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1.
Ambio ; 51(2): 471-483, 2022 Feb.
Article in English | MEDLINE | ID: mdl-34874530

ABSTRACT

The Arctic is undergoing unprecedented change. Observations and models demonstrate significant perturbations to the physical and biological systems. Arctic species and ecosystems, particularly in the marine environment, are subject to a wide range of pressures from human activities, including exposure to a complex mixture of pollutants, climate change and fishing activity. These pressures affect the ecosystem services that the Arctic provides. Current international policies are attempting to support sustainable exploitation of Arctic resources with a view to balancing human wellbeing and environmental protection. However, assessments of the potential combined impacts of human activities are limited by data, particularly related to pollutants, a limited understanding of physical and biological processes, and single policies that are limited to ecosystem-level actions. This manuscript considers how, when combined, a suite of existing tools can be used to assess the impacts of pollutants in combination with other anthropogenic pressures on Arctic ecosystems, and on the services that these ecosystems provide. Recommendations are made for the advancement of targeted Arctic research to inform environmental practices and regulatory decisions.


Subject(s)
Anthropogenic Effects , Ecosystem , Arctic Regions , Humans , Hunting , Oceans and Seas
2.
Environ Pollut ; 227: 498-504, 2017 Aug.
Article in English | MEDLINE | ID: mdl-28494402

ABSTRACT

Eighteen polycyclic aromatic hydrocarbons (PAHs) were measured in surficial sediments along a marine transect from the North Pacific into the Arctic Ocean. The highest average Σ18PAHs concentrations were observed along the continental slope of the Canada Basin in the Arctic (68.3 ± 8.5 ng g-1 dw), followed by sediments in the Chukchi Sea shelf (49.7 ± 21.2 ng g-1 dw) and Bering Sea (39.5 ± 11.3 ng g-1 dw), while the Bering Strait (16.8 ± 7.1 ng g-1 dw) and Central Arctic Ocean sediments (13.1 ± 9.6 ng g-1 dw) had relatively lower average concentrations. The use of principal components analysis with multiple linear regression (PCA/MLR) indicated that on average oil related or petrogenic sources contributed ∼42% of the measured PAHs in the sediments and marked by higher concentrations of two methylnaphthalenes over the non-alkylated parent PAH, naphthalene. Wood and coal combustion contributed ∼32%, and high temperature pyrogenic sources contributing ∼26%. Petrogenic sources, such as oil seeps, allochthonous coal and coastally eroded material such as terrigenous sediments particularly affected the Chukchi Sea shelf and slope of the Canada Basin, while biomass and coal combustion sources appeared to have greater influence in the central Arctic Ocean, possibly due to the effects of episodic summertime forest fires.


Subject(s)
Environmental Monitoring , Geologic Sediments/chemistry , Polycyclic Aromatic Hydrocarbons/analysis , Water Pollutants, Chemical/analysis , Arctic Regions , Canada , Coal/analysis , Geologic Sediments/analysis , Linear Models , Naphthalenes , Oceans and Seas , Principal Component Analysis , Wood/chemistry
3.
Sci Rep ; 7: 44438, 2017 03 20.
Article in English | MEDLINE | ID: mdl-28317844

ABSTRACT

Worldwide amphibian populations are declining due to habitat loss, disease and pollution. Vulnerability to environmental contaminants such as pesticides will be dependent on the species, the sensitivity of the ontogenic life stage and hence the timing of exposure and the exposure pathway. Herein we investigated the biochemical tissue 'fingerprint' in spawn and early-stage tadpoles of the Common frog, Rana temporaria, using attenuated total reflection-Fourier-transform infrared (ATR-FTIR) spectroscopy with the objective of observing differences in the biochemical constituents of the respective amphibian tissues due to varying water quality in urban and agricultural ponds. Our results demonstrate that levels of stress (marked by biochemical constituents such as glycogen that are involved in compensatory metabolic mechanisms) can be observed in tadpoles present in the pond most impacted by pollution (nutrients and pesticides), but large annual variability masked any inter-site differences in the frog spawn. ATR-FTIR spectroscopy is capable of detecting differences in tadpoles that are present in selected ponds with different levels of environmental perturbation and thus serves as a rapid and cost effective tool in assessing stress-related effects of pollution in a vulnerable class of organism.


