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Tom Harner

Publications and source records attributed to Tom Harner.

At least 19 recordsLinked to original sources

Polychlorinated naphthalenes in Great lakes air: assessing spatial trends and combustion inputs using PUF disk passive air samplers.

Passive air samplers made from polyurethane foam (PUF) disks housed in stainless steel chambers were deployed over four seasons during 2002-2003, at 15 sites in the Laurentian Great lakes, to assess spatial and temporal trends of polychlorinated naphthalenes (PCNs). Sampling rates, determined using depuration compounds pre-spiked into the PUF disk prior to exposure, were, on average, 2.9 +/- 1.1 m3 d(-1), consistent with previous studies employing these samplers. PCN air concentrations exhibited strong urban-rural differences-typically a few pg m(-3) at rural sites and an order of magnitude higher at urban sites (Toronto, 12-31 pg m(-3) and Chicago,13-52 pg m(-3)). The high concentrations at urban sites were attributed to continued emissions of historically used technical PCN. Contributions from combustion-derived PCNs seemed to be more important at rural locations where congeners 24 and 50, associated with wood and coal burning, were elevated. Congener 66/67, associated with incineration and other industrial thermal processes, was elevated at two sites and explained by nearby and/or upwind sources. Probability density maps were constructed for each site and for every integration period were shown to be a useful complement to seasonally integrated passive sampling data to resolve source-receptor relationship for PCNs and other pollutants.

Air Pollutants↗

Toward a global network for persistent organic pollutants in air: results from the GAPS study.

The Global Atmospheric Passive Sampling (GAPS) study aims to demonstrate the feasibility of using passive samplers to assess the spatial distribution of persistent organic pollutants on a worldwide basis. The GAPS network includes more than 40 sites on 7 continents, mainly in background locations, with some representation of urban and agricultural areas. Here we present concentrations of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in polyurethane foam disk samplers, deployed from December 2004 to March 2005. Legacy OCPs such as alpha-HCH (hexachlorocyclohexane), Chlordanes (trans- and cis-Chlordane and trans-Nonachlor), Dieldrin, and dichlorodiphenyltrichloroethane isomers were detected at most sites with some high values that may be related to possible continued use and/or re-emissions related to historic use. Geometric mean (GM) air concentrations (pg/m3) were: 8.5 for sigmaHCH (sum of alpha- and gamma-isomers), 2.6 for sigmaChlordanes, 0.8 for Dieldrin, and 0.8 for p,p'-DDE. Current-use pesticides such as gamma-HCH (lindane) and especially Endosulfan I exhibited more variable and higher concentrations with GMs of 5 and 58, respectively. PCBs and PBDEs were elevated at urban/suburban sites consistent with their historical use pattern. GM concentrations (pg/m3) were 17 for PCBs and 4 for PBDEs. Sampling under GAPS will continue and will eventually allow seasonality effects and longer-term temporal and spatial trends to be evaluated.

Air Movements↗

Regressing gas/particle partitioning data for polycyclic aromatic hydrocarbons.

Polycyclic aromatic hydrocarbons (PAHs) were measured in the rural atmosphere of Southern Ontario, Canada from October 2001 to November 2002. Sixty seven pairs of gaseous and particle-bound concentrations of PAHs were determined concurrently in a forest and a clearing. The gas/particle partitioning behavior of the PAHs was investigated by fitting the original Junge-Pankow equation to the fraction in the particle phase phi for each set of measured data, either allowing the slope m to deviate from -1 (two-parameter model) or not (one-parameter model). This fitting procedure was judged more robust than linear logarithmic regressions involving the gas/particle partition coefficient, because the latter is sensitive to the applied blank correction, tends to ignore a significant amount of analytical information, and gives undue weight to more uncertain data points. The experimental data fit was good for both nonlinear models, and discrepancies between experimental data and models and between models are mostly related to sampling/experimental artifacts. In particular, samples taken close to the freezing point appear to suffer from blow-off artifacts. Applying slopes m different from -1 appears only justified if it can be assured that a second parameter indeed provides a better fit and that this better fit is not due to experimental, analytical, or statistical artifacts. The magnitude of the differences in the model fitting parameters between sampling events is consistent with the reported variability in the nature and concentration of atmospheric particles. Statistical tests on the regression results indicate that the gas/particle partitioning was not significantly different between the forest and the clearing.

