Development of a biotic ligand model (BLM) predicting nickel toxicity to barley (Hordeum vulgare)

A biotic ligand model (BLM) was developed to predict nickel toxicity, affecting root growth of barley (Hordeum vulgare), in nutrient solutions. The extent to which Ca(2+), Mg(2+), Na(+), K(+) ions and pH each influenced nickel toxicity was determined. Higher activities of Mg(2+) linearly increased the 4d EC50 Ni (2+) , while Ca(2+), Na(+), K(+) and H(+) activities did not significantly influence Ni(2+) toxicity. Stability constants for the binding of Ni(2+) and Mg(2+) to the biotic ligand were obtained: logK(NiBL)=5.27 and logK(MgBL)=3.47. Further, it was calculated that on average 57% of the biotic ligand sites needed to be occupied by nickel to induce 50% root growth inhibition. Auto-validation of the BLM indicated that predicted EC50s differed from the observed EC50s by a factor of less than 2, indicating that the BLM concept may also be used to predict metal toxicity to terrestrial plants.     

A new hybrid system of QSAR models for predicting bioconcentration factors (BCF)

The aim was to develop a reliable and practical quantitative structure–activity relationship (QSAR) model validated by strict conditions for predicting bioconcentration factors (BCF). We built up several QSAR models starting from a large data set of 473 heterogeneous chemicals, based on multiple linear regression (MLR), radial basis function neural network (RBFNN) and support vector machine (SVM) methods. To improve the results, we also applied a hybrid model, which gave better prediction than single models. All models were statistically analysed using strict criteria, including an external test set. The outliers were also examined to understand better in which cases large errors were to be expected and to improve the predictive models. The models offer more robust tools for regulatory purposes, on the basis of the statistical results and the quality check on the input data.     

A new hybrid system of QSAR models for predicting bioconcentration factors (BCF)

The aim was to develop a reliable and practical quantitative structure-activity relationship (QSAR) model validated by strict conditions for predicting bioconcentration factors (BCF). We built up several QSAR models starting from a large data set of 473 heterogeneous chemicals, based on multiple linear regression (MLR), radial basis function neural network (RBFNN) and support vector machine (SVM) methods. To improve the results, we also applied a hybrid model, which gave better prediction than single models. All models were statistically analysed using strict criteria, including an external test set. The outliers were also examined to understand better in which cases large errors were to be expected and to improve the predictive models. The models offer more robust tools for regulatory purposes, on the basis of the statistical results and the quality check on the input data.     

Assessing chronic toxicity of bisphenol A to larvae of the African clawed frog (Xenopus laevis) in a flow-through exposure system

A number of currently used industrial chemicals are estrogenic, and therefore have potential to disrupt sexual differentiation in vertebrate wildlife during critical developmental windows. We assessed the effect of larval exposure to bisphenol A (BPA) on growth, development and sexual differentiation of the gonad in the African Clawed frog, Xenopus laevis. Larvae were maintained in flow-through conditions at 22 +/- 1 degrees C and exposed to BPA at mean measured concentrations of 0.83, 2.1, 9.5, 23.8, 100, and 497 microg/l, from developmental stages 43/45-66 (completion of metamorphosis). Each test concentration, plus dilution water control (DWC) and positive control (17beta-estradiol (E2), 2.7 microg/l) employed four replicate test vessels with 40 larvae per tank. Individual froglets were removed from test vessels upon reaching stage 66, and the study was terminated at 90 days. Froglets were dissected and sex was determined by inspection of gross gonadal morphology. Test concentrations of BPA had no effect on survival, growth, developmental stage distributions at exposure days 32 and 62, or mean time to completion of metamorphosis, compared to DWC. Analysis of post-metamorphic sex ratio, determined by gross gonadal morphology, indicated no significant deviations from expected (50:50) sex ratio, in DWC or any BPA test concentration. In contrast, exposure of larvae to (E2) resulted in feminisation, with sex ratio deviating significantly (31% male, replicates pooled). Exposure to BPA in the concentration range 0.83-497 microg/l in flow-through conditions had no observable effect on larval growth, development or sexual differentiation (as determined by gross gonadal morphology) in this study.     

