Biotic Ligand Research Articles

Application of biotic ligand and toxicokinetic–toxicodynamic modeling to predict the accumulation and toxicity of metal mixtures to zebrafish larvae

Predicting the accumulation and toxicity of mixtures of metals to aquatic organisms is a key challenge in ecotoxicological studies. In this study, the accumulation and toxicity of mixed essential (Cu) and nonessential (Cd and Pb) metals in zebrafish larvae exposed to a binary mixture of these elements at environmentally relevant concentrations were predicted using a refined toxicokinetic (TK)–toxicodynamic (TD) model aided with biotic ligand model (BLM) and toxic equivalent factor (TEF) approach. Competitive inhibition and non-competitive interaction/inhibition were observed in bio-uptake. Both Pb and Cd behaved as competitive inhibitors of Cu uptake at high Cu concentrations (>0.1 μM). By contrast, Cu uptake was independent of Cd or Pb when the Cu concentrations were below 10−7 M. Furthermore, low concentrations of Cu had an adiaphorous effect on Cd or Pb uptake. Cd uptake was inhibited by Pb, and the Pb uptake rates consistently decreased in the presence of Cd. The accumulation processes of Cd–Pb, Cu–Cd, and Cu–Pb were accurately predicted by the BLM-aided TK models. The traditional TD model could successfully predict the toxicity of Cd–Pb mixtures, but not those of Cu–Cd or Cu–Pb mixtures. The revised TD model, which considered the possible different killing rates (Kk) above or below the threshold, offered better prediction for the toxicity of Cu–Cd or Cu–Pb mixtures. The overall findings may be of key significance in understanding and predicting metal uptake, accumulation, and toxicity in binary or multiple metal exposure scenarios.

Predicting copper phytotoxicity based on pore-water pCu.

The free ion activity and "biotic ligand" models predict that the free metal ion and other pore-water parameters describe terrestrial phytotoxicity. In this study, pore-water chemistry and measured Cu(2+) was used to describe phytotoxicity of cucumber (Cucumis sativa L) in 10 contrasting soils at different soil Cu loadings. Both soil solution Cu (Cu(pw)) and Cu(2+) successfully described the response variable for all ten soils with R(2) values of 0.73 and 0.66, respectively. Separation of soils as acid and alkaline and fitting separately showed that there was a strongly significant fit for both log Cu(2+) and log Cu(pw) in acidic soils (R(2) = 0.92 and 0.86, respectively) but weakly significant fit for alkaline soils. The pCu EC50 and EC10 values in all acidic soils for cucumber were 5.83 (6.03-5.63) and 7.53 (8.27-7.00), respectively. In our dataset alkaline soils need to be treated individually. In addition, pCu could be predicted based on pH and total concentration alone. Despite only 12 weeks 'ageing' there was quantitative agreement between pCu model from this study and predicted pCu from Sauvé et al. This agreement from studies performed independently indicates that, at least in the case of Cu(2+), the difference in an ageing period of ≥10 years appears minimal.

塩分濃度が変化する汽水域中の銅のヤマトシジミに対する毒性のBiotic Ligand Modelによる予測

塩分濃度が変化する汽水域中の銅のヤマトシジミに対する毒性のBiotic Ligand Modelによる予測

Coupled metal partitioning dynamics and toxicodynamics at biointerfaces: a theory beyond the biotic ligand model framework.

A mechanistic understanding of the processes governing metal toxicity to microorganisms (bacteria, algae) calls for an adequate formulation of metal partitioning at biointerfaces during cell exposure. This includes the account of metal transport dynamics from bulk solution to biomembrane and the kinetics of metal internalisation, both potentially controlling the intracellular and surface metal fractions that originate cell growth inhibition. A theoretical rationale is developed here for such coupled toxicodynamics and interfacial metal partitioning dynamics under non-complexing medium conditions with integration of the defining cell electrostatic properties. The formalism explicitly considers intertwined metal adsorption at the biointerface, intracellular metal excretion, cell growth and metal depletion from bulk solution. The theory is derived under relevant steady-state metal transport conditions on the basis of coupled Nernst-Planck equation and continuous logistic equation modified to include metal-induced cell growth inhibition and cell size changes. Computational examples are discussed to identify limitations of the classical Biotic Ligand Model (BLM) in evaluating metal toxicity over time. In particular, BLM is shown to severely underestimate metal toxicity depending on cell exposure time, metal internalisation kinetics, cell surface electrostatics and initial cell density. Analytical expressions are provided for the interfacial metal concentration profiles in the limit where cell-growth is completely inhibited. A rigorous relationship between time-dependent cell density and metal concentrations at the biosurface and in bulk solution is further provided, which unifies previous equations formulated by Best and Duval under constant cell density and cell size conditions. The theory is sufficiently flexible to adapt to toxicity scenarios with involved cell survival-death processes.

