Biogeochemical mechanisms of selenium exchange between water and sediments in two contrasting lentic environments

The biogeochemical mechanisms of Se exchange between water and sediments in two contrasting lentic environments were assessed through examination of Se speciation in the water column, porewater, and sediment. High-resolution (7 mm) vertical profiles of <0.45 μm Se species across the sediment-water interface demonstrate that the behavior of dissolved Se(VI), Se(IV), and organo-Se are closely linked to redox conditions as revealed by porewater profiles of redox-sensitive species (dissolved O2, NO3-, Fe, Mn, SO4(2-), and ΣH2S). At both sites Se(VI) is removed from solution in suboxic near-surface porewaters demonstrating that the sediments are serving as diffusive sinks for Se. X-ray absorption near edge spectroscopy (XANES) of sediments suggests that elemental Se and organo-Se represent the dominant sedimentary sinks for dissolved Se. Dissolved Se(IV) and organo-Se are released to porewaters in the near-surface sediments resulting in the diffusive transport of these species into the water column, where between-site differences in the depths of release can be linked to differences in redox zonation. The presence or absence of emergent vegetation is proposed to present a dominant control on sedimentary redox conditions as well as on the recycling and persistence of reduced Se species in bottom waters.     

Uptake and elimination routes of inorganic mercury and methylmercury in Daphnia magna

Mercury (Hg) is an important environmental pollutant due to its highly toxic nature and widespread occurrence in aquatic systems. The biokinetics of Hg in zooplankton have been largely ignored in previous studies. This study examines the assimilation, dissolved uptake, and efflux of inorganic mercury [Hg(II)] and methylmercury (MeHg) in a freshwater cladoceran, Daphnia magna, and models the exposure pathways of Hg(II) and MeHg in the daphnids. The assimilation efficiencies (AEs) of both Hg species decreased significantly with increasing algal carbon concentrations. The dissolved uptake of Hg(II) and MeHg was proportional to the ambient concentration (ranging from environmentally realistic to high concentration over a 3-4 orders of magnitude variation), whereas MeHg had a slightly higher uptake rate constant (0.46 L g(-1) h(-1)) than Hg(II) (0.35 L g(-1) h(-1)). Surprisingly, the efflux rate constants of Hg(ll) and MeHg were rather comparable (0.041 -0.063 day(-1)). The release of both Hg(II) and MeHg via different routes (excretion, egestion, molting, and neonate production) was further examined at different food concentrations. It was found that regeneration into the dissolved phase was important for D. magna to eliminate both Hg species, but maternal transfer of Hg(II) (11-15%) and MeHg (32-41%) to neonates represented another important pathway for the elimination of Hg(II) and MeHg from the mothers. Modeling results suggest that food is an important source for MeHg exposure (47-98%), but water exposure represents 31-96% of Hg(II) accumulation in D. magna, depending on the variation of Hg bioconcentration factor in ingested food. Furthermore, MeHg predominates the bioaccumulation of Hg in D. magna even though MeHg constitutes only a small percentage of the total Hg in the water. The results strongly indicate that maternal transfer of Hg(II) and MeHg in freshwater zooplankton should be considered in manytoxicity testings and risk assessment in aquatic food chains.     

Experimental evidence of a linear relationship between inorganic mercury loading and methylmercury accumulation by aquatic biota

Developing effective regulations on mercury (Hg) emissions requires a better understanding of how atmospheric Hg deposition affects methylmercury (MeHg) levels in aquatic biota. This study tested the hypothesis that MeHg accumulation in aquatic food webs is related to atmospheric Hg deposition. We simulated a range of inorganic Hg deposition rates by adding isotopically enriched Hg(II) (90.9% 202Hg) to 10-m diameter mesocosms in a boreal lake. Concentrations of experimentally added ("spike") Hg were monitored in zooplankton, benthic invertebrates, and fish. Some Hg(II) added to the mesocosms was methylated and incorporated into the food web within weeks, demonstrating that Hg(II) deposited directly to aquatic ecosystems can become quickly available to biota. Relationships between Hg(II) loading rates and spike MeHg concentrations in zooplankton, benthic invertebrates, and fish were linear and significant. Furthermore, spike MeHg concentrations in the food web were directly proportional to Hg(II) loading rates (i.e., a percent change in Hg(II) loading rate resulted in, statistically, the same percent change in MeHg concentration). This is the first experimental determination of the relationship between Hg(II) loading and MeHg bioaccumulation in aquatic biota. We conclude that changes in atmospheric Hg deposition caused by increases or decreases in Hg emissions will ultimately affect MeHg levels in aquatic food webs.     

