This study reports the concentrations and congener partners of polychlorinated biphenyls (PCBs) in commercially available paints. Polycyclic-type pigments containing dioxazine violet (pigment violet (PV) 23, PV37) and diketopyrrolopyrrole (PR254, PR255) were found to contain PCB-56, PCB-77, PCB-40, PCB-5, and PCB-12, and PCB-6, PCB-13, and PCB-15, respectively, as major congeners. Dioxazine violet is contaminated with by-products during synthesis from o-dichlorobenzene, which is used as a solvent during synthesis, and diketopyrrolopyrrole is contaminated with by-products during synthesis from p-chlorobenzonitrile. The concentration of PCBs in paint containing PV23 or PV37 was 0.050–29 mg/kg, and toxic equivalency (TEQ) values ranged 1.1–160 pg-TEQ/g. The concentration of PCBs in paint containing PR254 or PR255 was 0.0019–2.4 mg/kg. Naphthol AS is an azo-type pigment, and PCB-52 was detected in paint containing pigment red (PR) 9 with 2,5-dichloroaniline as its source. PCB-146, PCB-149, and PCB-153 were identified from paint containing PR112 produced from 2,4,5-trichloroaniline, as major congeners. These congeners have chlorine positions similar to aniline, indicating that these congeners are by-products obtained during the synthesis of pigments. The concentrations of PCBs in paints containing PR9 and PR112 were 0.0042–0.43 and 0.0044–3.8 mg/kg, respectively. The corresponding TEQ for PR112 was 0.0039–8.6 pg-TEQ/g.

Integrated risk assessment approaches allow to achieve a sound evaluation of ecological status of river basins and to gain knowledge about the likely causes of impairment, useful for informing and supporting the decision-making process. In this paper, the integrated risk assessment (IRA) methodology developed in the EU MODELKEY project (and implemented in the MODELKEY Decision Support System) is applied to the Taizi River (China), in order to assess its Ecological and Chemical Status according to EU Water Framework Directive (WFD) requirements. The available dataset is derived by an extensive survey carried out in 2009 and 2010 across the Taizi River catchment, including the monitoring of physico-chemical (i.e. DO, EC, NH₃–_N, chemical oxygen demand (COD), biological oxygen demand in 5 days (BOD₅) and TP), chemical (i.e. polycyclic aromatic hydrocarbons (PAHs) and metals), biological (i.e. macroinvertebrates, fish, and algae), and hydromorphological parameters (i.e. water quantity, channel change and morphology diversity). The results show a negative trend in the ecological status from the highland to the lowland of the Taizi River Basin. Organic pollution from agriculture and domestic sources (i.e. COD and BOD₅), unstable hydrological regime (i.e. water quantity shortage) and chemical pollutants from industry (i.e. PAHs and metals) are found to be the main stressors impacting the ecological status of the Taizi River Basin. The comparison between the results of the IRA methodology and those of a previous study (Leigh et al. 2012) indicates that the selection of indicators and integrating methodologies can have a relevant impact on the classification of the ecological status. The IRA methodology, which integrates information from five lines of evidence (i.e., biology, physico-chemistry, chemistry, ecotoxicology and hydromorphology) required by WFD, allows to better identify the biological communities that are potentially at risk and the stressors that are most likely responsible for the observed alterations. This knowledge can be beneficial for a more effective restoration and management of the river basin ecosystem.

