A Comparative Analysis of Modeled and Monitored Ambient Hazardous Air Pollutants in Texas: A Novel Approach Using Concordance Correlation

Abstract

Often, in studies evaluating the health effects of hazardous air pollutants (HAPs), researchers rely on ambient air levels to estimate exposure. Two potential data sources are modeled estimates from the U.S. Environmental Protection Agency (EPA) Assessment System for Population Exposure Nationwide (ASPEN) and ambient air pollutant measurements from monitoring networks. The goal was to conduct comparisons of modeled and monitored estimates of HAP levels in the state of Texas using traditional approaches and a previously unexploited method, concordance correlation analysis, to better inform decisions regarding agreement. Census tract-level ASPEN estimates and monitoring data for all HAPs throughout Texas, available from the EPA Air Quality System, were obtained for 1990, 1996, and 1999. Monitoring sites were mapped to census tracts using U.S. Census data. Exclusions were applied to restrict the monitored data to measurements collected using a common sampling strategy with minimal missing values over time. Comparisons were made for 28 HAPs in 38 census tracts located primarily in urban areas throughout Texas. For each pollutant and by year of assessment, modeled and monitored air pollutant annual levels were compared using standard methods (i.e., ratios of model-to-monitor annual levels). Concordance correlation analysis was also used, which assesses linearity and agreement while providing a formal method of statistical inference. Forty-eight percent of the median model-to-monitor values fell between 0.5 and 2, whereas only 17% of concordance correlation coefficients were significant and greater than 0.5. On the basis of concordance correlation analysis, the findings indicate there is poorer agreement when compared with the previously applied ad hoc methods to assess comparability between modeled and monitored levels of ambient HAPs.     

National review of ambient air toxics observations

Ambient air observations of hazardous air pollutant (HAPs), also known as air toxics, derived from routine monitoring networks operated by states, local agencies, and tribes (SLTs), are analyzed to characterize national concentrations and risk across the nation for a representative subset of the 187 designated HAPs. Observations from the National Air Toxics Trend Sites (NATTS) network of 27 stations located in most major urban areas of the contiguous United States have provided a consistent record of HAPs that have been identified as posing the greatest risk since 2003 and have also captured similar concentration patterns of nearly 300 sites operated by SLTs. Relatively high concentration volatile organic compounds (VOCs) such as benzene, formaldehyde, and toluene exhibit the highest annual average concentration levels, typically ranging from 1 to 5 µg/m³. Halogenated (except for methylene chloride) and semivolatile organic compounds (SVOCs) and metals exhibit concentrations typically 2–3 orders of magnitude lower. Formaldehyde is the highest national risk driver based on estimated cancer risk and, nationally, has not exhibited significant changes in concentration, likely associated with the large pool of natural isoprene and formaldehyde emissions. Benzene, toluene, ethylbenzene, and 1,3-butadiene are ubiquitous VOC HAPs with large mobile source contributions that continue to exhibit declining concentrations over the last decade. Common chlorinated organic compounds such as ethylene dichloride and methylene chloride exhibit increasing concentrations. The variety of physical and chemical attributes and measurement technologies across 187 HAPs result in a broad range of method detection limits (MDLs) and cancer risk thresholds that challenge confidence in risk results for low concentration HAPs with MDLs near or greater than risk thresholds. From a national monitoring network perspective, the ability of the HAPs observational database to characterize the multiple pollutant and spatial scale patterns influencing exposure is severely limited and positioned to benefit by leveraging a variety of emerging measurement technologies.

Implications:?Ambient air toxics observation networks have limited ability to characterize the broad suite of hazardous air pollutants (HAPs) that affect exposures across multiple spatial scales. While our networks are best suited to capture major urban-scale signals of ubiquitous volatile organic compound HAPs, incorporation of sensing technologies that address regional and local-scale exposures should be pursued to address major gaps in spatial resolution. Caution should be exercised in interpreting HAPs observations based on data proximity to minimum detection limit and risk thresholds.     

