Multi-year hourly PM2.5 carbon measurements in New York: Diurnal,day of week and seasonal patterns

Multi-year hourly measurements of PM_2.5 elemental carbon (EC) and organic carbon (OC) from a site in the South Bronx, New York were used to examine diurnal, day of week and seasonal patterns. The hourly carbon measurements also provided temporally resolved information on sporadic EC spikes observed predominantly in winter. Furthermore, hourly EC and OC data were used to provide information on secondary organic aerosol formation. Average monthly EC concentrations ranged from 0.5 to 1.4 μg m^?3 with peak hourly values of several μg m^?3 typically observed from November to March. Mean EC concentrations were lower on weekends (approximately 27% lower on Saturday and 38% lower on Sunday) than on weekdays (Monday to Friday). The weekday/weekend difference was more pronounced during summer months and less noticeable during winter. Throughout the year EC exhibited a similar diurnal pattern to NO_x showing a pronounced peak during the morning commute period (7–10 AM EST). These patterns suggest that EC was impacted by local mobile emissions and in addition by emissions from space heating sources during winter months. Although EC was highly correlated with black carbon (BC) there was a pronounced seasonal BC/EC gradient with summer BC concentrations approximately a factor of 2 higher than EC. Average monthly OC concentrations ranged from 1.0 to 4.1 μg m^?3 with maximum hourly concentrations of 7–11 μg m^?3 predominantly in summer or winter months. OC concentrations generally correlated with PM_2.5 total mass and aerosol sulfate and with NO_x during winter months. OC showed no particular day of week pattern. The OC diurnal pattern was typically different than EC except in winter when OC tracked EC and NO_x indicating local primary emissions contributed significantly to OC during winter at the urban location. On average secondary organic aerosol was estimated to account for 40–50% of OC during winter and up to 63–73% during summer months.     

Linking biophysical models and public preferences for ecosystem service assessments: a case study for the Southern Rocky Mountains

Through extensive research, ecosystem services have been mapped using both survey-based and biophysical approaches, but comparative mapping of public values and those quantified using models has been lacking. In this paper, we mapped hot and cold spots for perceived and modeled ecosystem services by synthesizing results from a social-values mapping study of residents living near the Pike–San Isabel National Forest (PSI), located in the Southern Rocky Mountains, with corresponding biophysically modeled ecosystem services. Social-value maps for the PSI were developed using the Social Values for Ecosystem Services tool, providing statistically modeled continuous value surfaces for 12 value types, including aesthetic, biodiversity, and life-sustaining values. Biophysically modeled maps of carbon sequestration and storage, scenic viewsheds, sediment regulation, and water yield were generated using the Artificial Intelligence for Ecosystem Services tool. Hotspots for both perceived and modeled services were disproportionately located within the PSI’s wilderness areas. Additionally, we used regression analysis to evaluate spatial relationships between perceived biodiversity and cultural ecosystem services and corresponding biophysical model outputs. Our goal was to determine whether publicly valued locations for aesthetic, biodiversity, and life-sustaining values relate meaningfully to results from corresponding biophysical ecosystem service models. We found weak relationships between perceived and biophysically modeled services, indicating that public perception of ecosystem service provisioning regions is limited. We believe that biophysical and social approaches to ecosystem service mapping can serve as methodological complements that can advance ecosystem services-based resource management, benefitting resource managers by showing potential locations of synergy or conflict between areas supplying ecosystem services and those valued by the public.     

Adapting to climate change: an integrated biophysical and economic assessment for Mozambique

Mozambique, like many African countries, is already highly susceptible to climate variability and extreme weather events. Climate change threatens to heighten this vulnerability. In order to evaluate potential impacts and adaptation options for Mozambique, we develop an integrated modeling framework that translates atmospheric changes from general circulation model projections into biophysical outcomes via detailed hydrologic, crop, hydropower and infrastructure models. These sector models simulate a historical baseline and four extreme climate change scenarios. Sector results are then passed down to a dynamic computable general equilibrium model, which is used to estimate economy-wide impacts on national welfare, as well as the total cost of damages caused by climate change. Potential damages without changes in policy are significant; our discounted estimates range from US$ 2.3 to US $7.4 billion during 2003?C2050. Our analysis identifies improved road design and agricultural sector investments as key ??no-regret?? adaptation measures, alongside intensified efforts to develop a more flexible and resilient society. Our findings also support the need for cooperative river basin management and the regional coordination of adaptation strategies.     

