Diagenesis and bioavailability of mercury in the contaminated sediments of Ulhas Estuary, India

Sequential extraction of Hg was performed in a core collected from intertidal area in Ulhas Estuary in order to characterize the downward distribution and diagenetic behavior of Hg in a polluted estuary. Concentration of total Hg ranged between 0.46 and 6.40 μg g⁻¹ with significant decrease in surficial sediment as a result of closing of two Hg-cell based chlor-alkali plants. Results of sequential extraction showed that >65% Hg was strongly bound to organo-sulphur and inorganic sulphide species that are not bioavailable. Flux of only 18.8% of Hg was found compared to its value deposited on sediment–water interface. Hence, it is concluded that there is no significant diagenetic remobilization of Hg in Ulhas Estuary. This core also has been analyzed for ²¹⁰Pb geochronology. The estimated sedimentation rate is 0.31 cm y⁻¹ in the present sampling region.     

Reactive sulfides relationship with metals in sediments from an eutrophicated estuary in Southeast Brazil

The potential association of acid-volatile sulfides (AVS) and reactive (HCl soluble) Fe with the distribution of reactive trace metals (Cu, Cd, Ni, Pb and Zn) was investigated in sediment cores collected in the Igua?u river estuarine system (Guanabara bay, Brazil), within the river (core R) and the bay (core B) areas. Moderate to extremely high AVS concentrations (33-314 micromol g(-1)) were found in the rapidly-accumulated sediments of this eutrophicated estuary. AVS showed significant correlations with Fe, Ni and Pb in core B, whereas no correlation between AVS and metals was observed in core R. Results suggest that the AVS:Fe molar ratio may often reflect the diagenetic conditions controlling the distribution of Cd and Cu in core B better than AVS and Fe levels themselves. A shift in the biogeochemical controls of metal distribution from the river to the open bay sediments is suggested, with a greater association of most metals with AVS and Fe in bay sediments.     

Sedimentary record of anthropogenic metal inputs in the Tagus prodelta (Portugal)

Favourable oceanographic and environmental conditions allow the formation of a fine-grained deposit (Tagus prodelta) located at the mouth of the Tagus River. This fine-grained deposit results from the sink and accumulation of terrestrial and marine-derived materials. Three short sediment cores collected in the Tagus prodelta were investigated through the variability in grain-size, major and trace elements, C_org, N_tot, δ¹³C and ²¹⁰Pb dating to characterise the historical development of trace metal contamination. Historical trends indicated significant anthropogenic enrichments for Hg, Pb, Zn, Cu, Sb and Sn since the 1930s. Hg presents the highest level of anthropogenic enrichment (ca. EF_Hg=20) in cores 3576 (PO287-26-1B) and 3579 (PO287-27-1B) collected closer to the shore. Despite these elements were derived from distinct industrial sources, all of them presented similar temporal trends, which points to the importance of estuarine mixing processes originated by the tidal regime and wind before transfer to the adjoining coastal areas. The cores were characterised by smoothness of down-core variations and river flood events occurred in the last decades were not registered. Furthermore, the improvement of effluents treatment together with the closing of some industrial point sources in the last two decades is not evidenced in recent sediment composition of the Tagus prodelta. Besides sediment reworking in the upper sediment layers, sediment mixing inside the estuary may explain minor abrupt alterations with the depth.     

A 130 year record of pollution in the Suances estuary (southern Bay of Biscay): implications for environmental management

Geochemical composition (Al, Zn, Pb, Cd, Cu, Ni, Cr and As) and foraminiferal assemblages in surface and core sediments were determined to assess the current situation and the recent environmental transformation of the Suances estuary (southern Bay of Biscay, Spain). Dating of the historical record has been achieved using isotopic analysis (²¹⁰Pb, ¹³⁷Cs) and two benchmark events such as the beginning of the mineral exploitation in the Reocín Pb-Zn deposits and the evolution of the chlor-alkali industry (inputs of Hg). Concentrations of Zn, Pb and Cd in both surface and core samples are remarkably higher than background values, reflecting the existence of significant amounts of polluted materials. The dramatic environmental impact of this pollution is clearly recorded by the change of the foraminiferal assemblages that even reach an afaunal stage during recent decades. Application of two different sets of Sediment Quality Guidelines confirm that they exert potential risk to the environment, and therefore if dredged they should need specific management measures.The results provide a reference database to monitor future environmental changes in the Suances estuary, particularly as regards the contaminated sediment storage and the re-colonization by autochtonous meiofauna.     

