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Spatial distribution of mercury in the sediments and riparian environment of the River Yare, Norfolk, UK.

Concentrations of total mercury (T-Hg) were determined in sediments and riparian (bankside) soils from the River Yare, Norfolk, UK to assess the current extent of contamination arising from a historical point source discharge. The results demonstrate that the spatial distribution pattern in surficial sediments and soils follows that of a distinct pollution plume with an initial increase 2-3 km downstream from the point source discharge at Whitlingham Sewage Treatment Works (STW) outfall. Average T-Hg concentrations in the surficial sediments ranged from 0.1 to 8.13 mg kg(-1); bankside soil concentrations ranged from 0.1 to 2.63 mg kg(-1). There has been a decline in downstream background sediment concentrations of Hg over time. This is likely to be the result of burial by fresh relatively uncontaminated sediments and possibly in the lower reach as a consequence of the influence of the freshwater-saline interface occurring near Cantley. Channel morphology was also shown to be an important factor in determining the large variations of Hg concentrations between sample points within transects. The predominant source of Hg to the soils appears to be due to dredging and the deposition of sediments during flooding.

Disasters↗

Metal exposure and bioavailability to a marine deposit-feeding sipuncula, Sipunculus nudus.

Sediments often constitute the major repository of metals and may be a potential source for metal bioaccumulation by marine deposit- and suspension-feeding invertebrates. In this study, we compared the uptake of Cd, Cr, and Zn from solute and sedimentary sources by a deposit-feeding peanut worm, Sipuncula nudus. The uptake rate constants determined for the three metals were generally low and were 0.0016-0.0020 l g(-1) d(-1) for Cd, 0.0107-0.0269 l g(-1) d(-1) for Cr, and 0.0235-0.0463 l g(-1) d(-1) for Zn. The uptake rate of Zn increased at a disproportionately slower rate with increasing Zn concentrations in the ambient water, indicating that Zn may have been partially regulated at a high Zn concentration. The assimilation efficiency (AE) of the metals was determined using a pulse-chase radiotracer technique. The AEs were in the range of 6-30% for Cd, 0.5-8% for Cr, and 5-15% for Zn. The sediment grain size and radiolabeling duration (between 7 and 30 d) did not affect the metal AE. There was no major difference in the metal AE from natural sediment collected from a contaminated environment. The desorption of metals from the radiolabeled sediments was also concurrently measured using the gut juice extracted from the sipuncula. Up to 63% of Cd was extracted by the gut juice, whereas only <4% of Cr was extracted by the gut juice. There was a significant relationship between the metal AE and the metal extraction by gut juice for Cd, whereas no significant relationship was found for Cr and Zn. Thus, the bioavailability study using the gut juice extraction method may indicate Cd bioaccumulation in the sipuncula. With a simple kinetic model, we show that the bioaccumulation of Cd, Cr, and Zn in the worms is largely dominated by sediment ingestion due to the low uptake from the solute phase as well as the high metal concentrations in the sediment. Thus, sediment should be considered as a direct source for metal accumulation in sipuncula when setting the sediment quality criteria.

Animals↗

Rapid release of mercury from intertidal sediments exposed to solar radiation: a field experiment.

There is increasing evidence of the primary importance of photochemical reactions and transfer of gaseous mercury to the atmosphere. Although mercury in aquatic sediments is efficiently retained, resuspension and bioturbation in intertidal sediments may expose temporarily anoxic sediments to solar radiation. Field experiments were performed to investigate these processes. Anoxic sediments from two areas in the Tagus estuary with different degrees of Hg contamination (experiments I and II) were homogenized and distributed into two sets of 36 uncovered Petri dishes. The samples were placed on the intertidal sediments and exposed to direct solar radiation and kept under dark (control) for 6-8 h. The decrease rates of acid volatile sulfides (abrupt in the first 3 h) and of pyrite (linear) were the same in sediments under solar radiation and dark. The total Hg concentrations were relatively constant in sediments kept in dark, but decreased from 17.6 to 7.65 and 3.45 to 1.35 nmol g(-1) in experiments I and II, respectively. In those exposed to solar radiation during the period of higher UV intensity. Similar evolutions were found in nonreactive Hg in pore waters (3.00-2.59 and 0.725-0.105 nM). On the contrary, reactive Hg was higher in pore waters of the sediments exposed to solar radiation and increased with time, from 424 to 845 pM and 53 to 193 pM. These results indicate that most mercury released in pore waters was photochemically reduced in a short period of time and escaped rapidly to the atmosphere. Episodes of bottom resuspension and bioturbation in the intertidal sediments enhance the transfer of gaseous mercury to the atmosphere.

