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Seasonality of contamination, toxicity, and quality values in sediments from littoral ecosystems in the Gulf of Cádiz (SW Spain).

To seasonally evaluate littoral contamination, toxicity and quality values of sediments from the Gulf of Cádiz, we measured chemical concentrations and conducted toxicity tests in winter and summer and linked these results by means of multivariate analysis. Sediment samples were subjected to two separate, replicated sediment toxicity tests (Microdeutopus gryllotalpa amphipod survival, and Ruditapes philippinarum clam reburial), and to comprehensive sediment chemistry analyses (grain size, organic carbon, 14 heavy metals, and the surfactant linear alkylbenzenesulfonate (LAS)). Only sediments associated with an untreated urban discharge were toxic and related to high levels of surfactant LAS, Ag, and Pb. Multivariate analysis indicated that variables and chemicals associated with geochemical matrix and background levels (specific surface, Fe, Zn, Cu, V, Ni, and Co), chemicals associated with untreated urban discharge sources, and toxicity effects showed no seasonal variability. Only copper concentrations showed seasonal differences, being toxic during the winter and not toxic during summer. Multivariate analysis permits us to derive sediment quality values (SQVs); in terms of concentrations at or below which biological effects were not measured (mg kg(-1) dry sediment), are: LAS, 2.6; lead, 66.8; silver, 0.78; copper, 69.6.

Animals↗

The distribution of micro-organic contaminants in river bed-sediment cores.

There is little information available on the distributions of micro-organic contaminants in river bed-sediments below a depth of 5 cm. The aim of this study is to determine the concentrations and distributions of contaminants in river bed-sediments up to 1 m depth and to make an assessment of the results. The approach taken was to collect five cores from each of two lowland rivers in southern England, the first a rural river and the second a dominantly urban catchment. The cores were analysed for micro-organic compounds and sediment/sediment porewater characteristics. Compounds detected were polyaromatic hydrocarbons (naphthalene, fluoranthene and pyrene), pesticides (carbaryl, linuron, fenpropimorph, the synthetic pyrethroids, and prometryn), and non-ionic surfactant residue (nonylphenol). A particularly important finding was that some micro-organic contaminants penetrated to depths of 1 m, and in one of the rivers they were detected in undisturbed Eocene substrata. The more hydrophobic contaminants showed a clear depth distribution with higher concentrations towards the top of the cores. The less hydrophobic contaminants demonstrated no systematic trend suggesting they had become soluble in porewaters and subsequently travelled within the cores. Partition between the porewater and sediment appeared to be controlling the distribution of the compounds with depth.

England↗

Sedimentological research as a basis for environmental management: the Oresund fixed link.

A fixed 16 km link (immersed tunnel, artificial island and peninsula, bridges) to connect the Scandinavian countries of Denmark and Sweden is being constructed during the period 1995-2000. The link crosses Oresund, one of the three sounds connecting the brackish Baltic Sea to the oceanic North Sea. Dredging of approximately 8 x 10(6) m3 of limestone bedrock and clay till is being carried out during the construction phase. Environmental planning and management when constructing the fixed link were heavily dependent on extensive sedimentological and biological research prior to construction. Base-line turbidity and seabed sediments were investigated, and sediment spill parameters were measured during test dredging and test reclamation, in addition to the environmental impact. Now, when dredging and reclamation have been finalised in Oresund, it is clear that the environmental management approach used during construction of the fixed link has safeguarded the marine environment in Oresund. At the same time it has allowed the dredging and reclamation works to be carried out within the planned time period and expenses. A detailed base-line monitoring of the regional turbidity regime and the regional sedimentation regime in Oresund made post-dredging evaluation of the regional effects possible. The measurements in Oresund showed that the construction caused no permanent regional change in turbidity and sedimentation, as the base-line conditions did not change.

Conservation of Natural Resources↗

The stability and persistence of diflubenzuron in marine sediments studied under laboratory conditions and the dispersion to the sediment under a fish farm following medication.

