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PCB and PAH speciation among particle types in contaminated harbor sediments and effects on PAH bioavailability.

This research provides particle-scale understanding of PCB and PAH distribution in sediments obtained from three urban locations in the United States: Hunters Point, CA; Milwaukee Harbor, WI; and Harbor Point, NY. The sediments comprised mineral grains (primarily sand, silt, and clays) and carbonaceous particles (primarily coal, coke, charcoal, pitch, cenospheres, and wood). The carbonaceous sediment fractions were separated from the mineral fractions based on their lower density and were identified by petrographic analysis. In all three sediments, carbonaceous particles contributed 5-7% of the total mass and 60-90% of the PCBs and PAHs. The production of carbonaceous particles is not known to be associated with PCB contamination, and it is very unlikely that these particles can be the source of PCBs in the environment Thus, it appears that carbonaceous particles preferentially accumulate PCBs acting as sorbents in the aqueous environment if PCBs are released directly to the sediment or if deposited as airborne soot particles. Aerobic bioslurry treatment resulted in negligible PAH loss from the carbonaceous coal-derived material in Milwaukee Harbor sediment but resulted in 80% of the PAHs being removed from carbonaceous particles in Harbor Point sediment. Microscale PAH extraction and analysis revealed that PAHs in Harbor Point sediment were associated mainly with coal tar pitch residue. PAHs present in semisolid coal tar pitch are more bioavailable than PAHs sorbed on carbonaceous particles such as coal, coke, charcoal, and cenosphere. Results of this study illustrate the importance of understanding particle-scale association of hydrophobic organic contaminants for explaining bioavailability differences among sediments.

Adsorption↗

Spectroscopic and diffraction study of uranium speciation in contaminated vadose zone sediments from the Hanford site, Washington state.

Contamination of vadose zone sediments under tank BX-102 at the Hanford site, Washington, resulted from the accidental release of 7-8 metric tons of uranium dissolved in caustic aqueous sludge in 1951. We have applied synchrotron-based X-ray spectroscopic and diffraction techniques to characterize the speciation of uranium in samples of these contaminated sediments. UIII-edge X-ray absorption fine structure (XAFS) spectroscopic studies demonstrate that uranium occurs predominantly as a uranium(VI) silicate from the uranophane group of minerals. XAFS cannot distinguish between the members of this mineral group due to the near identical local coordination environments of uranium in these phases. However, these phases differ crystallographically, and can be distinguished using X-ray diffraction (XRD) methods. As the concentration of uranium was too low for conventional XRD to detect these phases, X-ray microdiffraction (microXRD) was used to collect diffraction patterns on approximately 20 microm diameter areas of localized high uranium concentration found using microscanning X-ray fluorescence (microSXRF). Only sodium boltwoodite, Na(UO2)(SiO3OH) x 1.5H20, was observed; no other uranophane group minerals were present. Sodium boltwoodite formation has effectively sequestered uranium in these sediments under the current geochemical and hydrologic conditions. Attempts to remediate the uranium contamination will likely face significant difficulties because of the speciation and distribution of uranium in the sediments.

Environmental Pollutants↗

Application of a sediment quality index to the lower Laurentian Great Lakes.

A sediment quality index (SQI) was developed using an equation incorporating three elements; scope--the % of variables that did not meet guidelines; area frequency--the % of failed tests divided by the total number of tests in a group of sites; and amplitude - the magnitude by which failed variables exceeded guidelines. The SQI calculation produces a numerical score with a maximum value of 100 representing the highest sediment quality. A modified SQI was also developed using only the scope and amplitude elements, which computed a score per site with no grouping. The SQI was applied to assessment of sediment quality in Lakes Erie and Ontario using Canadian Federal and Ontario Provincial guidelines for 34 compounds, Spatial trends in sediment quality in both lakes reflected overall trends for most individual contaminant classes, including mercury and polychlorinated biphenyls. In Lake Erie, there was a trend toward lower SQI values from the eastern basin to the western basin, and from the northern area to the southern area of the central basin. Sediment quality in the eastern basin and the northern area of the central basin was classified as excellent (>95); sediments in other areas of Lake Erie ranged from fair to good. In Lake Ontario, the poorest sediment quality was associated with the three major depositional basins; sediment quality among the three basins was quite consistent. The SQI values based on all three elements (scope, frequency and amplitude) for the Niagara basin. Mississauga Basin and Rochester Basin were 67 (fair), 65 (fair) and 70 (fair), respectively. Comparison of SQI values for all lower lake basins showed generally poorer sediment quality in Lake Ontario, compared to Lake Erie.