Air Pollutants↗

The partition behavior of fluorotelomer alcohols and olefins.

In this paper we present a number of equilibrium partition constants for fluorotelomer alcohols and olefins among them data for air/water and octanol/air partitioning. These data are typically required for environmental fate modeling. Our data deviate substantially from those in the literature. A comprehensive check for consistency and plausibility strongly suggests that the data published here are correct. As a consequence the fluorotelomer alcohols will sorb much more to organic phases and have a smaller tendency to remain in the water phase than expected based on previous data. The presented partition data also allow us to derive descriptors for the various kinds of specific (e.g., H-bonds) and nonspecific (e.g., van der Waals) intermolecular interactions thatthe compounds can undergo. These descriptors can be used in polyparameter linear free energy relationships (pp-LFER) in orderto predict a large variety of other partition coefficients (e.g., air/solvent, solvent/ water) as well as the temperature dependence of their air/ water partitioning. The experimental and theoretical approach that we present here can serve as a general example for what needs to be done in order to ensure high quality physicochemical data for organic pollutants.

Air↗

Continental scale passive air sampling of persistent organic pollutants using rapidly equilibrating thin films (POGs).

A novel design of rapidly equilibrating passive air sampler was deployed at 38 sites across 19 European countries to investigate short-term spatial variability of persistent organic pollutants (POPs). Devices were sealed in airtight containers to eliminate the possibility of contamination during transit and couriered to recipients with deployment instructions. Exposure times of 7days permitted the use of back trajectory analysis to further understand the factors responsible for influencing the large-scale spatial distribution of PCBs, PBDEs, PCNs, PAHs, lindane and HCB. Following sampler harvest, devices were sealed and returned for analysis. Comparison of sequestered levels showed that PAHs exhibited the greatest spatial variability (by a factor of 30) with higher levels often associated with greater population density. In contrast, HCB values were much more uniform, reflecting its well mixed distribution in the atmosphere. Spatial variation was strongly influenced by air mass origin, with lower levels being observed at most sites impacted by maritime air masses.

Air Movements↗

Global pilot study for persistent organic pollutants (POPs) using PUF disk passive air samplers.

Polyurethane foam (PUF) disks were deployed at global background sites, to test logistical issues associated with a global monitoring network for persistent organic pollutants (POPs). alpha-HCH, exhibited relatively high and uniform concentrations (17-150 pg/m3) at temperate and arctic sites with elevated concentrations associated with trans-Pacific inflow. Concentrations were much lower (<5 pg/m3) in Bermuda, Chile and Cape Grim. Concentrations for gamma-HCH, the main component of lindane, were spatially similar to the alpha-HCH pattern but lower in magnitude (typically, <10 pg/m3). Chlordane concentrations (sum of cis-chlordane, trans-chlordane and trans-nonachlor) were also low (<10 pg/m3). Dieldrin concentrations were in the range 2-25 pg/m3 at most sites but elevated in Bermuda. Back trajectories suggest that advection from Africa and the US may contribute. Endosulfan, a popular current-use pesticide, exhibited highest concentrations ranging from tens to hundreds of pg/m3. There was good agreement between duplicate samplers at each site and PUF disk-derived air concentrations agreed with high volume data. Few logistical/analytical problems were encountered in this pilot study.

Air Movements↗

Passive air sampling for persistent organic pollutants: introductory remarks to the special issue.

There have been a number of developments in the need, design and use of passive air samplers (PAS) for persistent organic pollutants (POPs). This article is the first in a Special Issue of the journal to review these developments and some of the data arising from them. We explain the need and benefit of developing PAS for POPs, the different approaches that can be used, and highlight future developments and needs.

Aerosols↗

Polyurethane foam (PUF) disks passive air samplers: wind effect on sampling rates.