Quality control for sampling of PCDD/PCDF emissions from open combustion sources

Both long duration (>6 h) and high temperature (up to 139 °C) sampling efforts were conducted using ambient air sampling methods to determine if either high volume throughput or higher than ambient air sampling temperatures resulted in loss of target polychlorinated dibenzodioxins/dibenzofurans (PCDDs/PCDFs) from a polyurethane foam (PUF) sorbent. Emissions from open burning of simulated military forward operating base waste were sampled using EPA Method TO-9A for 185 min duration using a filter/PUF/PUF in series combination. After a 54 m³ sample was collected, the sampler was removed from the combustion source and the second PUF was replaced with a fresh, clean PUF. An additional 6 h of ambient air sampling (171 m³) was conducted and the second PUF was analyzed to determine if the PCDD/PCDF transferred from the filter and the first PUF. Less than 4.4% of the initial PCDD/PCDF was lost to the second PUF. To assess the potential for blow off of PCDD/PCDF analytes during open air sampling, the mobility of spiked mono- to hepta-PCDD/PCDF standards across a PUF sorbent was evaluated from ambient air temperatures to 145 °C with total volumes between 600 L and 2400 L. Lower molecular weight compounds and higher flow amounts increased release of the spiked standards consistent with vapor pressure values. At 600 L total sampled volume, the release temperature for 1% of the tetra-CDD (the lowest chlorinated homologue with a toxic compound) was 87 °C; increasing the volume fourfold reduced this temperature to 73 °C.     

An analysis of candidates for addition to the Clean Air Act list of hazardous air pollutants

There are 188 air toxics listed as hazardous air pollutants (HAPs) in the Clean Air Act (CAA), based on their potential to adversely impact public health. This paper presents several analyses performed to screen potential candidates for addition to the HAPs list. We analyzed 1086 HAPs and potential HAPs, including chemicals regulated by the state of California or with emissions reported to the Toxics Release Inventory (TRI). HAPs and potential HAPs were ranked by their emissions to air, and by toxicity-weighted (tox-wtd) emissions for cancer and noncancer, using emissions information from the TRI and toxicity information from state and federal agencies. Separate consideration was given for persistent, bioaccumulative toxins (PBTs), reproductive or developmental toxins, and chemicals under evaluation for regulation as toxic air contaminants in California. Forty-four pollutants were identified as candidate HAPs based on three ranking analyses and whether they were a PBT or a reproductive or developmental toxin. Of these, nine qualified in two or three different rankings (ammonia [NH3], copper [Cu], Cu compounds, nitric acid [HNO3], N-methyl-2-pyrrolidone, sulfuric acid [H2SO4], vanadium [V] compounds, zinc [Zn], and Zn compounds). This analysis suggests further evaluation of several pollutants for possible addition to the CAA list of HAPs.     

Temporal variability of selected air toxics in the United States

Ambient measurements of hazardous air pollutants (HAPs, air toxics) collected in the United States from 1990 to 2005 were analyzed for diurnal, seasonal, and/or annual variability and trends. Visual and statistical analyses were used to identify and quantify temporal variations in air toxics at national and regional levels. Sufficient data were available to analyze diurnal variability for 14 air toxics, seasonal variability for 24 air toxics, and annual trends for 26 air toxics. Four diurnal variation patterns were identified and labeled invariant, nighttime peak, morning peak, and daytime peak. Three distinct seasonal patterns were identified and labeled invariant, cool, and warm. Multiple air toxics showed consistent decreasing trends over three trend periods, 1990–2005, 1995–2005, and 2000–2005. Trends appeared to be relatively consistent within chemically similar pollutant groups. Hydrocarbons such as benzene, 1,3-butadiene, styrene, xylene, and toluene decreased by approximately 5% or more per year at more than half of all monitoring sites. Concentrations of carbonyl compounds such as formaldehyde, acetaldehyde, and propionaldehyde were equally likely to have increased or decreased at monitoring sites. Chlorinated volatile organic compounds (VOCs) such as tetrachloroethylene, dichloromethane, and methyl chloroform decreased at more than half of all monitoring sites, but decreases among these species were much more variable than among the hydrocarbons. Lead particles decreased in concentration at most monitoring sites, but trends in other metals were not consistent over time.     