Environmental Monitoring↗

Toxicity of surficial sediments from Sydney Harbour and vicinity, Australia.

The toxicological responses of three species to 103 surficial saltwater sediment samples from Sydney Harbour, and coastal lakes and estuaries on the south-east coast of New South Wales, Australia, were tested in a battery of four to six laboratory toxicity tests. This is the first large-scale toxicological study of sediments in Australia, the objective of which is to assess the protective and predictive abilities of North American biological effects-based sediment quality guidelines, recently adopted in Australia. Amphipods were exposed to whole sediments in survival and reburial tests, sea urchin fertilisation and larval development tests were conducted on porewaters, and bacterial bio-luminescence (Microtox) tests were conducted on organic solvent extracts and porewaters. Local indigenous species were used for the amphipod and sea urchin tests (Corophium sp. and Heliocidaris tuberculata, respectively). A wide range of responses, from <25 to 100% of negative controls were observed in all tests. Mean control-adjusted responses ranged from 46 to 96% for all tests. The percentages of highly toxic samples ranged from 11 to 83% in the various tests. The order of test sensitivity was: amphipod survival < Microtox test of porewaters < amphipod reburial < sea urchin larval development < sea urchin fertilisation < Microtox test of solvent extracts. Concordance between toxicity tests in classifying samples as highly toxic or not, ranged from 47 to 79%, indicating some similarities between test results, but not complete equivalence. Combined toxicity test results showed that the incidence of highly toxic responses occurring in the majority of tests (75-100% of tests) was low (5% of samples), but a large percentage of samples had highly toxic results in at least one test (76% of samples). Toxicity was more pervasive in the Sydney region than in coastal lakes and estuaries south of Sydney. The current study demonstrated the utility of indigenous invertebrate species and the Microtox bacterium in a sediment toxicity test battery for Australian saltwater sediments.

Animals↗

Mercury speciation in sediments of a tropical coastal environment.

The speciation of mercury in tropical coastal areas, although scarcely studied, has presented an odd behaviour when compared with the results obtained in temperate environments. In this work, we measured the concentrations of mercury species (mercuric mercury, methyl-mercury and dimethyl-mercury) in the sediments of Sepetiba Bay (Brazil) and compared these with geochemical parameters. Twenty-eight sediment samples were extracted in an open microwave system and mercury speciation was carried out by ethylation, cryogenic focusing, gas chromatography and quartz furnace atomic absorption spectrometry. Fraction < 63 microm, organic carbon and total sulphur contents and redox potential were measured in order to outline the geochemical characteristics of the sediments. While mercuric mercury presented concentrations ranging between 22.65 and 134.61 ng g(-1), methyl-mercury concentrations ranged between < 2.0 and 4.4 ng g(-1). Only a few dimethyl-mercury concentrations were relatively high (up to 14.6 ng g(-1)). The results of mercuric mercury presented an unexpected positive correlation with sulphur contents showing that mercury is forming stable sulphide complexes, even under very reducing conditions. This would render mercury available for t he formation of methyl- or dimethyl-mercury that would be both fixed in the sediments and volatilised.

Brazil↗

Bacterial diversity in a deep-subsurface clay environment.

The presence of bacteria in a deep clay sediment was analyzed in a 20-m-long core horizontally drilled from a mine gallery at a depth of 224 m in the Boom clay formation (Mol, Belgium). This clay deposit is the result of a marine sedimentary process that occurred 35 million years ago. Bacterial activities were estimated by measuring respiration on [14C]glucose. Using the same samples, universal primers for the genes coding for eubacterial 16S rRNA were used to amplify extracted DNA. PCR products were then cloned, sequenced, and analyzed by molecular phylogeny. Our data showed a decrease in bacterial densities as a function of distance from the gallery, with few bacteria detectable by culture at more than 80 cm from the gallery wall. PCR experiments showed the presence of bacteria in all samples, and phylogenetic analyses were then used to tentatively identify these organisms. Because of low bacterial densities in deep clay samples, direct counts and enumeration of viable bacteria on diverse culture media remained negative. All experiments, both cultures and PCR, demonstrated the difficulty of analyzing samples that contain only a few poorly active bacteria as it is difficult to avoid a small contamination by active bacteria during sampling. Since the porosity of the Boom clay formation is less than the expected size of bacteria, it is possible that some of the bacteria present in this 35-million-year-old deep clay deposit derive from cells initially trapped during the sedimentation process.

Bacteria↗

Ecology of Thioploca spp.: nitrate and sulfur storage in relation to chemical microgradients and influence of Thioploca spp. on the sedimentary nitrogen cycle.