Different passive sampler housings were evaluated for their wind dampening ability and how this might translate to variability in sampler uptake rates. Polyurethane foam (PUF) disk samplers were used as the sampling medium and were exposed to a PCB-contaminated atmosphere in a wind tunnel. The effect of outside wind speed on PUF disk sampling rates was evaluated by exposing polyurethane foam (PUF) disks to a PCB-contaminated air stream in a wind tunnel over air velocities in the range 0 to 1.75 m s-1. PUF disk sampling rates increased gradually over the range 0-0.9 m s-1 at approximately 4.5-14.6 m3 d-1 and then increased sharply to approximately 42 m3 d-1 at approximately 1.75 m s-1 (sum of PCBs). The results indicate that for most field deployments the conventional 'flying saucer' housing adequately dampens the wind effect and will yield approximately time-weighted air concentrations.

Air Pollutants↗

Passive sampler derived air concentrations of PBDEs along an urban-rural transect: spatial and temporal trends.

Passive air samplers consisting of polyurethane foam (PUF) disks housed in chambers were deployed at several sites along a approximately 75 km urban-rural gradient in Toronto and analyzed for polybrominated diphenyl ethers (PBDEs). Samplers were allowed to integrate gas-phase PBDEs over three consecutive seasons starting in the summer of 2000. PBDEs were fairly uniform along the transect with air concentrations in Toronto (10-30 pgm(-3)) about a factor of two greater than at rural sites. Lowest concentrations were observed during the winter and probably associated with reduced inputs from indoor sources of PBDEs and to a preference for PBDEs to partition to the particle-phase at colder temperatures. The composition of PBDEs in the air samples did not differ across the transect or for the different seasons.

Air↗

Determination of polybrominated diphenyl ethers in indoor dust standard reference materials.

Polybrominated diphenyl ethers (PBDEs) have been measured for the first time in three different indoor dust Standard Reference Materials (SRMs) prepared by the National Institute of Standards and Technology (NIST). Two of these, SRM 2583 (Trace Elements in Indoor Dust) and SRM 2584 (Trace Elements in Indoor Dust), have been certified previously for lead and other inorganic constituents. A third, SRM 2585 (Organics in Indoor Dust), is a new indoor dust reference material prepared by NIST which will be certified for various organic compounds (polycyclic aromatic hydrocarbons, pesticides and polychlorinated biphenyls) in 2005 including certified concentrations for 16 individual PBDE congeners and reference values for an additional three PBDE congeners. Dust SRMs were analyzed for 30 PBDE congeners using high-resolution gas chromatography combined with low-resolution mass spectrometry operated in both negative chemical ionization (GC/ECNI-MS) and electron impact ionization (GC/EI-MS) modes. Sensitivity was an order of magnitude higher using GC/ECNI-MS relative to GC/EI-MS. These SRMs have been characterized and compared to the three PBDE commercial products (pentaBDE, octaBDE and decaBDE). PentaBDE and DecaBDE were present in all three SRMs and were the dominant commercial products, making up approximately 33% and 58%, respectively. Recent studies suggest that house dust may be a leading source of human exposure to PBDEs. These SRMs are the first reference materials with certified concentrations for PBDEs, which will aid in validating future measurements of PBDEs in house dust and other similar matrices.

Chromatography, High Pressure Liquid↗

Polybrominated diphenyl ethers in indoor dust in Ottawa, Canada: implications for sources and exposure.

