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Sediment disturbance off the Tagus Estuary, Western Portugal: chronic contamination, sewage outfall operation and runoff events.

Sediment disturbance patterns in the coastal area off the Tagus Estuary (Portugal) have been assessed using a set of combined techniques. The potential sources of disturbance in the area include chronic contamination of the fine sediments originating from the estuary, a local input from a long-sea sewage outfall and occasional high runoff episodes following torrential rain. The Sediment Quality Triad approach, combining environmental chemistry (namely organic contaminants), macrofaunal benthic communities and laboratory sediment toxicity assays, was performed on sediment samples from 20 sites. The samples were collected before the outfall commenced operation and four years after commissioning, in order to evaluate the relative magnitudes of the three potential sources of disturbance. The sediment contamination created by the estuary was identified as the most important cause of reduced sediment quality, as disturbance in all three components of the Sediment Quality Triad were only found in a site located near the estuary.

Environmental Monitoring↗

Determination of dioxin and dioxin-like compounds in sediments from UK estuaries using a bio-analytical approach: chemical-activated luciferase expression (CALUX) assay.

The DR-CALUX assay has been utilised for the bio-analytical screening of a number of estuarine sediments for dioxin-like activity. Total sediment extracts (samples containing all extracted compounds) and cleaned-up extracts (samples with the most stable compounds isolated from the total extracts) were screened. The concentration of the stable dioxin-like compounds in the cleaned-up sediment extracts was between 1.0 and 106 pgTEQCALUX g(-1) dry weight. The majority of sediments contained levels of dioxin-like compounds that were above concentrations that are considered to be a low risk to aquatic organisms. The CALUX bio-analytical approach showed some disparity with the traditional analytical approach. The reasons for these differences have been identified tentatively: firstly, the DR-CALUX assay responds to all dioxin-like compounds, and secondly, it measures non-additive effects. The dioxin-like activity of compounds in sediment total extracts, which contain both labile and stable compounds, were also assessed and were six orders of magnitude higher than the cleaned-up samples. This suggests the vast majority of the total dioxin-like activity is attributable to labile compounds. Overall, the DR-CALUX assay is shown to be a useful tool in the assessment of dioxin-like activity in estuarine sediments.

Animals↗

Quantity, composition, and source of sediment collected in sediment traps along the fringing coral reef off Molokai, Hawaii.

Sediment traps were used to evaluate the frequency, cause, and relative intensity of sediment mobility/resuspension along the fringing coral reef off southern Molokai (February 2000-May 2002). Two storms with high rainfall, floods, and exceptionally high waves resulted in sediment collection rates>1000 times higher than during non-storm periods, primarily because of sediment resuspension by waves. Based on quantity and composition of trapped sediment, floods recharged the reef flat with land-derived sediment, but had a low potential for burying coral on the fore reef when accompanied by high waves. The trapped sediments have low concentrations of anthropogenic metals. The magnetic properties of trapped sediment may provide information about the sources of land-derived sediment reaching the fore reef. The high trapping rate and low sediment cover indicate that coral surfaces on the fore reef are exposed to transient resuspended sediment, and that the traps do not measure net sediment accumulation on the reef surface.

Animals↗

Simultaneous release of sulfide with Fe, Mn, Ni and Zn in marine harbour sediment measured using a combined metal/sulfide DGT probe.

The technique of DGT (Diffusive Gradients in Thin Films) was further developed to allow simultaneous measurement of sulfide and trace metals at the same location in sediment. The new combined DGT probe consisted of a layer of gel impregnated with AgI, overlain by (1) a layer of gel containing Chelex, (2) a layer of gel and (3) a filter membrane. Diffusion of sulfide was controlled by layers (1) to (3), while diffusion of metals was controlled by layers (2) and (3). The Chelex gel trapped metals that were measured after elution with acid. The AgI gel trapped sulfide through the formation of Ag2S. This was then measured densitometrically as the colour changed from pale yellow to grey. Experiments demonstrated that concentrations of metal or sulfide measured by the combined device were no different to the concentrations measured by more conventional devices. The presence of Chelex in the gel did not impede the diffusion of sulfide. Deployment of a combined probe in marine sediment revealed simultaneous remobilisation of metals and sulfide at the same location. Solubility calculations indicated that some precipitation of amorphous FeS was probably occurring at the maxima in sulfide concentrations. There was general undersaturation with respect to NiS, but ZnS was supersaturated at all locations. There appeared to be localised active zones of organic matter decomposition, where reduction of manganese oxides, iron oxides and sulfate occurred simultaneously. Mass balance calculations indicated that Ni could not be supplied by release from decomposing organic matter. Manganese oxides were the most likely source, but supply from reductive dissolution of iron oxides could not be entirely discounted. Supply from either Fe or Mn oxides could account for the Zn maxima. Application of the newly developed combined probe provides new information that helps understanding of the complex nature of trace metal and sulfur chemistry in sediments.

