Coupled solar photo-Fenton and biological treatment for the degradation of diuron and linuron herbicides at pilot scale

A coupled solar photo-Fenton (chemical) and biological treatment has been used to remove biorecalcitrant diuron (42 mg l(-1)) and linuron (75 mg l(-1)) herbicides from water at pilot plant scale. The chemical process has been carried out in a 82 l solar pilot plant made up by four compound parabolic collector units, and it was followed by a biological treatment performed in a 40 l sequencing batch reactor. Two Fe(II) doses (2 and 5 mg l(-1)) and sequential additions of H2O2 (20 mg l(-1)) have been used to chemically degrade the initially polluted effluent. Next, biodegradability at different oxidation states has been assessed by means of BOD/COD ratio. A reagent dose of Fe=5 mg l(-1) and H2O2=100 mg l(-1) has been required to obtain a biodegradable effluent after 100 min of irradiation time. Finally, the organic content of the photo-treated solution has been completely assimilated by a biomass consortium in the sequencing batch reactor using a total suspended solids concentration of 0.2 g l(-1) and a hydraulic retention time of 24h. Comparison between the data obtained at pilot plant scale (specially the one corresponding to the chemical step) and previously published data from a similar system performing at laboratory scale, has been carried out.     

Effects of concentrated drinking water injection on glutathione and glutathione-dependent enzymes in liver of Cyprinus carpio L

Two drinking water production plants located in North Italy, collecting water from the River Po (Plants 1 and 2) were chosen for this study. Water samples were collected before and after the disinfection process and at two points along the piping system. Water samples were concentrated by the solid-phase extraction system and injected intraperitoneally into specimens of Cyprinus carpio. The concentration of water samples was 3 l/equiv. In order to assess the effects of the water samples on carp liver, total glutathione and glutathione-dependent enzymes, such as glutathione S-transferase, glutathione peroxidase, glutathione reductase and glyoxalase I, were measured following this treatment for 6 days at two experimental times (3 and 6 days). Both water plant-treated carp showed a general increase of the enzymatic activities of glutathione S-transferase, and glutathione reductase which might be employed as potential biomarkers of oxidative stress induced by disinfected river water. Plant 1-treated carp showed higher glyoxalase I and glutathione levels and lower glutathione peroxidase activity. A depleted level of total glutathione and of glyoxalase I for specimens of water plant 2 (for both experimental times), without correlation with the distances in the pipeline, suggests that river plant water can also lead to potentially adverse effects on selected biochemical parameters in C. carpio.     

Significance of urinary arsenic speciation in assessment of seafood ingestion as the main source of organic and inorganic arsenic in a population resident near a coastal area

In order to characterize the different sources of exposure to arsenic (As), urinary excretion of total As, the sum of inorganic As+MMA+DMA determined by the hydride generation-atomic absorption spectrophotometry technique, and the species As(3), As(5), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine were determined in 49 workers at a steel foundry, with presumed occupational exposure to As, and 50 subjects from the general population, all males. No evidence of occupational exposure to As resulted from environmental monitoring performed in the foundry, although the analysis of minerals used as raw materials showed the presence of As, particularly in fossils and fine ores. The urinary concentrations of As(3), MMA, DMA, the sum of inorganic As+MMA+DMA and total As were not different in the two groups, while arsenobetaine appeared significantly higher in the controls than in the workers. The different species of urinary As were all significantly correlated. Urinary excretion of As(3) was associated with the consumption of mineral water and with residence in an industrial zone, while MMA, DMA, arsenobetaine, the sum of inorganic As+MMA+DMA and total As urinary excretion were associated with the consumption of crustaceans and/or shellfish 3 days or less before urine collection. Multiple regression analysis confirmed these results. In conclusion, in populations with a high consumption of seafood, living in areas characterized by coastal/marine As pollution, only speciation of As can identify a prevalent role of environmental sources, like the consumption of seafood contaminated by As, in determining urinary As excretion, and exclude an occupational origin of the exposure.     

