Atmospheric Chemistry of Toxic Contaminants. 3. Unsaturated Aliphatics: Acrolein,Acrylonitrile, Maleic Anhydride

Detailed mechanisms are outlined for the chemical reactions that contribute to In-situ formation and atmospheric removal of the unsaturated aliphatic contaminants acrolein, acrylonitrile, and maleic anhydride. In-situ formation of small amounts of acrolein and maleic anhydride may Involve the reaction of OH (and O₃) with 1,3-dienes and the reaction of OH with aromatic hydrocarbons, respectively. There is no known pathway for In-situ formation of acrylonitrile. Rapid removal of acrolein (half-life = less than one day) and of maleic anhydride (half-life = several hours) is expected from their rapid reactions with OH (major), O₃, and NO₃. These reactions lead to formaldehyde and glyoxal from acrolein and to dicarbonyls from maleic anhydride. Acrylonitrile is removed at a slower rate (half-life = 2–7 days) by reaction with OH, leading to formaldehyde and formyl cyanide.     

Atmospheric Chemistry of Toxic Contaminants. 5. Unsaturated Halogenated Aliphatics: Allyl Chloride,Chloroprene, Hexachlorocyclopentadiene,Vinylidene Chloride

Detailed mechanisms are outlined for the chemical reactions involved In the atmospheric removal of four unsaturated chlorinated aliphatic contaminants, allyl chloride, chloroprene, hexachlorocyclopentadiene and vlnylldene chloride. Rate constants estimated from structure-reactivity relationships Indicate rapid removal for all four compounds by reactions with OH (major), ozone, and NO₃, with half-lives of 2-16 hrs for removal by reaction with OH. Reaction products of allyl chloride (formaldehyde, chloroacetaldehyde, peroxychloroacetyl nitrate) and vinylidene chloride (formaldehyde, phosgene, chloroacetyl chloride) are consistent with OH addition-Initiated pathways that include Cl atom elimination. The chlorine atoms produced In the OH reaction sequence react rapidly with all four unsaturated compounds, but these reactions are of negligible Importance for atmospheric removal of the four toxic contaminants studied. Analogous mechanisms are discussed for chloroprene (leading to formaldehyde, CH₂ = CCICHO, and CICOCHO) and for hexachlorocyclopentadlene (leading to oxalyl chloride and CICOCCI₂COCI).     

The Steubenville Comprehensive Air Monitoring Program (SCAMP): Overview and Statistical Considerations

Abstract

Average concentrations of particulate matter with an aerodynamic diameter less than or equal to 2.5 μm (PM_2.5) in Steubenville, OH, have decreased by more than 10 μg/m³ since the landmark Harvard Six Cities Study¹ associated the city’s elevated PM_2.5 concentrations with adverse health effects in the 1980s. Given the promulgation of a new National Ambient Air Quality Standard (NAAQS) for PM_2.5 in 1997, a current assessment of PM_2.5 in the Steubenville region is warranted. The Steubenville Comprehensive Air Monitoring Program (SCAMP) was conducted from 2000 through 2002 to provide such an assessment. The program included both an outdoor ambient air monitoring component and an indoor and personal air sampling component. This paper, which is the first in a series of four that will present results from the outdoor portion of SCAMP, provides an overview of the outdoor ambient air monitoring program and addresses statistical issues, most notably autocorrelation, that have been overlooked by many PM_2.5 data analyses. The average PM_2.5 concentration measured in Steubenville during SCAMP (18.4 μg/m³) was 3.4g/m³ above the annual PM_2.5 NAAQS. On average, sulfate and organic material accounted for ～31% and 25%, respectively, of the total PM_2.5 mass. Local sources contributed an estimated 4.6 μg/m³ to Steubenville’s mean PM_2.5 concentration. PM_2.5 and each of its major ionic components were significantly correlated in space across all pairs of monitoring sites in the region, suggesting the influence of meteorology and long-range transport on regional PM_2.5 concentrations. Statistically significant autocorrelation was observed among time series of PM_2.5 and component data collected at daily and 1-in-4-day frequencies during SCAMP. Results of spatial analyses that accounted for autocorrelation were generally consistent with findings from previous studies that did not consider autocorrelation; however, these analyses also indicated that failure to account for autocorrelation can lead to incorrect conclusions about statistical significance.     

