Heavy metals in surface sediments from nine estuaries along the coast of Bohai Bay,Northern China

Concentrations of heavy metals in river water and sediment were investigated in nine estuaries along the coast of Bohai Bay, Northern China. Multivariate statistical techniques such as principal component analysis and cluster analysis, in combination with metal concentration analysis and correlation analysis, were used to identify the possible sources of the metals and the pollution pattern in nine estuaries along the coast of Bohai Bay. The environmental risks of metals, evaluated by sediment quality guidelines and background values, revealed Hg contamination in the estuaries. However, levels of Cd in estuarine sediments were low, and they were less than those levels in river sediments, partly due to the high mobility and dilution of river or seawater. Cd did not contribute to sediment deposits in estuaries. High organic matter from effluents from large municipal sewage treatment plants was predominantly responsible for restricting Hg mobility from the river to Bohai Bay.     

Influence of the Aznalcóllar mining spill on the vertical distribution of heavy metals in sediments from the Guadalquivir estuary (SW Spain)

The Natural Park of Do?ana and the Guadalquivir estuary were impacted by the release of 6 million cubic meters of acid waste after the mine-tailing spill in Aznalcóllar (Andalusia, SW, Spain). Here is presented the monitoring of the accidental spill on vertical distribution of heavy metals in the estuarine sediments. The total concentration of six metals (Fe, Mn, Zn, Cd, Pb, Cu), their chemical speciation and the organic carbon concentration were analyzed in sediment vertical profiles. The results obtained determine background levels similar to previously reported in the area. The analysis catalogues the impact of the accident on the estuary as acute and mainly associated with high concentrations of Zn and Cd. The recent enrichment in Zn and Cd and their geochemical association with the more mobile fractions of the sediment determine an environmental risk associated with the acute impact and detected in some of the areas of the estuary.     

Effects of decreased pH on marine organisms

Sea water scrubbing of flue gas may result in a significant pH decrease in the waters of coastal areas with restricted dilution capacity. A review of the literature on pH tolerance of marine organisms indicates that there is little evidence of harm caused by decrease of 0.5–1.0 pH units. However, few long term or life cycle studies have been conducted. As pH may influence seawater chemistry in several important ways, notably the carbonic acid equilibrium, chemical form of metals, and the characteristics of dissolved substances, it is concluded that pH tolerance deserves more interest from marine biologists than it has received hitherto.     

Three-dimensional distributions of sewage markers in Tokyo Bay water--fluorescent whitening agents (FWAs)

Three-dimensional distributions of fluorescent whitening agents (FWAs: more specifically, DSBP and DAS1), which are sewage-derived water-soluble markers, were observed in Tokyo Bay water through multi-layer sampling of water at 20 locations. In summer, FWAs predominated in the surface layers, with trace but significant concentration of FWAs in bottom water due to stratification of seawater. In winter, on the other hand, FWAs were extensively mixed into the bottom layers because of the vertical mixing of seawater. In the surface layer, FWA concentrations and the DSBP/DAS1 ratio (the concentration ratio of DSBP to DAS1) were lower in summer than in winter, suggesting more efficient photodegradation of FWAs in euphotic zones during the summer due to stronger solar radiation. Horizontally, FWAs were widely distributed over the surface layer of Tokyo Bay. Surface water with DSBP concentrations above 50ng/L, corresponding to <200 times dilution of sewage effluent, was found to have spread up to 10km from the coastline. In addition, an offshore decline in FWA concentrations was observed, showing a half-distance of 10-20km. The decrease was caused by dilution by seawater of fresh water containing FWAs. The eastern part of the bay was different with respect to surface layers, with higher concentrations seen in northeastern parts. Furthermore, dispersion of combined sewer overflow (CSO)-derived water mass was observed in Tokyo Bay after heavy rain.     

The flocculation of dissolved Fe,Mn, Al,Cu, Ni,Co and Cd during estuarine mixing

A laboratory experiment was carried out in which the flocculation products, formed from the mixing of filtered (0.4 μm) river water and seawater, were analysed. This study established that Fe, Mn, Al, Cu, Ni, Cd and Co have resolvable and well-defined estuarine chemistries. Copper, Ni, Mn and Co have salinity dependences of removal which are similar to those of dissolved Fe and humic acids. The amount of removal of the above trace metals increases between 0 and 15–18‰, after which little additional removal occurs. The extents of removal from river water are very different: Fe, 95%; Al, 20%; Cu, Ni, 40%; Co, 10%; Cd, 5% and Mn, 25–45%. The basic removal mechanism appears to be the estuarine flocculation of trace metals which exist, in part, in river water as colloids in association with colloidal humic acids and hydrous iron oxides. A qualitative model, based on this mechanism, supports the observations of this flocculation study.The results of this study give the most complete and consistent set of data presently available, from which to postulate the most important processes controlling the estuarine chemistry of trace metals. The generality of their behaviours still needs to be determined by future investigations.     

