Brominated flame retardant concentrations and trends in abiotic media

BFR burdens in abiotic media have been less studied than in biota, despite their essential value as an aide to identifying sources, temporal and geographic trends and exposure routes. Many polymer products consist of several percent by weight of BFRs. Global trade in these can result in rapid and wholesale BFR movement. Loss from in-use products of nonreactive BFRs may be important, particularly in respect to indoor exposure. In the case of BDE-209, discharges from publicly owned treatment works may be substantial. BFR burdens in air, water and sewage sludge respond rapidly to changes in environmental BFR inputs. PBDEs have been the most widely studied. In many locales PBDE burdens in these media now surpass those of PCBs. Air and water near sources and urban areas are typically enriched relative to rural locales. The more volatile PBDEs dominate in the vapor phase, while BDE-209 typically predominates on particulates. Evidence exists for long-range transport of the more volatile PBDEs. A greater diversity of BFRs (mostly PBDEs, HBCD and TBBP-A) has been detected in sewage sludges. Land application of these sludges on agricultural fields is one conduit for soil contamination. In general, environmental concentrations of BDE-209 appear to be increasing, while penta-BDE burdens in Europe may have peaked. Sediments function as longer-term integrators of environmental burdens. Concentrations of common BFRs therein may be substantial near point sources. Evidence for debromination in the environment has been limited to date. However, some laboratory and field observations suggest it is possible to a limited extent.     

In situ and laboratory bioassays using Poecilia reticulata Peters, 1859 in the biomonitoring of an acidic lake at Camaçari, BA, Brazil

The suitability and viability of acute in situ bioassays were investigated in the biomonitoring program of an acidic lake contaminated with sulphur residues. Responses of organisms observed in laboratory and in situ bioassays were also assessed to determine whether or not they were similar and comparable, regarding accuracy and precision. Newborn Poecilia reticulata were employed as test organisms and exposed to the same water samples under in situ and laboratory conditions. Mortality/immobility was the endpoint assessed and dead/immobile organisms were counted at various time intervals during exposure. The mean calculated LT50 values and 95% confidence intervals were 1.61 (1.36-1.87) h in the laboratory bioassays and 0.72 (0.55-0.89) h in the in situ bioassays. Statistical comparison of these values revealed a significant difference (p<0.05). In situ bioassays were more accurate than those carried out in the laboratory, demonstrating higher sensitivity and better reproduction of what occurs in nature, while laboratory bioassays were more precise.     

Evaluation of ozone-nitrogen oxides-volatile organic compound sensitivity of Cincinnati, Ohio

Ambient concentrations of ozone (O3), nitrogen oxides (NOx), total reactive nitrogen (NOy), nitric acid (HNO3), and hydrogen peroxide (H2O2) were measured during September 2003 at an urban site of Cincinnati, OH. The aim of this study was two-fold: to investigate whether O3 formation in this population exposure-type site is NOx, sensitive or volatile organic compound (VOC) sensitive and to test the practicality of using two combined observational-based methods to identify the sensitivity of O3 formation in midlevel polluted locations. The evaluation of the indicator species: NOy, O3/NOy, O3/HNO3, H2O2/ HNO3, and O3/(estimated NOx reaction products), as well as the combined hypothesis testing analysis of the weekend/weekday (WE/WD) differences of 1-hr and 8-hr average maximum O3 and of the 6:00 a.m.-9:00 a.m. average nitric oxide and NOx concentrations, show evidence that Cincinnati is likely VOC sensitive. Average WE 1-hr and 8-hr maximum O3, as well as duration of WE O3 accumulation, were not lower than the corresponding WD levels in spite of the observed significant reduction in NO, emissions on WE, a typical situation in VOC-sensitive locations. The possibility that the seasonal transition from summer to autumn could have influenced the results was also investigated through an exploratory analysis of the afternoon O3 maximum/NOx measured and of the WE/WD differences of peak O3 and morning average NO and NO, concentrations observed at this site from June through September 2003. The results suggest that a VOC-sensitive chemistry regime dominated along the summer season. The findings of this study suggest that additional reductions in regional NO, emissions in Cincinnati, a potential nonattainment area under the 8-hr O3 standard, may cause an increase in local O3. Future strategies to reduce O3 in Southwest Ohio should be further evaluated carefully. The combination of observational-based methods might provide a consistent complementary approach in the identification of the NO,-VOC sensitive characteristics of mid-to-moderate polluted urban areas.     

