Influence of humic acid on arsenic bioaccumulation and biotransformation to zebrafish: A comparative study between As(III) and As(V) exposure.

Previous studies have indicated that natural organic matter in the aquatic environment could affect arsenic bioaccumulation and biotransformation to aquatic organisms. However, the differences between the effects of arsenite and arsenate exposure have not been studied and compared in fish exposure models. In this study, adult zebrafish (Danio rerio) were exposed to 5 mg/L inorganic As solutions, in the presence of a range of humic acid (HA) concentrations (1, 2.5, 5, 10, 20 mg/L) in 96 h waterborne exposure. Results showed that in the presence of HA, total As bioaccumulation was significantly reduced in zebrafish following arsenite exposure, while this reduction was not observed during arsenate exposure. The reduction in total arsenic bioaccumulation for arsenite exposure can be explained by the fact that HA forming a surface coating on the cell surface, hindering transport and internalization. However, this reduction in total As was not observed due to differences in uptake pathways for arsenate exposure. Results also showed that Arsenobetaine (AsB) was the main biotransformation product in zebrafish following inorganic As exposure, accounting for 44.8%-64.7% of extracted arsenic species in all exposure groups. The addition of HA caused levels of MMA and As(III) to decrease, while the distribution of AsB significantly increased in arsenite exposure groups. The increase in AsB could be because the As(III)-HA complex was formed, affecting the methylation of As(III). In contrast, the addition of HA to arsenate exposure groups, did not affect the reduction of As(V) to As(III) and therefore, an increase in the distribution of AsB was not observed in arsenate exposure groups. This study provides useful information on the mechanisms of toxicity, for improved risk assessment of As in natural aquatic environments.

The Characterization of Dissolved Organic Matter in Reclaimed Water and Its Influence on Copper Toxicity.

Water samples were collected from five phases of treatment in a municipal sewage reclaimed water plant and the DOM was characterized. Results indicated that the components and properties of DOM varied notably with sequential treatments, such as the fluorescence intensity, the molecular weight and the total acidity. Meanwhile the accumulation of Cu in Daphnia magna was analyzed following exposure to samples spiked with 50 µg/L copper, which were decreased by the presence of DOM in those water samples. Furthermore, this study found significant associations between fluorescence intensity and Cu accumulation (r2 = 0.778, p < 0.05), while increased total acidity was found to enhance the unit total organic carbon-Cu accumulation (r2 = 0.979, p < 0.01). This study provides useful information on the safety and effective management of reclaimed water as a potential water resource.

Two-generational effects and recovery of arsenic and arsenate on Daphnia magna in the presence of nano-TiO2.

The toxicity of arsenic (As) can be influenced by many environmental factors. Among them, nanomaterials can adsorb arsenic and alter its bioavailability in organisms. However, the studies on long-term effects of arsenic in the presence of nanoparticles are limited. Thus, the 21-d effect of titanium dioxide nanoparticles (nano-TiO2) on chronic toxicity of arsenic (arsenate and arsenite) was investigated in two generations of Daphnia magna. The exposed concentration of nano-TiO2 was 1 mg/L and the concentration of As(Ⅲ) or As(Ⅴ) was 0.2 mg/L which was lower than the 48 h-NOEC (no observed effect concentration). The survival, body length, average number of offspring and time of first brood were determined. Our results indicated that the exposure to nano-TiO2 and As during the parental generation can affect the health of offspring. Nano-TiO2 was found to significantly alleviate the mortality and reproduction inhibition of As on D. magna, and the alleviation of As(Ⅴ) was more prominent than that of As(Ⅲ). It is likely that nano-TiO2 alters the metabolism and adsorption condition of arsenic in the gastrointestinal tract of D. magna. Overall, these results indicate that the increase of arsenic adsorption onto nano-TiO2 in the gut of D. magna could alleviate the toxicity of arsenic. Nonetheless, further research should be conducted to study the influence of arsenic on the multi-generations of aquatic organisms, especially when it is coexisted with other substances.

Biostabilization of cadmium contaminated sediments using indigenous sulfate reducing bacteria: Efficiency and process.