Phytoremediation comprises a set of plant and microbe-based technologies for remediation of soil heavy metal contamination. In this work, four Pb-resistant bacteria (Agrobacterium tumefaciens, Rahnella aquatilis, and two Pseudomonas sp.) were selected among a collection of isolates from root nodule of Lens culinaris. They had a high degree of bioaccumulation ability in nutrient medium containing 2 mM Pb, and the maximum Pb accumulation of whole cell was found after 48-h incubation. These Pb-resistant bacteria synthesized plant growth promoting substances such as indole acetic acid and siderophore. The presence of the Pb resistance genes (pbrA) in these bacteria has been confirmed by PCR. L. culinaris cultivated in two experimental soils with different levels of contamination showed that Pb contamination affected plant growth; therefore, it’s co-inoculation with the consortium of Pb-resistant bacteria improved plant biomass. The present study demonstrated that lentil accumulated Pb primarily in their roots and poorly in their shoots; in addition, it’s co-inoculation in moderately Pb-contaminated soil induced a reduction in Pb accumulation in roots and shoots by 22 and 80 %, respectively. Whereas in highly Pb-contaminated soil, we registered a diminution in concentration of Pb in shoots (66 %) and an augmentation in roots (21 %). The contamination of soil by Pb caused an oxidative stress in lentil plant, inducing modulation in antioxidant enzymes activities, essentially in superoxide dismutase (SOD) and peroxidase (GPOX) activities which were more pronounced in lentil cultivated in highly Pb-contaminated soil, in addition, co-inoculation enhanced these activities, suggesting the protective role of enzymatic antioxidant against Pb-induced plant stress.Thus, the present study demonstrated that co-inoculation of lentil with A. tumefaciens, R. aquatilis, and Pseudomonas sp. formed a symbiotic system useful for phytostabilization of highly and moderately Pb-contaminated soils.

Adsorption of tetracycline (TC) on kaolinite and montmorillonite was investigated using batch adsorption experiments with different pH, ionic strength, and surface coverage. As a result, pH and ionic strength-dependent adsorption of TC was observed for the two clay minerals. The adsorption of TC decreased with the increase of pH and ionic strength, and high initial TC concentration had high adsorption. In addition, a triple-layer model was used to predict the adsorption and surface speciation of TC on the two minerals. As a result, four complex species on kaolinite (≡X⁻∙H₃TC⁺, ≡X⁻∙H₂TC±, ≡SOH⁰∙H₂TC±, and ≡SOH⁰∙HTC⁻) and three species on montmorillonite (≡X⁻∙H₃TC⁺, ≡X⁻∙H₂TC±, and ≡SOH⁰∙HTC⁻) were structurally constrained by spectroscopy, and these species were also successfully fitted to the adsorption edges of TC. Three functional groups of TC were involved in these adsorption reactions, including the positively charged dimethylamino group, the C=O amide I group, and the C=O group at the C ring. Combining adsorption experiments and model in this study, the adsorption of TC on kaolinite and montmorillonite was mainly attributed to cation exchange on the surface sites (≡X⁻) compared to surface complexation on the edge sites (≡SOH) at natural soil pH condition. Moreover, the surface adsorption species, the corresponding adsorption modes, and the binding constants for the surface reactions were also estimated.

In vitro bioassays are useful techniques for the determination of biological effects in sediment samples containing complex mixtures of contaminants. In this study, 28 surface sediment samples from Taihu Lake, East China, were collected for toxicity assessment using a battery of in vitro bioassays. The battery included a two-hybrid yeast bioassay for estrogenic and thyroidal effects, the H4IIE rat hepatoma cell bioassay for aryl hydrocarbon (Ah) receptor (Ah-agonists)-mediated effects as measured by ethoxyresorufin-O-deethylase (EROD) activity, and the SOS/umu bioassay for genotoxic effects. Toxicities were expressed as 17β-estradiol equivalents (EEQs), T₃(3,5,3′-triiodothyronine) equivalents (T₃-EQs), 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs), and induction ratios (IRs) of β-galactosidase activity. The results showed that total estrogenic effects in sediment samples ranged from 0.0011 to 12.4 pg EEQ/g sediment [dry weight (d.w.)], the thyroidal effects ranged from 0.35 to 24.8 pg T₃-EQ/g sediment (d.w.), the Ah-agonist effects varied from 2.70 to 37.8 pg TEQ/g sediment (d.w.), and the weight of soil required for the extracts to lead to a positive result (IR 2.0) in the SOS/umu bioassay was between 1.98 and 15.3 mg (d.w.) per well. Significantly positive correlations were only found between lgT₃-EQs and lgEEQs, which indicated similar spatial distributions of estrogenic and thyroidal effects in Taihu Lake. These results suggested that the applied battery of in vitro bioassays represented an efficient (fast and cost-effective) screening system for the identification of emerging contaminants in Taihu Lake and provided meaningful information for further analysis and risk evaluation.

