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Colloid-borne americium migration in Gorleben groundwater: significance of iron secondary phase transformation.

The mobility of actinides in natural water may be enhanced by colloid-mediated transport. In this context the reversibility of actinide colloid interaction is a key factor. Iron is an element that can generate colloids under conditions found in natural waters. In this paper, the impact of hematite and the low-crystalline precursor 2-line ferrihydrite on colloid-mediated transport of americium(III) is investigated. Am(III)-containing iron colloids are generated from two different approaches, namely contact between the two in aqueous solution or coprecipitation of Am(III) during iron colloid generation. Dissolved organic carbon (DOC), especially humic substances, has a strong influence on the stability of inorganic colloids. In addition, humic substances interfere in the distribution and kinetics of exchange between groundwater and sediments. Four groundwaters from the Gorleben aquifer system are used with DOC concentrations varying between 0.9 and 81.6 mgC/L together with Pleistocene Aeolian quartz sand from this site. Batch and column experiments are conducted under near-natural conditions (Ar + 1% CO2). To study the influence of kinetics, contact times up to one month are studied. The dynamic light-scattering investigations show that the colloidal stability of the 2-line ferrihydrite increases with increasing DOC concentration. The low-crystalline iron colloids have a marginal influence on the Am(III) transport due to reversibility of americium sorption. Contrary to this, the crystalline hematite generated from coprecipitation of Am(III) leads to an increase of unretarded colloid-mediated Am(III) transport up to a factor of almost five. Chemical characterization of these hematite colloids shows that Am(III) is structurally entrapped in the hematite. The distribution of Am(III) and 2-line ferrihydrite between groundwater and sand sediment remained in disequilibrium even after one month. This shows that the kinetics of Am(III) distribution between the different phases (bulk solution/colloidal form/ sediment) is a key issue.

Americium↗

Kinetic desorption and sorption of U(VI) during reactive transport in a contaminated Hanford sediment.

Column experiments were conducted to investigate U(VI) desorption and sorption kinetics in a sand-textured, U(VI)-contaminated (22.7 micromol kg(-1)) capillary fringe sediment from the U.S. Department of Energy (DOE) Hanford site. Saturated column experiments were performed under mildly alkaline conditions representative of the Hanford site where uranyl-carbonate and calcium-uranyl-carbonate complexes dominate aqueous speciation. A U(VI)-free solution was used to study contaminant U(VI) desorption in columns where different flow rates were applied. Sorbed, contaminant U(VI) was partially labile (11.8%), and extended leaching times and water volumes were required for complete desorption of the labile fraction. Uranium-(VI) sorption was studied after the desorption of labile, contaminant U(VI) using different U(VI) concentrations in the leaching solution. Strong kinetic effects were observed for both U(VI) sorption and desorption, with half-life ranging from 8.5 to 48.5 h for sorption and from 39.3 to 150 h for desorption. Although U(VI) is semi-mobile in mildly alkaline, subsurface environments, we observed substantial U(VI) adsorption, significant retardation during transport, and atypical breakthrough curves with extended tailing. A distributed rate model was applied to describe the effluent data and to allow comparisons between the desorption rate of contaminant U(VI) with the rate of shortterm U(VI) sorption. Desorption was the slower process. We speculate that the kinetic behavior results from transport or chemical phenomena within the phyllosilicate-dominated fine fraction present in the sediment. Our results suggest that U(VI) release and transport in the vadose zone and aquifer system from which the sediment was obtained are kinetically controlled.

Carbonates↗

Influence of pH on plutonium desorption/solubilization from sediment.