Subject(s)
Larva/drug effects , Pesticides/toxicity , Rana temporaria/metabolism , Water Pollutants, Chemical/toxicity , Zygote/drug effects , Amphibian Proteins/analysis , Amphibian Proteins/metabolism , Animals , Glycogen/analysis , Glycogen/biosynthesis , Larva/growth & development , Larva/metabolism , Lipids/analysis , Ponds/chemistry , Rana temporaria/growth & development , Spectroscopy, Fourier Transform Infrared , Water Quality , Zygote/growth & development , Zygote/metabolism
4.
Aquat Toxicol ; 178: 8-18, 2016 Sep.
Article in English | MEDLINE | ID: mdl-27450236

ABSTRACT

Amphibians are regarded as sensitive sentinels of environmental pollution due to their permeable skin and complex life cycle, which usually involves reproduction and development in the aquatic environment. Fungicides are widely applied agrochemicals and have been associated with developmental defects in amphibians; thus, it is important to determine chronic effects of environmentally-relevant concentrations of such contaminants in target cells. Infrared (IR) spectroscopy has been employed to signature the biological effects of environmental contaminants through extracting key features in IR spectra with chemometric methods. Herein, the Xenopus laevis (A6) cell line was exposed to low concentrations of carbendazim (a benzimidazole fungicide) or flusilazole (a triazole fungicide) either singly or as a binary mixture. Cells were then examined using attenuated total reflection Fourier-transform IR (ATR-FTIR) spectroscopy coupled with multivariate analysis. Results indicate significant changes in the IR spectra of cells induced by both agents at all concentrations following single exposures, primarily in regions associated with protein and phospholipids. Distinct differences were apparent in the IR spectra of cells exposed to carbendazim and those exposed to flusilazole, suggesting different mechanisms of action. Exposure to binary mixtures of carbendazim and flusilazole also induced significant spectral alterations, again in regions associated with phospholipids and proteins, but also in regions associated with DNA and carbohydrates. Overall these findings demonstrate that IR spectroscopy is a sensitive technique for examining the effects of environmentally-relevant levels of fungicides at the cellular level. The combination of IR spectroscopy with the A6 cell line could serve as a useful model to identify agents that might threaten amphibian health in a rapid and high throughput manner.


Subject(s)
Environmental Monitoring/methods , Epithelial Cells/drug effects , Fungicides, Industrial/toxicity , Water Pollutants, Chemical/toxicity , Animals , Benzimidazoles/toxicity , Biomarkers/metabolism , Carbamates/toxicity , Cell Culture Techniques , Cell Line , Cluster Analysis , Dose-Response Relationship, Drug , Environmental Monitoring/instrumentation , Epithelial Cells/metabolism , Humans , Multivariate Analysis , Silanes/toxicity , Spectroscopy, Fourier Transform Infrared , Triazoles/toxicity , Xenopus Proteins/metabolism , Xenopus laevis
5.
Environ Pollut ; 213: 322-337, 2016 Jun.
Article in English | MEDLINE | ID: mdl-26925755

ABSTRACT

Amphibians are undergoing large population declines in many regions around the world. As environmental pollution from both agricultural and urban sources has been implicated in such declines, there is a need for a biomonitoring approach to study potential impacts on this vulnerable class of organism. This study assessed the use of infrared (IR) spectroscopy as a tool to detect changes in several tissues (liver, muscle, kidney, heart and skin) of late-stage common frog (Rana temporaria) tadpoles collected from ponds with differing water quality. Small differences in spectral signatures were revealed between a rural agricultural pond and an urban pond receiving wastewater and landfill run-off; these were limited to the liver and heart, although large differences in body size were apparent, surprisingly with tadpoles from the urban site larger than those from the rural site. Large differences in liver spectra were found between tadpoles from the pesticide and nutrient impacted pond compared to the rural agricultural pond, particularly in regions associated with lipids. Liver mass and hepatosomatic indices were found to be significantly increased in tadpoles from the site impacted by pesticides and trace organic chemicals, suggestive of exposure to environmental contamination. Significant alterations were also found in muscle tissue between tadpoles from these two ponds in regions associated with glycogen, potentially indicative of a stress response. This study highlights the use of IR spectroscopy, a low-cost, rapid and reagent-free technique in the biomonitoring of a class of organisms susceptible to environmental degradation.