Contribution of coexisting sulfate and iron reducing bacteria to methylmercury production in freshwater river sediments

We investigated microbial methylmercury (CH(3)Hg) production in sediments from the South River (SR), VA, an ecosystem contaminated with industrial mercury (Hg). Potential Hg methylation rates in samples collected at nine sites were low in late spring and significantly higher in late summer. Demethylation of (14)CH(3)Hg was dominated by (14)CH(4) production in spring, but switched to producing mostly (14)CO(2) in the summer. Fine-grained sediments originating from the erosion of river banks had the highest CH(3)Hg concentrations and were potential hot spots for both methylation and demethylation activities. Sequencing of 16S rRNA genes of cDNA recovered from sediment RNA extracts indicated that at least three groups of sulfate-reducing bacteria (SRB) and one group of iron-reducing bacteria (IRB), potential Hg methylators, were active in SR sediments. SRB were confirmed as a methylating guild by amendment experiments showing significant sulfate stimulation and molybdate inhibition of methylation in SR sediments. The addition of low levels of amorphous iron(III) oxyhydroxide significantly stimulated methylation rates, suggesting a role for IRB in CH(3)Hg synthesis. Overall, our studies suggest that coexisting SRB and IRB populations in river sediments contribute to Hg methylation, possibly by temporally and spatially separated processes.     

Interpretation of in situ speciation measurements of inorganic and organically complexed trace metals in freshwater by DGT

The dynamic speciation technique, diffusive gradients in thin-films (DGT), has been used in freshwater to determine simultaneously, from a single set of in situ measurements, (1) the equilibrium distribution of metal ions between simple inorganic complexes and larger organic complexes and (2) information on the rates of dissociation of these complexes. DGT devices with different diffusion layer thicknesses (0.3, 0.54, 1.34, and 2.14 mm) were used to estimate the in situ dissociation kinetics. Information on the species distribution was obtained by using two types of gel, which allow relatively free (polyacrylamide, APA) and more retarded (restricted, RES) diffusion of the metal complexes. The full theoretical basis of the technique is developed and applied to in situ measurements of Mn, Fe, Co, Ni, Cu, Cd, and Pb in a pristine river (Wyre, U.K.), with high DOC(15mg L(-1)), assuming that organic complexes are dominated by fulvic acid. These first DGT measurements that do not rely on assumptions about complex lability or the distribution of species, are compared to total dissolved measurements, previously reported speciation calculations and measurements using alternative speciation techniques. Examination of calculation consistency suggests that the effective mean diffusion coefficients of metal complexes with organic matter under in situ conditions may be larger than those measured in the laboratory using extracted fulvic acid.     

离子色谱法测定酿造水和啤酒中的无机阴离子

啤酒中的无机阴离子主要来源于酿造水、麦芽、酒花及酿造辅料 ,其在啤酒中的含量及对啤酒质量的影响见表 1。表 1　啤酒中无机阴离子来源及对啤酒质量的影响无机阴离子啤酒中含量 (ｍｇ/ｋｇ)主要来源对啤酒质量的影响氯离子Ｃｌ- 1 2 2— 4 39酿造水淀粉水解粗糖添加赋予啤酒醇厚甜味感咸味硫酸根离子ＳＯ2 - 41 0 9— 4 2 9酿造水赋予啤酒淡泊口味草酸根离子ＣＯＯ- 6— 2 7麦芽酒花产生混浊和喷涌磷酸根离子ＰＯ3- 41 75— 587麦芽辅料硝酸根离子ＮＯ- 3 0 5— 2 0酿造水酒花啤酒异味高色度亚硝酸根离子ＮＯ- 2 微量酿造水麦芽致癌物啤…     

Absence of fractionation of mercury isotopes during trophic transfer of methylmercury to freshwater fish in captivity