Sulfate reducing bacteria (SRB) was used to stabilize cadmium (Cd) in sediments spiked with Cd. The study found that the Cd in sediments (≤600 mg kg-1) was successfully stabilized after 166 d SRB bio-treatment. This was verified by directly and indirectly examining Cd speciation in sediments, mobilization index, and Cd content in interstitial water. After 166 d bio-treatment, compared with control groups, Cd concentrations in interstitial water of Cd-spiked sediments were reduced by 77.6-96.4%. The bioavailable fractions of Cd (e.g., exchangeable and carbonate bound phases) were reduced, while more stable fractions of Cd (e.g., Fe-Mn oxide, organic bound, and residual phases) were increased. However, Cd mobilization in sediment was observed during the first part of bio-treatment (32 d), leading to an increase of Cd concentrations in the overlying water. Bacterial community composition (e.g., richness, diversity, and typical SRB) played an important role in Cd mobilization, dissolution, and stabilization. Bacterial community richness and diversity, including the typical SRB (e.g., Desulfobacteraceae and Desulfobulbaceae), were enhanced. However, bacterial communities were also influenced by Cd content and its speciations (especially the exchangeable and carbonate bound phases) in sediments, as well as total organic carbon in overlying water.

Development of multi-metal interaction model for Daphnia magna: Significance of metallothionein in cellular redistribution.

Despite the great progress made in metal-induced toxicity mechanisms, a critical knowledge gap still exists in predicting adverse effects of heavy metals on living organisms in the natural environment, particularly during exposure to multi-metals. In this study, a multi-metal interaction model of Daphnia manga was developed in an effort to provide reasonable explanations regarding the joint effects resulting from exposure to multi-metals. Metallothionein (MT), a widely used biomarker, was selected. In this model, MT was supposed to play the role of a crucial transfer protein rather than detoxifying protein. Therefore, competitive complexation of metals to MT could highly affect the cellular metal redistribution. Thus, competitive complexation of MT in D. magna with metals like Pb2+, Cd2+ and Cu2+ was qualitatively studied. The results suggested that Cd2+ had the highest affinity towards MT, followed by Pb2+ and Cu2+. On the other hand, the combination of MT with Cu2+ appeared to alter its structure which resulted in higher affinity towards Pb2+. Overall, the predicted bioaccumulation of metals under multi-metal exposure was consisted with earlier reported studies. This model provided an alternative angle for joint effect through a combination of kinetic process and internal interactions, which could help to develop future models predicting toxicity to multi-metal exposure.

Trophic transfer of Cu, Zn, Cd, and Cr, and biomarker response for food webs in Taihu Lake, China.

Water, sediments, and aquatic organism samples were collected from Taihu Lake in China. Four types of typical heavy metal (Cu, Zn, Cd, and Cr) were analyzed to evaluate their concentrations and trophic transfer in food webs. The stable nitrogen isotope δ15N was used to investigate the trophic interactions. The concentrations of Cd and Zn in the sediments of Taihu Lake exceeded Level I of the China National Quality Standards for Soil. Zn accumulation was identified to increase with the trophic level. The bioconcentration of the four heavy metals in aquatic organisms was evident, with the invertebrates showing the highest bioconcentration factor in the food webs. Several biomarkers were investigated, including metallothionein (MT), malondialdehyde, and Na+/K+-adenosine triphosphatase activity. A positive correlation relationship was found between the MT content and heavy metal accumulation in organism tissues.

The Daphnia magna role to predict the cadmium toxicity of sediment: Bioaccumlation and biomarker response.

To evaluate Daphnia magna role to predict the Cd toxicity in contaminated sediment, the Cd accumulation, metallothionein (MT), and mortality of D. magna exposed to overlying water system or water-sediment coexistence system were measured. The mortality, Cd accumulation, and MT in D. magna increased with the increasing Cd content in sediment. The Cd accumulation and MT in D. magna exposed to the coexistence system were significantly higher than those exposed to the overlying water system because of the ingestion of Cd-containing sediments by D. magna. However, the mortality did not significantly differ in the two systems, suggesting that mortality was less sensitive than accumulation and MT. The Cd accumulation/MT index can explain why the two systems had the similar mortality but different Cd accumulation and MT. Not all the percentage composition of nonresidual fractions (e.g., exchangeable, carbonate bound, and organic bound phases) significantly correlated with the difference values of Cd accumulation and MT, as well as Cd accumulation/MT. However, these indexes increased with the percentage composition of the nonresidual fractions, indicating that the distribution of Cd chemical fractions is crucial for its bioavailability and biotoxicity.

Influences of size-fractionated humic acids on arsenite and arsenate complexation and toxicity to Daphnia magna.