Anaerobic methane oxidation coupled to sulphate reduction and the use of ethane and propane as electron donors by sulphate-reducing bacteria represent new opportunities for the treatment of streams contaminated with sulphur oxyanions. However, growth of microbial sulphate-reducing populations with methane, propane or butane is extremely slow, which hampers research and development of bioprocesses based on these conversions. Thermodynamic calculations indicate that the growth rate with possible alternative terminal electron acceptors such as thiosulphate and elemental sulphur may be higher, which would facilitate future research. Here, we investigate the use of these electron acceptors for oxidation of methane, ethane and propane, with marine sediment as inoculum. Mixed marine sediments originating from Aarhus Bay (Denmark) and Eckernförde Bay (Germany) were cultivated anaerobically at a pH between 7.2 and 7.8 and a temperature of 15 °C in the presence of methane, ethane and propane and various sulphur electron acceptors. The sulphide production rates in the conditions with methane, ethane and propane with sulphate were respectively 2.3, 2.2 and 1.8 μmol S L⁻¹ day⁻¹. For sulphur, no reduction was demonstrated. For thiosulphate, the sulphide production rates were up to 50 times higher compared to those of sulphate, with 86.2, 90.7 and 108.1 μmol S L⁻¹ day⁻¹for methane, ethane and propane respectively. This sulphide production was partly due to disproportionation, 50 % for ethane but only 7 and 14 % for methane and propane respectively. The oxidation of the alkanes in the presence of thiosulphate was confirmed by carbon dioxide production. This is, to our knowledge, the first report of thiosulphate use as electron acceptor with ethane and propane as electron donors. Additionally, these results indicate that thiosulphate is a promising electron acceptor to increase start-up rates for sulphate-reducing bioprocesses coupled to short-chain alkane oxidation.

An investigation of atmospheric mercury was conducted in the urban coastal zone of the Gulf of Gdansk (Baltic Sea, Poland) in 2008. Rainwater samples were collected in bulk samplers and Hg concentration was determined using AAS method. Total mercury concentration ranged from 1.9 to 14.8 ng l⁻¹(the mean was 8.3 ng l⁻¹with standard deviation ±3.7), out of which about 34 % were water-soluble Hg(II) forms. Distribution of Hg species in rainwater was related to both the emission source and the atmospheric processes. During the sampling period, two maxima of Hg concentration in precipitation were observed: the first in the cold season and the second one in the warm season. Elevated concentrations of Hg in wintertime precipitation were generally the result of local urban atmospheric emission connected with the following anthropogenic sources: intensive combustion of fossil fuels in domestic furnaces, individual power/heat generating plants, and motor vehicles. During summertime, Hg° re-emitted from contaminated land and sea surfaces was photochemically oxidized by active atmospheric substances (e.g., hydroxyl radicals, hydrogen peroxide, halogens) and could be an additional source of atmospherically deposited Hg. The results presented in this work indicate that rainwater Hg concentration and deposition values are not much higher in comparison with other urban locations along the Baltic Sea basin and other coastal cities. However, the elevated mercury concentration in rainwater and, consequently, higher deposition ratio could appear occasionally as an effect of intensive anthropogenic emissions (domestic heating) and/or photochemical reactions.

