Interseasonal distribution and partitioning of heavy metals in subtidal sediment of Qua Iboe Estuary and associated Creeks, Niger Delta (Nigeria)

An analysis of the distribution and chemical forms of selected metals: cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni) and lead (Pb) in subtidal sediments of Qua Iboe Estuary and adjourning creeks, collected between June 2000 and January 2001, were studied using a sequential chemical extraction method. The concentration of metals in each extracted fraction was determined using inductively coupled plasma spectrometer (ICP-AES). Pb, Cd and Cu appear to be the most abundant metal in the sediments of the systems, and are predominantly associated with the residual, organic and oxidisable phases. Results indicate that there are also insignificant components that are bound to both the exchangeable and carbonates fractions. Ni is largely associated with bioavailable phases with insignificant bound to organic matter and residual fractions. In general, an insignificant component of Cd and Pb are bound to organic matter phase. Moreover, speciation results indicate that metal contamination in the ecosystems investigated primarily comes from human-mediated sources. Thus, based on index of geoaccumulation calculated, sediments of these ecosystems have been classified as uncontaminated by Cr, Cu and Ni, strongly contaminated by Pb and extremely contaminated by Cd.     

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.     

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.     

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.     

Speciation of metals in bed sediments and water of Qaraaoun Reservoir, Lebanon

Determination of only total element in sediments does not give an accurate estimate of the likely environmental impacts. Speciation study of metals in sediment provides information on the potential availability of metals (toxic) to biota under various environmental conditions. In water, the toxic metal specie is the free hydrated metal ion. The toxicity of metals depends especially on their chemical forms rather than their total metal content. The present study focuses on Qaraaoun Reservoir, Lebanon. Earlier studies focused only on total metal concentrations in sediment and water. The objective of this study was to determine metal speciation (Fe, Cr, Ni, Zn, Cu, Pb, Cd) in the (operationally defined) sediment chemical fractions and metal speciation in reservoir water. This would reflect on metal bioavailability and toxicity. Water samples and bed sediments were collected from nine sites during the dry season and a sequential chemical fraction scheme was applied to the <75-??m sieve sediment fraction. Metal content in each fraction was determined by the FAAS technique. The data showed that the highest percentages of total metal content in sediment fractions were for: Fe in residual followed by reducible, Cr and Ni in residual and in reducible, Cu in organic followed by exchangeable, Zn in residual and in organic, Pb in organic and carbonate, Cd was mainly in carbonate. Total metal content in water was determined by ICP-MS technique and aqueous metal speciation was predicted using AQUACHEM software interfaced to PHREEQC geochemical computer model. The water speciation data predicted that a high percentage of Pb and Ni were present as carbonate complex species and low percentages as free hydrated ions, highest percentage of Zn as carbonate complex species followed by free hydrated ion, highest percentage of Cd as free hydrated ion followed by carbonate complex species. The sensitivity attempt of free hydrated ion of Ni, Zn, Pb, and Cd in reservoir water revealed dependence of Zn and Cd on pH and alkalinity, while Ni and Pb were only dependent on pH.     

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

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

黑臭河道底泥特征分析及处理工艺筛选

以深圳市前海片区代表性河道黑臭底泥为研究对象,对其p H值、含水率、有机质、氮磷含量、重金属含量及粒径进行分析。结果表明,黑臭底泥主要为呈碱性的无机砂质成分,有机质含量低,重金属含量虽高但分布稳定。根据其特性,最终确定其主要处置方式为疏浚后机械脱水。     

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.     

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.     

