Performance evaluation of a sorbent tube sampling method using short path thermal desorption for volatile organic compounds

Air sampling, using sorbents, thermal desorption and gas chromatography, is a versatile method for identifying and quantifying trace levels of volatile organic compounds (VOCs). Thermal desorption can provide high sensitivity, appropropriate choices of sorbents and method parameters can accommodate a wide range of compounds and high humidity, and automated short-path systems can minimize artifacts, losses and carry-over effects. This study evaluates the performance of a short-path thermal desorption method for 77 VOCs using laboratory and field tests and a dual sorbent system (Tenax GR, Carbosieve SIII). Laboratory tests showed that the method requirements for ambient air sampling were easily achieved for most compounds, e.g., using the average and standard deviation across target compounds, blank emissions were < or = 0.3 ng per sorbent tube for all target compounds except benzene, toluene and phenol; the method detection limit was 0.05 +/- 0.08 ppb, reproducibility was 12 +/- 6%, linearity, as the relative standard deviation of relative response factors, was 16 +/- 9%, desorption efficiency was 99 +/- 28%, samples stored for 1-6 weeks had recoveries of 87 +/- 9%, and high humidity samples had recoveries of 102 +/- 12%. Due to sorbent, column and detector characteristics, performance was somewhat poorer for phenol groups, ketones, and nitrogen containing compounds. The laboratory results were confirmed in an analysis of replicate samples collected in two field studies that sampled ambient air along roadways and indoor air in a large office building. Replicates collected under field conditions demonstrated good agreement except for very low concentrations or large (> 41 volume) samples of high humidity air. Overall, the method provides excellent performance and satisfactory throughput for many applications.     

REGION,LANDSCAPE, AND SCALE EFFECTS ON LAKE SUPERIOR TRIBUTARY WATER QUALITY1

ABSTRACT: In 1998 and 1999, third‐order watersheds in high mature forest (HMF) and low mature forest (LMF) classes were selected along gradients of watershed storage within each of two hydrogeomorphic regions in the Lake Superior Basin to evaluate threshold effects of storage on hydrologic regimes and watershed exports. Differences were detected between regions (North and South Shore) for particulates, nutrients, and pH, with all but silica values higher for South Shore streams (p < 0.05). Mature forest effects were detected for turbidity, nutrients, color, and alkalinity, with higher values in the LMF watersheds, that is, watersheds with less that 50 percent mature forest cover. Dissolved N, ammonium, N:P, organic carbon, and color increased, while suspended solids, turbidity, and dissolved P decreased as a function of storage. Few two‐way interactions were detected between region and mature forest or watershed storage, thus threshold based classification schemes could be used to extrapolate effects across regions. Both regional differences in water quality and those associated with watershed attributes were more common for third‐order streams in the western Lake Superior drainage basin as compared with second‐order streams examined in an earlier study. Use of ecoregions alone as a basis for setting regional water quality criteria would have led to misinterpretation of reference condition and assessment of impacts in the Northern Lakes and Forest Ecoregion.     

Significance of Regional Source Contributions to Urban PM-10 Concentrations

Based on data collected in St. Louis, Philadelphia and other eastern U.S. cities, we conclude that a significant fraction of the PM-10 concentration is "background." In these urban areas the background fraction ranges from 35 to 80 percent of the daily, monthly or annual concentration. The bulk of the background appears to be of regional origin. The average chemical makeup of eastern U.S. PM-10 is sulfate as SO₄, 21-34 percent; crustal material, 14-39 percent; "unknown" (carbonaceous matter, ammonium, nitrate and water), 36-51 percent, all of which is difficult to apportion to specific sources. Dispersion modeling using a local source inventory can account only for a small portion of the total PM-10 mass. Emission roll-back of local sources may have a limited effect on reducing total concentrations of PM-10.     

Bioavailability of 2,3,7,8-tetrachlorodibenzo-p-dioxin from municipal incinerator fly ash to freshwater fish

The bioavailability of 2,3,7,8-TCDD from municipal incinerator fly ash to freshwater fish was determined. It was observed that carp exposed to fly ash containing all 22 TCDD isomers, or the solvent extract of the fly ash, retain only 2,3,7,8-TCDD. Exposures with fly ash appears to follow a dose response relationship for bioconcentration, however, the bioavailability of 2,3,7,8-TCDD was not directly related to the level of 2,3,7,8-TCDD in fly ash for two fly ash samples studied.     

