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.     

Influences of macroalga-derived dissolved organic carbon on the aquatic toxicity of copper and cadmium

In this study, the effect of dissolved organic carbon (DOC) derived from macroalga (Sargassum) on the acute toxicity of copper (Cu) and cadmium (Cd) to a freshwater cladoceran (Daphnia magna) was investigated. Potassium-loaded macroalga was incubated with ultrapure water to extract macroalgal DOC, which was then spiked with the constituents of the Elendt M7 hard water media. The 48 h median lethal concentration of Cu increased linearly with DOC levels but that of Cd was relatively independent of DOC levels (0-44 mg l(-1)). The independence of Cd toxicity on DOC level might be due to the competitive effect of high calcium concentrations in the media with Cd for the binding sites of DOC. The decreased Cu toxicity was a result of reduced Cu uptake as evidenced in a separate accumulation test. Also, the capability of the macroalgal DOC on reducing Cu toxicity was found to be comparable to DOC tested in other studies. Therefore, the present study suggested that the biosorption treatment process using macroalgae should consider the effect of DOC release from the biomass as a step of modifying the metal toxicity as well as influencing metal biosorption capacity.     

Probabilistic study of well capture zones distribution at the Lauswiesen field site

The delineation of well capture zones is of utmost environmental and engineering relevance as pumping wells are commonly used both for drinking water supply needs, where protection zones have to be defined, and for investigation and remediation of contaminated aquifers. We analyze the probabilistic nature of well capture zones within the well field located at the "Lauswiesen" experimental site. The test site is part of an alluvial heterogeneous aquifer located in the Neckar river valley, close to the city of Tübingen in South-West Germany. We explore the effect of different conceptual models of the structure of aquifer heterogeneities on the delineation of three-dimensional probabilistic well catchment and time-related capture zones, in the presence of migration of conservative solutes. The aquifer is modeled as a three-dimensional, doubly stochastic composite medium, where distributions of geo-materials and hydraulic properties are uncertain. We study the relative importance of uncertain facies geometry and uncertain hydraulic conductivity and porosity on predictions of catchment and solute time of travel to the pumping well by focusing on cases in which (1) the facies distribution is random, but the hydraulic properties of each material are fixed, and (2) both facies geometry and material properties vary stochastically. The problem is tackled within a conditional numerical Monte Carlo framework. Results are provided in terms of probabilistic demarcations of the three-dimensional well catchment and time-related capture zones. Our findings suggest that the uncertainty associated with the prediction of the location of the outer boundary of well catchment at the "Lauswiesen" site is significantly affected by the conceptual model adopted to incorporate the heterogeneous nature of the aquifer domain in a predictive framework. Taking into account randomness of both lithofacies distribution and materials hydraulic conductivity allows recognizing the existence of preferential flow paths that influence the extent of the well catchment and the solute travel time distribution at the site.     

Quality assured measurements of animal building emissions: gas concentrations

Comprehensive field studies were initiated in 2002 to measure emissions of ammonia (NH3), hydrogen sulfide (H2S), carbon dioxide (CO2), methane (CH4), nonmethane hydrocarbons (NMHC), particulate matter <10 microm in diameter, and total suspended particulate from swine and poultry production buildings in the United States. This paper focuses on the quasicontinuous gas concentration measurement at multiple locations among paired barns in seven states. Documented principles, used in air pollution monitoring at industrial sources, were applied in developing quality assurance (QA) project plans for these studies. Air was sampled from multiple locations with each gas analyzed with one high quality commercial gas analyzer that was located in an environmentally controlled on-farm instrument shelter. A nominal 4 L/min gas sampling system was designed and constructed with Teflon wetted surfaces, bypass pumping, and sample line flow and pressure sensors. Three-way solenoids were used to automatically switch between multiple gas sampling lines with > or =10 min sampling intervals. Inside and outside gas sampling probes were between 10 and 115 m away from the analyzers. Analyzers used chemiluminescence, fluorescence, photoacoustic infrared, and photoionization detectors for NH3, H2S, CO2, CH4, and NMHC, respectively. Data were collected using personal computer-based data acquisition hardware and software. This paper discusses the methodology of gas concentration measurements and the unique challenges that livestock barns pose for achieving desired accuracy and precision, data representativeness, comparability and completeness, and instrument calibration and maintenance.     

Evaluation of the persistence of micropollutants through pure-oxygen activated sludge nitrification and denitrification.

