Generation and analysis of mixed chlorinated/brominated homologs of the halogenated natural product heptachloro-1'-methyl-1,2'-bipyrrole

The 2,3,3′,4,4′,5,5′-heptachloro-1′-methyl-1,2′-bipyrrole (Q1, MBP-79) and further halogenated 1′-methyl-1,2′-bipyrroles (MBPs) are a class of marine natural products repeatedly detected in seafood and marine mammals from all over the world. Only Q1 is currently commercially available as reference standard and the full synthesis of mixed brominated-chlorinated compound is rather complicated. For this reason, synthetic Q1 (240 mg) was transferred into bromine-containing MBPs by UV-irradiation in the presence of bromine. Bromine, which rapidly vanished from the solutions, was re-newed during the reaction in order to generate higher amounts of Br-containing MBPs. A total of ∼150 mg Q1 was transferred after ∼10 min irradiation with high amounts of Br₂ to give 30.5 mg BrCl₆-MBPs along with lower proportions of Br₂Cl₅-, Br₃Cl₄-, Br₄Cl₃- and traces of Br₅Cl₂-MBPs. Longer UV-irradiation in the presence of Br₂ even allowed for the detection of Br₆Cl-MBPs and traces of Br₇-MBP. However, this reaction also provided some unknown by-products. A sample stored in the dark and later in in-door light (no UV irradiation) also eliminated Q1 after 76 d in favour of heptahalogenated MBPs with up to three bromine substituents. The irradiation products were separated on silica, and fractions containing only Q1 and BrCl₆-MBPs were then further fractionated by non-aqueous RP-HPLC. A pure isolate of the major BrCl₆-MBP (∼1.5 mg) was characterized by GC/MS and ¹³C NMR to be 2-bromo-3,3′,4,4′,5,5′-hexachloro-1-methyl-1,2′-bipyrrole (Br-MBP-75). Partial GC enantioseparation of the axially chiral Br-MBP-75 was achieved on a β-PMCD column. A full enantioseparation was managed by enantioselective HPLC using a NUCLEOCEL DELTA S column. Low amounts of pure BrCl₆-MBP enantiomers could be trapped.     

Microbial community response to addition of polylactate compounds to stimulate hexavalent chromium reduction in groundwater

To evaluate the efficacy of bioimmobilization of Cr(VI) in groundwater at the Department of Energy Hanford site, we conducted a series of microcosm experiments using a range of commercial electron donors with varying degrees of lactate polymerization (polylactate). These experiments were conducted using Hanford Formation sediments (coarse sand and gravel) immersed in Hanford groundwater, which were amended with Cr(VI) and several types of lactate-based electron donors (Hydrogen Release Compound, HRC; primer-HRC, pHRC; extended release HRC) and the polylactate-cysteine form (Metal Remediation Compound, MRC). The results showed that polylactate compounds stimulated an increase in bacterial biomass and activity to a greater extent than sodium lactate when applied at equivalent carbon concentrations. At the same time, concentrations of headspace hydrogen and methane increased and correlated with changes in the microbial community structure. Enrichment of Pseudomonas spp. occurred with all lactate additions, and enrichment of sulfate-reducing Desulfosporosinus spp. occurred with almost complete sulfate reduction. The results of these experiments demonstrate that amendment with the pHRC and MRC forms result in effective removal of Cr(VI) from solution most likely by both direct (enzymatic) and indirect (microbially generated reductant) mechanisms.     

Chemical extractions and predicted free ion activities fail to estimate metal transfer from soil to field land snails

This study investigates the relevance of several soil chemical extractions (calcium chloride, acetic acid, citric acid and a four-step sequential procedure) and predicted free metal ion activities in the soil solution to characterise the transfer of trace metals (Cd, Pb, and Zn) from soil to snail soft tissues over a large smelter-impacted area (Metaleurop Nord, Nord-Pas-de-Calais, France). The study was first performed on six snail species together and then specifically on Cepaea sp. and Oxychilus draparnaudi. When the six species were considered together, the accumulation of metals depended mostly on the species. When significant, total or extractable metal concentrations, or the predicted free ion activities, accounted for less than 7% of the variation of the metal concentrations in the snail tissues. Species-specific analyses showed that extractable concentrations explained approximately 25% of the variation of the metal concentrations in O. draparnaudi, and up to 8% in Cepaea snails. When using total soil concentrations and soil properties as explanatory variables, the models were generally slightly better, explaining up to 42% of the variance. The soil extraction procedures and predicted free ion activities used in this study did not accurately estimate the metal transfer from soil to snails and could not be used in risk assessment.     

