Analytical challenges hamper perfluoroalkyl research.
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Chemistry Techniques, Analytical↗
Biomedical subjects
Tom Harner
Publications and source records attributed to Tom Harner.
Indoor and outdoor air concentrations and phase partitioning of perfluoroalkyl sulfonamides and polybrominated diphenyl ethers.
Perfluoroalkyls (PFAs) and polybrominated diphenyl ethers (PBDEs) are two classes of emerging persistent organic pollutants (POPs) that are widely used in domestic and workplace products. These compounds also occur in remote locations such as the Arctic where they are accumulated in the food chain. This study makes connections between indoor sources of these chemicals and the potential and mode for their transport in air. In the case of the PFAs, three perfluoralkyl sulfonamides (PFASs) were investigated--N-methyl perfluorooctane sulfonamidoethanol (MeFOSE), N-ethyl perfluorooctane sulfonamidoethanol (EtFOSE), and N-methyl perfluorooctane sulfonamidethylacrylate (MeFOSEA). These are believed to act as precursors that eventually degrade to perfluorooctane sulfonate (PFOS), which is detected in samples from remote regions. High-volume samples were collected for indoor and outdoor air to investigate the source signature and strength. Mean indoor air concentrations (pg/m3) were 2590 (MeFOSE), 770 (EtFOSE), and 630 (sigmaPBDE). The ratios of concentration between indoor and outdoor air were 110 for MeFOSE, 85 for EtFOSE, and 15 for sigmaPBDE. The gas and particle phases were collected separately to investigate the partitioning characteristics of these chemicals. Measured particulate percentages were compared to predicted values determined using models based on the octanol-air partition coefficient (K(OA)) and supercooled liquid vapor pressure (pL(o)); these models were previously developed for nonpolar, hydrophobic chemicals. To make this comparison for the three PFASs, it was necessary to measure their K(OA) and vapor pressure. K(OA) values were measured as a function of temperature (0 to +20 degrees C). Values of log K(OA) at 20 degrees C were 7.70, 7.78, and 7.87 for MeFOSE, EtFOSE, and MeFOSEA, respectively. Partitioning to octanol increased at colder temperatures, and the enthalpies associated with octanol-air transfer (deltaH(OA), kJ/mol) were 68-73 and consistent with previous measurements for nonpolar hydrophobic chemicals. Solid-phase vapor pressures (pS(o)) were measured at room temperature (23 degrees C) by the gas saturation method. Values of pS(o) (Pa) were 4.0 x 10(-4), 1.7 x 10(-3), and 4.1 x 10(-4), respectively. These were converted to pL(o) for describing particle-gas exchange. Both the pL(o)-based model and the K(OA) model worked well for the PBDEs but were not valid for the PFASs, greatly underpredicting particulate percentages. These results suggest that existing K(OA)- and pL(o)-based models of partitioning will need to be recalibrated for PFASs.
Air Pollutants↗
Impacts of lindane usage in the Canadian Prairies on the Great Lakes ecosystem. 2. Modeled fluxes and loadings to the Great Lakes.