Distribution of 137Cs in the Lena River estuary-Laptev Sea system.

Surface sediment samples in the Laptev Sea have average 137Cs content of 7.1 Bq kg(-1), a value intermediate between that of the western Kara Sea (23 Bq kg(-1) and the East Siberian Sea (4.2 Bq kg-'). Both surface sediment content and sediment inventory of 137Cs in the Laptev Sea sediments show significant variability, and the influence of a variety of environmental factors.137Cs concentrations in the Laptev Sea surface sediments range from 0.8 to 16 Bq kg(-1). There is a marked increase in 137Cs content of surface sediment samples collected near the Lena River delta, and a local enrichment in the 137Cs inventories at these sites is also evident. Fine-grained mixed-layer illite/ smectite rich sediments in the estuary provide effective adsorption sites to fix 137Cs, in spite of desorption processes associated with low salinities in estuarine mixing. The Lena River-Laptev Sea mixing zone is a major site of sea-ice production. River and shelf sediments are incorporated into sea-ice formed in this region (Holmes and Creager, 1974). The irregular 137Cs activity profiles of the Lena River estuary cores indicate disturbance or removal of 137Cs-laden sediments via sea-ice related processes. Lena River and Estuary sediments may have served as a secondary source (i.e. other than direct fallout) of 137Cs in sea-ice. North-east of the Lena River estuary, sediment contains a thin layer of 137Cs-bearing material over an erosion surface. The 137Cs-laden surface layer may be the result of transient deposition of estuarine sediments being delivered by sea-ice or spring floods.     

The history of water salinity in the Pearl River estuary,China, during the Late Quaternary

This research reconstructed the Late Quaternary salinity history of the Pearl River estuary, China, from diatom records of four sedimentary cores. The reconstruction was produced through the application of a diatom–salinity transfer function developed based on 77 modern surface sediment samples collected across the estuary from shallow marine environment to deltaic distributaries. The statistical analysis indicates that the majority of sediment samples from the cores has good modern analogues, thus the reconstructions are reliable. The reconstructed salinity history shows the older estuarine sequence formed during the last interglacial was deposited under similar salinity conditions to the younger estuarine sequence, which was formed during the present interglacial. Further analysis into the younger estuarine sequence reveals the interplays between sea level, monsoon‐driven freshwater discharge, and deltaic shoreline movement, key factors that have influenced water salinity in the estuary. In particular, a core from the delta plain shows the effects of sea‐level change and deltaic progradation, while cores from the mouth region of the estuary reveal changes of monsoon‐driven freshwater discharge. This study demonstrates the advantages of quantitative salinity reconstructions to improve the quality of reconstruction and allow direct comparison with other quantitative records and the instrumentally observed values of salinity. Copyright © 2010 John Wiley & Sons, Ltd.     

One century sedimentary record of Hg and Pb pollution in the Sagua estuary (Cuba) derived from Pb and Cs chronology

The vertical distribution of Hg and Pb were determined in a sediment core collected from the Sagua estuary (North Cuba) that receives input from the Sagua river, one of the most polluted rivers discharging into the Cuban coastal environment. Depth profiles of metal concentrations were converted to time-based profiles using the ²¹⁰Pb dating method and confirmed with the ¹³⁷Cs fallout peak. The mean mass accumulation rate was estimated to be 0.17 ± 0.04 g cm⁻² y⁻¹ (mean sediment accumulation rate 0.52 ± 0.13 cm y⁻¹) and the core bottom was estimated to date back about 130 years. The historical sedimentary record showed a strong enrichment of mercury concentrations in the past decades, caused by the incomplete treatment of industrial wastes from a chlor-alkali plant with mercury-cell technology in the Sagua river basin. Lead fluxes to sediments showed a gradual increase from the 1920s to present, which agrees with a population increase in Sagua la Grande City. Fluxes of both metals have increased the past 25 years, with values reaching a maximum of 0.5 and 3.9 μg cm⁻² y⁻¹ for Hg and Pb, respectively.     