Background concentrations of 18 air toxics for North America

The U.S. Clean Air Act identifies 188 hazardous air pollutants (HAPs), or "air toxics," associated with adverse human health effects. Of these air toxics, 18 were targeted as the most important in a 10-City Pilot Study conducted in 2001 and 2002 as part of the National Air Toxics Trend Sites Program. In the present analysis, measurements available from monitoring networks in North America were used to estimate boundary layer background concentrations and trends of these 18 HAPs. The background concentrations reported in this study are as much as 85% lower than those reported in recent studies of HAP concentrations. Background concentrations of some volatile organic compounds were analyzed for trends at the 95% confidence level; only carbon tetrachloride (CCI4) and tetrachloroethylene decreased significantly in recent years. Remote background concentrations were compared with the one-in-a-million (i.e., 10(6)) cancer benchmarks to determine the possible causes of health risk in rural and remote areas; benzene, chloroform, formaldehyde, and chromium (Cr) fine particulate were higher than cancer benchmark values. In addition, remote background concentrations were found to contribute between 5% and 99% of median urban concentrations.     

Air concentrations of PCDD/Fs, PCBs and PCNs using active and passive air samplers

The concentrations of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) were determined in air samples collected at four sampling sites located in two zones of Barcelona (Spain): near a municipal solid waste incinerator (MSWI) and a combined cycle power plant (3 sites), and at a background/control site. Samples were collected using high-volume active samplers. Moreover, 4 PUF passive samplers were deployed at the same sampling points during three months. For PCDD/Fs, total WHO-TEQ values were 27.3 and 10.9 fg WHO-TEQm(-3) at the urban/industrial and the background sites, respectively. The sum of 7 PCB congeners and the Sigma PCN levels were also higher at the industrial site than at the background site. In order to compare active and passive sampling, the accumulated amounts of PCDD/Fs, PCBs and PCNs in the four passive air samplers, as well as the total toxic equivalents in each sampling site were also determined. To assess the use of PUF passive samplers as a complementary tool for PCDD/F, PCB and PCN monitoring, sampling rates were calculated in accordance with the theory of passive air samplers. PUF disks allowed establishing differences among zones for the POP levels, showing that they can be a suitable method to determine POP concentrations in air in areas with various potential emission sources. Although both particle and gas phase were sorbed by the PUFs, data of gas phase congeners are more reproducible.     

Sampling Frequency Guidance for Ambient Air Toxics Monitoring

Abstract

The U.S. Environmental Protection Agency (EPA) is in the process of designing a national network to monitor hazardous air pollutants (HAPs), also known as air toxics. The purposes of the expanded monitoring are to (1) characterize ambient concentrations in representative areas; (2) provide data to support and evaluate dispersion and receptor models; and (3) establish trends and evaluate the effectiveness of HAP emission reduction strategies. Existing air toxics data, in the form of an archive compiled by EPA’s Office of Air Quality Planning and Standards (OAQPS), are used in this paper to examine the relationship between estimated annual average (AA) HAP concentrations and their associated variability. The goal is to assess the accuracy, or bias and precision, with which the AA can be estimated as a function of ambient concentration levels and sampling frequency. The results suggest that, for several air toxics, a sampling schedule of 1 in 3 days (1:3) or 1:6 days may be appropriate for meeting some of the general objectives of the national network, with the more intense sampling rate being recommended for areas expected to exhibit relatively high ambient levels.     