Atmospheric loadings of gamma-hexachlorocyclohexane (gamma-HCH) from May 1, 1998, to April 30, 1999, to the Great Lakes simulated by a coupled soil-air and water-air atmospheric transport model are presented. Modeling results on an annual basis indicate that Lake Superior received the highest dry deposition load of 2.17 kg yr(-1). Dry deposition to the lower Great Lakes (Lakes Erie and Ontario) was 2-6 times lower as compared to the upper Great Lakes. Greater deposition in the upper Great Lakes is due mainly to their larger surface area and greater proximity to sources of gamma-HCH. Dry deposition fluxes (pg m(-2)) to lake surfaces were much lower than to land as a result of lower deposition velocities and lower air concentrations of gamma-HCH over the lakes. The highest gamma-HCH loading (kg yr(-1), in 1998-99) due to wet deposition occurred for Lake Ontario. This was mainly attributed to greater annual rainfall over Lake Ontario. An investigation of average seasonal fluxes predicted by the model shows that deposition fluxes to the Great Lakes are considerably higher in the summer than that in the autumn and winter seasons. The net direction of gas exchange also exhibits a seasonal dependence. Lakes Michigan, Huron, and Ontario show net absorption in the summer 1998 whereas at all other times net outgassing occurred at all of the lakes. Overall, gas exchange was the dominant process affecting loadings to the Great Lakes. Model-derived loadings and total deposition flows across the Great Lakes basin due to dry and wet depositions and net gas exchange agree reasonably well with the summer estimates compiled by the Integrated Atmospheric Deposition Network whereas autumn values show greater discrepancies. Better agreement was also observed for dry deposition as compared to wet deposition. Specifically, to improve short-term loading estimates (e.g., over days to months), the model results indicate the need for better spatially and temporally resolved information on concentrations in air and surface water and better estimates of precipitation and deposition velocities over the lakes.
Agriculture↗
Passive air sampling of PCBs, PBDEs, and organochlorine pesticides across Europe.
This study presents concurrently sampled ambient air data for a range of persistent organic pollutants at the continental scale. This was achieved using a passive air sampling system, deploying polyurethane foam disks, which was prepared in one laboratory, sealed to prevent contamination, sent out by courier to volunteers participating in different countries, exposed for 6 weeks, collected, resealed, and returned to the laboratory for analysis. Europe was the study area--a region with a history of extensive POPs usage and emission and with marked national differences in population density, the degree of urbanization and industrial/agricultural development. Samplers were deployed at remote/rural/urban locations in 22 countries and analyzed for PCBs, a range of organochlorine pesticides (HCB, alpha-HCH, gamma-HCH, ppDDT, ppDDE), and PBDEs. Calculated air concentrations were in line with those obtained by conventional active air sampling techniques. The geographical pattern of all compounds reflected suspected regional emission patterns and highlighted localized hotspots. PCB and PBDE levels varied by over 2 orders of magnitude; the highest values were detected in areas of high usage and were linked to urbanized areas. HCB was relatively uniformly distributed, reflecting its persistence and high degree of mixing in air. Higher gamma-HCH, ppDDT, and ppDDE levels generally occurred in South and East Europe.
Agriculture↗
Using experimental and forest soils to investigate the uptake of polycyclic aromatic hydrocarbons (PAHs) along an urban-rural gradient.
Spatial and temporal variation in the atmospheric deposition of PAHs to soil was examined by deploying experimental soils for approximately 165 days and conducting a survey of forest soils at several sites along an urban-rural transect extending from downtown Toronto to approximately 80 km north of the city. PAH concentrations decreased with distance from the urban centre-by a factor of 2 and 60 for the experimental and forest soils respectively. The large gradient for the forest soils is generally consistent with air concentrations of PAHs measured using high volume and passive air samplers. The smaller gradient for the experimental soils was due to kinetic limitations of PAH accumulation and the relatively short deployment period of approximately 165 days. Mean effective deposition velocities (gas+particle) for the full range of PAHs for the experimental soils at the urban, suburban, and the rural sites were 2, 31 and 26 cm s(-1), respectively. These were incorporated into a dynamic model that was used to assess the long-term uptake of PAHs in forest soils. Model results indicate that lower molecular weight PAHs may achieve equilibrium and become involved in soil-air exchange whereas higher molecular weight PAHs are accumulated for much longer time periods.
Air Pollutants↗
Universal predictive models on octanol-air partition coefficients at different temperatures for persistent organic pollutants.
