Multivariate analysis of heavy metals concentrations in river estuary

Multivariate statistical techniques such as multivariate analysis of variance (MANOVA) and discriminant analysis (DA) were applied for analyzing the data obtained from two rivers in the Penang State of Malaysia for the concentration of heavy metal ions (As, Cr, Cd, Zn, Cu, Pb, and Hg) using a flame atomic absorption spectrometry (F-AAS) for Cr, Cd, Zn, Cu, Pb, As and cold vapor atomic absorption spectrometry (CV-AAS) for Hg. The two locations of interest with 20 sampling points of each location were Kuala Juru (Juru River) and Bukit Tambun (Jejawi River). MANOVA showed a strong significant difference between the two rivers in terms of heavy metal concentrations in water samples. DA gave the best result to identify the relative contribution for all parameters in discriminating (distinguishing) the two rivers. It provided an important data reduction as it used four parameters (Zn, Pb, Cd and Cr) affording 100% correct assignations. Results indicated that the two rivers were different in terms of heavy metals concentrations in water, and the major difference was due to the contribution of Zn. A negative correlation was found between discriminate functions (DF) and Cr and As, whereas positive correlation was exhibited with other heavy metals. Therefore, DA allowed a reduction in the dimensionality of the data set, delineating a few indicator parameters responsible for large variations in heavy metal concentrations. Correlation matrix between the parameters exhibited a strong evidence of mutual dependence of these metals.     

Lake destratification and speciation of iron and manganese

A long-term study of the effect of artificial aeration (destratification) of a water storage dam upon the speciation of iron and manganese in the dam waters has been undertaken. Separation of dam samples into soluble and insoluble forms by selective membrane filtration was undertaken before using the techniques of EPR spectroscopy, ion chromatography and gel filtration to assess the speciation of soluble species, and selective extraction and surface analysis (ESCA, SIMS and SEM) techniques to determine the speciation of particulate iron and manganese species. The percentages of soluble iron and manganese before (1983–85) and after (1986–88) artificial aeration are compared for the periods Jan–Dec, Jan–Mar, and Jun–Aug at three depths 6 m, 15 m and 0.5 m above the dam base, to assess the importance of seasonal changes in the various depths of the dam. Although aeration had an initial marked reduction in levels of soluble iron and manganese at all depths of the dam, the concentrations of these mtals showed a steady increase over succeeding years. Analysis of the figures over summer and winter periods shows that the reduction of soluble iron was maintained in summer, but not during winter. Upon aeration, the initial reduction of soluble manganese concentration was maintained in succeeding years in the epilimnic regions of the dam, but not in the hypolimnion. Statistical analysis of data has been undertaken to correlate the changes in relationship between the various forms of iron and manganese with the advent of aeration.     

Distribution of endocrine disruptors in the Mondego River estuary, Portugal

Recent studies in the Mondego River estuary demonstrated signs of pollution in the area, but the nature of the contamination remains unexplored. Because there seems to be any studies in that zone checking for the simultaneous presence of xenoestrogenic endocrine disrupting compounds, either of animal (estradiol and estrone), vegetal (daidzein, genistein and biochanin A), pharmaceutical (17alpha-ethynylestradiol) or industrial (bisphenol A, 4-octylphenol, 4-nonylphenol) origins, the main objective of this study was to investigate their presence, in every year season and at eight points along the estuarine gradient. For this propose, water samples (2 L) were collected in high and low tides, preconcentrated in the Oasis HLB cartridges and cleaned in silica cartridges before their analysis by HPLC-DAD and GC-MS. The current data showed the absence of contamination by animal or pharmaceutical estrogens and by alkylphenols, but demonstrated the presence of high levels of phytoestrogens (up to 1.1 mug/L) and of bisphenol A (up to 880.0 ng/L). Because these two chemicals existed in high environmental concentrations in the most upstream sampling station, and taking in account that these pollutants may additively contribute to endocrine disruption, namely on fish, it was concluded that at least this particularly area of the Mondego estuary deserves continuous monitoring programmes.     

