Hourly and daily patterns of particle-phase organic and elemental carbon concentrations in the urban atmosphere

Two semicontinuous elemental and organic carbon analyzers along with daily integrated samplers, which were used for laboratory elemental and organic carbon analysis, were operated to measure PM2.5 organic carbon (OC) and elemental carbon (EC) for the entire year of 2002 at the St. Louis Midwest Supersite. The annual-average denuded OC and EC concentrations were 3.88 and 0.7 microg/m3, respectively. A comparison of the 24-hr average denuded and undenuded OC measurements showed a positive bias for the undenuded OC measurement that was best represented by a positive intercept of 0.34 +/- 0.1 microg/m3 and a slope of 1.06 +/- 0.02, with an R2 of 0.91. The full year of daily EC and OC measurements was used to demonstrate that a one-in-six-day sampling strategy at this site accurately represents the annual average concentrations. Although fine particle OC concentrations did not correlate with day of the week, EC concentrations showed a significant weekly pattern, with the highest concentration during the middle of the workweek and the lowest concentration on Sundays. Hourly EC and OC measurements yielded average diurnal patterns for the EC to OC ratio that peaked during morning rush hour traffic on weekdays but not on weekends.     

Metal-mediated chlorinated dibenzo-p-dioxin (CDD) and dibenzofuran (CDF) formation from phenols

Heterogeneous formation of chlorinated dibenzo-p-dioxins (CDDs) and dibenzofurans (CDFs) on CuCl2 from three phenols without ortho chlorine and one phenol with two ortho chlorines was studied in a flow reactor over a temperature range of 325-450 degrees C. Heated nitrogen gas streams containing 8% oxygen, 1.5% benzene vapor, and equal amounts of phenol, 3-chlorophenol, 3,4-dichlorophenol and 2,4,6-trichlorophenol vapor (700 ppmv, each) were passed through a 1 g particle bed of silica and 0.5% (Cu mass) CuCl2. Maximum product yields of greater than 1.4% phenol conversion to CDD and 5.7% phenol conversion to CDF were observed between 400 and 450 degrees C. CDDs formed with loss of one chlorine atom were favored. While total CDD/F yield varied with temperature, CDD/F homologue and isomer distributions did not vary significantly with temperature. Based on the results of experiments with single phenol precursors, phenol precursors could be assigned to all PCDD/F products. Of the chlorinated phenols without ortho chlorine that were studied, 3,4-dichlorophenol was found to have the greatest propensity to form CDFs.     

Near-field dispersion modeling for regulatory applications

This paper evaluates the application of dispersion models to estimate near-field pollutant concentrations in two case studies. The Industrial Source Complex Short-Term Model (ISCST3) was evaluated with hexavalent chromium measurements collected within 100 m of two facilities in Barrio Logan, San Diego, CA. ISCST3 provided reasonable estimates for higher pollutant concentrations but underestimated lower concentrations. To understand the observed distribution of concentrations in Barrio Logan, a recently conducted tracer experiment was analyzed. The tracer, sulfur hexafluoride, was released at ambient temperature from an urban facility at the University of California at Riverside, and concentrations were measured within 20 m of the source. Modeling results indicated that Industrial Source Complex-Plume Rise Model Enhancement and American Meteorological Society/U.S. Environmental Protection Agency Regulatory Model-Plume Rise Model Enhancement overestimated high concentrations and underestimated low concentrations. A diagnostic study with a simple Gaussian dispersion model that incorporated site-specific meteorology was used to evaluate model results. This study found that incorporating lateral meandering for nonbuoyant urban plumes in Gaussian dispersion models could improve concentration estimates even when downwash is not considered. Incorporating a meandering component in ISCST3 resulted in improvements in estimating hexavalent chromium concentrations in Barrio Logan. Credible near-source concentration estimates depend on accurate characterization of emissions, onsite micrometeorology, and a method to account for lateral meandering in the near field.     

Semicontinuous PM2.5 sulfate and nitrate measurements at an urban and a rural location in New York: PMTACS-NY summer 2001 and 2002 campaigns

Several collocated semicontinuous instruments measuring particulate matter with particle sizes < or =2.5 microm (PM2.5) sulfate (SO4(2-)) and nitrate (NO3-) were intercompared during two intensive field campaigns as part of the PM2.5 Technology Assessment and Characterization Study. The summer 2001 urban campaign in Queens, NY, and the summer 2002 rural campaign in upstate New York (Whiteface Mountain) hosted an operation of an Aerosol Mass Spectrometer, Ambient Particulate Sulfate and Nitrate Monitors, a Continuous Ambient Sulfate Monitor, and a Particle-Into-Liquid Sampler with Ion Chromatographs (PILS-IC). These instruments provided near real-time particulate SO4(2-) and NO3- mass concentration data, allowing the study of particulate SO4(2-)/NO3- diurnal patterns and detection of short-term events. Typical particulate SO4(2-) concentrations were comparable at both sites (ranging from 0 to 20 microg/m3), while ambient urban particulate NO3- concentrations ranged from 0 to 11 microg/m3 and rural NO3- concentration was typically less than 1 microg/m3. Results of the intercomparisons of the semicontinuous measurements are presented, as are results of the comparisons between the semicontinuous and time-integrated filter-based measurements. The comparisons at both sites, in most cases, indicated similar performance characteristics. In addition, charge balance calculations, based on major soluble ionic components of atmospheric aerosol from the PILS-IC and the filter measurements, indicated slightly acidic aerosol at both locations.     

