Reconciling models and measurements to assess trends in atmospheric mercury deposition

Changes in atmospheric mercury deposition are used to evaluate the effectiveness of regulations controlling emissions. This analysis can be complicated by seemingly incongruent data from different model runs, model types, and field measurements. Here we present a case study example that describes how to identify trends in regional scale mercury deposition using best-available information from multiple data sources. To do this, we use data from three atmospheric chemistry models (CMAQ, GEOS-Chem, HYSPLIT) and multiple sediment archives (ombrotrophic bog, headwater lake, coastal salt marsh) from the Bay of Fundy region in Canada. Combined sediment and modeling data indicate that deposition attributable to US and Canadian emissions has declined in recent years, thereby increasing the relative significance of global sources. We estimate that anthropogenic emissions in the US and Canada account for 28-33% of contemporary atmospheric deposition in this region, with the rest from natural (14-32%) and global sources (41-53%).     

Air pollutant source characterization using the revised regional haze tracking metric and a photochemical grid model and implications for regional haze planning

The 2017 revisions to the Regional Haze Rule clarify that visibility progress at Class I national parks and wilderness areas should be tracked on days with the highest anthropogenic contributions to haze (impairment). We compare the natural and anthropogenic contributions to haze in the western United States in 2011 estimated using the Environmental Protection Agency (EPA) recommended method and using model projections from the Comprehensive Air Quality Model with Extensions (CAMx) and the Particulate Source Apportionment Tool (PSAT). We do so because these two methods will be used by states to demonstrate visibility progress by 2028. If the two methods assume different natural and anthropogenic contributions, the projected benefits of reducing U.S. anthropogenic emissions will differ. The EPA method assumes that episodic elevated carbonaceous aerosols greater than an annual 95th percentile threshold are natural events. For western U.S. IMPROVE monitoring sites reviewed in this paper, CAMx-PSAT confirms these episodes are impacted by carbon from wildfire or prescribed fire events. The EPA method assumes that most of the ammonium sulfate is anthropogenic in origin. At most western sites CAMx-PSAT apportions more of the ammonium sulfate on the most impaired days to global boundary conditions and anthropogenic Canadian, Mexican, and offshore shipping emissions than to U.S. anthropogenic sources. For ammonium nitrate and coarse mass, CAMx-PSAT apportions greater contributions to U.S. anthropogenic sources than the EPA method assigns to total anthropogenic contributions. We conclude that for western IMPROVE sites, the EPA method is effective in selecting days that are likely to be impacted by anthropogenic emissions and that CAMx-PSAT is an effective approach to estimate U.S. source contributions. Improved inventories, particularly international and natural emissions, and further evaluation of global and regional model performance and PSAT attribution methods are recommended to increase confidence in modeled source characterization.

Implications: The western states intend to use the CAMx model to project visibility progress by 2028. Modeled visibility response to changes in U.S. anthropogenic emissions may be less than estimated using the EPA assumptions based on total U.S. and international anthropogenic contributions to visibility impairment. Additional model improvements are needed to better account for contributions to haze from natural and international emissions in current and future modeling years. These improvements will allow more direct comparison of model and EPA estimates of natural and anthropogenic contributions to haze and future visibility progress.     

METHODOLOGY OF DELINEATING WELLHEAD PROTECTION ZONES IN CRYSTALLINE BEDROCK IN MAINE1

ABSTRACT: Delineation of contributing areas for wellhead protection around supply wells drilled into bedrock in Maine, USA, is currently achieved by assigning a fixed radius circle around the well. This project develops a methodology that incorporates hydrogeologic processes and ground water modeling (MODFLOW) and accounts for variable data availability to estimate the areas that contribute water to 26 bedrock supply wells. Outcrop fracture mapping and lineament analysis are used to characterize the fracture system. Multiple simulations are constructed of each site using ranges of values for recharge, hydraulic conductivity, and anisotropy. Uncertainty in the delineation process is accounted for by portraying the delineated areas as confidence zones that are constructed by overlapping the capture zones from the multiple simulations. The results are variable and depend on the ability to characterize a site in a way that can be easily modeled. Sites with complex hydrogeology tend to have larger contributing areas that reflect the greater uncertainty in the parameters. The majority of the sites, however, produce reasonable results that provide a much more accurate depiction of the area likely to contribute to a bedrock well than the fixed radius circle.     