Distribution of heavy metals in sediment and water of river Gomti

Gomti river receives industrial as well as domestic wastes from various drains of Lucknow city. In the process the water and sediment of the river Gomti get contaminated with heavy metals and other pollutants. In the present study, impacts of domestic/industrial wastes on the water and sediment chemistry of river Gomti with special reference to heavy metals have been investigated in different seasons (summer, winter and rainy). For this, seven sampling sites: Gaughat, Mohan Meakin, Martyrs Memorial, Hanuman Setu, Nishatganj bridge, Pipraghat and Malhaur, in the river Gomti in Lucknow region were identified and samples of water and sediments were collected in all the three seasons. In the collected water and sediment samples, six metals (Cd, Cr, Cu, Ni, Pb, and Zn) were analyzed on ICP-AES (Inductively coupled plasma emission spectroscopy) Labtam Plasmalab 8440. High concentrations of all the metals were noticed in water and sediment in rainy season compared to summer and winter. Because in rainy season runoff from open contaminated sites, agricultural field and industries, directly comes into the river without any treatment. In both the cases, the concentration of zinc was maximum (0.091 g/ml in water and 182.13 g/g in sediment) and the concentration of cadmium (0.001 g/ml in water and 17.26 g/g in sediment) was minimum. Higher concentration of metal in water and sediment during rainy season could be due to the industrial/agricultural/domestic runoff coming into the river.     

Silver and thallium historical trends in the Seine River basin

Records on pollution by metals of minor economic importance (e.g. silver and thallium) but which prove to be toxic are rarely documented in river sediment. This study used two sediment cores collected downstream of the Seine River to describe the temporal evolution of Ag and Tl concentrations in an urban catchment. Radionuclide analysis (i.e. Cs-137 and Pb-210) allowed dating sediment deposition within the cores (1933-2003). Ag concentration reached maximum values of 14.3-24.6 mg kg(-1) in the 1960s and 1970s, before gradually decreasing up to values which approximated 4 mg kg(-1) in 2003. In contrast, Tl concentrations remained roughly constant throughout the core (median value of 0.86 mg kg(-1)). Suspended solids was collected at upstream locations in the catchment to derive the background concentrations in Ag and Tl. Very high Ag concentrations were measured in the upstream Seine River sites (0.33-0.59 mg kg(-1)), compared to the values reported in the literature (0.055 mg kg(-1)). This suggests the presence of a widespread and ancient Ag pollution in the Seine River basin, as demonstrated by the very high Ag enrichment ratios recorded in the cores. Annual flux of particulate Ag in the Seine River was estimated at 1.7 t yr(-1) in 2003. In contrast, Tl concentrations remained in the same order of magnitude as the natural background signal (0.3-0.5 mg kg(-1)). This study suggests that the Seine River basin is free of Tl contamination. Future concerns should hence mostly rely on Ag contamination, in a context of increasing Ag uses and possible releases to the environment.     

Distribution of heavy metals in plants and fish of the Yamuna river (India)

The distribution of cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), lead (Pb) and zinc (Zn) in the plants and fish of Yamuna river from Delhi to Allahabad, a distance of about 840 km, at five sampling stations was determined in the year 1981. The results have shown wide variations in the heavy metal levels from one sampling station to the other. The concentrations of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn in the plants (Eicchornia crassipes) were found to be 0.02–0.12, 2.7–21.3, 4.6–64.8, 9.8–114.0, 193.0–1835.0, 380.0–1443.0, 4.4–83.0, 4.8–30.2, and 22.1–356.5 g g^-1 respectively whereas in the fish (Heteropnuestes fossilis) were found to be ND-0.40, 2.3–13.7, 3.7–26.9, 8.33–58.1, 278.3–1108.0, 81.3–213.8, 2.8–32.7, 1.4–12.8 and 101.8–364.8 gg^-1 respectively on dry weight basis.     

