Behavior and prediction of photochemical degradation of chlorinated polycyclic aromatic hydrocarbons in cyclohexane

The photochemical degradation of 11 chlorinated polycyclic aromatic hydrocarbons (ClPAHs) and the corresponding 5 parent PAHs was examined to simulate the compound’s fate on aerosol surfaces. All the ClPAHs and PAHs decayed according to the first-order reaction rate kinetics. The photolysis rates of ClPAHs varied greatly according to the skeleton of PAHs; the rates of chlorophenanthrenes (ClPhes) and 1-chloropyrene were higher than those of corresponding parent PAHs, whereas chlorofluoranthenes, 7-chlorobenz[a]anthracene and 6-chlorobenzo[a]pyrene were more stable under irradiation compared to respective parent PAH. Considering the photoproducts of ClPhes detected, the oxidation could occur immediately at positions of the highest frontier electron density. Finally, the quantitative structure-property relationship models were developed for direct photolysis half-lives and average quantum yields of the ClPAHs and parent PAHs, in which the significant factors affecting photolysis were E_LUMO+1, total energy and surface area, and E_LUMO, E_LUMO − E_HOMO and total energy, respectively.     

Estrogen equivalent concentration of 13 branched para-nonylphenols in three technical mixtures by isomer-specific determination using their synthetic standards in SIM mode with GC-MS and two new diasteromeric isomers

Thirteen isomers of branched para-nonylphenols (para-NP) in three technical mixtures were isomer-specifically determined using their synthesized standards by SIM of structurally specific ions, m/z 135, 149 or 163 with GC–MS. Of the 13 isomers, four isomers, 4-(2,4-dimethylheptan-4-yl)phenol, 4-(4-methyloctan-4-yl)phenol, 4-(3-ethyl-2-methylhexan-2-yl)phenol (3E22NP) and 4-(2,3-dimethylheptan-2-yl)phenol synthesized for their determinations were first used as standard substances. The 13 isomers in the technical mixtures individually occurred at mass percent portion of more than 2%. The total mass percent portions in the mixtures from Tokyo Chemical Industry (TCI), Aldrich, and Fluka covered with 89 ± 2%, 75 ± 4% and 77 ± 2%, respectively. The abundance of 4-(3,6-dimethylheptan-3-yl)phenol in the three mixtures was the largest with 11.1 ± 2% to 9.9 ± 0.3%, while that of 4-(2-methyloctan-2-yl)phenol was the smallest with 2.9 ± 0.3% to 3.0 ± 0.2%. Additionally, structures of four new isomers of more than 1% portion present in a technical mixture were elucidated as two pairs of diastereomeric isomers: two types of 4-(3,4-dimethylheptan-4-yl)phenol (344NP) and those of 4-(3,4-dimethylheptan-3-yl)phenol (343NP). By estrogenic assay of 13 isomers with yeast estrogen screen system, the activity of 3E22NP was the highest, while that of 4-(3-methyloctan-3-yl)phenol was the least. Their relative activities to that of 3E22NP were individually calculated. Estrogenic equivalent concentrations of the three technical mixtures were predictively evaluated. The ratio of the EEC to the conventional concentration, total mass percent portions of the 13 isomers in technical mixtures were 0.208 for TCI, 0.206 for Aldrich and 0.205 for Fluka. The predicted estrogenic activity of measured concentration of para-NP in technical mixtures was approximately 5-fold greater than the measured estrogen agonist activity.     

Complexation-flocculation of organic contaminants by the application of oxyhumolite-based humic organic matter

Control of hazardous organic micropollutants is a challenging water quality issue. Dissolved humic organic matter (DOM) isolated from oxyhumolite coal mined in Bohemia was investigated as a complexation agent to remove polycyclic aromatic hydrocarbons (PAHs) and functionalized phenols from water by a two-stage process involving complexation and flocculation. After the formation of humic-contaminant complexes, ferric salts were added resulting in the precipitation and flocculation of the DOM and the associated pollutants. Flocculation experiments with ferric ion coagulants indicated that precipitation of oxyhumolite DOM together with the complexed contaminants occurred at lower ferric ion concentrations than with the reference DOM in acidic environments (pH approximately 3.5). The complexation-flocculation removal rates for non-reactive PAHs characterized by small localization energies of pi-electrons correlated well with the complexation constants. On the other hand, the combined complexation-flocculation removal rates for activated PAHs including trans-stilbene, anthracene and 9-methyl anthracene, as well as functionalized polar phenols, were higher than predicted from the complexation coefficients. Methodological studies revealed for the first time that the ferric ion coagulant contributed to enhanced removal rates, most probably due to ferric ion-catalyzed pollutant degradation resulting in oxidized products.     

