Use of a Continuous Nephelometer to Measure Personal Exposure to Particles During the U.S. Environmental Protection Agency Baltimore and Fresno Panel Studies

ABSTRACT

In population exposure studies, personal exposure to PM is typically measured as a 12- to 24-hr integrated mass concentration. To better understand short-term variation in personal PM exposure, continuous (1-min averaging time) nephelometers were worn by 15 participants as part of two U.S. Environmental Protection Agency (EPA) longitudinal PM exposure studies conducted in Baltimore County, MD, and Fresno, CA. Participants also wore iner-tial impactor samplers (24-hr integrated filter samples) and recorded their daily activities in 15-min intervals. In Baltimore, the nephelometers correlated well (R² = 0.66) with the PM₂₅ impactors. Time-series plots of personal nephelometer data showed each participant's PM exposure to consist of a series of peaks of relatively short duration. Activities corresponding to a significant instrument response included cooking, outdoor activities, transportation, laundry, cleaning, shopping, gardening, moving between microenvironments, and removing/putting on the instrument. On average, 63-66% of the daily PM exposure occurred indoors at home (about 2/3 of which occurred during waking hours), primarily due to the large amount of time spent in that location (an average of 7277%). Although not a reference method for measuring mass concentration, the nephelometer did help identify PM sources and the relative contribution of those sources to an individual's personal exposure.     

The Influence of Human Activity Patterns on Personal PM Exposure: A Comparative Analysis of Filter-Based and Continuous Particle Measurements

ABSTRACT

Particulate matter (PM) exposure data from the U.S. Environmental Protection Agency (EPA)-sponsored 1998 Baltimore and 1999 Fresno PM exposure studies were analyzed to identify important microenvironments and activities that may lead to increased particle exposure for select elderly (>65 years old) subjects. Integrated 24-hr filter-based PM_2.5 or PM₁₀ mass measurements [using Personal Environmental Monitors(PEMs)] included personal measurements, indoor and outdoor residential measurements, and measurements at a central indoor site and a community monitoring site. A subset of the participants in each study wore passive nephelometers that continuously measured (1-min averaging time) particles ranging in size from 0.1 to ~10 um. Significant activities and locations were identified by a statistical mixed model (p < 0.01) for each study population based on the measured PM_2.5 or PM₁₀ mass and time activity data. Elevated PM concentrations were associated with traveling (car or bus), commercial locations (store, office, mall, etc.), restaurants, and working.

The modeled results were compared to continuous PM concentrations determined by the nephelometers while participants were in these locations. Overall, the nephelometer data agreed within 6% of the modeled PM_2.5 results for the Baltimore participants and within ~20% for the Fresno participants (variability was due to zero drift associated with the nephelometer). The nephelom-eter did not agree as well with the PM₁₀ mass measurements, most likely because the nephelometer optimally responds to fine particles (0.3–2 um). Approximately one-half (54 ± 31%; mean ± standard deviation from both studies) of the average daily PM_2.5 exposure occurred inside residences, where the participants spent an average of 83 ± 10% of their time. These data also showed that a significant portion of PM_2.5 exposure occurred in locations where participants spent only 4–13% of their time.     

Preparing to Measure the Effects of the NOx SIP Call— Methods for Ambient Air Monitoring of NO,NO2, NOy,and Individual NOz Species

Abstract

The capping of stationary source emissions of NO_x in 22 states and the District of Columbia is federally mandated by the NO_x SIP Call legislation with the intended purpose of reducing downwind O₃ concentrations. Monitors for NO, NO₂, and the reactive oxides of nitrogen into which these two compounds are converted will record data to evaluate air quality model (AQM) predictions. Guidelines for testing these models indicate the need for semicontinuous measurements as close to real time as possible but no less frequently than once per hour. The measurement uncertainty required for AQM testing must be less than ±20% (±10% for NO₂) at mixing ratios of 1 ppbv and higher for NO, individual NO_z component compounds, and NO_y. This article is a review and discussion of different monitoring methods, some currently used in research and others used for routine monitoring. The performance of these methods is compared with the monitoring guidelines. Recommendations for advancing speciated and total NO_y monitoring technology and a listing of demonstrated monitoring approaches are also presented.     

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.     

