Heavy metal binding fractions in the sediments of the Godavari estuary,East Coast of India

Sequential chemical extraction was used to study the operationally determined chemical forms of five heavy metals (Pb, Cu, Zn, Co and Ni) and their spatial distribution in the sediments. The binding behaviour of heavy metals associating with Fe–Mn oxides showed a good correlation towards Cu, Zn and Co, but moderate linear dependence with Ni and Pb. Among the five metals, correlation between Fe–Mn oxide bound Cu and Fe–Mn oxides (r = 0.95) is highest. The coefficient of determination (r ²) in organically bound heavy metals versus organic matter (OM) ranges from 0.772 to 0.952, which indicates a good linear dependence. The OM fraction in the sediments is more accessible to heavy metals and is the major ligand available for complexation. In particular, Zn and Cu are preferentially bound to OM. In general, Zn co-precipitation with carbonates is the dominant chemical form when Fe–Mn oxide and OM are less abundant. In this study, however, carbonates were less abundant, hence Zn bound to carbonates was less pronounced. Based on the results, even if the excessive binding sites are contained in the sediments, competition of various complexation reactions between sediment phases and heavy metals could dominate metal association.     

Assessing organic contaminant fluxes from contaminated sediments following dam removal in an urbanized river

In this study, methods and approaches were developed and tested to assess changes in contaminant fluxes resulting from dam removal in a riverine system. Sediment traps and passive samplers were deployed to measure particulate and dissolved polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in the water column prior to and following removal of a small, low-head dam in the Pawtuxet River, an urbanized river located in Cranston, RI, USA. During the study, concentrations of particulate and dissolved PAHs ranged from 21.5 to 103 μg/g and from 68 to 164 ng/L, respectively. Overall, temporal trends of PAHs showed no increases in either dissolved or particulate phases following removal of the dam. Dissolved concentrations of PCBs were very low, remaining below 1.72 ng/L at all sites. Particulate PCB concentrations across sites and time showed slightly greater variability, ranging from 80 to 469 ng/g, but with no indication that dam removal influenced any increases. Particulate PAHs and PCBs were sampled continuously at the site located below the dam and did not show sustained increases in concentration resulting from dam removal. The employment of passive sampling technology and sediment traps was highly effective in monitoring the concentrations and flux of contaminants moving through the river system. Variations in river flow had no effect on the concentration of contaminants in the dissolved or particulate phases, but did influence the flux rate of contaminants exiting the river. Overall, dam removal did not cause measurable sediment disturbance or increase the concentration or fluxes of dissolved or particulate PAHs and PCBs. This is due in large part to low volumes of impounded sediment residing above the dam and highly armored sediments in the river channel, which limited erosion. Results from this study will be used to improve methods and approaches that assess the short- and long-term impacts ecological restoration activities such as dam removal have on the release and transport of sediment-bound contaminants.     

Distribution and ecotoxicological significance of polycyclic aromatic hydrocarbons in sediments from Iko River estuary mangrove ecosystem

The distribution of polycyclic aromatic hydrocarbons (PAHs) in epipelic and benthic sediments from Iko River estuary mangrove ecosystem has been investigated. Total PAHs ranged from 6.10 to 35.27 mg/kg dry weight. Quantitative difference between the total PAHs in epipelic and benthic sediments showed that the benthic sediment known for higher capability to serve as sink for chemical pollutants accumulated less PAHs. This implies that PAHs in the epipelic sediment may plausibly be from industrial sources via runoff and/or of biogenic origin. A strong pyrolytic source fingerprint has been detected with slight influence of petrogenic sources. Total organic carbon normalized PAHs (sum of 16 PAHs, 59.7 to 372.4 mg/kg OC) were under (except for ES3 and BS3) the threshold effects concentrations (TEC, 290 mg/kg OC). Total PAHs in Iko River estuary sediments were in the range between ERL and ERM.     

Natural heavy metal and metalloid concentrations in sediments of the Minho River estuary (Portugal): baseline values for environmental studies

Forty-nine surface sediment samples from the Minho estuary sector between Tui and Caminha were analyzed for grain-size contents, Al, As, Cr, Cu, Hg, Li, Pb, Sn, and Zn concentrations. Selected heavy metal (Cu, Cr, Hg, and Zn) and metalloid (As and Sn) distributions were normalized against Al and Li with the main goal of compensating for natural grain-size variability and to separate natural from anthropogenic contributions, by using a combination of normalization techniques (definition of regional geochemical baselines (RGB) and determination of enrichment factors (EF)). Lead did not reveal a significant relationship with Al and Li. Aluminum explained more variance than Li for As, Cu, Hg, and Zn. Assuming the general non-impacted metal character of the Minho River estuary sediments, RGBs are defined for differentiating between natural and anthropogenic contributions. Based on RGB defined for each heavy metal/metalloid, the degree of enrichment is estimated through the determination of EF. Despite the relatively low total heavy metal and metalloid concentrations, the defined RGB identifies a set of samples characterized by presenting As, Cu, Cr, Hg, and Zn enrichments relatively to expected natural levels. Mercury is the element showing the highest level of enrichment relative to the baseline values being spread through all the study area. Tin present enrichments relatively to Al and or Li always lower than 1.5 suggesting natural contributions.     