Effects of landfill leachate effluent and bisphenol A on glutathione and glutathione-related enzymes in the gills and digestive glands of the freshwater snail Bellamya purificata

Environmental contaminants with estrogenic activity have recently attracted attention due to their potential detrimental effects on the reproduction of human and wildlife. The aim of this study was to evaluate the use of endogenous glutathione and glutathione-related enzymes as biomarkers of exposure to landfill leachate effluent and bisphenol A (BPA) in the freshwater snail, Bellamya purificata. Following exposure to 1%, 5% and 10% landfill leachate effluent and 1, 10, 50 and 100mugl(-1) BPA for 0, 2, 7 and 15d, activities of glutathione S-transferase (GST), selenium-dependent glutathione peroxidase (SeGPx) and glutathione reductase (GR) and levels of total glutathione were measured in the gills and digestive glands of the snails. GST and total glutathione were the most sensitive parameters in both exposure scenarios. GST activities increased by about 80%, while total glutathione decreased to 70% and 80% in the gills and digestive glands, respectively. In contrast, SeGPx and GR activities remained at the same levels in all the treatment groups compared with those of controls. The results indicated that among glutathione and glutathione-related enzymes, GST activity and total glutathione level, which showed dose-dependent dynamics, could be used as biomarkers of aquatic ecosystems contaminated with landfill leachate.     

Analysis of perfluorooctanoate (PFOA) and other perfluorinated compounds (PFCs) in the River Po watershed in N-Italy

C7-C11 perfluorinated carboxylates (PFACs) and perfluorooctansulfonate (PFOS) were analysed in selected stretches of the River Po and its major tributaries. Analyses were performed by solid-phase extraction (SPE) with Oasis HLB cartridges and methanol elution followed by LC-MS-MS detection using 13C-labelled internal standards. High concentration levels ( approximately 1.3 microg l(-1)) of perfluorooctanoate (PFOA) were detected in the Tánaro River close to the city Alessandria. After this tributary, levels between 60 and 337 ng l(-1) were measured in the Po River on several occasions. The PFOA concentration close to the river mouth in Ferrara was between 60 and 174 ng l(-1). Using the river discharge flow data in m3 s(-1) at this point (average approximately 920 m3 s(-1) for the year 2006), a mass load of approximately 0.3 kg PFOA per hour or approximately 2.6 tons per year discharged in the Adriatic Sea has been calculated. PFOS concentration levels in the Po River at Ferrara were approximately 10 ng l(-1).     

Removal of thiobencarb in aqueous solution by zero valent iron

A cost-effective method with zero valent iron (ZVI) powder was developed for the purification of thiobencarb (TB)-contaminated water. The removal treatment was performed in the batch system. A sample solution of 10 ml containing 10 microg ml(-1) of TB could be almost completely treated by 100mg of ZVI at 25 degrees C for 12h of treatment time. Since the formation of chloride ion in the aqueous solution during the treatment of TB was observed, the removal of TB with ZVI may contain two processes: reduction (degradation) and adsorption. Because the present treatment for TB is simple, easy handling and cheap, the developed technology with ZVI can contribute to the treatment of agricultural wastewaters.     

Concentrations and specific loads of brominated flame retardants in sewage sludge

Many substances related to human activities end up in wastewater and accumulate in sewage sludge. The present study focuses on two classes of brominated flame retardants: polybrominated diphenyl ethers (BDE28, BDE47, BDE49, BDE66, BDE85, BDE99, BDE100, BDE119, BDE138, BDE153, BDE154, BDE183, BDE209) and hexabromocyclododecane (HBCD) detected in sewage sludge collected from a monitoring network in Switzerland. Mean concentrations (n=16 wastewater treatment plants) were 310, 149, 95 and 17microg per kg dry matter for decaBDE, HBCD, penta- and octaBDE, respectively. These numbers correspond well with other studies from European countries. DecaBDE, HBCD, penta- and octaBDE showed average specific loads (load per connected inhabitant per year) in sludge of 6.1, 3.3, 2.0 and 0.3mgcap(-1)yr(-1), respectively. This is in line with consumption and storage of the compounds in the environment and the anthroposphere. Discrepancies observed for octaBDE and HBCD can be explained by the release from materials where these compounds are incorporated in and/or their degradation during anaerobic sludge treatment. Loads from different types of monitoring sites showed that brominated flame retardants ending up in sewage sludge originate mainly from surface runoff, industrial and domestic wastewater.     

