Multivariate analysis of potentially toxic metals in sediments of a tropical coastal lagoon

Surface sediments collected from the Lagos Lagoon, Nigeria, and three adjoining rivers were analysed for their physicochemical properties and pseudo-total concentration of the potentially toxic metals (PTM) Cd, Cr, Cu, Pb and Zn. The concentration of the PTM varied seasonally and spatially. Odo-Iyaalaro was observed to be the most polluted river, with highest concentrations of 42.1 mg kg^?1, 102 mg kg^?1, 185 mg kg^?1, 154 mg kg^?1 and 1040 mg kg^?1 of Cd, Cr, Cu, Pb and Zn, respectively, while Ibeshe River was the least contaminated, apart from a site affected by Cu from the textile industry. Some of the sediments were found to be above the consensus-based probable effect concentrations and Dutch sediment guideline for metals. Overall metal concentrations were similar to those reported for other tropical lagoon and estuarine systems affected by anthropogenic inputs as a result of rapid urbanisation. Due to the large number of samples, principal component analysis was used to examine relationships within the data set. Generally, sediments collected during the dry season were observed to have higher concentration of PTM than those collected during the rainy season. This means that PTM could accumulate over a prolonged period and then be released relatively rapidly, on an annual basis, into tropical lagoon systems.     

Comparison of three sequential extraction procedures for partitioning of heavy metals in car park dusts

The aim of this study was to elucidate the amount of metal released at each step by using different extractants in three sequential extraction schemes for the partitioning of metal contents of car park deposited dust samples. For this purpose, three different sequential extraction procedures (SEP) were employed for the metal fractionation in car park dust samples collected from the campus of Erciyes University, Kayseri, Turkey. While two of the sequential extraction procedures contain five steps the other, namely the BCR sequential extraction scheme, has three steps. The first two methods fractionate metals to be exchangeable, bound to carbonates, bound to Mn oxides, bound to Fe oxides and bound to organic matter, and the BCR protocol fractionates the metals as acid soluble and exchangeable, reducible, and oxidisable. Determination of the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn was performed by flame atomic absorption spectrometry (FAAS). The results obtained by the three methods were compared and showed that the amount of metal released at each step of the leaching procedure depended both on the type of reagents used and the sequence in which they were applied. The most mobile elements were Cd, Pb and Zn which are metals potentially toxic to the environment and are also known to originate from traffic. The calculated enrichment factors for Cd and Pb were substantially high (73.5-187 and 18.4-27.5, respectively) and somewhat lower for Zn (5.1-6.8). These results confirm that they are important metal pollutants for car parks. Detection limits and recoveries were found in the range of 0.01-1.39 microg ml(-1) and 68-126%, respectively, for the metals studied and the three sequential extraction procedures.     

Evaluation of potentially toxic metals pollution in the sediments of the Kor river, southwest Iran

This study is carried out to evaluate potentially toxic metal concentrations (As, Cd, Cr, Cu, Hg, Mo, Ni, Pb, and Zn) together with their spatial distribution, degree of pollution, and potential ecological risk in Kor river sediments (southwest Iran) using sediment quality guidelines, geoaccumulation index (I _geo), Hakanson potential ecological risk index (RI), and standard methods of statistical analysis. The study area stretches some 140 km from the Drodzan Dam to Bakhtegan Lake, a stretch of river where different industrial and domestic activities (e.g., petrochemical complex, oil refinery, industrial meat processing complex, Marvdasht city sewage) and ecological value overlap with each other. Calculated geoaccumulation index indicate that 50 % of the stations are moderately to very extremely polluted. The potential ecological risk for nine investigated metals in Kor river is Hg (948)?>?Mo (51.9)?>?Ni (37.8)?>?Cd (29.8)?>?As (22)?>?Cu (16.6)?>?Pb (13.3)?>?Zn (3.3)?>?Cr (1). Results show that sediments in parts of Kor river sediments are heavily affected by effluents discharged from industrial plants and other parts are affected by agriculture and urban runoff from nearby lands. These phenomena may cause a risk of secondary water pollution under sediment disturbance and/or changes in the physical–chemical characteristics of the aquatic system.     

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.     

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

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

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.     

