A comparison of sampling and analysis methods for low-ppbC levels of volatile organic compounds in ambient air

A carefully designed study was conducted during the summer of 1998 to collect samples of ambient air by canisters and compare the analysis results to direct sorbent preconcentration results taken at the time of sample collection. Thirty-two 1 h sample sets were taken, each composed of a "near-real-time" sample analyzed by an autoGC-MS XonTech 930/Varian Saturn 2000 system, and Summa and Silco canisters. Hourly total non-methane organic carbon (TNMOC), ozone, and meteorological measurements were also made. Each canister was analyzed on the autoGC-MS system for a target list of 108 volatile organic compounds (VOCs) and on a manual cryosampling GC-FID system. Comparisons were made between the collection and analysis methods. Because of the low sample loading (150-250 ppbC TNMOC), these comparisons were a stringent test of sample collection and analysis capabilities. The following specific conclusions may be drawn from this study. Reasonable precision (within 15% mean difference of duplicate analyses from the same canister) can be obtained for analyses of target VOCs at low-ppbC concentrations. Relative accuracy between the GC-MS and GC-FID analysis methods is excellent, as demonstrated by comparisons of analyses of the same canisters, if measurements are sufficiently above the detection limits. This is especially significant as the GC-MS and GC-FID were independently calibrated. While statistically significant differences may be observed between the results from canister and near-real-time samples, the differences were generally small and there were clear correlations between the canister results and the near-real-time results. Canister cleanliness limits detection below the EPA Method TO-14 acceptance standard of 0.2 ppbv (0.2-2 ppbC for target analytes).     

Multi-adsorbent Preconcentration and Gas Chromatographic Analysis of Air Toxics with an Automated Collection/Analytical System

Section 507 of the 1990 Clean Air Act Amendments (CAAA) requires states to develop a small business stationary source and environmental compliance assistance program to aid small businesses impacted by applicable air quality regulations. In general, the program consists of three main components: (1) a small business assistance program (SBAP) for providing compliance and technical assistance to small businesses; (2) an ombudsman for providing direct oversight to the SBAP; and (3) a compliance advisory panel consisting of members from both the public and private sector responsible for determining the overall effectiveness of the SBAP. The key component of the program for assisting small businesses is the SBAP. Providing the necessary assistance to small businesses regarding such issues as permit applicability, rights under the CAAA and emission control options will require the SBAP to develop both proactive and reactive components. The proactive component involves providing outreach services in the form of collecting and disseminating compliance and technical information to small businesses. The reactive component includes the establishment of an information clearinghouse for handling the many inquiries from members of the small business community who have never been subject to air pollution control regulations. States without the available resources to fully implement an SBAP may need to rely on contractor assistance. This paper briefly describes the establishment of the program, provides an overview of each of the program components, discusses many of the ways in which states may implement both the proactive and reactive components of the SBAP, and lists the types of contractors most suitable for SBAP assistance.     

Methodology for Comparison of Open-Path Monitors with Point Monitors

The first measurements of a dispersed secondary pollutant (O₃) using a CO₂ laser based, open-path monitor are compared to readings from a chemiluminescence point monitor which traverses a common measurement path of 0.67 km. A statistical treatment is given which establishes the accuracy of comparison. Meteorological conditions as reflected by changes in pollutant variability are shown to influence the accuracy of comparison. The essential equivalence of data obtained by the point monitor and the path monitor is confirmed for selected measurement sequences while other measurement sequences identify non-optimized performance of the path monitor.     

Laboratory and field evaluation of instrumentation for the semicontinuous determination of particulate nitrate (and other water-soluble particulate components)

Studies conducted at the U.S. Environmental Protection Agency facility in Research Triangle Park, NC, and at a field study in Southern California have demonstrated the capability for the semicontinuous determination of particulate nitrate (and other water-soluble ionic species). Two instruments, an R&P Series 8400N Ambient Particulate Nitrate Monitor (8400N) and an ion chromatography (IC)-based prototype monitor developed at Texas Tech University, were evaluated both in the laboratory using aqueous standards and simulated ambient aerosols and in the field during a 3-week July 1-21, 2003) joint ambient comparison study with Brigham Young University and the South Coast Air Quality Management District (SCAQMD). The field study was conducted at the SCAQMD Rubidoux field site near Riverside, CA. During initial (before the field study) laboratory studies, both instruments were responsive to changes in the simulated aerosol concentration. However, potential problems were discovered involving both instruments during the laboratory-based studies both before and after the Rubidoux study, and these problems are currently being addressed. During the 3-week field study period, 15-minute average particulate nitrate concentrations approaching 30 microg/m3 were observed. Because of malfunctioning IC components (concentrator columns) of the Texas Tech University prototype monitor, limited data were obtained from this instrument during the 3-week sampling period. Initial ambient comparisons show general agreement between the 8400N and IC-based prototype instrument for the semicontinuous determination of ambient particulate nitrate at lower nitrate concentrations (<15 microg/m3) and an underdetermination by the 8400N at higher concentrations (>15 microg/m3). A decreased molybdenum converter efficiency in the pulse analyzer of the 8400N discovered during postfield study laboratory evaluation may explain the negative bias observed at higher nitrate concentrations. Semicontinuous results obtained from U.S. Environmental Protection Agency-operated instruments were averaged and compared with integrated sampler results obtained by Brigham Young University and SCAQMD.     

Analysis of VOCs in Ambient Air Using Multisorbent Packings for VOC Accumulation and Sample Drying

Abstract

Solid multisorbent packings have been characterized for trapping and release efficiency of trace (10-20 ppbv in humidified zero air) volatile organic compounds (VOCs). The use of a two-stage trapping system reduces sample water content typically by more than 95.5% while maintaining a trapping and release efficiency of 100% for 49 VOCs, including eight water-soluble VOCs. Three combinations of primary tube and focusing tube are examined in detail by using an atomic emission detector to monitor hydrogen as an indication of residual water vapor, and to monitor either chlorine, bromine, or carbon for target VOCs. Linearity of response to individual VOCs, the presence of artifacts, and a laboratory monitoring application are also discussed.