Subject(s)
Environmental Monitoring/methods , Rana temporaria , Spectroscopy, Fourier Transform Infrared , Agriculture , Animals , Larva/drug effects , Liver/drug effects , Muscles/drug effects , Pesticides/toxicity , Ponds/analysis , Water Quality
6.
Chemosphere ; 119: 1428-1435, 2015 Jan.
Article in English | MEDLINE | ID: mdl-25465948

ABSTRACT

Crops grown under plastic-clad structures or in greenhouses may be prone to an increased frequency of pesticide residue detections and higher concentrations of pesticides relative to equivalent crops grown in the open field. To test this we examined pesticide data for crops selected from the quarterly reports (2004-2009) of the UK's Pesticide Residue Committee. Five comparison crop pairs were identified whereby one crop of each pair was assumed to have been grown primarily under some form of physical protection ('protected') and the other grown primarily in open field conditions ('open'). For each pair, the number of detectable pesticide residues and the proportion of crop samples containing pesticides were statistically compared (n=100 s samples for each crop). The mean concentrations of selected photolabile pesticides were also compared. For the crop pairings of cabbage ('open') vs. lettuce ('protected') and 'berries' ('open') vs. strawberries ('protected') there was a significantly higher number of pesticides and proportion of samples with multiple residues for the protected crops. Statistically higher concentrations of pesticides, including cypermethrin, cyprodinil, fenhexamid, boscalid and iprodione were also found in the protected crops compared to the open crops. The evidence here demonstrates that, in general, the protected crops possess a higher number of detectable pesticides compared to analogous crops grown in the open. This may be due to different pesticide-use regimes, but also due to slower rates of pesticide removal in protected systems. The findings of this study raise implications for pesticide management in protected-crop systems.


Subject(s)
Agriculture/methods , Conservation of Natural Resources/methods , Crops, Agricultural/chemistry , Food Contamination/analysis , Pesticide Residues/analysis , Ultraviolet Rays/adverse effects , Brassica/chemistry , Conservation of Natural Resources/statistics & numerical data , Fruit/chemistry , Lactuca/chemistry
7.
Environ Toxicol Chem ; 30(3): 632-9, 2011 Mar.
Article in English | MEDLINE | ID: mdl-21298709

ABSTRACT

Organophosphorus pesticide (OPP) toxicity is believed to be mediated through inhibition of acetylcholinesterase (AChE). Given their widespread distribution in aquatic systems and their ability to undergo chemical transformation, their environmental impacts at sublethal concentrations in nontarget organisms have become an important question. We conducted a number of mammalian-cell genotoxic and gene expression assays and examined cellular biochemical changes that followed low-dose exposure of MCF-7 cells to fenitrothion, diazinon, and the aqueous degradate of diazinon, 2-isopropyl-6-methyl-4-pyrimidinol (IMP). After exposure to the OPPs at low concentrations (10(-12) M to 10(-8) M), greater than twofold elevations in micronucleus formation were noted in MCF-7 cell cultures that went on to exhibit greater than 75% clonogenic survival; these levels of chromosomal damage were comparable to those induced by 10(-6) M benzo[a]pyrene, a known genotoxic agent. At this low concentration range, a fenitrothion-induced twofold elevation in B-cell leukemia/lymphoma-2 (BCL-2) and cytochrome P450 isoenzyme (CYP1A1) gene expressions was observed. Principal component analysis-linear discriminant analysis (PCA-LDA) of derived infrared (IR) spectra of vehicle control (nonexposed) and OPP-exposed cells highlighted that both fenitrothion and diazinon induced marked biochemical alterations in the lipid, protein, and DNA/RNA absorbance regions. Our findings demonstrate that the two OPP parent chemicals and IMP degradate can mediate a number of toxic effects or cellular alterations at very low concentrations. These are independent of just selective inhibition of AChE, with potential consequences for nontarget organisms exposed at environmentally relevant concentrations. Further assays on relevant aquatic organism cell lines are now recommended to understand the mechanistic low-dose toxicity of these chemicals present in aquatic systems.