A high performance liquid chromatographic (HPLC) method was developed to determine the concentration of diflubenzuron, a delousing agent used in fish farming, in marine mud and shell sand. The recovery of diflubenzuron from mud was 100.8+/-1.1% and 105.5+/-4.3% for shell sand. The limit of quantitation was found to be 0.1 microg g(-1). The stability of diflubenzuron was studied under laboratory conditions in marine sediments at different temperatures (4 and 14 degrees C). No degradation of diflubenzuron occurred in the organic rich mud sediment or in the shell sand sediment during the experimental period of 204 days. Increasing the temperature from 4 to 14 degrees C had no effect on the stability. Furthermore, diflubenzuron showed to be persistent in both mud and shell sand sediment since no detectable diffusion from the sediment to the water phase occurred during the experimental period of 204 days. Increasing the water current in the tanks had no effect on the persistence. Under field conditions, the concentrations of diflubenzuron found in the organic material from sediment traps placed 2 m from the bottom under the cage in a fish farm during medication were high and ranged from 71 to 259 microg g(-1). The concentrations of diflubenzuron in the sediment under the fish farm were, however, low, with a maximum concentration of 5.4 microg g(-1). The dispersion of diflubenzuron to the sediment was limited to less than 20 m from the edge of the cage in every direction. Fifteen months following the medication, only traces (< 0.1 microg g(-1)) of diflubenzuron were detected in the sediment under the fish farm. Possible explanations for this decrease are resuspension and redistribution of sediment and/or oxic degradation of the drug.

Animals↗

Heavy metal contents in surface soils along the Upper Scheldt river (Belgium) affected by historical upland disposal of dredged materials.

For several decades, periodical dredging of river sediments has been necessary to allow for shipping traffic on the river Scheldt. Sediments were disposed along the shores in the alluvial plain without concern for the potential presence of contaminants. The aim of this study was to survey the alluvial plains of the Upper Scheldt river in Belgium for the presence of old dredged sediment landfills, and to appraise the heavy metal contamination at these sites. Up to 82% of the areas that were affected by dredged sediment disposal was found to be polluted by at least one of the metals Cd, Cr, Zn or Pb. Concentrations of Cd, Cr and Zn were, in 10% of the cases, higher than 26, 1900 and 2800 mg/kg, respectively. Cu and Ni concentrations were of no environmental concern on any site. Trends in metal concentrations as a function of location and time were explored and discussed. The highest average concentrations of Cd, Cr, Cu, Pb and Zn were found in the most downstream quarter of the Upper Scheldt. Contents of Pb and Cu were significantly lower for sediments disposed after 1965, but no indication for improvement of the sediment quality with time was observed for Cd, Cr and Zn. The pollution levels encountered warrant for caution as most of the soils affected by historical dredged sediment disposal are currently in use for agriculture, nature development or forestry.

Belgium↗

In situ bioassay chambers and procedures for assessment of sediment toxicity with Chironomus riparius.

The purpose of this study was to develop an in situ sediment bioassay chamber and respective procedures, suitable for performing toxicity bioassays with benthic invertebrates, using the midge Chironomus riparius. It was also our objective to compare the responses obtained under controlled conditions (laboratory 10-day larval growth and survival test) with those obtained in situ. Clean sand and a formulated sediment were incorporated in the in situ bioassay, along with local sediments, as a way of minimizing natural variability due to physicochemical differences among sediments or due to interactions with indigenous organisms. Recovery of organisms was good (80-100% in the control and reference site), indicating that the developed chamber and protocol were suitable for exposing and retrieving C. riparius in situ. Results also showed differences between responses obtained with formulated and natural sediment in situ, as well as between laboratory and in situ.

Animals↗

Biogeochemical and ecological considerations in designing wetland treatment systems in post-mining landscapes.

Although wetlands have gained acceptance as important components of ecosystems in post-mining landscapes in the past decade, their roles in contaminant retention/removal have not been well integrated into the designing of restoration programs. This paper describes the integration of sediment microbial activities and natural precipitation processes, along with approaches to defining the contaminant load from the mine wastes. The contaminant removal rates, which can be expected by a wetland sediment, are summarized and how they need to be reflected in the wetland size required, and the carbon supply which is needed. Contaminant loading from mining wastes can be balanced by wetland ecological processes, including wetland primary production and microbial mineralization in the sediment. This ecological engineering approach is demonstrated using case studies on hard-rock mining waste in Canada.

Canada↗

Determination of methylmercury and butyltin compounds in marine biota and sediments using microwave-assisted acid extraction, solid-phase microextraction, and gas chromatography with microwave-induced plasma atomic emission spectrometric detection.