Owing to the importance of octanol-air partition coefficients (KOA) in describing the partition of organic pollutants from air to environmental organic phases, the paucity of KOA data at different environmental temperatures, and the difficulty or high expenditures involved in experimental determination, the development of predictive models for KOA is necessary. Approaches such as this are greatly needed to evaluate the environmental fate of the ever-increasing list of production chemicals. Partial least squares (PLS) regression with 18 molecular structural descriptors was used to develop predictive models based on directly measured KOA values of selected chlorobenzenes, polychlorinated biphenyls (PCBs), polychlorinated naphthalenes, polychlorinated dibenzo-p-dioxins/dibenzofurans, polybrominated diphenyl ethers, polycyclic aromatic hydrocarbons, and organochlorine pesticides (OPs). An optimization procedure resulted in two temperature-dependent universal predictive models that explained at least 91 % of the variance of log KOA. Model 1 was the more general of the two models that could be used for all the persistent organic pollutant (POP) classes investigated. Although model 1 performed poorly for select OPs, this was attributed to wide variability in structural types within this subset of POPs and their diversity compared to the other POP classes that were investigated. The exclusion of the structurally complex OP subset resulted in a more precise model, model 5. Intermolecular dispersive interactions (induced dipole-induced dipole forces) between octanol and solute molecules play a decisive role in governing KOA and its temperature dependence. Further investigations are needed to better characterize the steric structures of the POPs under study, especially of OPs.
Air↗
Passive air sampling of polycyclic aromatic hydrocarbons and polychlorinated naphthalenes across Europe.
This study presents concurrently sampled ambient air data for a range of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated naphthalenes (PCNs) at the continental scale. This was achieved with a passive air sampling system, by deploying polyurethane foam disks, which were prepared in one laboratory, sealed to prevent contamination, sent out by courier to volunteers participating in different countries, exposed for six weeks, collected, resealed, and returned to the laboratory for analysis. The study area was Europe, a region with a history of extensive persistent organic pollutants usage and emission, and with marked national differences in population density, the degree of urbanization and industrial and agricultural development. Samplers were deployed at remote, rural, and urban locations in 22 countries. Calculated air concentrations were broadly in line with those obtained by conventional active air sampling techniques, for both compound classes and for compounds existing predominantly in the gas and particle phases. The geographical compound distribution reflected suspected regional emission patterns and highlighted localized source areas. Both PAH and PCN levels varied by more than two orders of magnitude. The implications for sources are discussed.
Air Pollutants↗
Impacts of lindane usage in the Canadian prairies on the Great Lakes ecosystem. 1. Coupled atmospheric transport model and modeled concentrations in air and soil.
A coupled atmospheric transport, soil-air, water-air exchange model was developed to investigate the impacts of gamma-hexachlorocyclohexane (gamma-HCH or lindane) usage in the Canadian prairies over the Great Lakes region. The fate of gamma-HCH in air and soil is governed by atmospheric dynamics and physical and chemical processes that are described by the coupled model. These processes include transport and turbulent diffusion in the atmosphere, dry and wet deposition, exchange at the interfacial boundaries of air-water and soil-air, and removal processes from the soil such as diffusion, leaching, and degradation. Numerical experiments were conducted for the period of May 1, 1998-April 30, 1999, starting with application of lindane in the spring. The coupled model was executed with two lindane emission (usage) inventories in the model domain. The first scenario contained all known fresh emission sources in Canada-98% was usage in the prairies; the second excluded emission sources from Ontario and Quebec. The model showed that, in the absence of the reemission from past application of lindane, usage of lindane in Ontario and Quebec has a negligible impact on air concentrations in these regions and that the lindane budget in the Great Lakes ecosystem is mostly attributed to applications of lindane in the canola fields in Canadian prairie provinces. Model-predicted air concentrations and seasonal trends agreed well with measured data over the same time period for several background sites operated under the Integrated Atmospheric Deposition Network. Air temperature was shown to play a key role on surface-air exchange dynamics of gamma-HCH. A future paper will assess loadings to the Great Lakes based on these validated model results.
Air Movements↗
Characterization of polymer coated glass as a passive air sampler for persistent organic pollutants.