When are metal complexes bioavailable?

Environmental contextThe concentration of a free metal cation has proved to be a useful predictor of metal bioaccumulation and toxicity, as represented by the free ion activity and biotic ligand models. However, under certain circumstances, metal complexes have been shown to contribute to metal bioavailability. In the current mini-review, we summarise the studies where the classic models fail and organise them into categories based on the different uptake pathways and kinetic processes. Our goal is to define the limits within which currently used models such as the biotic ligand model (BLM) can be applied with confidence, and to identify how these models might be expanded. AbstractNumerous data from studies over the past 30 years have shown that metal uptake and toxicity are often best predicted by the concentrations of free metal cations, which has led to the development of the largely successful free-ion activity model (FIAM) and biotic ligand model (BLM). Nonetheless, some exceptions to these classical models, showing enhanced metal bioavailability in the presence of metal complexes, have also been documented, although it is not yet fully understood to what extent these exceptions can or should be generalised. Only a few studies have specifically measured the bioaccumulation or toxicity of metal complexes while carefully measuring or controlling metal speciation. Fewer still have verified the fundamental assumptions of the classical models, especially when dealing with metal complexes. In the current paper, we have summarised the exceptions to classical models and categorised them into five groups based on the fundamental uptake pathways and kinetic processes. Our aim is to summarise the mechanisms involved in the interaction of metal complexes with organisms and to improve the predictive capability of the classic models when dealing with complexes.

Regulatory Implementation of the Copper Biotic Ligand Model for Aquatic Life Protection: What Have We Learned and How Are We Doing?

Regulatory Implementation of the Copper Biotic Ligand Model for Aquatic Life Protection: What Have We Learned and How Are We Doing?

Silver Biotic Ligand Model (BLM): Refinement of an Acute BLM for Silver

The biotic ligand model (BLM) is a computational tool that may be used to predict toxic effect levels of metals, including Ag. The BLM considers the effect of site-specific water quality characteristics on Ag speciation and bioavailability. This provides a basis for extrapolating from laboratory waters, used for most Ag toxicity tests, to natural waters, where the bioavailability and toxicity of Ag may differ. The original version of the BLM for the acute toxicity of Ag was reviewed by the USEPA Science Advisory Board (SAB) in 1999 and they recommended the completion of additional Ag chemistry and toxicity studies to provide data to test and refine the model. This project was completed to satisfy these recommendations. A chemistry component was completed to improve the representation of Ag speciation in natural waters and to characterize the important effect of sulfide on Ag bioavailability. These investigations added to the information that was available to characterize Ag chemistry and provided a basis for updating the earlier version of the Ag BLM. The BLM was also calibrated to laboratory toxicity data that were generated for a Ag-sensitive invertebrate, Ceriodaphnia dubia, a cladoceran that had previously been tested to only a limited degree. The studies were carried out in laboratory waters in which the chemistry was systematically varied to provide a basis for calibration of the BLM to the toxicity data for C. dubia. Toxicity tests were also performed with both Pimephales promelas and C. dubia in natural water samples that were well characterized chemically, with the data then used to test the model. While the C. dubia BLM results were relatively successful at simulating the observed effect levels the P. promelas results highlighted the need for further testing and refinement of the Ag BLM as it was applied to this fish species. Physiological tests were performed to explore the apparent increase in sensitivity of P. promelas in some of the test waters that were relatively low in ionic strength. It was determined that acclimation to such low ionic strength waters, in the absence of Ag, did not significantly reduce their sensitivity to Ag. Rather, it appeared that any benefit that may have been realized by acclimation, such as an enhanced ability to upregulate ion uptake rates in low ionic strength waters, was apparently offset by a concomitant increase in the rate at which Ag was accumulated. The Ag BLM was modified to account for the effect of low ionic strength water on the sensitivity to Ag of > 4-day old P. promelas. This led to an improved ability of the BLM to predict P. promelas effect levels in the natural waters. Physiological tests were also performed to investigate the apparent species-specific protection against Ag toxicity that is provided by chloride. Investigations with P. promelas suggested that the differences in degree of protection may be related to differences in how Ag affects the ionoregulation of Na+ and Cl− by different fish species. Although questions remain with regard to chloride, it appears that the BLM is able to predict this response reasonably well, particularly for the relatively sensitive <4 day old P. promelas. In summary, the WERF program yielded an improved chemistry and toxicity database, including data over an extended range of water quality characteristics and for an additional Ag-sensitive invertebrate, thereby providing a basis for refining the acute Ag BLM and improving its overall predictive ability.This title belongs to WERF Research Report SeriesISBN: 9781780403656 (eBook)ISBN: 9781843397960 (Print)