Impact of three interactive Texas state regulatory programs to decrease ambient air toxic levels

The Federal Clean Air Act (FCAA) framework envisions a federal-state partnership whereby the development of regulations may be at the federal level or state level with federal oversight. The U.S. Environmental Protection Agency (EPA) establishes National Ambient Air Quality Standards to describe “safe” ambient levels of criteria pollutants. For air toxics, the EPA establishes control technology standards for the 187 listed hazardous air pollutants (HAPs) but does not establish ambient standards for HAPs or other air toxics. Thus, states must ensure that ambient concentrations are not at harmful levels. The Texas Clean Air Act authorizes the Texas Commission on Environmental Quality (TCEQ), the Texas state environmental agency, to control air pollution and protect public health and welfare. The TCEQ employs three interactive programs to ensure that concentrations of air toxics do not exceed levels of potential health concern (LOCs): air permitting, ambient air monitoring, and the Air Pollutant Watch List (APWL). Comprehensive air permit reviews involve the application of best available control technology for new and modified equipment and ensure that permits protect public health and welfare. Protectiveness may be demonstrated by a number of means, including a demonstration that the predicted ground-level concentrations for the permitted emissions, evaluated on a case-by-case and chemical-by-chemical basis, do not cause or contribute to a LOC. The TCEQ's ambient air monitoring program is extensive and provides data to help assess the potential for adverse effects from all operational equipment in an area. If air toxics are persistently monitored at a LOC, an APWL area is established. The purpose of the APWL is to reduce ambient air toxic concentrations below LOCs by focusing TCEQ resources and heightening awareness. This paper will discuss examples of decreases in air toxic levels in Houston and Corpus Christi, Texas, resulting from the interactive nature of these programs.

Implications: Texas recognized through the collection of ambient monitoring data that additional measures beyond federal regulations must be taken to ensure that public health is protected. Texas integrates comprehensive air permitting, extensive ambient air monitoring, and the Air Pollutant Watch List (APWL) to protect the public from hazardous air toxics. Texas issues air permits that are protective of public health and also assesses ambient air to verify that concentrations remain below levels of concern in heavily industrialized areas. Texas developed the APWL to improve air quality in those areas where monitoring indicates a potential concern. This paper illustrates how Texas engaged its three interactive programs to successfully address elevated air toxic levels in Houston and Corpus Christi.     

U. S. EPA Views as “Unwarranted” Federal Regulatory Involvement in Odor Control

ABSTRACT

Although there have been several studies examining emissions of criteria pollutants from in-use alternative fuel vehicles (AFVs), little is known about emissions of hazardous air pollutants (HAPs) from these vehicles. This paper explores HAP tailpipe emissions from a variety of AFVs operating in the federal government fleet and compares these emissions to emissions from identical vehicles operating on reformulated gasoline. Emissions estimates are presented for a variety of fuel/model combinations and on four HAPs (acetaldehyde, 1,3-butadi-ene, benzene, and formaldehyde). The results indicate that all AFVs tested offer reduced emissions of HAPs, with the following exceptions: ethanol fueled vehicles emit more acetaldehyde than RFG vehicles, and ethanol- and methanol-fueled vehicles emit more formaldehyde than RFG vehicles. The results from this paper can lead to more accurate emissions factors for HAPs, thus improving HAP inventory and associated risk estimates for both AFVs and conventional vehicles.     

Vapor-Phase and Fine Particulate Matter Concentrations of Polycyclic Aromatic Hydrocarbons Measured during the Winter Months in a Northern Rocky Mountain Urban Airshed