The impact of wood stove technology upgrades on indoor residential air quality

Fine particulate matter (PM_2.5) air pollution has been linked to adverse health impacts, and combustion sources including residential wood-burning may play an important role in some regions. Recent evidence suggests that indoor air quality may improve in homes where older, non-certified wood stoves are exchanged for lower emissions EPA-certified alternatives. As part of a wood stove exchange program in northern British Columbia, Canada, we sampled outdoor and indoor air at 15 homes during 6-day sampling sessions both before and after non-certified wood stoves were exchanged. During each sampling session two consecutive 3-day PM_2.5 samples were collected onto Teflon filters, which were weighed and analyzed for the wood smoke tracer levoglucosan. Residential PM_2.5 infiltration efficiencies (F_inf) were estimated from continuous light scattering measurements made with nephelometers, and estimates of F_inf were used to calculate the outdoor- and indoor-generated contributions to indoor air. There was not a consistent relationship between stove technology and outdoor or indoor concentrations of PM_2.5 or levoglucosan. Mean F_inf estimates were low and similar during pre- and post-exchange periods (0.32 ± 0.17 and 0.33 ± 0.17, respectively). Indoor sources contributed the majority (～65%) of the indoor PM_2.5 concentrations, independent of stove technology, although low indoor-outdoor levoglucosan ratios (median ≤ 0.19) and low indoor PM_2.5-levoglucosan correlations (r ≤ 0.19) suggested that wood smoke was not a major indoor PM_2.5 source in most of these homes. In summary, despite the potential for extensive wood stove exchange programs to reduce outdoor PM_2.5 concentrations in wood smoke-impacted communities, we did not find a consistent relationship between stove technology upgrades and indoor air quality improvements in homes where stoves were exchanged.     

Assessment and monitoring tools for aerobic bioremediation of vinyl chloride in groundwater

Direct aerobic biodegradation of vinyl chloride (VC) offers a remedial solution for persistent vinyl chloride plumes that are not amenable to the anaerobic process of reductive dechlorination because of either prevailing geochemical conditions or the absence of active Dehalococcoides ethenogenes. However, tools are needed to evaluate and optimize aerobic VC bioremediation. This article describes the development and testing of two techniques—a microbiological tool and a molecular tool—for this purpose. Both methods are based on detection of bacteria that can use vinyl chloride and ethene as growth substrates in the presence of oxygen. The microbiological tool is an activity assay that indicates whether bacteria capable of degrading ethene under aerobic conditions are present in a groundwater sample. This activity assay gave positive results in the area of active VC degradation of an aerobic VC bioremediation test site. A rapid semiquantitative genetic assay was also developed. This molecular tool, based on polymerase chain reaction (PCR) detection of a gene involved in the metabolism of both ethene and VC, revealed the presence of potential VC degraders in an enrichment culture and site groundwater. These tools could provide a basis for judging the potential of aerobic VC degradation by ethenotrophs at other sites in addition to offering a mechanism for treatment monitoring and system optimization. © 2009 Wiley Periodicals, Inc.     

Detecting and Coping with Disruptive Shocks in Arctic Marine Systems: A Resilience Approach to Place and People

It seems inevitable that the ongoing and rapid changes in the physical environment of the marine Arctic will push components of the region’s existing social-ecological systems—small and large—beyond tipping points and into new regimes. Ongoing changes include warming, freshening, acidification, and alterations to food web structure. In anticipation we pose three distinct but interrelated challenges: (1) to explore existing connectivities within components of the marine system; (2) to seek indicators (if they exist) of approaching regime change through observation and modeling; and (3) to build functional resilience into existing systems through adaptation-oriented policy and to have in hand transformative options when tipping points are crossed and new development trajectories are required. Each of the above challenges is scale dependent, and each requires a much deeper understanding than we currently have of connectivity within existing systems and their response to external forcing. Here, we argue from a global perspective the need to understand the Arctic’s role in an increasingly nonlinear world; then describe emerging evidence from new observations on the connectivity of processes and system components from the Canada Basin and subarctic seas surrounding northern North America; and finally posit an approach founded in “resilience thinking” to allow northern residents living in small coastal communities to participate in the observation, adaption and—if necessary—transformation of the social-ecological system with which they live.     

DFT M06-2X investigation of alkaline hydrolysis of nitroaromatic compounds

The nitroaromatic compounds 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT) and 2,4-dinitroanisole (DNAN) are potential environmental contaminants and their transformations under a variety of environmental conditions are consequently of great interest. One possible method to safely degrade these nitrocompounds is alkaline hydrolysis. A mechanism of the initial stages of this reaction was investigated computationally. Simulations of UV-VIS and NMR spectra for this mechanism were also produced. The results obtained were compared to available experimental data on the alkaline hydrolysis of TNT and suggest that the formation of Meisenheimer complexes and an anion of TNT are potential first-step intermediates in the reaction path. As the reaction proceeds, computational results indicate that polynegative complexes dominate the degradation pathway, followed by cycles of carbon chain opening and breaking. A second possible pathway was identified that leads to polymeric products through Janovsky complex formation. Results from this study indicate that the order of increasing resistance to alkaline hydrolysis is TNT, DNT and DNAN.     

An Index of Air Pollution and its Relation to Health

Atmospheric pollution by sulfur oxides is discussed in terms of the sources of the pollutant and the possible methods of control. Possible approaches to control are classified in general categories, including fuel desulfurization, process modifications, and flue-gas desulfurization. Some of the more promising specific possibilities are discussed in relation to the organizations developing them.