The origin of stable halogenated compounds in volcanic gases

BACKGROUND: Halogenated compounds in the atmosphere are of great environmental concern due to their demonstrated negative effect on atmospheric chemistry and climate. Detailed knowledge of the emission budgets of halogenated compounds has to be gained to understand better their specific impact on ozone chemistry and the climate. Such data are also highly relevant to guide policy decisions in connexion with international agreements about protection of the ozone layer. In selected cases, the relevance of specific emission sources for certain compounds were unclear. In this study we present new and comprehensive evidence regarding the existence and relevance of a volcanic contribution of chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), halons (bromine containing halo(hydro)carbons), and fully fluorinated compounds (e.g. CF4 and SF6) to the atmospheric budget. METHODS: In order to obtain new evidence of a volcanic origin of these compounds, we collected repeatedly, during four field campaigns covering a period of two years, gases from fumaroles discharging over a wide range of temperatures at the Nicaraguan subduction zone volcanoes Momotombo, Cerro Negro and Mombacho, and analysed them with very sensitive GC/MS systems. RESULTS AND DISCUSSION: In most fumarolic samples certain CFCs, HFCs, HCFCs, halons, and the fully fluorinated compounds CF4 and SF6 were present above detection limits. However, these compounds occur in the fumarole gases in relative proportions characteristic for ambient air. CONCLUSION: This atmospheric fingerprint can be explained by variable amounts of air entering the porous volcanic edifices and successively being incorporated into the fumarolic gas discharges. Recommendation and Outlook. Our results suggest that the investigated volcanoes do not constitute a significant natural source for CFCs, HFCs, HCFCs, halons, CF4, SF6 and NF3.     

Bisphenol A concentrations in receiving waters near US manufacturing and processing facilities

Bisphenol A (BPA) (CAS 80-05-7) was analyzed in receiving waters upstream and downstream of US manufacturers (1996 and 1997) and processors (1997) during seasonal low flow periods. BPA was not detected (< 1 microgram/l) in any surface water sample in 1996 or at six of seven sites in 1997. Concentrations near the seventh site ranged from 2 to 8 micrograms/l; however, its receiving stream had no measurable flow and concentrations represent undiluted effluent. All surface water concentrations from this and other studies were less than the freshwater predicted no effect concentration (PNEC) of 64 micrograms/l, suggesting that BPA discharges from manufacturing and processing facilities to surface water do not pose an environmental concern.     

Comparison of the particle size distribution of heavy-duty diesel exhaust using a dilution tailpipe sampler and an in-plume sampler during on-road operation

Originally constructed to develop gaseous emission factors for heavy-duty diesel trucks, the U.S. Environmental Protection Agency's (EPA) On-Road Diesel Emissions Characterization Facility has been modified to incorporate particle measurement instrumentation. An electrical low-pressure impactor designed to continuously measure and record size distribution data was used to monitor the particle size distribution of heavy-duty diesel truck exhaust. For this study, which involved a high-mileage (900,000 mi) truck running at full load, samples were collected by two different methods. One sample was obtained directly from the exhaust stack using an adaptation of the University of Minnesota's air-ejector-based mini-dilution sampler. The second sample was pulled from the plume just above the enclosed trailer, at a point approximately 11 m from the exhaust discharge. Typical dilution ratios of about 300:1 were obtained for both the dilution and plume sampling systems. Hundreds of particle size distributions were obtained at each sampling location. These were compared both selectively and cumulatively to evaluate the performance of the dilution system in simulating real-world exhaust plumes. The data show that, in its current residence-time configuration, the dilution system imposes a statistically significant bias toward smaller particles, with substantially more nanoparticles being collected than from the plume sample.     

Phosphate-induced metal immobilization in a contaminated site

To assess the efficiency of P-induced metal immobilization in soils, a pilot-scale field experiment was conducted at a metal contaminated site located in central Florida. Phosphate was applied at a P/Pb molar ratio of 4.0 with three treatments: 100% of P from H3PO4, 50% of P from H3PO4+ 50% of P from Ca(H2PO4)2, and 50% of P from H3PO4+5% phosphate rock in the soil. Approximately 1 year after P application, soil and plant samples were collected to determine mobility and bioavailability of selected metals (Pb, Zn, and Cu) using sequential extraction procedure and mineralogical characterization using X-ray diffraction (XRD) and scanning electron microscope-energy dispersive X-ray (SEM-EDX) analysis. Phosphorus distribution and soil pH effects were also evaluated. Phosphate was more effective in transforming soil Pb (to 53%) from the non-residual to the residual phase than soil Zn (to 15%) and soil Cu (to 13%). This was because Pb was immobilized by P via formation of an insoluble pyromorphite-like mineral in the surface and subsurface of the soil, whereas no phosphate mineral Zn or Cu was identified. While P amendment enhanced metal uptake in the roots of St. Augustine grass (Stenotaphrum secundatum), it significantly reduced metal translocation from root to shoot, especially Pb via formation of a pyromorphite-like mineral on the membrane surface of the root. A mixture of H3PO4 and phosphate rock was effective in metal immobilization, with less soil pH reduction and less soluble P. Although H3PO4 was effective in immobilizing Pb, its use should be limited to minimize soil pH reduction and potential eutrophication risk.     

Microenvironmental time-activity patterns in Chongqing, China

An investigation using recall questionnaires was conducted in winter and autumn 2006 to evaluate the time-activity patterns in Chongqing, China. The average time spent in seven microenvironments (MEs) including outdoors, transit, living room, bedroom, kitchen, classroom/office, and other indoors were found to be about 3.5, 1.1, 2.5, 9.7, 1.4, 4.2, and 1.7 h per day, respectively. According to the results of a nonparametric test, the sampling period and day of week were significant for the variation of the time spent in all MEs except for transit and outdoors. The time budget was analyzed using a general linear model (GLM), which exhibited significant variability by demographic factors such as gender, age, residence, education, and household income.