Abstract

A fine particulate matter (PM_2.5) sampling program was conducted in Missoula, MT, to investigate both the particle and vapor phases of PM_2.5-associated polycyclic aromatic hydrocarbons (PAHs) found in a northern Rocky Mountain urban airshed. Twenty-four-hour samples were collected during the cold winter months of January through April 2002, when many of the more volatile organic components of PM_2.5 were expected to be found in the condensed particle form. To meet analytical detection limits, each of the 12 individual sample days were aggregated into four total filter and polyurethane foam (PUF) samples, respectively, with each aggregate containing 3 sample days. Quartz filter (particle-phase PAHs) and PUF (vapor-phase PAHs) aggregates were analyzed separately for 18 individual PAHs and phenolics by gas chromatography/mass spectrometry. Results showed that 87% of the PM_2.5-associated phenolics and PAHs measured in this study were found in the vapor phase. PM_2.5-associated gas/particle partition coefficients (K_p,2.5) ranged from 0 for the lighter phenolics and PAHs to ~0.1 for some of the heavier PAHs, such as fluoranthene and pyrene. Calculating K_p,2.5 for the heaviest measured PAHs was not feasible because of low or undetectable concentrations in the vapor phases of these compounds. Phenolics and two-ringed and three-ringed PAHs were found almost exclusively in the vapor phase. Four-ringed PAHs were distributed between the particle and vapor phases, with more mass measured in the vapor phase. Very little five-ringed and higher PAHs were measured from either the filter or PUF sampling medium. These results provide information on both the concentrations and different phases of PM_2.5-associated PAHs measured during the winter months in a northern Rocky Mountain urban airshed, when concentrations of PM_2.5 are generally at their highest compared with the rest of the year.     

Measurements of selected PCBs in open urban ambient air of Madrid (Spain)

The focus of this study was to characterize the concentration levels of selected PCBs and compare them to compiled data in order to contribute to the international database. The sampling site is located in the outskirts of Madrid and can be considered an open urban area. 32 samples of air were taken from February 1998 to June 1998 by using a high volume air sampler. Glass fiber filters and polyurethane foam (PUF) were used to collect the paniculate and gas phase material, respectively. PUF plugs were Soxhlet extracted and filters were ultrasonically extracted by using pesticide-grade hexane and dichloromethane, respectively. The cleanup procedure was carried out on a florisil column with hexane and hexane/dichloromethane as elution solvents. GC/MS in a selected ion monitoring mode was used for quantification and 29 selected PCBs congeners were analyzed.     

Protecting Off-Site Populations and Site Workers from Vapor Discharges during Shallow Soil Mixing at the North Carolina State University National Priorities List Site

Abstract

Although vapor monitoring is generally a component of remedial action activities, most sites do not have routine gaseous releases or vapor clouds erupting from the soil during implementation of the cleanup process (or during cleanup of the site). At the North Carolina State University Lot 86 National Priorities List Site, over 8410 m³ (11,000 yd³) of chemical waste was disposed at the Site, including organic solvents and shock-sensitive and airand water-reactive compounds. During the Remedial Action, it was imperative to protect site workers and off-site populations from potential inhalation exposures. Engineering controls were incorporated into the shallow soil mixing process to limit the release of gaseous compounds. To quantify potential exposures to on-site and off-site receptors, modeling was conducted to evaluate potential exposure routes and migration pathways. To demonstrate acceptable levels of airborne constituents, a multifaceted air sampling and monitoring program was implemented. To ensure that potential exposures could be quantified, passive dosimeters, continuous real-time monitoring, time-weighted whole air sampling, and grab samples of vapor clouds were all critical components of the air monitoring program. After the successful completion of the Remedial Action, the pre-Resource Conservation and Recovery Act (RCRA) chemical waste generated from the University’s educational and research laboratories was entirely encapsulated and neither on-site workers nor off-site populations were exposed to analyzed compounds above any health-based action level (i.e., 15-min short-term exposure limit [STEL], 8-hr threshold limit value, or time-weighted average permissible exposure limit)     

Vapor-phase and fine particulate matter concentrations of polycyclic aromatic hydrocarbons measured during the winter months in a northern Rocky Mountain urban airshed