Air Pollutants↗

Controlled release of nitrate and sulfate to enhance anaerobic bioremediation of phenanthrene in marine sediments.

Experimental measurements demonstrated that rates of in situ microbial anaerobic biodegradation of phenanthrene in undisturbed marine sediments were enhanced when controlled-release electron acceptors (i.e., nitrate and sulfate (for comparison)) were employed. The experimental method used whole and interval cores injected with radiolabeled 14C-phenanthrene, which were incubated, sacrificed, and processed for 14CO2 recovery to determine degradation rates. Nitrocellulose and CaSO4 were formulated to release the electron acceptors into the sediments at rates consistent with bacterial utilization (i.e., that avoided inhibition observed previously at high soluble nitrate (although not sulfate) concentrations). The controlled-release of both compounds, measured in collateral experiments, enhanced the natural anaerobic phenanthrene biodegradation rates by factors up to 2-3. Biodegradation via sulfate reduction was most rapid in the early stages (24 days) of experiments, consistent with reports that many marine bacteria in submerged sediments are sulfate reducers. In comparison, in longer experiments (after 42 days), the anaerobic biodegradation rates were observed at least as high with the addition of nitrocellulose (over 40% of added phenanthrene recovered as 14CO2). Both nitrate and sulfate reduction was observed during anaerobic incubation, although the presence of nitrate seemed to reduce the sulfate reduction. The studied forms of the controlled-release nitrate and sulfate may provide capping amendments to decontaminate marine harbor sediments.

Bacteria, Anaerobic↗

Black carbon and ecological factors affect in situ biota to sediment accumulation factors for hydrophobic organic compounds in flood plain lakes.

Ecological factors may play an important role in the bioaccumulation of polychlorobiphenyls (PCBs) and polyaromatic hydrocarbons (PAHs). Geochemical and bioaccumulation behavior of these chemicals also appears to be related to the presence of black carbon (BC) in sediment. In situ PCB and PAH biota to sediment accumulation factors (BSAF) for benthic invertebrates, as well as 6h Tenax-extractable (fast-desorbing) concentrations and lake characteristics (including BC in sediment), were determined for different seasons in chemically similar but ecologically different lakes (fish-dominated turbid, algae-dominated turbid, and macrophyte-dominated). BSAFs could be explained with a model including a term for Freundlich sorption to BC and a term for uptake from fast-desorbing concentrations in ingested sediments. Freundlich coefficients for in situ sorption to BC (KF) were calculated from slow desorbing fractions and BC contents and agreed well with literature values for KF. Furthermore, in contrast to BSAFs based on total extracted concentrations, Tenax-based BSAF showed a strong positive correlation with log Kow. We therefore argue that BC caused slow desorption and limited BSAFs in these lakes. Seasonal and lake effects on BSAFs were detected, while the differences between oligochaetes and other invertebrates were small for PCBs and within a factor of 10 for PAHs. BSAFs for pyrogenic PAHs were much lower than for PCBs, which was explained by stronger sorption to BC and lesser uptake from ingested sediment.

Adsorption↗

Analysis of non-extractable DDT-related compounds in riverine sediments of the Teltow Canal, Berlin, by pyrolysis and thermochemolysis.

Eighteen pre-extracted samples derived from a subaquatic riverine sediment core taken from the Teltow Canal, Berlin (Germany), were treated by off-line TMAH-thermochemolysis and subsequently analyzed by GC-MS to investigate release and thermodegradation of non-extractable anthropogenic organic compounds (bound residues). Furthermore, six selected samples from the lower core section were additionally treated by off-line pyrolysis. Due to former investigations of the extractable fraction of Teltow Canal sediments, high amounts of compounds structurally related to the pesticide DDT (1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane) were anticipated within the nonextractable fraction. It has been shown that DDT-related bound residues can be gathered by pyrolysis and TMAH-thermochemolysis. Among other compounds, the experiments revealed two DDT-related degradation products (DDPU (3,3-bis(4-chlorphenyl)-1-propene) and DDPS (1,1-bis(4-chlorophenyl)propane)) which were detected for the first time in the environment. The latter compounds may represent formerly unknown metabolites or hints for the existence of carbon-carbon incorporated DDT-metabolites. Both methods tend to produce artifacts which complicate the interpretation of the results. With more knowledge on mechanisms occurring during application of pyrolysis and thermochemolysis, both methods can serve as valuable tools for analyzing bound residues in sediments.