Aqueous Pu concentrations and oxidation state transformations as a function of pH were quantified and compared between sorption/desorption studies and literature solubility values. When Pu(V) was added to a red subsurface sandy-clay-loam sediment collected near Aiken, South Carolina, 99% of the Pu sorbed to the sediment within 48 h. Throughout the study, > or = 94% of the Puaq remained as Pu(V), whereas < or = 6% was Pu(VI) and < or = 1% was Pu(IV). This is in stark contrast to the sorbed Pu which was almost exclusively in the +4 oxidation state. The fraction of aqueous Pu (Puaq/Pusolid) decreased by >2 orders-of-magnitude when the contact time was increased from 1- to 33-days, presumably the result of Pu(V) reduction to Pu(IV). The desorption studies were conducted with a sediment that had been in contact with Pu (originally as PuIV(NO3)4) for 24 years. At near neutral pH, a decrease of 1-pH unit resulted in almost an order-of-magnitude increase in the concentration of Puaq (7.5 x 10(-10) M at pH 7 and 3.6 x 10(-9) M at pH 6). Similar to the sorption experiment, > or = 96% of the Puaq was Pu(V/VI). The Puaq concentrations from the desorption experiment were similar to those of the Pu(V) amended sorption studies that were permitted to equilibrate for 33 days, suggesting that the latter had reached steady state. The Puaq concentrations as a function of pH followed near identical trends with literature solubility values for PuO2(am), except that the desorption values were lower by a fixed amount, suggesting either Pu sorption was occurring in this sediment system or that a more crystalline, less soluble form of Pu existed in the sediment than in the literature water-PuO2(am) system. Based on Pu sorption experiments and measured sediment surface charge properties as a function of pH, the latter explanation appears more likely. pH had a more pronounced effect on solubility and Puaq concentrations than on sediment charge density (or Puaq oxidation state distribution). Slight changes in system pH can have a large impact on Pu solubility and the tendency of Pu to sorb to sediment, thereby influencing Pu subsurface mobility.

Adsorption↗

Codeposition of organic carbon and arsenic in Bengal Delta aquifers.

We present data showing that arsenic (As) was codeposited with organic carbon (OC) in Bengal Delta sediments as As and OC concentrations are highly (p < 0.001) positively correlated in core profiles collected from widely dispersed geographical sites with different sedimentary depositional histories. Analysis of modern day depositional environments revealed that the As-OC correlations observed in cores are due to As retention and high OC inputs in vegetated zones of the deltaic environment. We hypothesize that elevated concentrations of As occur in vegetated wetland sediments due to concentration and retention of arsenate in aerated root zones and animal burrows where copious iron(III) oxides are deposited. On burial of the sediment, degradation of organic carbon from plant and animal biomass detritus provides the reducing conditions to dissolve iron(III) oxides and release arsenite into the porewater. As tubewell abstracted aquifer water is an invaluable resource on which much of Southeast Asia is now dependent, this increased understanding of the processes responsible for As buildup and release will identify, through knowledge of the palaeosedimentary environment, which sediments are at most risk of having high arsenic concentrations in porewater. Our data allow the development of a new unifying hypothesis of how As is mobilized into groundwaters in river flood plains and deltas of Southeast Asia, namely that in these highly biologically productive environments, As and OC are codeposited, and the codeposited OC drives As release from the sediments.

Arsenic↗

Biodegradation of synthetic base fluid surrogates in Gulf of Mexico sediments under simulated deep-sea conditions.

In this study, an anaerobic marine biodegradability test was adapted to study the fate of synthetic base fluid (SBF) surrogates, ethyl oleate and tetradecene, by deep-sea microorganisms. Sediment samples from hundreds of meters deep in the Gulf of Mexico were incubated at low temperatures (4 degrees C) and high hydrostatic pressure in steel vessels. Stimulation of indigenous microbial communities to SBF biodegradation was evident in the fact that the rate of removal of ethyl oleate was greater in sediments that had some previous exposure to SBF (first-order decay coefficient kof -0.22 +/- 0.02 week(-1)) compared to unexposed control sediments (first-order decay coefficient k of -0.11 +/- 0.02 week(-1)). When sulfate-linked tetradecene degradation occurred within the test period, the activity could also be modeled as a first-order decay following an initial lag phase, with an average decay coefficient of k = -0.05 +/- 0.01 week(-1). This study also revealed that the degradation of SBF surrogates by microorganisms collected from deep-sea sediments was not significantly effected by the hydrostatic incubation pressure.

Alkenes↗

Historical pollution trends in coastal environments of India.