A fine particulate matter (PM2.5) sampling program was conducted in Missoula, MT, to investigate both the particle and vapor phases of PM2.5-associated polycyclic aromatic hydrocarbons (PAHs) found in a northern Rocky Mountain urban airshed. Twenty-four-hour samples were collected during the cold winter months of January through April 2002, when many of the more volatile organic components of PM2.5 were expected to be found in the condensed particle form. To meet analytical detection limits, each of the 12 individual sample days were aggregated into four total filter and polyurethane foam (PUF) samples, respectively, with each aggregate containing 3 sample days. Quartz filter (particle-phase PAHs) and PUF (vapor-phase PAHs) aggregates were analyzed separately for 18 individual PAHs and phenolics by gas chromatography/mass spectrometry. Results showed that 87% of the PM2.5-associated phenolics and PAHs measured in this study were found in the vapor phase. PM2.5-associated gas/particle partition coefficients (Kp,2.5) ranged from 0 for the lighter phenolics and PAHs to approximately 0.1 for some of the heavier PAHs, such as fluoranthene and pyrene. Calculating Kp,2.5 for the heaviest measured PAHs was not feasible because of low or undetectable concentrations in the vapor phases of these compounds. Phenolics and two-ringed and three-ringed PAHs were found almost exclusively in the vapor phase. Four-ringed PAHs were distributed between the particle and vapor phases, with more mass measured in the vapor phase. Very little five-ringed and higher PAHs were measured from either the filter or PUF sampling medium. These results provide information on both the concentrations and different phases of PM2.5-associated PAHs measured during the winter months in a northern Rocky Mountain urban airshed, when concentrations of PM2.5 are generally at their highest compared with the rest of the year.     

National estimates of outdoor air toxics concentrations

The Clean Air Act identifies 189 hazardous air pollutants (HAPs), or "air toxics," associated with a wide range of adverse human health effects. The U.S. Environmental Protection Agency has conducted a modeling study with the Assessment System for Population Exposure Nationwide (ASPEN) to gain a greater understanding of the spatial distribution of concentrations of these HAPs resulting from contributions of multiple emission sources. The study estimates year 1990 long-term outdoor concentrations of 148 air toxics for each census tract in the continental United States, utilizing a Gaussian air dispersion modeling approach. Ratios of median national modeled concentrations to estimated emissions indicate that emission totals without consideration of emission source type can be a misleading indicator of air quality. The results also indicate priorities for improvements in modeling methodology and emissions identification. Model performance evaluation suggests a tendency for underprediction of observed concentrations, which is likely due, at least in part, to a number of limitations of the Gaussian modeling formulation. Emissions estimates for HAPs have a high degree of uncertainty and contribute to discrepancies between modeled and monitored concentration estimates. The model's ranking of concentrations among monitoring sites is reasonably good for most of the gaseous HAPs evaluated, with ranking accuracy ranging from 66 to 100%.     

Polycyclic aromatic hydrocarbons in ambient air in the Philippines derived from passive sampler with polyurethane foam disk

Passive samplers with polyurethane disks (PUF) were applied in the determination of the concentration of polycyclic aromatic hydrocarbons (PAHs) in ambient air in six residential areas in the Philippines during four simultaneous sampling periods. The uptake profiles of PAHs were determined at one site during one sampling period. Most of the PAHs that were detected in air at concentrations that were significantly higher than their analytical detection limits exhibited a linear uptake trend on the PUF disk. The linear uptake profiles of some high molecular weight (HMW) PAHs were not established and this is attributed to the low concentration of the compounds in air in the gaseous phase. The retention concentrations of phenanthrene-d-10 were determined after depuration in four sampling sites during two sampling periods. The sampling rate for phenanthrene-d-10 was calculated at the linear phase of the uptake using the k_A derived from depuration experiments and the relationship of k_A and sampling rate which was established in a previous passive sampling study. The average sampling rate obtained for phenanthrene d-10 (2.94±0.69 m³ d⁻¹) was applied for derivation of the concentrations of the PAHs in the field samples.The passive sampler with PUF disk and short integration time of 42–56 days is applicable for the derivation of the concentrations of PAHs in ambient air in the Philippines. The concentrations of the organic pollutants derived from the passive sampler showed variability for the six residential areas; reflecting the influence of possible sources of emission of the pollutants at the sites at the different sampling periods. The weather conditions, including the occurrence of a tropical cyclone, increased rainfall and high-relative humidity during the rainy season, had an influence on the concentrations of PAHs derived by the passive sampler.     

