Indoor/Outdoor Measurements of Volatile Organic Compounds in the Kanawha Valley of West Virginia

The Kanawha Valley region of West Virginia which is comprised of Charleston and surrounding communities Is the center of a heavily industrialized area known for its chemical manufacturing. As part of a larger study designed to investigate the Impact of the chemical industry on human exposures to volatile organic compounds (VOC), a study of the relationship between indoor and outdoor concentrations was conducted. Thirty-five homes were selected for monitoring from among volunteers; approximately ten in each of three distinct population-industry centers and four outside the Valley to act as controls. Monitoring was performed using passive, badge samplers with a three-week monitoring period. Two separate questionnaires were administered: one for characterization of the residence; and one to characterize source use during monitoring. Participants were also asked to keep a record of their activities with respect to in-home, outdoors and other Indoor environments. Analysis of the samplers was performed by solvent extraction followed by gas chromatography using a flame-ionization detector. Results suggest that indoor VOC concentrations are higher than outdoor concentrations. Additionally, certain ventilation-related parameters were identified that afforded some predictive power for indoor concentrations. No statistically significant differences between regions were identified.     

Evaluation of Regenerative-air Vacuum Street Sweeping on Geological Contributions to PM10

Street sweeping is often proposed as a means of reducing the emissions from paved roads. The objective of this study was to evaluate the effectiveness of street sweeping on ambient particulate matter concentrations and to determine the difference In source contributions to PM10 concentrations between street sweeping and non-street sweeping periods.

Chemically-speciated measurements of PM10 and PM2.5 were taken in the commercial section of Reno, Nevada, for a one-month sampling period. The Chemical Mass Balance (CMB) model was applied to these data and an average of approximately 50 percent of the PM10 was apportioned to resuspended geological material. During half of the sampling period, streets In the vicinity of the sampling site were completely swept with a regenerative-air vacuum sweeper, while no sweeping was performed during the remainder of the experiment. Ratios of primary geological contributions divided by primary motor vehicle contributions to PM10 were compared between sweeping and non-sweeping periods using analysis of variance. This ratio of source contributions minimizes the effects of variations in traffic volume and meteorological dispersion. No significant differences in geological contributions to PM10 were detected as a result of regenerative-air vacuum street sweeping.     

Reactivity-Based Hydrocarbon Controls: Scientific Issues and Potential Regulatory Applications

The California Air Resources Board and the South Coast Air Quality Management District hosted a conference on April 8-9, 1991 to examine the scientific issues associated with reactivity-based hydrocarbon controls, and to identify the obstacles to potential regulatory applications. Owing to residual uncertainties in the underlying science, and the complex emission measurement capabilities required for enforcement, a general consensus emerged on the need for further research before application of reactivity-based controls. A number of recommendations were made for research on the remaining scientific, enforcement, and policy issues, many of which have led to cooperative efforts initiated since the conference.     

Black Carbon Aerosol at McMurdo Station,Antarctica

ABSTRACT

Aerosol light absorption as black carbon (BC) was measured from November 19, 1995, to February 6, 1996, at a location 0.65 km downwind of the center of McMurdo Station on the Antarctic coast. The results show a bimo-dal frequency distribution of BC concentrations. Approximately 65% of the measurements were found in a mode at a low range of concentrations centered at ~20 ng/m³. These concentrations are higher than those found at other remote Antarctic locations and probably represent contamination from the station. The remaining measurements were in a high-concentration mode (BC ~300 ng/m³), indicating direct impact of local emissions from combustion activities at the station. High values of BC were associated with winds from the direction of the station, and the BC flux showed a clear directionality. Maximum BC concentrations occurred between 7:00 and 11:00 a.m. The "polluted" mode accounted for more than 80% of the BC frequency-weighted impact at this location.     