The use of thin-film polymer-coated glass surfaces or POGs as passive air samplers was investigated during an uptake experiment in an indoor environment with high levels of gas-phase polychlorinated biphenyls (PCBs). POGs consisted of a micron thick layer of ethylene vinyl acetate (EVA) coated onto glass cylinders. The uptake was initially linear with time and governed by the air-side mass transfer coefficient and surface area of the sampler. This was followed by a curvilinear region and finally a constant phase when equilibrium was established between air and EVA. The high surface area-to-volume ratio of the POGs allowed rapid equilibrium with gas-phase PCBs; equilibration times were on the order of hours for the low molecular weight congeners. The equilibrium concentration was dependent on the EVA-air partition coefficient, K(EVA-A), which was shown to be very well correlated to the octanol-air partition coefficient, K(OA). When POGs of varying thickness were equilibrated with air, the amount of PCB accumulated increased with increasing thickness of the EVA, indicating that uptake was by absorption into the entire polymer matrix. A wind field of 4 m s(-1) resulted in an increased uptake rate by a factor of approximately six compared to uptake in relatively still air. This wind speed effect was diminished, however, when POGs were housed in deployment chambers consisting of inverted stainless steel bowls. Relationships based on the air-side mass transfer coefficient and K(EVA-A) were developed for PCBs that describe the entire uptake profile and allow air concentrations to be determined from the amount of chemical accumulated in the POG. It is believed that these relationships are also valid when POGs are used to detect other classes of persistent organic pollutants.
Adsorption↗
Interlaboratory study for the polychlorinated naphthalenes (PCNs): phase 1 results.
An interlaboratory study was initiated to investigate consistency in reported concentrations of polychlorinated naphthalenes (PCNs). Results are reported from the first phase of a study that examined the variability associated with different quantification methodologies, instrumentation and standards. Nine participating labs from seven countries quantified individual homolog groups, summation operator PCN (the sum of 2-8 chlorinated homologs), and selected congeners in two test solutions derived from Halowax 1014. The means of the reported summation operator PCN values were within less than 15% of the known concentrations of the two test solutions and the relative standard deviation among laboratories was 11%. However, the among laboratory variability was in the range 20-40% for individual PCN homologs and individual PCN congeners. These results suggest the need for additional interlaboratory studies and for the development of reference materials for PCN analysis. Future PCN interlaboratory comparison exercises are discussed that will utilize control materials and unknowns consisting of suitable environmental matrices.
Chlorine Compounds↗
Quantitative relationships between molecular structures, environmental temperatures and octanol-air partition coefficients of polychlorinated biphenyls.
A quantitative model that incorporates information on both environmental temperatures (T) and molecular structures, for logarithm of octanol-air partition coefficient to base 10 (logK(OA)) of polychlorinated biphenyls (PCBs) was developed. Partial least squares (PLS) analysis together with 16 theoretical molecular structural descriptors was used to develop the Quantitative relationships between structures, environmental temperatures and properties (QRSETP) model. The cross-validated Q(cum)(2) value for the optimal QRSETP model is 0.976, indicating a good predictive ability for logK(OA) of PCBs at different environmental temperatures. T, E(LUMO) (the energy of the lowest unoccupied molecular orbital), molecular size or average molecular polarizability (alpha), and the net atomic charges on chlorine, hydrogen and carbon atoms of PCB molecules, are major factors governing logK(OA). The lower the E(LUMO), the greater the intermolecular interactions between octanol and PCB molecules, and thus the greater the logK(OA) values. Because of intermolecular dispersive forces, the more chlorine atoms in PCB molecules, the greater the molecular size or alpha, the greater the logK(OA). The largest negative net atomic charge on a carbon atom (q(C)(-)) and molecular size or average molecular polarizability (alpha) are major factors governing temperature dependence of logK(OA). PCB molecules with low q(C)(-) values and more chlorines (big size or alpha) tend to have strong temperature dependence, due to intermolecular electrostatic interactions and dispersive forces, respectively.