Microsensors, including a recently developed NO3(-) biosensor, were applied to measure O(2) and NO3(-) profiles in marine sediments from the upwelling area off central Chile and to investigate the influence of Thioploca spp. on the sedimentary nitrogen metabolism. The studies were performed in undisturbed sediment cores incubated in a small laboratory flume to simulate the environmental conditions of low O(2), high NO3(-), and bottom water current. On addition of NO3(-) and NO2(-), Thioploca spp. exhibited positive chemotaxis and stretched out of the sediment into the flume water. In a core densely populated with Thioploca, the penetration depth of NO3(-) was only 0.5 mm and a sharp maximum of NO3(-) uptake was observed 0.5 mm above the sediment surface. In sediments with only few Thioploca spp., NO3(-) was detectable down to a depth of 2 mm and the maximum consumption rates were observed within the sediment. No chemotaxis toward nitrous oxide (N2O) was observed, which is consistent with the observation that Thioploca does not denitrify but reduces intracellular NO3(-) to NH(4)(+). Measurements of the intracellular NO3(-) and S(0) pools in Thioploca filaments from various depths in the sediment gave insights into possible differences in the migration behavior between the different species. Living filaments containing significant amounts of intracellular NO3(-) were found to a depth of at least 13 cm, providing final proof for the vertical shuttling of Thioploca spp. and nitrate transport into the sediment.

Biosensing Techniques↗

Production of N(2) through anaerobic ammonium oxidation coupled to nitrate reduction in marine sediments.

In the global nitrogen cycle, bacterial denitrification is recognized as the only quantitatively important process that converts fixed nitrogen to atmospheric nitrogen gas, N(2), thereby influencing many aspects of ecosystem function and global biogeochemistry. However, we have found that a process novel to the marine nitrogen cycle, anaerobic oxidation of ammonium coupled to nitrate reduction, contributes substantially to N(2) production in marine sediments. Incubations with (15)N-labeled nitrate or ammonium demonstrated that during this process, N(2) is formed through one-to-one pairing of nitrogen from nitrate and ammonium, which clearly separates the process from denitrification. Nitrite, which accumulated transiently, was likely the oxidant for ammonium, and the process is thus similar to the anammox process known from wastewater bioreactors. Anaerobic ammonium oxidation accounted for 24 and 67% of the total N(2) production at two typical continental shelf sites, whereas it was detectable but insignificant relative to denitrification in a eutrophic coastal bay. However, rates of anaerobic ammonium oxidation were higher in the coastal sediment than at the deepest site and the variability in the relative contribution to N(2) production between sites was related to large differences in rates of denitrification. Thus, the relative importance of anaerobic ammonium oxidation and denitrification in N(2) production appears to be regulated by the availability of their reduced substrates. By shunting nitrogen directly from ammonium to N(2), anaerobic ammonium oxidation promotes the removal of fixed nitrogen in the oceans. The process can explain ammonium deficiencies in anoxic waters and sediments, and it may contribute significantly to oceanic nitrogen budgets.

Anaerobiosis↗

pmoA-based analysis of methanotrophs in a littoral lake sediment reveals a diverse and stable community in a dynamic environment.

Diversity and community structure of aerobic methane-oxidizing bacteria in the littoral sediment of Lake Constance was investigated by cloning analysis and terminal restriction fragment length polymorphism (T-RFLP) fingerprinting of the pmoA gene. Phylogenetic analysis revealed a high diversity of type I and type II methanotrophs in the oxygenated uppermost centimeter of the sediment. T-RFLP profiles indicated a high similarity between the active methanotrophic community in the oxic layer and the inactive community in an anoxic sediment layer at a 10-cm depth. There were also no major changes in community structure between littoral sediment cores sampled in summer and winter. By contrast, the fingerprint patterns showed substantial differences between the methanotrophic communities of littoral and profundal sediments.

Cloning, Molecular↗

Effect of surfactants at low concentrations on the sorption of atrazine by natural sediment.

A series of experiments were carried out to determine the effect of surfactants at low concentrations on the sorption of atrazine by natural sediments. With surfactant concentrations ranging from 0 to 20 mg/ L, anionic and cationic surfactants appreciably reduce the adsorption of atrazine, while nonionic surfactant decreases the adsorption of atrazine at concentrations equal to or less than 1 mg/L and increases adsorption at higher concentrations. Desorption of atrazine in the presence of different sodium dodecylbenzene sulfonate (SDBS) concentrations shows that a portion of the bound pesticide resists desorption in the SDBS free system. However, the addition of SDBS accelerates the desorption of atrazine. Furthermore, the nature of sediment and the contacting sequence of SDBS, at 10 mg/L, with the sediment, also influence the adsorption of atrazine. The conclusions in this study could be explained partially by the effect of the type and concentration of surfactants and the characteristics of sediments.