Petroleum hydrocarbon residues in the marine environment of Bassein-Mumbai

The paper reports PHc contamination in water, sediment and biota of the coastal area of Bassein-Mumbai in relation to relatively less polluted sites (Dabhol and Ratnagiri) off the west coast of India. To facilitate inter-comparison three standards have been used though the results are reported in terms of SAM (Residue of Saudi Arabian Mix crude). The concentration of PHc in water off Bassein-Mumbai varies widely (2.9-39.2 microg l(-1)) as compared to the average baseline (2.8 microg l(-1)) with higher values generally confined to creeks and estuaries. The higher concentration of PHc in the bottom water of shallow areas is attributed to the contribution from the sediment-associated petroleum residue. High concentration of PHc in the surficial sediment of inshore area Ratnagiri (107.7 ppm, dry wt) is perhaps the remnants of an oil spill that occurred in the Bombay High region on May 17, 1993. The majority of values of PHc concentration in the surficial sediment of the Bassein-Mumbai region exceed 15 ppm (dry wt) against the expected background (<3 ppm, dry wt) and the trend is indicative of transfer of PHc loads from the inshore areas to the open-shore sediments. The PHc concentration of 0.8-2.6 ppm (dry wt) in sediment deposited prior to the first global commercial use of petroleum in core R5 represents the biogenic background. Based on the period of industrialisation and the horizon of PHc accumulation, a sedimentation rate of 0.2 and 1.0 cm y(-1) respectively is estimated for cores U11 and U12. Substantial increase in the concentration of PHc in sediment after 1950 in cores T8 and T10 correlates well with the establishment of refineries on the western shore of the Thane Creek in 1955-1960. A minor peak in most cores in the top 10 cm sediment probably results from biological transfer of PHc lower into the sediment by benthic organisms. Excess of PHc retained in the sediment of the Bassein-Mumbai region over the biogenic background is estimated at 40,000 t. The PHc residues (1.8-10.8 ppm, wet wt) in fish caught off Bassein-Mumbai do not suggest bioaccumulation.     

Controls of the chemical composition of particle populations in a macrotidal estuary (Tamar Estuary, U.K.)

The chemical composition of suspended particulate material (SPM) in the Tamar Estuary and its response to tidal sediment resuspension at the turbidity maximum have been investigated. The results discriminate four regions: (1) the outer estuary where spatial changes in the composition of SPM reflect the dispersal of estuarine particles modified by in situ generation of organic particles, (2) the middle estuary where the composition of SPM is mainly determined by hydrodynamic mixing although there is some evidence of in situ chemical reactivity, (3) the upper estuary where sharply distinct and temporally variable SPM compositions are centred at the turbidity maximum; these are largely the result of particle-selective accumulation, sedimentation and resuspension processes rather than of local particle-water chemical exchanges, and (4) the fluvial estuary where the SPM composition reflects the influx of riverine particles.     

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.     

Toxic metal (Pb, Cd and Hg) levels in the nearshore surface sediments from the European and Anotolian Shores of Bosphorus, Turkey

In this study, some toxic metal such as Pb, Cd and Hg analyzes have been done in the nearshore surface sediments. Sediment samples have been collected from five parts from the European and Anotolian Shores of the Bosphorus during 2003-2004. Total Pb, Cd and Hg contents vary between <0.01μgg(-1) and 238μgg(-1); <0.01μgg(-1) and 0.92μgg(-1); 0.001μgg(-1) and 0.45μgg(-1), respectively. Contamination Factor (CF) values of Pb and Cd range between 1 and 3 whilst CF values of Hg are lower than 1 in all the stations. It means that there are no Hg metal enrichment by natural or anthropogenic inputs contrary to moderately contamination for Pb and Cd metals throughout the Bosphorus sediments.     

Mercury distribution in Douro estuary (Portugal)

Determinations of dissolved reactive and total dissolved mercury, particulate and sedimentary mercury, dissolved organic carbon (DOC), particulate organic carbon (POC) and suspended particulate matter (SPM) have been made in the estuary of river Douro, in northern Portugal. The estuary was stratified by salinity along most of its length, it had low concentrations of SPM, typically <20 mg dm(-3), and concentrations of DOC in the range <1.0-1.8 mg dm(-3). The surface waters had a maximum dissolved concentration of reactive mercury of about 10 ng dm(-3), whereas for the more saline bottom waters it was about 65 ng dm(-3). The surface waters had maximum concentrations of total suspended particulate mercury of approximately 7 microg g(-1) and the bottom waters were always <1 microg g(-1). Concentrations of mercury in sediments was low and in the range from 0.06 to 0.18 microg g(-1). The transport of mercury in surface waters was mainly associated with organic-rich particulate matter, while in bottom waters the dissolved phase transport of mercury is more important. Lower particulate organic matter, formation of chlorocomplexes in more saline waters and eventually the presence of colloids appear to explain the difference of mercury partitioning in Douro estuarine waters.     