Journal Article↗
Quantitative relationships between molecular structures, environmental temperatures and octanol-air partition coefficients of PCDD/Fs.
A concise quantitative model that incorporates information on both environmental temperature (T) and molecular structures, for logarithm of octanol-air partition coefficient (K(OA)) to base 10 (logK(OA)) of PCDDs, was developed. Partial least squares (PLS) analysis together with 14 quantum chemical descriptors were used to develop the quantitative relationships between structures, environmental temperatures and properties (QRSETP) model. It has been validated that the obtained QRSETP model can be used to predict logK(OA) of other PCDDs. Molecular size, environmental temperature (T), q+ (the most positive net atomic charge on hydrogen or chlorine atoms in PCDD molecules) and E(LUMO) (the energy of the lowest unoccupied molecular orbital) are main factors governing logK(OA) of PCDD/Fs under study. The intermolecular dispersive interactions and thus the size of the molecules play a leading role in governing logK(OA). The more chlorines in PCDD molecules, the greater the logK(OA) values. Increasing E(LUMO) values of the molecules leads to decreasing logK(OA) values, implying possible intermolecular interactions between the molecules under study and octanol molecules. Greater q+ values results in greater intermolecular electrostatic repulsive interactions between PCDD and octanol molecules and smaller logK(OA) values.
Journal Article↗
Characterization and comparison of three passive air samplers for persistent organic pollutants.
The accumulation of persistent organic pollutants by three passive sampling media--semipermeable membrane devices (SPMDs), polyurethane foam (PUF) disks, and an organic-rich soil--was investigated. The media were exposed to contaminated indoor air over a period of 450 days, and concentrations in the air and in the media were monitored for individual polychlorinated biphenyl (PCB) congeners and polychlorinated naphthalene homologue groups. Uptake was initially linear and governed by the surface area of the sampler and the boundary layer airside mass transfer coefficient (MTC). Mean values of the MTC were 0.13, 0.11, and 0.26 cm s-1 for SPMD, PUF, and soil, respectively. As the study progressed, equilibrium was established between ambient air and the passive sampling media for the lower molecular weight PCB congeners. This information was used to calculate passive sampler-air partition coefficients, KPSM-A. These were correlated to the octanol-air partition coefficient, and the resulting regressions were used to predict KPSM-A for the full suite of PCBs. Information on MTC, KPSM-A, surface area, and effective thickness of each sampler was used to estimate times to equilibrium for each medium. These ranged from tens of days for the lower molecular weight congeners to tens of years for the higher molecular weight PCBs. Expressions were also developed to relate the amount of chemical accumulated by the passive sampling media to average ambient air concentrations over the integration period of the sample.
Air Pollutants↗
Estimating octanol-air partition coefficients of nonpolar semivolatile organic compounds from gas chromatographic retention times.
Relative gas chromatographic retention times on a non-polar stationary phase can be used to determine the octanol-air partition coefficient (K(OA)) and the energy of phase transfer between octanol and the gas phase (delta(OA)U) for semivolatile, nonpolar organic compounds. The only prerequisites are knowledge of the temperature-dependent K(OA) of a standard reference compound and directly measured K(OA) values at one temperature for a sufficient number of calibration compounds. It is shown that the technique is capable of predicting the K(OA) of polychlorinated benzenes, biphenyls and naphthalenes as well as polybrominated diphenyl ethers within the environmentally relevant temperature range with an average deviation from directly measured values of <0.2 log units.
Journal Article↗
Chiral pesticides in soil and water and exchange with the atmosphere.