Input and behaviour of linear alkylbenzenesulphonates (LAS) in a stratified estuary

Input and distribution of linear alkylbenzenesulphonates (LAS) in the highly stratified Krka River estuary were studied during 1990–1991. Determinations of individual LAS homologues in wastewater and estuarine waters were performed using reversed-phase high-performance liquid chromatography (HPLC) with spectrofluorimetric detection. The investigated municipal wastewaters contained LAS homologues with alkyl-chain lengths from C₁₀ to C₁₃ at total concentrations in the range of 285–1041 μg l⁻¹. Total LAS input via wastewaters into ibenik Harbour, the most polluted part of the estuary, was estimated at 12.6 kg day⁻¹. A relatively large fraction of total LAS, depending on the wastewater particle load, was found in particulate form (11–59%). Distributions of the individual homologues in dissolved and particulate fractions were rather different, the latter being significantly enriched in higher homologues (C₁₂, C₁₃). The LAS concentration in the estuary was quite low (0.2–23.9 μg l⁻¹) which was caused chiefly by a strong and fast dilution process. However, characteristic vertical distribution of LAS in the estuarine water column indicated that the wastewater plume spreads almost exclusively in the upper (brackish) layer. The concentration maxima were observed in the surface microlayer and at the brackish water/seawater boundary.     

Biomonitoring with benthic macroalgae and direct assay of heavy metals in seawater of the Oporto coast (northwest Portugal)

The concentrations of dissolved Cd, Cu, Hg and Pb in seawater and algae (Enteromorpha spp. and Porphyra spp.) were determined in parallel on three beaches located in the Oporto coast (Portugal), during 8 successive months, comprising periods of low and high biological productivity. The concentrations of dissolved metals in seawater varied markedly during the sampling period and exhibited seasonality. The concentrations of Cd were high in autumn and winter, but low in spring. The concentrations of Cu and Hg were high in autumn, low in winter and peaked in May. The concentrations of Pb were low in autumn and winter, and also peaked in May. It is likely that biological activity was, at least partially, responsible for the observed seasonal changes. The mean concentrations of dissolved metals in seawater were similar to those reported for polluted and industrialized european coastal areas. Metal concentration factors, calculated month-to-month for each alga, metal and site, varied markedly during the sampling period, indicating that concentration factors based on single or few determinations could be misleading. On the contrary, mean concentration factors (calculated by dividing the mean metal concentration in the algae by the mean metal concentration in seawater) were relatively constant at all three sites, indicating that in the Oporto coast, Enteromorpha spp. can be used to estimate the mean concentration of dissolved Cd, Cu and Hg in seawater, and Porphyra spp., the mean concentration of Cd, Cu and Pb. However, considering that future estimates of the concentrations of these metals in seawater should be based on determinations of the metal contents in Enteromorpha spp. and Porphyra spp. carried out on several occasions spanning a considerable period of time, the use of these algae as monitors of heavy metal pollution can have limited practical advantages over the direct assay of the metals in seawater.     

Effects of 12 years' operation of a sewage treatment plant on trace metal occurrence within a Mediterranean commercial sponge (Spongia officinalis, Demospongiae)

The present field study uses Spongia officinalis for assessing trace metals occurrence in time and space within Mediterranean rocky communities. Nine sites were selected in the Marseille area for studying spatial trends in 12 metal concentrations. Long term changes in 8 metal concentrations were assessed at sites that had been sampled before and 12 years after the opening of a treatment plant. Spongia officinalis highly concentrated all the trace metal surveyed excepted Hg and Cd. The overall contamination level registered provided a classification of the study sites which is congruent with that given by other studies on pollutant accumulation in neighbouring sandy-bottoms or benthic assemblages. Among the metals studied, Fe, Pb, Cr are those that best highlighted a pollution gradient. In the present study, only Cd concentration did not vary in space. Except for Ni, all pollutant concentrations clearly decreased between 1984 and 1999. This very impressive decrease in heavy metal concentrations within the Marseille area represents an indisputable evidence of the improvement of the seawater quality resulting from 12 years' operation of the Marseille sewage plant. Moreover, the significant decrease also recorded in the reference population at Port-Cros might reflect an overall improvement in the seawater quality of the NW Mediterranean.     

