Short-chain chlorinated paraffins (SCCPs) are ubiquitous in the environment and might cause adverse environmental and human health effects. Little is known about the relative toxicity of different SCCP compounds especially during development. The objective of this study was to characterize and compare effects of seven SCCP groups at environmentally relevant levels, using a zebrafish (Danio rerio) model. Observations on malformation, survival rates at 96 h post fertilization (hpf), and hatching rates at 72 hpf indicated that the C10- groups (C10H18Cl4, 1,2,5,6,9,10-C10H16Cl6 and C10H15Cl7) were more toxic than the C12- groups (C12H22Cl4, C12H19Cl7 and 1,1,1,3,10,12,12,12-C12H18Cl8) and Cereclor 63L. The C10- groups were also more potent than C12- groups and Cereclor 63L in decreasing thyroid hormone levels. Among the three compounds within the C10- group, the compounds with less chlorine content had stronger effects on sub-lethal malformations but less effects on triiodothyronine (T3) and tetraiodothyronine (T4). Only C10H18Cl4 significantly decreased the mRNA expression of tyr, ttr, dio2 and dio3 at a dose-dependent manner suggesting that the specific mode of actions differ with different congeners. The mechanisms of disruption of thyroid status by different SCCPs could be different. C10H18Cl4 might inhibit T3 production through the inhibition effect on dio2. These results indicate that SCCP exposure could alter gene expression in the hypothalamic-pituitary-thyroid (HPT) axis and thyroid hormone levels. The mechanisms of disruption of thyroid status by different SCCPs could be different. Our results on the relative developmental toxicities of SCCPs will be useful to reach a better understanding of SCCP toxicity supporting environmental risk evaluation and regulation and used as a guidance for environmental monitoring of SCCPs in the future.

Ectomycorrhizal (ECM) fungi contribute to the survival of host trees on metal-rich soils by reducing the transfer of toxic metals into roots. However, little is known about the ability of ECM fungi to accumulate elements in ectomycorrhizae (ECMs). Here we report Ag, As, Cd, Cl, Cu, Sb, V, and Zn contents in wild-grown Norway spruce ECMs collected in a smelter-polluted area at Lhota near Příbram, Czech Republic. The ECMs data were compared with the element concentrations determined in the corresponding non-mycorrhizal fine roots, soils, and soil extracts. Bioaccumulation factors were calculated to differentiate the element accumulation ability of ECMs inhabited by different mycobionts, which were identified by ITS rDNA sequencing. Among the target elements, the highest contents were observed for Ag, Cl, Cd, and Zn; Imleria badia ECMs showed the highest capability to accumulate these elements. ECMs of Amanita muscaria, but not of other species, accumulated V. The analysis of the proportions of I. badia and A. muscaria mycelia in ECMs by using species-specific quantitative real-time PCR revealed variable extent of the colonization of roots, with median values close to 5% (w/w). Calculated Ag, Cd, Zn and Cl concentrations in the mycelium of I. badia ECMs were 1 680, 1 510, 2 670, and 37,100 mg kg−1 dry weight, respectively, indicating substantial element accumulation capacity of hyphae of this species in ECMs. Our data strengthen the idea of an active role of ECM fungi in soil-fungal-plant interactions in polluted environments.

Polychlorinated dibenzo-p-dioxins (PCDDs) are of global concern due to their persistence, bioaccumulation and toxicity. Although the fate of PCDDs in the environment is determined by their physical-chemical properties, such as aqueous solubility, vapor pressure, octanol/water-, air/water-, and octanol/water-partition coefficients, experimental property data on the entire set of 75 PCDD congeners are limited. The quantitative structure-property relationship (QSPR) approach is applied to predict the properties of all PCDD congeners. Experimental property data available from the literature are correlated against 16 molecular descriptors of five types. Reported and newly developed QSPR models for PCDDs are presented and reviewed. The values calculated by the best QSPRs are further adjusted to satisfy fundamental thermodynamic relationships. Although the single-descriptor models with chlorine number, molar volume, solvent accessible surface area and polarizability are based on good statistical results, these models cannot distinguish among PCDDs having the same chlorine number. The QSPR model based on the hyper-Wiener index of quantum-chemical descriptor gives useful statistical results and is able to distinguish among congeners with the same chlorine number, as well as satisfying thermodynamic relationships. The resulting consistent properties of the 75 PCDD congeners can be used for environmental modeling.

