Methylmercury degradation and exposure pathways in streams and wetlands impacted by historical mining.

Monomethyl mercury (MMHg) and total mercury (THg) concentrations and Hg stable isotope ratios (δ(202)Hg and Δ(199)Hg) were measured in sediment and aquatic organisms from Cache Creek (California Coast Range) and Yolo Bypass (Sacramento Valley). Cache Creek sediment had a large range in THg (87 to 3870ng/g) and δ(202)Hg (-1.69 to -0.20‰) reflecting the heterogeneity of Hg mining sources in sediment. The δ(202)Hg of Yolo Bypass wetland sediment suggests a mixture of high and low THg sediment sources. Relationships between %MMHg (the percent ratio of MMHg to THg) and Hg isotope values (δ(202)Hg and Δ(199)Hg) in fish and macroinvertebrates were used to identify and estimate the isotopic composition of MMHg. Deviation from linear relationships was found between %MMHg and Hg isotope values, which is indicative of the bioaccumulation of isotopically distinct pools of MMHg. The isotopic composition of pre-photodegraded MMHg (i.e., subtracting fractionation from photochemical reactions) was estimated and contrasting relationships were observed between the estimated δ(202)Hg of pre-photodegraded MMHg and sediment IHg. Cache Creek had mass dependent fractionation (MDF; δ(202)Hg) of at least -0.4‰ whereas Yolo Bypass had MDF of +0.2 to +0.5‰. This result supports the hypothesis that Hg isotope fractionation between IHg and MMHg observed in rivers (-MDF) is unique compared to +MDF observed in non-flowing water environments such as wetlands, lakes, and the coastal ocean.

Isotopic Composition of Inorganic Mercury and Methylmercury Downstream of a Historical Gold Mining Region.

We measured total mercury (THg) and monomethyl mercury (MMHg) concentrations and mercury (Hg) isotopic compositions in sediment and aquatic organisms from the Yuba River (California, USA) to identify Hg sources and biogeochemical transformations downstream of a historical gold mining region. Sediment THg concentrations and δ(202)Hg decreased from the upper Yuba Fan to the lower Yuba Fan and the Feather River. These results are consistent with the release of Hg during gold mining followed by downstream mixing and dilution. The Hg isotopic composition of Yuba Fan sediment (δ(202)Hg = -0.38 ± 0.17‰ and Δ(199)Hg = 0.04 ± 0.03‰; mean ± 1 SD, n = 7) provides a fingerprint of inorganic Hg (IHg) that could be methylated locally or after transport downstream. The isotopic composition of MMHg in the Yuba River food web was estimated using biota with a range of %MMHg (the percent of THg present as MMHg) and compared to IHg in sediment, algae, and the food web. The estimated δ(202)Hg of MMHg prior to photodegradation (-1.29 to -1.07‰) was lower than that of IHg and we suggest this is due to mass-dependent fractionation (MDF) of up to -0.9‰ between IHg and MMHg. This result is in contrast to net positive MDF (+0.4 to +0.8‰) previously observed in lakes, estuaries, coastal oceans, and forests. We hypothesize that this unique relationship could be due to differences in the extent or pathway of biotic MMHg degradation in stream environments.

Assessment of typical pollutants in waterborne by combining active biomonitoring and integrated biomarkers response.

Organic pollutants, heavy metals and pharmaceuticals are continuously dispersed into the environment and have become a relevant environmental emerging concern. In this study, a situ assay to assess ecotoxicity of mixed pollutants was carried out in three typical sites with different priority contaminations in Guangzhou, China. Chemical analysis of organic pollutants, metals and quinolones in three exposure sites were determined by GC-ECD/MS, ICP-AES and HPLC, as well as, a combination of biomarkers including: ethoxyresorufin O-deethylase (EROD); aminopyrine N-demethylase (APND); erythromycin N-demethylase (ERND); glutathione S-transferase (GST); malondialdehyde (MDA); CYP1A; and P-glycoprotein (P-gp) mRNA expressions were evaluated in Mugilogobius abei. Results of chemical analysis in sediment samples revealed that the dominant chemicals were organic pollutants and heavy metals in Huadi River while quinolones in the pond. Bioassays indicated that differences among sites were in relation to some specific biomarkers. EROD and GST activities significantly increased after 72 h in situ exposure, but no difference was observed among the exposure sites. APND, ERND and MDA exhibited dissimilar change patterns for different priority pollutants. CYP1A and P-gp mRNA expressions were significantly induced at all exposure sites, whilst P-gp activity was typical for S2 with the highest levels of quinolones. The molecular biomarkers seemed to be more susceptible than enzyme activities. These assays confirmed the usefulness of applying a large array of various combined biomarkers at different levels, in assessing the toxic effects of mixed pollutants in a natural aquatic environment.