Spatial variability of metals in the inter-tidal sediments of the Medway Estuary,Kent, UK

Concentrations of major and trace metals were determined in eight sediment cores collected from the inter-tidal zone of the Medway Estuary, Kent, UK. Metal associations and potential sources have been investigated using principal component analysis. These data provide the first detailed geochemical survey of recent sediments in the Medway Estuary. Metal concentrations in surface sediments lie in the mid to lower range for UK estuarine sediments indicating that the Medway receives low but appreciable contaminant inputs. Vertical metal distributions reveal variable redox zonation across the estuary and historically elevated anthropogenic inputs. Peak concentrations of Cu, Pb and Zn can be traced laterally across the estuary and their positions indicate periods of past erosion and/or non-deposition. However, low rates of sediment accumulation do not allow these sub surface maxima to be used as accurate geochemical marker horizons. The salt marshes and inter-tidal mud flats in the Medway Estuary are experiencing erosion, however the erosion of historically contaminated sediments is unlikely to re-release significant amounts of heavy metals to the estuarine system.     

Sedimentation and chronology of heavy metal pollution in Oslo harbor, Norway

Stratigraphic profiles of Cu, Cd and Hg in ten sediment cores from the Oslo harbor, Norway, combined with results of radiometric dating demonstrate that pollution by these metals peaked between 1940 and 1970. Dating results indicate that Hg discharges peaked between 1940 and 1950, Cd reached maximum ca. 1955-1960, and Cu has the highest concentration in sediment interval corresponding to ca. 1970. Geochemical profiles and maxima of Cu, Cd and Hg concentrations can be used as chronostratigraphic markers for sediment cores from the Oslo harbor. Acoustic backscatter and sediment core data indicate that propeller wash affects the seabed in the Oslo harbor. The propeller-induced turbulence causes erosion, and in places exposes and remobilizes contaminated sediments that accumulated in the harbor during previous decades. Such re-exposure of contaminated sediments could be detrimental to local ecosystems and offset remediation efforts, warranting further impact studies and potential mitigation strategies to prevent redistribution.     

Evaluations of heavy metal pollution in sediment and Mullus barbatus from the Izmir Bay (Eastern Aegean) during 1997-2009

Izmir Bay is one of the great natural bays of the Mediterranean. The surface sediment and fish samples were collected during 1997-2009. The sediment concentrations of inner bay showed significant enrichments during sampling periods. Outer and middle bays exhibited low levels of metal enrichments except the estuary of Gediz River. The concentrations were generally higher than the background levels from the Mediterranean and Aegean except Cd and Pb levels gradually decreased. Metal EF is used as an index to evaluate anthropogenic influences of metals in sediments. Maximum metal enrichment was found for Hg in the outer bay, while Pb indicated maximum enrichment in the middle-inner bays. Metal levels were evaluated in sediments in accordance with the numerical SQG of the USEPA. The levels of fish tissues were lower than the results reported from polluted areas of the Mediterranean. The highest BAFs were detected for Hg and Cd in fish.     

Environmental transformation of the Bilbao estuary,N. Spain: microfaunal and geochemical proxies in the recent sedimentary record

The distribution and abundance of benthic foraminifera and a range of elements have been analysed in six long cores (up to 10 m long) from the Bilbao estuary, N. Spain, to document environmental transformation of this estuarine ecosystem and to determine sediment contamination levels. Three different environmental zones could be distinguished in the recent sedimentary record based on its microfaunal and geochemical contents. Initially, a pre-industrial zone containing very abundant and diverse foraminiferal assemblages together with baseline metal levels. Secondly, an older industrial zone exhibiting co-existence of abundant and diverse foraminiferal assemblages with high concentrations of metals. Finally, a younger industrial zone with extreme concentrations of metals and barren of indigenous foraminifera. This environmental transformation has been caused by the discharge of untreated domestic and industrial effluents during the last 150 years. The occurrence of foraminifera in the two industrial zones and along the estuary is not related to defined levels of metals, and this seems to confirm oxygen limitation as the key factor to explain complete estuarine defaunation during deposition of the younger industrial zone (period 1950-2000). Effectiveness of current regeneration schemes could be assessed using microfaunal and geochemical proxies as environmental quality indicators.     