Silica reduces the toxicity of aluminium to a tropical freshwater fish (Mogurnda mogurnda)

The toxicity of aluminium (Al) to fish in acidic waters has been well documented. It was therefore expected that Al toxicity would be significant in fish communities in Gadjarrigamarndah (Gadji) Creek, a seasonally flowing stream in tropical northern Australia. This creek receives acidic groundwater containing elevated concentrations of Al from earlier land irrigation of treated mine tailings water from the former Nabarlek uranium mine. It was hypothesised that Al toxicity was reduced by high levels of silica (Si) in the water, and the subsequent formation of Al-silicate complexes. This prompted a laboratory assessment of the toxicity of Gadji Creek water to sac-fry of the native fish, Mogurnda mogurnda, followed by more detailed investigation of the toxicity of Al and the influence of Si in reducing Al toxicity. No mortality of M. mogurnda sac-fry was observed in two toxicity tests using Gadji Creek water collected in August 1997 and September 1998. The majority of Al (80-95%) was calculated to be complexed with humic substances and sulfate, with < 1% being complexed with silicate. Assessment of the influence of silica on the acute toxicity of Al in the absence of natural organic complexants (i.e. in reconstituted freshwater, pH 5) revealed that Si reduced Al toxicity. As the molar ratio of Si:Al was increased, the percent survival of M. mogurnda sac-fry increased until there was no significant (P > 0.05) difference from the controls. However, speciation modelling again predicted that little (< 3%) Al complexed with silicate, with the speciation and bioavailability of Al remaining constant as the molar ratio of Si:Al increased. Therefore, the original hypothesis that Al-silicate complexes in solution reduced the toxicity of Al to M. mogurnda could not be supported. This potential mechanism, and an alternative hypothesis, that Si competes with Al for binding sites at the fish gill surface, requires further investigation.     

Biochar reduces the toxicity of silver to barley (Hordeum vulgare) and springtails (Folsomia candida) in a natural soil

Environmental Science and Pollution Research - The use of biochar in soil remediation is a promising method to deal with metal contamination. In the present study, the influence of biochar...     

Development and validation of a terrestrial biotic ligand model predicting the effect of cobalt on root growth of barley (Hordeum vulgare)

A Biotic Ligand Model was developed predicting the effect of cobalt on root growth of barley (Hordeum vulgare) in nutrient solutions. The extent to which Ca(2+), Mg(2+), Na(+), K(+) ions and pH independently affect cobalt toxicity to barley was studied. With increasing activities of Mg(2+), and to a lesser extent also K(+), the 4-d EC50(Co2+) increased linearly, while Ca(2+), Na(+) and H(+) activities did not affect Co(2+) toxicity. Stability constants for the binding of Co(2+), Mg(2+) and K(+) to the biotic ligand were obtained: logK(CoBL)=5.14, logK(MgBL)=3.86 and logK(KBL)=2.50. Limited validation of the model with one standard artificial soil and one standard field soil showed that the 4-d EC50(Co2+) could only be predicted within a factor of four from the observed values, indicating further refinement of the BLM is needed.     

Three-dimensional quantitative structure activity relationship (3D-QSAR) analysis for in vitro toxicity of chlorophenols to HepG2 cells

In the present paper, comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) were applied to investigate two 3D-QSAR models for the cytotoxicity of chlorophenols. These models have evaluated the intensity of chlorophenols' toxicity on HepG2 cells in vitro. The CoMFA model has both high consistency and predictability. The contribution of the electrostatic field to biological activity is greater than that of the steric field. The CoMSIA model used in this study includes two fields, one is hydrophobic field, and the other is electrostatic field. The relative contribution of them is 0.789:0.211. Consisted with the CoMFA model, the CoMSIA electrostatic filed also plays a dominant role. The CoMFA and CoMSIA contour maps significantly elucidated that the electrostatic field is more important than the other fields and might be one of the reasons resulting in potential reactive mechanism involved in cell proliferation inhibition.     

Influence of sediment on the fate and toxicity of a polyethoxylated tallowamine surfactant system (MON 0818) in aquatic microcosms

The fate and toxicity of a polyethoxylated tallowamine (POEA) surfactant system, MON 0818, was evaluated in water-sediment microcosms during a 4-d laboratory study. A surfactant solution of 8 mg l(-1) nominal concentration was added to each of nine 72-l aquaria with or without a 3-cm layer of one of two natural sediments (total organic carbon (TOC) 1.5% or 3.0%). Control well water was added to each of nine additional 72-l aquaria with or without sediment. Water samples were collected from the microcosms after 2, 6, 24, 48, 72, and 96 h of aging to conduct 48-h toxicity tests with Daphnia magna and to determine surfactant concentrations. Elevated mortality of D. magna (43-83%) was observed in overlying water sampled from water-only microcosms throughout the 96-h aging period, whereas elevated mortality (23-97%) was only observed in overlying water sampled from water-sediment microcosms during the first 24h of aging. Measured concentrations of MON 0818 in water-only microcosms remained relatively constant (4-6 mg l(-1)) during the 96-h period, whereas the concentrations in overlying water from microcosms containing either of the two types of sediment dissipated rapidly, with half-lives of 13 h in the 3.0% TOC sediment and 18 h in the 1.5% TOC sediment. Both toxicity and the concentration of MON 0818 in overlying water decreased more rapidly in microcosms containing sediment with the higher percent TOC and clay and with a higher microbial biomass. Mortality of D. magna was significantly correlated with surfactant concentrations in the overlying water. These results indicate that the toxicity of the POEA surfactant in water rapidly declines in the presence of sediment due to a reduction in the surfactant concentration in the overlying water above the sediment.     

