic bound Zn and Co contributed highest percentages among NL fractions. Residual fraction contributed more than 50% in most of the cases, reflected the predominance of physical weathering, high erosion rate along the drainage basin.     

Speciation and ecological risk of heavy metals in intertidal sediments of Quanzhou Bay, China

The chemical speciation of nine heavy metals in intertidal sediments from Quanzhou Bay was determined using a modified sequential extraction procedure, proposed by the Commission of the European Community Bureau of Reference. The results show that Mn presents the highest percentage in the acid-soluble fraction, and Pb and Cu present the highest percentages in the reducible fraction. The highest percentages of Fe, V, Cr, Ni, Zn, and Co were found in the residual fraction. The mobility order of the heavy metals studied on the basis of the nonresidual content of the elements is Mn > Pb > Cu > Co > Zn > Ni > Cr > V > Fe. The assessment on potential ecological risk indices of some heavy metals indicates that Zn, Ni, and Cr show moderate contamination, while Cu and Pb show slighter contamination. On the whole, the comprehensive potential ecological risk index of Cu, Zn, Ni, Cr, and Pb in the sediments presents moderate degree.     

Distribution and chemical partitioning of heavy metals in marine near-shore sediment cores: a case study from the Xugou, Lianyungang, China

The concentrations and chemical partitioning of heavy metals (Co, Cr, Ni, Zn, Cu, and Pb) in the marine near-shore sediment cores were investigated. Typically, the mean concentrations from Core B sediment samples were 98.6, 21.1, 47.0, 46.4, 107.6, and 31.9 mg kg^???1 for Cr, Co, Ni, Cu, Zn, and Pb, respectively. The heavy metal concentrations were normalized to commonly used reference elements Al, Li, Sc, and total organic carbon. Based on Pearson coefficients, Li was found to be a good normalizer for Co (r?= 0.974), Cr (r?= 0.967), Ni (r?= 0.898), and Zn (r?= 0.929) in 80 sediment samples from three sampling sites. However, the correlation coefficients between Li and Cu, and Li and Pb were relatively low. Multivariate statistic approaches (Principal Component Analysis and Cluster Analysis) were adopted for data treatment, allowing the identification of two main factors controlling the heavy metal variability in the sediments. Heavy metals in the enrichment sections were evaluated by a sequential extraction method for possible chemical forms in sediments. The results showed that the residual, Fe/Mn oxides and Organic/sulfide fractions were dominant geochemical phases in the enriched sections, indicating low bioavailability of heavy metals in sediments.     

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%.     

Pollution in the urban soils of Lianyungang,China, evaluated using a pollution index,mobility of heavy metals,and enzymatic activities

Soil samples from 16 urban sites in Lianyungang, China were collected and analyzed. A pollution index was used to assess the potential ecological risk of heavy metals and a sequential extraction procedure was used to evaluate the relative distribution of Cu, Zn, Pb, Cd, Cr, and As in exchangeable, carbonate, Fe/Mn oxide, organic/sulfide, and residual fractions. The mobility of heavy metals and urease (URE) activity, alkaline phosphatase (ALP) activity, and invertase (INV) activity of soils was determined. The results showed that the average concentrations of Cu, Zn, Pb, Cd, Cr, and As in Lianyungang soils were much higher than those in the coastal city soil background values of Jiangsu and China. Among the five studied regions (utilities, commercial, industrial, tourism, and roadside), the industrial region had the highest metal concentrations demonstrating that land use had a significant impact on the accumulation of heavy metals in Lianyungang soils. Compared to the other metals, Cd showed the highest ecological risk. According to chemical partitioning, Cu was associated with the organic/sulfides and Pb and Zn were mainly in the carbonate and the Fe/Mn oxide phase. The greatest amounts of Cd were found in exchangeable and carbonate fractions, while Cr and As were mainly in the residual fraction. Cd had the highest mobility of all metals, and the order of mobility (highest to lowest) of heavy metals in Lianyungang soils was Cd > Zn > Pb > Cu > As > Cr. Soil urease activity, alkaline phosphatase activity, and invertase activity varied considerably in different pollution degree sites. Soil enzyme activities had the lowest levels in roadside and industrial regions. Across all the soil data in the five regions, the total Cu, Zn, Pb, Cd, Cr, and As level was negatively correlated with urease activity, alkaline phosphatase activity, and invertase activity, but the relationship was not significant. In the industrial region, alkaline phosphatase activity had significant negative correlations with total Cu, Pb, Cr, Zn, Cd, and heavy metal fractions. This showed that alkaline phosphatase activity was sensitive to heavy metals in heavily contaminated regions, whereas urease and invertase were less affected. The combination of the various methods may offer a powerful analytical technique in the study of heavy metal pollution in street soil.     

