Uptake and efflux of Cd and Zn by the green mussel Perna viridis after metal preexposure

Cadmium and zinc uptake from the dissolved phase, assimilation efficiency from the dietary phase, efflux rate constants, and body burden as well as clearance rate were measured in the green mussel Perna viridis with or without laboratory preexposure to Cd or Zn. Efflux rate constants and clearance rates were little affected by preexposure to either Cd or Zn. In contrast, the assimilation of Cd increased by 1.2-1.6 in mussels preexposed to Cd (subsequent Cd concentrations 10.2-25.9 microg(-1)) as compared to controls (0.19-0.39 microg g(-1)). This increase corresponded to an elevation in the proportion of Cd associated with the metallothionein-like proteins (MTLPs) in the mussels, suggesting that exposure to Cd and subsequent induction of MTLPs affected Cd accumulation. Exposure to Zn only resulted in elevated body concentrations following 7-d exposure to 250 microg L(-1), although Zn and Cd uptake from the dissolved phase were reduced by 24-47% by exposure to a lower concentration (100 microg L(-1)) for 7 and 21 d. Despite the lack of an increase in body Zn concentration, the subcellular distribution was altered such that the proportion of Zn associated with the metal-rich granules increased. This study indicates the importance of the subcellular distribution of metals in affecting the biokinetics and thus the toxic effects of metals on aquatic animals. Cd preexposure has potential effects on its influx from the dietary phase, e.g., increasing the importance of dietary uptake and further increasing the body burdens. In contrast, preexposure to Zn has a negative effect on Cd and Zn influx from the dissolved phase, suggesting the mechanism of Zn regulation but also potentially reducing Cd uptake and body concentrations over the long-term exposure. Such effects may have implications for biomonitoring studies involving a single species that modifies physiological processes affecting metal uptake (and hence bioavailability). Caution is needed in extrapolating data to species not capable of making such changes, particularly for Cd, which is not regulated and for which the effects of an elevated body burden are most obvious.     

Cd and Zn uptake kinetics in Daphnia magna in relation to Cd exposure history

The uptake kinetics of Cd and Zn in a freshwater cladoceran Daphnia magna after exposure to different concentrations of Cd for various durations was quantified. The accumulated Cd concentrations increased with ambient Cd concentration and exposure duration. As a detoxification mechanism, metallothioneins (MTs) were induced when the Cd preexposure condition was beyond the noneffect threshold. The MT induction was dependent on both Cd concentration and duration of preexposure. Increasing the Cd exposure concentration to 20 microg L(-1) for 3 d caused a 44% reduction in Cd assimilation efficiency (AE, the fraction assimilated by the animals after digestion) by the daphnids from the dietary phase, but a 2.4-fold increase in Zn AE. Generally, the dissolved metal uptake rate was not significantly affected by the different Cd preexposure regimes, except at a much higher Cd concentration (20 microg L(-1)) when the Zn influx was enhanced. Significant effects from Cd exposure on the ingestion rate of the daphnids were also observed. When the MT synthesis was not coupled with the accumulated Cd tissue burden (e.g., a delay in MT synthesis), apparent Cd toxicity on the feeding behavior and the Cd AE was observed, thus highlighting the importance of MTs in modifying the metal uptake kinetics of D. magna. Overall, daphnids responded to acute Cd exposure by reducing their Cd AE and ingestion, whereas they developed a tolerance to Cd following chronic exposure. The bioavailability of Zn was enhanced as a result of Cd preexposure. This study highlights the important influences of Cd preexposure history on the biokinetics and potential toxicity of Cd and Zn to D. magna.     

Uptake of aqueous and dietary metals by mussel Perna viridis with different Cd exposure histories

