Chemical status of selenium in evaporation basins for disposal of agricultural drainage

Evaporation basins (or ponds) are the most commonly used facilities for disposal of selenium-laden saline agricultural drainage in the closed hydrologic basin portion of the San Joaquin Valley, California. However concerns remain for potential risk from selenium (Se) toxicity to water fowl in these evaporation basins. In this study, we examined the chemical status of Se in both waters and sediments in two currently operating evaporation pond facilities in the Tulare Lake Drainage District. Some of the saline ponds have been colonized by brine-shrimp (Artemia), which have been harvested since 2001. We evaluated Se concentration and speciation, including selenate [Se(VI)], selenite [Se(IV)], and organic Se [org-Se or Se(-II)] in waters and sediment extracts, and fractionation (soluble, adsorbed, organic matter (OM)-associated, and Se(0) and other resistant forms) in sediments and organic-rich surface detrital layers from the decay of algal blooms. Selenium in ponds without vascular plants exhibited similar behavior to wetlands with vascular plant present, indicating that similar Se transformation processes and mechanisms had resulted in Se immobilization and an increase of reduced Se species [Se(IV), org-Se, and Se(0)] from Se(VI)-dominated input waters. Selenium concentrations in most pond waters were significantly lower than the influent drainage water. This decrease of dissolved Se concentration was accompanied by the increase of reduced Se species. Selenium accumulated preferentially in sediments of the initial pond cell receiving drainage water. Brine-shrimp harvesting activities did not affect Se speciation but may have reduced Se accumulation in surface detrital and sediments.     

Characterizing kinetics of transport and transformation of selenium in water-sediment microcosm free from selenium contamination using a simple mathematical model

This study developed a seven-compartment model for predicting the fate of selenium (Se) in an aquatic environment containing a water-sediment boundary. Speciation of Se in water-sediment microcosms under microaerobic conditions was measured to evaluate first-order kinetics of Se transportation and transformation. The microcosm consisted of a 10-ml solution containing 1mM soluble Se as selenate (Se6+) or selenite (Se4+) and 8 g wet sediment that was free from Se contamination, sampled from the Senri, Yamato, or Yodo Rivers in Osaka, Japan. Stepwise reaction coefficients describing transportation and transformation were determined using an inverse method on this model which includes: selenate (Se(W)6+) and selenite (Se(W)4+) in ponded water; selenate (Se(S)6+) and selenite (Se(S)4+), elemental Se (Se0), organic Se (Se2-) in sediment; and gaseous Se (DMSe). During this 1-month experiment, soluble Se was transported from ponded water to the sediment and Se was transformed sequentially to other Se species through biochemical reactions. Experimental and kinetic analyses indicated quantitatively that the Yamato River microcosm, with its high organic matter content, had a high adsorption rate of soluble Se. The Yodo River microcosm had a low adsorption rate for Se6+ and a low Se reduction rate. The Senri River microcosm had an apparent high volatilization rate of DMSe. The model developed in this study is extremely useful for predicting fate of Se in aquatic environment in the field.     

Selenium speciation and localization in chironomids from lakes receiving treated metal mine effluent

A lake system in northern Saskatchewan receiving treated metal mine and mill effluent contains elevated levels of selenium (Se). An important step in the trophic transfer of Se is the bioaccumulation of Se by benthic invertebrates, especially primary consumers serving as a food source for higher trophic level organisms. Chironomids, ubiquitous components of many northern aquatic ecosystems, were sampled at lakes downstream of the milling operation and were found to contain Se concentrations ranging from 7 to 80 mg kg⁻¹ dry weight. For comparison, laboratory-reared Chironomus dilutus were exposed to waterborne selenate, selenite, or seleno-DL-methionine under laboratory conditions at the average total Se concentrations found in lakes near the operation. Similarities in Se localization and speciation in laboratory and field chironomids were observed using synchrotron-based X-ray fluorescence (XRF) imaging and X-ray absorption spectroscopy (XAS). Selenium localized primarily in the head capsule, brain, salivary glands and gut lining, with organic Se species modeled as selenocystine and selenomethionine being the most abundant. Similarities between field chironomids and C. dilutus exposed in the laboratory to waterborne selenomethionine suggest that selenomethionine-like species are most readily accumulated, whether from diet or water.     