Seventeen sediment cores were collected from different coastal ecosystems of Tamil Nadu, India that include coastal lagoon (Pulicat), polluted rivers in Chennai (Adyar and Cooum), Coral reef (Gulf of Mannar) and a perennial river (Tamiraparani). Radiometric dating has been used to determine the modern sedimentation rates in these ecosystems. The Pulicat Lake and the polluted rivers (Adyar and Cooum) yield an average sediment accumulation rate of 12.34 and 7.85 mm yr(-1), respectively. In the Gulf of Mannar coral reef, the sedimentation rate averages 17.37 mm yr(-1), while the rate in Tamiraparani River is 11.00 mm yr(-1). In the Tamiraparani River basin, the deposition rates were an order of magnitude higher when compared to the erosion rates, which may be due to bank erosion and the intense human activity. In general high rates of sedimentation observed in the coastal ecosystems not only reflect the capacity of the coastal regions as sinks for trace metals but also denote increased input of pollutants into the coastal environments in the recent past. The deposition rates of heavy metals--Fe, Mn, Zn, Cu, Cr and Ni in the depth profiles have been computed using sedimentation rates and their distribution is discussed. It can be seen that the mean deposition rates of all the measured elements in the Tamil Nadu coastal ecosystems are high compared with rates determined for the sediments of the deltaic regions of India and the Bay of Bengal.

Ecosystem↗

Heavy metals in sandy sediments of the Rías Baixas (NW Spain).

We studied the concentrations of certain heavy metals in the total and labile fractions of sandy sediments from four embayments situated on the northwestern coast of Spain. In order to compensate for the effects of the heterogeneity in texture of the different samples, data were normalized. Organic carbon was the most suitable normalizing factor for copper, lead and zinc in the total fraction and copper in the labile fraction, and iron was the most suitable for the other metals in both fractions. Enrichment of copper, lead and zinc in these sediments may have been caused by sewage contamination. The percentages of extractability for chromiun were remarkable.

Environmental Monitoring↗

Heavy metal levels in biota and sediments in the northern coast of the Marmara Sea.

Concentration of Cd, Co, Cr, Ni, Zn, Fe, Mn, Pb and Cu were determined in biota and sediment samples collected from the Marmara Sea in Turkey. The levels of Zn, Fe, Mn, Pb and Cu in the macroalgae are higher than previous studies in the Marmara Sea. Moreover, Cu and Zn concentrations at the present study are significantly high than Bosphorus and Black Sea algae. The order heavy metal concentrations in the mussel samples was: Fe > Zn > Ni > Mn > Cu > Pb > Cr > Cd > Co. The metal concentrations are generally lower when compared with the Black Sea mussels except Pb. At the same time, concentrations of Pb, Cu and Zn in the mussel species are lower when compared with the results in the Aegean Sea. The ranges of Mn and Cu in the tested fish samples are higher than Black Sea fish. On the other hand, Cd, Co, Cr, Zn and Pb concentrations are lower. The northern coast of the Marmara Sea having the highest metal concentrations in sediments as follows: Co, Cr, Ni, Fe at Sarköy; Pb, Cu at M. Ereğli; Cd, Zn, Mn at Menekşe. The heavy metal levels in the sediment samples are lower than other areas in the Marmara Sea.

Animals↗

Thermal analysis in the evaluation of sediment pollution.

Characterization of organic matter in four sediments in the infuence area of wastewater discharges was carried out by both chemical and thermal analysis in order to assess their pollution level. Oxidisable organic carbon and organic matter were calculated by the standard methodology in laboratory. Thermogravimetry (TG), between 50 and 900 degrees C, was simultaneously performed in oxidizing conditions on ground sediments samples after three different pretreatments. Linear regression adjust of thermal analysis results versus chemical parameters provides the better Pearson's coefficients, leading to the best coefficients for weight loss in 250-400 degree C temperature range versus oxidisable organic carbon and organic matter at 360 degrees C, respectively. These results demonstrated the utility of thermoanalysis technique for the evaluation of the organic matter content of fresh sediments.

Differential Thermal Analysis↗

More realistic soil cleanup standards with dual-equilibrium desorption.

The desorption of contaminants from soils/sediments is one of the most important processes controlling contaminant transport and environmental risks. None of the currently adopted desorption models can accurately quantify desorption at relatively low concentrations; these models often overestimate the desorption and thus the risks of hydrophobic organic chemicals, such as benzene and chlorinated solvents. In reality, desorption is generally found to be biphasic, with two soil-phase compartments. A new dual-equilibrium desorption (DED) model has been developed to account for the biphasic desorption. This model has been tested using a wide range of laboratory and field data and has been used to explain key observations related to underground storage tank plumes. The DED model relates the amount of a chemical sorbed to the aqueous concentration, with simple parameters including octanol-water partition coefficient, solubility, and fractional organic carbon; thus, it is the only biphasic model, to date, that is based on readily available parameters. The DED model can be easily incorporated into standard risk and transport models. According to this model, many regulatory standards of soils and sediments could be increased without increasing the risks.