Ambient ozone effects on gas exchange and total non-structural carbohydrate levels in cutleaf coneflower (Rudbeckia laciniata L.) growing in Great Smoky Mountains National Park

Ozone-sensitive and -tolerant individuals of cutleaf coneflower (Rudbeckia laciniata L.) were compared for their gas exchange characteristics and total non-structural carbohydrates at Purchase Knob, a high elevation site in Great Smoky Mountains National Park, USA. Photosynthesis and stomatal conductance decreased with increased foliar stipple. Sensitive plants had lower photosynthetic rates for all leaves, except the very youngest and oldest when compared to tolerant plants. Stomatal conductance decreased with increasing leaf age, but no ozone-sensitivity differences were found. Lower leaves had less starch than upper ones, while leaves on sensitive plants had less than those on tolerant plants. These results show that ambient levels of ozone in Great Smoky Mountains National Park can adversely affect gas exchange, water use efficiency and leaf starch content in sensitive coneflower plants. Persistence of sensitive genotypes in the Park may be due to physiological recovery in low ozone years.     

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.     

Comparative phototoxicity of nanoparticulate and bulk ZnO to a free-living nematode Caenorhabditis elegans: the importance of illumination mode and primary particle size

The present study evaluated phototoxicity of nanoparticulate ZnO and bulk-ZnO under natural sunlight (NSL) versus ambient artificial laboratory light (AALL) illumination to a free-living nematode Caenorhabditis elegans. Phototoxicity of nano-ZnO and bulk-ZnO was largely dependent on illumination method as 2-h exposure under NSL caused significantly greater mortality in C. elegans than under AALL. This phototoxicity was closely related to photocatalytic reactive oxygen species (ROS) generation by the ZnO particles as indicated by concomitant methylene blue photodegradation. Both materials caused mortality in C. elegans under AALL during 24-h exposure although neither degraded methylene blue, suggesting mechanisms of toxicity other than photocatalytic ROS generation were involved. Particle dissolution of ZnO did not appear to play an important role in the toxicity observed in this study. Nano-ZnO showed greater phototoxicity than bulk-ZnO despite their similar size of aggregates, suggesting primary particle size is more important than aggregate size in determining phototoxicity.     

The environmental and biosecurity characteristics of livestock carcass disposal methods: A review

Livestock mortalities represent a major waste stream within agriculture. Many different methods are used throughout the world to dispose of these mortalities; however within the European Union (EU) disposal options are limited by stringent legislation. The legal disposal options currently available to EU farmers (primarily rendering and incineration) are frequently negatively perceived on both practical and economic grounds. In this review, we assess the potential environment impacts and biosecurity risks associated with each of the main options used for disposal of livestock mortalities in the world and critically evaluate the justification for current EU regulations. Overall, we conclude that while current legislation intends to minimise the potential for on-farm pollution and the spread of infectious diseases (e.g. transmissible spongiform encephalopathies, bacterial pathogens), alternative technologies (e.g. bioreduction, anaerobic digestion) may provide a more cost-effective, practical and biosecure mechanism for carcass disposal as well as having a lower environmental footprint. Further social, environmental and economic research is therefore warranted to assess the holistic benefits of alternative approaches for carcass disposal in Europe, with an aim to provide policy-makers with robust knowledge to make informed decisions on future legislation.     

Removal potential of toxic 2378-substituted PCDD/F from incinerator flue gases by waste-derived activated carbons

The application of activated carbons has become a commonly used emission control protocol for the removal or adsorption of persistent organic pollutants from the flue gas streams of waste incinerators. In this study, the 2378-substituted PCDD/F removal efficiency of three types of activated carbons derived from the pyrolysis of refuse derived fuel, textile waste and scrap tyre was investigated and compared with that of a commercial carbon. Experiments were carried out in a laboratory scale fixed-bed reactor under a simulated flue gas at 275 °C with a reaction period of four days. The PCDD/F in the solid matrices and exhaust gas, were analyzed using gas chromatography coupled with a triple quadrupole mass spectrometer. In the absence of activated carbon adsorbent, there was a significant increase in the concentration of toxic PCDD/F produced in the reacted flyash, reaching up to 6.6 times higher than in the raw flyash. In addition, there was a substantial release of PCDD/F into the gas phase, which was found in the flue gas trapping system. By application of the different commercial, refuse derived fuel, textile and tyre activated carbons the total PCDD/F toxic equivalent removal efficiencies in the exhaust gas stream were 58%, 57%, 64% and 52%, respectively. In general, the removal of the PCDDs was much higher with an average of 85% compared to PCDFs at 41%. Analysis of the reacted activated carbons showed that there was some formation of PCDD/F, for instance, a total of 60.6 μg I-TEQ kg⁻¹ toxic PCDD/F was formed in the refuse derived fuel activated carbon compared to 34 μg I-TEQ kg⁻¹ in the commercial activated carbon. The activated carbons derived from the pyrolysis of waste, therefore, showed good potential as a control material for PCDD/F emissions in waste incinerator flue gases.