Heavy metal speciation in solid-phase materials from a bacterial sulfate reducing bioreactor using sequential extraction procedure combined with acid volatile sulfide analysis

Heavy metal mobility, bioavailability and toxicity depends largely on the chemical form of metals and ultimately determines potential for environmental pollution. For this reason, determining the chemical form of heavy metals and metalloids, immobilized in sludges by biological mediated sulfate reduction, is important to evaluate their mobility and bioavailability. A modified Tessier sequential extraction procedure (SEP), complemented with acid volatile sulfide (AVS) and simultaneous extracted metals (SEM) measurements, were applied to determine the partitioning of five heavy metals (defined as Fe, Ni, Zn and Cu, and the metalloid As) in anoxic solid-phase material (ASM) from an anaerobic, sulfate reducing bioreactor into six operationally defined fractions. These fractions were water soluble, exchangeable, bound to carbonates (acid soluble), bound to Fe-Mn oxides (reducible), bound to organic matter and sulfides (oxidizable) and residual. It was found that the distribution of Fe, Ni, Zn, Cu and As in ASM was strongly influenced by its association with the above solid fractions. The fraction corresponding to organic matter and sulfides appeared to be the most important scavenging phases of As, Fe, Ni, Zn and Cu in ASM (59.8-86.7%). This result was supported by AVS and SEM (Sigma Zn, Ni and Cu) measurements, which indicated that the heavy metals existed overwhelmingly as sulfides in the organic matter and sulfide fraction. A substantial amount of Fe and Ni at 16.4 and 20.1%, respectively, were also present in the carbonate fraction, while an appreciable portion of As (18.3%) and Zn (19.4%) was bound to Fe-Mn oxides. A significant amount of heavy metals was also associated with the residual fraction, ranging from 2.1% for Zn to 18.8% for As. Based on the average total extractable heavy metal (TEHM) values, the concentration of heavy metals in the ASM was in the order of Cu > Ni > Zn > Fe > As. If the mobility and bioavailability of heavy metals are assumed to be related to their solubility and chemical forms, and that they decrease with each successive extraction step, then the apparent mobility and bioavailability of these five heavy metals in ASM increase in the order of Cu < As < Ni < Fe < Zn. The SEM/AVS ratio was less than one in eight replicate ASM samples, indicating that the ASM was non-toxic with regards to having a low probability of bioavailable metals in the pore water.     

Heavy metals in bottom sediments of Lake Umbozero in Murmansk Region, Russia

Sediment cores collected from different locations of Lake Umbozero were studied with respect to concentration and mobility of trace and heavy metals Co, Cu, Fe, Mn, Ni, Pb, U, and Zn. Lake Umbozero is the second largest lake in the Murmansk Region and subjected to contamination by air-borne emissions and river transportation from the nearby metallurgical and mining industries. Unlike its neighboring, more industry-prone Lake Imandra, Lake Umbozero is relatively unexplored with respect to its state of pollution. In our study, metal distribution in sediments was found to vary with respect to the cores, although in general the concentrations were at the same level throughout the lake indicating uniform horizontal distribution of metals. When compared to Lake Imandra, the concentrations of most of the metals studied were significantly lower and represented the levels in sediments measured in lakes of Kola Peninsula located further off from industrial pollutant sources. An exception was Pb the concentration of which was at the same level as in Lake Imandra, probably due to long-distance transport. Sediment layers were subjected to four-step sequential extraction procedure to reveal the metal distribution in soluble, exchangeable, acid-soluble, and residual fractions. Indicative of their potential higher lability, Mn, U, and Zn were generally found in exchangeable fraction; as also Mn and U extensively in the acid-soluble fraction.