Perfluorinated acids as novel chemical tracers of global circulation of ocean waters

Perfluorinated acids (PFAs) such as perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are global environmental contaminants. The physicochemical properties of PFAs are unique in that they have high water solubilities despite the low reactivity of carbon-fluorine bond, which also imparts high stability in the environment. Because of the high water solubilities, the open-ocean water column is suggested to be the final sink for PFOS and PFOA. However, little is known on the distribution of PFAs in the oceans around the world. Here we describe the horizontal (spatial) and vertical distribution of PFAs in ocean waters worldwide. PFOS and PFOA concentrations in the North Atlantic Ocean ranged from 8.6 to 36pg l(-1) and from 52 to 338pg l(-1), respectively, whereas the corresponding concentrations in the Mid Atlantic Ocean were 13-73pg l(-1) and 67-439pg l(-1). These were completely different from the surface waters of the South Pacific Ocean and the Indian Ocean (overall range of <5-11pg l(-1) for PFOS and PFOA). Vertical profiles of PFAs in the marine water column were associated with the global ocean circulation theory. Vertical profiles of PFAs in water columns from the Labrador Sea reflected the influx of the North Atlantic Current in surface waters, the Labrador Current in subsurface waters, and the Denmark Strait Overflow Water in deep layers below 2000m. Striking differences in the vertical and spatial distribution of PFAs, depending on the oceans, suggest that these persistent acids can serve as useful chemical tracers to allow us to study oceanic transportation by major water currents. The results provide evidence that PFA concentrations and profiles in the oceans adhere to a pattern consistent with the global "Broecker's Conveyor Belt" theory of open ocean water circulation.     

Chemical solutions for greywater recycling

Greywater recycling is now accepted as a sustainable solution to the general increase of the fresh water demand, water shortages and for environment protection. However, the majority of the suggested treatments are biological and such technologies can be affected, especially at small scale, by the variability in strength and flow of the greywater and potential shock loading. This investigation presents the study of alternative processes, coagulation and magnetic ion exchange resin, for the treatment of greywater for reuse. The potential of these processes as well as the influence of parameters such as coagulant or resin dose, pH or contact time were investigated for the treatment of two greywaters of low and high organic strengths. The results obtained revealed that magnetic ion exchange resin and coagulation were suitable treatment solutions for low strength greywater sources. However, they were unable to achieve the required level of treatment for the reuse of medium to high strength greywaters. Consequently, these processes could only be considered as an option for greywater recycling in specific conditions that is to say in case of low organic strength greywater or less stringent standards for reuse.     

Patterns and sources of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in surficial sediments of Lakes Erie and Ontario

This study determines spatial trends and congener patterns of 2378-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in surficial sediments of Lakes Erie and Ontario. Sediments are enriched in 2378-PCDFs in Lake Ontario, and the PCDD/F concentrations increased from shallow near-shore sediments towards deep-water depositional zone sediments. In Lake Erie, sediments were dominated by octachlorodibenzo-p-dioxin, and the highest PCDD/F concentrations were observed in the western basin and the southern shoreline of the central basin with a decrease towards the eastern basin and the northern shoreline of the central basin. Principal components analysis revealed that chemical manufacture and disposal of chemical waste along the Niagara River has been a major PCDD/F source to Lake Ontario; while PCDD/Fs in Lake Erie are from multiple sources including industrial sources along the Detroit River, major tributaries along the southern shoreline of the lake, and atmospherically-derived material from the upper lakes and connecting channels.     

Inorganic arsenic levels in baby rice are of concern

Inorganic arsenic is a chronic exposure carcinogen. Analysis of UK baby rice revealed a median inorganic arsenic content (n = 17) of 0.11 mg/kg. By plotting inorganic arsenic against total arsenic, it was found that inorganic concentrations increased linearly up to 0.25 mg/kg total arsenic, then plateaued at 0.16 mg/kg at higher total arsenic concentrations. Inorganic arsenic intake by babies (4-12 months) was considered with respect to current dietary ingestion regulations. It was found that 35% of the baby rice samples analysed would be illegal for sale in China which has regulatory limit of 0.15 mg/kg inorganic arsenic. EU and US food regulations on arsenic are non-existent. When baby inorganic arsenic intake from rice was considered, median consumption (expressed as μg/kg/d) was higher than drinking water maximum exposures predicted for adults in these regions when water intake was expressed on a bodyweight basis.     