Quantitative structure-activity relationships of nitroaromatics toxicity to the algae (Scenedesmus obliguus)

The DFT-B3LYP method, with the basis set 6-311G( * *), was employed to calculate the molecular geometries and electronic structures of 25 nitroaromatics. The acute toxicity (-lgEC(50)) of these compounds to the algae (Scenedesmus obliguus) along with hydrophobicity described by logK(OW), and two quantum chemical parameters-energy of the lowest unoccupied molecular orbital, E(LUMO), and the charge of the nitro group, [ForQ(NO2), were used to establish the quantitative structure-activity relationships (QSARs). For 18 mononitro derivatives, the hydrophobicity parameter logK(OW) could interpret the toxic mechanism successfully. Dinitro aromatic compounds were susceptible to be reduced to aniline for their electrophilic nature. Their toxicity was controlled mainly by electronic factors instead of hydrophobicity. The electronic parameters, E(LUMO) and Q(NO2), were used to yield the following model: -lg EC(50) = 3.746 - 25.053 E(LUMO) + 6.481 Q(NO2) (n=22, R=0.926, SE=0.206, F=56.854, P<0.001). The predicted toxic values using the above equation are in good agreement with the experimental values.     

Acute toxicity of alpha-cypermethrin to guppy (Poecilia reticulata, Pallas, 1859)

Alpha-cypermethrin is a synthetic pyrethroid insecticide used to control pests in domestic, industrial and agricultural situations. Adult male guppy fish (Poecilia reticulata standard test species) were selected for the bioassay experiments. The experiments were performed in four series and the 96-h LC50 value was determined for guppies. The acute toxicity experiments were carried out by static method and behavioral changes in guppies were determined for each alpha-cypermethrin (98% technical grade) concentration. Data obtained from the alpha-cypermethrin investigation were evaluated by the use of probit analysis statistical method and the 96-h LC50 value for guppy was estimated as 9.43 microg/l.     

Biological detection and analysis of mercury toxicity to alfalfa (Medicago sativa) plants

Mercury has become one of the major causes of toxic metal pollution in agricultural lands. Accumulation of mercury by plants may disrupt many cellular functions and block growth and development. To assess mercury toxicity, we performed an experiment focusing on the responses of alfalfa (Medicago sativa) to Hg(2+)-induced oxidative stress. Alfalfa plants were treated with 0-40microM HgCl(2) for 7d. The concentrations of Hg(2+) were positively correlated with the generation of O2- and H(2)O(2) in leaves. Treatment with Hg(2+) increased the activities of NADH oxidase and lipoxygenase (LOX) and damaged the biomembrane lipids. To understand biochemical responses under Hg stress, activities of several antioxidant enzymes, superoxide dismutase (SOD), peroxidase (POD), catalase (CAT), ascorbate peroxidase (APX) and glutathione reductase (GR) were assayed. Analysis of SOD activity by non-denaturing polyacrylamide gel electrophoresis revealed five isoforms in leaves, but they showed different patterns. Also, eight isoenzymes of APX and seven of POD in leaves were detected. However, only one isoform of CAT was visualized. The total activities of APX, POD and CAT were generally enhanced. We also measured several antioxidative metabolites such as ascorbate and glutathione (GSH), and found that both differentially accumulated in leaves. These results indicate that the increased levels of O2- and H(2)O(2) under Hg stress were closely linked to the improved capacity of antioxidant enzymes. The data not only provide the important information for better understanding of the toxic and tolerance mechanisms, but as well can be used as a bio-indicator for soil contamination by Hg.     

