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T Harner

Publications and source records attributed to T Harner.

14 recordsLinked to original sources

Concentrations of decabromodiphenyl ether in air from Southern Ontario: implications for particle-bound transport.

Atmospheric concentrations are reported for the main component of the brominated flame retardant decaBDE (BDE-209) in air samples collected from Southern Ontario for the period January 23-June 06, 2002. Levels ranged from below detection to 105pgm(-3) with virtually all of BDE-209 being trapped by the filter and thus deduced to be sorbed to aerosol particles. Thus, it is likely that the long-range atmospheric transport (LRAT) of BDE-209 is controlled by the transport characteristics of the aerosols. This conclusion that BDE-209 does not have the same potential for LRAT as other more volatile PBDEs is subject to possible complications arising from the uncertainties about the LRAT potential of aerosols.

Air↗

Passive and active air samplers as complementary methods for investigating persistent organic pollutants in the Great Lakes Basin.

Data obtained using passive air samplers (PAS) are compared to active high-volume air sampling data in order to assess the feasibility of the PAS as a method, complementary to active high-volume air sampling (AAS), for monitoring levels of organochlorine (OC) pesticides, polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in the Laurentian Great Lakes. PAS were deployed at 15 of the Integrated Atmospheric Deposition Network (IADN) sites on a quarterly basis between July 2002 and June 2003, and PAS and AAS results are compared. Levels for the OC pesticides are typically highest in agricultural areas, with endosulfan I dominating air concentrations with values ranging between 40 and 1090 pg x m(-3), dieldrin values between 15 and 165 pg x m(-3), and gamma-HCH values between 13 and 100 pg x m(-3). alpha-HCH was seen to be relatively uniform across the Great Lakes Basin with values ranging between 15 and 73 pg x m(-3). Large urban centers, such as Chicago and Toronto, have the highest levels of PCBs and PBDEs that range between 400 and 1200 pg x m(-3) and 10 and 70 pg x m(-3), respectively. Comparison of the AAS and the PAS data collected during this study shows good agreement, within a factor of 2 or 3, suggesting that the two sample methods produce comparable results. It is suggested that PAS networks, while providing data that are different in nature from AAS, can provide a cost-effective and complementary approach for monitoring the spatial and temporal trends of persistent organic pollutants.

Air Pollutants↗

Recent climate change in the Arctic and its impact on contaminant pathways and interpretation of temporal trend data.

The Arctic has undergone dramatic change during the past decade. The observed changes include atmospheric sea-level pressure, wind fields, sea-ice drift, ice cover, length of melt season, change in precipitation patterns, change in hydrology and change in ocean currents and watermass distribution. It is likely that these primary changes have altered the carbon cycle and biological systems, but the difficulty of observing these together with sporadic, incomplete time series makes it difficult to evaluate what the changes have been. Because contaminants enter global systems and transport through air and water, the changes listed above will clearly alter contaminant pathways. Here, we review what is known about recent changes using the Arctic Oscillation as a proxy to help us understand the forms under which global change will be manifest in the Arctic. For Pb, Cd and Zn, the Arctic is likely to become a more effective trap because precipitation is likely to increase. In the case of Cd, the natural cycle in the ocean appears to have a much greater potential to alter exposure than do human releases of this metal. Mercury has an especially complex cycle in the Arctic including a unique scavenging process (mercury depletion events), biomagnifying foodwebs, and chemical transformations such as methylation. The observation that mercury seems to be increasing in a number of aquatic species whereas atmospheric gaseous mercury shows little sign of change suggests that factors related to change in the physical system (ice cover, permafrost degradation, organic carbon cycling) may be more important than human activities. Organochlorine contaminants offer a surprising array of possibilities for changed pathways. To change in precipitation patterns can be added change in ice cover (air-water exchange), change in food webs either from the top down or from the bottom up (biomagnification), change in the organic carbon cycle and change in diets. Perhaps the most interesting possibility, presently difficult to predict, is combination of immune suppression together with expanding ranges of disease vectors. Finally, biotransport through migratory species is exceptionally vulnerable to changes in migration strength or in migration pathway-in the Arctic, change in the distribution of ice and temperature may already have caused such changes. Hydrocarbons, which tend to impact surfaces, will be mostly affected by change in the ice climate (distribution and drift tracks). Perhaps the most dramatic changes will occur because our view of the Arctic Ocean will change as it becomes more amenable to transport, tourism and mineral exploration on the shelves. Radionuclides have tended not to produce a radiological problem in the Arctic; nevertheless one pathway, the ice, remains a risk because it can accrue, concentrate and transport radio-contaminated sediments. This pathway is sensitive to where ice is produced, what the transport pathways of ice are, and where ice is finally melted-all strong candidates for change during the coming century. The changes that have already occurred in the Arctic and those that are projected to occur have an effect on contaminant time series including direct measurements (air, water, biota) or proxies (sediment cores, ice cores, archive material). Although these 'system' changes can alter the flux and concentrations at given sites in a number of obvious ways, they have been all but ignored in the interpretation of such time series. To understand properly what trends mean, especially in complex 'recorders' such as seals, walrus and polar bears, demands a more thorough approach to time series by collecting data in a number of media coherently. Presently, a major reservoir for contaminants and the one most directly connected to biological uptake in species at greatest risk-the ocean-practically lacks such time series.