Comparison of total mercury and methylmercury cycling at five sites using the small watershed approach

The small watershed approach is well-suited but underutilized in mercury research. We applied the small watershed approach to investigate total mercury (THg) and methylmercury (MeHg) dynamics in streamwater at the five diverse forested headwater catchments of the US Geological Survey Water, Energy, and Biogeochemical Budgets (WEBB) program. At all sites, baseflow THg was generally less than 1ng L(-1) and MeHg was less than 0.2ng L(-1). THg and MeHg concentrations increased with streamflow, so export was primarily episodic. At three sites, THg and MeHg concentration and export were dominated by the particulate fraction in association with POC at high flows, with maximum THg (MeHg) concentrations of 94 (2.56)ng L(-1) at Sleepers River, Vermont; 112 (0.75)ng L(-1) at Rio Icacos, Puerto Rico; and 55 (0.80)ng L(-1) at Panola Mt., Georgia. Filtered (<0.7microm) THg increased more modestly with flow in association with the hydrophobic acid fraction (HPOA) of DOC, with maximum filtered THg concentrations near 5ng L(-1) at both Sleepers and Icacos. At Andrews Creek, Colorado, THg export was also episodic but was dominated by filtered THg, as POC concentrations were low. MeHg typically tracked THg so that each site had a fairly constant MeHg/THg ratio, which ranged from near zero at Andrews to 15% at the low-relief, groundwater-dominated Allequash Creek, Wisconsin. Allequash was the only site with filtered MeHg consistently above detection, and the filtered fraction dominated both THg and MeHg. Relative to inputs in wet deposition, watershed retention of THg (minus any subsequent volatilization) was 96.6% at Allequash, 60% at Sleepers, and 83% at Andrews. Icacos had a net export of THg, possibly due to historic gold mining or frequent disturbance from landslides. Quantification and interpretation of Hg dynamics was facilitated by the small watershed approach with emphasis on event sampling.     

Phototransformation of herbicide metsulfuron methyl

Phototransformation of the herbicide metsulfuron methyl was investigated on glass surface under sunlight and ultraviolet (UV) light and compared with dark condition. The half-lives of metsulfuron methyl under UV light and sunlight were found to be 0.5 and 7.8 days respectively. Rate of phototransformation followed first order kinetics with significant correlation coefficient. The major photoproducts were identified as methyl-2-sulfonyl-amino-benzoate, 2-amino-6-methoxy-4-methyltriazine and saccharin (O-sulfobenzoimide). Various metabolites from this study were identified by high performance liquid chromatography (HPLC). Authentic samples required for HPLC comparison were prepared in laboratory and characterized on the basis of nuclear magnetic resonance (NMR) and infra red (IR) spectral data. These metabolites were also identified from metsulfuron methyl treated wheat field soil.     

Secondary particulate matter in the United States: insights from the Particulate Matter Supersites Program and related studies

Secondary aerosols comprise a major fraction of fine particulate matter (PM2.5) in all parts of the country, during all seasons, and times of day. The most abundant secondary species include sulfate, nitrate, ammonium, and secondary organic aerosols (SOAs). The relative abundance of each species varies in space and time as a function of meteorology, source emissions strength and type, thermodynamics, and atmospheric processing. Transport of secondary aerosols from upwind locations can contribute significantly at downwind receptor sites, especially regionally in the eastern United States, and across a given urbanized area, such as in Los Angeles. Processes governing the formation of the inorganic secondary species (sulfate, nitrate, and ammonium) are fairly well understood, although the occurrence of nucleation bursts initiated with the formation of ultrafine sulfuric acid particles observed regionally on clean days in the eastern United States was unexpected. Because of the complex nature of organic material in air, much is still to be learned about the sources, formation, and even spatial and temporal distributions of SOAs. For example, a considerable fraction of ambient organic PM is oxidized organic species, many of which still need to be identified, quantified, and their sources and formation mechanisms determined. Furthermore, significant uncertainty (approaching 50% or more) is associated with estimating the SOA fraction of organic material in air with current methods. This review summarizes the findings of the Supersites Program and related studies addressing secondary particulate matter (PM), including spatial and temporal variations of secondary PM and its precursor species, data and methods for determining the primary and secondary fractions of PM mass, and findings on the anthropogenic and natural fractions of secondary PM.     

