Tom Harner

Contaminants in the Canadian Arctic: 5 years of progress in understanding sources, occurrence and pathways

Recent studies of contaminants under the Canadian Northern Contaminants Program (NCP) have substantially enhanced our understanding of the pathways by which contaminants enter Canadas Arctic and move through terrestrial and marine ecosystems there. Building on a previous review (Barrie et al., Arctic contaminants: sources, occurrence and pathways. Sci Total Environ 1992:1-74), we highlight new knowledge developed under the NCP on the sources, occurrence and pathways of contaminants (organochlorines, Hg, Pb and Cd, PAHs, artificial radionuclides). Starting from the global scale, we examine emission histories and sources for selected contaminants focussing especially on the organochlorines. Physical and chemical properties, transport processes in the environment (e.g. winds, currents, partitioning), and models are then used to identify, understand and illustrate the connection between the contaminant sources in industrial and agricultural regions to the south and the eventual arrival of contaminants in remote regions of the Arctic. Within the Arctic, we examine how contaminants impinge on marine and terrestrial pathways and how they are subsequently either removed to sinks or remain where they can enter the biosphere. As a way to focus this synthesis on key concerns of northern residents, a number of special topics are examined including: a mass balance for HCH and toxaphene (CHBs) in the Arctic Ocean; a comparison of PCB sources within Canadas Arctic (Dew Line Sites) with PCBs imported through long-range transport; an evaluation of concerns posed by three priority metals--Hg, Pb and Cd; an evaluation of the risks from artificial radionuclides in the ocean; a review of what is known about new-generation pesticides that are replacing the organochlorines; and a comparison of natural vs. anthropogenic sources of PAH in the Arctic. The research and syntheses provide compelling evidence for close connectivity between the global emission of contaminants from industrial and agricultural activities and the Arctic. For semi-volatile compounds that partition strongly into cold water (e.g. HCH) we have seen an inevitable loading of Arctic aquatic reservoirs. Drastic HCH emission reductions have been rapidly followed by reduced atmospheric burdens with the result that the major reservoir and transport agent has become the ocean. In the Arctic, it will take decades for the upper ocean to clear itself of HCH. For compounds that partition strongly onto particles, and for which the soil reservoir is most important (e.g. PCBs), we have seen a delay in their arrival in the Arctic and some fractionation toward more volatile compounds (e.g. lower-chlorinated PCBs). Despite banning the production of PCB in the 1970s, and despite decreases of PCBs in environmental compartments in temperate regions, the Arctic presently shows little evidence of reduced PCB loadings. We anticipate a delay in PCB reductions in the Arctic and environmental lifetimes measured in decades. Although artificial radionuclides have caused great concern due to their direct disposal on Russian Shelves, they are found to pose little threat to Canadian waters and, indeed, much of the radionuclide inventory can be explained as remnant global fallout, which was sharply curtailed in the 1960s, and waste emissions released under license by the European reprocessing plants. Although Cd poses a human dietary concern both for terrestrial and marine mammals, we find little evidence that Cd in marine systems has been impacted by human activities. There is evidence of contaminant Pb in the Arctic, but loadings appear presently to be decreasing due to source controls (e.g. removal of Pb from gasoline) in Europe and North America. Of the metals, Hg provokes the greatest concern; loadings appear to be increasing in the Arctic due to global human activities, but such loadings are not evenly distributed nor are the pathways by which they enter and move within the Arctic well understood.

Octanol-air partition coefficient as a predictor of partitioning of semi-volatile organic chemicals to aerosols

Abstract From a review of existing correlations for KP the partition coefficient of semi-volatile organic chemicals (SOCs) between aerosol and gaseous phases, it is suggested that the octanol-air partition coefficient (KOA) may be a valuable direct descriptor of SOCs volatility and may be preferable to the use of the experimentally inaccessible subcooled liquid-vapor pressure. Successful two parameter correlations are developed between log KP and log KOA, and an even simpler one parameter correlation is suggested that the ratio K P K OA is approximately constant for a class of SOCs.