Effect of farmyard manure application on boron adsorption-desorption characteristics of some soils

Boron (B) availability to crop plants depends on soil properties as well as management practices like liming, fertilization and use of organic manures. To assess the effect of farmyard manure (FYM) application on availability of added B, adsorption-desorption of B was investigated in five different soils receiving varying doses of FYM (0, 5 and 10 g FYM kg(-1) soil). Two surfaces Freundlich model was found best to account for B adsorption-desorption data of all soils. Application of FYM increased B adsorption capacities pertaining to low (K1) and high (K2) concentration ranges in all soils, except Soil C (Alfisol) having a pH of 9.8, in which the higher rate of FYM decreased the value of K2. Application of FYM did not change B desorption capacities of soils corresponding to low B concentration range (K(1)(1)) significantly, however, it increased B desorption capacity pertaining to high B concentration (K(1)(2)) in all soils, except Soils C (Alfisol) and E (Entisol) having pH of 9.8 and 5.1, respectively. Application of FYM increased the desorption slope factor applicable to low concentration range (1/n(1)(1)) in Soil A (Inceptisol), but decreased it in Soil E (Entisol). The 1/n(1)(2) (desorption slope factor applicable to high concentration range) decreased with FYM application in all soils except Soil E (Entisol), where it was increased. Boron desorption index (slope(ads)/slope(des)) decreased with FYM application in low B concentration range, but increased in high concentration range for all soils except soil E (Entisol, pH 5.1), in which a reverse trend was observed. Application of FYM increased the retention of added B in soils and may help reducing the leaching losses.     

Pyrolysis behavior of tire-derived fuels at different temperatures and heating rates

Pyrolytic product distribution rates and pyrolysis behavior of tire-derived fuels (TDF) were investigated using thermogravimetric analyzer (TGA) techniques. A TGA was designed and built to investigate the behavior and products of pyrolysis of typical TDF specimens. The fundamental knowledge of TGA analysis and principal fuel analysis are applied in this study. Thermogravimetry of the degradation temperature of the TDF confirms the overall decomposition rate of the volatile products during the depolymerization reaction. The principal fuel analysis (proximate and ultimate analysis) of the pyrolytic char products show the correlation of volatilization into the gas and liquid phases and the existence of fixed carbon and other compounds that remain as a solid char. The kinetic parameters were calculated using least square with minimizing sum of error square technique. The results show that the average kinetic parameters of TDF are the activation energy, E = 1322 +/- 244 kJ/mol, a pre-exponential constant of A = 2.06 +/- 3.47 x 10(10) min(-1), and a reaction order n = 1.62 +/- 0.31. The model-predicted rate equations agree with the experimental data. The overall TDF weight conversion represents the carbon weight conversion in the sample.     

Source and persistence of pesticides in a semi-confined chalk aquifer of southeast England

Pesticide contamination in groundwater is an increasing problem that poses a significant long-term threat to water quality. Following the detection of elevated concentrations of diuron in boreholes in a semi-confined chalk aquifer from southeast England, a sampling programme was undertaken. Between 2003 and 2004 diuron was observed in 90% of groundwaters analysed. In 60% of groundwater samples metabolites of diuron were more prevalent than the parent compound. Longer-term (1989-2005) monitoring shows that pollution of the aquifer by atrazine, simazine, and more recently diuron, shows a positive correlation with periods of high groundwater levels. Results from groundwater residence time indicators suggest that the highest diuron concentrations are associated with waters containing the greatest proportion of recent recharge. There is some evidence to indicate that diuron occurrence can be spatially related to areas of urban and industrial development and is probably correlated with amenity usage.     