Variably saturated flow and multicomponent biogeochemical reactive transport modeling of a uranium bioremediation field experiment

Three-dimensional, coupled variably saturated flow and biogeochemical reactive transport modeling of a 2008 in situ uranium bioremediation field experiment is used to better understand the interplay of transport and biogeochemical reactions controlling uranium behavior under pulsed acetate amendment, seasonal water table variation, spatially variable physical (hydraulic conductivity, porosity) and geochemical (reactive surface area) material properties. While the simulation of the 2008 Big Rusty acetate biostimulation field experiment in Rifle, Colorado was generally consistent with behaviors identified in previous field experiments at the Rifle IFRC site, the additional process and property detail provided several new insights. A principal conclusion from this work is that uranium bioreduction is most effective when acetate, in excess of the sulfate-reducing bacteria demand, is available to the metal-reducing bacteria. The inclusion of an initially small population of slow growing sulfate-reducing bacteria identified in proteomic analyses led to an additional source of Fe(II) from the dissolution of Fe(III) minerals promoted by biogenic sulfide. The falling water table during the experiment significantly reduced the saturated thickness of the aquifer and resulted in reactants and products, as well as unmitigated uranium, in the newly unsaturated vadose zone. High permeability sandy gravel structures resulted in locally high flow rates in the vicinity of injection wells that increased acetate dilution. In downgradient locations, these structures created preferential flow paths for acetate delivery that enhanced local zones of TEAP reactivity and subsidiary reactions. Conversely, smaller transport rates associated with the lower permeability lithofacies (e.g., fine) and vadose zone were shown to limit acetate access and reaction. Once accessed by acetate, however, these same zones limited subsequent acetate dilution and provided longer residence times that resulted in higher concentrations of TEAP reaction products when terminal electron donors and acceptors were not limiting. Finally, facies-based porosity and reactive surface area variations were shown to affect aqueous uranium concentration distributions with localized effects of the fine lithofacies having the largest impact on U(VI) surface complexation. The ability to model the comprehensive biogeochemical reaction network, and spatially and temporally variable processes, properties, and conditions controlling uranium behavior during engineered bioremediation in the naturally complex Rifle IFRC subsurface system required a subsurface simulator that could use the large memory and computational performance of a massively parallel computer. In this case, the eSTOMP simulator, operating on 128 processor cores for 12h, was used to simulate the 110-day field experiment and 50 days of post-biostimulation behavior.     

Evaluation of alternative PCB clean-up strategies using an individual-based population model of mink

Population models can be used to place observed toxic effects into an assessment of the impacts on population-level endpoints, which are generally considered to provide greater ecological insight and relevance. We used an individual-based model of mink to evaluate the population-level effects of exposure to polychlorinated biphenyls (PCBs) and the impact that different remediation strategies had on mink population endpoints (population size and extinction risk). Our simulations indicated that the initial population size had a strong impact on mink population dynamics. In addition, mink populations were extremely responsive to clean-up scenarios that were initiated soon after the contamination event. In fact, the rate of PCB clean-up did not have as strong a positive effect on mink as did the initiation of clean-up (start time). We show that population-level approaches can be used to understand adverse effects of contamination and to also explore the potential benefits of various remediation strategies.     

Odor emission rate estimation of indoor industrial sources using a modified inverse modeling method

Odor emission rates are commonly measured in the laboratory or occasionally estimated with inverse modeling techniques. A modified inverse modeling approach is used to estimate source emission rates inside of a postdigestion centrifuge building of a water reclamation plant. Conventionally, inverse modeling methods divide an indoor environment in zones on the basis of structural design and estimate source emission rates using models that assume homogeneous distribution of agent concentrations within a zone and experimentally determined link functions to simulate airflows among zones. The modified approach segregates zones as a function of agent distribution rather than building design and identifies near and far fields. Near-field agent concentrations do not satisfy the assumption of homogeneous odor concentrations; far-field concentrations satisfy this assumption and are the only ones used to estimate emission rates. The predictive ability of the modified inverse modeling approach was validated with measured emission rate values; the difference between corresponding estimated and measured odor emission rates is not statistically significant. Similarly, the difference between measured and estimated hydrogen sulfide emission rates is also not statistically significant. The modified inverse modeling approach is easy to perform because it uses odor and odorant field measurements instead of complex chamber emission rate measurements.     

Combined MODFLOW‐FRACTRAN Application to Assess Chlorinated Solvent Transport and Remediation in Fractured Sedimentary Rock