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.     

Heavy metal enrichment in surface sediments from the SW Gulf of Mexico

The south west coastal zone in the Gulf of Mexico is an area with great industrial and agricultural development, which experiences intensive prospecting and extraction of hydrocarbons. After running through industrial, agricultural, and urban areas, waters from both the Jamapa River and La Antigua River arrive here. The rivers’ discharge areas of influence were estimated considering the textural and chemical composition of the supplied sediments. The main factors that determine sediment distribution were mineralogy, heavy minerals, carbonates, and anthropic contributions. The presence of metals in excess was evaluated using various pollution indicators, such as the enrichment factor, contamination factor, modified contamination factor, and geo-accumulation indexes. Data from different used contamination indexes show metal enrichments in As, Cu, Zn, Co, Cr, and V in La Antigua; As, Cu, and Cr in Jamapa; and As, Zn, and Pb in the Continental slope area. The adverse effects of metals on aquatic organisms were assessed using sediment quality guidelines that show Ni, As, Cu, and Cr may produce adverse effects on coastal areas. There was no evidence of contamination associated to the oil industry.     

Polychlorinated biphenyls in marine sediments from the southern North Sea and Scheldt estuary: a ten-year study of concentrations, patterns and trends

The paper reports the concentrations and patterns of CBs in sediments of the Belgian part of the southern North Sea and the Scheldt estuary for the period 1991-2001. The long-term analytical performance was well within the quality assurance boundaries set at the outset of the study and is consistent with the state of the art for this type of analysis. The CB concentrations (given as the median of the sum of IUPAC Nos 28, 52, 101, 118, 138, 153 and 180) vary between 0.1 microg kg(-1) and 50 microg kg(-1) dry weight in the total sediment and it could be demonstrated that CB patterns in the fine fraction of the sediment were closely similar throughout the investigated area. Isolation of the fine fraction (<63 microm) by sieving can be regarded as a physical normalisation to reduce the differences in sediment granulometric composition. It allows for a better understanding of CB distribution and patterns and improves the trend analysis. A significant downward trend could not be found at any of the stations, which suggests that CB levels have not been changing in the area of interest in the past decade.     

Sediment quality in the Douro river estuary based on trace metal contents, macrobenthic community and elutriate sediment toxicity test (ESTT)

The aim of this study was to evaluate the sediment quality in the mesotidal Douro River estuarine environment, in order to identify areas where sediment contamination could cause ecosystem degradation. Samples were obtained in five locations and sediment characterised for grain size, total organic matter, total-recoverable metals (Al, Fe, Cu, Pb, Cr, Ni, Cd, Zn and Mn), as well as acid volatile sulfide (AVS) and simultaneously extracted metals (SEM). In situ effects were evaluated by examining the macrobenthic community structure. An elutriate sediment toxicity test (ESTT) was used to estimate the amount of metals and nutrients that could be exchanged with the water column through resuspension, and its positive or negative effects on the growth of the micro-alga Emiliania huxleyi in a 10 day test. Anthropogenic metal contamination was identified at the north bank of the Douro estuary, with deleterious effects on the macrobenthic community, namely decrease in number of species and diversity. This contamination could possibly also be toxic for water column organisms, in case of resuspension, as shown by the ESTT. Sediments from the salt marsh at the south bank showed an impoverished macrobenthic community and elutriate toxicity, which appeared to be due to anaerobic conditions. This study clearly shows the usefulness of the ESST approach to assess the biological effect of resuspension of estuarine sediments.     

Assessment of contaminant impacts in a semi-enclosed estuary (Amvrakikos Gulf, NW Greece): Bioenergetics and biochemical biomarkers in mussels

A combination of bioenergetics and biochemical biomarkers in mussels was applied to assess possible pollution impacts in a protected semi-enclosed estuary (Amvrakikos Gulf, NW Greece) that receives pesticide discharges through riverine transport. Scope for growth, a physiological condition index representing the energy budget of the organism, was applied to detect general stress effects on the health status of mussels. The low energy budgets of mussels revealed stress conditions and provided early warning signals of possible consequences at higher levels of biological organization. Biochemical markers of exposure confirmed a risk of pesticide contamination. Decreased acetylcholinesterase activities indicated exposure to organophosphate and carbamate pesticides. Responses of the antioxidant enzyme glutathione peroxidase suggested the presence of contaminants capable of reactive oxygen species production that could be related to organochlorine pesticide contamination in the area. On the other hand, metallothionein levels implied low metal contamination.     