This study determined the effect of monsoonal changes on the composition of atmospheric surfactants in coastal areas. The composition of anions (SO42−, NO3−, Cl−, F−) and the major elements (Ca, K, Mg, Na) in aerosols were used to determine the possible sources of surfactants. Surfactant compositions were determined using a colorimetric method as methylene blue active substances (MBAS) and disulphine blue active substances (DBAS). The anion and major element compositions of the aerosol samples were determined by ion chromatography (IC) and inductively coupled plasma mass spectrometry (ICP-MS), respectively. The results indicated that the concentrations of surfactant in aerosols were dominated by MBAS (34–326pmolm−3). Monsoonal changes were found to significantly affect the concentration of surfactants. Using principal component analysis-multiple linear regressions (PCA-MLR), major possible sources for surfactants in the aerosols were motor vehicle emissions, secondary aerosol and the combustion of biomass along with marine aerosol.

Seven full-scale wastewater treatment plants were investigated to highlight the effectiveness of each treatment stage on removing Escherichia coli. The primary sedimentation achieved an average E. coli removal efficiency of 30.5% which was much lower than the suspended solids (58%), thus, revealing the absence of a linear relationship between the two parameters. Biological processes proved to be very important in the removal of E. coli through adsorption inside the sludge flocs and complex decay (mortality). In biological processes with a long retention time, such as activated sludge denitrification-nitrification, the decay was very important, whereas in the more traditional activated sludge process, without nitrification, the contribution of adsorption and mortality was quite balanced. Overall, the mechanical-biological treatment achieved a removal efficiency of 91.8–96.5% depending on the process. Additional removal can be achieved by disinfection. The effectiveness of E. coli removal with sodium hypochlorite was strictly depended on the product of residual chlorine (C R) with the contact time (t). The experimental curve fitted the Collins model well, with a standard deviation of less than 7%.

For the purpose of clarifying the chemical nature of fly ashes, the raw fly ashes were collected from the stacks of 17 fixed sources consisting of 15 municipal waste incinerators, a metal melting factory, and a cement plant all of which are located in the western Japan from Nov. 2000 to Jan. 2007. The municipal waste incinerators were successfully classified into four groups in terms of the relative mass ratios between chloride, potassium, and sodium. Sodium, potassium, and calcium were found abundantly in fly ashes collected from all four types of municipal waste incinerators. The theoretical estimation of chlorine form suggested that the form of NaCI, KCl, MgCl, and CaCl₂ accounted for approximately 55 % of total chlorine in raw fly ash. Trace heavy metals (i.e., Zn, Mn, Pb, Cu, Cr, Ni, and V) were preferentially enriched in the ambient PM₂.₅ which was strongly influenced by regional stationary sources (including municipal waste incinerators). The water-soluble OC to TC fraction in the fly ashes of municipal waste incinerator, metal furnace, and cement plant was estimated as 56.8, 79.0, and 89.6 %, respectively.

Chlorine added to drinking water as a disinfectant is a concern of this generation. This is because chlorine reacts with dissolved organic compounds to form polychlorinated complexes that are carcinogenic. Available methods for the removal of chlorine and chlorinated compounds include adsorption, precipitation, electrolysis and ozonation, but some result in the generation of more toxic compounds. This study explored the use of zero-valent bimetals Fe/Zn for the degradation of chlorinated compounds in water which did not generate toxic by-products. The zero-valent bimetallic material was anchored on a polystyrene waste material as a green method of cleaning the environment. It was prepared through nitration, amination, complexation and reduction. The resulting solid material was characterised using Fourier transform infrared (FTIR). The material was also characterised using XPS which confirmed the presence of metals anchored on the material through complexation. The metals were also found to be present upon reduction to zero valence and even after the degradation process of the chlorinated organic compounds. It was then applied for the removal process. Optimization parameters such initial halide concentration, effect of time and bimetal dosage variation were established using synthetic water samples. It was found that the substrate-anchored ZVB material had a degradation capacity of 4.532, 5.362 and 4.513 μmol l⁻¹ for 1,2-dichloroethane, 2-chloro-2-methylpropane and 1-chlorobutane, respectively. The material was then applied on real samples sourced from Nairobi. Quantification of chlorine was done using potentiometric methods and the results confirmed that the degradation was first order. The degradation capacities were found to be 2.37 ± 0.01, 3.55 ± 0.01 and 3.72 ± 0.01 in that order.