Acute toxicity of binary-metal mixtures of copper, zinc, and nickel to Pimephales promelas: Evidence of more-than-additive effect.

Metal mixture toxicity has been studied for decades. However, the results are not consistent, and thus ecological risk assessment and regulation of mixtures has been difficult. The objective of the present study was to use a systematic experimental design to characterize the toxicity of binary-metal mixture of Cu, Zn, and Ni to Pimephales promelas, typically to determine whether the effect of these binary-metal mixtures on P. promelas is more-than-additive. Standard 96-h toxicity tests were conducted with larval P. promelas based on US Environmental and Protection Agency methods to determine metal mixture effects. All experiments were conducted in synthetic moderately hard water with no addition of dissolved organic matter. Three different effect analysis approaches, the MixTox model, the Finney model, and the toxic unit method, were used for comparison. The results indicate that the toxicity of Cu+Zn, Cu+Ni, and Zn+Ni mixtures to P. promelas was more-than-additive. Among the 3 mixtures, the effect of the Cu+Ni mixture was the most profound. The results of the present study are useful for applications to models such as the metal mixture biotic ligand model. More research should be conducted to determine the mechanisms of acute and chronic toxicity of metal mixtures.

Acute dysprosium toxicity to Daphnia pulex and Hyalella azteca and development of the biotic ligand approach

The toxicological understanding of rare earth elements (REEs) in the aquatic environment is very limited but of increasing concern. The objective of this research is to compare the toxicological effect of the REE dysprosium to the freshwater invertebrates Daphnia pulex and Hyalella azteca and in the more sensitive organism, understand the toxicity modifying influence of Ca, Na, Mg, pH and dissolved organic matter (DOM). Standard methods (Environment Canada) were followed for testing and culture in media of intermediate hardness (60mg CaCO3 mg/L) at pH 7.8 with Ca at 0.5, Na 0.5, Mg 0.125 (mM) and 23°C. Acute toxicity tests were done with <24h old neonates for 48h in the case of D. pulex and with 2–9 days old offspring for 96h tests with Hyalella. The potential protective effect of cationic competition was tested with Ca (0.5–2.0mM), Na (0.5–2.0mM) and Mg (0.125–0.5mM). The effect of pH (6.5–8.0) and Suwannee River DOM complexation (at dissolved organic carbon (DOC) concentrations of 9 and 13mg C/L) were evaluated. Dissolved Dy concentrations were lower than total (unfiltered) indicating precipitation, particularly at higher concentrations. Acute toxicity of Dy to H. azteca and D. pulex revealed Hyalella to be 1.4 times more sensitive than Daphnia. Additions of Ca and Na but not Mg provided significant protection against Dy toxicity to Hyalella. Similarly, low pH was associated with reduction in toxicity. Exposures which were pH buffered with and without MOPS were significantly different and indicated that MOPS enhanced Dy toxicity. DOM also mitigated Dy toxicity. Biotic ligand based parameters (LogK values) were calculated based on free ion relationships as determined by geochemical equilibrium modeling software (WHAM ver. 7.02). The logK value for Dy3+ toxicity to Hyalella was 7.75 while the protective influence of Ca and Na were 3.95 and 4.10, respectively. This study contributes data towards the development of site specific water quality guidelines and criteria for Dy and possibly REEs in general and offers insight into the complex bio-geochemical nature of this element.