Spatial distribution and potential ecologic risk assessment of heavy metals in the sediments of the Nansi Lake in China

The contamination levels and ecological risks of heavy metals in the sediments of the Nansi Lake were investigated. The contents of Cd, Cr, Cu, Pb, Zn, Ni, and Co in the surface sediments collected at 20 sites ranged from 0.08 to 1.12, 58.92 to 135.62, 38.09 to 78.65, 24.51 to 53.95, 110.51 to 235.36, 11.30 to 65.40, and 4.12 to 20.14 mg/kg, respectively. The results of partitioning analysis revealed that the proportions of soluble and exchangeable fraction were less than 1 %, the proportions of carbonate, amorphous oxides, organic matter, and crystalline oxides fraction were less than 10 %, and 10.52 % of Cd was associated with carbonate. The average proportions in the residual fraction ranged from 48.62 % for Cu to 73.76 % for Ni, indicating low mobility and bioavailability. The geoaccumulation index (I _geo), relative enrichment factor (REF), sediment pollution index (SPI), and potential effect concentration quotient (PECQ) values of the heavy metals in the sediments were not in agreement with each another. The average REF values of Cd and Zn were higher than those of other metals. However, the average PECQ values were higher for Cr and Ni than those of other metals, indicating that these two metals would cause higher adverse biological effects. Therefore, it is suggested that future management and pollution control might focus on Cd, Zn, Cr, and Ni in the sediments of the Nansi Lake.     

Distribution and fractionation of cadmium, copper, lead, nickel, and zinc in a calcareous sandy soil receiving municipal solid waste

This study was conducted to evaluate the degree of mobility and fractionation of cadmium (Cd), copper (Cu), lead (Pb), nickel (Ni), and zinc (Zn) after the addition of municipal solid sewage sludge (MSS) in a sandy calcareous soil. Treatments were (1) soil application of MSS, (2) soil application of enriched municipal solid waste compost (EMSS), and (3) control soil. The MSS application represented a dose of 200 Mg dry weight per hectare. Soil columns were incubated at room temperature for 15 days and irrigated daily with deionized water to make a total of 505 mm. At the end of leaching experiments, soil samples from each column were divided into 14 layers, each being 1 cm down to 10 and 2.5 cm below that and analyzed for diethylenetriaminepentaacetic acid (DTPA)-extractable Cd, Cu, Pb, Ni, and Zn. The fractionation of the heavy metals in the top five layers of the surface soil samples was investigated by the sequential extraction method. All soil layers of the columns receiving MSS and EMSS had significantly higher concentrations of DTPA-extractable heavy metals than control soil. The maximum concentration of heavy metals in treated soil was in the surface layer and declined significantly with depth. Sequential extraction results showed that in the treated soil, a major proportion of Cd, Pb, and Ni was associated with organic matter (OM) and exchangeable (EXCH) fractions, and a major proportion of Cu and Zn was associated with residual (RES) and OM fractions. Based on relative percent, Pb, Cd, and Ni in the EXCH fraction was higher than Cu and Zn in soil leached with MSS and EMSS, suggesting that application of this MSS to a sandy calcareous soil, at the loading rate used here, may pose a risk in terms of groundwater contamination with Pb, Cd, and Ni.     

Application of the positive matrix factorization approach to identify heavy metal sources in sediments. A case study on the Mexican Pacific Coast

During the last two decades, sediments collected in different sources of water bodies of the Tehuantepec Basin, located in the southeast of the Mexican Pacific Coast, showed that concentrations of heavy metals may pose a risk to the environment and human health. The extractable organic matter, geoaccumulation index, and enrichment factors were quantified for arsenic, cadmium, copper, chromium, nickel, lead, vanadium, zinc, and the fine-grained sediment fraction. The non-parametric SiZer method was applied to assess the statistical significance of the reconstructed metal variation along time. This inference method appears to be particularly natural and well suited to temperature and other environmental reconstructions. In this approach, a collection of smooth of the reconstructed metal concentrations is considered simultaneously, and inferences about the significance of the metal trends can be made with respect to time. Hence, the database represents a consolidated set of available and validated water and sediment data of an urban industrialized area, which is very useful as case study site. The positive matrix factorization approach was used in identification and source apportionment of the anthropogenic heavy metals in the sediments. Regionally, metals and organic matter are depleted relative to crustal abundance in a range of 45–55 %, while there is an inorganic enrichment from lithogenous/anthropogenic sources of around 40 %. Only extractable organic matter, Pb, As, and Cd can be related with non-crustal sources, suggesting that additional input cannot be explained by local runoff or erosion processes.     