Speciation of iron in river water using a specific catalytic determination and size fractionation

A comprehensive speciation scheme was proposed for the speciation of iron in river water (0.45 microm filtrate). The speciation was based on the catalytic determination of reactive iron as Fe3+ and Fe(III)Li/(3 -in)+, where i = 1 or 2 for a unidentate and i = 1 for a bidentate ligand, Ln-. The scheme incudes size fractionation and acid decomposition of the sample and determination of the coexisting species. The proposed scheme was applied to natural and artificial samples and acidified preparations of these. Resulting fractionation patterns of reactive and unreactive iron and of coexisting humic acid were useful for the characterization of iron species in the natural samples. The reactive iron in the molecular weight (Mr) > or = 10(4) fraction was associated with humic iron aggregates and estimated as iron complexed with them. The unreactive iron in this fraction dissociated in 0.1 M HCI and was estimated as iron in the aggregates of iron(III) hydroxide (s) and humic iron. From the fractionation results of the artificial sample, the reactive and unreactive iron in the Mr < 10(3) fraction may be formed by complexing simple anions like F- and C2O4(2-) at their naturally-occurring concentration levels. The fractionation results also suggested that humic acid and Si contributed to the formation of reactive and unreactive iron in the Mr > or = 10(4) fraction.     

Cadmium,zinc and total mercury levels in the tissues of several fish species from La Plata river estuary,Argentina

A survey of the concentrations of heavy metals — cadmium, zinc and total mercury — in the tissues of fifteen fish species from Samborombón Bay, La Plata river estuary, in Argentina, has been carried out. Liver appeared to be the main organ accumulating cadmium and zinc, while both liver and muscle showed a similar ability for accumulating mercury. The bioaccumulation process was verified for the three metals analyzed, even though low concentrations have been determined. The biomagnification process of the metals studied was not verified in this environment. The highest metal concentrations were recorded in Mugil liza, and particulate matter and sediments — which are closely related to its trophic and ecological habits — seemed to be the main source of metals for this species. Both Micropogonias furnieri and Mugil liza were recognized as possible indicator species for future monitoring programmes for heavy metals in Samborombón Bay. Considering the present results, this area of La Plata river estuary is characterized as a non-polluted environment.Scientific Researcher from the National Council for Scientific and Technological Researches (CONICET), of Argentina     

Risk assessment of contaminated sediments in river basins--theoretical considerations and pragmatic approach

In order to ensure chemical quality of river basins, measures as required in the Water Framework Directive will also have to address contaminated sediments with subsequent monitoring of their successful application. Financial resources need to be allocated as part of a river basin plan to those contaminated sites that pose the biggest risk to the river basin. In order to differentiate between areas with elevated contaminant levels ("areas of concern") and those sites from which contaminated sediments can become resuspended and transported with the river, affecting the water phase and downstream sites in the catchment ("areas of risk"), the dynamics of sediment and suspended matter need to come into focus. Hydrological data have to be combined with concentration of suspended matter and its contaminant concentration to allow assessment of particle bound contaminant load. Each of these kinds of data, however, are subject to uncertainties--e.g. due to natural variability, heterogeneity of the matrix, challenges during sampling and chemical analyses of the suspended matter. Considering these uncertainties throughout the traceability chains of data collection, use of different lines of evidence and tools like fuzzy logic will increase the confidence of potentially costly management decisions.     

Assessing the impacts of water abstractions on river ecosystem services: an eco-hydraulic modelling approach

The provision of important river ecosystem services (ES) is dependent on the flow regime. This requires methods to assess the impacts on ES caused by interventions on rivers that affect flow regime, such as water abstractions. This study proposes a method to i) quantify the provision of a set of river ES, ii) simulate the effects of water abstraction alternatives that differ in location and abstracted flow, and iii) assess the impact of water abstraction alternatives on the selected ES. The method is based on river modelling science, and integrates spatially distributed hydrological, hydraulic and habitat models at different spatial and temporal scales. The method is applied to the hydropeaked upper Noce River (Northern Italy), which is regulated by hydropower operations. We selected locally relevant river ES: habitat suitability for the adult marble trout, white-water rafting suitability, hydroelectricity production from run-of-river (RoR) plants. Our results quantify the seasonality of river ES response variables and their intrinsic non-linearity, which explains why the same abstracted flow can produce different effects on trout habitat and rafting suitability depending on the morphology of the abstracted reach. An economic valuation of the examined river ES suggests that incomes from RoR hydropower plants are of comparable magnitude to touristic revenue losses related to the decrease in rafting suitability.     