Heavy metals fractionation in surface sediments of Gowatr bay-Iran

Establishing the effectiveness of habitat features to act as surrogate measures of diversity and abundance of juvenile reef fish provides information that is critical to coral reef management. When accurately set on a broader spatial context, microhabitat information becomes more meaningful and its management application becomes more explicit. The goal of the study is to identify coral reef areas potentially important to juvenile fishes in Ngederrak Reef, Republic of Palau, across different spatial scales. To achieve this, the study requires the accomplishment of the following tasks: (1) structurally differentiate the general microhabitat types using acoustics; (2) quantify microhabitat association with juvenile reef fish community structure; and (3) conduct spatial analysis of the reef-wide data and locate areas optimal for juvenile reef fish settlement. The results strongly suggest the importance of branching structures in determining species count and abundance of juvenile reef fish at the outer reef slope of Ngederrak Reef. In the acoustic map, the accurate delineation of these features allowed us to identify reef areas with the highest potential to harbor a rich aggregation of juvenile reef fish. Using a developed spatial analysis tool that ranks pixel groups based on user-defined parameters, the reef area near the Western channel of Ngederrak is predicted to have the most robust aggregation of juvenile reef fish. The results have important implications not only in management, but also in modeling the impacts of habitat loss on reef fish community. At least for Ngederrak Reef, the results advanced the utility of acoustic systems in predicting spatial distribution of juvenile fish.     

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.     

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.     

The effect of oxidation and acidification on the speciation of heavy metals in sulfide-rich freshwater sediments using a sequential extraction procedure

The speciation of metals in a contaminated, anoxic, sulfide-rich, freshwater sediment was determined experimentally, using a sequential extraction procedure based on the method of Tessier et al. Taking into account the advantages and disadvantages of sequential extractions, the applied methodology allowed the investigation of the influence of aeration and acidification on the distribution of various metals in the sediment. Aeration caused Zn and Cd to be released from sulfides. Carbonates were partly dissolved by the oxidation process, causing mobilisation of Ca. Fe became less mobile owing to a stronger binding to organic matter. The speciation of K, Al, Ni, Pb and Mn and to a lesser extent of Cu was not affected by aeration. As a result of acidification of the aerated sediment, Ca, Mn, Ni, Zn and Cd became more mobile owing to the dissolution of carbonates.     

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.     

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.     

Comparison of different methods for extraction of polycyclic aromatic hydrocarbons (PAHs) from Sicilian (Italy) coastal area sediments

This paper describes a work aimed at improving the conditions of an extraction method, coupling GC-MS determination, for the analysis without cleanup phase, of polycyclic aromatic hydrocarbons (PAHs) from sediment samples. The automatic Soxhlet extraction in warm mode (using Extraction System B-811 Standard, Büchi) has demonstrated advantages for automation, reduced extraction time, and lower solvent use than for conventional Soxhlet extraction. Under these conditions, the recoveries are very good as they resulted greater than 85 % and, in most of the cases, near 100 %. The repeatability is also satisfactory (relative standard deviation less than 15 %). The detection limits are also acceptable and ranged from 0.001 to0.01 μg/kg dry weight. Fifty-four sediment samples were collected. The total concentration of the 17 compounds investigated, in samples of sediments collected from three Sicilian coastal areas, expressed as the sum of concentrations, varies from 99 to 11,557 μg/kg of dry matrix; concentrations of total PAHs in the sediments of Cala are two to three times higher than the other stations.     

Comparison of leaching tests for the study of trace metals remobilisation in soils and sediments

Several leaching tests were applied and compared to study metal remobilisation on various unpolluted and contaminated soils and on several contaminated sediments. The trace elements considered were Cd, Cr, Cu, Ni, Pb and Zn, and leaching tests consisted of the application of reagents with contrasting characteristics and strengths in order to assess the information provided. An extraction with aqua regia permitted the estimation of the pseudo-total metal content in the sample. Mild extractants such as H2O, CaCl2 and NaNO3 showed low and similar leaching capacities. Acid (CH3COOH) and complexing (EDTA) agents were more effective in remobilising trace metals from soils and sediments. Cd and Zn showed similar extraction characteristics under both extractant solutions, whereas Cu and Pb were more sensitive to complexation, and Ni and Cr to acidification processes. Sequential chemical extractions provided additional information on the association of the trace elements with the different soil and sediment phases. Cd and Zn showed the highest mobility, Pb was associated to reducible solid phases, Cu and Ni to oxidisable phases, and Cr remained mostly in the residual fraction. The results obtained in this paper provided valuable information for choosing a leaching test, which is an instrument of environmental analysis for the estimation of trace metal mobility.     