Validation of the Digital Opacity Compliance System under Regulatory Enforcement Conditions

Abstract

U.S. Environmental Protection Agency (EPA) Emission Measurement Center in conjunction with EPA Regions VI and VIII, the state of Utah, and the U.S. Department of Defense have conducted a series of long-term pilot and field tests to determine the accuracy and reliability of a visible opacity monitoring system consisting of a conventional digital camera and a separate computer software application for plume opacity determination. This technology, known as the Digital Opacity Compliance System (DOCS), has been successfully demonstrated at EPA-sponsored Method-9 “smoke schools,” as well as at a number of government and commercially operated industrial facilities.

Results from the current DOCS regulatory pilot study demonstrated that, under regulatory enforcement conditions, the average difference in opacity measurement between the DOCS technology and EPA Reference Method 9 (Method 9) was 1.12%. This opacity difference, which was computed from the evaluation of 241 regulated air sources, was found to be statistically significant at the 99% confidence level. In evaluating only those sources for which a nonzero visible opacity level was recorded, the average difference in opacity measurement between the DOCS technology and Method 9 was 1.20%. These results suggest that the two opacity measurement methods are essentially equivalent when measuring the opacity of visible emissions.

Given the costs and technical limitations associated with use of Method 9, there is a recognized need to develop accurate, reproducible, and scientifically defensible alternatives to the use of human observers. The use of digital imaging/processing brings current technology to bear on this important regulatory issue. Digital technology offers increased accuracy, a permanent record of measurement events, lower costs, and a scientifically defensible approach for opacity determination.     

An energy systems view of sustainability: emergy evaluation of the San Luis Basin, Colorado

Energy Systems Theory (EST) provides a framework for understanding and interpreting sustainability. EST implies that "what is sustainable" for a system at any given level of organization is determined by the cycles of change originating in the next larger system and within the system of concern. The pulsing paradigm explains the ubiquitous cycles of change that apparently govern ecosystems, rather than succession to a steady state that is then sustainable. Therefore, to make robust decisions among environmental policies and alternatives, decision-makers need to know where their system resides in the cycles of change that govern it. This theory was examined by performing an emergy evaluation of the sustainability of a regional system, the San Luis Basin (SLB), CO. By 1980, the SLB contained a climax stage agricultural system with well-developed crop and livestock production along with food and animal waste processing. The SLB is also a hinterland in that it exports raw materials and primary products (exploitation stage) to more developed areas. Emergy indices calculated for the SLB from 1995 to 2005 revealed changes in the relative sustainability of the system over this time. The sustainability of the region as indicated by the renewable emergy used as a percent of total use declined 4%, whereas, the renewable carrying capacity declined 6% over this time. The Emergy Sustainability Index (ESI) showed the largest decline (27%) in the sustainability of the region. The total emergy used by the SLB, a measure of system well-being, was fairly stable (CV?=?0.05). In 1997, using renewable emergy alone, the SLB could support 50.7% of its population at the current standard of living, while under similar conditions the U.S. could support only 4.8% of its population. In contrast to other indices of sustainability, a new index, the Emergy Sustainable Use Index (ESUI), which considers the benefits gained by the larger system compared to the potential for local environmental damage, increased 34% over the period.     