Identification of Selected Hormonally Active Agents and Animal Mammary Carcinogens in Commercial and Residential Air and Dust Samples

ABSTRACT

In order to characterize typical indoor exposures to chemicals of interest for research on breast cancer and other hormonally mediated health outcomes, methods were developed to analyze air and dust for target compounds that have been identified as animal mammary carcinogens or hormonally active agents and that are used in commercial or consumer products or building materials. These methods were applied to a small number of residential and commercial environments to begin to characterize the extent of exposure to these classes of compounds. Phenolic compounds, including nonylphenol, octylphenol, bisphenol A, and the methoxychlor metabolite 2,2-bis (p-hydroxyphenyl)-1,1,1-trichloroethane (HPTE), were extracted, derivatized, and analyzed by gas chromatography/mass spectrometry (GC/MS)–selective ion monitoring (SIM). Selected phthalates, pesticides, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) were extracted and analyzed by GC/MS-SIM. Residential and workplace samples showed detectable levels of twelve pesticides in dust and seven in air samples. Phthalates were abundant in dust (0.3524 μg/g) and air (0.005-2.8 μg/m³). Nonylphenol and its mono- and di-ethoxylates were prevalent in dust (0.82-14 μg/g) along with estrogenic phenols such as bisphenol A and o-phenyl phenol. In this 7-sample pilot study, 33 of 86 target compounds were detected in dust, and 24 of 57 target compounds were detected in air. In a single sample from one home, 27 of the target compounds were detected in dust and 15 in air, providing an indication of chemical mixtures to which humans are typically exposed.     

The Southeastern Aerosol Research and Characterization Study: Part 1—Overview

Abstract

This paper presents an overview of a major, long-term program for tropospheric gas and aerosol research in the southeastern United States. Building on three existing ozone (O₃)-focused research sites begun in mid-1992, the Southeastern Aerosol Research and Characterization Study (SEARCH) was initiated in mid-1998 as a 7-year observation and research program with a broader focus including aerosols and an expanded geographical coverage in the Southeast. The monitoring network comprises four urban-rural (or urban-suburban) site pairs at locations along the coast of the Gulf of Mexico and inland, including two moderately sized and two major urban areas (Pensacola, FL; Gulfport, MS; Atlanta, GA; and Birmingham, AL). The sites are equipped with an extensive suite of instruments for measuring particulate matter (PM), gases relevant to secondary O₃ and the production of secondary aerosol particles, and surface meteorology. The measurements taken to date have added substantially to the knowledge about the temporal behavior and geographic variability of tropospheric aerosols in the Southeast. Details are presented in four papers to follow.     

Spatial Differences in Outdoor PM10 Mass and Aerosol Composition in Mexico City

Abstract

Twenty-five MiniVol samplers were operated throughout the Mexico City metropolitan region from February 22 through March 22, 1997, to evaluate the variability of PM₁₀ concentrations and composition. The highest PM₁₀ concentrations were found in neighborhoods with unpaved or dirty roads, and elements related to crustal material were the main cause of differences from nearby (<200 m) monitors that were not adjacent to the roadbed. SO₄ ^2?concentrations were homogeneous across the city. SO₄ ^2?measured at the city boundaries was about two-thirds of the concentrations measured within the urbanized area, indicating that most SO₄ ^2? is of regional origin. Elemental carbon (EC) and organic carbon (OC) concentrations were highly variable, with higher concentrations in areas that had high diesel traffic and older vehicles. Spatial correlations among PM₁₀ concentrations were high, even though absolute concentrations were variable, indicating a common effect of meteorology on the concentration or dispersion of local emissions.     

Fundamentals of Successful Monitoring,Reporting, and Verification under a Cap-and-Trade Program

Abstract

The U.S. Environmental Protection Agency (EPA) developed and implemented the Acid Rain Program (ARP), and NO_x Budget Trading Programs (NBTP) using several fundamental monitoring, reporting, and verification (MRV) elements: (1) compliance assurance through incentives and automatic penalties; (2) strong quality assurance (QA); (3) collaborative approach with a petition process; (4) standardized electronic reporting; (5) compliance flexibility for low-emitting sources; (6) complete emissions data record required; (7) centralized administration; (8) level playing field; (9) publicly available data; (10) performance-based approach; and (11) reducing conflicts of interest. Each of these elements is discussed in the context of the authors’ experience under two U.S. cap-and-trade programs and their potential application to other capand-trade programs.