Polychlorinated Biphenyls in Global Air and Surface Soil: Distributions, Air−Soil Exchange, and Fractionation Effect†

Polychlorinated biphenyl (PCB) concentrations in air and soil, measured by various research groups from around the world, were compiled and analyzed. Data for air were available from most regions, particularly in Europe and Asia. The average air concentrations (pg/m(3)) for SigmaPCB at background sites were 70 (5.1-170) for Europe, 79 (49-120) for North America, 66 (18-110) for South America, 270 (9-670) for Central America, 59 (17-150) for Asia, and 15 (13-17) for Australia. Data for soils exhibited better global coverage compared to air and were available from most regions. The average soil concentrations (pg/g dry weight) for SigmaPCB at background sites were 7500 (47-97 000) for Europe, 4300 (110-25 000) for North America, 1400 (61-9 500) for South America, 580 (120-2 900) for Asia, 390 (94-620) for Africa, and 280 (140-540) for Australia. Based on available studies where coupled measurements of PCBs in air and soil were made, the equilibrium status of PCBs in the air-soil system was investigated for China, West Midlands of the UK, central and southern Europe, and along a latitudinal transect from the south of the UK to the north of Norway. Differences were observed in plots of the soil-air equilibrium status (expressed as the soil-air fugacity fraction, ff) for different PCB homologues. This was explained by varying contributions from primary and secondary emissions-spatially and temporally. The net effect after several decades of PCB emissions to air, preferential transport of lower molecular weight PCBs through primary and secondary emission, and reductions in emissions to air in recent decades is that the lower molecular weight PCBs have achieved (and in some cases exceeded) soil-air equilibrium in many parts of the world. The exception is remote and background sites that are still dominated by primary sources.

Measurement of Octanol-Air Partition Coefficients for Chlorobenzenes, PCBs, and DDT

Novel methods are developed and tested for measuring the octanol-air partition coefficient (K oA ), which is suggested to be a valuable descriptor of air-vegetation and air-soil equilibrium. Data are reported for six chlorobenzenes (CBs), five polychlorinated biphenyls (PCBs), and DDT over the temperature range -10 to +20 °C with values approaching 10 12 . K OA varies log-linearly with reciprocal absolute temperature and increases by a factor of approximately 30 over this temperature range, the temperature coefficient being approximately 62 kJ/mol for CBs and 70 kJ/mol for PCBs. For PCBs, the values of K OA are within a factor of 4 of values calculated as the ratio of the octanol-water and the air-water partition coefficients, with a factor of 7.4 applying to DDT. It is suggested that for hydrophobic chemicals it is preferable to measure K OA directly since this avoids handling aqueous solutions.

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.

Modelling the environmental fate of the polybrominated diphenyl ethers

In response to growing alarm over the occurrence of polybrominated diphenyl ethers (PBDEs) in remote regions, this study considers their physical chemistry, environmental partitioning and considerations regarding potential for long-range atmospheric transport (LRAT). Internally consistent physical-chemical property data are presented for five representative congeners (PBDE-15, -28, -47, -99, -153) and used in a multimedia modelling approach. Results of the Level II model indicate that PBDEs will largely partition to organic carbon in soil and sediment and that their persistence will be strongly influenced by degradation rates in these media that are not well known. TaPL3 model estimates of their characteristic travel distance (CTD) suggest limited LRAT potential. The LRAT is also evaluated qualitatively, in terms of surface-air exchange behaviour. PBDEs are shown to be sensitive to seasonally and diurnally fluctuating temperatures. When vegetation is included in the model, 50% of the total mass of PBDE-47 deposited to vegetation returns to the atmosphere, suggesting that it may migrate through a series of deposition/volatilisation hops. Key data that needs to be identified in this evaluation include a better understanding of air-surface exchange, particularly to foliage, and measurements of degradation rates in soil, sediment and vegetation.

Indoor Sources of Poly- and Perfluorinated Compounds (PFCS) in Vancouver, Canada: Implications for Human Exposure

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are widely detected in human blood and serum and are of concern due to their potential toxicity. This study investigated the indoor sources of these compounds and their neutral precursors through a survey of 152 homes in Vancouver, Canada. Samples were collected of indoor air, outdoor air, indoor dust, and clothes dryer lint and analyzed for neutral [i.e., fluorotelomer alcohols (FTOHs), perfluorooctane sulfonamide (FOSA), and perfluorooctane sulfonamidoethanol (FOSE)] and ionic [i.e., PFOS and perfluoroalkyl carboxylates (PFCAs)] poly- and perfluorinated compounds (PFCs). Indoor air was dominated by 8:2 FTOH with a geometric mean concentration (pg/m(3)) of 2900. Among the FOSAs and FOSEs, MeFOSE exhibited the highest air concentration with a geometric mean of 380 pg/m(3). PFOA was the major ionic PFC and was detected in all indoor air samples with a geometric mean of 28 pg/m(3), whereas PFOS was below the detection limit. The results for the ionic PFCs in indoor air are the first for North America. The pattern of the neutral PFCs in house dust was also dominated by 8:2 FTOH, with a geometric mean of 88 ng/g. Dusts were enriched (relative to air) with sulfonamidoethanol (FOSE) which comprised ∼22% of the total neutral PFC content compared to only ∼3% in air. PFOS and PFOA were the most prominent compounds detected in dust samples. Levels of neutral PFCs in clothes dryer lint were an order of magnitude lower compared to house dust. Human exposure estimates to PFCs for adults and children showed that inhalation was the main exposure route for neutral and ionic PFCs in adults. For toddlers, ingestion of PFCs via dust was more relevant and was on the order of a few mg/day. Results from this study contribute to our understanding of exposure pathways of PFCs to humans. This will facilitate investigations of related health effects and human monitoring data.