The influences of different Cd pre-exposure regimes (route, concentration, and duration of Cd exposure) on the bioavailability of Cd, Ag, Hg, and Zn to the green mussels Perna viridis were quantified in this study. Following pre-exposing the mussels to Cd, we measured the mussel's tissue Cd concentration and clearance rate, as well as the metal dietary assimilation efficiency (AE) and the influx rate from the dissolved phase of the four studied metals. Differences in the route (aqueous and dietary pathways) and the history of pre-exposure (combined Cd concentration and duration) did not significantly affect the subsequent Cd dietary and aqueous uptake. The Cd dietary AEs increased following both the dissolved and dietary Cd pre-exposure. There was a significant correlation between the Cd AE and the accumulated Cd body concentration in the mussels. Dietary assimilation of Hg and Zn also increased slightly (but not significantly) after Cd pre-exposure, but the AEs of Ag remained constant. Except for the significant decrease in the dissolved uptake of Hg, Cd pre-exposure did not apparently affect the uptake of the other three metals from the solution. Metal-metal interactions are likely to be affected by the specificity of metallothionein induction. Our study demonstrated that the Cd body concentration as well as the environmental Cd concentration instead of the history of pre-exposure was more important in affecting the Cd accumulation in the mussels. Such factors need to be considered in interpreting metal body concentrations in biomonitors.     

Effect of dissolved organic matter on the uptake of trace metals by American oysters

To examine the effects of dissolved organic matter on metal bioavailability, uptake of trace metals (Cd, Co, Hg, Cr, Ag, Zn) by American oysters (Crassostrea virginica) was compared between treatments with different dissolved organic carbon (DOC) concentrations and contrasting low molecular weight (LMW, 1 kDa) and high molecular weight (HMW, 1 kDa-0.2 micron) DOC fractions, using radiotracer techniques and short-term exposure experiments. Uptake rate constants (mL g-1 h-1) of metals, in general, increased with increasing DOC concentrations, with an initial decrease at lower DOC concentrations. Oyster dry weight concentration factors (DCF, mL g-1), determined at the end of exposure experiments (8 h), also increased for Cd, Co, Cr, Ag, and Zn, but decreased for Hg, with increasing DOC concentrations. Changes of metal uptake rate constants and DCF values with DOC concentration suggest that metal uptake pathways by American oysters vary from predominantly uptake (by diffusion of neutral) of free ionic, inorganically complexed, and LMW organic ligand complexed metals at very low DOC concentration to direct ingestion and digestion of HMW or colloidally complexed metals at higher DOC concentrations. Measured partition coefficients (Kc) between dissolved and colloidal phases were comparable between metals, ranging from 10(5.12) to 10(5.75) mL g-1. However, DCF values and uptake rate constants differed considerably between metals, with the highest DCF values and uptake rate constants found for B-type metals, e.g., Ag, Hg, Zn, and Cd, and the lowest ones for several intermediate-type metals (e.g., Co, Cr). Metal types and thus the interaction of metals with organic ligands, such as strong complexation of B-type metals with S-containing organic ligands, may play an important role in the bioavailability and toxicity of metals to aquatic organisms. Differences in metal uptake in contrasting LMW and HMW DOC treatments suggest a generally depressed bioavailability of colloidally complexed metals at low DOC concentration (0.5 ppm) but a generally enhanced uptake at higher DOC concentrations.     

Characterizing dissolved Cu and Cd uptake in terms of the biotic ligand and biodynamics using enriched stable isotopes

The biotic ligand model considers the biological and geochemical complexities that affect metal exposure. It relates toxicity to the fraction of physiological active sites impacted by reactive metal species. The biodynamic model is a complementary construct that predicts bioaccumulation and assumes that toxicity occurs when influx rates exceed rates of loss and detoxification. In this paper we presume that metal influx rates are mechanistically the resulting processes that characterize transmembrane transport. We use enriched stable isotopes to characterize, both in terms of the biotic ligand and biodynamics, dissolved metal uptake by a freshwater snail at water hardness varying up to 180-fold. Upon 24 h exposure, metal uptake was linear over a range encompassing most environmental concentrations; although saturation kinetics were observed at higher concentrations. Cadmium influx rates correlate with changes in the affinity of the biotic ligand, whereas those of Cu correlate with changes in both site affinity and capacity. A relationship between metal influx rate and ligand character asks whether toxicity is the result of accumulation at the biotic ligand or the rate at which metal is transported by that ligand.     