Changes in the biochemical oxygen demand procedure in the 21st edition of Standard Methods for the Examination of Water and Wastewater.

The dilution biochemical oxygen demand (BOD) test has widespread application for design and operation of wastewater treatment processes, evaluating the quality of natural waters, and assessing the effect of wastewater discharges on these waters. While standardization of the BOD-measuring method has become of prime importance in maintaining dependable data acquisition, changes are made as needed in response to questions raised by analysts and to accommodate new applications. The purpose of this article is to describe changes that have been incorporated in the 20th and 21st editions of Standard Methods for the Examination of Water and Wastewater (APHA et al., 1998 and 2004). These changes include changes in text format to clarify the procedural steps, allowance for use of bottle sizes ranging from 60 mL or larger, improvements in quality-control procedures, and improvements in the method of calculating BOD. Other changes include allowance for the use of allylthiourea for nitrification inhibition and broadening the source of seed that can be used for inoculation of BOD samples.     

Preparing to measure the effects of the NOx SIP call--methods for ambient air monitoring of NO,NO2, NOy,and individual NOz species

The capping of stationary source emissions of NOx in 22 states and the District of Columbia is federally mandated by the NOx 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 NOz component compounds, and NOy. 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 NOy monitoring technology and a listing of demonstrated monitoring approaches are also presented.     

Environmental exposure to PCBs and cancer incidence in eastern Slovakia

In a population-based cross-sectional study, we compared serum levels of 15 polychlorinated biphenyl (PCB) congeners and three organochlorine pesticides in residents of two districts in eastern Slovakia, one with extensive environmental contamination from a former PCB production site (Michalovce) and the other matched on geography but with low (background) levels (Svidnik). The age-adjusted geometric means for sum of 15 measured PCB congeners were statistically significantly higher in subjects from the Michalovce district for both sexes: 3327.6 versus 1331.4 ng/g of lipid in males, 2751.8 versus 992.2 ng/g of lipid in females. Levels of DDE and DDT were also significantly higher, although the absolute differences were less pronounced. There was no substantial difference in HCB levels between the districts. We also conducted an ecologic study to compare cancer incidence occurring in these same two districts from 1985 through 1994. We calculated standardized incidence ratios (SIRs) and 95% confidence intervals for each district using indirect standardization and rates from eastern Slovakia. Among males from Michalovce (exposed), but not Svidnik (unexposed), there was an excess of cancer of the tongue (SIR=1.46; 1.06-1.96), stomach (SIR=1.15; 1.00-1.32), lung (SIR=1.14; 1.04-1.24), testis (SIR=1.40; 0.97-1.97), and kidney (SIR=1.23; 0.98-1.52), and lower than expected incidence of prostate cancer (SIR=0.83; 0.69-0.97); in contrast, there was an excess of peritoneal (SIR=3.05; 1.11-6.63) and laryngeal cancer (SIR=1.43; 0.99-1.98) in Svidnik not observed Michalovce. Among females from Michalovce, but not Svidnik, there was an excess of cancer of the lip (SIR=2.54; 1.53-3.96), stomach (SIR=1.22; 1.02-1.44), and lung (SIR=1.17; 0.94-1.45); in contrast, there was an excess of kidney (SIR=1.61; 1.03-2.40) and thyroid (SIR=1.97; 1.12-3.20) cancer in Svidnik not observed in Michalovce. Taken together, these results raise the possibility that high environmental exposure to organochlorines in the Michalovce district may be associated with higher rates of certain cancers, particularly stomach and lung cancer.     

Comparisons of the dust/smoke particulate that settled inside the surrounding buildings and outside on the streets of southern New York City after the collapse of the World Trade Center, September 11, 2001

The collapse of the World Trade Center (WTC) on September 11, 2001, generated large amounts of dust and smoke that settled in the surrounding indoor and outdoor environments in southern Manhattan. Sixteen dust samples were collected from undisturbed locations inside two uncleaned buildings that were adjacent to Ground Zero. These samples were analyzed for morphology, metals, and organic compounds, and the results were compared with the previously reported outdoor WTC dust/smoke results. We also analyzed seven additional dust samples provided by residents in the local neighborhoods. The morphologic analyses showed that the indoor WTC dust/smoke samples were similar to the outdoor WTC dust/smoke samples in composition and characteristics but with more than 50% mass in the <53-microm size fraction. This was in contrast to the outdoor samples that contained >50% of mass above >53 microm. Elemental analyses also showed the similarities, but at lower concentrations. Organic compounds present in the outdoor samples were also detected in the indoor samples. Conversely, the resident-provided convenience dust samples were different from either the WTC indoor or outdoor samples in composition and pH, indicating that they were not WTC-affected locations. In summary, the indoor dust/smoke was similar in concentration to the outdoor dust/smoke but had a greater percentage of mass <53 microm in diameter.