We performed two controlled experiments to determine the amount of mass-dependent and mass-independent fractionation (MDF and MIF) of methylmercury (MeHg) during trophic transfer into fish. In experiment 1, juvenile yellow perch (Perca flavescens) were raised in captivity on commercial food pellets and then their diet was either maintained on unamended food pellets (0.1 μg/g MeHg) or was switched to food pellets with 1.0 μg/g or 4.0 μg/g of added MeHg, for a period of 2 months. The difference in δ(202)Hg (MDF) and Δ(199)Hg (MIF) between fish tissues and food pellets with added MeHg was within the analytical uncertainty (δ(202)Hg, 0.07 ‰; Δ(199)Hg, 0.06 ‰), indicating no isotope fractionation. In experiment 2, lake trout (Salvelinus namaycush) were raised in captivity on food pellets and then shifted to a diet of bloater (Coregonus hoyi) for 6 months. The δ(202)Hg and Δ(199)Hg of the lake trout equaled the isotopic composition of the bloater after 6 months, reflecting reequilibration of the Hg isotopic composition of the fish to new food sources and a lack of isotope fractionation during trophic transfer. We suggest that the stable Hg isotope ratios in fish can be used to trace environmental sources of Hg in aquatic ecosystems.     

Accumulation and depuration of polychlorinated biphenyls from field-collected sediment in three freshwater organisms

As laboratory-based bioaccumulation methods are standardized and expanded to include other test species, kinetic studies assessing the major classes of contaminants with these species are needed to adequately select the standard duration for bioaccumulation tests. In the present study we measured the uptake (28-d exposure) of polychlorinated biphenyls (PCBs; total and selected congeners) from field-contaminated sediment in the oligochaete Lumbriculus variegatus, mayfly nymph Hexagenia spp., and fathead minnow Pimephales promelas. Depuration (25 d) of PCBs was measured in organisms that had been transferred to clean sediment after the 28-d exposure. Uptake and elimination of PCBs was rapid in L. variegatus and Hexagenia spp. Tissue residues reached steady-state concentrations within 28 d; elimination rates and biota-sediment accumulation factors (BSAFs) of the PCB congeners were not correlated with K(OW). Uptake and elimination rates of PCBs were slower in P. promelas, and it is not clear whether steady-state was reached in fish tissues. Elimination rates of the PCB congeners significantly decreased with increasing K(OW) in fish. The appropriateness of a 28-d exposure for measuring steady-state concentrations in tissue of the invertebrates was confirmed, but further study is required for fish.     

高压离子色谱法快速测定水中7种无机阴离子

目的：建立高压离子色谱法快速测定水中氟离子、亚氯酸根离子、氯离子、硝酸根离子、氯酸根离子、溴离子、硫酸根离子7种无机阴离子含量的方法。方法：选用Dionex Integrion高压离子色谱仪和Ionpac AS19色谱分析柱，KOH淋洗液浓度为20 mmol/L、流速为2.00 mL/min条件下，通过抑制型电导检测器测定水中7种无机阴离子含量。结果：7种无机阴离子在7 min内实现分离，该方法的线性相关系数≥ 0.999，相对标准偏差＜2%，7种阴离子的样品加标回收率为95.3%~105.8%。结论：该方法具有简便快速、准确灵敏、环保高效等优点，适用于水质分析中7种无机阴离子的同时快速测定。     

Accumulation of copper and zinc in periphyton in response to dynamic variations of metal speciation in freshwater

Although the free ion activity model (FIAM) has been well-established in laboratory studies, there remains the need for field data in order to validate the applicability of this model in natural systems. The objective of this study was to investigate the response of copper and zinc accumulation in periphyton to short-term variations in metal concentration and speciation in freshwater. During heavy rain events, dissolved Cu in the Furtbach stream increased from 40 to 118 nM, while dissolved Zn increased from 45 to 147 nM due to the release of metals from contaminated sediments. Increases in free copper and free zinc ions in the water (from 10(-14) to 10(-11.5) M for Cu2+; from 1 to 15 nM for Zn2+) were observed during the onset of heavy rain events. Periphytic algae collected from artificial substrates had an intracellular copper content (0.2-2.8 micromol/g dry weight (dw)) that varied as a function of the exchangeable copper in the water (labile form) rather than the free Cu2+. Intracellular zinc content (1.5-8.0 micromol/g dw) was found to follow the same trend as the free zinc ion concentration. Adsorbed Cu and Zn on periphyton showed a very dynamic response to variations in dissolved metal concentration. Different concentrations of dissolved manganese during the two time periods may affect the accumulation of zinc and copper by competition for metal uptake.     