Subject(s)
Diazinon/toxicity , Fenitrothion/toxicity , Insecticides/toxicity , Mutagens/toxicity , Aquatic Organisms/drug effects , Benzo(a)pyrene/toxicity , Cell Line, Tumor , Cholinesterase Inhibitors/chemistry , Cholinesterase Inhibitors/toxicity , Diazinon/chemistry , Fenitrothion/chemistry , Humans , Insecticides/chemistry , Mutagenicity Tests , Mutagens/chemistry , Reverse Transcriptase Polymerase Chain Reaction , Spectroscopy, Fourier Transform Infrared , Water Pollutants, Chemical/toxicity
8.
Sci Total Environ ; 408(15): 2966-84, 2010 Jul 01.
Article in English | MEDLINE | ID: mdl-19939436

ABSTRACT

This review investigates the fate and behaviour of endosulfan, a current-use organochlorine pesticide, in temperate environments and the Arctic. Usage data and patterns, physical-chemical properties, environmental partitioning and degradation, environmental levels, global distribution and temporal trends are evaluated and discussed in the context of criteria that designate a substance as a persistent organic pollutant. Endosulfan is one of the most abundant OC pesticides in the global atmosphere and is capable of undergoing long range transport to remote locations such as the Arctic. Degradation of the two isomers, alpha- and beta-endosulfan, does occur in temperate/tropical soil and aquatic systems, both by abiotic and biotic processes, although this is highly dependent on the prevailing environmental conditions. Endosulfan sulfate is the major metabolite and this recalcitrant compound has been detected in air and is present in remote mountain lake sediments, although in comparison to alpha-endosulfan, data for this compound in the wider environment are lacking. Temporal trends from ice/snow cores as well as mountain lake sediments reveal a marked increase in endosulfan accumulation from the 1980s onwards. Furthermore, unlike other 'legacy' OC pesticides, levels of alpha-endosulfan do not show a decline in atmospheric monitoring data, reflecting ongoing use of this pesticide in the northern hemisphere. Endosulfan is present at low concentrations (relative to the pesticide, lindane) in surface Arctic Ocean waters, with the atmosphere likely to be the major contemporary source. Residues of endosulfan have been detected in marine biota for different geographical regions of the Arctic, with higher bioaccumulation factors (>10(3)-10(7)) for zooplankton and various species of fish, compared to studies in warmer/temperate systems. Endosulfan is present in marine mammals, although there is uncertainty in the various Arctic biota datasets due to differences in analytical techniques. For some biota, biomagnification factors for alpha-endosulfan are >1, notably from fish to seal, although there is a wide variability in values between the same species for different regions of the Arctic. There is little if any evidence of trophic magnification of alpha-endosulfan in well-defined marine foodwebs, with some evidence of bio-dilution at higher trophic levels, presumably due to increased metabolism. Endosulfan does fulfil several of the criteria under the UNEP Stockholm Convention for designation as a persistent organic pollutant. The alpha- and beta-isomer have similar physical-chemical properties and environmental behaviour to some of the obsolete organochlorine pesticides, although an assessment of their persistence and toxicity should be viewed alongside endosulfan sulfate, as 'Sigmaendosulfan'. Persistence of 'Sigmaendosulfan' coupled to ongoing use of endosulfan pesticides, will ensure continued long-range transport and contamination of remote environments.


Subject(s)
Endosulfan/analysis , Environmental Monitoring , Environmental Pollutants/analysis , Insecticides/analysis , Arctic Regions , Atmosphere/chemistry , Endosulfan/chemistry , Environmental Pollutants/chemistry , Environmental Pollution/statistics & numerical data , Food Chain , Insecticides/chemistry , Kinetics , Seawater/chemistry , Time
9.
Environ Pollut ; 157(12): 3308-13, 2009 Dec.
Article in English | MEDLINE | ID: mdl-19540637

ABSTRACT

Here we investigate the photodegradation of structurally similar organophosphorus pesticides; methyl-parathion and fenitrothion in water (20 degrees C) and ice (-15 degrees C) under environmentally-relevant conditions with the aim of comparing these laboratory findings to limited field observations. Both compounds were found to be photolyzed more efficiently in ice than in aqueous solutions, with quantum yields of degradation being higher in ice than in water (fenitrothion > methyl-parathion). This rather surprising observation was attributed to the concentration effect caused by freezing the aqueous solutions. The major phototransformation products included the corresponding oxons (methyl-paraoxon and fenitroxon) and the nitrophenols (3-methyl-nitrophenol and nitrophenol) in both irradiated water and ice samples. The presence of oxons in ice following irradiation, demonstrates an additional formation mechanism of these toxicologically relevant compounds in cold environments, although further photodegradation of oxons in ice indicates that photochemistry of OPs might be an environmentally important sink in cold environments.