Impact of millennial mining activities on sediments and microfauna of the Tinto River estuary (SW Spain)

In this paper, we analyze two short cores collected in the Tinto estuary (SW Spain), and describe the palaeoenvironmental evolution of this area during the last two millennia, along with the influence of historical mining activities and recent industrial pollution on sediments and microfauna (foraminifera and ostracoda). Although there were no significant changes in the distribution of microorganisms, a first pollution period (0-150 AD) was recorded in high sediment pollution by Cu in the shallow palaeochannels of the middle estuary. During this period and the following 1700 years, tolerant pioneer species of both foraminifera and ostracoda were found predominantly in the inner, protected areas of the estuary, while the bottom sediments were subjected to high hydrodynamic gradients, and consequently showed lower density and diversity of organisms. In the last 150 years, acid mine drainage processes, introduction of a new mining period, and the polluted inputs derived from two industrial processes resulted in increased heavy metal contamination of the bottom sediments, and corresponding extirpation of ostracodes and restriction of foraminifers to the inner zones of the estuary.     

Tracing anthropogenic contamination in the Pearl River estuarine and marine environment of South China Sea using sterols and other organic molecular markers

5beta-Coprostanol together with eight other sterols and unresolved complex mixtures (UCMs) were quantitatively investigated for surficial sediments and surface waters to assess the impacts of anthropogenic activities on the Pearl River estuarine and marine environment of South China Sea. The studied area extends from the Pearl River Estuary southward to the open sea. 5beta-Coprostanol concentrations ranged from trace amounts to 53 microgg(-1) TOC in surficial sediments. The highest levels and highest percentages of coprostanol were found in the Pearl River estuary, especially in the inner estuary and those sites close to the submarine outfalls of Hong Kong. For waters, only in estuarine samples was coprostanol quantitatively detected, ranging from 11 to 299 ngL(-1). Bimodal UCM "humps" were observed for most sediment samples, with concentrations ranging from 215 to 10,491 microg g(-1) TOC in sediments and from 2 to 26 mcirogL(-1) in waters, respectively. Progressive seaward declines in concentrations were found for both 5beta-coprostanol and UCM in surficial sediments. Trace or no 5beta-coprostanol was found in open-sea samples. Concentrations of coprostanol and UCM in surficial sediments are correlated. These results imply that there are obvious anthropogenic contaminations in the Pearl River estuary. The submarine outfalls in Hong Kong represent important sources of the sewage pollution to the Pearl River estuarine sediments evidenced by a combination of coprostanol concentration, diagnostic indices, sterol profiles and UCM. No obvious dispersion or transport of the sewage contamination occurred from the Pearl River estuary to the open South China Sea indicated by fecal sterol biomarkers.     

Persistence and metallic composition of paint particles in sediments from a tidal inlet

Concentrations of Cu, Pb, Sn and Zn have been determined in sediment (<500 μm) and macroscopic paint particles (>500 μm) retrieved from sections of two cores collected from a tidal inlet of the Plym estuary, southwest England. Paint particles contributed up to about 0.2% of the total mass retrieved from each section and were most abundant towards the base of the cores where, according to (210)Pb dating, deposition took place about a decade prior to sampling. Metal concentrations in the paint particles pooled from the sections were highly variable, typically spanning two orders of magnitude in each core, and were greatest for Cu and Zn (up to 460,000 and 170,000 μg g(-1), respectively) due to their use in contemporary antifouling formulations applied to boat hulls. Concentrations of metals in the sediment were, however, relatively invariant, an effect attributed to the abundance and dispersion of microscopic paint particles throughout the cores.     

Crustacean assemblages in a polluted estuary from South-Western Spain

The spatial-temporal variation in crustacean assemblages of the Odiel-Tinto estuary, one of the most polluted areas in the world, was studied in 2000, 2002 and 2004. The crustacean assemblages were mainly established according to the natural gradient from estuarine to marine environment (based on water and sediment characteristics such as dissolved oxygen, salinity, granulometry or organic content). Pollutants such as copper, zinc or phosphates could also explain partially this pattern based on BIOENV and canonical correspondence analyses. However, there were clear symptoms of perturbation, mainly in the inner areas, such as a low number of species and a low abundance, especially in relation to the typical estuarine species (e.g. Cyathura carinata, Corophium spp.). This study provides baseline information which can be used as a reference point in a long-term perspective.