Accumulation of arsenic in drinking water distribution systems

The tendency for iron solid surfaces to adsorb arsenic is well-known and has become the basis for several drinking water treatment approaches that remove arsenic. It is reasonable to assume that iron-based solids, such as corrosion deposits present in drinking water distribution systems, have similar adsorptive properties and could therefore concentrate arsenic and potentially re-release it into the distribution system. The arsenic composition of solids collected from drinking water distribution systems (pipe sections and hydrant flush solids), where the waters had measurable amounts of arsenic in their treated water, were determined. The elemental composition and mineralogy of 67 solid samples collected from 15 drinking water utilities located in Ohio (7), Michigan (7), and Indiana (1) were also determined. The arsenic content of these solids ranged from 10 to 13 650 microg of As/g of solid (as high as 1.37 wt %), and the major element of most solids was iron. Significant amounts of arsenic were even found in solids from systems that were exposed to relatively low concentrations of arsenic (<10 microg/L) in the water.     

Spatial and seasonal variability of dissolved methylmercury in two stream basins in the eastern United States

We assessed methylmercury (MeHg) concentrations across multiple ecological scales in the Edisto (South Carolina) and Upper Hudson (New York) River basins. Out-of-channel wetland/floodplain environments were primary sources of filtered MeHg (F-MeHg) to the stream habitat in both systems. Shallow, open-water areas in both basins exhibited low F-MeHg concentrations and decreasing F-MeHg mass flux. Downstream increases in out-of-channel wetlands/floodplains and the absence of impoundments result in high MeHg throughout the Edisto. Despite substantial wetlands coverage and elevated F-MeHg concentrations at the headwater margins, numerous impoundments on primary stream channels favor spatial variability and lower F-MeHg concentrations in the Upper Hudson. The results indicated that, even in geographically, climatically, and ecologically diverse streams, production in wetland/floodplain areas, hydrologic transport to the stream aquatic environment, and conservative/nonconservative attenuation processes in open water areas are fundamental controls on dissolved MeHg concentrations and, by extension, MeHg availability for potential biotic uptake.     

Abiotic production of methylmercury by solar radiation

Methylmercury [MeHg(I) in the aerobic surface water of lakes is thought to be rapidly degraded, but contrary to expectations, we show that MeHg(I) concentrations often increase during sunlight hours or remain relatively constant. We hypothesized that there were water column processes that generated MeHg(I) and that these processes were linked to dissolved organic matter (DOM) and solar radiation. A 2-day diurnal pattern of MeHg(I) in surface water with corresponding bottled controls was assessed for two contrasting lakes in Kejimikujik, Nova Scotia, Canada. Following this study, a tangential ultrafiltrator was used to size-fractionate and generate a concentration gradient of DOM from four different lakes located near Lac Berthelot, Quebec, Canada. The watersheds of two of these lakes were not substantially logged whereas the other two had been extensively logged. Different size fractions of DOM as well as different concentrations of DOM were exposed to sunlight for varying periods of time. We observed that, in Keiimikujik, the concentration of MeHg(I) in surface waters peaked in the early afternoon. Furthermore, this also occurred in bottled water for one of the lakes, Puzzle, eliminating the possibility that in-lake mixing played a role in this pattern. The formation of MeHg(I) was found to be dependent on the size fraction and amount of DOM present in the water. Specifically, DOM less than 5 kDa or between 30 and 300 kDa generated MeHg(I) when exposed to sunlight, but larger fractions did not. Furthermore, although data are limited, we found that water from lakes with logged watersheds generated MeHg(I) when exposed to sunlight, whereas water from lakes with low levels of logging in the undisturbed watersheds did not. Our results demonstrate that MeHg(I) can be formed in freshwaters of certain lakes in response to solar radiation. This photoproduction of MeHg(I) is dependent on DOM concentrations and type, with the importance of water chemistry not yet clear. The significance of this process to freshwater lakes and the mechanism responsible for MeHg(I) photoproduction is still unclear, but a correction in the conventional wisdom that MeHg(I) is rapidly photodegraded is timely.     

