Analysis of a Summertime PM2.5 and Haze Episode in the Mid-Atlantic Region

Abstract

Observations of the mass and chemical composition of particles less than 2.5 μm in aerodynamic diameter (PM_2.5), light extinction, and meteorology in the urban Baltimore-Washington corridor during July 1999 and July 2000 are presented and analyzed to study summertime haze formation in the mid-Atlantic region. The mass fraction of ammoniated sulfate (SO₄ ^2-) and carbonaceous material in PM_2.5 were each ～50% for cleaner air (PM_2.5 < 10 μg/m³) but changed to ～60% and ～20%, respectively, for more polluted air (PM_2.5 > 30 μg/m³). This signifies the role of SO₄ ^2- in haze formation. Comparisons of data from this study with the Interagency Monitoring of Protected Visual Environments network suggest that SO₄ ^2? is more regional than carbonaceous material and originates in part from upwind source regions. The light extinction coefficient is well correlated to PM_2.5 mass plus water associated with inorganic salt, leading to a mass extinction efficiency of 7.6 ± 1.7 m²/g for hydrated aerosol. The most serious haze episode occurring between July 15 and 19, 1999, was characterized by westerly transport and recirculation slowing removal of pollutants. At the peak of this episode, 1-hr PM_2.5 concentration reached ～45 μg/m³, visual range dropped to ～5 km, and aerosol water likely contributed to ～40% of the light extinction coefficient.     

Characterization of physicochemical properties of beryllium aerosols associated with prevalence of chronic beryllium disease

Little is known about the physicochemical properties of beryllium aerosols associated with increased risk of beryllium sensitization and chronic beryllium disease (CBD). Such information is needed to evaluate whether airborne mass of beryllium is the appropriate metric of exposure or alternatively to provide a scientific basis for using information on particle size, surface area, and chemistry to support an improved exposure limit based on bioavailability through the inhalation and dermal routes of exposure. Thus, we used a suite of analytical techniques to characterize aerodynamically size-fractionated beryllium particles and powders that have been associated in epidemiological studies with higher prevalence of CBD. Aerosol particles were sampled from the ventilation systems of production lines for powders of beryllium metal and beryllium oxide and for ingots of copper-beryllium alloy. End product powders from the metal and oxide production lines were also collected.Particles released during production of beryllium metal were found to be complex, having heterogeneous composition, including reactive species such as fluorine. Powders from beryllium metal production were of high purity with only a minor component of beryllium oxide. Both particles and powders from oxide production were high-purity oxide. Particles released during production of copper-beryllium alloy were heterogeneous, being predominantly copper oxides. Thus, all particles and powders contain at least some beryllium in the form of beryllium oxide.These data justify efforts to thoroughly characterize beryllium aerosol properties when performing exposure assessments. The data also suggest that differences in particle chemical composition, size, number, and surface area may influence bioavailability of beryllium and contribute to risk of CBD. However, a scientific basis does not yet exist to replace mass as the current metric of exposure.     

Part I: lead peroxide candles and dustfall collectors

A diffusion flame burner was operated to determine the effect of several parameters on the quantity of NO_x and unburned hydrocarbons produced. The statistical analysis indicated the unburned hydrocarbon emissions to be dependent upon the rate of heat release in the system, the amount of excess combustion air, the fuel molecular structure, and the interaction between the fuel structure and the amount of excess air. Analysis of the NO_x emissions, after an adjustment to a common temperature to eliminate the temperature effect, showed them to be dependent upon the fuel molecular structure and the amount of excess air. The NO_x emissions reached a maximum at the conditions which yielded minimum unburned hydrocarbon emissions. Multiple regressions were made which yielded predicting equations for both the unburned hydrocarbon and the NO_x for the apparatus used.     

Environmental Monitoring Of Remedial Dredging At The New Bedford Harbor, Ma, Superfund Site

New Bedford Harbor (NBH), MA, is a Superfund site because of high polychlorinated biphenyl (PCB) concentrations in the sediment. From April 1994 to September 1995, a remedial dredging operation (termed the “Hot Spot”) removed the most contaminated sediments (PCB concentrations greater than 4000μg/g) from the upper harbor. During remediation, a monitoring program assessed the potential environmental impacts to NBH and adjacent Buzzards Bay. The monitoring program was developed with input from federal, state, and local authorities. Site-specific decision criteria were established to assess net PCB transport, water column toxicity, and PCB bioaccumulation in blue and ribbed mussels (Mytilus edulis and Geukensia demissa, respectively). The remediation was completed without exceeding PCB net transport or acute toxicity effects specified in the decision criteria. In addition, PCB bioaccumulation in mussels during this time period was not significantly greater than pre- or post-operational measurements. The results indicated that approximately 14000 cubic yards of highly PCB contaminated sediment were permanently removed with minimal environmental effects. The lessons learned during this operation, as well as previous pilot studies at the site, will be used to make full-scale remedial efforts in NBH more efficient and environmentally protective.     