Chemistry Techniques, Analytical↗

Assessing contamination levels of Laguna Lake sediments (Philippines) using a contact assay with zebrafish (Danio rerio) embryos.

The present study investigated the suitability of a sediment contact assay using zebrafish (Danio rerio) embryos to evaluate the degree of lake sediment contamination. As endpoints, developmental parameters (mortality, abnormality, heart rate, and hatching rate) as well as stress protein responses (hsp 70 levels) in the developing embryos were recorded during a 96-h exposure. Fertilized zebrafish eggs were exposed to both the whole as well as organic extract concentrations prepared from collected sediments from 5 sites along Laguna Lake, Philippines. Compared to whole sediment exposure, more severe embryotoxic and teratogenic responses were elicited in embryos exposed to organic extracts. However, since whole sediment-exposed embryos also revealed significant developmental defects, this exposure phase served as the more realistic exposure scenario in our study. Weak to strong upregulation of hsp 70 levels was also registered among embryos exposed to both whole sediments and organic extracts. The observed embryotoxic and proteotoxic responses by zebrafish embryos to Laguna Lake sediment exposures were discussed in relation to the analyzed contaminants in the sediments (heavy metals, PAHs (perylene), solvent). Overall, the present study points out that the sediment contact assay with zebrafish embryos offers a practicable and highly sensitive bioassay for the general assessment of sediment toxicity.

Animals↗

Effects of antibacterials use in aquaculture on biogeochemical processes in marine sediment.

The effects of chloramphenicol on microorganism in marine sediment were studied by spiked experiments in this paper. The results showed that high concentrations of chloramphenicol could inhibit the activities of microorganism in sediment, and that the growth of strains Pseudomons and Acinetobacter in sediment that can degrade organic matters were inhibited apparently. Furthermore, the resistance of heterotrophic bacteria in sediment had developed due to the use of antibacterials. Based on the above results potential environmental effects of antibacterials on microorganism in marine sediment were analyzed.

Acinetobacter↗

PAH content, toxicity and genotoxicity of coastal marine sediments from the Rovinj area, Northern Adriatic, Croatia.

Surface marine sediments collected from 8 sampling sites within the Rovinj coastal area, Northern Adriatic, Croatia, were used for determining priority pollutant polycyclic aromatic hydrocarbons (PAHs) and toxic/genotoxic potential of sediment organic extracts. Total PAH concentrations ranged from 32 microg/kg (protected area) to 13.2 mg/kg dry weight (harbor) and showed clear differences between pristine, urban industrial and harbor areas. PAHs distribution revealed their pyrogenic origin with some biogenic influence in harbor. At all sampling sites sediment extracts showed toxic potential that was consistent with the sediment type. No correlation between toxicity measured by Microtox assay and concentrations of individual or total PAHs was found. Noncytotoxic dose of sediment extracts showed no genotoxic potential in bacterial umu-test. DNA damage is positively related to total PAHs at 4 sampling sites (S-1, S-2, S-3, S-6), but the highest DNA damage was not observed at the site with the highest total sediment PAH content (S-5).

Aliivibrio fischeri↗

Long-term variation in mercury concentrations in estuarine organisms with changes in releases into Lavaca Bay, Texas.

Mercury releases into Lavaca Bay resulted in public health notices and a fishing closure for crabs and finfish. Mercury containing wastewater discharges were halted in 1970, but sediments were contaminated with mercury. The sediments are a source of mercury to the benthic food web via methylation. Mercury in water column feeding organisms has decreased markedly. Concentrations in benthic food web organisms remain elevated. Human consumption concerns for oysters have ended, but a closure for fishing for crabs and finfish continues. Monitoring of mercury in organisms since 1977 shows a gradual downward trend in mercury in crabs and finfish, but this was not sufficient to remove the closure. Continued releases of mercury, man's activities, and resuspension of sediments keep mercury in the sediment's biologically active zone. This enables the uptake of mercury via the benthic food web. If releases are ended, it will take years for the mercury to decrease to concentrations not of concern for human consumption. If more remediation to reduce the mercury concentrations in the sediments takes place, decrease of mercury in the organisms might occur more quickly.