Modeling of acute cadmium toxicity in solution to barley root elongation using biotic ligand model theory

Protons (H+) as well as different major and trace elements may inhibit cadmium (Cd) uptake in aquatic organisms and thus alleviate Cd toxicity. However, little is known about such interactions in soil organisms. In this study, the independent effects of the cations calcium (Ca2+), magnesium (Mg2+), potassium (K+), H+ and zinc (Zn2+) on Cd toxicity were investigated with 5-day long barley root elongation tests in nutrient solutions. The tested concentrations of selected cations and trace metal ions were based on the ranges that occur naturally in soil pore water. The toxicity of Cd decreased with increasing activity of Ca2+, Mg2+, H+ and Zn2+, but not K+. Accordingly, conditional binding constants were obtained for the binding of Cd2+, Ca2+, Mg2+, H+, and Zn2+ with the binding ligand: logKCdBL 5.19, logKCaBL 2.87, logKMgBL 2.98, logKHBL 5.13 and logKZnBL 5.42, respectively. Furthermore, it was calculated that on average 29% of the biotic ligand sites needed to be occupied by Cd to induce a 50% decrease in root elongation. Using the estimated constants, a biotic ligand model was successfully developed to predict the Cd toxicity to barley root elongation as a function of solution characteristics. The feasibility and accuracy of its application for predicting Cd toxicity in soils were discussed.

Prediction of acute toxicity of cadmium and lead to zebrafish larvae by using a refined toxicokinetic-toxicodynamic model

The biotic ligand model (BLM) and the toxicokinetic-toxicodynamic (TK-TD) model are essential in predicting the acute toxicity of metals in various species and exposure conditions; however, these models are usually separately utilized. In this study, a mechanistic TK-TD model was developed to predict the acute toxicity of 10−6M Cd and 10−6M Pb to zebrafish (Danio rerio) larvae. The novel approach links the BLM with relevant TK processes to simulate the bioaccumulation processes of Cd or Pb as a function of the maximum uptake rate of each metal, the affinity constants, and the concentrations of free metal ions and H+ in test solutions. Results showed that the refined TK-TD model can accurately predict the accumulation and acute toxicity of Cd and Pb to zebrafish larvae at pH 5.5, 6.5, and 7.0.

Predictions of Cu toxicity in three aquatic species using bioavailability tools in four Swedish soft freshwaters.

BackgroundThe EU member countries are currently implementing the Water Framework Directive to promote better water quality and overview of their waters. The directive recommends the usage of bioavailability tools, such as biotic ligand models (BLM), for setting environmental quality standards (EQS) for metals. These models are mainly calibrated towards a water chemistry found in the south central parts of Europe. However, freshwater chemistry in Scandinavia often has higher levels of DOC (dissolved organic carbon), Fe and Al combined with low pH compared to the central parts of Europe. In this study, copper (Cu) toxicities derived by two different BLM software were compared to bioassay-derived toxicity for Pseudokirchneriella subcapitata, Daphnia magna and D. pulex in four Swedish soft water lakes.ResultsA significant under- and over prediction between measured and BLM calculated toxicity was found; for P. subcapitata in three of the four lakes and for the daphnids in two of the four lakes. The bioassay toxicity showed the strongest relationship with Fe concentrations and DOC. Furthermore, DOC was the best predictor of BLM results, manifested as positive relationships with calculated LC50 and NOEC for P. subcapitata and D. magna, respectively.ConclusionResults from this study indicate that the two investigated BLM softwares have difficulties calculating Cu toxicity, foremost concerning the algae. The analyses made suggest that there are different chemical properties affecting the calculated toxicity as compared to the measured toxicity. We recommend that tests including Al, Fe and DOC properties as BLM input parameters should be conducted. This to observe if a better consensus between calculated and measured toxicity can be established.