Trends of brominated diphenyl ethers in fresh and archived Great Lakes fish (1979-2005)

While few environmental measurements of brominated diphenyl ethers (BDEs) were completed prior to the mid-1990s, analysis of appropriately archived samples might enable the determination of contaminant trends back to the introduction of these chemicals. In this paper, we first investigate the stability of BDEs in archived frozen and extracted fish samples, and then characterize trends of these chemicals in rainbow smelt (Osmerus mordax) and lake trout (Salvelinus namaycush) in each of the Great Lakes between 1979 and 2005. We focus on the four most common congeners (BDE-47, 100, 99 and 153) and use a change-point analysis to detect shifts in trends. Analyses of archived fish samples yielded precise BDE concentration measurements with only small losses (0.8% per year in frozen fish tissues, 2.2% per year in refrigerated extracts). Trends in fish from all Great Lakes showed large increases in BDE concentrations that started in the early to mid-1980s with fairly consistent doubling times (generally 2-4 years except in Lake Erie smelt where levels increased very slowly), though concentrations and trends show differences by congener, fish species and lake. The most recent data show that accumulation rates are slowing, and concentrations of penta- and hexa-congeners in trout from Lakes Ontario and Michigan and smelt from Lake Ontario started to decrease in the mid-1990s. Trends in smelt and trout are evolving somewhat differently, and trout concentrations in the five lakes are now ranked as Michigan>Superior=Ontario>Huron=Erie, and smelt concentrations as Michigan>Ontario>Huron>Superior>Erie. The analysis of properly archived samples permits the reconstruction of historical trends, congener distributions, biomagnification and other information that can aid the understanding and management of these contaminants.     

Ethnicity,housing and personal factors as determinants of VOC exposures

Previous studies investigating effects of personal, demographic, housing and other factors on exposures to volatile organic compounds (VOC) have focused on mean or median exposures, and generally not the high exposures that are of great interest. This paper identifies determinants of personal VOC exposures on a quantile-specific basis using a nationally representative sample. The NHANES 1999–2000 VOC dataset was merged with personal, demographic, housing, smoking and occupation variables. Bivariate analyses tested for differences in geometric means and quantiles across levels of potential exposure determinants. Multivariate sample-weighted ordinary least-squares (OLS) and quantile regression (QR) models were then used to adjust for covariates. We identify a number of exposure determinants, most of which varied by exposure quantile. The most striking finding was the much higher exposures experienced by Hispanics and Blacks for aromatic VOCs (BTEX: benzene, toluene, ethylbenzene and xylenes), methyl tert-butyl ether (MTBE), and 1,4-dichlorobenzene (DCB). Exposure to gasoline, paints or glues, and having a machine-related occupation also were associated with extremely high BTEX and MTBE exposures. Additional determinants included the presence of attached garages and open windows, which affected exposures of BTEX (especially at lower quantiles) and MTBE (especially at higher quantiles). Smoking also increased BTEX exposures. DCB was associated with air freshener use, and PERC with dry-cleaned clothing. After adjusting for demographic, personal and housing factors, age and gender were not significant predictors of exposure. The use of QR in conjunction with OLS yields a more complete picture of exposure determinants, and identifies subpopulations and heterogeneous exposure groups in which some individuals experience very elevated exposures and which are not well represented by changes in the mean. The high exposures of Hispanics and Blacks are perplexing and disturbing, and they warrant further investigation.     

An Evaluation of Commercial Hazardous Waste Thermal Destruction Capacity

Thermal destruction capacity for commercial hazardous waste in the United States is examined to determine current and future capacity requirements. This study focuses on commercial incinerators and cement kilns burning conventional hazardous wastes. Aggregate maximum and available capacity estimates are derived using the most recent information. On a national basis, available capacity far exceeds present demand. On a regional basis, capacity appears sufficient with the exception of the California area. However, this shortfall appears insignificant given the overall capacity situation. While incineration demand may increase for solids and sludges as a consequence of Land Ban disposal restrictions and other reasons, capacity for these wastes again appears sufficient to meet current and projected demands. Thus, arguments that additional commercial incineration capacity will be needed to accommodate an expected increase in incinerable hazardous waste cannot be supported by the available information. The analysis raises concerns about the determination of realistic capacity estimates, and the lack of interaction between the capacity assurance process that documents the need for capacity and state siting processes for new waste management facilities. The excess incineration capacity shown in this paper will contribute to the successful implementation of EPA’s goal to reduce national capacity.     