Minimization of the environmental impact in the unhairing of bovine hides

This study tests an alternative method to the traditional unhairing method used during the process of tanning the hides. The new method is based on the substitution of sodium sulfide by hydrogen peroxide as an unhairing agent in both hair recovery and recirculation of the floats employed in the process. The properties of the hides obtained using the two methods have been compared and the results indicate that those hides have similar physical, chemical, and organoleptic properties. However, the differences existing from an environmental point of view are significant. These include reductions of water consumption (approx 70%), chemical oxygen demand (approx 35%), toxicity (98%) and total kjendhal nitrogen (50%). Also, the risk associated with the production of hydrogen sulfide is eliminated, which implies a great improvement in terms of safety for the workers. Given the large amounts of water and chemical pollution discharged in the process, the reductions in absolute values represent a significant improvement. A financial assessment was carried out to demonstrate that the proposed new system is 16% more economic than the traditional one.     

Biochemical effects of clomazone herbicide on piava (Leporinus obtusidens)

This study aims to verify the effects of the clomazone concentration used in rice fields on acetylcholinesterase (AChE), thiobarbituric acid reactive substances (TBARS), protein carbonyl and catalase activity in tissues of piava (Leporinus obtusidens). LC(50)-96h was 5.0 mg L(-1) and the fish were exposed to 1/10 of LC(50)-96 h: 0.5 mg L(-1) of clomazone for 96 and 192h. The same parameters were also assayed after a recovery period of 192 h in clean water. AChE activity was reduced only in the brain and heart of fish exposed for 96 h. AChE activity was decreased in the brain, muscle and heart tissues after 192 h of exposure. After 192 h of recovery period, AChE activity remained diminished in brain and muscle and showed a decrease in eye. However, after 192 h of recovery, AChE activity in heart was recovered. Fish showed increased TBARS levels in brain at all experimental periods. TBARS levels decreased in liver and muscle tissues after 192 h of exposure. The increase in muscle TBARS persisted in fish transferred to clean water. Protein carbonyl in the liver was increased in all periods studied including the recovery period. Catalase activity was reduced during all periods. The present study demonstrates the occurrence of disorders in AChE, TBARS, protein carbonyl and catalase activity in piava. The results also show changes in fish after exposure to an environmentally relevant concentration of clomazone. Most effects observed persisted after the recovery period. Thus, these parameters may be used to monitor clomazone toxicity in fish.     

Effects of a selenium-enriched diet on antioxidant response in adult crayfish (Procambarus clarkii)

Many diets employed in aquaculture are enriched with selenium to improve the diet quality and its conservation. The aim of the study was to investigate the effects of a diet enriched in selenium (1.21 mg kg(-1)) on the antioxidant response of Procambarus clarkii (Girard, 1852). Crayfish fed a diet with lower selenium content (0.30 mg kg(-1)) were the control. Selenium accumulation, enzymatic activities, and total glutathione were evaluated in hepatopancreas of adults of both sexes fed with both diets for 50 days at two experimental times (T(30), T(50) days). Treated females exhibited the highest selenium bioaccumulation during both experimental times, while treated males displayed the highest selenium concentration after 30 days, compared to control crayfish. A sex-related difference was found for the response of the analyzed enzymes in the selenium diet-treated specimens. In fact, superoxide dismutase, glutathione peroxidase and glyoxalase I activities in males were more sensitive compared with females, showing depleted activities in both experimental times. Catalase activity was induced in females (T(50)), while glutathione S-transferase activity was the highest in treated females and the lowest in treated males, compared with own controls. Only glutathione reductase activity and glutathione content showed the same trend in both sexes, which were both lowered in treated specimens, when compared with control crayfish. This result might be due to the effect of selenium toxicity on this freshwater species. Males and females of P. clarkii showed a different susceptibility to the prooxidant effects in a Se-enriched diet.     

Absorption of nitro-polycyclic aromatic hydrocarbons by biomembrane models: effect of the medium lipophilicity

To demonstrate the relationship between the structure of nitro-polycyclic aromatic hydrocarbons and their effect on biomembranes, we have investigated the influence of three structurally different nitro-polycyclic aromatic hydrocarbons, 2-nitrofluorene, 2,7-dinitrofluorene and 3-nitrofluoranthene, on the thermotropic behavior of dimyristoylphosphatidylcholine multilamellar vesicles, used as biomembrane models, by means of differential scanning calorimetry. The obtained results indicate that the studied nitro-polycyclic aromatic hydrocarbons affected the thermotropic behavior of multilamellar vesicles to various extents, modifying the pretransition and the main phase transition peaks and shifting them to lower temperatures. The effect of the aqueous and lipophilic medium on the absorption process of these compounds by the biomembrane models has been also investigated revealing that the process is hindered by the aqueous medium but strongly allowed by the lipophilic medium.     