Uptake of dissolved Ag,Cd, and Co by the clam,Macoma balthica: relative importance of overlying water,oxic pore water,and burrow water

The facultative deposit-feeding clam Macoma balthica is used as a bioindicator organism for assessing coastal metal contamination. Previous work has evaluated the assimilation of metals from different possible food sources for this clam, but no studies have measured the uptake rates of metals from different dissolved sources. This study specifically compares three different dissolved sources: overlying water (SW), oxic pore water (OPW) from a depth of <1 cm (entrained during surface deposit feeding), and burrow water (BW) (a mixture of anoxic pore water and overlying water). Uptake rates of dissolved Ag, Cd, and Co in M. balthica were measured in short-term laboratory experiments using radiotracers. Clams were exposed to metals in water only for SW and surface OPW treatments. In the BW treatment, metal uptake was compared in clams placed in radiolabeled organic-poor or organic-rich sediment under conditions in which feeding was inhibited. Uptake rate constantsfrom SW for Ag, Cd, and Co were 0.35, 0.033, and 0.035 L g(-1) day(-1), respectively. Lower uptake of dissolved metals from OPW was noted but was only significant for Co. Metal uptake from BW and SW were also comparable; however, the trend showed lower Ag and higher Co uptake from BW. Metal distributions and concentrations in the two radiolabeled sediments were affected by active irrigation of SW into the burrows; dissolved metal concentrations in BW were approximately 30% lower than that in the bulk pore water concentrations. In the organic-rich sediment, Cd and Ag partitioned more in the dissolved phase (<0.2 microm) and Co more in the particulate phase as compared with the organic-poor sediment. A sensitivity analysis using measured rate constants for uptake and a range of metal concentrations from field studies suggested that, under most conditions, uptake of dissolved Ag is primarily from OPW, Co is mostly from BW, and Cd uptake varies depending on its concentration in each compartment. Little Co or Ag is likely to be taken up from SW, whereas 20-50% of Cd may be accumulated from this source. Thus, SW, OPW, and BW are all potential sources of metals for M. balthica, and the relative importance of these sources differs among metals and is dependent on the dissolved metal concentrations in each compartment.     

A biodynamic understanding of dietborne metal uptake by a freshwater invertebrate

Aquatic organisms accumulate metals from dissolved and particulate phases. Dietborne metal uptake likely prevails in nature, but the physiological processes governing metal bioaccumulation from diet are not fully understood. We characterize dietborne copper, cadmium, and nickel uptake by a freshwater gastropod (Lymnaea stagnalis) both in terms of biodynamics and membrane transport characteristics. We use enriched stable isotopes to trace newly accumulated metals from diet, determine food ingestion rate (IR) and estimate metal assimilation efficiency (AE). Upon 18-h exposure, dietborne metal influx was linear over a range encompassing most environmental concentrations. Dietary metal uptake rate constants (k(uf)) ranged from 0.104 to 0.162 g g(-1) day(-1), and appeared to be an expression of transmembrane transport characteristics. Although k(uf) values were 1000-times lower than uptake rate constants from solution, biodynamic modeling showed that diet is the major Cd, Cu, and Ni source in nature. AE varied slightly among metals and exposure concentrations (84-95%). Suppression of Cd and Cu influxes upon exposure to extreme concentrations coincided with a 10-fold decrease in food IR, suggesting that feeding inhibition could act as an end point for dietary metal toxicity in L. stagnalis.     

Acute toxicity of cadmium in Daphnia magna under different calcium and pH conditions: importance of influx rate

Water chemistry is generally thought to influence metal toxicity via affecting metal bioavailability and bioaccumulation, but its effects on tissue residue-based toxicity are poorly known. We conducted toxicity tests in parallel with uptake kinetics experiments of cadmium (Cd) in waters of different calcium (Ca) concentrations and pH levels using acclimated Daphnia magna as a model organism. Both the acute toxicity and uptake of Cd were reduced by higher Ca concentration and lower pH. Strikingly constant median effective influx rates (EJ(50), 1.3-1.6 μg g(-1) h(-1)) of Cd were observed when the concentration of Ca varied from 0.5 to 200 mg L(-1), indicating that acclimation to different Ca levels did not affect the tissue residue-based toxicity. The EJ(50) values increased consistently with decreasing pH level, showing that acclimation to acidic water decreased the tissue residue-based toxicity. With the use of calcium uptake inhibitors, we demonstrated that both Ca channel and Ca(2+)/Na(+) exchanger were involved in Cd uptake in daphnids, but there were also other possible pathways with higher affinity. The relative importance of different pathways was clearly dependent on the ambient Ca availability. Our findings are helpful for the development of a more accurate biotic ligand model in predicting the acute toxicity of Cd to daphnids.     