Development of quantitative structure-property relationship model for predicting the field sampling rate ( R s ) of Chemcatcher passive sampler

Passive sampling technology has been considered as a promising tool to measure the concentration of environmental contaminants. With this technology, sampling rate (Rs) is an important parameter. However, as experimental methods employed to obtain the Rs value of a given compound were time-consuming, laborious, and expensive. A cost-effective method for deriving Rs is urgent. In addition, considering the great dependence of Rs value on water matrix properties, the laboratory measured Rs may not be a good alternative for field Rs. Thus, obtaining the field Rs is very necessary. In this study, a multiparameter quantitative structure-property relationship (QSPR) model was constructed for predicting the field Rs of 91 polar to semi-polar organic compounds. The determination coefficient (R2Train), leave-one-out cross-validated coefficient (Q2LOO), bootstrap coefficient (Q2BOOT), and root mean square error (RMSETrain) of the training set were 0.772, 0.706, 0.769, and 0.230, respectively, while the external validation coefficient (Q2EXT) and RMSEEXT of the validation set were 0.641 and 0.253, respectively. According to the acceptable criteria (Q2 > 0.600, R2 > 0.700), the model had good robustness, goodness-of-fit, and predictive performances. Therefore, we could use the model to fill the data gap for substances within the applicability domain on their missing Rs value.     

Chronic toxicity of sediment-associated linear alkylbenzene sulphonates (LAS) to freshwater benthic organisms

The toxicity of linear alkylbenzene sulphonates (LAS), to freshwater benthic organisms was assessed during exposure to spiked sediment. Lethal and sub-lethal end-points were monitored for two organisms (oligochaete Lumbriculus variegatus and nematode Caenorhabditis elegans). Results demonstrated relatively low toxicity (LOECs>100 mg/kg dry weight). No observed effect concentrations (NOECs) of 81 mg/kg dw (Lumbriculus) and 100 mg/kg dw (Caenorhabditis) were determined. For the oligochaete, no specific endpoint was particularly sensitive to LAS. For the nematode, egg production was the most sensitive endpoint. Significant degradation was measured over the 28-day duration of the Lumbriculus study, equating to a half-life of 20 days in sediment.     

Combined toxicity of imidacloprid,acetochlor, and tebuconazole to zebrafish ( Danio rerio ): acute toxicity and hepatotoxicity assessment

Compound pollution refers to two or more kinds of pollutants with different properties, a pollutant from different sources, or the simultaneous existence of two or more different types of pollutants in the same environment. In this study, we aimed to investigate the individual and combined toxicity of the insecticide imidacloprid (IMI), the herbicide acetochlor (ACT), and the fungicide tebuconazole (TBZ) to zebrafish. The acute toxicity test results showed that the 96-h LC50 values of IMI, ACT, and TBZ were 276.84 (259.62–294.35) mg active ingredient (a.i.) L−1, 1.52 (1.34–1.74) mg a.i. L−1, and 8.16 (7.7–8.6) mg a.i. L−1, respectively. The combinations of IMI, ACT, and TBZ with toxicity ratios of 1:2:2, 1:4:4, 2:4:1, and 4:1:4 displayed synergistic toxic effects on zebrafish, while the toxicity ratios of 1:1:1, 1:1:2, 2:1:2, 2:2:1, and 4:2:1 of IMI, ACT, and TBZ, respectively, exhibited antagonistic toxic effects on zebrafish. The following experiments were performed with a toxicity ratio of 1:4:4 (IMI:ACT:TBZ). The activities of four enzyme biomarkers related to oxidative stress in the liver, catalase (CAT), superoxide dismutase (SOD), glutathione S-transferase (GST), and malondialdehyde (MDA) content were evaluated in each exposure group on days 7, 14, 21, and 28. Compared with those of the control group, the activities of CAT, SOD, and GST and the MDA content were significantly altered at different time points in the individual and combined exposure groups. Additionally, the activities of CAT, SOD, and GST and the MDA content were significantly altered in the combined group compared with those of the individual group after 14 days or 21 days of exposure. Therefore, it was confirmed that combined toxicity studies are indispensable in risk assessment.     

Comparison of arsenate and cadmium toxicity in a freshwater amphipod (Gammarus pulex)

Cadmium is largely documented on freshwater organisms while arsenic, especially arsenate, is rarely studied. The kinetic of the LC50s values for both metals was realized on Gammarus pulex. Physiological [i.e. metal concentration in body tissues, bioconcentration factor (BCF)] effects and behavioural responses (via pleopods beats) were investigated after 240-h exposure. Arsenate LC50 value was 100 fold higher than Cd-LC50 value after 240-h exposure, while concentrations in gammarids were similar for both metals at their respective LC50s. BCF decreased with increasing cadmium concentration while BCF remained stable with increasing arsenate concentration. Moreover, BCF was between 148 and 344 times lower for arsenate than cadmium. A significant hypoventilation was observed for cadmium concentrations exceeding or close to the 240h-LC50(Cd), while gammarids hyperventilated for the lowest arsenate concentrations and hypoventilated for the highest arsenate concentrations. We discussed the relationships between potential action mechanisms of these two metals and observed results.