Influence of form and quantity of selenium on the development and survival of an insect herbivore

Even plants classified as 'nonaccumulators' can sequester concentrations of sodium selenate, sodium selenite, selenocystine and selenomethionine that can strongly influence insect development and survival. These forms of selenium (Se), tested in diet-incorporation bioassays, proved toxic to larvae of a generalist insect herbivore at relatively low levels. Sodium selenite was the most toxic form tested against Spodoptera exigua (Hübner), with an LC(50) of 9.14 microg g(-1) wet wt (21.11 microg g(-1) dry wt). Selenocystine was intermediate with an LC(50) of 15.2 microg g(-1) wet wt. The least toxic forms, sodium selenate and selenomethionine, had LC(50)s below 50 microg g(-1) dry wt, the upper level for tissues of plants classified as nonaccumulators. Ingestion of some forms of Se also affected growth and development. Increasing concentrations of sodium selenate and sodium selenite decreased pupal weight and added significantly to the time needed for development to the pupal and adult stages. The time required to complete the larval stage increased by over 25% and the time from egg to adult emergence was extended by 22% to nearly 30%. Selenocystine and selenomethionine did not significantly increase developmental times, even at concentrations that killed 90% or more of the test populations. Analyses of relative growth rate, relative growth index, and an analysis of covariance technique for measuring growth indicated that the form of Se affected growth rates, growth inhibition responses of the larvae, and toxicological effects. Thus, quantity and the form of Se accumulating in plants grown on Se-contaminated sites are likely to influence the population dynamics of insect herbivores. The implications of these results for the ecology of contaminated sites are discussed.     

Phosphorus and sulfur in a tropical soil and their effects on growth and selenium accumulation in Leucaena leucocephala (Lam.) de Wit

Selenium (Se) is an essential metalloid element for mammals. Nonetheless, both deficiency and excess of Se in the environment are associated with several diseases in animals and humans. Here, we investigated the interaction of Se, supplied as selenate (Se⁺⁶) and selenite (Se⁺⁴), with phosphorus (P) and sulfur (S) in a weathered tropical soil and their effects on growth and Se accumulation in Leucaena leucocephala (Lam.) de Wit. The P-Se interaction effects on L. leucocephala growth differed between the Se forms (selenate and selenite) supplied in the soil. Selenate was prejudicial to plants grown in the soil with low P dose, while selenite was harmful to plants grown in soil with high P dose. The decreasing soil S dose increased the toxic effect of Se in L. leucocephala plants. Se tissue concentration and total Se accumulation in L. leucocephala shoot were higher with selenate supply in the soil when compared with selenite. Therefore, selenite proved to be less phytoavailable in the weathered tropical soil and, at the same time, more toxic to L. leucocephala plants than selenate. Thus, it is expected that L. leucocephala plants are more efficient to phytoextract and accumulate Se as selenate than Se as selenite from weathered tropical soils, for either strategy of phytoremediation (decontamination of Se-polluted soils) or purposes of biofortification for animal feed (fertilization of Se-poor soils).

     

Factors controlling the bioaccumulation of mercury and methylmercury by the estuarine amphipod Leptocheirus plumulosus

The bioaccumulation of inorganic mercury (HgI) and monomethylmercury (MMHg) by benthic organisms and subsequent trophic transfer couples the benthic and pelagic realms of aquatic systems and provides a mechanism for transfer of sedimentary contaminants to aquatic food chains. Experiments were performed to investigate the bioavailability and bioaccumulation of particle-associated HgI and MMHg by the estuarine amphipod Leptocheirus plumulosus to further understand the controls on bioaccumulation by benthic organisms. HgI and MMHg are particle reactive and have a strong affinity for organic matter, a potential food source for amphipods. Microcosm laboratory experiments were performed to determine the effects of organic matter on Hg bioaccumulation and to determine the major route of Hg uptake (i.e. sediment ingestion, uptake from water/porewater, or uptake from 'food'). Amphipods living in organic-rich sediment spiked with Hg accumulated less Hg than those living in sediments with a lower organic matter content. Feeding had a significant impact on the amount of HgI and MMHg accumulated. Similarly, amphipods living in water with little organic matter accumulated more Hg than those living in water with a greater percentage of organic matter. MMHg was more readily available for uptake than HgI. Experimental results, coupled with results from a bioaccumulation model, suggest that accumulation of HgI and MMHg from sediment cannot be accurately predicted based solely on the total Hg, or even the MMHg, concentration of the sediment, and sediment-based bioaccumulation factors. All routes of exposure need to be considered in determining the accumulation of HgI and MMHg from sediment to benthic invertebrates.     