A method is described for the determination of methylmercury and butyltin compounds in marine sediment and tissue using microwave-assisted acid extraction or digestion and solid-phase microextraction (SPME) followed by analysis using gas chromatography with microwave-induced plasma atomic emission spectrometric detection (GC-MIP-AES). Using the SPME-GC-MIP-AES method, enrichment factors for methylmercury and butyltin compounds of 50-100 were achieved, as compared to the typical hexane extraction, and measurements in marine tissue and sediment matrixes were possible at 1-2 microg/kg (methylmercury) and 10-100 ng/kg (butyltins). The SPME-GC-MIP-AES method was validated using several marine sediment and tissue matrix certified reference materials (CRMs) with certified values for methylmercury and butyltin compounds. The SPME-GC-MIP-AES method was used to measure methylmercury in four marine tissue CRMs ranging from oyster tissue at 13.0 +/- 1.0 microg/kg to fish tissue at 397 +/- 13 microg/kg (as Hg dry mass). Results from the SPME-GC-MIP-AES method were used in conjunction with results from other techniques to assign certified values for methylmercury in oyster, mussel, and fish tissue CRMs. Mono-, di-, and tributyltin were measured in three sediment CRMs at concentration levels of (0.08 +/- 0.03)-(0.35 +/- 0.05) mg/kg (as Sn dry mass).

Animals↗

Metal distribution in Clark Fork River sediments.

Accurate sampling of pore waters and sediments in gravel river beds is problematic because cobbles preclude most coring techniques, while the angularity of sand grains destroys the membranes of standard pore water samplers. In the Clark Fork River, the recipient of over 100 years of mining activity, a modified single tube core-freezing device was used to profile bed sediment (approximately 65% cobbles and 35% gravel substrate), and a novel pore water sampler was developed to collect interstitial water. In the sediment, the <63 microm fraction comprised <4 wt % yet contained approximately an order of magnitude higher metal concentrations compared to the 63 microm-2 mm fraction (constituting approximately 20% of the mass). However, on a mass basis the sand fraction contained 60% of the metals, compared to 40% in the clay/silt fraction in the gravels, while in point bars the distribution was approximately 50:50. The metals occur predominantly in sulfides frequently armored with an oxide rim and other sparingly soluble phases that may explain the low pore water metal concentrations. These data demonstrate that consideration of multiple particle size cutoffs is necessary to accurately characterize fluvial bed sediment metal conditions and that the form of the metal is important in understanding metal solubility in the benthos.

Animals↗

Effects of sediment characteristics on the toxicity of chromium(III) and chromium(VI) to the amphipod, Hyalella azteca.

We evaluated the influence of sediment characteristics, acid-volatile sulfide (AVS) and organic matter (OM), on the toxicity of chromium (Cr) in freshwater sediments. We conducted chronic (28-42-d) toxicitytests with the amphipod Hyalella azteca exposed to Cr(VI) and Cr(III) in water and in spiked sediments. Waterborne Cr(VI) caused reduced survival of amphipods with a median lethal concentration (LC50) of 40 microg/L. Cr(VI) spiked into test sediments with differing levels of AVS resulted in graded decreases in AVS and sediment OM. Only Cr(VI)-spiked sediments with low AVS concentrations (< 1micromol/g) caused significant amphipod mortality. Waterborne Cr(III) concentrations near solubility limits caused decreased survival of amphipods at pH 7 and pH 8 but not at pH 6. Sediments spiked with high levels of Cr(III) did not affect amphipod survival but had minor effects on growth and inconsistent effects on reproduction. Pore waters of some Cr(III)-spiked sediments contained measurable concentrations of Cr(VI), but observed toxic effects did not correspond closely to Cr concentrations in sediment or pore waters. Our results indicate that risks of Cr toxicity are low in freshwater sediments containing substantial concentrations of AVS.

Amphipoda↗

Interactions between microbial iron reduction and metal geochemistry: effect of redox cycling on transition metal speciation in iron bearing sediments.

Microbial iron reduction is an important biogeochemical process that can affect metal geochemistry in sediments through direct and indirect mechanisms. With respectto Fe(III) (hydr)oxides bearing sorbed divalent metals, recent reports have indicated that (1) microbial reduction of goethite/ferrihydrite mixtures preferentially removes ferrihydrite, (2) this process can incorporate previously sorbed Zn(II) into an authigenic crystalline phase that is insoluble in 0.5 M HCl, (3) this new phase is probably goethite, and (4) the presence of nonreducible minerals can inhibit this transformation. This study demonstrates that a range of sorbed transition metals can be selectively sequestered into a 0.5 M HCl insoluble phase and that the process can be stimulated through sequential steps of microbial iron reduction and air oxidation. Microbial reduction experiments with divalent Cd, Co, Mn, Ni, Pb, and Zn indicate that all metals save Mn experienced some sequestration, with the degree of metal incorporation into the 0.5 M HCl insoluble phase correlating positively with crystalline ionic radius at coordination number = 6. Redox cycling experiments with Zn adsorbed to synthetic goethite/ferrihydrite or iron-bearing natural sediments indicate that redox cycling from iron reducing to iron oxidizing conditions sequesters more Zn within authigenic minerals than microbial iron reduction alone. In addition, the process is more effective in goethite/ferrihydrite mixtures than in iron-bearing natural sediments. Microbial reduction alone resulted in a -3x increase in 0.5 M HCl insoluble Zn and increased aqueous Zn (Zn-aq) in goethite/ferrihydrite, but did not significantly affect Zn speciation in natural sediments. Redox cycling enhanced the Zn sequestration by approximately 12% in both goethite/ferrihydrite and natural sediments and reduced Zn-aq to levels equal to the uninoculated control in goethite/ferrihydrite and less than the uninoculated control in natural sediments. These data suggest that in situ redox cycling may serve as an effective method for