Toxic effects of erythromycin, ciprofloxacin and sulfamethoxazole on photosynthetic apparatus in Selenastrum capricornutum.

The effects of three antibiotics (erythromycin, ciprofloxacin and sulfamethoxazole) on photosynthesis process of Selenastrum capricornutum were investigated by determining a battery of parameters including photosynthetic rate, chlorophyll fluorescence, Hill reaction, and ribulose-1.5-bisphosphate carboxylase activity, etc. The results indicated that three antibiotics could significantly inhibit the physiological progress including primary photochemistry, electron transport, photophosphorylation and carbon assimilation. Erythromycin could induce acute toxic effects at the concentration of 0.06 mg L(-1), while the same results were exhibited for ciprofloxacin and sulfamethoxazole at higher than 1.0 mg L(-1). Erythromycin was considerably more toxic than ciprofloxacin and sulfamethoxazole and may pose a higher potential risk to the aquatic ecosystem. Some indices like chlorophyll fluorescence, Mg(2+)-ATPase activity and RuBPCase activity showed a high specificity and sensitivity to the exposure of erythromycin, and may be potentially used as candidate biomarkers for the exposure of the macrolide antibiotics.

Acute toxicity of mercury to Daphnia magna under different conditions.

We investigated the variations of acute toxicity of mercury (Hg) in Daphnia magna under different temperatures, population origins, body sizes, and Hg pre-exposures. We measured Hg concentrations in the water and in the surviving daphnids, and used the subcellular fractionation approach to determine Hg in the metal-sensitive fraction (MSF) to predict Hg toxicity. The 24-h median lethal concentrations and 24-h lethal body burden were 12-55 microg L(-1) and 10-26 mg kg(-1) wet wt, respectively. High Hg tolerance accompanied by reduced Hg uptake occurred in the daphnids under extreme conditions (low temperature and high pre-exposure to Hg). Correlating Hg levels in different compartments and daphnid survival resulted in the following order of sequence: aqueous Hg > whole body Hg > Hg in the MSF. However, the threshold lethal concentration of Hg (concentration causing 1% mortality) based on the concentration of Hg in the MSF was the best indicator of Hg toxicity. Therefore, the subcellular fractionation approach is less useful in explaining acute toxicity than is sub-lethal Hg toxicity. The number of Hg binding sites in the animals varied under different conditions but the affinity of the transporter to Hg generally decreased as the animals' tolerance increased. Mercury tolerance under different conditions could be enhanced by reducing the Hg uptake, enhancing the intrinsic tolerance, and/or increasing the detoxification activity.

Influences of macroalga-derived dissolved organic carbon on the aquatic toxicity of copper and cadmium.

In this study, the effect of dissolved organic carbon (DOC) derived from macroalga (Sargassum) on the acute toxicity of copper (Cu) and cadmium (Cd) to a freshwater cladoceran (Daphnia magna) was investigated. Potassium-loaded macroalga was incubated with ultrapure water to extract macroalgal DOC, which was then spiked with the constituents of the Elendt M7 hard water media. The 48 h median lethal concentration of Cu increased linearly with DOC levels but that of Cd was relatively independent of DOC levels (0-44 mg l(-1)). The independence of Cd toxicity on DOC level might be due to the competitive effect of high calcium concentrations in the media with Cd for the binding sites of DOC. The decreased Cu toxicity was a result of reduced Cu uptake as evidenced in a separate accumulation test. Also, the capability of the macroalgal DOC on reducing Cu toxicity was found to be comparable to DOC tested in other studies. Therefore, the present study suggested that the biosorption treatment process using macroalgae should consider the effect of DOC release from the biomass as a step of modifying the metal toxicity as well as influencing metal biosorption capacity.

A comparative study on metal sorption by brown seaweed.