Pollutant Transport During a Regional O3 Episode in the Mid-Atlantic States

ABSTRACT

Ozone (O₃) concentrations in the Baltimore-Washington (B-W) metropolitan area frequently exceed the National Ambient Air Quality Standard (NAAQS) in the summer months. The most extreme O₃ events occur in multi-day high O₃ episodes.¹ These events can be regional in scale, with O₃ concentrations exceeding the NAAQS at numerous locations along the eastern U.S. seaboard, and are typically associated with slow-moving or stagnant high pressure systems.^2-5 In the B-W region, the most extreme events typically occur with surface high pressure overhead or just west of the region and an upper air high-pressure area (ridge) to the west or northwest.¹ Besides providing conditions conducive to local O₃ production (subsidence and strong low-level inversions, weak horizontal winds, little cloud cover), this weather pattern may also result in transport of O₃ and its precursors from heavily industrialized areas west and north of the B-W region. In this paper, observations and back trajectories made during the severe regional O₃ event of July 12-15, 1995, are used to confirm the hypothesis that significant regional-scale transport of O₃ and its precursors occur during extreme O₃ events of the standard type in the B-W area.     

Assessment of the 16S-23S rDNA intergenic spacer region in Enterococcus spp. for microbial source tracking

A new library-based microbial source tracking (MST) approach intended for initial application in the coastal waters of Virginia was evaluated. Host-origin isolates of Enterococcus spp. were collected from beaches and the surrounding tidewater region of Virginia and used to construct a library based on the pattern of DNA band lengths produced by the amplification of the 16S-23S rDNA intergenic spacer (IGS) region, and subsequent digestion with MboI. Initial results from small host-origin libraries (64 and 200 total isolates) with discriminant analysis (DA) and logistic regression (LR) yielded high average rates of correct classification (ARCC) for a four-source classification split (birds, dogs, sewage, and wildlife), with ARCCs ranging from 83 to 100%. However, the poor results obtained when classification was attempted on a non-library validation set (VS, ARCCs of 47 and 48%, respectively, using DA and LR) demonstrated that a library of 200 isolates was insufficient to adequately represent the diversity of the enterococci in the sampled region. An increase in the library size to 1029 total isolates was accompanied by a reduction in the ARCC of the library to 42.7% with DA and 45.7% with LR, plus similarly poor results obtained from the VS. The low correct classification rates generated by the larger known-source library were unsuitable for field application. Many reported MST methods have been based on results obtained using small host-origin libraries without external validation. Our results indicate that such an approach can be very misleading, and that larger libraries and external validation is essential for the confirmation of preliminary results.     

Effects of binary mixtures of six xenobiotics on hormone concentrations and morphometric endpoints of northern bobwhite quail (Colinus virginianus)

This study investigated the effects of six endocrine disrupters in five different doses (0.1, 0.3, 1, 3, 10 mg/kg or microg/kg) in ethanol administered by oral gavage to bobwhite quail eggs. Six eggs each were in each dose group of coumestrol, ethynyl estradiol, indole-3-carbinol, o,p'-DDE, p,p'-DDE, or TCDD. Eggs were also dosed in two sets. One set was ethynyl estradiol (0, 0.03, 0.1, 0.3, 1.0, 3.0, 10.0 microg/kg) and TCDD (0, 0.003, 0.01, 0.03, 0.1, 0.3 microg/kg). This set was dosed below the air cell with corn oil as vehicle. Also, northern bobwhite quail eggs were injected in ovo with nine binary mixtures of six xenobiotics prior to incubation (coumestrol (0.3 mg/kg), ethynyl estradiol (3.0 microg/kg), indole-3-carbinol (3.0 mg/kg), o,p'-DDE (1.0 mg/kg), p,p'-DDE (1.0 mg/kg), TCDD (0.1 microg/kg)). The mixtures injected were p,p'-DDE+indole-3-carbinol, coumestrol+indole-3-carbinol, TCDD+indole-3-carbinol, p,p'-DDE+o,p'-DDE, p,p'-DDE+ethynyl estradiol, coumestrol+ethynyl estradiol, coumestrol+TCDD, o,p'-DDE+ethynyl estradiol, TCDD+ethynyl estradiol. Eggs were dosed once prior to initiating incubation. Quail were allowed to hatch and were sacrificed at 21 days of age. Blood, measurements, and tissues were collected. Survival was significantly affected by increasing concentrations of TCDD in ethanol as revealed by trend analysis. Survival was also affected significantly by o,p'-DDE in ethanol but not by trend. Survival results of mixtures indicate significant differences among mixture, mixture components, and controls for coumestrol+TCDD, ethynyl estradiol+TCDD, and indole-3-carbinol+TCDD. Some trends from doses of single compounds that are supported by results in the literature were observed for hatchling weight of ethynyl estradiol dosed females, weight gain of indole-3-carbinol dosed males, weight gain and liver somatic index of o,p'-DDE dosed males, spleen somatic index of TCDD dosed males, and weight gain, gonad somatic index and egg gland somatic index of TCDD dosed females. In conclusion, the dose response treatments appeared to have effects beyond effects on survival of in ovo dosed quail. For mixtures, plasma estradiol concentrations were significantly different among coumestrol+ethynyl estradiol, ethynyl estradiol, coumestrol, and vehicle treatments. Liver somatic index among the same treatments was also significantly different. Kidney somatic index among ethynyl estradiol+p,p'-DDE, ethynyl estradiol, p,p'-DDE, and vehicle treatments was significantly different. Plasma estradiol and plasma testosterone ratios were very different among o,p'-DDE+p,p'-DDE, o,p'-DDE, p,p'-DDE, and vehicle treatments. Coumestrol and ethynyl estradiol appear antagonistic for plasma estradiol concentrations and liver somatic index when both chemicals are present together. Ethynyl estradiol and p,p'-DDE appear to act additively on kidney somatic index when combined together. Mixtures of compounds, used in this study indicate effects very different from either or both mixture components, indicating the lack of predictability of chemicals when combined in mixtures.