Polybrominated diphenyl ethers (PBDEs) are widely used as additive flame retardants in plastics, soft furnishings, electrical and electronic equipment, and insulation in the indoor environment, and may be released indoors via volatilization or as dusts. The penta-and octa-brominated mixes are now banned in most parts of Europe, and phasing out of their use has recently begun in North America. This study follows a previous investigation into indoor air levels of PBDEs. House dust was analyzed from the family vacuum cleaners of 68 of the same 74 randomly selected homes, in Ottawa, Canada during the winter of 2002-2003. PBDEs, comprising on average 42% BDE-209, were found in all samples. The levels were log-normally distributed with a geometric mean sigmaPBDE of 2000 ng g(-1), and a median of 1800 ng g(-1) dust. The levels in dust did not correlate with questionnaire information on house characteristics. Correlations were found between pentamix congener levels in dust and in air from the same homes, but not for congeners of the more highly brominated mixes. Exposure scenarios are presented for mean and high dust ingestion rates, and compared against exposures from other pathways, for both adults and toddlers (6 months-2 years). Assuming a mean dust ingestion rate and median dust and air concentrations, adults would be exposed to ca. 7.5 ng sigmaPBDE d(-1) via the dust ingestion pathway, which represents approximately 14% of total daily exposure when compared to diet (82%) and inhalation (4%). However, for toddlers the equivalent intakes would be 99 ng d(-1), representing 80% of their daily PBDE exposure. At high dust ingestion rates these values increase to 180 ng d(-1) (80% daily intake) for adults and 360 ng d(-1) (89% daily intake) for toddlers. The data give a clearer picture of sources of PBDE exposure in the home environment and suggest that dust could be a significant exposure pathway for some individuals, particularly children.

Adult↗

Perfluorinated sulfonamides in indoor and outdoor air and indoor dust: occurrence, partitioning, and human exposure.

Perfluorinated alkyl sulfonamides (PFASs) which are used in a variety of consumer products for surface protection were investigated through a comprehensive survey of indoor air, house dust, and outdoor air in the city of Ottawa, Canada. This study revealed new information regarding the occurrence and indoor air source strength of several PFASs including N-methylperfluorooctane sulfonamidoethanol (MeFOSE), N-ethylperfluorooctane sulfonamidoethanol (EtFOSE), N-ethylperfluorooctane sulfonamide (EtFOSA), and N-methylperfluorooctane sulfonamidethylacrylate (MeFOSEA). Passive air samplers consisting of polyurethane foam disks were calibrated and used to conduct the indoor and outdoor survey. Indoor air concentrations for MeFOSE and EtFOSE (1490 and 740 pg m(-3), respectively) were about 10-20 times greater than outdoor concentrations, establishing indoor air as an important source to the outside environment. EtFOSA and MeFOSEA concentrations were lower in indoor air (40 and 29 pg m(-3) respectively) and below detection in outdoor air samples. For indoor dust, highest concentrations were recorded for MeFOSE and EtFOSE with geometric mean concentrations of 110 and 120 ng g(-1), while concentrations for EtFOSA and MeFOSEA were below detection and 7.9 ng g(-1) respectively. MeFOSE and EtFOSE concentrations in house dust followed levels in indoor air. However, resolution of the coupled air and dust data (for the same homes) was not successful using existing KoA-based models for surface-air exchange. The partitioning to house dust was greatly underpredicted. The difficulties with existing models may be due to the high activity coefficient of PFASs in octanol and/or a situation where the dust is greatly oversaturated with respect to the air due to components of the dust being contaminated with PFASs. A human exposure assessment based on median air and dust concentrations revealed that human exposure through inhalation (100% absorption assumed) and dust ingestion were approximately 40 and approximately 20 ng d(-1), respectively. However, for children the dust ingestion pathway was dominant and accounted for approximately 44 ng d(-1).

Air Pollutants↗

Using passive air samplers to assess urban-rural trends for persistent organic pollutants and polycyclic aromatic hydrocarbons. 2. Seasonal trends for PAHs, PCBs, and organochlorine pesticides.