两种无机纤维的分析鉴别方法

通过8种不同的物理及化学方法,对陶瓷纤维和玄武岩纤维的鉴别进行探索,总结出一套针对这两种无机纤维的系统鉴别方法:先用感官法确定未知纤维的归属类别,再选用热分析法达到对这两种无机纤维的鉴别目的。     

Muscle fibre characteristics of two contrasting sheep breeds: Scottish Blackface and Texel

This study evaluates the effects of breed and sex, together with those of birth weight and litter size, on muscle fibre type characteristics in Texel (TEX) and Scottish Blackface sheep (SBF). The M.longissimus thoracis et lumborum (LTL) of TEX had a significantly higher total muscle cross-sectional area (16%), a higher total fibre number (20%) and a higher muscle CT density (5%) than the SBF but had a similar average muscle fibre size. The frequency of slow fibres in the LTL in TEX was lower than in SBF (7.5% vs. 9.6%). Muscle fibre histochemistry similarly demonstrated that the oxidative fibre frequency in TEX was 10% lower than in SBF. The inter-fibre lipid content in TEX was also significantly lower than in SBF. Correspondingly, TEX displayed higher frequency (91.7% vs. 90.9% in SBF) and higher relative total area (92.5% vs. 90.4% in SBF) of fast fibres. These breed differences in muscle fibre traits indicate underlying genetic variation, and future analyses will evaluate the link of these traits to meat quality and assess the usefulness of these traits in breeding programmes.     

EPA and DHA quantification in two species of freshwater fish from Central Amazonia

The levels of the fatty acids EPA and DHA were determined for two species of fish (Hypophthalmus sp. and Cichla sp.), in the muscular tissue and in the orbital cavity, in two different seasonal periods in the Brazilian Amazonian area. Relatively high amounts (oil mg/g) for freshwater fish were found for DHA in the two species. Hypophthalmus sp. presented a higher concentration of EPA (20 ± 3 mg/g) and DHA (18 ± 3 mg/g) in the wet seasonal period in the muscular tissue, without a significant difference between the two acids. Higher concentrations of DHA were detected in the flood period in the muscular tissue (55 ± 9 mg/g) of Cichla sp. but with reduced concentrations of EPA (5 ± 1 mg/g).     

Kinetics and uptake mechanisms for monomethylmercury between freshwater algae and water

Uptake kinetics of monomethylmercury chloride (MeHgCl) were measured for two species of green algae (Selenastrum capricomutum and Cosmarium botrytis), one blue-green algae (Schizothrix calcicola), and one diatom (Thalassiosira weissflogii), algal species that are commonly found in natural surface waters. Species differences were found with the two green algae giving the highest uptake rates, and one of them (Cosmarium) showing differences between cultures having widely different cell age (exponential versus stationary), where increases in uptake rate for cells 30 days old were about 25 times greater than cells only 3 days old when weights of cells were considered. Both Schizothrix and Thalassiosira exhibited nearly the same lower uptake rates, approximately 20 times lower than the two green algal species. Experiments with photosystem inhibitors, uncouplers, gamma-radiation, light deprivation, and extended range uptake all point to an active transport mechanism for MeHgCl.     

Mercury and methylmercury bioaccessibility in swordfish

Concentrations of mercury (Hg) in swordfish (Xiphias gladius) present a food safety problem for many countries. This study analyses total Hg (t-Hg) concentrations in 27 samples of swordfish marketed in Spain in 2005 and in their bioaccessible fractions (soluble concentration in gastrointestinal medium), obtained after applying an in vitro digestion method. Methylmercury (MeHg) was also determined in the bioaccessible fractions. t-Hg concentrations in the samples were 0.41–2.11 mg kg^?1 wet weight, with a mean of 0.96 ± 0.47 mg kg^?1 wet weight. A total of 37% of the samples exceeded the Hg limit set by Spanish legislation (1.0 mg kg^?1 wet weight). Bioaccessible t-Hg concentrations were 0.17–1.72 mg kg^?1 wet weight (0.63 ± 0.4 mg kg^?1 wet weight), corresponding to 38–83% (64% ± 14%) of t-Hg. Bioaccessible MeHg concentrations, representing 94% of the bioaccessible t-Hg concentrations, were 0.16–1.53 mg kg^?1 wet weight, with a mean of 0.49 ± 0.32 mg kg^?1 wet weight. Children and adults who regularly consume this product in Spain have Hg and MeHg intakes that exceed the tolerable daily intake limits recommended by the Food and Agricultural Organization/World Health Organization (FAO/WHO) and US Environmental Protection Agency (USEPA). These results show the need for recommendations about swordfish consumption by population groups at risk in Spain.