Influence of chloride and metals on silver bioavailability to Atlantic salmon (Salmo salar) and Rainbow trout (Oncorhynchus mykiss) yolk-sac fry

The effects of differing water chloride concentrations (0-10 mM) or competing metals [Cu(II), Cd(II), Zn(II), Pb(II), Co(II) (1-10,000 nM)] on Ag(I) uptake in yolk-sac fry of two salmonid species, the Atlantic salmon (Salmo salar) and rainbow trout (Oncorhynchus mykiss), were studied. None of the metals tested were strong competitors of Atlantic salmon yolk-sac fry whole body Ag(I) influx. Inhibition of Ag(I) influx was only seen with a 100-fold excess of Cu(II) or Cd(II) or a 1000-fold excess of Pb(II) or Co(II). At these concentrations, the degree of competition appears to be directly proportional to the conditional stability constant of the competing metal to the gill (metal-gill log K). The range of [Cl-] allowed an assessment of Ag+, AgCl(aq), and AgCl2- bioavailability. The pattern of Ag(I) uptake was similar for each fish species. At <1 mM Cl-, where the [Ag+] dominates, the Ag(I) accumulation rate was constant. Above 1 mM Cl-, where the [AgCl(aq)] is dominant and the [AgCl2-] increases, there was a decline in Ag(I) uptake rate. However, even when very little Ag+ was present (i.e., at 10 mM Cl-) Ag(I) accumulated, albeit at a lower rate. This was suggestive of passive influx by AgCl(aq) and indicated little or no entry of negatively charged silver chloride complexes. The decline in Ag(I) uptake above 1 mM Cl- demonstrated that, if Ag(I) was present as both Ag+ and AgCl(aq), salmonid Ag(I) accumulation was dominated by Ag+ uptake. Therefore, the order of bioavailability of the Ag(I) species was determined as Ag+ > AgCl(aq) > AgCl2-.     

Shifts in biodegradation kinetics of the herbicides MCPP and 2,4-D at low concentrations in aerobic aquifer materials

Biodegradation kinetics of two phenoxy acid herbicides, MCPP [(+/-)-2-(4-chloro-2-methylphenoxy)propanoic acid; mecoprop] and 2,4-D [2,4-dichlorophenoxyacetic acid] were studied in laboratory batch microcosms at low concentrations (0.025-100 microg/L) using 14C technique with sediments and groundwater from a shallow aerobic sandy aquifer. Below a certain threshold concentration of approximately 1 microg/L for 2,4-D and 10 microg/L for MCPP, the biodegradation followed first-order nongrowth kinetics, and no adaptation was observed within the experimental period of 341 d. Half-lifes for ultimate degradation were 500 d for 2,4-D and 1100 d for MCPP at 10 degrees C in unpolluted aquifer sediment in this environmentally relevant concentration regime. Above the threshold concentrations, the biodegradation rate accelerated gradually due to selective growth of specific biomass, which was ascertained from 14C most probable number enumerations of specific phenoxy acid degraders. Atthe highest concentration tested (100 microg/ L), specific degraders increased from 10(-1) to 10(5) cells/g during the experiment, and half-lifes after adaptation decreased to approximately 5 d. The enhanced rate of degradation by adapted systems was maintained during degradation of the last residuals measured to less than 0.1 microg/L. In situ long-term preexposure of the aquifer sediment also resulted in significant higher degradation rates of the phenoxy acids.     