An Ecoregional Context for Forest Management on National Wildlife Refuges of the Upper Midwest,USA

To facilitate forest planning and management on National Wildlife Refuges, we synthesized multiple data sources to describe land ownership patterns, land cover, landscape pattern, and changes in forest composition for four ecoregions and their associated refuges of the Upper Midwest. We related observed patterns to ecological processes important for forest conservation and restoration, with specific attention to refuge patterns of importance for forest landbirds of conservation priority. The large amount of public land within the ecoregions (31–80%) suggests that opportunities exist for coarse and meso-scale approaches to conserving and restoring ecological processes affecting the refuges, particularly historical fire regimes. Forests dominate both ecoregions and refuges, but refuge forest patches are generally larger and more aggregated than in associated ecoregions. Broadleaf taxa have increased in dominance in the ecoregions and displaced fire-dependent taxa such as pine (Pinus spp.) and other coniferous species; these changes in forest composition have likely also affected refuge forests. Despite compositional changes, larger forest patches on refuges suggests that they may provide better habitat for area-sensitive forest landbirds of mature, compositionally diverse forests than surrounding lands if management continues to promote increased patch size. We reason that although fine-scale research and monitoring for species of conservation priority is important, broad scale (ecoregional) assessments provide crucial context for effective forest and wildlife management in protected areas.     

Mapping adaptation opportunities and activities in an interactive atlas

The need for transparency is taking more prominence in international climate negotiations as developed countries pledge large sums of money to foster adaptation efforts in developing countries. Tools that provide accurate and up-to-date spatial information that can be easily used and vetted by local practitioners may provide effective and affordable ways to improve transparency. The Global Adaptation Atlas is such a tool, combining vetted, publicly available climate impact data with timely maps of on the ground adaptation projects to highlight confluences of effects of climate change with actions taken to address those effects. Here, we describe the structure and general functions of the Global Adaptation Atlas and explain how it may be utilized to track short-term investments in adaptation. Over longer time scales, it may also help gauge the effectiveness of specific adaptation investments as well as reveal how different climate impacts affect long-term investment in differing regions.     

Whole effluent toxicity assessment at a wastewater treatment plant upgraded with a full-scale post-ozonation using aquatic key species

Ozonation as final wastewater (WW) polishing step, following conventional activated sludge treatment is increasingly implemented in sewage treatment for contaminant degradation to prevent surface water pollution. While the oxidative degradation of chemicals has been extensively investigated, the in vivo toxicological characteristics of ozonated whole effluents are rarely a matter of research.In the present study, whole effluents were toxicologically evaluated with an in vivo test battery before and after full-scale ozonation and subsequent sand filtration on site at a treatment plant. One aquatic plant (duckweed, Lemna minor) and five invertebrate species of different systematic groups (Lumbriculus variegatus, Chironomus riparius, Potamopyrgus antipodarum, Daphnia magna) were exposed to the effluents in a flow-through-designed test system with a test duration of 7-28 d.None of the considered toxicity endpoints correlated with the pollutant elimination. A tendency towards an increased toxicity after ozonation was apparent in three of the test systems showing [statistically] significant adverse effects in the L. variegatus toxicity test (decrease in reproduction and biomass). After sand filtration, adverse effects were reduced to a similar level like after conventional treatment. Solely the Daphnia reproduction test revealed beneficial effects after ozonation in combination with sand filtration.Results of the test battery indicate the formation of adverse oxidation products during WW ozonation. L. variegatus appeared to be the most sensitive of the five test species. Sand filtration effectively removes or detoxifies toxic oxidation products, as toxic effects were subsequently reduced to the level after conventional treatment.     

Increases of dissolved organic carbon in temperate and boreal lakes in Quebec, Canada

Purpose  

Increases in dissolved organic carbon (DOC) concentrations have been reported in surface waters worldwide in the last 10 to 20 years. The causes behind these increases have been attributed to many factors, including climate change and decreasing depositions of atmospheric sulphate ( \textSO₄^{2 -} {\text{SO}}_4^{{{2} - }} ). Trends in DOC concentrations and their potential causal factors were examined in a network of 30 lakes lying in undisturbed temperate and boreal catchments in the province of Quebec, Canada.