Copper toxicity and the influence of water quality of Dongnai River and Mekong River waters on copper bioavailability and toxicity to three tropical species

The present study investigated copper (Cu) toxicity and the influence of water quality characteristics of Dongnai River and Mekong River (Vietnam) surface waters to three tropical species; Daphnia lumholtzi, Ceriodaphnia cornuta, and Danio rerio. The river waters had a range of water quality parameters that modify Cu bioavailability and toxicity. The range of total hardness, alkalinity, pH and dissolved organic carbon were 15-64 mg/L as CaCO3, 18-58 mg/L as CaCO3, 6.62-7.88, and 6.9-14.7 mg/l, respectively. The US EPA acute toxicity test method with a modification to the light photoperiod and temperature for tropical organisms was used to investigate Cu toxicity. Result of the present study found that Cu produced toxic effect to the studied organisms at low concentrations. The 48-h LC50 ranged from 3.92 to 8.61 µg/l, 2.92-9.56 µg/l, and 15.71-68.69 µg/l dissolved Cu for D. lumholtzi, C. cornuta, and D. rerio, respectively. In general, water quality had an influence on Cu bioavailability and toxicity to the studied organisms. The toxicity of Cu was higher in water with lower hardness, DOC, and/or pH. The present study indicates a contribution of Cu hydroxide and carbonate to Cu bioavailability to Mekong organisms. Results of the present study will be used for calibrating the US Cu Biotic Ligand Model (BLM) to Mekong River water and organisms in support of application of the BLM for setting site-specific Cu water quality guidelines in the ecosystem of the Lower Mekong River Basin.

Uptake routes and toxicokinetics of silver nanoparticles and silver ions in the earthworm Lumbricus rubellus.

Current bioavailability models, such as the free ion activity model and biotic ligand model, explicitly consider that metal exposure will be mainly to the dissolved metal in ionic form. With the rise of nanotechnology products and the increasing release of metal-based nanoparticles (NPs) to the environment, such models may increasingly be applied to support risk assessment. It is not immediately clear, however, whether the assumption of metal ion exposure will be relevant for NPs. Using an established approach of oral gluing, a toxicokinetics study was conducted to investigate the routes of silver nanoparticles (AgNPs) and Ag(+) ion uptake in the soil-dwelling earthworm Lumbricus rubellus. The results indicated that a significant part of the Ag uptake in the earthworms is through oral/gut uptake for both Ag(+) ions and NPs. Thus, sealing the mouth reduced Ag uptake by between 40% and 75%. An X-ray analysis of the internal distribution of Ag in transverse sections confirmed the presence of increased Ag concentrations in exposed earthworm tissues. For the AgNPs but not the Ag(+) ions, high concentrations were associated with the gut wall, liver-like chloragogenous tissue, and nephridia, which suggest a pathway for AgNP uptake, detoxification, and excretion via these organs. Overall, the results indicate that Ag in the ionic and NP forms is assimilated and internally distributed in earthworms and that this uptake occurs predominantly via the gut epithelium and less so via the body wall. The importance of oral exposure questions the application of current metal bioavailability models, which implicitly consider that the dominant route of exposure is via the soil solution, for bioavailability assessment and modeling of metal-based NPs.

Biotic ligand modeling approach: Synthesis of the effect of major cations on the toxicity of metals to soil and aquatic organisms.

The biotic ligand model (BLM) approach is used to assess metal toxicity, taking into account the competition of other cations with the free metal ions for binding to the biotic ligand sites of aquatic and soil organisms. The bioavailable fraction of metals, represented by the free metal ion, is a better measure than the total concentration for assessing their potential risk to the environment. Because BLMs are relating toxicity to the fraction of biotic ligands occupied by the metal, they can be useful for investigating factors affecting metal bioaccumulation and toxicity. In the present review, the effects of major cations on the toxicity of metals to soil and aquatic organisms were comprehensively studied by performing a meta-analysis of BLM literature data. Interactions at the binding sites were shown to be species- and metal-specific. The main factors affecting the relationships between toxicity and conditional binding constants for metal binding at the biotic ligand appeared to be Ca(2+) , Mg(2+) , and protons. Other important characteristics of the exposure medium, such as levels of dissolved organic carbon and concentrations of other cations, should also be considered to obtain a proper assessment of metal toxicity to soil and aquatic organisms.