Animals↗

Toxicity of 1,4-dichlorobenzene in sediments to juvenile polychaete worms.

Investigation of sediment contamination associated with a marine sewage outfall in Victoria (BC, Canada) found elevated concentrations of 1,4-dichlorobenzene (1,4-DCB). Juvenile polychaete worm (Neanthes) growth was significantly reduced at or near the outfall, roughly corresponding to elevated 1,4-DCB concentrations. There are few data on 1,4-DCB toxicity to marine organisms and no published literature on its toxicity to benthic marine organisms. To determine whether reduced polychaete growth (measured as dry weight) was due to 1,4-DCB exposure, a laboratory investigation was conducted. Uncontaminated marine sediment was spiked with 1,4-DCB and juvenile Neanthes were exposed in 20-d sublethal toxicity tests. There were no adverse effects on survival at any test concentration; mean survival was 80-100%. Statistically significant decreases in average dry weight only occurred at the highest 1,4-DCB concentration (19,900 microg/kg, dry weight); this represented a 1,4-DCB concentration more than 10 times higher than previously measured at the outfall (1,710 microg/kg, dry weight). There were no adverse effects on survival or dry weight at the range of concentrations previously measured in sediments from the vicinity of the outfall.

Animals↗

Arsenic pollution in Patos Lagoon estuarine sediments, Brazil.

Arsenic distribution in sediments of the Mirim-Patos lagoonal system is investigated. Deposits of fresh water Mirim Lagoon and those of the fresh water part of the Patos Lagoon contain 2.5 and 7.7 mg kg(-1), respectively, on average of total arsenic. In contrast, estuarine sediments of the Patos Lagoon are evidently contaminated by arsenic in high concentrations (up to 50 mg kg(-1)), and about 80% of the arsenic there is found in a bioavailable form. Analytical data coupled with direct, visual observations of estuarine water contamination by raw phosphorites and fertilizers suggest that the major source of arsenic in the estuarine sediments originated from the fertilizer industry.

Arsenic↗

Ecological condition of US Mid-Atlantic estuaries, 1997-1998.

The Mid-Atlantic Integrated Assessment (MAIA-Estuaries) evaluated ecological conditions in US Mid-Atlantic estuaries during the summers of 1997 and 1998. Over 800 probability-based stations were monitored in four main estuarine systems--Chesapeake Bay, the Delaware Estuary, Maryland and Virginian coastal bays, and the Albemarle-Pamlico Estuarine System. Twelve smaller estuaries within the four main systems were also assessed to establish variance at the local scale. A subset of the MAIA-Estuaries data is used here to estimate the extent of eutrophication, sediment contamination, and benthic degradation in mid-Atlantic estuaries. An Environmental Report Card and Index of Environmental Integrity summarize conditions in individual estuaries, the four estuarine systems, and the entire MAIA region. Roughly 20-50% of the region showed signs of eutrophication (high nutrients, excessive production of organic matter, poor water clarity, or depleted dissolved oxygen), 30% had contaminated sediments, and 37% had degraded benthic communities. Compared with the Environmental Monitoring and Assessment Program (EMAP)-Virginian Province study in 1990-1993, larger fractions of Chesapeake Bay (17%) and Delaware River (32%) had increased metals or organics in sediments.

Biodiversity↗

Determination of Irgarol 1051 in Western Mediterranean sediments. Development and application of supercritical fluid extraction-immunoaffinity chromatography procedure.

A supercritical fluid extraction (SFE) procedure for Irgarol 1051 (i.e. 2-(tert-butylamino)-4-(cyclopropylamino)-6-(methylthio)-1,3,5-triazine) determination in marine sediments, which minimises the solvent usage, is developed and compared to a conventional extraction technique (i.e. sonication). First, the use of methanol (MeOH) in the presence of trifluoroacetic acid (TFA) as secondary modifier of supercritical carbon dioxide was evaluated. Extraction efficiency was strongly dependent on the modifier content but lesser on pressure (100-410 bar) and temperature (60-200 degrees C). In the selected extraction conditions (20% MeOH/TFA 0.65M, 370 bar, 150 degrees C) recoveries higher than 87% were obtained and the limit of detection was 3 ngg(-1) and the relative standard deviation of 10% (N=3) by GC coupled to mass spectrometry (GC-MS) in the electron impact mode. The developed SFE procedure is more convenient to extract Irgarol 1051 than the agitation plus sonication methods concerning on solvent usage (1.5 vs. 20 mL) being compatible with immunochemical procedures avoiding any solvent transfer step. The developed SFE combined with immunoaffinity chromatography (IAC) is highly selective allowing the determination of Irgarol by gas chromatography with nitrogen-phosphorus detection or in sediments at low ngg(-1) level (11-35 ngg(-1)) from Mediterranean marina and harbour sediments.