Ferric Compounds↗

Atmospheric deposition and marine sedimentation fluxes of polycyclic aromatic hydrocarbons in the Eastern Mediterranean Basin.

Atmospheric input was studied and found to be the major source of PAHs in the eastern Mediterranean open marine ecosystem. Dry and wet atmospheric deposition, air-sea exchange, and sediment trap fluxes of polycyclic aromatic hydrocarbons (PAHs) in the eastern Mediterranean basin were estimated from November 2000 to July 2002. Seven dry and four wet deposition samples were analyzed in total and PAH concentrations were determined. Airsea exchange fluxes based on air-water concentration gradientwere drawn from five air and water samples collected concurrently from a coastal area in the eastern Mediterranean. Total annual average deposition fluxes of dry, wet, and air-sea exchange sigma35PAHs were 58.0, 165.7, and -706.4 microg m(-2) y(-1), respectively. Only 1.1 and 0.7% of the total atmospheric deposition flux of PAHs was measured in the sediment traps at 280 and 1440 m depth, respectively.

Air↗

High temporal resolution oxygen imaging in bioirrigated sediments.

A technique is presented for temporal characterization of the bioirrigation activity of benthic macrofauna and for quantitative estimation of its effects on the oxygen exchange between the sediment and the overlying water. The technique is based on high temporal resolution (15-30 s) oxygen imaging aided by a planar oxygen optode and can be applied under laboratory and field conditions, both freshwater and marine. It allows direct observation of the complex 2D oxygen dynamics in the sediment around the burrow while the animal dwells undisturbed in its natural environment. The conditions to which the animal is exposed can easily be controlled or manipulated. Chironomus plumosus, widely distributed freshwater insect larvae, were used in a case study. Their bioirrigation activity was divided into a random succession of pumping intervals (duration 5.4 +/- 1.7 min) and rest periods (duration 9.2 +/- 5.8 min). The burrow ventilation resulted in a highly variable volume of the oxygenated sediment surrounding the burrow and the associated sedimentary oxygen uptake rate through the burrow wall (OUB), both changing dramatically within minutes. Their variability was higher in a burrow under construction than around a stationary burrow. The average OUB rate (approximately 0.15 micromol O2 h(-1)), when translated into a time-averaged 02 flux across the burrow wall, constituted approximately 64% of the stationary diffusive oxygen flux measured at the sediment-water interface (approximately0.9 mmol O2 m(-2) h(-1)).

Aerobiosis↗

Metabolism of 14C-naphthalene in marine sediments.

Metabolism of 14C-naphthalene was studied in aerobic and anaerobic marine sediments from the Mumbai coast, India using a continuous flow-through system for 5 weeks. There was no volatilisation of naphthalene from anaerobic sediment. Naphthalene underwent more extensive mineralization in aerobic sediment (31.6% of the applied activity) than in anaerobic sediment (5% of the applied activity). No metabolite of naphthalene was present in sediments at the end of the incubation period.

Bacteria, Aerobic↗

Effect of phosphogypsum on respiration and methane emissions in sediment.

The impact of adding phosphogypsum (PG) to freshwater wetland areas, and potential effect on methane production and respiration in sediment was studied in the laboratory. Two organic matter levels (native and enriched with 0.5% by weight ground dry plant material) were studied using five sediment treatments each: (1) no PG added, (2) 4% PG by dry weight (homogenized), (3) 20% PG by dry weight (homogenized), (4) 2000 kg ha(-1) (surface applied), and (5) 5000 kg ha (surface applied), and the experiment was run in triplicate. There was a net flux of methane into sediment for all treatments that were maintained at the native organic matter level, indicating net methane oxidation. In the organic-enriched cores, both of the homogenized treatments exhibited no methane emissions, while the surface applied treatments retained the potential for high emissions. Soil respiration was depressed in all treatments when compared to controls, especially in the organic-enriched cores. The results conclude that it may be possible to add PG to non-vegetated areas with few observable effects on sediment respiration, but organic matter content and method of application are critical concerns.