Global distribution of linear and cyclic volatile methyl siloxanes in air.

The global distribution of linear and cyclic volatile methyl silxoanes (VMS) was investigated at 20 sites worldwide, including 5 locations in the Arctic, using sorbent-impregnated polyurethane foam (SIP) disk passive air samplers. Cyclic VMS are currently being considered for regulation because they are high production volume chemicals that are potentially persistent, bioaccumulative, and toxic. Linear and cyclic VMS (including L3, L4, L5, D3, D4, D5, and D6) were analyzed for in air at all urban, background, and Arctic sites. Concentrations of D3 and D4 are significantly correlated, as are D5 and D6, which suggests different sources for these two pairs of compounds. Elevated concentrations of D3 and D4 on the West coast of North America and at high elevation sites suggest these sites are influenced by trans-Pacific transport, while D5 and D6 have elevated concentrations in urban areas, which is most likely due to personal care product use. Measured concentrations of D5 were compared to modeled concentrations generated using both the Danish Eulerian Hemispheric Model (DEHM) and the Berkeley-Trent Global Contaminant Fate Model (BETR Global). The correlation coefficients (r) between the measured and modeled results were 0.73 and 0.58 for the DEHM and BETR models, respectively. Agreement between measurements and models indicate that the sources, transport pathways, and sinks of D5 in the global atmosphere are fairly well understood.

Model of the Long-Term Exchange of PCBs between Soil and the Atmosphere in the Southern U.K.

Measurements of concentrations of four PCB congeners (PCB-28, -52, -138, and -153) in air, herbage, and soil of the southern U.K. over the period 1942-1992 are compiled to demonstrate that emissions of PCB to the atmosphere increased from low levels in 1940 to a peak in the late 1960s and then fell to low current levels. This emission pulse resulted in a corresponding peak in air concentrations. Soil concentrations have responded to this pulse but with some delay, reaching a maximum in the early 1970s. At that time PCB fugacities in soil apparently exceeded atmospheric fugacities by about a factor of 10 because of nondiffusive deposition processes. Since then, fugacities in air and soil have fallen with a half-life of 10-20 yr probably as a result of volatilization or «degassing» of PCB, although it is possible (but not proved) that the degradation processes are also occurring with a half-life of approximately 15 yr. A simple two-compartment (air-soil) mass balance model is developed and applied to these data which gives a reasonable simulation of the long-term trends in concentration. It is concluded that there is a need to develop and improve models of this type to explain and predict the extent to which soils and vegetation act as a buffer of atmospheric concentrations of persistent chemicals

The transport of β-hexachlorocyclohexane to the western Arctic Ocean: a contrast to α-HCH

Abstract A large database for α-hexachlorocyclohexane (α-HCH), together with multimedia models, shows this chemical to have exhibited classical ‘cold condensation’ behavior. The surface water of the Arctic Ocean became loaded between 1950 and 1990 because atmospheric transport of α-HCH from source regions to the Arctic was rapid and because α-HCH partitioned strongly into cold water there. Following emission reductions during the 1980s, α-HCH remained trapped under the permanent ice pack, with the result that the highest oceanic concentrations in the early 1990s were to be found in surface waters of the Canada Basin. Despite a much stronger partitioning into water than for α-HCH, β-HCH did not accumulate under the pack ice of the Arctic Ocean, as might be expected from the similar emission histories for the two chemicals. β-HCH appears to have loaded only weakly into the high Arctic through the atmosphere because it was rained out or partitioned into North Pacific surface water. However, β-HCH has subsequently entered the western Arctic in ocean currents passing through Bering Strait. β-HCH provides an important lesson that environmental pathways must be comprehensively understood before attempting to predict the behavior of one chemical by extrapolation from a seemingly similar chemical.