This study compared the sorption of Ag, Cd, Co, Cd, Mn, Ni, Pb and Zn by a Ca-treated Sargassum biomass at pH 5.0, under low and high ionic strength (IS) conditions. The sorption isotherms of As [As(V)] and Cr [Cr(III) and Cr(VI)] were also determined at low IS. The isotherm data for the eight cationic metals and Cr(III) were well fitted by Langmuir equations. Generally, the maximum metal uptake (Umax) followed: Cr(III) > Pb approximately Cu > Ag approximately Zn approximately Cd > Ni approximately Mn approximately Co >> Cr(VI) >> As(V) at low IS and Pb > Cu > Co > Mn approximately Cd > Zn approximately Ag > Ni at high IS. As(V) did not bind to the seaweed at pH 5.0. The results indicated that sorption of Pb was not affected by the increasing IS, though the percentage of free Pb ions in the water was greatly reduced as predicted by the speciation model. High IS lowered Umax by 10-36% (except Co and Pb), and lowered the affinity constant of the metal by 33-91% for all cationic metals, as compared to low IS. Moreover, the removal efficiency of the cationic metals and Cr decreased exponentially with initial metal concentrations and was lower at high IS. Ion-exchange was the mechanism responsible for the cationic metal sorption onto the seaweed, and Na ion interfered with the cationic metal binding through electrostatic interaction. In conclusion, this study showed the differential binding capacity of the Sargassm biomass for different metals and oxidation states and the differential effects of IS. According to the present results, Sargassum may be considered a good biosorbent for cationic metals (especially Pb) in both low and high-salt containing wastewater.

Influences of maternal exposure on the tolerance and physiological performance of Daphnia magna under mercury stress.

We examined the tolerance development to mercury (Hg) by a population of freshwater zooplankton (Daphnia magna) with different pre-exposure histories to Hg. The growth and reproductive performance of the F1 offspring as affected by the maternal (F0) and offspring (F1) exposures was quantified. The F0 daphnids exposed to 2.5 and 25 nM of Hg for 4 d and followed by 4 d of depuration had elevated levels of Hg and metallothionein-like proteins (MTLPs), as well as higher tolerance to Hg toxicity than the control daphnids. The higher Hg tolerance may be attributed to the higher proportion of Hg partitioned to the MTLPs. Moreover, significant enhancement of Hg tolerance also was found in the F1 offspring originating from the F0 mothers exposed to 25 nM of Hg, but there was no significant induction of MTLPs in these F1 offspring when compared to the offspring from the control mothers. The Hg tissue concentrations in the F1 neonates were approximately 25% of those in the F0 adults. However, there was similar Hg tolerance in the F2 offspring originating from both the control and Hg-exposed F0 mothers, indicating that the Hg tolerance in the daphnids disappeared two generations after Hg contamination. Further exposure of the F1 offspring to different Hg concentrations (1.5 and 15 nM for 28 d) indicated that maternal exposure history did not affect their growth and reproductive performance, which solely were influenced by the offspring exposure. Unexpectedly, the F1 offspring exposed to Hg had significantly higher final wet weights and reproductive rates than the control groups, suggesting the possibility of Hg hormesis. Furthermore, the maternal exposure had no effect on the Hg accumulation and the MTLP concentrations in the F1 offspring. Therefore, we concluded that the Hg tolerance might disappear quickly once the Hg contamination was removed and the maternal exposure history was not important in determining the physiological performance and Hg accumulation of the subsequent generations.

Influence of glyphosate and its formulation (Roundup) on the toxicity and bioavailability of metals to Ceriodaphnia dubia.

This study examined the toxicological interaction between glyphosate (or its formulation, Roundup) and several heavy metals to a freshwater cladoceran, Ceriodaphnia dubia. We demonstrated that all binary combinations of Roundup and metals (Cd, Cu, Cr, Ni, Pb, Se and Zn) exhibited "less than additive" mixture toxicity, with 48-h LC50 toxic unit > 1. Addition of glyphosate alone could significantly reduce the acute toxicity of Ag, Cd, Cr, Cu, Ni, Pb and Zn (but not Hg and Se). The ratio between glyphosate and metal ions was important in determining the mitigation of metal toxicity by glyphosate. A bioaccumulation study showed that in the presence of glyphosate the uptake of some metals (e.g. Ag) was halted but that of others (e.g. Hg) was increased significantly. Therefore, our study strongly suggests that glyphosate and its commercial formulations can control the toxicity as well as the bioavailability of heavy metals in aquatic ecosystems where both groups of chemicals can co-occur.