This is the second of two papers demonstrating the feasibility of using passive air samplers to investigate persistent organic pollutants along an urban-rural transect in Toronto. The first paper investigated spatial trends for polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). This second paper investigates the seasonality of air concentrations for polycyclic aromatic hydrocarbons (PAHs), PCBs, and OCPs along this transect. Air samplers, consisting of polyurethane foam (PUF) disks housed in stainless steel domed chambers, were deployed for three 4-month integration periods from June 2000 to July 2001. The seasonal variations of derived air concentrations for PAHs, PCBs, and OCPs reflected the different source characteristics for these compounds. PAHs showed a strong urban-rural gradient with maximum concentrations at urban sites during the summer period (July-October). These high summer values in Toronto were attributed to increases in evaporative emissions from petroleum products such as asphalt. PCBs also exhibited a strong urban-rural gradient with maximum air concentrations (approximately 2-3 times higher) during the spring period (April-June). This was attributed to increased surface-air exchange of PCBs that had accumulated in the surface layer over the winter. alpha-HCH was fairly uniformly distributed, spatially and temporally, as expected. This pattern and the derived air concentration of approximately 35 to approximately 100 pg m(-3) agreed well with high volume air data from this region, adding confidence to the operation of the passive samplers and showing that site-to-site differences in sampling rates was not an issue. For other OCPs, highest concentrations were observed during the spring period. This was associated with either (i) their local and/or regional application (gamma-HCH, endosulfan) and (ii) their revolatilization (chlordanes, DDT isomers, dieldrin, and toxaphene). Principal component analysis resulted in clusters for the different target chemicals according to their chemical class/source type. The results of this study demonstrate how such a simple sampling technique can provide both spatial and seasonal information. These data, integrated over seasons, can be used to evaluate contaminant trends and the potential role of large urban centers as sources of some semivolatile compounds to the regional environment, including the Great Lakes ecosystem.

Air↗

Is house dust the missing exposure pathway for PBDEs? An analysis of the urban fate and human exposure to PBDEs.

Polybrominated diphenyl ether (PBDE) body burdens in North America are 20 times that of Europeans and some "high accumulation" individuals have burdens up to 1-2 orders of magnitude higher than median values, the reasons for which are not known. We estimated emissions and fate of sigma PBDEs (minus BDE-209) in a 470 km2 area of Toronto, Canada, using the Multi-media Urban Model (MUM-Fate). Using a combination of measured and modeled concentrations for indoor and outdoor air, soil, and dust plus measured concentrations in food, we estimated exposure to sigma PBDEs via soil, dust, and dietary ingestion and indoor and outdoor inhalation pathways. Fate calculations indicate that 57-85% of PBDE emissions to the outdoor environment originate from within Toronto and that the dominant removal process is advection by air to downwind locations. Inadvertent ingestion of house dust is the largest contributor to exposure of toddlers through to adults and is thus the main exposure pathway for all life stages other than the infant, including the nursing mother, who transfers PBDEs to her infant via human milk. The next major exposure pathway is dietary ingestion of animal and dairy products. Infant consumption of human milk is the largest contributor to lifetime exposure. Inadvertent ingestion of dust is the main exposure pathway for a scenario of occupational exposure in a computer recycling facility and a fish eater. Ingestion of dust can lead to almost 100-fold higher exposure than "average" for a toddler with a high dust intake rate living in a home in which PBDE concentrations are elevated.

Adolescent↗

Hexachlorocyclohexanes and endosulfans in urban, rural, and high altitude air samples in the Fraser Valley, British Columbia: evidence for trans-Pacific transport.

High-volume air samples collected over the period Aug. 14-30, 2001, in the Lower Fraser Valley, BC, Canada, were used to assess urban/rural differences of organochlorine pesticides (OCPs) for ground level samples and to attempt to directly measure events of trans-Pacific inputs through the mid-troposphere. Hexachlorocyclohexanes (alpha- and gamma-isomers; 2-25 pg m(-3)) and endosulfan1 and -2 (5-150 pg m(-3)) were detected in all ground level samples. Seven air samples were collected during mid-troposphere flights (approximately 4400 m altitude) over the Lower Fraser Valley. These flights occurred concurrently with ground level sampling. Trajectory analysis identified three events of substantial mid-troposphere, trans-Pacific flow where 10-day back trajectories stemmed from potential source regions in Asia. These events were also characterized by higher air concentrations of alpha-HCH at 4400 m as compared to the ground level stations. This represents the first event-based, aircraft measurement of advection inputs of OCPs in the mid-troposphere of the west coast of North America.

Air Movements↗

Passive-sampler derived air concentrations of persistent organic pollutants on a north-south transect in Chile.