The partitioning of Triclosan between aqueous and particulate bound phases in the Hudson River Estuary

The distribution of Triclosan within the Hudson River Estuary can be explained by a balance among the overall effluent inputs from municipal sewage treatment facilities, dilution of Triclosan concentrations in the water column with freshwater and seawater inputs, removal of Triclosan from the water column by adsorption to particles, and loss to photodegradation. This study shows that an average water column concentration of 3 ± 2 ng/l (in the lower Hudson River Estuary) is consistent with an estimate for dilution of average wastewater concentrations with seawater and calculated rates of adsorption of Triclosan to particles. An average Triclosan sediment concentration of 26 ± 11 ng/g would be in equilibrium with the overlying water column if Triclosan has a particle-to-water partitioning coefficient of k_d  10⁴, consistent with laboratory estimates.     

Comprehensive assessment of heavy metal contamination in sediment of the Pearl River Estuary and adjacent shelf

Total metal concentrations (Cr, Ni, Cu, Zn, and Pb), acid volatile sulfide and simultaneously extracted metals (AVS-SEM), and heavy metal fractionation were used to assess the heavy metals contamination status and ecological risk in the sediments of the Pearl River Estuary (PRE) and adjacent shelf. Elevated concentrations at estuarine sites and lower concentrations at adjacent shelf sites are observed, especially for Cu and Zn. Within the PRE, the concentration of heavy metals in the western shore was mostly higher than that in the middle shore. The metals from anthropogenic sources mainly occur in the labile fraction and may be taken up by organisms as the environmental parameters change. A combination of total metal concentrations, metal contamination index and sequential extraction analysis is necessary to get the comprehensive information on the baseline, anthropogenic discharge and bioavailability of heavy metals.     

The mussel Mytilus edulis as a bio-assay organism for mercury in seawater

Surveys of natural populations of mussels have identified areas of mercury contamination in the Firth of Forth, Scotland. A field bio-assay technique has been devised which accurately reflects the mean total mercury concentration in the surrounding seawater. The detection limit of the technique is estimated at 5–20 ng Hg l.^?1, and consequently the method can detect comparatively small enhancements over background mercury concentrations in estuarine and sea water.     

Modelling of colloidal particle and heavy metal transfer behaviours during seawater intrusion and refreshing processes

The proper management of coastal aquifers commonly requires an understanding of regional mass flow and complete seawater–freshwater circulation. In this study, time series observations of seawater intrusion and refreshing were conducted using a column experiment based on natural flow conditions in coastal groundwater and a sampled medium from a coastal sandy aquifer without chemical treatment. Ranges of hydrodynamic and hydrochemical variables were tested and analysed. The results showed that the zeta potential of suspended colloids in aqueous solution in an aquifer polluted with 0.5 g/kg of heavy metals exhibited an isoelectric point for pH values ranging from 5.70 to 6.07 when freshwater or seawater completely occupied the aquifer pores, which is representative of natural hydrochemical conditions. In this scenario, a high background concentration of heavy metals induced colloidal immobilization. Otherwise, seawater–freshwater circulation enabled colloid mobilization due to ionic strength and pH fluctuations. The migration of multiple heavy metals occurred at a characteristic time of approximately 1 pore volume after each intrusion stage began and when the peak rate of colloid release was reached. At these times, the colloid behaviour determined the quantity and pathway of heavy metal transport. On the basis of the influences of seawater and freshwater interactions, the quantity of mobilized particles generally decreased and was uniformly distributed in each fraction due to particle loss and decreased porous connectivity. We speculate that the decrease in the total surface area of the migratory colloids may cause colloid‐associated heavy metal transport to decrease. The experimental results provide a useful basis for testing coastal groundwater flow and mass transport models because these phenomena require full characterization to precisely evaluate the associated fluxes from the field scale to the microscopic dimension.     

The Eurobulker oil spill: mid-term changes of some ecosystem indicators

The sinking of the tanker Eurobulker in Southern Evoikos gulf (Aegean Sea, Greece) in September 2000 resulted in a spill of 700 tons of crude oil. The environmental impact of the spill was studied by the National Centre for Marine Research. The hydrocarbon concentrations in water, sediment and coastal benthic organisms were measured and the response of the benthic communities to the disturbance caused by the oil spill was studied along the direction to the coast and over three sampling seasons. The most severe and direct effects were evidenced on the muddy benthic communities of the accident site and the stations in the close vicinity sampled shortly after the spill. The effects included reduction of the species richness and community diversity, but the communities reached full recovery 8 months later. The impact of the spill was more indirect and delayed in the coastal stations, where as the hydrocarbon measurements indicated, the pollutants were transported later and induced their effects on the benthic communities 6 months after the accident.     