Enrichment and fractionation of heavy metals in bed sediments of River Narmada, India

A metal fractionation study on bed sediments of River Narmada in Central India has been carried out to examine the enrichment and partitioning of different metal species between five geochemical phases (exchangeable fraction, carbonate fraction, Fe/Mn oxide fraction, organic fraction and residual fraction). The river receives toxic substances through a large number of tributaries and drains flowing in the catchment of the river. The toxic substances of particular interest are heavy metals derived from urban runoff as well as municipal sewage and industrial effluents. Heavy metals entering the river get adsorbed onto the suspended sediments, which in due course of time settle down in the bottom of the river. In this study fractionation of metal ions has been carried out with the objective to determine the eco-toxic potential of metal ions. Although, in most cases (except iron) the average trace/heavy metal concentrations in sediments were higher than the standard shale values, the risk assessment code as applied to the present study reveals that only about 1–3% of manganese, <1% of copper, 16–19% of nickel, 4–20% of chromium, 1–4% of lead, 8–13% of cadmium and 1–3% of zinc exist in exchangeable fraction and therefore falls under low to medium risk category. According to the Geo-accumulation Index (GAI), cadmium shows high accumulation in the river sediments, rest of other metals are under unpolluted to moderately polluted class.     

Total concentrations and speciation of heavy metals in soils of the Shenyang Zhangshi Irrigation Area, China

The Shenyang Zhangshi Irrigation Area (SZIA) was used for the spreading of municipal and industrial waste water, which is an economic way of irrigating crops, recycling nutrients and water treatment. Long-term irrigation resulted in a severe metal contamination of soils. To identify the soil phases implicated in retaining the metals, sequential extractions were performed. The most predominant metal was cadmium which was mainly associated with mobile, easily soluble and easily reducible fractions. Copper was mainly associated with the residual, EDTA extractable and moderately reducible fractions. Lead was bound to organic matter and poorly crystalline Fe-oxides. Nickel and zinc were mainly associated with the residual and strongly reducible fractions. Although copper, lead, nickel and zinc concentrations were of minor importance mobile metal concentrations of these metals as well as of cadmium exceeded German trigger values for plant production and plant growth.     

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.     

Historical variation of elements with respect to different geochemical fractions in recent sediments from Pigeon Lake, Alberta, Canada

Geochemical analysis of elements and organic matter were conducted on vertical profiles of the recent sediments from Pigeon Lake, Alberta, Canada, to determine historical variations in elemental content of the sediments as related to their geochemical fractions. The elements are grouped according to their affinity with different geochemical fractions, by using cluster analysis and sequential extraction experiments. As a result, four elemental fractions were identified: clastic mineral detritus; carbonate; organic; and elements that show less similarity to the previous groups perhaps due to anthropogenic input or the influence of other fractions, such as oxyhydroxides. Following the identification of geochemical fractions in the sediments, a three-step normalizing method was applied using parameters that represent each geochemical fraction. These normalizing techniques appear to be important in verifying whether the variation of elements is indeed the result of anthropogenic and/or natural activities. The normalized data are correlated with the recent history of human activity and natural events near Pigeon Lake. Given the age of the lake sediments, this correlation indicates that the depth profiles of elements after being normalized to the organic and carbonate fractions reflect the variation of detrital input into the lake. However, the former mainly corresponds to the coarse-grained clastic minerals originating from high-energy erosion as the result of natural events (e.g., flooding), whereas the latter corresponds to the low-energy erosion of the fine particles (enriched in lithophile elements) due to deforestation in the drainage basin. Normalizing to the clastic mineral detritus fraction results in the increase of heavy metals in the uppermost part of the sediment profiles, which coincides with industrial activities during the past two decades in central Alberta. However, the concentration of these elements is negligible, as compared to the quantities released by geogenic processes (erosion).     

Heavy Metal Levels in Marine Sediments of Singapore

Marine environmental levels of the metals copper (Cu), zinc (Zn), lead (Pb) and cadmium (Cd) were measured from sediments collected around 20 coastal locations around Singapore, over a 2-year period. Sediment-size analysis was conducted on sediment samples, and Atomic Absorption Spectrophotometry was used in the analyses of sediment heavy metal concentrations. The levels of heavy metals in marine sediment was largely dependant on sediment particle size, as illustrated by the correlation of sediment size with Multidimensional Scaling (MDS) configurations of sediment metal concentrations. In addition, the proximity to shipping activity, and the release of anti-fouling paint from boats also influence heavy metal concentrations in marine sediments of Singapore.     