Uranium speciation in moorland river water samples: a comparison of experimental results and computer model predictions

An on-line method has been developed for separating inorganic and organic bound uranium species present in river water samples. The method utilised a small chelating resin (Hyphan) column incorporated into the sample introduction manifold of an ICP-MS instrument. The method was evaluated for samples from rivers on Dartmoor (Devon, UK), an area of granite overlain with peat bogs. The results indicate that organic-uranium species form a major proportion (80%) of the total dissolved uranium present. Further work with synthetic water samples indicated that the level of dissolved organic carbon played a greater role in determining the level of organic-uranium species than did sample pH. Computer models for the water samples were constructed using the WHAM program (incorporating uranium data from the Nuclear Energy Agency Thermochemical Database project) in order to predict the levels of organic-uranium species that would form. By varying the proportion of humic and fulvic acids used in the humic component, predictions within 10% of the experimental results were obtained. The program did exhibit a low bias at higher pH values (7.5) and low organic carbon concentrations (0.5 microg ml(-1)), but under the natural conditions prevalent in the Dartmoor water samples, the model predictions were successful.     

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.     

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.     

Assessment of anthropogenic influences on surface water quality in urban estuary, northern New Jersey: multivariate approach

Concentrations of selected heavy metals (Cd, Cr, Cu, Pb, Ni, Fe, and Zn), nutrients (NO ₃ ^? and NH₃), fecal coliform colonies, and other multiple physical–chemical parameters were measured seasonally from 12 locations in an urban New Jersey estuary between 1994 and 2008. Stepwise regression, principal component analysis, and cluster analysis were used to group water quality results and sampling locations, as well as to assess these data’s relationship to sewage treatment effluents and the distance to the mouth of the river. The BOD₅, NH₃, NO ₃ ^? and fecal coliform counts clustered as one group and positively correlated to the distances from treated effluent and the measures of magnitude at the discharge points. Dissolved solids and most metal species scored high along a single principal component axes and were significantly correlated with the proximity to the industrialized area. From these data, one can conclude that the effluent discharge has been a main source of anthropogenic input to the Hackensack River over the past 15 years. Therefore, the greatest improvement to water quality would come from eliminating the few remaining combined sewer overflows and improving the removal of nutrients from treated effluents before they are discharged into the creeks and river.     

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.     

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.     

Distribution of mercury and other trace metals in the sediments of Cochin estuary (a Ramsar site), Kerala, India

Sediment quality data provide essential information for evaluating ambient environmental quality conditions. Sediments are important carriers of trace metals in the environment and reflect the current quality of the system. In the present study, distribution of mercury, lead, cadmium, copper, zinc, chromium and manganese in Cochin estuary were studied. The distribution of oxides of metals and textural quality were also studied in detail. It was found that the concentration of metals in the sediments near the industrial belt was extremely high. Correlation of different metals and metal oxides were analysed. It was found that all the alloys were correlated significantly (α?<?0.01) but in case of metals, correlation was only among certain metals.     

Distribution of heavy metals in water and sediments of selected sites of Yamuna river (India)

The concentration of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn metals in water and sediments of Yamuna river were determined by atomic absorption spectrophotometry in the year 1981. The data showed that there was considerable variation in the concentration of elements from one sampling station to the other which may be due to the variation in the quality of industrial and sewage wasters being added to the river at different sampling stations. The sediment samples collected from different sampling stations were also analysed for calcium carbonate, organic matter, potassium, and phosphorus.     

深圳市南山区大沙河底泥毒物污染特征及对策探讨

运用生物毒性监测方法,对深圳市南山区大沙河底泥毒物污染特征进行了分析。结果表明,大沙河底泥不同程度受到了毒物污染,底泥毒物污染趋势与水体毒物污染趋势基本一致;文章还结合化学监测方法,分析了大沙河底泥毒物主要为有机毒物。此外,就大沙河底泥毒物的治理方法提出了自己的见解。