Differences in uptake and translocation of selenate and selenite by the weeping willow and hybrid willow

BACKGROUND, AIM, AND SCOPE: Due to its essentiality, deficiency, and toxicity to living organisms and the extensive use in industrial activities, selenium (Se) has become an element of global environmental and health concern. Se removal from contaminated sites using physical, chemical, and engineering techniques is quite complicated and expensive. The goal of this study was to investigate uptake and translocation of Se in willows and to provide quantitative information for field application whether Se phytoremediation is feasible and ecologically safe. MATERIALS AND METHODS: Intact pre-rooted plants of hybrid willows (Salix matsudana Koidz x alba L.) and weeping willows (Salix babylonica L.) were grown hydroponically and treated with selenite or selenate at 24.0 +/- 1 degrees C for 144 h. Removal of leaves was also performed as a treatment to quantify the effect of transpiration on translocation and volatilization of Se. At the end of the study, total Se in the hydroponic solution and in different parts of plant tissues was analyzed quantitatively by hydride generation-atomic fluorescence spectrometry. The capacity of willows to assimilate both chemical forms of Se was also evaluated using detached leaves and roots in sealed glass vessels in vivo. Translocation efficiency of Se in both plants was estimated. RESULTS: Significant amounts of the applied selenite and selenate were eliminated from plant growth media by willows during the period of incubation. Both willows showed a significantly higher removal rate for selenate than for selenite (p < 0.05). Substantial differences existed in the distribution of both chemical forms of Se in plant materials: lower stems and roots were the major sites for accumulation of selenite and selenate, respectively. Translocation efficiency for selenite was significantly higher than that for selenate in both willow species (p < 0.01). Compared to the intact trees, remarkable decrease in the removal rate of both chemical forms of Se was found for willows without any leaves (p < 0.01). Volatilization of Se by plant leaves was estimated to be approximately 10% of the total applied selenite or selenate. Significant reduction (>20%) of selenate was observed in the sealed vessel with excised roots of willows, whereas trace amounts of selenite were eliminated from the hydroponic solution in the presence of roots. Detached leaves from neither of them reduced the concentration of selenite or selenate in the solution. DISCUSSION: Due to the significant difference in the removal rate and the distribution of the two chemical forms of Se in plant materials, the conversion of selenate to selenite in hydroponic solution prior to uptake and within plant tissues is unlikely. An independent uptake and translocation mechanisms are likely to exist for each Se chemical species. Uptake of selenate is mediated possibly through an active transport mechanism, whereas that of selenite may possibly depend on plant transpiration. Uptake velocities of selenite are linear (zero-order kinetics), while selenate removal processes obey first-order kinetics. In experiments with detached leaves in closed bottles, the cuticle of leaves was the major obstacle to extract both chemical forms of Se from the hydroponic solution. Phytovolatilization is a biological process playing an important role in Se removal. CONCLUSIONS: Although faster removal rates of selenate than selenite from plant growth media were observed by both willow species, selenite in plant materials was more mobile than selenate. Significant decrease in removal rates of both chemical forms of Se was detected for willows without any leaves. Significant differences in extraction, assimilation and transport pathways for selenite and selenate exist in willow trees. RECOMMENDATIONS AND PERSPECTIVES: Phytoremediation of Se is an attractive approach of cleaning up Se contaminated environmental sites. More detailed investigation on the assimilation of Se in plant roots and transport in tissues will provide further biochemical evidence to explain the differences in uptake and translocation mechanisms between selenite and selenate in willows. A relevant phytoremediation scheme can then be designed to clean up Se contaminated sites. Willows show a great potential for uptake, assimilation and translocation of both selenite and selenate. Phytotreatment of Se is potentially an efficient and practical technology for cleaning up contaminated environmental sites.     