Adsorption↗

Bedout: a possible end-Permian impact crater offshore of northwestern Australia.

The Bedout High, located on the northwestern continental margin of Australia, has emerged as a prime candidate for an end-Permian impact structure. Seismic imaging, gravity data, and the identification of melt rocks and impact breccias from drill cores located on top of Bedout are consistent with the presence of a buried impact crater. The impact breccias contain nearly pure silica glass (SiO2), fractured and shock-melted plagioclases, and spherulitic glass. The distribution of glass and shocked minerals over hundreds of meters of core material implies that a melt sheet is present. Available gravity and seismic data suggest that the Bedout High represents the central uplift of a crater similar in size to Chicxulub. A plagioclase separate from the Lagrange-1 exploration well has an Ar/Ar age of 250.1 +/- 4.5 million years. The location, size, and age of the Bedout crater can account for reported occurrences of impact debris in Permian-Triassic boundary sediments worldwide.

Argon↗

Impact of humans on the flux of terrestrial sediment to the global coastal ocean.

Here we provide global estimates of the seasonal flux of sediment, on a river-by-river basis, under modern and prehuman conditions. Humans have simultaneously increased the sediment transport by global rivers through soil erosion (by 2.3 +/- 0.6 billion metric tons per year), yet reduced the flux of sediment reaching the world's coasts (by 1.4 +/- 0.3 billion metric tons per year) because of retention within reservoirs. Over 100 billion metric tons of sediment and 1 to 3 billion metric tons of carbon are now sequestered in reservoirs constructed largely within the past 50 years. African and Asian rivers carry a greatly reduced sediment load; Indonesian rivers deliver much more sediment to coastal areas.

Agriculture↗

Isolation of broad-host-range replicons from marine sediment bacteria.

Naturally occurring plasmids isolated from heterotrophic bacterial isolates originating from coastal California marine sediments were characterized by analyzing their incompatibility and replication properties. Previously, we reported on the lack of DNA homology between plasmids from the culturable bacterial population of marine sediments and the replicon probes specific for a number of well-characterized incompatibility and replication groups (P. A. Sobecky, T. J. Mincer, M. C. Chang, and D. R. Helinski, Appl. Environ. Microbiol. 63:888-895, 1997). In the present study we isolated 1.8- to 2.3-kb fragments that contain functional replication origins from one relatively large (30-kb) and three small (<10-kb) naturally occurring plasmids present in different marine isolates. 16S rRNA sequence analyses indicated that the four plasmid-bearing marine isolates belonged to the alpha and gamma subclasses of the class Proteobacteria. Three of the marine sediment isolates are related to the gamma-3 subclass organisms Vibrio splendidus and Vibrio fischeri, while the fourth isolate may be related to Roseobacter litoralis. Sequence analysis of the plasmid replication regions revealed the presence of features common to replication origins of well-characterized plasmids from clinical bacterial isolates, suggesting that there may be similar mechanisms for plasmid replication initiation in the indigenous plasmids of gram-negative marine sediment bacteria. In addition to replication in Escherichia coli DH5alpha and C2110, the host ranges of the plasmid replicons, designated repSD41, repSD121, repSD164, and repSD172, extended to marine species belonging to the genera Achromobacter, Pseudomonas, Serratia, and Vibrio. While sequence analysis of repSD41 and repSD121 revealed considerable stretches of homology between the two fragments, these regions do not display incompatibility properties against each other. The replication origin repSD41 was detected in 5% of the culturable plasmid-bearing marine sediment bacterial isolates, whereas the replication origins repSD164 and repSD172 were not detected in any plasmid-bearing bacteria other than the parental isolates. Microbial community DNA extracted from samples collected in November 1995 and June 1997 and amplified by PCR yielded positive signals when they were hybridized with probes specific for repSD41 and repSD172 replication sequences. In contrast, replication sequences specific for repSD164 were not detected in the DNA extracted from marine sediment microbial communities.