Berlin↗

Extraction of tricyclazole from soil and sediment with subcritical water.

The use of subcritical water to extract tricyclazole from soils and sediments was examined. Extraction efficiency and kinetics were determined as a function of temperature, sample age, sample matrix, sample size, and flow rate. Extraction temperature was the most influential experimental factor affecting extraction efficiency and kinetics, with increasing temperature (up to 150 degrees C) yielding faster and higher efficiency extractions. Higher extraction temperatures were also important for quantitative recovery of tricyclazole from aged samples. Extraction at 50 degrees C yielded 97% recoveries from samples aged 1 day but only 30% recoveries for samples aged 202 days, whereas extraction at 150 degrees C yielded recoveries of 85-100% that were independent of incubation time and sample matrix, with the exception of one sediment that contained a large amount of organic matter. Sample extracts from subcritical water extraction were generally a pale yellow color, contrasted with a dark brown color from organic solvent extractions of the same matrixes. Less sample cleanup was therefore required prior to analysis, with the total time for the extraction and analysis of a single sample being approximately 2 h. Subcritical water extraction is an effective technique for the rapid and quantitative extraction of tricyclazole from soils and sediments.

Antifungal Agents↗

The application of solid-phase micro-extraction (SPME) to the analysis of polycyclic aromatic hydrocarbons (PAHs).

There are many established extraction techniques regularly used in the isolation and analysis of PAHs and similar organic compounds from various phases. These include Soxhlet or ultrasonic extractions from solids, and liquid-liquid or solid-phase extraction from aqueous samples. However, these methods have some inherent disadvantages; most require large volumes of organic solvents, they can be time consuming and many involve multi-step processes that always present the risk of the loss of some analytes (Zhang et al., 1994). Solid-phase micro-extraction (SPME) is a relatively new technique that has been used with much success in the analysis of a variety of compounds including PAHs. Experiments are being carried out to determine the optimum range of conditions for the extraction of a range of PAHs. Parameters under investigation include temperature, equilibration time, salinity and compound concentration. Presented here are some preliminary experiments into the applicability of SPME for PAH analysis. Further work will investigate the reproducibility of the technique, limits of detection and matrix effects. When an optimised method has been developed the technique will be used in investigations into PAH profiles in sediment cores.

Chemistry Techniques, Analytical↗

LC-ESI-MS-MS method for the analysis of tetrabromobisphenol A in sediment and sewage sludge.

Tetrabromobisphenol A (4,4'-isopropylidenebis(2,6-dibromophenol), TBBPA) is the most widely used brominated flame retardant in the world. Due to its low water solubility TBBPA released in aquatic ecosystems ultimately accumulates in sediments, but the lack of data on its environmental level and temporal trend in sediment cores precludes establishing if the input of TBBPA is an on-going environmental problem. We developed an analytical method involving HPLC-ESI-MS-MS (ion trap) with detection of the negative pseudo-molecular ion of TBBPA and its fragmentation pattern. Recovery of TBBPA from spiked marine sediment (both lyophilized and wet) and dehydrated sewage sludge was better than 95%. The current detection limit of TBBPA is 60 pg injected and the linearity of the response is at least three orders of magnitude, ranging from 7 ng ml(-1) to 7000 ng ml(-1). The method was also applied to the analysis of urban sewage sludge where TBBPA was detected at a concentration of 300 ng g(-1)(dry weight). With an analysis time of less than 20 min, this method is adequate for a rapid re-assessment of archived sediment samples avoiding cumbersome derivatization procedures.

Chromatography, Liquid↗

Sediment quality in the Douro river estuary based on trace metal contents, macrobenthic community and elutriate sediment toxicity test (ESTT).

The aim of this study was to evaluate the sediment quality in the mesotidal Douro River estuarine environment, in order to identify areas where sediment contamination could cause ecosystem degradation. Samples were obtained in five locations and sediment characterised for grain size, total organic matter, total-recoverable metals (Al, Fe, Cu, Pb, Cr, Ni, Cd, Zn and Mn), as well as acid volatile sulfide (AVS) and simultaneously extracted metals (SEM). In situ effects were evaluated by examining the macrobenthic community structure. An elutriate sediment toxicity test (ESTT) was used to estimate the amount of metals and nutrients that could be exchanged with the water column through resuspension, and its positive or negative effects on the growth of the micro-alga Emiliania huxleyi in a 10 day test. Anthropogenic metal contamination was identified at the north bank of the Douro estuary, with deleterious effects on the macrobenthic community, namely decrease in number of species and diversity. This contamination could possibly also be toxic for water column organisms, in case of resuspension, as shown by the ESTT. Sediments from the salt marsh at the south bank showed an impoverished macrobenthic community and elutriate toxicity, which appeared to be due to anaerobic conditions. This study clearly shows the usefulness of the ESST approach to assess the biological effect of resuspension of estuarine sediments.