Interaction effects of metals and salinity on biodegradation of a complex hydrocarbon waste

The presence of high levels of salts because of produced brine water disposal at flare pits and the presence of metals at sufficient concentrations to impact microbial activity are of concern to bioremediation of flare pit waste in the upstream oil and gas industry. Two slurry-phase biotreatment experiments based on three-level factorial statistical experimental design were conducted with a flare pit waste. The experiments separately studied the primary effect of cadmium [Cd(II)] and interaction effect between Cd(II) and salinity and the primary effect of zinc [Zn(II)] and interaction effect between Zn(II) and salinity on hydrocarbon biodegradation. The results showed 42-52.5% hydrocarbon removal in slurries spiked with Cd and 47-62.5% in the slurries spiked with Zn. The analysis of variance showed that the primary effects of Cd and Cd-salinity interaction were statistically significant on hydrocarbon degradation. The primary effects of Zn and the Zn-salinity interaction were statistically insignificant, whereas the quadratic effect of Zn was highly significant on hydrocarbon degradation. The study on effects of metallic chloro-complexes showed that the total aqueous concentration of Cd or Zn does not give a reliable indication of overall toxicity to the microbial activity in the presence of high salinity levels.     

Contribution of anthropogenic pollutants to the increase of tropospheric ozone levels in the Oporto Metropolitan Area, Portugal since the 19th century

The main purpose of this study was to evaluate the contribution of anthropogenic pollutants to the increase of tropospheric ozone levels in the Oporto Metropolitan Area (Portugal) since the 19th century. The study was based on pre-industrial and recent data series, the results being analyzed according to the atmospheric chemistry. The treatment of ozone and meteorological data was performed by classical statistics and by time-series analysis. It was concluded that in the 19th century the ozone present in the troposphere was not of photochemical origin, being possible to consider the respective concentrations as reference values. For recent data a cycle of 8h for ozone concentrations could be related to traffic. Compared to the 19th century, the current concentrations were 147% higher (252% higher in May) due to the increased photochemical production associated with the increased anthropogenic emissions.     

Mobility of heavy metals from tailings to stream waters in a mining activity contaminated site

In this paper the results of a recent characterization of Rio Piscinas (SW of Sardinia, Italy) hydrological basin are reported. In such area (about 50 km2), previous mining activities caused a serious heavy metal contamination of surface waters, groundwater, soils and biota. Acid mine drainage phenomena were observed in the area. The main sources of contamination are the tailings stored in mine tunnels and abandoned along fluvial banks. A methodological approach was adopted in order to identify relations between tailings and water contamination. Representative samples of tailings and stream sediments samples were collected. XRD analyses were performed for mineralogical characterization, while acid digestion was carried out for determining metal contents. Batch sequential leaching tests were performed in order to assess metal mobility. Also groundwater and stream water were sampled in specific locations and suitably characterized. All information collected allowed the understanding of the effect of tailings on water contamination, thus contributing to the qualitative prediction of pollution evolution on the basis of metal mobility. Finally, a potential remediation strategy of stream water is proposed.     

Removal of trichloroethylene from water by cellulose acetate supported bimetallic Ni/Fe nanoparticles

In this study, cellulose acetate (CA) supported Ni/Fe nanoparticles were prepared and the ability of these nanoparticles to remove trichloroethylene (TCE) from water was studied. The effects of TCE reduction by the nanoparticles and sorption by the CA support were accounted for separately in the model. CA supported post-coated Ni/Fe nanoparticles were used to investigate the effect of metal particle composition on the observed reduction rate constant. The results show that the metal mass normalized observed reduction rate constant was proportional to the Ni content in the post-coated Ni/Fe nanoparticles in the range of 0-14.3 wt.%. This constant reached a maximum between 14.3 and 21.4 wt.% and decreased with further increase in Ni content. CA supported co-reduced Ni/Fe bimetallic nanoparticles gave poorer performance compared to CA supported post-coated Ni/Fe bimetallic nanoparticles at the same Ni content in Ni/Fe nanoparticles.