Bacteria↗

Analysis of the sulfate-reducing bacterial and methanogenic archaeal populations in contrasting Antarctic sediments.

The distribution and activity of communities of sulfate-reducing bacteria (SRB) and methanogenic archaea in two contrasting Antarctic sediments were investigated. Methanogenesis dominated in freshwater Lake Heywood, while sulfate reduction dominated in marine Shallow Bay. Slurry experiments indicated that 90% of the methanogenesis in Lake Heywood was acetoclastic. This finding was supported by the limited diversity of clones detected in a Lake Heywood archaeal clone library, in which most clones were closely related to the obligate acetate-utilizing Methanosaeta concilii. The Shallow Bay archaeal clone library contained clones related to the C(1)-utilizing Methanolobus and Methanococcoides and the H(2)-utilizing Methanogenium: Oligonucleotide probing of RNA extracted directly from sediment indicated that archaea represented 34% of the total prokaryotic signal in Lake Heywood and that Methanosaeta was a major component (13.2%) of this signal. Archaea represented only 0.2% of the total prokaryotic signal in RNA extracted from Shallow Bay sediments. In the Shallow Bay bacterial clone library, 10.3% of the clones were SRB-like, related to Desulfotalea/Desulforhopalus, Desulfofaba, Desulfosarcina, and Desulfobacter as well as to the sulfur and metal oxidizers comprising the Desulfuromonas cluster. Oligonucleotide probes for specific SRB clusters indicated that SRB represented 14.7% of the total prokaryotic signal, with Desulfotalea/Desulforhopalus being the dominant SRB group (10.7% of the total prokaryotic signal) in the Shallow Bay sediments; these results support previous results obtained for Arctic sediments. Methanosaeta and Desulfotalea/Desulforhopalus appear to be important in Lake Heywood and Shallow Bay, respectively, and may be globally important in permanently low-temperature sediments.

Antarctic Regions↗

Potential role of a novel psychrotolerant member of the family Geobacteraceae, Geopsychrobacter electrodiphilus gen. nov., sp. nov., in electricity production by a marine sediment fuel cell.

Previous studies have shown that members of the family Geobacteraceae that attach to the anodes of sediment fuel cells are directly involved in harvesting electricity by oxidizing organic compounds to carbon dioxide and transferring the electrons to the anode. In order to learn more about this process, microorganisms from the anode surface of a marine sediment fuel cell were enriched and isolated with Fe(III) oxide. Two unique marine isolates were recovered, strains A1(T) and A2. They are gram-negative, nonmotile rods, with abundant c-type cytochromes. Phylogenetic analysis of the 16S rRNA, recA, gyrB, fusA, rpoB, and nifD genes indicated that strains A1(T) and A2 represent a unique phylogenetic cluster within the Geobacteraceae. Both strains were able to grow with an electrode serving as the sole electron acceptor and transferred ca. 90% of the electrons available in their organic electron donors to the electrodes. These organisms are the first psychrotolerant members of the Geobacteraceae reported thus far and can grow at temperatures between 4 and 30 degrees C, with an optimum temperature of 22 degrees C. Strains A1(T) and A2 can utilize a wide range of traditional electron acceptors, including all forms of soluble and insoluble Fe(III) tested, anthraquinone 2,6-disulfonate, and S(0). In addition to acetate, both strains can utilize a number of other organic acids, amino acids, long-chain fatty acids, and aromatic compounds to support growth with Fe(III) nitrilotriacetic acid as an electron acceptor. The metabolism of these organisms differs in that only strain A1(T) can use acetoin, ethanol, and hydrogen as electron donors, whereas only strain A2 can use lactate, propionate, and butyrate. The name Geopsychrobacter electrodiphilus gen. nov., sp. nov., is proposed for strains A1(T) and A2, with strain A1(T) (ATCC BAA-880(T); DSM 16401(T); JCM 12469) as the type strain. Strains A1(T) and A2 (ATCC BAA-770; JCM 12470) represent the first organisms recovered from anodes that can effectively couple the oxidation of organic compounds to an electrode. Thus, they may serve as important model organisms for further elucidation of the mechanisms of microbe-electrode electron transfer in sediment fuel cells.