Sampling frequency guidance for ambient air toxics monitoring

The U.S. Environmental Protection Agency (EPA) is in the process of designing a national network to monitor hazardous air pollutants (HAPs), also known as air toxics. The purposes of the expanded monitoring are to (1) characterize ambient concentrations in representative areas; (2) provide data to support and evaluate dispersion and receptor models; and (3) establish trends and evaluate the effectiveness of HAP emission reduction strategies. Existing air toxics data, in the form of an archive compiled by EPA's Office of Air Quality Planning and Standards (OAQPS), are used in this paper to examine the relationship between estimated annual average (AA) HAP concentrations and their associated variability. The goal is to assess the accuracy, or bias and precision, with which the AA can be estimated as a function of ambient concentration levels and sampling frequency. The results suggest that, for several air toxics, a sampling schedule of 1 in 3 days (1:3) or 1:6 days maybe appropriate for meeting some of the general objectives of the national network, with the more intense sampling rate being recommended for areas expected to exhibit relatively high ambient levels.     

空气中多环芳烃的研究现状

本文比较系统地讨论了空气中多环芳烃（ＰＡＨｓ）的研究现状。重点介绍了空气颗粒物及气相中多环芳烃的采样分析新办法，城市大气及居民室内外空气中多环芳烃的污染状况及其来源，简单介绍了人体接触多环芳烃的水平，指标及空气中多环芳烃的健康风险评价的研究概况。共引文献１２９篇。     

Comparative application of solid-phase microextraction fibre assemblies and semi-permeable membrane devices as passive air samplers for semi-volatile chlorinated organic compounds. A case study on the landfill "Grube Antonie" in Bitterfeld, Germany

Solid phase microextraction (SPME) fibres coated with Carbowax/divinylbenzene and semi-permeable membrane devices (SPMDs) of standard configuration were used to obtain time-weighted average (TWA) field air concentrations of selected chlorinated semi-volatile compounds on a landfill, where large amounts of lindane by-products were deposited, together with other hazardous chemical residues in the past. Additionally, spot sampling with SPME fibres was performed to identify the emission hotspot and sampling rates were determined/predicted for the substances of interest. Both samplers yield comparable TWA air concentrations of lindane and its isomers and of DDT with its metabolites and gain in certainty about the landfill as remaining source of air pollution with these compounds in the region. Both SPME fibres and SPMDs (respective their modifications) can be recommended as sampling tools in process studies and larger air monitoring programmes. However, further calibration studies and field tests are necessary to obtain reliable sampling rates for a wider range of semi-volatile compounds.     

New passive samplers for chlorinated semivolatile organic pollutants in ambient air

Two new types of passive samplers were designed and tested on semivolatile organic compounds. The first type (a spiral-rod sampler) consists of a low-density polyethylene membrane acting as a permeation film and a silicone elastomer as the receiving material; the second (a stir-bar sampler) has the same membrane material but a polydimethylsiloxane-coated stir bar acting as the collector phase and installed radially symmetrically in the sampler. The advantages of the new samplers are their simple design, low costs, and their easy processing via thermodesorption coupled with capillary gas chromatography and mass selective detection. In both samplers, the uptake of selected analytes was integrative over exposure periods of up to 384 h. The sampling rates calculated from a laboratory calibration study using the chlorinated semivolatiles hexachlorobenzene, hexachlorocyclohexane isomers and polychlorinated biphenyls ranged from 88.1 ml h-1 for delta-hexachlorocyclohexane to 3443 ml h-1 for 2,2',5,5'-tetrachlorobiphenyl. A field trial at a hazardous waste dump near Bitterfeld, Germany, for up to 21 days combined with periodical determinations of air concentrations using low-volume sampling indicated that the new samplers can in principle be used in the field, although the sampling rates derived from the field results differed considerably from the laboratory findings. Nevertheless the preliminary results suggest that the new sampler types are promising for the long-term air monitoring of semivolatiles.