The persistence of pharmaceuticals, hormones, and household and industrial chemicals through a pure-oxygen activated sludge, nitrification, denitrification wastewater treatment facility was evaluated. Of the 125 micropollutants that were tested in this study, 55 compounds were detected in the untreated wastewater, and 27 compounds were detected in the disinfected effluent. The persistent compounds included surfactants, fire-retardant chemicals, pesticides, fragrance compounds, hormones, and one pharmaceutical. Physical-chemical properties of micropollutants that affected partitioning onto wastewater solids included vapor pressure and octanol-water partition coefficients.     

HCHs and DDTs in sediment-dwelling animals from the Yangtze Estuary, China

HCHs and DDTs in sediment-dwelling animals including mollusks and crabs from the Yangtze Estuary were determined by GC-ECD. Levels of t-HCH were in the range of 1.2-5.5 ng g(-1) and averaged 3.5 ng g(-1) in mollusks, while t-DDT concentrations ranged from 26.0 to 68.8 ng g(-1), with a mean of 34.5 ng g(-1). In crabs t-HCH concentrations varied from 2.0 to 25.7 ng g(-1) and averaged 13.8 ng g(-1), whereas the concentrations of t-DDT were in the range of 1.5-24.8 ng g(-1) with a mean value of 5.9 ng g(-1). The HCHs and DDTs levels depend on geographical position and sources, showing the high levels at fresh water area in the estuary, such as XP, CM and LHK sites, and lower at brackish water area, such as FX site, and little difference between species. Results also indicate there was no significant relationship between t-HCH (t-DDT) concentrations and lipid contents both in mollusks and crabs because of non-equilibrium state under a specific estuarine dynamics; smaller individuals accumulated more HCHs and DDTs than larger individuals of mollusks at LHK site, showing different uptake rate for these pesticides; moreover, HCHs and DDTs levels were lower in female crab bodies than male crab bodies suggesting that the release of spawning. BSAFs (Biota- Sediment Accumulation Factors) from sediment-dwelling animals for HCHs and DDTs show a significant "one high with two low" and "one low with two high" effect in the Yangtze Estuary.     

Evaluating the role of desorption in bioavailability of sediment-associated contaminants using oligochaetes, semipermeable membrane devices and Tenax extraction

The success of the rapidly desorbing fraction as an available fraction was challenged by using sediment ingesting and non-ingesting oligochaetes (Lumbriculus variegatus) together with passive samplers (semipermeable membrane devices, SPMDs) in accumulation and kinetic modelling exercises for carbon-14 labelled model compounds (pyrene, benzo[a]pyrene and 3,4,3',4'-tetrachlorobiphenyl). Passive samplers clearly produced lower uptake rate constants and steady state factors than either of the oligochaete treatments when residue concentrations were based on animal lipid or total SPMD weight. The rapidly desorbing chemical fractions in sediments did not show a significant relationship with the biota sediment accumulation factors or SPMD accumulation factors. A distinctly better relationship was observed between the accumulation factors and the desorption rate constants. The results support the assumption that desorption plays an important role in bioavailability, although animal behaviour and the diffusional limitations of hydrophobic contaminants in sediment together probably affect the actual available pool.     

Anthropogenic metal enrichment of snow and soil in north-eastern European Russia

Trace metal composition of winter snowpack, snow-melt filter residues and top-soil samples were determined along three transects through industrial towns in the Usa basin, North-East Russia: Inta, Usinsk and Vorkuta. Snow was analysed for Ag, Al, As, Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr and Zn using ICP-MS (Ca and K by F-AAS for Vorkuta only), pH and acidity/alkalinity. Filter residues were analysed for: Al, Ba, Ca, Cd, Cu, K, Mg, Mn, Ni, Pb, Sr and Zn using F-AAS and GF-AAS; top-soil samples were analysed for Ba, Cu, Mg, Mn, Na, Ni, Pb, Sr, Zn using F-AAS. Results indicate elevated concentrations of elements associated with alkaline combustion ash around the coal mining towns of Vorkuta and Inta. There is little evidence of deposition around the gas and oil town of Usinsk. Atmospheric deposition in the vicinity of Vorkuta, and to a lesser extent Inta, added significantly to the soil contaminant loading as a result of ash fallout. Acid deposition was associated with pristine areas whereas alkaline combustion ash near to emission sources more than compensated for the acidity caused by SO2.