Air Movements↗

Field deployment of thin film passive air samplers for persistent organic pollutants: a study in the urban atmospheric boundary layer.

This paper reports on the first field deployment of rapidly equilibrating thin-film passive air samplers under ambient conditions. The POlymer-coated Glass (POG) samplers have a coating of ethylene vinyl acetate (EVA) less than 1 microm thick applied to a glass surface. This can be dissolved off after exposure and prepared for the quantification of persistent organic pollutants (POPs) that have partitioned into the film during field exposure. In this study, POGs were deployed at various heights on the CN Tower in Toronto, Canada, to investigate the vertical distribution of selected compounds (PCBs, PAHs, organochlorine pesticides) in the atmospheric boundary layer of an urban area. The feasibility of the method to detect POPs from a few cubic meters of air was demonstrated, indicating the potential for rapid, low-volume sampling of air for ambient levels of POPs. PAH levels declined sharply with height, confirming ground-level emissions in urban areas as sources of these compounds; PCBs did the same, although less strongly. Different sampling events detected different vertical distributions of OC pesticides which could be related to local or distantsources, and variations in POPs on the samplers in these different events/heights demonstrate the dynamic nature of sources and atmospheric mixing of POPs.

Air Movements↗

Evidence for the "grasshopper" effect and fractionation during long-range atmospheric transport of organic contaminants.

Although there is indisputable evidence that long-range atmospheric transport (LRAT) of organic contaminants occurs on a global scale, uncertainties remain about the detailed mechanism and extent of this phenomenon as well as the physical-chemical properties which facilitate LRAT. In this study, we discuss how mass balance models and monitoring data can contribute to a fuller understanding of the mechanism and extent of LRAT. Specifically we address the issues of "grasshopping" or "hopping" (the extent to which molecules are subject to multiple hops as distinct from a single emission-deposition event) and "global fractionation" (the differing behavior of chemicals as they are transported). It is shown that simple mass balance models can be used to assist the interpretation of monitoring data while also providing an instrument that can be used to assess the LRAT potential and the extent of hopping that organic substances may experience. The available evidence supports the notion that many persistent organic pollutants experience varying degrees of "hopping" during their environmental journey and as a consequence become fractionated with distance from source.

Air Movements↗

Quantitative predictive models for octanol-air partition coefficients of polybrominated diphenyl ethers at different temperatures.

Quantitative predictive models for octanol-air partition coefficients of polybrominated diphenyl ethers at different environmental temperatures (T) were developed. Partial least squares (PLS) regression was used for model development. A list of 18 theoretical molecular structural descriptors was screened by PLS analysis. The optimal model was selected from the one containing nine theoretical molecular descriptors and 1/T as predictor variables. The cross-validated Q(2)(cum) value for the optimal model is 0.975, indicating a good predictive ability and stability of the model. Intermolecular dispersive interactions play a leading role in governing the magnitude of logK(OA). The lower the E(LUMO) (the energy of the lowest unoccupied molecular orbital), the greater the intermolecular interactions between octanol and PCB molecules, and thus the greater the logK(OA) values.