Evaluation of metal contamination in sediments from north of Morocco: geochemical and statistical approaches

Concentrations of Fe, Mn, Cr, Cu, Ni, Pb, Zn, Cd and Hg were evaluated in surface sediments of two rivers from north of Morocco, known as Souani and Mghogha rivers. Significantly higher concentrations in mg kg^???1 dry weight (dw) of Mn (747.6 vs. 392.9), Cr (86.4 vs. 56.3), Zn (299.5 vs. 138.5) were found in sediment samples from Mghogha when compared with Souani river. Average concentrations of Cd and Hg in several sediment samples from both rivers were above the effect range median that predicts toxic effects to aquatic organisms. The calculation of enrichment factors showed that Mn, Cr, Cu and Ni were depleted, whereas Pb and Hg were enriched. The results of geoaccumulation index revealed that sediments of both rivers were unpolluted with most of the metals and moderately contaminated with Fe and Hg. Some of elevated concentrations of Hg, principally in Mghogha River, were due to anthropogenic sources including the direct discharges of industrial zone.     

Heavy metal contents of refined and unrefined table salts from Turkey, Egypt and Greece

Trace metal contents of 28 of refined and unrefined table salt samples from Turkey, Egypt and Greece have been determined by flame atomic absorption spectrometry after coprecipitation by dysprosium(III) hydroxide. Copper, nickel, cobalt, manganese, lead and cadmium levels were found in the range of 0.17-0.47, 0.16-1.57, 0.22-0.48, 0.26-4.68, 0.50-1.64 and 0.14-0.30 microg g(-1), respectively. The results found in the presented work were compared with literature values.     

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.     

Geochemical characterisation of major and trace elements in the coastal sediments of India

Thirty-five surface sediment samples from the Indian continental shelf were recovered offshore from the mouths of the major rivers (Brahmaputra, Ganges, Narmada, Tapti, Godavari, Krishna and Cauvery) discharging into the coastal region of both east and west coasts were analysed using inductively coupled plasma atomic emission spectroscopy for selected major (i.e. Al, Ca, Fe, K, Ti, Mg and Na) and trace elements (e.g. Ba, Co, Cr, Cu, Ga, Ni, P and V), after total dissolution. The main objectives are to understand the processes controlling major and trace elements in the surface sediments and to identify natural and anthropogenic sources in the coastal environment using statistically regressed elemental concentrations to establish regional baseline levels. Metal enrichments observed close to the major urban areas in the east and west coasts are associated with the industrialised activities areas rich in Cu and Co in both the east and west coast sediments. Normalisation of metals to Al indicated that high enrichment factors are in the order of Ca>Ti≥Fe>Na>Mg>Co>Cu>Ga>V>Ba except K and P depletion. This indicated that the characteristic of estuarine sediment showed higher level along the west coast of India, which was reflected in the coastal sediments as similar to the source of its origin from the riverine composition and its abundances.     

Heavy metal contamination of road-deposited sediments in a medium size city of China

The aim of this paper is to determine and compare the environmental factors controlling vertical colonisation of periphyton on Sparganium erectum in a shallow eutrophic turbid lake, Manyas Lake, and an oligo-mesotrophic deep lake, Sapanca Lake, Turkey during the July 1997--November 1998. To investigate the effect of the environmental factors on periphyton colonization on S. erectum, the stem was cut above the rhizomes and subdivided into three equal sections. Multivariate statistical analyses have been applied to clarify relationships between environmental variables and periphyton colonization on S. erectum. Results indicated that physical disturbance and trophic level of the lakes influenced the colonization of the periphyton. Among the measured parameters, low light intensity, total suspended solids, temperature and water level fluctuation were observed as driving factors in Manyas Lake whereas nutrient deficiency was found as key factor in Sapanca Lake. The zonation of the periphyton, density, composition and dominant/subdominant taxa were significantly different in these lakes. However, Oedogonium sp., Mougeotia sp., Cylindrocapsa sp., Cladophora glomerata (Linn.), Aulacoseira italica (Ehr.) Simonsen, Melosira varians C. Agardh, Navicula tripunctata (O.F. Müller) Bory and Fragilaria ulna (Nitzsch) Lange-Bertalot were found as dominant species at all sections of S. erectum both in Manyas Lake and Sapanca Lake. It can be thought that these species have a broad range of tolerance to several physical, chemical and hydrologic disturbances. This is the first study to introduce how much the water quality and hydrologic drivers have affected vertical colonization of periphyton on S. erectum in two lakes with different mixing regimes.     

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.     

Monitoring trace metal contamination in salt marshes of the Westerschelde estuary

A survey is given of the possibilities and restrictions of (bio)monitoring trace metals in the salt marsh as exemplified for the Scheldt estuary. The objectives for monitoring in the salt marsh are enumerated as well as the requirements they should meet. Previous studies on monitoring trace metals in the salt marsh are reviewed.Problems in monitoring trace metals in the soil subsystem are due to variations in the input of these metals, the type of esturine circulation and the distribution of physical and chemical conditions in the salt-marsh deposits. The degree of metal enrichment and the spectrum of chemical speciation of the metals by means of a sequential extraction procedure is shortly discussed.Problems in monitoring trace metals in salt-marsh plants are discussed with respect to the bioavailability of these metals from soil and inundation water as sources of contamination, the allocation and seasonal variation in metal accumulations, and the role of adhesive particulate matter carried on the shoots by the floods. Aster tripolium seems to be a good species for biomonitoring trace metals in the vegetational component of the salt-marsh ecosystem.Communication Nr. 346.