Temporal assessment of copper speciation, bioavailability and toxicity in UK freshwaters using chemical equilibrium and biotic ligand models: Implications for compliance with copper environmental quality standards

Although significant progress has been made in understanding how environmental factors modify the speciation, bioavailability and toxicity of metals such as copper in aquatic environments, the current methods used to establish water quality standards do not necessarily consider the different geological and geochemical characteristics of a given site and the factors that affect copper fate, bioavailability potential and toxicity. In addition, the temporal variation in the concentration and bioavailable metal fraction is also important in freshwater systems. The work presented in this paper illustrates the temporal and seasonal variability of a range of water quality parameters, and Cu speciation, bioavailability and toxicity at four freshwaters sites in the UK. Rivers Coquet, Cree, Lower Clyde and Eden (Kent) were selected to cover a broad range of different geochemical environments and site characteristics. The monitoring data used covered a period of around six years at almost monthly intervals.Chemical equilibrium modelling was used to study temporal variations in Cu speciation and was combined with acute toxicity modelling to assess Cu bioavailability for two aquatic species, Daphnia magna and Daphnia pulex. The estimated copper bioavailability, toxicity levels and the corresponding ecosystem risks were analysed in relation to key water quality parameters (alkalinity, pH and DOC). Although copper concentrations did not vary much during the sampling period or between the seasons at the different sites; copper bioavailability varied markedly. In addition, through the chronic-Cu BLM-based on the voluntary risk assessment approach, the potential environmental risk in terms of the chronic toxicity was assessed. A much higher likelihood of toxicity effects was found during the cold period at all sites. It is suggested that besides the metal (copper) concentration in the surface water environment, the variability and seasonality of other important water quality parameters should be considered in setting appropriately protective environmental quality standards for metals.

Incorporating bioavailability into toxicity assessment of Cu-Ni, Cu-Cd, and Ni-Cd mixtures with the extended biotic ligand model and the WHAM-F(tox) approach.

There are only a limited number of studies that have developed appropriate models which incorporate bioavailability to estimate mixture toxicity. Here, we explored the applicability of the extended biotic ligand model (BLM) and the WHAM-F(tox) approach for predicting and interpreting mixture toxicity, with the assumption that interactions between metal ions obey the BLM theory. Seedlings of lettuce Lactuca sativa were exposed to metal mixtures (Cu-Ni, Cu-Cd, and Ni-Cd) contained in hydroponic solutions for 4 days. Inhibition to root elongation was the endpoint used to quantify the toxic response. Assuming that metal ions compete with each other for binding at a single biotic ligand, the extended BLM succeeded in predicting toxicity of three mixtures to lettuce, with more than 82% of toxicity variation explained. There were no significant differences in the values of f(mix50) (i.e., the overall amounts of metal ions bound to the biotic ligand inducing 50% effect) for the three mixture combinations, showing the possibility of extrapolating these values to other binary metal combinations. The WHAM-F(tox) approach showed a similar level of precision in estimating mixture toxicity while requiring fewer parameters than the BLM-f(mix) model. External validation of the WHAM-F(tox) approach using literature data showed its applicability for other species and other mixtures. The WHAM-F(tox) model is suitable for delineating mixture effects where the extended BLM also applies. Therefore, in case of lower data availability, we recommend the lower parameterized WHAM-F(tox) as an effective approach to incorporate bioavailability in quantifying mixture toxicity.