Calcium Sulfate↗

Quantification of ammonia-oxidizing bacteria and factors controlling nitrification in salt marsh sediments.

To elucidate the geomicrobiological factors controlling nitrification in salt marsh sediments, a comprehensive approach involving sediment geochemistry, process rate measurements, and quantification of the genetic potential for nitrification was applied to three contrasting salt marsh habitats: areas colonized by the tall (TS) or short (SS) form of Spartina alterniflora and unvegetated creek banks (CBs). Nitrification and denitrification potential rates were strongly correlated with one another and with macrofaunal burrow abundance, indicating that coupled nitrification-denitrification was enhanced by macrofaunal burrowing activity. Ammonia monooxygenase (amoA) gene copy numbers were used to estimate the ammonia-oxidizing bacterial population size (5.6 x 10(4) to 1.3 x 10(6) g of wet sediment(-1)), which correlated with nitrification potentials and was 1 order of magnitude higher for TS and CB than for SS. TS and CB sediments also had higher Fe(III) content, higher Fe(III)-to-total reduced sulfur ratios, higher Fe(III) reduction rates, and lower dissolved sulfides than SS sediments. Iron(III) content and reduction rates were positively correlated with nitrification and denitrification potential and amoA gene copy number. Laboratory slurry incubations supported field data, confirming that increased amounts of Fe(III) relieved sulfide inhibition of nitrification. We propose that macrofaunal burrowing and high concentrations of Fe(III) stimulate nitrifying bacterial populations, and thus may increase nitrogen removal through coupled nitrification-denitrification in salt marsh sediments.

Ammonia↗

Dynamic modeling of food-chain accumulation of brominated flame retardants in fish from the Ebro River Basin, Spain.

Since the 1980s, brominated flame retardants (BFRs) have been detected in air, sewage sludge, sediment, fish, shellfish, birds, and mammals, including humans. However, model studies regarding BFR food-chain accumulation are scarce. In the present study, the accumulation of hexabromocyclododecane and brominated diphenyl ethers (BDEs) 47, 153, 154, and 183 in benthivorous barbel (Barbus graellsii) and pelagic bleak (Alburnus alburnus) from four locations in the Ebro river basin in Spain was modeled using a first-order, one-compartment model with sediment interaction. The model accounted for BFR uptake from water, ingested sediment, and food; release via water and feces; growth; and in situ binding of BFRs to black carbon. Rate constants were derived from allometric regressions. For most BFRs, dynamically modeled biota-sediment accumulation factors (BSAFs) were close to measured values, whereas steady-state model BSAFs were too high, especially for BDEs 153, 154, and 183. Differences between BSAFs for individual fish were explained by differences in age, growth, and feeding behavior. On average, modeled BSAFs for barbel were 50% higher than those for bleak because of extra BFR uptake through sediment ingestion and older age of barbel specimens.

Animals↗

Nonlinear and competitive sorption of apolar compounds in black carbon-free natural organic materials.

Numerous studies have reported a spectrum of sorption phenomena in soils, sediments, and organic matter isolates of those materials that are inconsistent with a partition model proposed in the late 1970s and early 1980s, a model predicated on a hypothesis that sorption is linear and noncompetitive. To explain these nonideal phenomena, prior studies have proposed a hard-soft (glassy-rubbery) model for SOM (soil and sediment organic matter), while others have attributed them singularly to BC (black carbon: soot and charcoal) particles present in topsoils and sediments. In this study, we demonstrated nonideal sorption behavior (isotherm nonlinearity, competitive effects) for a group of apolar compounds in a large set of natural and model organic materials, including a commercial lignin and humic acids from different sources. Complete oxidation of samples by an acidic dichromate method was taken to signify the absence of BC. (However, polymethylene units are stable even if functionalized on both ends, making the technique unreliable for quantifying BC.) Other samples were inferred free of BC by their source and method of preparation. Characterization by thermalanalytical methods indicated the glassy character of the organic materials. The origin of the nonideal behaviors appears to be the glassy character of these materials. Sorption nonlinearity increased or decreased by changing temperature, cosolvent content, or degree of cross-linking by metal ions as predicted for organic solids in a glassy state. We conclude that macromolecular humic substances in the environment may exhibit nonideal sorption behavior in soils and sediments, quite apart from any such behaviors attributable to BC.

Adsorption↗