Uncertainties and data needs in risk assessment of three commercial polybrominated diphenyl ethers: probabilistic exposure analysis and comparison with European Commission results

Some environmental monitoring programs have reported increasing levels of certain polybrominated diphenyl ether (PBDE) isomers in aquatic biota and in human breast milk. The commercial PBDE products are known as penta-, octa-, and deca-brominated diphenyl ethers (PeBDE, OBDE and DBDE, respectively). Aside from the current European Commission's risk assessment initiative and efforts underway in Sweden, Canada and elsewhere to evaluate environmental levels, little is understood about sources of exposure and risks to humans. In this study, a multi-pathway human health risk assessment was performed to predict theoretical chronic daily intakes (CDIs) of PeBDE, OBDE, and DBDE by five different age groups: 0-2, 2-6, 6-12, 12-18, and 18-70 years. Sources of exposure included air, drinking water, consumption of fish, vegetables, meat and dairy products, and ingestion of breast milk by infants. In addition to a deterministic analysis, the risk assessment included a probabilistic analysis to derive the probability density functions describing the range of plausible exposures associated with eight different pathways, as well as aggregate lifetime exposures for each age group. The results were compared to CDI point estimates calculated by the European Chemicals Bureau as part of the European Commission's Existing Substances Programme. The major sources of uncertainties are discussed, including environmental sources, levels in different environmental compartments, toxicity, and human exposure. This paper also discusses the limitations in the current state-of-the-science and provides recommendations for improving the scientific relevance and accuracy of future environmental risk assessments of PBDEs.     

Influence of plants on the chemical extractability and biodegradability of 2,4-dichlorophenol in soil

This study investigated the fate and behaviour of [UL-(14)C] 2,4-dichlorophenol (DCP) in planted (Lolium perenne L.) and unplanted soils over 57 days. Extractability of [UL-(14)C] 2,4-DCP associated activity was measured using calcium chloride (CaCl(2)), acetonitrile-water and dichloromethane (DCM) extractions. Biodegradability of [UL-(14)C] 2,4-DCP associated activity was assessed through measurement of (14)CO(2) production by a degrader inoculum (Burkholderia sp.). Although extractability and mineralisation of [UL-(14)C] 2,4-DCP associated activity decreased significantly in both planted and unplanted soils, plants appeared to enhance the sequestration process. After 57 days, in unplanted soil, 27% of the remaining [UL-(14)C] 2,4-DCP associated activity was mineralised by Burkholderia sp., and 13%, 48%, and 38% of (14)C-activity were extracted by CaCl(2), acetonitrile-water and DCM, respectively. However, after 57 days, in planted soils, only 10% of the [UL-(14)C] 2,4-DCP associated activity was available for mineralisation, whilst extractability was reduced to 2% by CaCl(2), 17% by acetonitrile-water and 11% by DCM. This may be due to the effect of plants on soil moisture conditions, which leads to modification of the soil structure and trapping of the compound. However, the influence of plants on soil biological and chemical properties may also play a role in the ageing process.     

Methodology for siting ambient air monitors at the neighborhood scale

In siting a monitor to measure compliance with U.S. National Ambient Air Quality Standards (NAAQS) for particulate matter (PM), there is a need to characterize variations in PM concentration within a neighborhood-scale region to achieve monitor siting objectives. A simple methodology is provided here for the selection of a neighborhood-scale site for meeting either of the two objectives identified for PM monitoring. This methodology is based on analyzing middle-scale (from 100 to 500 m) data from within the area of interest. The required data can be obtained from widely available dispersion models and emissions databases. The performance of the siting methodology was evaluated in a neighborhood-scale field study conducted in Hudson County, NJ, to characterize the area's inhalable particulate (PM10) concentrations. Air monitors were located within a 2- by 2-km area in the vicinity of the Lincoln Tunnel entrance in Hudson County. Results indicate the siting methodology performed well, providing a positive relationship between the predicted concentration rank at each site and the actual rank experienced during the field study. Also discussed are factors that adversely affected the predictive capabilities of the model.     

Open-path tunable diode laser absorption spectroscopy for acquisition of fugitive emission flux data

Air pollutant emission from unconfined sources is an increasingly important environmental issue. The U.S. Environmental Protection Agency (EPA) has developed a ground-based optical remote-sensing method that enables direct measurement of fugitive emission flux from large area sources. Open-path Fourier transform infrared spectroscopy (OP-FTIR) has been the primary technique for acquisition of pollutant concentration data used in this emission measurement method. For a number of environmentally important compounds, such as ammonia and methane, open-path tunable diode laser absorption spectroscopy (OP-TDLAS) is shown to be a viable alternative to Fourier transform spectroscopy for pollutant concentration measurements. Near-IR diode laser spectroscopy systems offer significant operational and cost advantages over Fourier transform instruments enabling more efficient implementation of the measurement strategy. This article reviews the EPA's fugitive emission measurement method and describes its multipath tunable diode laser instrument. Validation testing of the system is discussed. OP-TDLAS versus OP-FTIR correlation testing results for ammonia (R2 = 0.980) and methane (R2 = 0.991) are reported. Two example applications of tunable diode laser-based fugitive emission measurements are presented.     