Investigation of heavy metal pollutants at various depths in the Gulf of Izmit

In this study, we report results concerning the accumulation of heavy metals in seawater from Izmit Bay. The bay was divided into the three parts: the eastern, the central and the western basins. The goal of this study was to determine levels of heavy metals at various depths in the bay between April 2008 and May 2010. Liquid–liquid extractions were performed on seawater samples. An atomic absorption spectrophotometer was used to measure levels of six metals: lead, cadmium, chromium, iron, manganese and zinc. We applied our results to evaluate the status of pollution in the Gulf of Izmit. Significant seasonal differences in metal concentrations and higher concentrations of many metals in water near the shore are evidence for uncontrolled release of pollutants in the water.     

Hydrodynamics and suspended particulate matter retention in macrotidal estuaries located in Amazonia-semiarid interface (Northeastern-Brazil)

The aim of the current study was to determine the nature of the seasonal variability of the Suspended Particulate Matter (SPM) fluxes from the drainage basin to the estuary in a macrotidal region (Northeastern Brazil), and the estuarine response to a seawater intrusion regarding sediment deposition, which will support the understanding of the global transport of materials at the continent-ocean interface. Thermohaline structure data was acquired using a Conductivity, Temperature, and Depth (CTD) probe with a sampling frequency of 4 Hz. Suspended particulate material was measured by gravimetric measurements applied to exact filtered volume samples. The outflows were measured through the use of an Acoustic Doppler Current Profiler (ADCP) with frequency of 1.5 MHz. The horizontal thermal and saline gradients varied from warmer and less saline waters (2014) to cooler and saline waters (2015). The gradient behavior when linked to volume transport and SPM flows, suggests a minimization of the fluvial flows in 2015, easing the advance of coastal water (CW) towards the inner estuary, leading to an inversion of the baroclinic pressure gradient. The bottom saline front, generated by the entrance of coastal water masses, caused an increase in SPM concentrations due to increased fluid density, resuspension of previously deposited sediment, and erosion of banks. High concentrations of SPM indicate higher volume transport suggesting a hydraulic barrier due to the change/inversion of the baroclinic pressure gradient, resulting in water and material retention. Material deposition was observed during neap tide, while during spring tide the material is resuspended, increasing the concentration, generating cycles of deposition and erosion during the neap-spring tides. The sediment in suspension that reach the estuary, even with low fluvial volume, stay in this environment forming new islands because of deposition. High deposition rates or sediment cycling, if generated by the hydraulic barrier, may indicate that the flows of SPM from the continental drainage to the estuary and adjacent continental shelf are interrupted and the residence time is increased.     

Ecological Conditions of Watercourses in the Middle Amur Lowland in the Areas of Drainage Reclamation

The effect of land reclamation on the migration and accumulation of heavy metals and some pollutants in small rivers is determined. The study was conducted in the Middle Amur lowland in different phases of hydrological regime and at different extent of floodplain inundation. The formation of the hydrological regime in small rivers in this area is governed by the irregular annual runoff distribution. The seasonal character of flood periods requires water samples to be taken before spring flood (April) and after floods have passed (September–October), and at various extent of floodplain inundation. The field studies of water-courses were carried out in 2009–2014. The water samples were analyzed to determine the concentrations of heavy metals (iron, manganese, copper, nickel, cobalt, lead and zinc), suspended substances, organic carbon (total, dissolved, and suspended), humic and fulvic acids, and volatile organic compounds. The mobility of heavy metals in surface watercourses was shown to reflect the effect of drainage and surface runoff from soil horizons, an increase in the concentrations of suspended and organic compounds, especially, fulvic acids, which enhance their geochemical mobility. During floods, an increase in heavy metals washout from floodplain soils and the dilution of their concentrations causes the formation of a single-type concentration series of heavy metals. In addition, the processes of pollutants migration show an effect of changes in the geomorphological characteristics of floodplain–channel complexes and a decrease in flow velocity in watercourses in the areas where land reclamation was applied. Thus, all factors mentioned above lead to a decrease in water pollution index in the river.     