Adsorption↗

Ranavirus in wood frogs (Rana sylvatica): potential sources of transmission within and between ponds.

Members of the genus Ranavirus (family Iridoviridae) can cause catastrophic mortality of pond-breeding amphibians and are associated with an emerging infectious disease that may be contributing to amphibian declines. We conducted three experiments to examine factors that may affect transmission both within and between local breeding populations of the wood frog (Rana sylvatica). In a laboratory study, when exposed to moribund tadpoles collected during a local ranaviral die-off, uninfected tadpoles died as soon as 4 days after exposure. The onset of death was accelerated when tadpoles were allowed to scavenge on carcasses of infected tadpoles. In a mesocosm experiment that was conducted in outdoor wading pools, die-offs of tadpoles began approximately 19 days after infected tadpoles were added to pools containing uninfected tadpoles. Mass die-offs with greater than 98% mortality occurred in all pools, regardless of the initial tadpole density. In a second mesocosm experiment, the addition of water and bottom sediments that were collected from a pond during a ranaviral die-off did not result in lower tadpole survival or growth relative to controls. Only a small percentage of tadpoles appeared to be sick, and most tadpoles survived until the first individuals began metamorphosing within a pool. However, tests for ranavirus using polymerase chain reaction were positive for most pools that received contaminated sediment, suggesting that some infections were sublethal. Our results indicate that transmission within ponds is enhanced by scavenging and that spread between local ponds could occur via the transport of contaminated sediment by animals or humans.

Animals↗

Field monitoring of toxic organic pollution in the sediments of Pearl River estuary and its tributaries.

Field monitoring of the toxic organic compounds (PCBs, PAHs, organochlorine pesticides) in the top sediments of Pearl River Estuary and its up-streams were made. It was found that the highest concentrations of these toxic organic compounds occurred in the sediment sampled at Macau inner harbor (ZB013), which is a sink of suspended fine particles transported from the upstream waterways. Because of the affinity of the hydrophobic organic compounds (PAHs, PCBs) for the solid phase, these fine particle depositions led to accumulation of these compounds in the sediment of Macau. The atmospheric dry deposition may be another source of the toxic organic pollution in the sediment.

Air Movements↗

[Distribution of polycyclic aromatic hydrocarbon in core sediments of the Bohai Straight].

Thirteen compounds of PAHs were identified by GC in the core sediments of Bohai Straight (S44 and T4 Stations). The distribution and source identification were studied with the two core sediments. The total concentrations changed from 60.3 ng/g to 2076.5 ng/g. Though the contamination of PAHs in the study area is quite modest, some carcinogenic compounds were detected in most samples. From the indicators such as Pen/Anth and Fluo/Pyr etc. the dominated origin of PAHs in S44 Station is pyrolytic origins. However, in T4 Station, a mixture of pyrolysis and petroleum origin is suggested in this area. The distribution of PAHs in the core sediments also could be a good indicative of the contribution of human activity.

Geologic Sediments↗

Application of membrane filters for spectrophotometric determination of cationic surfactants in river water and sediment.

Cationic surfactant (CS+) in urban river water and sediment was extracted and determined spectrophotometrically with 2 membrane filters. The CS+ in the water samples, mostly in the form of an ion associate with the coexisting anionic surfactant (AS), was collected on a polytetrafluoroethylene (PTFE) membrane filter and eluted with methanol. Bromphenol blue (BPB), hydrochloric acid, and water were added to the methanol solution successively, and the mixed solution was filtered through a mixed cellulose ester membrane filter. The CS+-BPB- ion associate, formed by a counter ion exchange, was collected on the filter and dissolved into N,N-dimethylformamide (DMF) together with the mixed cellulose ester membrane filter. After addition of 2 drops of triethanolamine, the absorbance of the DMF solution was measured. The CS+ in sediment samples was extracted with methanol by ultrasonic irradiation; the methanol solution was then passed through a PTFE membrane filter and evaporated to dryness. The CS+ was redissolved in a small amount of methanol. For water samples, recoveries and relative standard deviations for 0.30 microM benzyldimethyl-tetradecylammonium ion, a standard material, were > or =93 and < or =5%, with a detection limit of 0.02 microM. Concentrations of CS+ in sediments were much higher than those in water samples, indicating that CS+ is adsorbed on the surface of the sediment.