Subject(s)
Fenitrothion/chemistry , Methyl Parathion/chemistry , Pesticides/chemistry , Photolysis/radiation effects , Cold Temperature , Models, Chemical
10.
Environ Sci Technol ; 43(8): 2746-52, 2009 Apr 15.
Article in English | MEDLINE | ID: mdl-19475944

ABSTRACT

In 1974, Junge derived an empirical relationship between the variability of concentrations of volatile trace gases in air at remote locations and their atmospheric residence time. Here, the Junge relationship is adapted to incorporate the deposition and revolatilization of semivolatile chemicals and applied to interpret nearly a decade of data on polychlorinated biphenyl (PCB) concentrations in air. A multimedia fate model, which accounts for deposition and revolatilization, is used to estimate the characteristic travel distance (CTD) for PCBs, where CTD serves as a measure of the effective atmospheric lifetime for semivolatile organic chemicals. Data are taken from sites of the Integrated Atmospheric Deposition Network in the North American Great Lakes and the Alert monitoring station in the Arctic, which is operated by the Canadian Northern Contaminants Program. Five factors that may introduce variability into measured concentrations are defined. By suppressing the effect of three of these factors in the data analysis, we identified variability consistent with the Junge relationship in many of the annual data sets (62%), with the relationship showing statistical significance (p < 0.05) in 23% of these annual data sets. The more remote monitoring sites from the Great Lakes region display the highest number of statistically significant Junge-type relationships between the variability in concentrations in air and estimated long-range transport potential in air. At sites in close proximity to areas of high population density, variability in PCB concentrations in air displays patterns that are consistent with primary or secondary temperature-driven volatilization sources. Analysis of variability in long-term monitoring data, using the techniques developed and illustrated here, provides useful insights into the factors that control the behavior of persistent semivolatile chemicals in the environment.


Subject(s)
Air Pollutants/analysis , Environmental Monitoring/methods , Polychlorinated Biphenyls/analysis , Empirical Research , Models, Theoretical
11.
J Environ Monit ; 11(3): 654-9, 2009 Mar.
Article in English | MEDLINE | ID: mdl-19280044

ABSTRACT

Aqueous solutions of fenitrothion and methyl parathion were photochemically degraded in an Atlas Suntest solar simulator (500 W m(-2)) as well as under ambient sunlight at Lancaster University (June & August 2007, 54 degrees N) and the degradation kinetics and disappearance quantum yields are reported. Fenitrothion degradation confirmed to first order kinetics (r(2) = 0.90-0.99) with a half-life range of 4.9 h-5.3 h, shorter than previously reported studies. In contrast, methyl parathion did not show significant degradation over the duration of these experiments. Light irradiances were monitored with a spectroradiometer during the Suntest simulator and outdoor experiments. The filtered-xenon arc lamp of the Suntest yielded spectral irradiances comparable to natural sunlight in the UVB and UVA wavelength range (280-400 nm), but with higher irradiances in the visible region (400-750 nm). Nonetheless, as both compounds have light absorption spectra at wavelengths < 400 nm, then the half-lives and disappearance quantum yields were similar between the Suntest and natural sunlight, and demonstrated that the Suntest is suitable for environmentally-relevant photochemical degradation experiments.


Subject(s)
Fenitrothion/chemistry , Methyl Parathion/chemistry , Pesticides/chemistry , Sunlight , Water/chemistry , Molecular Structure , Photolysis , Water Pollutants, Chemical/chemistry
12.
Chemosphere ; 76(1): 147-50, 2009 Jun.
Article in English | MEDLINE | ID: mdl-19282019