Multigenerational acclimation of Daphnia magna to mercury: relationships between biokinetics and toxicity.

We examined the effects of multigenerational exposure of mercury (Hg) on Hg toxicity and biokinetics in a population of Daphnia magna. After chronic Hg exposure at 3.8 microg Hg/L, the first generation (F0) adults had an elevated 24-h median lethal concentration (LC50) of Hg (76 microg/L) when compared to the control adults (56 microg/L). The dissolved influx rate of Hg was depressed significantly in the Hg-treated adults, which was accompanied by a reduced ingestion rate and enhanced induction of metallothionein-like proteins (MTLP). The second-generation (F1) juveniles originating from the control and exposed lines had no major differences in these parameters (except the dietary assimilation efficiency). Recovery from Hg stress enhanced the vulnerability of F1 adults to Hg toxicity, with a reduced 48-h LC50 (44 microg/L) and a decreased concentration of MTLP (80% of control). Nevertheless, Hg-treated F1 adults had similar tolerance (in terms of LC50s) as the control line, indicating that D. magna acclimated to Hg stress after the first generation of exposure. No major difference occurred in the Hg biokinetics and toxicity among different groups of F2 daphnids. However, the F2 neonates produced by the Hg-treated F1 adults had much higher 48-h LC50 (149 microg/L) and MTLP concentration (148% of control) when there was continuous Hg exposure after birth. We concluded that acclimation to Hg stress occurred quickly in D. magna, though animals recovering from Hg stress were more vulnerable to Hg toxicity. Both ingestion rate and MTLP may not be good biomarkers of Hg stress in the field, because acclimation can be achieved through multigenerational exposure to elevated Hg concentrations.

Temperature influences on the accumulation and elimination of mercury in a freshwater cladoceran, Daphnia magna.

Temperature is an important environmental variable affecting the physiology and metabolism of aquatic invertebrates and can potentially affect the rate and pathway of the uptake and elimination of contaminants. In this study, we studied the effects of the ambient temperature on the uptake (from water and food) and elimination of inorganic mercury [Hg(II)] and methymercury (MeHg) in a freshwater cladoceran, Daphnia magna, in the laboratory. At different temperatures (i.e., 14, 19 and 24 degrees C), the assimilation efficiencies of both Hg species from ingested alga were not significantly different while the dissolved uptake rates were 32 and 73% lower at 14 degrees C than at 24 degrees C for Hg(II) and MeHg, respectively. The reduced uptake rates of Hg(II) at 14 degrees C could be adequately explained by the reduced filtration rate (40% reduction), but for MeHg, the reduced filtration rate could not completely explain reduction in MeHg uptake rate. Despite the elimination rates of both Hg compounds not being affected by the temperature, the relative importance of different routes of Hg loss (i.e., excretion, egestion, molting and reproduction) was significantly different at various temperatures. The relative importance of excretion to MeHg loss increased from 24 to 14 degrees C (i.e., 52 to 85% of Hg loss) while that of reproduction to MeHg loss decreased from 43 to 11% simultaneously. Using a kinetic model, we showed that the fraction of MeHg accumulated in the daphnids coming from the dietary phase was higher at lower temperature, while there was increased accumulation of both Hg(II) and MeHg in the daphnids at higher temperatures. Nevertheless, the trophic transfer potentials for both Hg species in this algae-daphnids food chain were not influenced by the temperature.

Maternal transfer efficiency and transgenerational toxicity of methylmercury in Daphnia magna.