Cadmium and methylmercury bioaccumulation by nymphs of the burrowing mayflyHexagenia rigida from the water column and sediment

Based on a three compartment microcosm-water column, natural sediment,Hexagenia rigida nymphs-an experimental study was set up to compare cadmium (Cd) and methylmercury (MeHg) bioaccumulation by a burrowing mayfly species, after exposure via the water column or the sediment as initial contamination sources. Results from a wide concentration range for each exposure condition revealed very marked differences between the two metals: MeHg was readily accumulated from the two contamination sources, leading to important metal concentrations in the nymphs after the 2 weeks’ exposure; Cd bioaccumulation, on the other hand, was negligible when the metal was added to the water compartment, even though significant transfers were observed from the sediment source. The average Cd concentrations in the nymphs were proportional to the sediment contamination levels. Turbidity measurements in the water column, reflecting the bioturbation activity of the nymphs, revealed that the effect of Cd was significant, but only when the metal was initially added to the sediment. The results are discussed according to the uptake routes and the structural and functional properties of the biological barriers involved (gills and gut).     

Trophic relationships and health risk assessments of trace metals in the aquaculture pond ecosystem of Pearl River Delta,China

Cadmium, lead, zinc, Chromium, copper, nickel and manganese in sediments and in aquatic organisms were collected from the aquaculture pond ecosystem of the Pearl River Delta (PRD), China and analyzed to evaluate bioaccumulation and trophic transfer in food chains, as well as the potential health risk of exposure to the Hong Kong residents via dietary intake of these aquatic products. The results revealed that based on the biota–sediment accumulation factor, omnivorous fish and zooplankton accumulated more trace metals from sediment than carnivorous fish. Concentrations of seven trace metals in aquaculture pond of PRD significantly decreased with increasing trophic levels, showing that these trace metals were trophically diluted in predatory and omnivorous food chains. The hazard index values of all fish species were smaller than 1 for adults and children, indicating there was no health risk from the multiple metals via ingestion of the freshwater fish for the inhabitants.     

Absorption of selenium by Lactuca sativa as affected by carboxymethylcellulose

Several organic compounds of high molecular weight present in soil interact with selenium and may act as active binding agents affecting its availability in soil, and, consequently, selenium uptake by plants. This study is aimed at investigating the effects of polysaccharides on selenium speciation in soil and on selenium absorption by Lactuca sativa L. plants. Three-week-old seedlings were transplanted into pots filled with soil, and sodium selenite at rates of 1.5 and 5mgSekg(-1) of soil, or sodium selenate at a rate of 1.5mgSekg(-1) of soil were applied. Carboxymethylcellulose (CMC) was added to the soil at rates of 0, 3 and 30mgkg(-1) of soil. After 48 and 110d from transplanting plants were harvested, separated into root and shoot, and fresh and dry matter weights were recorded. Total selenium was determined in both soil and plant samples. A sequential extraction was used to investigate the different Se oxidation states and assess the availability of Se in soil after the final harvesting. Both selenite and selenate were absorbed by roots, but plants amended with Se(VI+) showed higher selenium concentration than plants amended with Se(IV+). Selenite appears to be less mobile than selenate both in soil and plants. The addition of carboxymethylcellulose to soil decreased the amount of selenium absorbed by plants. CMC interacted with Se, making it less mobile as evidenced by the increase in the insoluble fractions. The insoluble Se forms in soil may represent environmental Se sinks potentially available for plants if the substrate is re-used for subsequent growth cycles and selenium species are mobilized as a result of biological and chemical processes.     