ABSTRACT

Plastic cladding is increasingly used in agriculture to create micro-environments to improve crop yield/growth. Many of these plastics can alter the solar light spectrum by inhibiting or reducing the transmittance of certain parts of the solar spectrum. In this study, we investigated the aqueous photolysis of fenitrothion, under a selection of different plastic films commonly used in agriculture. Three different grades of polyethylene film were used: 'standard', 'transparent' and 'opaque'. The transmittance of light wavelengths in the UV region (290-400 nm), measured with a spectroradiometer, was found to decrease in the order of transparent>standard>opaque. Fenitrothion, an organophosphorothioate insecticide possesses molar absorptivity in the solar wavelength range of 290-400 nm. Aqueous first order degradation rate constants for fenitrothion determined over a 12 h period were found to be considerably less for those experiments conducted under the standard and opaque plastic films, compared to the transparent film and no-film control. The experiments were conducted in an Atlas Suntest solar simulator using a UV-filtered Xenon arc lamp to simulate sunlight. The first order half-life for fenitrothion was 100 and 250 h under the standard and opaque films, respectively, compared to approximately 10 h for the transparent film and no-film experiments. Our results suggest that pesticide longevity could be greatly extended within these plastic micro-environments, especially for those chemicals which may degrade/transform via photolytic or photochemical pathways.


Subject(s)
Fenitrothion/analysis , Pesticide Residues/analysis , Plastics/chemistry , Agriculture , Fenitrothion/metabolism , Pesticide Residues/metabolism , Photolysis , Time Factors , Ultraviolet Rays , Water/chemistry
13.
Environ Sci Technol ; 42(9): 3213-8, 2008 May 01.
Article in English | MEDLINE | ID: mdl-18522096

ABSTRACT

Internationally there are few long-term air monitoring programs, which are necessary to assess the effectiveness of source abatement measures as required underthe UNECE POPs protocol. In the United Kingdom, the Toxic Organic Micropollutants (TOMPS) program, funded by the Department for Environment, Food, and Rural Affairs (Defra), was started in 1991 and includes regular monitoring of a range of compounds including polycyclic aromatic hydrocarbons (PAHs). In this study, the time series (1991-2005) of atmospheric concentrations of 15 PAHs at six U.K. monitoring sites were investigated. Most show a statistically significant decrease in PAH levels over time, broadly consistent with the reported decline in emissions. Higher levels of heavier PAHs were noted in winter than in summer at most sites. At one coastal site, higher levels of lighter PAHs were noted in summer, possibly due to temperature-driven outgassing of these compounds from seawater. Current annual averages of benzo[a]pyrene are below the recently introduced annual air quality standard of 0.25 ng m(-3) at all sites, although quarterly averages have exceeded 0.25 ng m(-3) in recent years but only at the urban sites in winter. The atmospheric signature of total PAHs closely mirrors the emission signature, which lends strength to the idea that levels of PAHs in air are still mostly influenced by direct/local sources.


Subject(s)
Air Pollutants/analysis , Environmental Monitoring/methods , Polycyclic Aromatic Hydrocarbons/analysis , Air Pollution , Atmosphere , Benzo(a)pyrene/chemistry , Chemistry, Organic/methods , Cities , Organic Chemicals/analysis , Particulate Matter , Polycyclic Aromatic Hydrocarbons/chemistry , Seasons , Temperature , Time Factors , United Kingdom , Urban Population
14.
Environ Sci Technol ; 42(8): 2943-8, 2008 Apr 15.
Article in English | MEDLINE | ID: mdl-18497148

ABSTRACT

A dynamic snowpack module was implemented in the Danish Eulerian Hemispheric Model Persistant Organic Pollutants (DEHM-POP), an atmospheric chemistry-transport model designed to study the environmental fate of persistent organic pollutants in the Northern Hemisphere. The role of the snowpack on the fate of alpha-hexachlorocyclohexane (alpha-HCH) was investigated by making simulations both with and without the formation of a snowpack and comparing model results with data from 21 air monitoring sites. The inclusion of a dynamic snowpack module in the DEHM-POP model generally improves the fit between modeled and observed alpha-HCH air concentrations for the winter and spring seasons and the overall correlation coefficient between predicted and observed concentrations are improved at 8 of the sites. The predicted snowpack concentrations are in good agreement with the few available snow measurements from the Arctic. The presence of a snowpack increases surface boundary layer air concentrations of alpha-HCH at midlatitudes, while the effect is more pronounced in the Arctic due to the longer periods of snow cover. The results indicate that the snowpack module in DEHM-POP acts as a fast-exchanging temporary storage medium for alpha-HCH, as significant fractions were rapidly revolatilized back into the atmosphere following deposition with snowfall, although the current parametrization for vapor-exchange probably over emphasizes this process. Nonetheless, increased air concentrations observed between March and May ("spring maximum events"; SME) at several high latitude monitoring stations are also predicted by the model. The model results indicate that the SMEs are associated with the revolatilization of previously deposited chemical from the snowpack, following a reduction in the capacity of the snowpack to retain alpha-HCH with increasing temperatures toward the end of the winter period, rather than the actual melting of the snowpack. The SMEs are not predicted at all the Arctic monitoring sites by the model, and the significance of the snowpack in controlling these in the model is, therefore, open to question given the uncertainties in the snow-air partition coefficient (K(sa)) and the reliance of the model on a one-layer snowpack rather than a multilayered snowpack.