Soft and sour: The challenge of setting environmental quality standards for bioavailable metal concentration in Fennoscandinavian freshwaters

The European Union Water Framework Directive (WFD) requires member states to ensure that all inland and coastal waters achieve ‘good’ water quality status. To this end, the WFD has set environmental quality standards (EQS) or Water quality criteria (WQC) for priority pollutants that include the four metals Cd, Ni, Pb and Hg. Many states have also chosen to set EQS for Cu and Zn. The use of bioavailability models to set EQS, paves the way for accepting higher local metal concentrations in waters where metal bioavailability is deemed low. The Biotic Ligand Model (BLM) concept has been proposed as a tool for estimating metal bioavailability and for calculating local EQS in the EU guidance document. The BLM estimates metal bioavailability based on the dissolved metal concentration and key ancillary water chemistry parameters (acidity, hardness and organic carbon content). The BLMs developed so far, have only been validated for water chemistry input parameters typical of Central Europe. However, the pH, alkalinity and dissolved organic carbon levels of a significant fraction of Fennoscandinavian (Finland, Norway and Sweden) freshwaters are outside the calibration range of currently available BLMs. The levels of Ca2+, alkalinity and pH in 75%, 29% and 22%, respectively, of the ca. 2500 Fennoscandinavian freshwater bodies investigated in this survey were outside the calibration range of tested BLMs. Moreover, a comparison of the ability of the tested BLMs to predict the acute and chronic copper toxicity to Daphnia magna and Rainbow trout indicated that the BLMs should be used with caution outside their current validation range. We conclude that more work is needed to extend the application of BLMs in the practical risk assessment to encompass a broader range of European freshwater bodies.

Citrate coated silver nanoparticles change heavy metal toxicities and bioaccumulation of Daphnia magna

Citrate-coated AgNPs (c-AgNPs) have negatively charged surfaces and their surface interactions with heavy metals can affect metal toxicity in aquatic environments. This study used Daphnia magna to compare the acute toxicities and bioaccumulation of As(V), Cd, and Cu when they interact with c-AgNPs. The 24-h acute toxicities of As(V) and Cu were not affected by the addition of c-AgNPs, while bioaccumulation significantly decreased in the presence of c-AgNPs. In contrast, both the 24-h acute toxicity and bioaccumulation of Cd increased in the presence of c-AgNPs. These toxicity and bioaccumulation trends can be attributed to the interactions between the AgNP surface and the heavy metals. As(V) and c-AgNPs compete by negative charge, decreasing As(V) toxicity. Copper adheres readily to c-AgNP citrate, decreasing Cu bioavailability, and thus reducing Cu toxicity and bioaccumulation. Citrate complexes with divalent cations such as Ca and Mg reduce the competition between divalent cations and Cd on biotic ligand, increasing toxicity and bioaccumulation of Cd. This study shows that surface properties determine the effect of c-AgNPs on heavy metal toxicities and bioaccumulations; hence, further studies on the effect of nanoparticle by it surface properties are warranted.

Linking the chemical speciation of cerium to its bioavailability in water for a freshwater alga.

Over the past decade, researchers have begun to use metals of the lanthanide family for numerous applications, including liquid crystal display (LCD) screens, optical fibers, and laser technology. Unfortunately, little is presently known about their bioavailability or the mechanisms by which they might cause toxicity. The present study focuses on cerium (Ce), one of the most widely used lanthanides, and on validating the biotic ligand model as a means to predict Ce bioaccumulation. Short-term exposures to Ce were performed using the unicellular alga Chlamydomonas reinhardtii, to better relate Ce bioavailability to its chemical speciation in solution. Maximum uptake fluxes (Jmax ) and affinity constants for the binding of Ce to the biological uptake sites (KS ) were established at pH 5.0 and pH 7.0. An apparent affinity constant of 1.8 × 10(7) M(-1) was observed at pH 5.0, with a larger value obtained at pH 7.0 (6 × 10(7) M(-1) ), albeit under conditions where equilibrium could not be confirmed. By evaluating Ce speciation using centrifugal ultrafiltration and single-particle inductively coupled plasma spectrometry, it could be concluded that very little (∼30%) Ce was truly dissolved at pH 7.0, with the majority of the metal being present in colloidal species. Speciation was also monitored by fluorescence to evaluate Ce complexation by natural organic matter (NOM). The presence of NOM decreased Ce bioaccumulation in line with free Ce concentrations. Finally, competition with calcium for the metal uptake sites was shown to result in a decrease in Ce uptake by C. reinhardtii.