The U.S. Office of Management and Budget found that the Acid Rain Program has accounted for the largest quantified human health benefits of any federal regulatory program implemented in the last 10 yr, with annual benefits exceeding costs by >40 to 1. The authors believe that the elements described in this paper greatly contributed to this success. EPA has used the ARP fundamental elements as a model for other cap-and-trade programs, including the NBTP, which went into effect in 2003, and the recently published Clean Air Interstate Rule and Clean Air Mercury Rule. The authors believe that using these fundamental elements to develop and implement the MRV portion of their cap-and-trade programs has resulted in public confidence in the programs, highly accurate and complete emissions data, and a high compliance rate (>99% overall).     

Particulate Emissions from Construction Activities

Abstract

Although it has long been recognized that road and building construction activity constitutes an important source of particulate matter (PM) emissions throughout the United States, until recently only limited research has been directed to its characterization. This paper presents the results of PM₁₀ and PM_2.5 (particles ≤10 μm and ≤2.5 μm in aerodynamic diameter, respectively) emission factor development from the onsite testing of component operations at actual construction sites during the period 1998 –2001. Much of the testing effort was directed at earthmoving operations with scrapers, because earthmoving is the most important contributor of PM emissions across the construction industry. Other sources tested were truck loading and dumping of crushed rock and mud and dirt carryout from construction site access points onto adjacent public paved roads. Also tested were the effects of watering for control of scraper travel routes and the use of paved and graveled aprons at construction site access points for reducing mud and dirt carryout. The PM₁₀ emissions from earthmoving were found to be up to an order of magnitude greater than predicted by AP-42 emission factors drawn from other industries. As expected, the observed PM_2.5:PM₁₀ emission factor ratios reflected the relative importance of the vehicle exhaust and the resuspended dust components of each type of construction activity. An unexpected finding was that PM_2.5 emissions from mud and dirt carryout were much less than anticipated. Finally, the control efficiency of watering of scraper travel routes was found to closely follow a bilinear moisture model.     

PM2.5 source apportionment with organic markers in the Southeastern Aerosol Research and Characterization (SEARCH) study

Positive matrix factorization (PMF) and effective variance (EV) solutions to the chemical mass balance (CMB) were applied to PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) mass and chemically speciated measurements for samples taken from 2008 to 2010 at the Atlanta, Georgia, and Birmingham, Alabama, sites. Commonly measured PM_2.5 mass, elemental, ionic, and thermal carbon fraction concentrations were supplemented with detailed nonpolar organic speciation by thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). Source contribution estimates were calculated for motor vehicle exhaust, biomass burning, cooking, coal-fired power plants, road dust, vegetative detritus, and secondary sulfates and nitrates for Atlanta. Similar sources were found for Birmingham, with the addition of an industrial source and the separation of biomass burning into open burning and residential wood combustion. EV-CMB results based on conventional species were qualitatively similar to those estimated by PMF-CMB. Secondary ammonium sulfate was the largest contributor, accounting for 27–38% of PM_2.5, followed by biomass burning (21–24%) and motor vehicle exhaust (9–24%) at both sites, with 4–6% of PM_2.5 attributed to coal-fired power plants by EV-CMB. Including organic compounds in the EV-CMB reduced the motor vehicle exhaust and biomass burning contributions at both sites, with a 13–23% deficit for PM_2.5 mass. The PMF-CMB solution showed mixing of sources within the derived factors, both with and without the addition of speciated organics, as is often the case with complex source mixtures such as those at these urban-scale sites. The nonpolar TD-GC/MS compounds can be obtained from existing filter samples and are a useful complement to the elements, ions, and carbon fractions. However, they should be supplemented with other methods, such as TD-GC/MS on derivitized samples, to obtain a wider range of polar compounds such as sterols, sugars, and organic acids. The PMF and EV solutions to the CMB equations are complementary to, rather than replacements for, each other, as comparisons of their results reveal uncertainties that are not otherwise evident.

Implications:?Organic markers can be measured on currently acquired PM_2.5 filter samples by thermal methods. These markers can complement element, ion, and carbon fraction measurements from long-term speciation networks. Applying the positive matrix factorization and effective variance solutions for the chemical mass balance equations provides useful information on the accuracy of the source contribution estimates. Nonpolar compounds need to be complemented with polar compounds to better apportion cooking and secondary organic aerosol contributors.