Hexagenia rigida (ephemeroptera) as a biological model in aquatic ecotoxicology: experimental studies on mercury transfers from sediment

The accumulation of two mercury compounds--HgCl(2) and CH(3)HgCl--by Hexagenia rigida (burrowing mayfly nymphs) from contaminated sediments was investigated experimentally. Three exposure periods were selected: 7, 14 and 28 days. Results reveal a high capacity of this species for Hg accumulation and considerable differences between the two chemical forms of the metal. Thus, the amount of total mercury accumulated after 28 days' exposure would be 60 times greater for the organic form if the two compounds were initially added to the sediment in the same concentrations. No significant growth inhibition appears for the different experimental conditions studied. Data treatment at the organism level showed a positive linear correlation between the fresh weight and Hg content in the nymphs; this was especially marked when the exposure time was relatively long and Hg was in the form of CH(3)HgCl. The study of mercury distribution in the organs of Hexagenia rigida (gills and gut) and the examination of results obtained in similar experimental conditions after contamination of the nymphs via the water column showed the importance of the trophic route, via ingested sediment, for the bioaccumulation of the metal initially introduced into the sediment.     

Influence of sediment on the fate and toxicity of a polyethoxylated tallowamine surfactant system (MON 0818) in aquatic microcosms

The fate and toxicity of a polyethoxylated tallowamine (POEA) surfactant system, MON 0818, was evaluated in water-sediment microcosms during a 4-d laboratory study. A surfactant solution of 8 mg l(-1) nominal concentration was added to each of nine 72-l aquaria with or without a 3-cm layer of one of two natural sediments (total organic carbon (TOC) 1.5% or 3.0%). Control well water was added to each of nine additional 72-l aquaria with or without sediment. Water samples were collected from the microcosms after 2, 6, 24, 48, 72, and 96 h of aging to conduct 48-h toxicity tests with Daphnia magna and to determine surfactant concentrations. Elevated mortality of D. magna (43-83%) was observed in overlying water sampled from water-only microcosms throughout the 96-h aging period, whereas elevated mortality (23-97%) was only observed in overlying water sampled from water-sediment microcosms during the first 24h of aging. Measured concentrations of MON 0818 in water-only microcosms remained relatively constant (4-6 mg l(-1)) during the 96-h period, whereas the concentrations in overlying water from microcosms containing either of the two types of sediment dissipated rapidly, with half-lives of 13 h in the 3.0% TOC sediment and 18 h in the 1.5% TOC sediment. Both toxicity and the concentration of MON 0818 in overlying water decreased more rapidly in microcosms containing sediment with the higher percent TOC and clay and with a higher microbial biomass. Mortality of D. magna was significantly correlated with surfactant concentrations in the overlying water. These results indicate that the toxicity of the POEA surfactant in water rapidly declines in the presence of sediment due to a reduction in the surfactant concentration in the overlying water above the sediment.     

Separate dissolved and particulate trace metal budgets for an estuarine system: an aid for management decisions

The sources and sinks of dissolved and particulate Pb, Cu and Zn were determined for the main basin of Puget Sound to understand the effect man has had on metal concentrations in both the water column and in the sediments. Municipal, industrial and atmospheric sources contributed about 66% of the total Pb added to the main basin of Puget Sound during the early 1980s. Advective inputs were the major sources of total Cu and Zn (approximately 40%) while riverine and erosional sources contributed about 30%. The discharge of the particle-bound trace metals from rivers minimized the influence of particulate anthropogenic sources, which constituted 50%, 23% and 18% of the total particulate Pb, Cu and Zn inputs, respectively. While advective transport was the major source of dissolved Cu and Zn (approximately 60% of all dissolved inputs), industrial, municipal and atmospheric inputs contributed about 85%, 30% and 38% of the dissolved Pb, Cu and Zn inputs, respectively. The sources of dissolved and particulate Cu and Zn were comparable with the sinks within the errors of the analyses indicating their quasi-conservative nature. Advection removed about 60% of the total Cu and Zn added to the main basin while 40% was deposited in the sediments of Puget Sound. Because of this quasi-conservative nature of Cu and Zn, anthropogenic inputs of Cu and Zn were dispersed from the system more than they were contained within main basin sediments. About 75% of the dissolved Pb discharged into the main basin of Puget Sound was lost from the dissolved phase and was balanced by a similar gain in the particulate phase. Because of this extensive scavenging and the effective retention of particles within the main basin, about 70% of the total Pb added to the main basin was retained within its sediments. These separate mass balances have utility in management decisions because they show the relative contributions from different sources and demonstrate whether the influences of dissolved and particulate inputs are reflected solely in the water column or the sediments, respectively.     