This work reported a comparative study on the electrochemical incineration of nitrilotriacetic acid (NTA) in the presence of different supporting electrolytes (Na₂SO₄ and NaCl). Galvanostatic electrolyses were conducted in an undivided electrochemical cell containing boron-doped diamond (BDD) anode and platinum cathode. Initial solution pH, flow rate, applied current density, and supporting electrolyte concentration were selected as variables, besides the mineralization efficiency of NTA that was selected as response. Central composite rotatable design and response surface methodology were employed here to examine the statistical significance of the selected variables, as well as to determine the optimal conditions of the degradation process. Under the same operating conditions, two regression models were thus constructed to illustrate the differing impact of supporting electrolytes in BDD anode cells. The kinetics for NTA degradation followed different reaction orders for the two scenarios (in the absence and presence of NaCl), indicating the complex interaction between hydroxyl radicals and active chlorine. Despite this, the experimental results demonstrated that effective mineralization of NTA might also be achieved in the presence of chlorides (of lower concentrations). Besides, in the case of chlorides, the average mass transfer coefficient of the system was found to be strongly dependent on the initial solution pH. Lastly, a plausible reaction sequence concerning the electrolytic oxidation of NTA in chloride media was also proposed.

The influence of chloride ion concentration during the photo-assisted electrochemical degradation of simulated textile effluent, using a commercial Ti/Ru₀.₃Ti₀.₇O₂ anode, was evaluated. Initially, the effect of applied current and supporting electrolyte concentration on the conversion of chloride ions to form reactive chlorine species in 90 min of experiment was analyzed in order to determine the maximum production of reactive chlorine species. The optimum conditions encountered (1.5 A and 0.3 mol dm⁻³ NaCl) were subsequently employed for the degradation of simulated textile effluent. The efficiency of the process was determined through the analysis of chemical oxygen demand (COD), total organic carbon (TOC), of the presence of organochlorine products and phytotoxicity. Photo-assisted electrochemical degradation was more efficient for COD and TOC removal than the electrochemical technique alone. With simultaneous UV irradiation, a reduced quantity of reactive chlorine was produced, indicating that photolysis of the chlorine species led to the formation of hydroxyl radicals. This fact turns a simple electrochemical process into an advanced oxidation process.

Polychlorinated biphenyls (PCBs) are a group of 209 individual congeners widely used as industrial chemicals. PCBs are found as by-products in dye and paint manufacture and are legacy, ubiquitous, and persistent as human and environmental contaminants. PCBs with fewer chlorine atoms may be metabolized to hydroxy- and dihydroxy-metabolites and further oxidized to quinoid metabolites both in vitro and in vivo. Specifically, quinoid metabolites may form adducts on nucleophilic sites within cells. We hypothesized that the PCB-quinones covalently bind to cytochrome c and, thereby, cause defects in the function of cytochrome c. In this study, synthetic PCB quinones, 2-(4′-chlorophenyl)-1,4-benzoquinone (PCB3-pQ), 4-4'-chlorophenyl)-1,2-benzoquinone (PCB3-oQ), 2-(3′, 5′-dichlorophenyl)-1,4-benzoquinone, 2-(3′,4′, 5′-trichlorophenyl)-1,4-benzoquinone, and 2-(4′-chlorophenyl)-3,6-dichloro-1,4-benzoquinone, were incubated with cytochrome c, and adducts were detected by liquid chromatography-mass spectrometry (LC-MS) and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI TOF). Sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) was employed to separate the adducted proteins, while trypsin digestion and liquid chromatography-tandem mass spectrometry (LC-MS/MS) were applied to identify the amino acid binding sites on cytochrome c. Conformation change of cytochrome c after binding with PCB3-pQ was investigated by SYBYL-X simulation and cytochrome c function was examined. We found that more than one molecule of PCB-quinone may bind to one molecule of cytochrome c. Lysine and glutamic acid were identified as the predominant binding sites. Software simulation showed conformation changes of adducted cytochrome c. Additionally, cross-linking of cytochrome c was observed on the SDS-PAGE gel. Cytochrome c was found to lose its function as electron acceptor after incubation with PCB quinones. These data provide evidence that the covalent binding of PCB quinone metabolites to cytochrome c may be included among the toxic effects of PCBs.