The intrinsic physicochemical properties of dissolved organic matter (DOM) may affect the mobility and toxicity of arsenic in aquatic environments. In the present study, the humic acid (HA) was ultra-filtered into five fractions according to molecular weight, and their physicochemical properties were characterized. Complexation of HA fractions with arsenite and arsenate was first determined by differential pulse polarography (DPP). The influences of HA fractions on arsenic toxicity were then examined using Daphnia magna as a model organism. As(V) had a higher affinity with HA than As(III), and their complexation was dependent on the total acidity and fluorescence characteristics of DOM. We demonstrated that the acidity and fluorescence also better explained the As toxicity to daphnids than UV absorbance and hydraulic diameter. Arsenic speciation determined by DPP significantly affected the toxicity of arsenite and arsenate. The results extended the free-ion activity model application to the case of arsenic. The present study clearly indicated that DOM with different molecular weights has distinct physicochemical properties, and could influence the speciation and toxicity of As to different extent.

Effect of titanium dioxide nanoparticles on copper toxicity to Daphnia magna in water: Role of organic matter.

Inevitably released into natural water, titanium dioxide nanoparticles (nano-TiO2) may affect the toxicity of other contaminants. Ubiquitous organic matter (OM) may influence their combined toxicity, which has been rarely reported. This study investigated the effect of nano-TiO2 on Cu toxicity to Daphnia magna and the role of OM (dissolved or particle surface bound) in inducing combined effects. The effect of nano-TiO2 on heavy metal accumulation depended on the adsorption capacity for heavy metals of nano-TiO2 and the uptake of nano-TiO2-metal complexes by organisms. Nano-TiO2 significantly decreased Cu accumulation in D. magna, but the reducing effect of nano-TiO2 was eliminated in the presence of humic acid (HA, a model OM). In the Cu and HA solution, nano-TiO2 slightly affected the bioavailability of Cu2+ and Cu-HA complexes and thus slightly influenced Cu toxicity. The nanoparticle surface-bound HA reduced the effect of nano-TiO2 on the speciation of the accumulated Cu; therefore, the combined effects of nano-TiO2 and Cu on biomarkers similarly weakened. HA-altered Cu speciation may be the main factor responsible for the influence of HA on the combined effects of nano-TiO2 and Cu. This study provides insights into the combined effects of nano-TiO2 and heavy metals in natural water.

Bioaccumulation and oxidative stress in Daphnia magna exposed to arsenite and arsenate.

Arsenic pollution and its toxicity to aquatic organisms have attracted worldwide attention. The bioavailability and toxicity of arsenic are highly related to its speciation. The present study investigated the differences in bioaccumulation and oxidative stress responses in an aquatic organism, Daphnia magna, induced by 2 inorganic arsenic species (As(III) and As(V)). The bioaccumulation of arsenic, Na(+) /K(+) -adenosine triphosphatase (ATPase) activity, reactive oxygen species (ROS) content, total superoxide dismutase (SOD) activity, total antioxidative capability, and malondialdehyde content in D. magna were determined after exposure to 500 µg/L of arsenite and arsenate for 48 h. The results showed that the oxidative stress and antioxidative process in D. magna exposed to arsenite and arsenate could be divided into 3 phases, which were antioxidative response, oxidation inhibition, and antioxidative recovery. In addition, differences in bioaccumulation, Na(+) /K(+) -ATPase activity, and total SOD activity were also found in D. magna exposed to As(III) and As(V). These differences might have been the result of the high affinity of As(III) with sulfhydryl groups in enzymes and the structural similarity of As(V) to phosphate. Therefore, arsenate could be taken up by organisms through phosphate transporters, could substitute for phosphate in biochemical reactions, and could lead to a change in the bioaccumulation of arsenic and activity of enzymes. These characteristics were the possible reasons for the different toxicity mechanisms in the oxidative stress process of arsenite and arsenate.

Using enriched stable isotope technique to study Cu bioaccumulation and bioavailability in Corbicula fluminea from Taihu Lake, China.

In this study, we measured trace metals (Cd, Cr, Cu, Ni, Pb, and Zn) in water and sediment from representative sites of Taihu Lake, with focus on the analysis of trace metal accumulation in Corbicula fluminea (bivalve). The results showed that the quality of water in Taihu Lake was generally good and the correlation was not found between Cu bioaccumulation in C. fluminea and the concentration in water and sediment. Thus, using the stable isotope tracer method, we studied Cu uptake from the water phase, the assimilation of Cu from the food phase, and the efflux of Cu in vivo by C. fluminea. The result revealed that this species exhibited a relatively lower efflux rate constant of Cu compared with other zoobenthos species. Using a simple bioenergetics-based kinetic model, Cu concentrations in the C. fluminea were calculated with the measured efflux rate. We put forward a novel method, which was taking the influence of biological kinetic on metal bioaccumulation into account to explain the field survey data.