Do tubificid worms influence the fate of organic matter and pollutants in stormwater sediments?

In urban area, management of stormwater leads to the accumulation of polluted sediments at the water-sediment interface of various aquatic ecosystems. In many cases, these sediments are colonised by dense populations of tubificid worms. However, the influence of tubificid worms on the fate of stormwater sediments has never been tackled. The aim of this study was to measure in sediment columns the influence of tubificid worms on sediment reworking, organic matter processing (O(2) uptake and release of NH(4)(+), NO(3)(-), PO(4)(3-), and dissolved organic carbon), release of hydrocarbons and heavy metals, and microbial characteristics. Results showed that tubificid worms increased the release of NH(4)(+), PO(4)(3-), and dissolved organic carbon by 2-, 4-, and 3-fold, respectively. O(2) uptake also increased by more than 35% due to tubificid activity. The increase in the percentages of active bacteria and hydrolytic activity in the presence of worms indicated that the higher sediment respiration was caused by the stimulation of microbial communities. A reduction of the number of sulphate-reducing bacteria in the uppermost layers of the sediment was attributed to the penetration of O(2) due to worm activity. These significant effects of tubificid worms were probably linked to the dense network of burrows, which enhanced the exchange surface between the water column and the sediment. No release of heavy metals and hydrocarbons to the water phase was detected in the sediment columns. Understanding the fate and effect of organic stormwater sediments in the natural environment requires the integration of the role of bioturbation in urban pollution studies.     

Uptake kinetics and interaction of selenium species in tomato (Solanum lycopersicum L.) seedlings

Environmental Science and Pollution Research - Selenite and selenate are two main selenium (Se) forms absorbed by plants. The comparative effects of selenite and/or selenate on Se uptake and...     

Modelling PCB bioaccumulation in a Baltic food web

A steady state model is developed to describe the bioaccumulation of organic contaminants by 14 species in a Baltic food web including pelagic and benthic aquatic organisms. The model is used to study the bioaccumulation of five PCB congeners of different chlorination levels. The model predictions are evaluated against monitoring data for five of the species in the food web. Predicted concentrations are on average within a factor of two of measured concentrations. The model shows that all PCB congeners were biomagnified in the food web, which is consistent with observations. Sensitivity analysis reveals that the single most sensitive parameter is log K(OW). The most sensitive environmental parameter is the annual average temperature. Although not identified amongst the most sensitive input parameters, the dissolved concentration in water is believed to be important because of the uncertainty in its determination. The most sensitive organism-specific input parameters are the fractional respiration of species from the water column and sediment pore water, which are also difficult to determine. Parameters such as feeding rate, growth rate and lipid content of organism are only important at higher trophic levels.     

Overexpressing both ATP sulfurylase and selenocysteine methyltransferase enhances selenium phytoremediation traits in Indian mustard

A major goal of our selenium (Se) phytoremediation research is to use genetic engineering to develop fast-growing plants with an increased ability to tolerate, accumulate, and volatilize Se. To this end we incorporated a gene (encoding selenocysteine methyltransferase, SMT) from the Se hyperaccumulator, Astragalus bisulcatus, into Indian mustard (LeDuc, D.L., Tarun, A.S., Montes-Bayón, M., Meija, J., Malit, M.F., Wu, C.P., AbdelSamie, M., Chiang, C.-Y., Tagmount, A., deSouza, M., Neuhierl, B., B?ck, A., Caruso, J., Terry, N., 2004. Overexpression of selenocysteine methyltransferase in Arabidopsis and Indian mustard increases selenium tolerance and accumulation Plant Physiol. 135, 377-383.). The resulting transgenic plants successfully enhanced Se phytoremediation in that the plants tolerated and accumulated Se from selenite significantly better than wild type. However, the advantage conferred by the SMT enzyme was much less when Se was supplied as selenate. In order to enhance the phytoremediation of selenate, we developed double transgenic plants that overexpressed the gene encoding ATP sulfurylase (APS) in addition to SMT, i.e., APSxSMT. The results showed that there was a substantial improvement in Se accumulation from selenate (4 to 9 times increase) in transgenic plants overexpressing both APS and SMT.     