Detailed field investigations and numerical modeling were conducted to evaluate transport and fate of chlorinated solvent contamination in a fractured sedimentary bedrock aquifer (sandstone/siltstone/mudstone) at a Superfund site in central New Jersey. Field investigations provided information on the fractured rock system hydrogeology, including hydraulic gradients, bulk hydraulic conductivity, fracture network, and rock matrix, and on depth discrete contaminant distribution in fractures (via groundwater sampling) and matrix (via detailed subsampling of continuous cores). The numerical modeling endeavor involved application of both an equivalent porous media (EPM) model for flow and a discrete fracture network (DFN) model for transport. This combination of complementary models, informed by appropriate field data, allowed a quantitative representation of the conceptual site model (CSM) to assess relative importance of various processes, and to examine efficacy of remedial alternatives. Modeling progressed in two stages: first a large‐scale (20 km x 25 km domain) 3‐D EPM flow model (MODFLOW) was used to evaluate the bulk groundwater flow system and contaminant transport pathways under historic and current aquifer stress conditions and current stresses. Then, results of the flow model informed a 2‐D DFN transport model (FRACTRAN) to evaluate transport along a 1,000‐m flowpath from the source represented as a 2‐D vertical cross‐section. The combined model results were used to interpret and estimate the current and potential future extent of rock matrix and aqueous‐phase contaminant conditions and evaluate remedial strategies. Results of this study show strong effects of matrix diffusion and other processes on attenuating the plume such that future impacts on downgradient well fields under the hydraulic stresses modeled should be negligible. Results also showed futility of source remediation efforts in the fractured rock, and supported a technical impracticability (TI) waiver for the site. © 2013 Wiley Periodicals, Inc.     

Spatial Distribution of Geobacteraceae and Sulfate‐Reducing Bacteria During In Situ Bioremediation of Uranium‐Contaminated Groundwater

Analysis of the physiological status of subsurface microbial communities generally relies on the study of unattached microorganisms in the groundwater. These approaches have been employed in studies on bioremediation of uranium‐contaminated groundwater at a study site in Rifle, Colorado, in which Geobacter species typically account for over 90 percent of the microbial community in the groundwater during active uranium reduction. However, to develop efficient in situ bioremediation strategies it is necessary to know the status of sediment‐associated microorganisms as well. In order to evaluate the distribution of the natural community of Geobacter during bioremediation of uranium, subsurface sediments were packed into either passive flux meters (PFMs) or sediment columns deployed in groundwater monitoring wells prior to acetate injection during in situ biostimulation field trials. The trials were performed at the Department of Energy's (DOE's) Rifle Integrated Field Research Challenge site. Sediment samples were removed either during the peak of Fe(III) reduction or the peak of sulfate reduction over the course of two separate field experiments and preserved for microscopy. Direct cell counts using fluorescence in situ hybridization (FISH) probes targeting Geobacter species indicated that the majority of Geobacter cells were unattached during Fe(III) reduction, which typically tracks with elevated rates of uranium reduction. Similar measurements conducted during the sulfate‐reducing phase revealed the majority of Geobacter to be attached following exhaustion of more readily bioavailable forms of iron minerals. Laboratory sediment column studies confirmed observations made with sediment samples collected during field trials and indicated that during Fe(III) reduction, Geobacter species are primarily unattached (90 percent), whereas the majority of sulfate‐reducing bacteria and Geobacter species are attached to sediment surfaces when sulfate reduction is the predominant form of metabolism (75 percent and 77 percent, respectively). In addition, artificial sediment experiments showed that pure cultures of Geobacter uraniireducens, isolated from the Rifle site, were primarily unattached once Fe(III) became scarce. These results demonstrate that, although Geobacter species must directly contact Fe(III) oxides in order to reduce them, cells do not firmly attach to the sediments, which is likely an adaptive response to sparsely and heterogeneously dispersed Fe(III) minerals in the subsurface. © 2013 Wiley Periodicals, Inc.     

Methods for Determining Paniculate Mass and Size Properties: Laboratory and Field Measurements

No single particle size measuring device was found suitable in both the fine and ultrafine particle size regimes, however, combinations of devices have been used successfully. Methods of measurement and applications in the laboratory and field are discussed.     

An Analysis of Michigan and California CO Remote Sensing Measurements

Abstract

Remote sensing measurements of CO emissions from on-road vehicles were made in California in 1991 and in Michigan in 1992. It was determined that both fleets had a small linear increase in the high emitter frequency (vehicles emitting more than 4% CO) as a function of vehicle age for 1986 and newer model vehicles. Although high emitting vehicles were only a small minority of the fleet, they had a dominant impact on the mean CO and total CO emitted by the fleet. In Michigan, the highest emitting 5% of passenger cars generated 45% of the CO from cars. In California, the highest emitting 5% of passenger cars generated 38% of the CO from cars. There was a high correlation between the mean CO emitted by each model year of vehicle and the frequency of high emitting vehicles within the model year for both the Michigan and California fleets. The frequency of high emitters within any model year had no obvious relation to that model year’s certification standards. The high emitter frequencies for vehicles less than nine years old were very similar for the California and Michigan fleets. An increase in the high emitter frequency in the ten-year-old and older Michigan passenger car fleet (relative to the California passenger car fleet), suggests, but does not conclusively demonstrate, that the rate of high emitters in Michigan and California is reduced by the inspection and maintenance (I/M) programs.