Polychlorinated biphenyls (PCBs) and hydroxy-PCBs in adipose tissue of women in Southeast Spain

Polychlorinated biphenyls (PCBs) and hydroxylated PCBs (OH-PCBs) were investigated in human adipose tissue samples collected from 20 women undergoing surgery. Mean sum of PCB and sum of OH-PCB levels were 737ng/g of lipid and 8pg/g of lipid, respectively. Among PCBs, congeners 180, 153, 138 and 170 were the most frequent and abundant, and together constituted 72% of the total amount of PCBs in adipose tissue. The PCB congener pattern and the frequencies and concentrations of non-dioxin-like and non-hydroxylated congeners observed in adipose tissue were similar in distribution and order of magnitude to the profile previously published in Spain but lower than that found in other European countries. Among OH-PCB congeners studied, 4-OH-PCB 107/118 was found at the highest concentrations followed by 3'-OH-PCB 180 and 3-OH-PCB 138. To date, no information on levels of PCB metabolites in the Spanish population is available for comparison. These three predominant OH-PCBs contributed 97% of all OH-PCBs. Twelve dioxin-like PCBs contributed around 8% of the total PCB exposure, and all were present in all study subjects. Further research is required to determine trends in human exposure to PCBs and OH-PCBs and how existing banning measures affect exposure.     

Interactions between glyphosate and autochthonous soil fungi surviving in aqueous solution of glyphosate

The survival of autochthonous fungi in soil treated with 1mM aqueous solution of glyphosate was investigated. Significant differences in the total number of fungi in the studied objects were observed, and additionally significant qualitative changes were encountered. The dominating group of fungi belonged to genus Fusarium: Fusarium solani H30, Fusarium solani H50 and Fusarium oxysporum H80. Interactions between the isolated strains of fungi and varying concentrations of glyphosate were determined. The studied strains possessed high tolerance against the applied doses of glyphosate (0.5-2.0 mM). In the presence of glyphosate (as a sole source of phosphorus) applied in concentrations of 1.0-1.5 mM the increase in dry mass of the tested fungi was highly significant. In the presence of glyphosate the phenotypic changes of studied strains were observed as was shown as the presence of colorants being indicators of such changes. Thus, their color and intensity depended on the age, pH and species present in the culture. The degradation of glyphosate by studied fungi was determined by means of TLC. Two types of compounds were formed. One of them (Rf=0.21-0.35) contained free amino group but was not either glycine nor AMPA. Survival of Fusarium in soil environment is potentially dangerous.     

Evaluation of copper effects upon Girardia tigrina freshwater planarians based on a set of biomarkers

Copper is a common environmental contaminant, which is particularly toxic to living organisms when in high concentrations. To monitor environmental contamination by Cu2+ and other heavy metals, well characterized bioindicator organisms and standardized assays are needed. As a first step toward this end, we have analysed Cu2+ effects upon Girardia tigrina freshwater planarians, based on the assessment of mobility, regeneration performance, micronucleus (MN) frequency in regenerating animals, and reproductive performance. These four biomarkers provided complementary information on Cu2+ toxicity, teratogenicity, mutagenicity and chronic (>96 h of exposure) effects, respectively. The LC50 was calculated for newborn, adult and regenerating planarians, and values of 12+/-0.02 mg l(-1), 42+/-0.08 mg l(-1), 48+/-0.13 mg l(-1), respectively, were obtained after 96 h of exposure. Mobility, for intact adults, and time of regeneration and MN frequency, for regenerating animals, were significantly affected by Cu2+ concentrations as low as 0.10 mg l(-1). MN assay for regenerating G. tigrina neoblasts showed higher sensitivities than MN assays performed with other bioindicator freshwater organisms, such as moluscs or fish. Chronic exposure effects were clearly evidenced by assessment of reproductive performance, with significant reduction in fecundity and fertility rates upon exposure to Cu2+ concentrations as low as 0.05 mg l(-1). Therefore, G. tigrina can be regarded as a useful bioindicator species for the detection and evaluation of Cu2+ effects upon freshwater invertebrates, allowing insights on the effects of Cu2+ (and possibly other heavy metals) in a freshwater environment.