Environmental Pollutants↗

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.

Atmosphere↗

The transport of beta-hexachlorocyclohexane to the western Arctic Ocean: a contrast to alpha-HCH.

A large database for alpha-hexachlorocyclohexane (alpha-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 alpha-HCH from source regions to the Arctic was rapid and because alpha-HCH partitioned strongly into cold water there. Following emission reductions during the 1980s, alpha-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 alpha-HCH, beta-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. Beta-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, beta-HCH has subsequently entered the western Arctic in ocean currents passing through Bering Strait. Beta-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.

Arctic Regions↗

Polychlorinated naphthalenes in U.K. soils: time trends, markers of source, and equilibrium status.

Polychlorinated naphthalenes (PCNs) have been analyzed in archived soil from the U.K. to investigate historical trends. Samples were obtained from the Broadbalk experiment plots (1944-1986) and Luddington experiment station (1968-1990). Luddington samples also include a set of soils that received a one-time sludge treatment in 1968, and duplicate samples of this archived sludge were also analyzed. Peak residues of sumPCN (sum of all PCN congeners quantified) were approximately 9000 pg g(-1) dry weight in 1956, declining to approximately 300 pg g(-1) in contemporary soils. The one-time sludge application resulted in elevated soil residues that were 1.5-6 times higher than the control plot over the time series. This increase is consistent with the known application rate and the amount of sumPCN in the applied sludge (approximately 250,000 pg g(-1) dry wt). Half-lives forthe Luddington control soil and the sludge-amended soil for the period 1972-1990 were 5.3 and 9.9 years, respectively. Investigation of time trends revealed differences between homologue groups with the higher molecular weight congeners peaking earlier in the time series (pre-1950) and the lower molecular weight congeners peaking later, ca. 1970. Time trends of individual congeners were investigated in terms of their relative mass percent contribution to the sum of their homologue group. Significant (p < 0.05) increasing trends were observed for several congeners associated with combustion sources (CN-29, -51, -52/60, -54, and -66/67) suggesting that combustion related sources are more important now than they were in the past. However, no decreasing trend was observed for congeners that were thought to be susceptible to degradation by photolysis suggesting that this may not be a key elimination pathway of PCNs in the environment. A simple calculation of the fugacity status of PCNs in air and soil showed that the tri-CNs are exhibiting net outgassing, while the penta-CNs are still being deposited to soil. Interestingly, the penta-CNs associated with combustion show the largest gradient for air-to-soil transfer, supporting the notion that combustion sources are important contributors to contemporary air burdens of these congeners.

Air Pollutants↗

Organochlorine pesticide residues in archived UK soil.

Archived background soils ("Broadbalk', 1944-1986) and sludge-amended soils ("Luddington", 1968-1990), collected from long-term agricultural experiments in the UK, were analyzed for a range of organochlorine (OC) pesticides to establish trends over time. Concentrations typically ranged from 0.1 to 10 ng/g of soil (dry weight), with gamma-hexachlorocyclohexane (gamma-HCH), dieldrin, and p,p'-DDE consistently having the highest concentrations. The trends in the Broadbalk background soils are largely consistent with usage patterns, with peak concentrations occurring in the 1960s for DDTs and between the 1960s and the 1980s for the other OCs. In the Luddington control and sludge-amended soils, several of the OCs show a significant decline in concentrations from the late 1960s to 1990, with half-lives ranging from approximately 7 years (alpha-HCH) to approximately 25 years (dieldrin). The sludge-amended plot received 125 tonnes of sludge per ha in 1968, which was mixed in to a depth of 15 cm. It appears that the sludge treatment had little effect on concentrations in the soil, with no significant difference between control soil and sludge-amended soil for most compounds, except for HCB, p,p'-DDE, and dieldrin. Enantiomeric fractions (EFs) of some chiral pesticides (alpha-HCH, cis- and trans-chlordane, and o,p'-DDT) were determined in the Luddington soils. Results reveal that enantioselective degradation of OC pesticides is occurring in these soils for trans-chlordane (TC) and cis-chlordane (CC). However, the depletion over time is not statistically significant, and there is no statistically significant difference between EFs in the control soil and sludge-amended soil. This indicates that enantioselective microbial degradation was not consistent over time and that the addition of sludge to soil did not significantly alter the enantiomeric preference of the microbial community.