Animals↗

Mutagenicity of water and sediment extracts from the Yongdinghe Watershed.

Potential mutagenicities of water and sediment in Guanting Reservoir/Yongdinghe River Watershed in Beijing, China were assessed using the Ame's tests for the organic pollutants. For different sampling sites, the results were indicative for the existence of mutagens. Furthermore, by using different types of Ames tests, different types of mutagens in water and in sediment were elucidated. The results on Ames tests for water concentrates and sediment extracts could be obviously differentiated. Mutagens in water were mainly direct-acting mutagens whereas in sediment they were mainly pro-mutagens, which exhibit mutagenic effects only after metabolic activation. In general, among all the six sampling sites, site-1, site-2 and site-4 were potentially at mutagenic risk. In a trial to find the causes of mutagenicities in the sediment samples, chemical analysis was performed for polychlorinated biphenyls (PCBs) and organochlorinated pesticides. However, the available data were not sufficient to explain the mutagenicity in the sediment. Integration of the results of Ames test and chemical analysis on overlying water and sediment samples in Guanting Reservoir and Yongdinghe River indicated that this catchment was moderately contaminated by PCBs and organochlorinated pesticides thereby causing a significant mutaginicity in water and sediment. Special attention should be given to the water quality in site-1 and sediment quality in site-4.

China↗

Quantitation of ergosterol in river sediment by liquid chromatography.

The ergosterol content of a river sediment can be used as an indicator of fungal activity. A method is developed for the extraction and determination of ergosterol in river sediment as part of a study to assess the correlation between fungal activity and biodegradation of pyrene, which is an environmental pollutant. This method is based on saponification and the liquid-liquid extraction of ergosterol by ethyl acetate. Quantitation and detection are performed isocratically by liquid chromatography on a 5-microm Hypersil C18 column with methanol-acetonitrile (80:20, v/v) as the mobile phase and detection at 282 nm. The detection limit is 50 ng/mL ergosterol, which is equivalent to 0.1 microg/g. The recovery of ergosterol at a concentration level in the range of 2 to 12 microg/mL is 91.7% +/- 3.1% without interferences. This method is applied in order to successfully quantitate the ergosterol content in a river sediment with or without a fungus supply.

Chromatography, Liquid↗

Bacterial diversity in organically-enriched fish farm sediments.

The bacterial diversity and community structure within both organically enriched and adjacent, unimpacted, near-shore marine sediments at two fish farms in southern Tasmania, Australia, was examined using 16S rRNA gene clone library construction and analysis. Sediments at both caged and reference sites at both farms showed a very high level of microbial diversity. Over 900 clones were analysed and grouped into 631 unique phylotypes. Reference sites were dominated by Delta- and Gammaproteobacteria and the Cytophaga-Flavobacteria-Bacteroides group. Cage site sediments were also dominated by these phylotypes, as well as members of the Alpha- and Epsilonproteobacteria. Diversity and coverage indices indicated that the actual diversity of the sediments was much greater than that detected, despite a large sampling effort. All libraries were shown to be statistically different from one another (P < 0.05). Many phylotypes did not group with cultured bacteria, but grouped with other environmental clones from a wide array of marine benthic environments. Diversity and evenness indices suggested that although both parameters changed after farming, diverse communities were present in all sediments. The response of the microbial community to organic load suggested that random, rather than predictable, succession events determine community composition and diversity, and that sediment type may influence bacterial community and sediment response to organic perturbation.

Animal Husbandry↗

Mercury-resistant actinomycetes from the Chesapeake Bay.

Two actinomycete strains, CHR3 and CHR28, were isolated from metal-contaminated sediments from Baltimore Inner Harbor. The isolates were classified as Streptomyces spp. Agar diffusion assays showed both isolates to be resistant to mercuric chloride and phenylmercuric acetate. Hybridization experiments indicated that genes homologous to the mercuric reductase and organomercurial lyase of Streptomyces lividans 1326 were present in strains CHR3 and CHR28. Strain CHR28 grew at both low and high salt concentrations; however, strain CHR3 showed enhanced growth in the presence of salt, evidence of its habitat being marine or estuarine sediment.