Accumulation and toxicity of cadmium in the aquatic oligochaete Tubifex tubifex: a kinetic modeling approach

Heavy metal pollution is a serious threat to ecosystem functioning. Different approaches have been developed to relate the exposure of heavy metals to their accumulation and toxicity. One approach is to relate metal toxicity to the concentrations of the metals in the whole body or a specific target tissue instead of the external exposure concentrations. To test the usefulness of this approach, the relationship between cadmium exposure, accumulation, and toxicity was investigated using an oligochaete worm and kinetic modeling. The uptake and elimination of cadmium by the aquatic oligochaete Tubifex tubifex from the aqueous phase was studied as function of time at different exposure concentrations using both radioactive and non-radioactive cadmium. A two-compartmental pharmacokinetic model was constructed and parametrized by fitting the model to the measured cadmium body concentrations during exposure to different cadmium concentrations. The uptake rate constants were dependent on the cadmium exposure concentration, and this relation could be well-described by incorporation of Michaelis-Menten type uptake kinetics. The toxicity of cadmium was analyzed by determining the lethal exposure concentration associated with a mortality of 50% (LC50) at different time points. LC50 values decreased with increasing exposure time reaching the incipient lethal level after 15 d. Critical body concentrations (CBC) associated with 50% mortality were calculated by combining the model-predicted pharmacokinetic parameters and the measured LC50 values. The predicted mean CBC (0.32 micromol/g wet weight +/- 0.02) was in good agreement with the experimentally obtained CBC for cadmium found in T. tubifex (0.37 micromol/g wet weight +/- 0.07) and appeared to be independent of exposure time and exposure concentration. Our results show that a pharmacokinetic modeling approach provides a tool to link metal exposure to availability, accumulation, and toxicity under variable exposure scenarios taking into account the kinetics of the processes.     

Cadmium bioavailability and accumulation in the presence of humic acid to the zebra mussel, Dreissena polymorpha

Metal speciation in aquatic systems is mainly determined by the type and concentration of ligands present in solution. A very important group of complexing agents is dissolved organic matter (DOM), e.g., humic and fulvic acids. According to the free-ion activity model, only the free metal ion is available to biota. Nevertheless, DOM has been reported to decrease or increase metal uptake, leading to uncertainty concerning the bioavailability of metal-DOM complexes. In this work the effect of Aldrich humic acid on cadmium accumulation by the zebra mussel, Dreissena polymorpha, was studied under laboratory conditions. Mussels, collected in a drinking water reservoir, were exposed to varying environmentally relevant concentrations of cadmium in the presence and absence of humic acid. Cadmium concentrations in the mussel tissues were analyzed, and measurements with a cadmium-ion-selective electrode were made to determine the free cadmium ion activity in the exposure waters. The uptake of humic acid by the zebra mussels was measured by the decrease of the total organic carbon (TOC) concentration in the water over time. The free cadmium ion activity in the water decreased from 51.6% to 19.9% of the total cadmium concentration in the presence of humic acid. This decrease by a factor of 2.6 resulted in a decrease in the cadmium uptake rate in the soft tissue of zebra mussels from 12.9 to 7.9 nmol/g dry wt/day, which corresponds to a decrease by a factor of 1.6. This implies that cadmium uptake rates were higher than predicted by the free-ion activity model and indicates that cadmium-humic acid complexes are partly available to zebra mussels.     

Co-transport of metal complexes by the green mussel Perna viridis

We examined the uptake of ligand-bound metals (Cd and Zn) by the green mussel Perna viridis using defined artificial seawater. Different free ion concentrations (1 pM to 10 microM) in uptake solutions were created by adding different amounts of total metals (Cd 0.1 nM to 0.1 mM; Zn 0.5 nM to 0.05 mM) and ligands (EDTA, NTA, citric acid). Our results showed that Cd and Zn uptake could not be fully explained by the free Cd and Zn concentrations in the presence of different ligands, indicating that metal-ligand complexes were at least partially available for uptake by the mussels. Total Zn concentrations appeared to be a better predictor of metal uptake than the free Zn ion concentrations in the presence of different ligands. Uptake of lipophilic organic metal complexes was substantially greater than the hydrophilic metal complexes, even though the free ion concentration was comparable or lower. Moreover, the radiolabeled ligand compounds were directly accumulated by the mussels. The accumulation of metal complexes may explain the increased metal uptake with increasing ligand and total metal concentration, even though the free ion metal concentration was constant. Overall, our experimental results indicated that free metal ion cannot fully explain metal uptake since metal complex species were also available to the mussels to some extent, apparently through a co-transport process.     