Agriculture↗

Chiral analysis of organochlorine pesticides in Alabama soils.

The enantiomeric composition of organochlorine (OC) pesticide residues was investigated in 32 agricultural and 3 cemetery soils from Alabama. The enantiomeric signatures were similar to those from other soils in US and Canada. The enantiomer fractions (EFs) of o,p'-DDT showed great variability, ranging from 0.41 to 0.57 while the EFs of chlordanes and chlordane metabolites were less variable and differed in general significantly from racemic. Enantioselective depletion of (+)trans-chlordane, (-)cis-chlordane, the first eluting enantiomer of MC5, and enrichment of (+)heptachlor-exo-epoxide and (+)oxychlordane was found in a large majority of the samples with detectable residues. The enantiomeric composition of alpha-hexachlorocyclohexane was racemic or close to racemic.

Agriculture↗

Soil-air exchange model of persistent pesticides in the United States cotton belt.

Measurements of organochlorine pesticides (lindane, cis-chlordane [CC], trans-chlordane [TC], trans-nonachlor [TN]), dieldrin, p,p'-dichlorodiphenyldichloroethylene [DDE], and toxaphene) in Alabama, USA, air and soil were used to assess the soil-air equilibrium status and to identify compounds with significant contributions to observed air burdens. Of the compounds tested, p,p'-DDE and toxaphene showed a significant potential for outgasing, followed by dieldrin and trans-nonachlor, which showed moderate outgasing potentials. Lindane, cis-chlordane, and trans-chlordane were near soil-air equilibrium. A fugacity-based, multilayered soil-air exchange model was used to predict temporal trends of chemical in air and soil resulting from reemission of soil residues to a presumed clean atmosphere (maximum emission scenario). Results showed that p,p'-DDE and toxaphene accounted for up to 50% of the observed air burden and that approximately 200 to 600 kg of p,p'-DDE and 3,000 to 11,000 kg to toxaphene are released to the atmosphere each year by soils in Alabama (area = 1.23 x 10(11) m2). High annual net fluxes were also predicted for dieldrin and trans-nonachlor (300-1,100 kg and 150-500 kg, respectively), but these only account for up to approximately 20% of their observed air burdens.

Agriculture↗

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 Canada's 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 Canada's 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.

Animals↗

Residues of organochlorine pesticides in Alabama soils.

A survey was made of 36 Alabama agricultural soils to assess residues of formerly used organochlorine pesticides. Compounds determined comprised alpha- and gamma-hexachlorocyclohexane, heptachlor, heptachlor-exo-epoxide, trans- and cis-chlordane, trans-nonachlor, dieldrin, toxaphene, DDT and DDE. Concentrations varied by several orders of magnitude among farms and appeared to be log-normally distributed. Highest concentrations (ng g(-1) dry soil, arithmetic means) were found for toxaphene (285+/-390) and DDTs (p,p'-DDE, 22.7+/-21.4; p,p'-DDT, 24.6+/-30.5; o,p'-DDT, 4.00+/-5.86; p,p'-DDD, 2.40+/-2.41) which were once heavily used in the southern USA. Pesticide residues were not proportional to soil organic carbon content indicating that residue concentrations were a reflection of pesticide application history and dissipation rates rather than air-soil equilibrium. Mean ratios of DDT/DDE in six regions of the state ranged from 0.39 to 1.5, and compound ratios for chlordanes and toxaphene were different from those in the technical mixtures.

Journal Article↗