Subject(s)
Air Pollutants/analysis , Hexachlorocyclohexane/analysis , Models, Chemical , Snow , Computer Simulation
15.
Environ Sci Technol ; 40(10): 3217-22, 2006 May 15.
Article in English | MEDLINE | ID: mdl-16749684

ABSTRACT

Polycyclic aromatic hydrocarbon (PAH) air concentrations measured over the period 1992-2000 at the Canadian High Arctic station of Alert were subject to time-series analysis using dynamic harmonic regression (DHR). For most of the PAHs, the DHR model fit to the observed data was good, with DHR capable of interpolating over missing data points during periods when air concentrations were below detection limits. As expected, DHR identified seasonal increases in PAH air concentrations. However, it has also identified additional, subtler "seasonal" patterns as a series of harmonics with varying periodicity. For example, a regular summer high in air concentrations was apparent for many PAHs, particularly the lower molecular weight (two- to three-ringed) compounds, which may be attributed to summertime regional combustion events such as forestfires and/or revolatilization from surfaces (e.g., soil and oceans, as well as arctic surfaces). Comparison of wintertime PAH concentrations (where sigmaPAH ranged from 260 to 516 pg m(-3)) with an earlier arctic study did not reveal a reduction in PAH levels. However, removal of the seasonal components by DHR revealed a declining trend in PAH concentrations over the 1992-2000 period. For many lighter PAHs, this was typified by a linear decrease over the whole time series, although, for the higher molecular weight PAHs, a marked reduction was apparent in the first few years of sampling followed by a leveling off in concentrations by the mid/late-1990s. This behavior is similar to reported trends of other air pollutants in the Arctic, may be attributed to the decline in Soviet industry during the early 1990s, and has implications regarding the major PAH sources affecting the Arctic.


Subject(s)
Air Pollutants/analysis , Atmosphere/analysis , Environmental Monitoring , Polycyclic Aromatic Hydrocarbons/analysis , Arctic Regions , Canada , Seasons , Time Factors
16.
Environ Sci Technol ; 40(8): 2644-52, 2006 Apr 15.
Article in English | MEDLINE | ID: mdl-16683604

ABSTRACT

An arctic snow model was developed to predict the exchange of vapor-phase persistent organic pollutants between the atmosphere and the snowpack over a winter season. Using modeled meteorological data simulating conditions in the Canadian High Arctic, a single-layer snowpack was created on the basis of the precipitation rate, with the snow depth, snow specific surface area, density, and total surface area (TSA) evolving throughout the annual time series. TSA, an important parameter affecting the vapor-sorbed quantity of chemicals in snow, was within a factor of 5 of measured values. Net fluxes for fluorene, phenanthrene, PCB-28 and -52, and alpha- and gamma-HCH (hexachlorocyclohexane) were predicted on the basis of their wet deposition (snowfall) and vapor exchange between the snow and atmosphere. Chemical fluxes were found to be highly dynamic, whereby deposition was rapidly offset by evaporative loss due to snow settling (i.e., changes in TSA). Differences in chemical behavior over the course of the season (i.e., fluxes, snow concentrations) were largely dependent on the snow/air partition coefficients (K(sa)). Chemicals with relatively higher K(sa) values such as alpha- and gamma-HCH were efficiently retained within the snowpack until later in the season compared to fluorene, phenathrene, and PCB-28 and -52. Average snow and air concentrations predicted by the model were within a factor of 5-10 of values measured from arctic field studies, but tended to be overpredicted for those chemicals with higher K(sa) values (i.e., HCHs). Sensitivity analysis revealed that snow concentrations were more strongly influenced by K(sa) than either inclusion of wind ventilation of the snowpack or other changes in physical parameters. Importantly, the model highlighted the relevance of the arctic snowpack in influencing atmospheric concentrations. For the HCHs, evaporative fluxes from snow were more pronounced in April and May, toward the end of the winter, providing evidence that the snowpack plays an important role in influencing the seasonal increase in air concentrations for these compounds at this time of year.