Participatory conservation approaches for satoyama,the traditional forest and agricultural landscape of Japan

The traditional agricultural landscape of Japan, known as satoyama, consists of a mixture of forests, wet rice paddy fields, grasslands, and villages. This landscape supports a great diversity of plant and animal species, many of which are significant to the Japanese culture. The satoyama landscape is currently being rapidly converted to residential and industrial uses in Japan's expanding metropolitan areas, with the local loss of many species. Only 7% of the land in the Yokohama area remains as satoyama. City residents and older farmers have become key participants in programs to protect examples of satoyama. Many urban residents value the experience of participating in agricultural and conservation activities once they are made aware of the threat faced by the satoyama landscape. In one particularly successful program, conservation efforts and fund-raising are linked to "Totoro", an imaginary forest animal featured in a popular animated film.     

Development of the IM147: an alternative inspection/maintenance mass-emission transient test to address vehicle preconditioning concerns

A series of studies was performed to develop an alternative to the U.S. Environmental Protection Agency's gold standard IM240 mass-based emission test. The new IM147 test was based on the second phase of the IM240 that consists of 147 sec of transient vehicle operation. Paired IM240/IM147 tests were conducted on vehicles ranging from 1981 to 1996 to determine IM147 cutpoints and excess emissions were identified. Additionally, an optimized test procedure was developed that combined possible triplicate IM147s with improved drive trace quality control, fast-pass, and retest methods. The optimized procedure was found to provide improved vehicle preconditioning with a relatively minor decrease in excess emissions identification. Resulting identification rates ranged from 96 to 100% for hydrocarbons (HC), 93-100% for CO, and 93-100% for NOx, depending on cutpoint selection, while false failures caused by lack of vehicle preconditioning were reduced to essentially zero. Significant vehicle throughput improvements were achieved through the development of software algorithms involving modal fast-pass and retest procedures. Modal drive trace variation limits also were developed to improve test accuracy. The combination of the algorithms reduced average IM147 test times by nearly 60%.     

Effects of pH on the toxicity of cadmium, copper, lead and zinc to Folsomia candida Willem, 1902 (Collembola) in a standard laboratory test system

EC₅₀s for cadmium, copper, lead and zinc were determined for juvenile production of Folsomia candida at pH6.0, 5.0 and 4.5 in a standard laboratory test system. In contrast to most previous studies where metal toxicity was increased at low pHs, in our experiments there was no clear relationship between soil acidity and EC_{50-reproduction} in this species. The EC_{50-reproduction} values (μg g⁻¹) for cadmium and zinc were similar at all three pHs (pH6.0: Cd 590, Zn 900; pH5.0: Cd 780, Zn 600; pH4.5: Cd 480, Zn 590). In contaminated field sites adjacent to primary zinc smelters, zinc is invariably present in soils at concentrations of at least 50 times that of cadmium Thus deleterious effects of mixtures of these metals on populations of Collembola in such sites can be attributed to zinc rather than cadmium.     

Reactive oxygen species responsible for the enhanced desorption of dodecane in modified Fenton's systems.

The enhanced treatment of sorbed contaminants has been documented in modified Fenton's reactions; contaminants are desorbed and degraded more rapidly than they desorb by fill-and-draw or gas-purge desorption. The reactive species responsible for this process was investigated using dodecane as a model sorbent. Hydroxyl radical, hydroperoxide anion, and superoxide radical anion were generated separately to evaluate their roles in enhanced dodecane desorption. Dodecane desorption from silica sand over 180 minutes was negligible in gas-purge systems and in the hydroxyl radical and hydroperoxide anion systems. In contrast, enhanced desorption of dodecane occurred in superoxide systems, with >80% desorption over 180 minutes. Scavenging of superoxide eliminated the enhanced desorption of dodecane in both superoxide and modified Fenton's systems, confirming that superoxide is the desorbing agent in modified Fenton's reactions. Conditions that promote superoxide generation in Fenton's reactions may enhance their effectiveness for in situ subsurface remediation of sorbed hydrophobic contaminants.     

Ultraviolet spectrophotometric determination of nitrate: detecting nitrification rates and inhibition.

Simple methods that rapidly detect nitrification inhibition are needed to enforce pretreatment programs and prevent upsets. The objective of this study was to demonstrate a rapid method for measuring nitrification inhibition by using nitrate generation rates (NGRs) coupled with direct UV detection of nitrate. The NGRs were measured with UV spectrophotometry at wavelengths between 225 and 240 nm, without chemical manipulation, and verified against ion chromatography. The method was shown to quickly and accurately measure nitrate concentrations after correcting for nitrite interference. Cadmium, hypochlorite and 1-chloro-2,4-dintrobenzene (CDNB) were tested for their ability to cause nitrification inhibition using this method. The CDNB was found to cause a correctable interference with the test, while hypochlorite provided an uncorrectable interference. Used as a batch method coupled with biotic and abiotic controls, this approach can be deployed at full-scale treatment plants as a relatively rapid (1.5 hours) means of identifying nitrification-inhibiting wastewaters.