Chromatography, Supercritical Fluid↗

Seasonal variations in phosphorus species in the surface sediments of the Gulf of Riga, Baltic Sea.

The redox-dependent variations in concentrations of phosphorus at two different accumulation bottom areas were investigated in the Gulf of Riga (Baltic Sea) between December 1993 and January 1995. The sediment samples from nine sampling occasions were analyzed for phosphorus forms and redox potential. The average concentrations of total phosphorus measured in 0-1 cm (65 and 89 micromol P g(-1) for sites G5 and T3, respectively) were among the highest reported from the entire Baltic Sea. Redox-dependent "mobile" phosphorus (MP) contributed more than 50% of total in the uppermost-oxidized centimeter, whereas in reduced layers it was 16-18% throughout the year. The significant differences (ANOVA, P<0.01) among months of inorganic phosphorus (IP) concentration at 0-1 cm were observed at site G5 due to temporary accumulation of mobile phosphorus mediated by redox-dependent bacteria activity during summer. On the contrary no accumulation was observed at T3 probably as a result of low redox potential caused by high accumulation rates and low bioturbation. Although the water column above sediments remained oxic throughout the investigation period, the redox potential at site T3 was close to the redoxcline (i.e., +230 mV) during summer. Further increase of eutrophication might lead to development of anoxic conditions at sediment-water interface and that in turn will result in rapid release of redox-dependent phosphorus stored in surface sediments. The availability of excess phosphorus will further enhance eutrophication in partly phosphorus-limited Gulf of Riga.

Baltic States↗

Distribution and fate of organochlorine pesticide residues in sediments from the selected rivers in Taiwan.

The contamination of organochlorine pesticides (OCPs) in sediments from selected rivers in Taiwan was investigated to evaluate the pollution potentials and hazard in river sediments. Da-han River and Erh-jen River were selected as the target rivers due to their serious pollution. A total of 40 surface sediment samples were collected at five sampling stations along the rivers. Results showed that the concentrations of various pesticides in sediments were in the range of 0.57-14.1 ng/g for sigmaHCH, 0.05-0.15 ng/g for aldrin, 0.12-5.8 ng/g for dieldrin, 0.22-0.64 for endrin, 0.24-6.37 ng/g for endosulfan and 0.21-8.81 ng/g for EDDT (p,p'-DDD, p,p'-DDE, p,p'-DDT). Among the OCPs, sigmaHCH, endosulfan and sigmaDDT were the most dominant compounds in the river sediments. Endosulfan sulfate was the most frequent detected compound in the sediments from the selected rivers. Also, sigmaDDT, dieldrin and beta-HCH were in abundance. Different contamination patterns between the selected river sediments were also observed. Da-han River was mainly contaminated with endosulfan sulfate and sigmaDDT. Whereas the main pesticides in Erh-jen River were beta-HCH and sigmaDDT. Among the cyclodiene compounds, dieldrin was in abundance in most of the sediments. Moreover, the frequencies of detection of the metabolites were higher than those of parent compounds, depicting that the sediments have contaminated for a long time. The results obtained in this study showed that there still exist a variety of OCP residues in the river sediments in Taiwan.

Environmental Monitoring↗

Chemical and biological profiles of sediments as indicators of sources of contamination in Hamilton Harbour. Part II: bioassay-directed fractionation using the Ames Salmonella/microsome assay.