Subject(s)
Air Pollutants/analysis , Models, Chemical , Snow/chemistry , Air Pollutants/chemistry , Canada , Fluorenes/analysis , Fluorenes/chemistry , Gases , Hydrocarbons, Chlorinated/analysis , Hydrocarbons, Chlorinated/chemistry , Phenanthrenes/analysis , Phenanthrenes/chemistry , Seasons , Wind
17.
Environ Sci Technol ; 40(24): 7570-6, 2006 Dec 15.
Article in English | MEDLINE | ID: mdl-17256496

ABSTRACT

Arctic seawater concentrations of two currently used pesticides, endosulfan and gama-HCH, were collated from a variety of cruises undertaken throughout the 1990s up to 2000 for different regions of the Arctic Ocean. Surface seawater concentrations for alpha- and beta-endosulfan ranged from <0.1-8.8 (mean 2.3) pg/L and 0.1-7.8 (mean 1.5) pg/L, while gamma-HCH concentrations were approximately 100 fold higher than alpha-endosulfan, ranging between <0.70 and 894 (mean 250) pg/L. Geographical distributions for alpha-endosulfan revealed the highest concentrations in the western Arctic, specifically in the Bering and Chukchi Seas with lowest levels toward the central Arctic Ocean. In contrast, gamma-HCH revealed higher concentrations toward the central Arctic Ocean, with additional high concentrations in the coastal regions near Barrow, Alaska and the White Sea in northwest Russia, respectively. A fugacity approach was employed to assess the net direction of air-water transfer of these two pesticides, using coupled seawater and air concentrations. For alpha-endosulfan, water-air fugacity ratios (FR) were all <1 indicating net deposition to all regions of the Arctic Ocean, with the lowest values (0.1-0.2) evident in the Canadian Archipelago. Given the uncertainty in the temperature-adjusted Henry's Law constant (factor approximately10), it is plausible that equilibrium may have been reached for this compound in the western fringes of the Arctic Ocean where the highest water concentrations were observed. Similarly, FR values for gamma-HCH were generally <1 and in agreement


Subject(s)
Air Pollutants/analysis , Endosulfan/analysis , Hexachlorocyclohexane/analysis , Pesticides/analysis , Water Pollutants, Chemical/analysis , Arctic Regions , Seawater
18.
Environ Pollut ; 128(1-2): 163-75, 2004.
Article in English | MEDLINE | ID: mdl-14667726

ABSTRACT

POPs in the Arctic are the focus of international concern due to their occurrence and accumulation in Arctic food webs. This paper presents an overview of the major pathways into the Arctic and details contemporary studies that have focused on the occurrence and transfer of POPs between the major Arctic compartments, highlighting areas where there is a lack of quantitative information. The behaviour of these chemicals in the Arctic atmosphere is scrutinised with respect to long-term trends and seasonal behaviour. Subtle differences between the PCBs and OC pesticides are demonstrated and related to sources outside of the Arctic as well as environmental processes within the Arctic. Unlike temperate regions, contaminant fate is strongly affected by the presence of snow and ice. A description of the high Arctic snow pack is given and the physical characteristics that determine chemical fate, namely the specific surface area of snow and wind driven ventilation, are discussed. Using a well-characterised fresh snow event observed at Alert (Canadian high Arctic) [Atmos. Environ. 36(2002) 2767] the flux of gamma-HCH out of the snow is predicted following snow ageing. Under conditions of wind (10 m/s) it is estimated that approximately 75% of the chemical may be re-emitted to the atmosphere within 24 h following snowfall, compared with just approximately 5% under conditions of no wind. The implications of this are raised and areas of further research suggested.


Subject(s)
Air Pollutants/analysis , Organic Chemicals/analysis , Seasons , Snow , Arctic Regions , Atmosphere/chemistry , Pesticides/analysis , Polychlorinated Biphenyls/analysis , Time Factors , Water Pollutants, Chemical/analysis , Wind
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