Sediment pollution and its effect on fish through food chain in the Yangtze River

Suspended sediment adsorbs pollutants from flowing water in rivers and deposits onto the bed. However, the pollutants accumulated in the river bed sediment may affect the bio-community through food chain for a long period of time. To study the problem the concentration of heavy metals （Cr, Cd, Hg, Cu, Fe, Zn, Pb and As） in water, sediment, and fish/invertebrate were investigated in the middle and lower reaches of the Yangtze River during 2006-2007. The concentrations of heavy metals were 100-10,000 times higher in the sediment than in the water. Benthic invertebrates had relatively high concentrations of heavy metals in their tissues due to their proximity to contaminated sediments. Benthic invertivore fish had moderately high concentrations of heavy metals whereas phytoplanktivore fish, such as the silver carp, accumulated the lowest concentration of heavy metals. The concentrations of Cu, Zn, and Fe were higher than Hg, Pb, Cd, Cr, and As in the tissue samples. The concentration of heavy metals was lower in the river sediments than in the lake sediments. Conversely, the concentration of heavy metals was higher in river water than in lake water. While a pollution event into a water body is often transitory, the effects of the pollutants may be long-lived due to their tendency to be absorbed in the sediments and then released into the food chain. The heavy metals were concentrated in the following order： bottom material 〉 demersal fish and benthic fauna 〉 middle-lower layer fish 〉 upper-middle layer fish 〉 water.     

Naturally Occurring Arsenic in Sandstone Aquifer Water Supply Wells of Northeastern Wisconsin

The U.S. Environmental Protection Agency (EPA) maximum contaminant level (MCL) of 50 μg/L for arsenic was exceeded in 86 of 2125 water supply wells sampled over a broad geographic range in pails of Drown. Outagamie and Winnebago Counties, Wisconsin. The hydrologic and geochemical properties of the area were examined and the source of arsenic was determined to be natural, Ground water collected from two geologic formations, the St. Peter Sandstone and the overlying Platteville/Galena Dolomite, was found to be the principal source of the elevated arsenic concentrations. These two Formations supply a large portion of eastern Wisconsin private wells with their drinking water.
Three wells were found within Outagamie County to have an unusually low pH. Results suggest that the cause of the low pH in these wells is of natural origin induced by the oxidation of iron sulfide minerals. In this reaction iron sulfide minerals are oxidized. forming sulfuric acid causing a low pH and a high concentration of various metals to leach from native rock formations into the water supply.
Based on the data gathered from this study, an arsenic advisory area was designated for both Outagamie and Winnebago Counties. Guidelines were developed for well drillers and owners constructing new wells within the advisory area to reduce the likelihood of arsenic presence in the water supply. Fifteen wells containing arsenic exceeding the MCL were successfully reconstructed or new wells were constructed based on the guidelines developed. These constructions substantially reduced arsenic levels in the well water supplies.     

Analysis of bacterial diversity and metals in produced water, seawater and sediments from an offshore oil and gas production platform

Produced water is one of the largest waste products routinely discharged into the ocean from offshore oil and gas platforms. This study analyzed bacterial communities and metals in the produced water, surrounding seawater, and sediment around the Thebaud platform. The bacterial community within the produced water was different from the seawater (SAB = 13.3), but the discharge had no detectable effect on the bacterial communities in the seawater (SAB > 97). In contrast, genomic analysis of sediments revealed that the bacterial community from 250 m was different (SAB = 70) from other locations further from the discharge, suggesting that the produced water had a detectable effect on the bacterial community in the sediment closest to the discharge. These near-field sediments contained elevated concentrations of manganese and iron that are associated with the produced water effluent. The results suggested that the discharge of produced water has influenced the bacterial community structure of sediments adjacent to the platform.     

Contribution to the study of thermal waters in Greece: chemical patterns and origin of thermal water in the thermal springs of Lesvos

The occurrence of thermal/spa waters on Lesvos Island is related to the presence of a major faulting system. Thermal waters are the result of mixing of meteoric and infiltrating seawater at great depth, and their total salinity depends on the percentage of seawater in their composition. According to the diagrams of main elements, trace elements and environmental isotopes, most of the components that determine the chemical composition of thermal waters such as sodium, chloride and sulphates originate from seawaters. On the other hand, the concentration of calcium, magnesium, boron, lithium, etc., was affected by water–rock interaction under high temperature conditions. Moving towards the surface, thermal waters may become polluted by influx of recent seawater, allowing their chemical composition to become similar to that of seawater. The thermal waters of Lesvos Island present relatively high concentrations of ammonia and redox sensitive metals because they are hosted in a reducing environment. They also exhibit low nitrate concentrations due to their mixture with recent fresh water. Finally, they show increased radon concentrations, ranging from 20 to 60 kBq m^?3 in the eastern and southern parts of the island, and about 230 kBq m^?3 in the north, in the area of Eftalou–Argenos. Copyright © 2007 John Wiley & Sons, Ltd.