Bioaccumulation dynamics and modeling in an estuarine invertebrate following aqueous exposure to nanosized and dissolved silver

Predicting the environmental impact of engineered nanomaterials (ENMs) is increasingly important owing to the prevalence of emerging nanotechnologies. We derived waterborne uptake and efflux rate constants for the estuarine snail, Peringia ulvae, exposed to dissolved Ag (AgNO(3)) and silver nanoparticles (Ag NPs), using biodynamic modeling. Uptake rates demonstrated that dissolved Ag is twice as bioavailable as Ag in nanoparticle form. Biphasic loss dynamics revealed the faster elimination of Ag from Ag NPs at the start of depuration, but similar slow efflux rate constants. The integration of biodynamic parameters into our model accurately predicted Ag tissue burdens during chronic exposure with 85% of predicted values within a factor of 2 of observed values. Zeta potentials for the Ag NPs were lower in estuarine waters than in waters of less salinity; and uptake rates in P. ulvae were slower than reported for the freshwater snail Lymnaea stagnalis in similar experiments. This suggests aggregation of Ag NPs occurs in estuarine waters and reduces, but does not eliminate, bioavailability of Ag from the Ag NPs. Biodynamic modeling provides an effective methodology to determine bioavailable metal concentrations (originating from metal and metal-oxide nanoparticles) in the environment and may aid future ENM risk assessment.     

Silver Nanoparticles Inhibit Sodium Uptake in Juvenile Rainbow Trout (Oncorhynchus mykiss)

The silver ion (Ag(+)) is well documented to be a potent inhibitor of sodium (Na(+)) transport in fish. However, it has not been determined whether silver nanoparticles (Ag NPs) elicit this same effect and, if so, if the NP itself and/or the dissociation of ionic Ag(+) causes this effect. Citrate-capped Ag NPs were dialyzed in water to determine the dissolution rate of ionic Ag(+) from the NPs and the maximum concentration of free Ag(+) released from the NPs was used as a paired Ag(+) control to distinguish NP effects from ionic metal effects. The maximum concentration of ionic Ag(+) released from these NPs over 48 h was 0.02 μg l(-1). Juvenile rainbow trout were exposed to 1.0 mg l(-1) citrate-capped Ag NPs and dialyzed citrate-capped Ag NPs or 10 μg l(-1) and 0.02 μg l(-1) ionic Ag(+) (as AgNO(3)) as controls. Both nondialyzed and dialyzed Ag NPs and 10 μg l(-1) ionic Ag(+) significantly inhibited unidirectional Na(+) influx by over 50% but had no effect on unidirectional Na(+) efflux. Na(+),K(+)-ATPase was significantly inhibited by the Ag NPs with no discernible effect on carbonic anhydrase activity. This study is the first to show that sodium regulation is disrupted by the presence of citrate-capped Ag NPs, and the results suggest that there are nanospecific effects.     

Use of transplanted Zebra mussels (Dreissena polymorpha) to assess the bioavailability of microcontaminants in Flemish surface waters

Zebra mussels (Dreissena polymorpha) were translocated in cages to 56 water bodies in Flanders (Belgium) during summer 2001. After six weeks, concentrations of polychlorinated biphenyls (PCBs), hexachlorobenzene (HCB), p,p'-DDE, and trace metals were measured in the transplanted mussels. It was investigated whether total dissolved water and sediment pollutant levels or bioaccumulation factors (BAFs) and biota-sediment accumulation factors (BSAFs) were predictive for mussel tissue levels. The sample sites covered a broad range both in terms of the type and concentration of the pollutants, and this was reflected in large differences in tissue concentrations of all pollutants among the sites. The highest pollutant levels in mussels were among the highest reported in the literature. For Cd and Zn levels up to 33 and 1994 microg/g dry wt. respectively were found. The lowest levels were comparable to those from uncontaminated sites in Europe and the U.S. For Cd and Zn respectively 51 and 75% of the variation in tissue levels was described. For both metals, dissolved and particulate metal contributed to the variation in accumulation. For other pollutants, relationships between tissue concentration and water or sediment concentration were weak or nonsignificant. Then the measured environmental factors (dissolved calcium, pH, oxygen, organic carbon and clay content in the sediment) were taken into account applying multiple regression analysis, and no increase in the described variation of pollutant accumulation was observed. The BAF and BSAF for all pollutants varied up to 1000-fold even after TOC-normalization. Clear negative relationships were found between BAFs/ BSAFs and environmental levels. However, even at constant environmental concentrations a 10- to 100-fold variation in BAFs/BSAFs was observed. This study illustrated the need for biological monitoring since neither environmental     

