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.     

Organochlorine contaminants in complete clutches of Morelet's crocodile (Crocodylus moreletii) eggs from Belize

Seven complete clutches of Morelet's crocodile (Crocodylus moreletii) eggs were collected in northern Belize and examined for organochlorine (OC) pesticide residues. The primary OC detected, p,p-DDE, was found in every egg analyzed (n=175). Other OCs detected included p,p-DDT, p,p-DDD, methoxychlor, aldrin, and endosulfan I. Concentrations of individual OCs ranged from 4 ppb (ng chemical/g egg wet weight) to greater than 500 ppb. A statistical evaluation of p,p-DDE levels in three complete clutches was used to derive the minimum number of eggs needed from a clutch to precisely determine the mean p,p-DDE concentration representative of that clutch. Sample sizes of 8 (80% confidence level) and 11 (90% confidence level) were determined to yield an accurate estimate of contaminant levels in a full clutch of eggs. The statistically recommended sample size of 11 eggs (at 90% confidence level) was successfully tested on the four additional clutches.     

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.     

Effects of medetomidine, a novel antifouling agent, on the burrowing bivalve Abra nitida (Müller)

The effects of medetomidine, a novel antifouling candidate, on the burrowing bivalve Abra nitida were studied. The burrowing behaviour, sediment reworking activity and faeces production were assessed after 24 h exposure of A. nitida to sublethal concentrations of medetomidine. Medetomidine caused a significant decrease in the burrowing response and in the sediment reworking activity. The median effective concentrations (EC50) were 430 nM (86 microg/l) and 4.4 nM (0.9 microg/l), respectively. No effects on the faeces production were detected. Although significant effects of medetomidine on A. nitida were registered, a reversibility of the effects was observed when 24 h-exposed animals were incubated in clean seawater and sediment for 24 h. Considerations relating to the future commercialisation of medetomidine for antifouling purposes are discussed.     

Seasonal and spatial patterns of metals at a restored copper mine site II. Copper in riparian soils and Bromus carinatus shoots

Soil and plants were sampled throughout winter and spring near a perennial stream traversing a restored mine site in a winter-rainy climate. Within 1m of an acidic reach of the stream, soil had pH 3-5 and 50-100 microg/g "bioavailable" copper (extractable with 0.01 M CaCl2). Soil 2-3 m from the stream had pH 5-8 and lower (less than 3 microg/g) bioavailable copper. "Oxide-bound" copper (extractable with 2N HCl) was 50-100 microg/g at most locations. Copper concentrations in the shoots of field-collected Bromus carinatus declined from 20 microg/g in winter to 2 microg/g in spring at all sampling sites. A similar temporal pattern was found in plants grown under controlled conditions. Thus B. carinatus has a developmental program for control of shoot copper concentration, causing a seasonally-varying pattern of copper phytoaccumulation over a large range of copper availability in the soil.     

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.     

Effects of initial saturation on properties modification and displacement of tetrachloroethene with aqueous isobutanol

Packed column experiments were conducted to study effects of initial saturation of tetrachloroethene (PCE) in the range of 1.0-14% pore volume (PV) on mobilization and downward migration of the non-aqueous phase liquid (NAPL) product upon contact with aqueous isobutanol ( approximately 10 vol.%). This study focused on the consequences of swelling beyond residual saturation. Columns were packed with mixtures of neat PCE, water and glass beads and waterflooded to establish a desired homogeneous residual saturation, and then flooded with aqueous isobutanol under controlled hydraulic conditions. Results showed a critical saturation of approximately 8% PV for these packed column experimental conditions. At low initial PCE saturations (<8% PV), experimental results showed reduced risk of NAPL-product migration upon contact with aqueous isobutanol. At higher initial PCE saturations (>8% PV), results showed NAPL-product mobilization and downward migration which was attributed to interfacial tension (IFT) reduction, swelling of the NAPL-product, and reduced density modification. Packed column results were compared with good agreement to theoretical predictions of NAPL-product mobilization using the total trapping number, N(T). In addition to the packed column study, preliminary batch experiments were conducted to study the effects of PCE volumetric fraction in the range of 0.5-20% on density, viscosity, and IFT modification as a function of time following contact with aqueous isobutanol ( approximately 10 vol.%). Modified NAPL-product fluid properties approached equilibrium within approximately 2 h of contact for density and viscosity. IFT reduction occurred immediately as expected. Measured fluid properties were compared with good agreement to theoretical equilibrium predictions based on UNIQUAC. Overall, this study demonstrates the importance of initial DNAPL saturation, and the associated risk of downward NAPL-product migration, in applying alcohol flooding for remediation of DNAPL contaminated ground water sites.     

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.