Lead (Pb) environmental contamination remains prevalent. Pisum sativum L. plants have been used in ecotoxicological studies, but some cultivars showed to tolerate and accumulate some levels of Pb, opening new perspectives to their use in phytoremediation approaches. However, the putative use of pea plants in phytoremediation requires reliable toxicity endpoints. Here, we evaluated the sensitivity of a large number of photosynthesis-related biomarkers in Pb-exposed pea plants. Plants (cv. “Corne de Bélier”) were exposed to Pb concentrations up to 1,000 mg kg⁻¹ soil during 28 days. The photosynthetic potential biomarkers that were analyzed included pigments, chlorophyll (Chl) a fluorescence, gas exchange, ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO) activity, and carbohydrates. Flow cytometry (FCM) was also used to assess the morpho-functional status of chloroplasts. Finally, Pb-induced nutrient disorders were also evaluated. Net CO₂ assimilation rate (A) and RuBisCO activity decreased strongly in Pb-exposed plants. Plant dry mass (DM) accumulation, however, was only reduced in the higher Pb concentrations tested (500 and 1,000 mg kg⁻¹ soil). Pigment contents increased solely in plants exposed to the largest Pb concentration, and in addition, the parameters related to the light-dependent reactions of photosynthesis, F ᵥ/F ₘ and ΦPSII, were not affected by Pb exposure. In contrast to this, carbohydrates showed an overall tendency to increase in Pb-exposed plants. The morphological status of chloroplasts was affected by Pb exposure, with a general trend of volume decrease and granularity increase. These results point the endpoints related to the light-independent reactions of photosynthesis as more sensitive predictors of Pb-toxicity than the light-dependent reactions ones. Among the endpoints related to the light-independent photosynthesis reactions, RuBisCO activity and A were found to be the most sensitive. We discuss here the advantages of using these parameters as biomarkers for Pb toxicity in plants. Finally, we report that, despite showing physiological disorders, these cultivar plants survived and accumulated high doses of Pb, and their use in environmental/decontamination studies is open to debate.

Rarely is it possible to obtain absolute numbers in free-ranging populations and although various direct and indirect methods are used to estimate abundance, few are validated against populations of known size. In this paper, we apply grounding, calibration and verification methods, used to validate mathematical models, to methods of estimating relative abundance. To illustrate how this might be done, we consider and evaluate the widely applied passive tracking index (PTI) methodology. Using published data, we examine the rationality of PTI methodology, how conceptually animal activity and abundance are related and how alternative methods are subject to similar biases or produce similar abundance estimates and trends. We then attune the method against populations representing a range of densities likely to be encountered in the field. Finally, we compare PTI trends against a prediction that adjacent populations of the same species will have similar abundance values and trends in activity. We show that while PTI abundance estimates are subject to environmental and behavioural stochasticity peculiar to each species, the PTI method and associated variance estimate showed high probability of detection, high precision of abundance values and, generally, low variability between surveys, and suggest that the PTI method applied using this procedure and for these species provides a sensitive and credible index of abundance. This same or similar validation approach can and should be applied to alternative relative abundance methods in order to demonstrate their credibility and justify their use.

The aquatic carnivorous plant Utricularia gibba has one of the smallest known genomes among flowering plants, and therefore, it is an excellent model organism for physiological and developmental studies. The main aim of our work was to check whether the ubiquitous U. gibba might be useful for the phytoremediation of the highly toxic and mobile hexavalent chromium in waters. Plants were incubated for 1 week in a 50 μM (2.6 mg dm⁻³) Cr(VI) solution in laboratory conditions. Our results revealed that the plant exhibits a very high accumulation capacity for Cr. The accumulation level was higher than 780 mg kg⁻¹ and a bioconcentration factor >300. On the other hand, the plants showed a low tolerance to the elevated Cr concentration, which was expressed in a significant decrease of the photosystem II activity. However, the most pronounced negative influence of chromate was found on the morphology and activity of the traps. Due to its high accumulation capacity, we suggest that U. gibba may be efficient in the removal of chromate over a short time scale. It can also provide a new molecular resource for studying the mechanisms of Cr(VI) detoxification.