Adsorption↗

Modeling polychlorinated biphenyl congener patterns and dechlorination in dated sediments from the Ashtabula River, Ohio, USA.

Polychlorinated biphenyl (PCB) congeners were analyzed in four deep, dated sediment cores from the Ashtabula River (OH, USA), for the purpose of identifying relevant PCB sources and congener patterns. The time span for three of the cores is from the mid 1960s to 1998, whereas the fourth has a time span of six years. The total PCB concentrations are in the range of 0.4 to 6.8 microg/g dry weight, with the highest concentrations observed in samples from the 1970s. A factor analysis (FA) model with nonnegative constraints was used to investigate the sources and patterns of PCBs. Additionally, a new model, based on a least squares method, was developed to identify possible patterns of anaerobic dechlorination of PCBs in the sediments, and to quantify the relevant dechlorination pathways. Both models were validated successfully either by artificially created data sets (FA model) or by using laboratory data from the literature (dechlorination model). The FA model revealed two significant sources. The first was identified as a slightly altered Aroclor 1248. The second did not resemble any Aroclor closely, but was very similar to the overall average congener profile of all samples. Simulation of anaerobic dechlorination on an Aroclor 1248 profile from the literature, according to dechlorination activities H/H', as defined in the literature, yielded a congener profile very similar to that of the second pattern. This indicates the likelihood of anaerobic dechlorination of PCBs in Ashtabula River sediments.

Anaerobiosis↗

Bioturbation effects on cadmium and zinc transfers from a contaminated sediment and on metal bioavailability to benthic bivalves.

The two main objectives of this study were to compare cadmium and zinc fluxes from a contaminated sediment to the water column in bioturbated and unbioturbated systems and jointly to analyze accumulation kinetics of these released metals by benthic filter-feeder bivalves. The experimental approach was based on indoor microcosms containing a two-compartment biotope: natural contaminated sediment (45 +/- 5 microg Cd/g, dry wt, and 1,938 +/- 56 microg Zn/g, dry wt) and water column. Four experimental conditions were studied: no organism added to the sediment-water biotope, presence of bivalves Corbicula fluminea, presence of Hexagenia rigida nymphs (bioturbation source), and presence of C. fluminea and H. rigida simultaneously. Results reveal that bioturbation produces a significant metal release into the water column via the resuspended sediment particles. The use of C. fluminea as an indicator of transferred metals in the water column shows that the metal bioavailability is very limited, quantities of cadmium and zinc bioaccumulated in the soft bodies being less than those measured in unbioturbated systems. This experimental study demonstrates that only the dissolved fraction resulting from diffusive metal fluxes across the sediment-water interface is bioavailable for this bivalve species.

Animals↗

[Copper sorption and desorption by loess in water-sediment systems].

A series of experiments were designed to investigate copper sorption and desorption by loess in hyper-concentrated sediment systems. The results demonstrate that loess had large copper sorption capacity because of its specific adsorption and precipitation of carbonate and hydroxide. Copper sorption decreased with increasing ionic strength of solution, but the effects of varying cationic charge of supporting electrolyte were still detected. Less than 4% of copper was desorbed in the neutral saline solution, and increased with increasing ionic strength of solution. The pH was the most dominant factor on copper desorption. More than 70% of copper can be desorbed in the acid solution, and copper desorption increased with the decrease of solution pH. When pH of solid-liquid system was fixed, copper desorption from equivalent loess increased with the increase of solution volume, and copper desorption in the same sediment concentration increased with the adsorptive capacity.

Adsorption↗

Sediment distribution pattern mapped from the combination of objective analysis and geostatistics in the large shallow Taihu Lake, China.

Investigation was made into sediment depth at 723 irregularly scattered measurement points which cover all the regions in Taihu Lake, China. The combination of successive correction scheme and geostatistical method was used to get all the values of recent sediment thickness at the 69 x 69 grids in the whole lake. The results showed that there is the significant difference in sediment depth between the eastern area and the western region, and most of the sediments are located in the western shore-line and northern regimes but just a little in the center and eastern parts. The notable exception is the patch between the center and Xishan Island where the maximum sediment depth is more than 4.0 m. This sediment distribution pattern is more than likely related to the current circulation pattern induced by the prevailing wind-forcing in Taihu Lake. The numerical simulation of hydrodynamics can strong support the conclusion. Sediment effects on water quality was also studied and the results showed that the concentrations of TP, TN and SS in the western part are obviously larger than those in the eastern regime, which suggested that more nutrients can be released from thicker sediment areas.

China↗