Passive air samplers consisting of polyurethane foam (PUF) disks, were deployed in six locations in Chile along a north-south transect to investigate gas-phase concentrations of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and polybrominated diphenyl ethers (PBDEs). The study provides new information on air concentrations of these persistent organic pollutants (POPs) which is lacking in this region. It also provides insight into potential sources and long-range transport (LRT). The samplers were deployed for a 2-month period in five remote sites and one site in the city of Concepción. Mean concentrations (pg m(-3)) for sigmaPCB were 4.7 +/- 2.7 at remote sites and 53 +/- 13 in Concepción. PCB levels at remote sites were related to proximity to urban source regions and/or air back trajectories. With the exception of endosulfan I, mean concentrations (pg m(-3)) of OCPs at background sites were consistently low: 5.4 +/- 1.4 for alpha-HCH, 7.0 +/- 1.1 for gamma-HCH, 2.5 +/- 0.5 for TC, 2.5 +/- 0.6 for CC, 1.9 +/- 1.2 for dieldrin, and less than 3.5 for toxaphene. Endosulfan I showed a decreasing concentration gradient from 99 to 3.5 pg m(-3) from the north to south of Chile. Concentrations of OCPs in the Concepción City were generally 10-20 times higher than at the background sites suggesting continued usage and/or re-emission from past use. For instance, at remote sites, the alpha/gamma ratio (0.76) was typical of background air, while the ratio in Concepción (0.12) was consistent with fresh use of gamma-HCH. Levels of sigmaPBDEs were below the detection limit of 6 pg m(-3) at all sites.

Air Movements↗

Passive sampling survey of polybrominated diphenyl ether flame retardants in indoor and outdoor air in Ottawa, Canada: implications for sources and exposure.

The polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants in plastics of soft furnishings, TV sets and computers, and insulation in the indoor environment. The penta-BDEs--now banned in most parts of Europe but still used in North America--are additive flame retardants that may be released to the indoor environment via volatilization or as dusts. In this study, to investigate general population PBDE exposure, air was sampled in 74 randomly selected homes in Ottawa, Canada and at seven outdoor sites during the winter of 2002--3, using polyurethane foam (PUF) disk passive air samplers. The passive sampling rate (2.5 m3 day(-1)) was determined through a pilot study employing active and passive samplers side-by-side at selected indoor locations. Indoor air concentrations of PBDEs were log-normally distributed with a geometric mean of 120 pg m(-3) and a median of 100 pg m(-3), approximately 50 times higher than the range of outdoor air concentrations (<0.1-4.4 pg m(-3)). The maximum daily human exposure via the inhalation pathway based on median PBDE levels found in this survey was estimated to be 1.9 ng day(-1) (female) and 2.0 ng day(-1) (male), representing 4.1% (f) and 4.4% (m) of overall daily intake.

Air Pollutants↗

Using passive air samplers to assess urban-rural trends for persistent organic pollutants. 1. Polychlorinated biphenyls and organochlorine pesticides.

Passive air samplers were used to investigate urban-rural differences of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) over an integrated time period. Samplers consisting of polyurethane foam (PUF) disks and semi-permeable membrane devices (SPMDs) were housed in protective chambers and deployed at six sites for a 4 month duration in the summer of 2000. The sampling transect originated in downtown Toronto and extended approximately 75 km northward into a rural region. Results for the two types of samplers agreed well with one another. Higher blank levels were encountered for the SPMDs, especially for the OCPs, whereas blanks were very low for the PUF disks. Passive sampler-derived air concentrations were consistent with previous measurements of PCBs and OCPs in the region. The largest urban-rural gradient was observed for PCBs (approximately 5-10 times). Chlordanes also showed an urban-rural gradient, possibly reflecting past usage of chlordane on residential lawns and emissions from treated house foundations. Other OCPs exhibited a rural-urban gradient (dieldrin, endosulfan 1, and DDT isomers), which was attributed either to off-gassing from previously treated agricultural soils (dieldrin and DDTs) or to continued usage in agriculture (endosulfan 1). The results of this study demonstrated the feasibility of using such devices to determine air concentrations of persistent organic pollutants (POPs) and to assess their spatial distribution for time-integrated samples. Data such as this is essential for: model validation and for process research and addressing international monitoring strategies on POPs.

Air Pollutants↗