Modeling the primary size effects of citrate-coated silver nanoparticles on their ion release kinetics

Ion release is an important environmental behavior of silver nanoparticles (AgNPs), and characterization of Ag(+) release is critical for understanding the environmental fate, transport, and biological impacts of AgNPs. The ion release kinetics of AgNPs with three primary diameters (20, 40, and 80 nm) were studied by dispersing them in quarter-strength Hoagland medium at two initial concentrations (300 and 600 μg/L). Ag(+) release rates were found to depend on primary particle size and concentration, when other environmental factors (e.g., dissolved oxygen and protons) were kept constant. A kinetic model was developed to describe the Ag(+) release based on the hard sphere theory using the Arrhenius equation. The model fitted the experimental data well with correlation coefficients of 0.97-0.99, and the model usefully interpreted the dependence of ion release kinetics on the primary particle size and concentration. Moreover, the effects of environmental factors (e.g., dissolved oxygen, pH, temperature, and salinity) potentially can be interpreted as well. This model provides fundamental insight into the ion release kinetics of AgNPs in aqueous environments, allowing us to better understand and predict the nanotoxicity of AgNPs.     

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.     

Understanding the differences in Cd and Zn bioaccumulation and subcellular storage among different populations of marine clams

The marine clams Mactra veneriformis were collected from three different locations in a contaminated bay in Northern China. Another species of clams Ruditapes philippinarum was collected from the same contaminated bay as well as from a relatively clean site in Hong Kong. The indices of Cd and Zn bioaccumulation (assimilation efficiency, dissolved uptake rate, and efflux rate), tissue concentration, subcellular distribution, metallothionein (MT) content, and clearance rate of the clams were subsequently quantified in these populations in the laboratory. In the two species of clams, the population with a higher Cd tissue concentration assimilated Cd and Zn more efficiently, in correlation with an increase in the Cd associated with the metallothionein-like protein (MTLP) fraction. The subcellular partitioning of Zn was similar among the different populations. The dissolved uptake rates of Cd and Zn were not influenced by the different tissue concentrations of metals in the clams. However, the clam R. philippinarum from the contaminated site reduced their Zn uptake rate constants in response to increasing Zn concentration in the water. Differences in Cd and Zn tissue concentrations had little influence on the metal efflux rate constant and the clams' clearance rate. Our results indicate that the higher Cd and Zn tissue concentrations observed in these two species may be partially caused by the high levels of metal assimilation. Populations living in contaminated environments may be able to modify their physiological and biochemical responses to metal stress, which can subsequently alter trace metal bioaccumulation to aquatic animals. The relative significance of dietary uptake and the potential trophic transfer of metals in the contaminated areas may be substantially different from those in the clean environments.     

Dynamic passive dosing for studying the biotransformation of hydrophobic organic chemicals: microbial degradation as an example

Biotransformation plays a key role in hydrophobic organic compound (HOC) fate, and understanding kinetics as a function of (bio)availability is critical for elucidating persistence, accumulation, and toxicity. Biotransformation mainly occurs in an aqueous environment, posing technical challenges for producing kinetic data because of low HOC solubilities and sorptive losses. To overcome these, a new experimental approach based on passive dosing is presented. This avoids using cosolvent for introducing the HOC substrate, buffers substrate depletion so biotransformation is measured within a narrow and defined dissolved concentration range, and enables high compound turnover even at low concentrations to simplify end point measurement. As a case study, the biodegradation kinetics of two model HOCs by the bacterium Sphingomonas paucimobilis EPA505 were measured at defined dissolved concentrations ranging over 4 orders of magnitude, from 0.017 to 658 μg L(-1) for phenanthrene and from 0.006 to 90.0 μg L(-1) for fluoranthene. Both compounds had similar mineralization fluxes, and these increased by 2 orders of magnitude with increasing dissolved concentrations. First-order mineralization rate constants were also similar for both PAHs, but decreased by around 2 orders of magnitude with increasing dissolved concentrations. Dynamic passive dosing is a useful tool for measuring biotransformation kinetics at realistically low and defined dissolved HOC concentrations.