Mutagenic and recombinagenic activity of airborne particulates, PM10 and TSP, organic extracts in the Drosophila wing-spot test

The genotoxicity associated with air pollution in the city of Canoas, Rio Grande do Sul (Brazil), was assessed in November (spring) and January (summer). We applied the somatic mutation and recombination test (SMART) in Drosophila melanogaster in its standard version with normal bioactivation (ST) and in its variant with increased cytochrome P450-dependent biotransformation capacity (HB). The data indicated the genotoxicity of TSP and PM10 collected in November, in both ST and HB crosses. The genotoxic activity of the PM10 material in the spring sample was exclusively associated with the induction of mitotic recombination, whereas the TSP genetic toxicity was due to both recombinational as well as point and/or chromosomal mutation events. Considering PM10 collected in January, a positive response--100% (17.10 m3/ml) concentration--was observed in the HB cross, which was not detected in the ST cross.     

Estimation of pollutant partition in sandy soils with different water contents

The objectives of this work were: (1) to identify an isotherm model to relate the contaminant contents in the gas phase with those in the solid and non-aqueous liquid phases; (2) to develop a methodology for the estimation of the contaminant distribution in the different phases of the soil; and (3) to evaluate the influence of soil water content on the contaminant distribution in soil. For sandy soils with negligible contents of clay and natural organic matter, contaminated with benzene, toluene, ethylbenzene, xylene, trichloroethylene (TCE), and perchloroethylene (PCE), it was concluded that: (1) Freundlich’s model showed to be adequate to relate the contaminant contents in the gas phase with those in the solid and non-aqueous liquid phases; (2) the distribution of the contaminants in the different phases present in the soil could be estimated with differences lower than 10% for 83% of the cases; and (3) an increase of the soil water content led to a decrease of the amount of contaminant in the solid and non-aqueous liquid phases, increasing the amount in the other phases.     

Mullet and gudgeon liver histopathology and macroinvertebrate indexes and metrics upstream and downstream from a wastewater treatment plant (Febros River—Portugal)

The increased pollution in ecosystems reinforces the importance of both chemical monitoring and biological monitoring of streams and rivers, as an effective water quality-based approach to assess aquatic ecosystem health. In this study, gudgeon (Gobio gobio) and mullet (Mugil cephalus) liver histopathology (biomarker) and some macroinvertebrate community indexes and metrics (bioindicator) were used to evaluate the effect of the wastewater treatment plant (WWTP) of Febros (Avintes) in Febros River water quality and ecosystem health. Regarding macroinvertebrate communities, the Belgian Biotic Index (BBI) and Iberian Biological Monitoring Working Party (IBMWP) indexes suggested that Febros water was slightly polluted, even though the worst situation was found downstream the WWTP discharge. Concerning community metrics, upstream percent of individuals in five numerically dominant taxa (80%) was slightly more superior than the downstream (78%). The presence of intolerant or sensible individuals, determined by percent of Ephemeroptera, Plecoptera, and Trichoptera individuals and number of Ephemeroptera, Plecoptera, and Trichoptera families metrics, was higher upstream WWTP, reflecting a better water quality. The histopathology shows the presence of hepatic lesions in gudgeon and mullet. The statistical analysis of the lesion gradation showed that only necrosis was significantly higher in gudgeon captured downstream the WWTP, while differences were not observed for mullet. The multivariate analysis of data confirmed the existence of differences in hepatic lesions between gudgeon and mullet and between sampling sites. Regarding macroinvertebrate community, this analysis showed that the organic contamination reflected by the BBI and IBMWP indexes values was a determinant factor in the spatial distribution of macroinvertebrates. This work showed that the study of different biological organization levels can be used for a better assessment of ecosystem ecological integrity and can be used as a tool to reveal anthropogenic activity effects in macroinvertebrate diversity and in fish liver pathology from Febros River.