Antecedents of intention to help mitigate wildfire: Implications for campaigns promoting wildfire mitigation to the general public in the wildland–urban interface

The current investigation sought to examine the association between knowledge of the causes of wildfire in the wildland–urban interface (WUI) and intentions on the part of members of the public to help mitigate wildfire. In doing so, antecedents from the theory of planned behavior were employed to enhance our understanding of the relationships among wildfire knowledge, attitudes, subjective norms, perceived behavioral control, and intention to help mitigate wildfire in the WUI. Participants (N = 408) living in the WUI in Appalachian Ohio were sampled as a means of conducting formative research prior to developing messages promoting wildfire mitigation. Our results reveal that, among the variables in the theory of planned behavior, the only paths that consistently explain individual’s intention to help mitigate wildland fire in the WUI in protecting both homes and the environment are associations between knowledge about wildfire and perceived behavioral control and between perceived behavioral control and intention. Our findings are discussed with a focus on message design for wildland fire mitigation professionals and a focus on implications for the theory of planned behaviors for academics with interests in wildland fire and other environmental issues.     

Spatially differentiated and source-specific population exposure to ambient urban air pollution

Models assessing exposure to air pollution often focus on macro-scale estimates of exposure to all types of sources for a particular pollutant across an urban study area. While results based on these models may aid policy makers in identifying larger areas of elevated exposure risk, they often do not differentiate the proportion of population exposure attributable to different polluting sources (e.g. traffic or industrial). In this paper, we introduce a population exposure modeling system that integrates air dispersion modeling, Geographic Information Systems (GIS), and population exposure techniques to spatially characterize a source-specific exposure to ambient air pollution for an entire urban population at a fine geographical scale. By area, total population exposure in Dallas County in 2000 was more attributable to vehicle polluting sources than industrial polluting sources at all levels of exposure. Population exposure was moderately correlated with vehicle sources (r = 0.440, p < 0.001) and weakly with industrial sources (r = 0.069, p = 0.004). Population density was strongly correlated with total exposure (r = 0.896, p < 0.001) but was not significantly correlated with individual or combined sources. The results of this study indicate that air quality assessments must incorporate more than industrial or vehicle polluting sources-based population exposure values alone, but should consider multiple sources. The population exposure modeling system proposed in this study shows promise for use by municipal authorities, policy makers, and epidemiologists in evaluating and controlling the quality of the air in the process of urban planning and mitigation measures.     

Perceptions of climate change on the Island of Providencia

Climate change-related impacts have the capacity to substantially influence Small Island Developing States (SIDS) in the Caribbean. Currently, many SIDS are engaged in large-scale vulnerability assessments that aim to identify, analyse, and inform solutions to mitigate climate change-related impacts. Many of these assessments, while useful, place little emphasis on the local stakeholders' perceptions of climate change. One such Caribbean community impacted by climate-related change is Providence Island in Colombia. Using a vulnerability assessment framework (Marshall, P.A. et al. 2010. A framework for social adaptation to climate change: sustaining tropical coastal communities and industries. Gland: IUCN Publication Services), researchers interviewed island residents (N = 23) about their perceptions of climate change, impacts on the local environment, and how the island community may adapt. All interviews were transcribed and analysed using a priori and open coding to identify patterns of and relationships between stakeholders' responses. Results indicate that local perceptions of climate change are linked to (1) environmental knowledge, (2) environmental awareness, attitudes, and beliefs, and (3) perceptions of risk. Implications for local adaptive strategies, education, communication, and suggestions for engagement at the local level are discussed.     

Impacts of climate change on land-use and wetland productivity in the Prairie Pothole Region of North America

Wetland productivity in the Prairie Pothole Region (PPR) of North America is closely linked to climate. A warmer and drier climate, as predicted, will negatively affect the productivity of PPR wetlands and the services they provide. The effect of climate change on wetland productivity, however, will not only depend on natural processes (e.g., evapotranspiration), but also on human responses. Agricultural land use, the predominant use in the PPR, is unlikely to remain static as climate change affects crop yields and prices. Land use in uplands surrounding wetlands will further affect wetland water budgets and hence wetland productivity. The net impact of climate change on wetland productivity will therefore depend on both the direct effects of climate change on wetlands and the indirect effects on upland land use. We examine the effect of climate change and land-use response on semipermanent wetland productivity by combining an economic model of agricultural land-use change with an ecological model of wetland dynamics. Our results suggest that the climate change scenarios evaluated are likely to have profound effects on land use in the North and South Dakota PPR, with wheat displacing other crops and pasture. The combined pressure of land-use and climate change significantly reduces wetland productivity. In a climate scenario with a +4 °C increase in temperature, our model predicts that almost the entire region may lack the wetland productivity necessary to support wetland-dependent species.     