Assessment of toxic heavy metals in urban lake sediments as related to urban stressor and bioavailability

Aquatic pollution pose a serious challenge to the scientific community worldwide, since lakes or reservoirs find multifarious use and most often their water is used for drinking, bathing, irrigation, and aquaculture. Nine metals and several physicochemical parameters, from four sampling sites in a tropical lake receiving the discharges from a thermal power plant, a coal mine, and a chlor-alkali industry, were studied from 2004 to 2005. Pertaining to metal pollution, the site most polluted with heavy metals was Belwadah, i.e., waters and sediments had the highest concentration of all the metals examined. The reference site was characterized by the presence of low concentrations of metals in waters and sediments. Following the water quality monitoring, 2-month field phytoremediation experiments were conducted using large enclosures at the discharge point of different polluted sites of the lake. During field phytoremediation experiments using aquatic macrophytes, marked percentage reduction in metals concentrations were recorded. The percentage decrease for different metals was in the range of 25% to 67.90% at Belwadah (with Eichhornia crassipes and Lemna minor), 25% to 77.14% at Dongia nala (with E. crassipes, L. minor and Azolla pinnata), and 25% to 71.42% at Ash pond site of G.B. Pant Sagar (with L. minor and A. pinnata). Preliminary studies of polluted sites are useful for improved microcosm design and for the systematic extrapolation of information from experimental ecosystems to natural ecosystems.     

Determination of heavy metals in lower Sakarya river sediments using a BCR-sequential extraction procedure

A BCR-sequential extraction procedure for the determination of extractable heavy metals was applied to sediments of various rivers and lakes. There are many rivers basins in Turkey. Sakarya River Basin is one of the most important basins, which consists of three parts: Upper, Middle and Lower Sakarya River Basins. In this study, the Lower Sakarya River was selected as the study area for sediments. The samples were collected monthly from 10 pre-determined stations through the river for 10 months time and analysed for the distribution of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn elements. The determination of extractable heavy metals in sediments was carried out by using Flame Atomic Absorption Spectrometer. The validation of the results was performed by the analysis of a BCR 701 standard reference material.     

Spatial variation of potentially toxic elements in different grain size fractions of marine sediments from Gulf of Mannar, India

Marine sediments of the Gulf of Mannar (GoM), India are contaminated by potential toxic elements (PTEs) due to anthropogenic activities posing a risk to the existing fragile coral ecosystem and human health. The current study aimed to assess the distribution of PTEs (arsenic—As; cobalt—Co; copper—Cu, molybdenum—Mo; lead—Pb; and zinc—Zn) in marine sediments of different grain size fractions, viz., medium sand (710 μm), fine sand (250 μm), and clay (<63 μm) among the different coastal regions of Pamban, Palk Bay, and Rameswaram coasts of GoM, using grain size as one of the key factor controlling their concentrations. The concentrations of PTEs were measured in the different size fractions of sediment using inductively coupled plasma mass spectrophotometer. The order of accumulation of all PTEs in the three fractions was ranked as Zn > Cu > Pb > As > Co > Mo and in the three locations as Rameswaram > Palk Bay > Pamban. The concentration of PTEs in Palk Bay and Rameswaram coast was significantly different (P?<?0.05), when compared to Pamban coast. Measured geoaccumulation index (I _geo) and contamination factor (CF) indicated significant enrichment of Co and Pb from Rameswaram coast when compared to other two coasts. Although the concentration of Co was low but the measured I _geo and CF values indicated significant enrichment of this PTE in Rameswaram coast. The increased input of PTEs in the coastal regions of GoM signifies the need to monitor the coast regularly using suitable monitoring tools such as sediments to prevent further damage to the marine ecosystem.     

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.     

Distribution and solid-phase speciation of toxic heavy metals of bed sediments of Bharali tributary of Brahmaputra River

Heavy metal (Fe, Mn, Zn, Cu, Ni, Pb, and Cd) concentrations and their chemical speciations were investigated for the first time in bed sediments of Bharali River, a major tributary of the Brahmaputra River of the Eastern Himalayas. Levels of Fe, Mn, Pb, and Cd in the bed sediments were much below the average Indian rivers; however, Cu and Zn exhibit levels on the higher side. Enrichment factors (EF) of all metals was greater than 1 and a higher trend of EF was seen in the abandoned channel for most metals. Pb showed maximum EF of 32 at site near an urban center. The geoaccumulation indices indicate that Bharali river is moderately polluted. The metals speciations, done by a sequential extraction regime, show that Cd, Cu, and Pb exhibit considerable presence in the exchangeable and carbonate fraction, thereby showing higher mobility and bioavailability. On the other hand, Ni, Mn, and Fe exhibit greater presence in the residual fraction and Zn was dominant in the Fe?CMn oxide phase. Inter-species correlations at three sites did not show similar trends for metal pairs indicating potential variations in the contributing sources.