Emissions from carpet combustion in a pilot-scale rotary kiln: comparison with coal and particle-board combustion

The use of post-consumer carpet as a potential fuel substitute in cement kilns and other high-temperature processes is being considered to address the problem of huge volumes of carpet waste and the opportunity of waste-to-energy recovery. Carpet represents a high volume waste stream, provides high energy value, and contains other recoverable materials for the production of cement. This research studied the emission characteristics of burning 0.46-kg charges of chopped nylon carpet squares, pulverized coal, and particle-board pellets in a pilot-scale natural gas-fired rotary kiln. Carpet was tested with different amounts of water added. Emissions of oxygen, carbon dioxide, nitric oxide (NO), sulfur dioxide (SO2), carbon monoxide (CO), and total hydrocarbons and temperatures were continuously monitored. It was found that carpet burned faster and more completely than coal and particle board, with a rapid volatile release that resulted in large and variable transient emission peaks. NO emissions from carpet combustion ranged from 0.06 to 0.15 g/MJ and were inversely related to CO emissions. Carpet combustion yielded higher NO emissions than coal and particle-board combustion, consistent with its higher nitrogen content. SO2 emissions were highest for coal combustion, consistent with its higher sulfur content than carpet or particle board. Adding water to carpet slowed its burn time and reduced variability in the emission transients, reducing the CO peak but increasing NO emissions. Results of this study indicate that carpet waste can be used as an effective alternative fuel, with the caveats that it might be necessary to wet carpet or chop it finely to avoid excessive transient puff emissions due to its high volatility compared with other solid fuels, and that controlled mixing of combustion air might be used to control NO emissions from nylon carpet.     

Soil suspension/dispersion modeling methods for estimating health-based soil cleanup levels of hexavalent chromium at chromite ore processing residue sites

The primary health concern associated with exposures to chromite ore processing residue (COPR)-affected soils is inhalation of hexavalent chromium [Cr(VI)] particulates. Site-specific soil alternative remediation standards (ARSs) are set using soil suspension and dispersion models to be protective of the theoretical excess cancer risk associated with inhalation of soil suspended by vehicle traffic and wind. The purpose of this study was to update a previous model comparison study that identified the 1995 AP-42 particulate emission model for vehicle traffic over unpaved roads and the Fugitive Dust Model (FDM) as the most appropriate model combination for estimating site-specific ARSs. Because the AP-42 model has been revised, we have updated our past evaluation. Specifically, the 2006 AP-42 particulate emissions model; the Industrial Source Complex-Short Term model, version 3 (ISCST3); and the American Meteorological Society/Environmental Protection Agency Regulatory Model (AERMOD) air dispersion models were evaluated, and the results were compared with those from the previously used modeling approaches. Two sites with and two sites without vehicle traffic were evaluated to determine if wind erosion is a significant source of emissions. For the two sites with vehicle traffic, both FDM and ISCST3 produced total suspended particulate (TSP) estimates that were, on average, within a factor of 2 of measured; whereas AERMOD produced estimates that were as much as 5-fold higher than measured. In general, the estimated TSP concentrations for FDM were higher than those for ISCST3. For airborne Cr(VI), the ISCST3 model produced estimates that were only 2- to 8-fold of the measured concentrations, and both FDM and AERMOD estimated airborne Cr(VI) concentrations that were approximately 4- to 14-fold higher than measured. Results using the 1995 AP-42 model were closer to measured than those from the 2006 AP-42 model. Wind erosion was an insignificant contributor to particulate emissions at COPR sites.     

Perceived landscape impacts of mobile telecommunications development in the Peak District National Park,England

This study explored the public perceptions of mobile telecommunications development – new landscape elements installed to deliver new technology – in a protected area. It examined: (1) the perceived landscape impacts of such development; (2) the importance attached to the socio-economic value of mobile telecommunications; and (3) the factors underlying the perceived landscape impacts of mobile telecommunications development. A postal questionnaire survey was conducted in the Peak District National Park, England with 420 respondents drawn from National Park residents and visitors, urban dwellers and members of environmental organisations. The study suggests that: (1) there was a prevailing antipathy towards the landscape impacts of mobile telecommunications development in the National Park; (2) apart from emergency uses, the other socio-economic benefits of mobile telecommunications technology were thought to be relatively unimportant in the National Park; and (3) rather than socio-demographic characteristics, it was respondents' understandings of protected areas' needs for the technology and potential health risks that had significant effects on the perceived landscape impacts. Overall, this study suggests that the significance of National Park landscapes is respected by the public, even when setalongside the convenience of modern technology, which has substantial implications for landscape planning and management in protected areas.