Fractionation of selected metals in the sediments of Cochin estuary and Periyar River, southwest coast of India

Cochin estuary is one of the highly polluted aquatic systems of the southwest coast of India. The present study focuses on the assessment of heavy metals (Zn, Cd, Pb, and Cu) present in the sediments of Cochin estuary and the adjoining Periyar River. The sediments were analyzed for total metal content and various chemically bound fractions such as exchangeable, carbonate bound, easily reducible, organic, and residual. Total metal content of sediment was found higher than the average values reported from other Indian rivers. The mean concentration of Zn, Cd, Pb, and Cu in the sediments was 1,249.44, 9.5, 221.37, and 166.14???g/g, respectively. The results of sequential extraction showed that the concentration of Cd was high in the first two weakly bound fractions (exchangeable and carbonate bound) than the other metals, which are high in residual and organic bound fractions. Risk-assessment code analysis and environmental indices (enrichment factor and pollution load index) suggest that the sediments are highly polluted with metals, especially Cd.     

The Southeastern Aerosol Research and Characterization Study,Part 3: Continuous Measurements of Fine Particulate Matter Mass and Composition

Abstract

Deployment of continuous analyzers in the Southeastern Aerosol Research and Characterization Study (SEARCH) network began in 1998 and continues today as new technologies are developed. Measurement of fine particulate matter (PM_2.5) mass is performed using a dried, 30 °C tapered element oscillating microbalance (TEOM). TEOM measurements are complemented by observations of light scattering by nephelometry. Measurements of major constituents include: (1) SO₄ ^2? via reduction to SO₂; (2) NH₄ ⁺ and NO₃ ^? via respective catalytic oxidation and reduction to NO, (3) black carbon (BC) by optical absorption, (4) total carbon by combustion to CO₂, and (5) organic carbon by difference between the latter two measurements. Several illustrative examples of continuous data from the SEARCH network are presented. A distinctive composite annual average diurnal pattern is observed for PM_2.5 mass, nitrate, and BC, likely indicating the influence of traffic-related emissions, growth, and break up of the boundary layer and formation of ammonium nitrate. Examination of PM_2.5 components indicates the need to better understand the continuous composition of the unmeasured “other” category, because it contributes a significant fraction to total mass during periods of high PM_2.5 loading. Selected episodes are presented to illustrate applications of SEARCH data. An SO₂ conversion rate of 0.2%/hr is derived from an observation of a plume from a coal-fired power plant during early spring, and the importance of local, rural sources of NH₃ to the formation of ammonium nitrate in particulate matter (PM) is demonstrated.     

The Southeastern Aerosol Research and Characterization Study: Part II. Filter-Based Measurements of Fine and Coarse Particulate Matter Mass and Composition

Abstract

The Southeastern Aerosol Research and Characterization Study (SEARCH) was implemented in 1998–1999 to provide data and analyses for the investigation of the sources, chemical speciation, and long-term trends of fine particulate matter (PM_2.5) and coarse particulate matter (PM_10–2.5) in the Southeastern United States. This work is an initial analysis of 5 years (1999–2003) of filter-based PM_2.5 and PM_10–2.5 data from SEARCH. We find that annual PM_2.5 design values were consistently above the National Ambient Air Quality Standards (NAAQS) 15 µg/m³ annual standard only at monitoring sites in the two largest urban areas (Atlanta, GA, and North Birmingham, AL). Other sites in the network had annual design values below the standard, and no site had daily design values above the NAAQS 65 µg/m³ daily standard. Using a particle composition monitor designed specifically for SEARCH, we found that volatilization losses of nitrate, ammonium, and organic carbon must be accounted for to accurately characterize atmospheric particulate matter. In particular, the federal reference method for PM_2.5 underestimates mass by 3–7% as a result of these volatilization losses. Organic matter (OM) and sulfate account for ≥60% of PM_2.5 mass at SEARCH sites, whereas major metal oxides (MMO) and unidentified components (“other”) account for ≥80% of PM_10–2.5 mass. Limited data suggest that much of the unidentified mass in PM_10–2.5 may be OM. For paired comparisons of urban-rural sites, differences in PM_2.5 mass are explained, in large part, by higher OM and black carbon at the urban site. For PM₁₀, higher urban concentrations are explained by higher MMO and “other.” Annual means for PM_2.5 and PM_10–2.5 mass and major components demonstrate substantial declines at all of the SEARCH sites over the 1999–2003 period (10–20% in the case of PM_2.5, dominated by 14–20% declines in sulfate and 11–26% declines in OM, and 14–25% in the case of PM_10–2.5, dominated by 17–30% declines in MMO and 14–31% declines in “ other”). Although declining national emissions of sulfur dioxide and anthropogenic carbon may account for a portion of the observed declines, additional investigation will be necessary to establish a quantitative assessment, especially regarding trends in local and regional emissions, primary carbon emissions, and meteorology.