The enantiomers of chiral pesticides are often metabolised at different rates in soil and water, leading to nonracemic residues. This paper reviews enantioselective metabolism of organochlorine pesticides (OCPs) in soil and water, and the use of enantiomers to follow transport and fate processes. Residues of chiral OCPs and their metabolites are frequently nonracemic in soil, although exceptions occur in which the OCPs are racemic. In soils where enantioselective degradation and/or metabolite formation has taken place, some OCPs usually show the same degradation preference--e.g., depletion of (+)trans-chlordane (TC) and (-)cis-chlordane (CC), and enrichment of the metabolite (+)heptachlor exo-epoxide (HEPX). The selectivity is ambivalent for other chemicals; preferential loss of either (+) or (-)o,p-DDT and enrichment of either (+) or (-)oxychlordane (OXY) occurs in different soils. Nonracemic OCPs are found in air samples collected above soil which contains nonracemic residues. The enantiomer profiles of chlordanes in ambient air suggests that most chlordane in northern Alabama air comes from racemic sources (e.g., termiticide emissions), whereas a mixture of racemic and nonracemic (volatilisation from soil) sources supplies chlordane to air in the Great Lakes region. Chlordanes and HEPX are also nonracemic in arctic air, probably the result of soil emissions from lower latitudes. The (+) enantiomer of alpha-hexachlorocyclohexane (alpha-HCH) is preferentially metabolised in the Arctic Ocean, arctic lakes and watersheds, the North American Great Lakes, and the Baltic Sea. In some marine regions (the Bering and Chukchi Seas, parts of the North Sea) the preference is reversed and (-)alpha-HCH is depleted. Volatilisation from seas and large lakes can be traced by the appearance of nonracemic alpha-HCH in the air boundary layer above the water. Estimates of microbial degradation rates for alpha-HCH in the eastern Arctic Ocean and an arctic lake have been made from the enantiomer fractions (EFs) and mass balance in the water column. Apparent pseudo first-order rate constants in the eastern Arctic Ocean are 0.12 year(-1) for (+)alpha-HCH, 0.030 year(-1) for (-)alpha-HCH, and 0.037 year(-1) for achiral gamma-HCH. These rate constants are 3-10 times greater than those for basic hydrolysis in seawater. Microbial breakdown may compete with advective outflow for long-term removal of HCHs from the Arctic Ocean. Rate constants estimated for the arctic lake are about 3-8 times greater than those in the ocean.
Animals↗
Using measured octanol-air partition coefficients to explain environmental partitioning of organochlorine pesticides.
Octanol-air partition coefficients (Koa) were measured directly for 19 organochlorine (OC) pesticides over the temperature range of 5 to 35 degrees C. Values of log Koa at 25 degrees C ranged over three orders of magnitude, from 7.4 for hexachlorobenzene to 10.1 for 1,1-dichloro-2,2-bis(p-chlorophenyl) ethane. Measured values were compared to values calculated as KowRT/H (where R is the ideal gas constant [8.314 J mol(-1) K(-1)], T is absolute temperature, and H is Henry's law constant) were, in general, larger. Discrepancies of up to three orders of magnitude were observed, highlighting the need for direct measurements of Koa. Plots of Koa versus inverse absolute temperature exhibited a log-linear correlation. Enthalpies of phase transition between octanol and air (deltaHoa) were determined from the temperature slopes and were in the range of 56 to 105 kJ mol(-1) K(-1). Activity coefficients in octanol (gamma(o)) were determined from Koa and reported supercooled liquid vapor pressures (pL(o)), and these were in the range of 0.3 to 12, indicating near-ideal solution behavior. Differences in Koa values for structural isomers of hexachlorocyclohexane were also explored. A Koa-based model was described for predicting the partitioning of OC pesticides to aerosols and used to calculate particulate fractions at 25 and -10 degrees C. The model also agreed well with experimental results for several OC pesticides that were equilibrated with urban aerosols in the laboratory. A log-log regression of the particle-gas partition coefficient versus Koa had a slope near unity, indicating that octanol is a good surrogate for the aerosol organic matter.
Aerosols↗