Baltimore↗

Stratified communities of active Archaea in deep marine subsurface sediments.

Archaeal 16S rRNA was extracted from samples of deep marine subsurface sediments from Peru Margin site 1227, Ocean Drilling Program leg 201. The amounts of archaeal 16S rRNA in each extract were quantified by serial dilution and reverse transcription (RT)-PCR. The results indicated a 1,000-fold variation in rRNA content with depth in the sediment, with the highest concentrations found near the sediment surface and in the sulfate-methane transition zone (SMTZ). The phylogenetic composition of the active archaeal population revealed by cloning and sequencing of RT-PCR products changed with depth. Several phylotypes affiliated with marine benthic group B (MBGB) dominated clone libraries from the upper part of the SMTZ and were detected only in this layer. Members of the miscellaneous crenarchaeotal group (MCG) dominated clone libraries from the other layers. These results demonstrate that archaeal communities change in activity and community composition over short distances in geochemically distinct zones of deep subseafloor sediments and that these changes are traceable in the rRNA pool. It was shown for the first time that members of both the MCG and MBGB Archaea are more active in the SMTZ than in layers above and below. This indicates that they benefit either directly or indirectly from the anaerobic oxidation of methane. They also appear to be ecophysiologically flexible, as they have been retrieved from a wide range of marine sediments of various geochemical properties.

Archaea↗

Microbial dechlorination of 2,3,5,6-tetrachlorobiphenyl under anaerobic conditions in the absence of soil or sediment.

Bacterial enrichment cultures developed with Baltimore Harbor (BH) sediments were found to reductively dechlorinate 2,3,5, 6-tetrachlorobiphenyl (2,3,5,6-CB) when incubated in a minimal estuarine medium containing short-chain fatty acids under anaerobic conditions with and without the addition of sediment. Primary enrichment cultures formed both meta and ortho dechlorination products from 2,3,5,6-CB. The lag time preceding dechlorination decreased from 30 to less than 20 days as the cultures were sequentially transferred into estuarine medium containing dried, sterile BH sediment. In addition, only ortho dechlorination was observed following transfer of the cultures. Sequential transfer into medium without added sediment also resulted in the development of a strict ortho-dechlorinating culture following a lag of more than 100 days. Upon further transfer into the minimal medium without sediment, the lag time decreased to less than 50 days. At this stage all cultures, regardless of the presence of sediment, would produce 2,3,5-CB and 3,5-CB from 2,3,5,6-CB. The strict ortho-dechlorinating activity in the sediment-free cultures has remained stable for more than 1 year through several transfers. These results reveal that the classical microbial enrichment technique using a minimal medium with a single polychlorinated biphenyl (PCB) congener selected for ortho dechlorination of 2,3,5,6-CB. Furthermore, this is the first report of sustained anaerobic PCB dechlorination in the complete absence of soil or sediment.

Anaerobiosis↗

Use of the [(14)C]leucine incorporation technique to measure bacterial production in river sediments and the epiphyton.

Bacterial production is a key parameter for the understanding of carbon cycling in aquatic ecosystems, yet it remains difficult to measure in many aquatic habitats. We therefore tested the applicability of the [(14)C]leucine incorporation technique for the measurement of bulk bacterial production in various habitats of a lowland river ecosystem. To evaluate the method, we determined (i) extraction efficiencies of bacterial protein from the sediments, (ii) substrate saturation of leucine in sediments, the biofilms on aquatic plants (epiphyton), and the pelagic zone, (iii) bacterial activities at different leucine concentrations, (iv) specificity of leucine uptake by bacteria, and (v) the effect of the incubation technique (perfused-core incubation versus slurry incubation) on leucine incorporation into protein. Bacterial protein was best extracted from sediments and precipitated by hot trichloroacetic acid treatment following ultrasonication. For epiphyton, an alkaline-extraction procedure was most efficient. Leucine incorporation saturation occurred at 1 microM in epiphyton and 100 nM in the pelagic zone. Saturation curves in sediments were difficult to model but showed the first level of leucine saturation at 50 microM. Increased uptake at higher leucine concentrations could be partly attributed to eukaryotes. Addition of micromolar concentrations of leucine did not enhance bacterial electron transport activity or DNA replication activity. Similar rates of leucine incorporation into protein calculated for whole sediment cores were observed after slurry and perfused-core incubations, but the rates exhibited strong vertical gradients after the core incubation. We conclude that the leucine incorporation method can measure bacterial production in a wide range of aquatic habitats, including fluvial sediments, if substrate saturation and isotope dilution are determined.

Bacteria↗