Rapid determination of ETS markers with a prototype field-portable GC employing a microsensor array detector

The adaptation of a portable gas chromatograph (GC) prototype with several unique design features to the determination of vapor-phase markers of environmental tobacco smoke (ETS) is described. This instrument employs a dual-stage adsorbent preconcentrator, two series-coupled separation columns that can be independently temperature programmed, and a detector consisting of an array of nanoparticle-coated chemiresistors, whose response patterns are used together with retention times for vapor recognition. An adsorbent pre-trap was developed to remove semi-volatile organics from the sample stream. Conditions were established to quantitatively capture two ETS markers, 2,5-dimethylfuran (2,5-DMF) and 4-ethenylpyridine (4-EP, as a surrogate for 3-EP), and to separate them from the 34 most prominent co-contaminants present in ETS using ambient air as the carrier gas. A complete analysis can be performed every 15 min. Projected detection limits are 0.58 and 0.08 ppb for 2,5-DMF and 4-EP, respectively, assuming a 1 L sample volume, which are sufficiently low to determine these markers in typical smoking-permitted environments.     

Optimized acid rain abatement strategies using ecological goals

This article addresses the use of critical loads in optimized emission abatement strategies. Critical loads represent the maximum tolerable deposition possible without adverse impacts, a limit that is highly spatially variable. As deposition targets, critical loads cannot be satisfied at all receptors in Europe. Consequently, there is a need for alternative criteria that still relate to ecological indicators, yet that are feasible, consistent, and equitable. Two criteria are suggested: the relative critical load coverage and the relative deposition reduction. Deposition goals based on these criteria will guarantee that a specified fraction of ecosystems will attain target loads and thus will be protected from adverse environmental impacts. In areas that cannot achieve target loads with the best available control measures, deposition can be reduced to a specified fraction of the unabated level. Examples are presented that demonstrate their derivation and application of the two criteria. The criteria have been implemented in the European-scale Regional Acidification Information and Simulation (RAINS) model. Results obtained indicate that optimized emission strategies based on critical loads may be similar to emission strategies based on deposition reductions at certain levels of the two criteria. This suggests that it may not be necessary to utilize critical loads to formulate deposition targets. A second example shows the effect of excluding countries from European cost minimization. A country's participation can save costs with moderate deposition targets; however, significant costs can be imposed with low (stringent) deposition targets. These preliminary results have significant implications for multilateral negotiations.     

Continuous, intermittent and passive sampling of airborne VOCs

Long sampling periods are often advantageous or required for measuring air quality and characterizing exposures. However, sampling periods exceeding 8 to 24 h using thermally desorbable adsorbent tube (TDT) samplers for the measurement of airborne volatile organic compounds (VOCs) face several challenges, including maintaining stable and low flow rates, and avoiding breakthrough of the adsorbent. These problems may be avoided using intermittent sampling; however, the literature contains few if any reports that have evaluated this technique in environmental, occupational or other applications. The purpose of this study is to evaluate continuous, intermittent and passive sampling methods using both laboratory and real-world tests. Laboratory tests compared continuous and intermittent (active) samplers in a controlled dynamic test gas generation system. Field tests used side-by-side active and passive samplers in an office, home workshop and four smokers' homes. All samples were analyzed for a wide range of VOCs by GC-MS. In most instances, intermittent sampling yielded better reproducibility (duplicate precision of 10 +/- 6%) than continuous low-flow sampling (18 +/- 5%), in part due to difficulty maintaining low flows. Concentrations obtained using intermittent sampling agreed with those for continuous sampling, with downward biases resulting primarily from errors in flow rate measurements. In the field, more VOC species were detected using active rather than passive sampling. Passive measurements were 12% lower than continuous measurements, a difference attributed to declining uptake rates at higher concentrations over the 3 to 4 d sampling period. Overall, most measurements obtained using the three sampling methods agreed within 20% for a wide range of concentrations (0.1 to 230 microg m(-3)). Both passive and intermittent sampling approaches are suitable for long sampling periods, but intermittent sampling provides greater flexibility with respect to sampling period, and permits the use of multi-bed adsorbents that can capture a wider range of VOCs.