Variation of Metals in Bed Sediments of Qaraaoun Reservoir, Lebanon

The Qaraaoun Reservoir (impoundment of the River Litani) is the only artificial surface water body in the country, Lebanon. Earlier study on the water quality of the Qaraaoun Reservoir identified three water quality zoning with a central distinct zone suitable for multipurpose water usage. The objective of this study was to extend the earlier work by considering the total metal content of reservoir bed sediments and hence to evaluate factors that control metal deposition or capture. Water samples were collected from 15 sampling sites and sediment samples were simultaneously collected from 9 sites. Water parameters analyzed were pH, Eh, DO and temperature. Sediment samples were dried and sieved and sediment < 75 μ m was retained for analysis. Sediments were subjected to a stepwise heating process with aqua regia to extract the metals, and their content in sediments determined by ICP-MS. The sediment data revealed higher metal contents where the river entered the reservoir which matched higher concentrations of water parameters at the influx site. Regression analysis of total metals in sediments with distance from the river Litani influx point to the dam revealed a log trend for Fe, Cr and Ni, whereas, the concentrations of Cu, Zn, Cd, Pb were better described by a polynomial regression. Three sediment zones were identified: entrance, oxidation (central) and reducing (near dam) zones. Sediment contents of Zn, Cu and Pb correlated with organic content, whereas sediment Cr and Ni were associated with iron. It was concluded that sediments act as a sink for metals and the deposition of metals is primarily related to sediment organic content and the level of dissolved oxygen in water.     

Trace metals biogeochemistry of Kumaun Himalayan Lakes,Uttarakhand, India

The increasing urbanization, along with tourism, has posed a major threat to the Kumaun Himalayan Lakes, Uttarakhand, India. The total metal concentration in the water, interstitial water, and sediments along with the metal fractionation studies were carried out to understand the remobilization of the trace metals from the sediments of the lakes. The high concentration of the metals in the water column of the lakes generally decreases with depth and the metals release from the sediment is mainly due to the prevalence of anoxic condition at the sediment–water interface and sediment column. The sediment shows that metals Fe and Cr are derived from detrital source, whereas Co, Ni, and Zn are derived mainly from the organic matter dissolution. The sparse correlation of the trace metals with Ti shows most of the metals have chiefly re-precipitated from the water column. The metals speciation studies also supports that metals experience a high rate of anoxic dissolution and their precipitation onto the sediments are determined by the sediment composition and organic matter content. The high concentration of manganese in the interstitial water in the lakes indicates dissolution of organic matter. The released manganese is adsorbed/precipitated as carbonate phase (Nainital Lake) and oxide pahse (in other lakes). The study shows that the trace metals are regenerated from the sediments due to oxyhydroxide dissolution and organic matter decomposition.     

Determination and speciation of heavy metals in sediments of the Juru River,Penang, Malaysia

The Juru River flows through largely urbanized areas and is grossly polluted by domestic wastes and discharges from pig farms. Other than carrying highly polluting organic materials, these wastes are also contaminated with heavy metals. To ascertain the extent of heavy metal pollution in the river, total and non-residual concentrations of Cu, Pb, Zn, Mn and Fe in sediment samples collected along the river were determined. The results indicate that both the total and non-residual metal concentrations in sediments can successfully be used to identify heavy metal pollution sources. The speciation of Zn, Mn and Fe in the sediment samples were investigated using a sequential leaching technique which identifies the elements among six operationally defined host fractions: (1) exchangeable, (2) carbonate and surface-associated, (3) easily reducible, (4) moderately reducible, (5) bound to organic matter and sulphides and (6) residual. The results indicate that Zn is mainly associated with the reducible fractions. Zn and Fe found in the moderately reducible fraction are significantly correlated, indicating that iron oxides is the preferred host phase by Zn.