Bottom sediment and suspended sediment samples from Hamilton Harbour (western Lake Ontario) and from a major tributary were profiled using a bioassay-directed fractionation approach. Sample extracts were fractionated using an alumina/Sephadex gel clean-up procedure to afford non-polar aromatic fractions which were characterized using chemical analyses and the Ames/microsome bacterial assay in Salmonella typhimurium strains YG1025 with the addition of oxidative metabolism (S9), and YG1024 without S9. Non-polar aromatic fractions of selected samples were separated by normal phase HPLC into 1-min fractions which were subjected to bioassay analyses. The bioassays using strain YG1025+S9, a TA100-type strain, were performed to assess genotoxicity arising from the presence of polycyclic aromatic hydrocarbons (PAH). Fractions which exhibited mutagenic activity contained PAH with molecular masses of 252, 276 and 278 amu; these fractions contained over 80% of the genotoxicity attributable to PAH. Individual compounds identified using Gas Chromatography-Mass Spectrometry analyses in these active fractions included benzo[a]pyrene, indeno[cd]pyrene and dibenz[a,h]anthracene. The YG1025+S9 mutagenic activity profiles were similar for all samples. Mutagenic activity profiles generated using strain YG1024-S9, a TA98-type strain sensitive to compounds characteristic of mobile source emissions, were very different. The mutagenic activities in strain YG1024-S9 were greatest for harbour-suspended sediment samples collected from sites impacted by a major tributary. Suspended sediments collected near areas known to contain high levels of coal tar-contamination in the bottom sediments contained higher levels of genotoxic PAH than suspended sediments collected from other areas of the harbour.

Coal↗

Butyltins in shellfish, finfish, water and sediment from the Coos Bay estuary (Oregon, USA).

Butyltin was measured in tissue, water and sediment samples collected throughout Coos Bay estuary between 1986 and 1997. Butyltin-induced shell deformation in commercial oysters prompted this assessment. Butyltins are released from tributyltin oxide (TBTO)-containing boat paint. Clams from three sites contained tributyltin (TBT) levels ranging from 168 to 457 microg/kg in 1992-1994. Consequently, Oregon Health Division (OHD) issued a shellfish consumption advisory in 1995; it was rescinded in 1997 after US Environmental Protection Agency (EPA) revised the TBTO oral reference dose (RfD). The revised RfD changed the tissue screening level from 112 to 1120 microg TBT/kg. Fifty percent of sediment samples collected during 1991-1997 and analyzed for total butyltins (TotBT) exceeded the Puget Sound Dredge Disposal Analysis Screening Level (PSDDA SL) of 73 microg TBT/kg dw. TotBT at three shipyards selected for site assessment by EPA ranged from 24 to 68,613 microg/kg dw. Sediment and tissue butyltins have been decreasing in all but one area of the estuary.

Animals↗

Analytical aspects of the gas chromatographic determination of tributyltin and metabolites in environmental samples.

Tributyltin and its metabolites were determined in environmental samples by gas chromatography using a flame photometric detection method. The analytical method involved the propylation of the organotins and the use of a recovery standard to correct for inefficient recovery. A detection limit of 5 ng Sn l(-1) for seawater, and 5 ng Sn g(-1) for sediments, was obtained when the detector was equipped with an optical filter; however, this concentration limit, which is higher than the environmental quality standard for TBT, could be improved by a factor of 100 on removing the filter. The limitations imposed by the choice of recovery and internal standards were discussed and it was shown that the possible presence of Sn(II) had no effect on the total extractable inorganic tin, as determined by the analytical protocol. The identification of unexpected mixed methylbutyltins in TBT-contaminated sediments was described, and the implications of the existence of such compounds were discussed.

Chromatography, Gas↗

Heavy metal contents (Cd, Cu, Zn) in spiders (Pirata piraticus) living in intertidal sediments of the river Scheldt estuary (Belgium) as affected by substrate characteristics.

Metals are transferred into the food web by ground-dwelling organisms, among others. This study aimed to identify the most important factors that determine the bioavailability of heavy metals to the spider Pirata piraticus living in the intertidal sediments of the Scheldt estuary (Flanders, Belgium). At five locations, which represent a varying degree of metal contamination and salinity, the superficial layer of sediments was characterised for physico-chemical properties and heavy metal (Cd, Cu, Zn) content and extractability. Spiders were sampled at the same locations and analysed for Cd, Cu and Zn. Higher Cd, Cu and Zn contents were found in spiders on sites with lower total metal contents in the sediment. These sites were closest to the river mouth and were characterised by a higher salinity. Significant, positive correlations were found between the chloride content of the sediments and the Cd, Cu and Zn content of P. piraticus. Similarly, a strong relationship was observed between the ratio of exchangeable Cd and Zn to the total cation exchange capacity and the contents of these elements in P. piraticus. These field data indicated that salinity, cation exchange capacity and exchangeable metal contents were of most importance in determining bioavailability of heavy metals in these intertidal sediments.

Animals↗