We examined maternal transfer efficiency, retention by subsequent generations, and transgenerational toxicity of methylmercury (CH3Hg or MeHg) in a population of freshwater zooplankton (Daphnia magna). The effect of dietary MeHg residence time in the daphnids on the efflux system also was quantified. After ingesting a relatively high dosage of MeHg, D. magna exhibited a reduction of live neonates and an increase of undeveloped eggs (or embryos), which reflected the sublethal toxicity of MeHg. The daily maternal transfer efficiency of MeHg to both reproductive outputs ranged from 0.42 to 4.9% over different ages of the parental daphnids, which was dependent on the daily reproductive output. During the lifetime of D. magna, reproduction contributed to 10.8% +/- 1.74% (n = 3) SD of total MeHg loss from the parental daphnids. The percentage of MeHg retention by the second generation (F1) of D. magna (40-60%) was generally higher than that by the parental generation (F0; approximately 25%) after 20 d of depuration. Methylmercury imposed sublethal toxicity to the F0 and F1 generations, but a smaller effect was observed on the F2 generation. Because of the very low MeHg body burden in the subsequent generations, we hypothesized that factors other than MeHg, such as nutritional deficiency in the offspring contributed to the transgenerational toxicity. Different MeHg residence times did not significantly affect the efflux rate of MeHg but did significantly affect the relative importance of reproduction as the elimination pathway for MeHg. Based on the MeHg body burden of neonates, we estimated that MeHg took 2.5 to 3.0 d to be optimally transferred from assimilation (e.g., gut) to the site of egg development (e.g., brood chamber) in D. magna. Our study demonstrated that maternal transfer of MeHg in freshwater zooplankton is an important predictor of MeHg concentration in their offspring and is a time-dependent and highly dynamic process.

Comparative toxicity of glyphosate-based herbicides: aqueous and sediment porewater exposures.

Glyphosate-based herbicides are widely used for aquatic weed control. However, their aquatic toxicity data, especially those on sediment, are relatively scarce. In this study, the water-only acute toxicity of three formulations based on glyphosate (Rodeo, Roundup Biactive, and Roundup) were compared using a water-column organism (cladoceran: Ceriodaphnia dubia) and a benthic organism (amphipod: Hyalella azteca). In addition, Roundup Biactive and Roundup were spiked into a clean sediment which was amended with appropriate amounts of peat moss to study the effect of different organic carbon levels (0, 0.4, 1.2, and 2.1%) on their sediment toxicity, with C. dubia exposed to overlying water or porewater prepared from the contaminated sediments. Results showed that the toxicity based on 48-h LC50s for the three herbicides in the water-only tests was Roundup (1.5-5.7 mg L(-1)) > Roundup Biactive (82-120 mg L(-1)) > Rodeo (225-415 mg L(-1)), and H. azteca was generally more sensitive than C. dubia to these herbicides. Toxicity differences between formulations were due to the different surfactant components in these herbicides. From the porewater toxicity tests, Roundup Biactive (340 mg kg(-1)) and Roundup (244 mg kg(-1)) were similarly toxic in the sediment tests at 0% organic carbon, indicating that the surfactants in Roundup were considerably more adsorptive than those in Roundup Biactive to the sediment of the same organic carbon. Also, an increase in organic carbon significantly decreased the toxicity of Roundup in sediment, but not for Roundup Biactive. Sediment-porewater partitioning of glyphosate was found to be influenced by sediment organic carbon (i.e., glyphosate adsorption increased with sediment organic carbon).

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.

Aquatic toxicity of glyphosate-based formulations: comparison between different organisms and the effects of environmental factors.

Glyphosate-based herbicides (e.g. Roundup) are extensively used in the aquatic environment, but there is a paucity of data on the toxicity of the formulated products and the influences by environmental factors. In this study, the acute toxicity of technical-grade glyphosate acid, isopropylamine (IPA) salt of glyphosate, Roundup and its surfactant polyoxyethylene amine (POEA) to Microtox bacterium (Vibrio fischeri), microalgae (Selenastrum capricornutum and Skeletonema costatum), protozoa (Tetrahymena pyriformis and Euplotes vannus) and crustaceans (Ceriodaphnia dubia and Acartia tonsa) was examined and the relative toxicity contributions of POEA to Roundup were calculated. The effects of four environmental factors (temperature, pH, suspended sediment and algal food concentrations) on the acute toxicity of Roundup to C. dubia were also examined. Generally, the toxicity order of the chemicals was: POEA>Roundup>glyphosate acid>IPA salt of glyphosate, while the toxicity of glyphosate acid was mainly due to its high acidity. Microtox bacterium and protozoa had similar sensitivities towards Roundup toxicity (i.e. IC50 from 23.5 to 29.5 mg AE/l). In contrast, microalgae and crustaceans were 4-5 folds more sensitive to Roundup toxicity than bacteria and protozoa. Except photosynthetic microalgae, POEA accounted for more than 86% of Roundup toxicity and the toxicity contribution of POEA was shown to be species-dependent. Increase in pH (6-9) and increase of suspended sediment concentration (0-200 mg/l) significantly increased the toxicity of Roundup to C. dubia, but there were no significant effects due to temperature change and food addition.