Bioelectric Energy Sources↗

Accelerated sulfur cycle in coastal marine sediment beneath areas of intensive shellfish aquaculture.

Prokaryotes in marine sediments taken from two neighboring semi-enclosed bays (the Yamada and Kamaishi bays) at the Sanriku coast in Japan were investigated by the culture-independent molecular phylogenetic approach coupled with chemical and activity analyses. These two bays were chosen in terms of their similar hydrogeological and chemical characteristics but different usage modes; the Yamada bay has been used for intensive shellfish aquaculture, while the Kamaishi bay has a commercial port and is not used for aquaculture. Substantial differences were found in the phylogenetic composition of 16S rRNA gene clone libraries constructed for the Yamada and Kamaishi sediments. In the Yamada library, phylotypes affiliated with delta-Proteobacteria were the most abundant, and those affiliated with gamma-Proteobacteria were the second-most abundant. In contrast, the Kamaishi library was occupied by phylotypes affiliated with Planctomycetes, gamma-Proteobacteria, delta-Proteobacteria, and Crenarchaeota. In the gamma-Proteobacteria, many Yamada phylotypes were related to free-living and symbiotic sulfur oxidizers, whereas the Kamaishi phylotype was related to the genus Pseudomonas. These results allowed us to hypothesize that sulfate-reducing and sulfur-oxidizing bacteria have become abundant in the Yamada sediment. This hypothesis was supported by quantitative competitive PCR (qcPCR) with group-specific primers. The qcPCR also suggested that organisms closely related to Desulfotalea in the Desulfobulbaceae were the major sulfate-reducing bacteria in these sediments. In addition, potential sulfate reduction and sulfur oxidation rates in the sediment samples were determined, indicating that the sulfur cycle has become active in the Yamada sediment beneath the areas of intensive shellfish aquaculture.

Animals↗

Distribution of atrazine into three chemical fractions: impact of sediment depth and organic carbon content.

The fate and transport of organic contaminants in aquatic sediments are impacted largely by microbial degradation and sorption to organic matter. Atrazine, a pre-emergent herbicide, has the potential to contaminate groundwater because of its slight water solubility, long half-life, and sorption to organic matter. Mineralization and distribution of 14C-atrazine into three chemical fractions were monitored over time in surface and subsurface coastal aquatic sediments of different land use. Sediments were extracted with an organic solvent followed by an alkali hydrolysis, and 14C activity was measured in the aqueous, solvent, and basic fractions (representing nonsorbed compounds, loosely sorbed compounds, and humic or fulvic acid bound compounds, respectively). Limited mineralization of atrazine occurred (< 4%). The 14C activity in the aqueous and basic fractions increased over time, was greater in surface versus subsurface sediments, and was positively correlated with sediment organic carbon (SOC) content, indicating greater biological and chemical activity. Total 14C recovered ranged from 50 to 90%, was less in surface versus subsurface sediments, and was not correlated with SOC after 80 d. These results suggest that in native aquatic surface sediments, atrazine sorption plays a major role, whereas in subsurface sediments atrazine may be available for degradation and transport to shallow groundwater.

Atrazine↗

Experimental and modeling investigation of metal release from metal-spiked sediments.

In sediments that contain iron monosulfide, cadmium, nickel, lead, zinc, and silver(I) form insoluble metal sulfides that lower the metal ion activity in the sediment-pore water system, thereby reducing toxicity. However, metal sulfides are susceptible to oxidation by molecular oxygen resulting in metal solubilization. To better understand the sources and sinks of metal sulfides in sediments, iron monsulfide-rich freshwater sediments were spiked with cadmium, nickel, lead, zinc, or silver(I) and placed into cylindrical cores with an overlying layer of oxygen-saturated water. Measurements of the dissolved metal concentration in the overlying water were made as a function of time and the vertical profiles of acid-volatile sulfide (AVS) and simultaneously extracted metal (SEM) were measured after 150 d. A one-dimensional reactive and transport model has been employed to help elucidate processes controlling the fate of metals in sediments. The model incorporates metal-sulfide formation, metal-sulfide oxidation, and metal partitioning onto sediment organic carbon and iron oxyhydroxide to simulate the vertical transport of metals throughout the sediment core.

Acids↗