Sediment processes and mercury transport in a frozen freshwater fluvial lake (Lake St. Louis, QC, Canada)

An open-bottom and a closed-bottom mesocosm were developed to investigate the release of mercury from sediments to the water column in a frozen freshwater lake. The mesoscosms were deployed in a hole in the ice and particulate mercury (Hg_P) and total dissolved mercury (TDHg) were measured in sediments and in water column vertical profiles. In addition, dissolved gaseous mercury (DGM) in water and mercury water/airflux were quantified. Concentrations of TDHg, DGM, and mercury flux were all higher in the open-bottom mesocosm than in the closed-bottom mesocosm. In this paper we focus on the molecular diffusion of mercury from the sediment in comparison with the TDHg accumulation in the water column. We conclude that the molecular diffusion and sediment resuspension play a minor role in mercury release from sediments suggesting that solute release during ebullition is an important transport process for mercury in the lake.     

Resuspension of contaminated field and formulated reference sediments Part I: Evaluation of metal release under controlled laboratory conditions

In aquatic systems where metal contaminated sediments are present, the potential exists for metals to be released to the water column when sediment resuspension occurs. The release and partitioning behavior of sediment-bound heavy metals is not well understood during resuspension events. In this study, the release of Cd, Cu, Hg, Ni, Pb and Zn from sediments during resuspension was evaluated using reference sediments with known physical and chemical properties. Sediment treatments with varying quantities of acid volatile sulfide (AVS), total organic carbon (TOC), and different grain size distributions were resuspended under controlled conditions to evaluate their respective effects on dissolved metal concentrations. AVS had the greatest effect on limiting release of dissolved metals, followed by grain size and TOC. Predictions of dissolved concentrations of Cd, Ni, Pb and Zn were developed based on the formulated sediment Σ_metal/AVS ratios with Σ_metal being the total sediment metal concentration. Predicted values were compared to measured dissolved metal concentrations in contaminated field sediments resuspended under identical operating conditions. Metal concentrations released from the field sediments were low overall, in most cases lower than predicted values, reflecting the importance of other binding phases. Overall, results indicate that for sulfidic sediments, low levels of the study metals are released to the dissolved phase during short-term resuspension.     

Oxygen,carbon, and nutrient exchanges at the sediment–water interface in the Mar Piccolo of Taranto (Ionian Sea,southern Italy)

In the shallow environment, the nutrient and carbon exchanges at the sediment–water interface contribute significantly to determine the trophic status of the whole water column. The intensity of the allochthonous input in a coastal environment subjected to strong anthropogenic pressures determines an increase in the benthic oxygen demand leading to depressed oxygen levels in the bottom waters. Anoxic conditions resulting from organic enrichment can enhance the exchange of nutrients between sediments and the overlying water. In the present study, carbon and nutrient fluxes at the sediment–water interface were measured at two experimental sites, one highly and one moderately contaminated, as reference point. In situ benthic flux measurements of dissolved species (O₂, DIC, DOC, N-NO₃ ^?, N-NO₂ ^?, N-NH₄ ⁺, P-PO₄ ^3?, Si-Si(OH)₄, H₂S) were conducted using benthic chambers. Furthermore, undisturbed sediment cores were collected for analyses of total and organic C, total N, and biopolymeric carbon (carbohydrates, proteins, and lipids) as well as of dissolved species in porewaters and supernatant in order to calculate the diffusive fluxes. The sediments were characterized by suboxic to anoxic conditions with redox values more negative in the highly contaminated site, which was also characterized by higher biopolymeric carbon content (most of all lipids), lower C/N ratios and generally higher diffusive fluxes, which could result in a higher release of contaminants. A great difference was observed between diffusive and in situ benthic fluxes suggesting the enhancing of fluxes by bioturbation and the occurrence of biogeochemically important processes at the sediment–water interface. The multi-contamination of both inorganic and organic pollutants, in the sediments of the Mar Piccolo of Taranto (declared SIN in 1998), potentially transferable to the water column and to the aquatic trophic chain, is of serious concern for its ecological relevance, also considering the widespread fishing and mussel farming activities in the area.