A dynamic model to study the exchange of gas-phase persistent organic pollutants between air and a seasonal snowpack

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.     

Peer reviewed: tracking the distribution of persistent organic pollutants

Control strategies for these contaminants will require a better understanding of how they move around the globe.     

On the reversibility of environmental contamination with persistent organic pollutants

An understanding of the factors that control the time trends of persistent organic pollutants (POPs) in the environment is required to evaluate the effectiveness of emission reductions and to predict future exposure. Using a regional contaminant fate model, CoZMo-POP 2, and a generic bell-shaped emission profile, we simulated time trends of hypothetical chemicals with a range of POP-like partitioning and degradation properties in different compartments of a generic warm temperate environment, with the objective of identifying the processes that may prevent the reversibility of environmental contamination with POPs after the end of primary emissions. Evaporation from soil and water can prevent complete reversibility of POP contamination of the atmosphere after the end of emissions. However, under the selected conditions, only for organic chemicals within a narrow range of volatility, that is, a logarithm of the octanol air equilibrium partition coefficient between 7 and 8, and with atmospheric degradation half-lives in excess of a few month can evaporation from environmental reservoirs sustain atmospheric levels that are within an order of magnitude of those resulting from primary emissions. HCB and α-HCH fulfill these criteria, which may explain, why their atmospheric concentrations have remained relatively high decades after their main primary emissions have been largely eliminated. Soil-to-water transfer is found responsible for the lack of reversibility of POP contamination of the aqueous environment after the end of emissions, whereas reversal of water-sediment exchange, although possible, is unlikely to contribute significantly. Differences in the reversibility of contamination in air and water suggests the possibility of changes in the relative importance of various exposure pathways after the end of primary emissions, namely an increase in the importance of the aquatic food chain relative to the agricultural one, especially if the former has a benthic component. Since simulated time trends were strongly dependent on degradation half-lives, partitioning properties and selected environmental input parameters, it should not be surprising, that different field studies often generate highly divergent time trends.     

Wet deposition of persistent organic pollutants to the global oceans

Wet deposition fluxes of polychlorinated biphenyls and polychlorinated dibenzo-p-dioxins and furans to the Atlantic Ocean have been estimated by combining meteorological satellite data and measured atmospheric field concentrations. They are then compared to other atmospheric depositional mechanisms on a global scale. Additional features not treated in traditional studies are addressed such as contaminant adsorption onto raindrops and enhancement of dry gaseous diffusive fluxes due to rain-induced turbulence. Wet deposition estimates show a high spatial and seasonal variability, with maxima located in the Intertropical Convergence Zone (ITCZ) and in low-temperature regions. Seasonal variability reflects the northward shift of ITCZ in July. Average wet deposition fluxes estimated for the Atlantic Ocean in this study are 110 and 45 ng m(-2) yr(-1) for sigmaPCB and sigmaPCDD/Fs, respectively. Furthermore, the total wet deposition to the Atlantic results in 4100 kg yr(-1) (sigmaPCB) and 2500 kg yr(-1) (sigmaPCDD/Fs). Model validation shows good agreement with available coastal data measurements of wet deposition fluxes. When compared to other atmospheric depositional mechanisms and during precipitation events, wet deposition is found to be dominant. However, when raining events and non-raining time periods are integrated, air-water diffusive exchange fluxes acquire an important role, which can be dominant in some regions and for some POPs.     

Food web magnificaton of persistent organic pollutants in poikilotherms and homeotherms

Food web magnification of persistent organic pollutants (POPs) was determined for the Barents Sea food web using 615N as a continuous variable for assessing trophic levels (TL). The food web investigated comprised zooplankton, ice fauna and fish (poikilotherms, TL 1.7-3.3), and seabirds and seals (homeotherms, TL 3.3-4.2), with zooplankton representing the lowest and glaucous gull the highest trophic level. Concentrations of lipophilic and persistent organochlorines were orders of magnitude higher in homeotherms than in poikilotherms. These compounds had significantly higher rates of increase per trophic level in homeotherms relative to poikilotherms, with the highest food web magnification factors (FWMFs) for cischlordane and p,p'-DDE. Some compounds, such as transnonachlor and HCB, had similar rates of increase throughout the food web, whereas compounds that are more readily eliminated (gamma-HCH) showed no relationship with trophic level. It is preferable to calculate FWMFs with regard to thermal groups, because the different energy requirements and biotransformation abilities between poikilotherms and homeotherms may give different rates of contaminant increase with trophic level. When biomagnification is compared between ecosystems, FWMFs are preferable to single predator-prey biomagnification factors. FWMFs represent a trophic level increase of contaminants that is average for the food chain rather than an increase for a specific predator-prey relationship. The Barents Sea FWMFs were generally comparable to those determined for marine food webs with similar food chain lengths in the Canadian Arctic.     

Bioamplification and the selective depletion of persistent organic pollutants in Chinook salmon larvae

The maternal provisioning of yolk to eggs transfers significant quantities of persistent organic pollutants (POPs). As yolk utilization progresses via metabolic activity, there is a potential to realize further increases in POP concentrations if yolk lipids are depleted at a faster rate than POPs, a condition referred to as bioamplification. This study investigated the bioamplification of POPs in Chinook salmon ( Oncorhynchus tshawytscha ) eggs and larvae. Chinook eggs were sampled from the Credit River, ON, Canada, and brought to an aquaculture facility where they were fertilized, incubated, and maintained posthatch until maternally derived lipid reserves became depleted (approximately 168 days). The loss of chemicals having an octanol-water partition coefficient (log K(OW)) greater than 5.8 was slow to negligible from days 0-135. However, during the increase in water temperatures in early spring, K(OW)-dependent elimination of POPs was observed. Bioamplification was maximized for the highest log K(OW) POPs, with an approximate 5-fold increase in lipid equivalents concentrations in 168 day old larvae as compared to newly fertilized eggs. This study demonstrates that later yolk-sac Chinook larvae (before exogenous feeding) are exposed to higher lipid equivalents POP concentrations than predicted by maternal deposition, which could lead to underestimates in the toxicity of critical life stages.     

Quantifying the perturbations of persistent organic pollutants induced by climate change

A perturbed air-surface coupled model has been developed to simulate and predict perturbations of POPs concentrations in various environmental media under given climate change scenarios. By introducing the perturbations in air temperature and precipitation induced by climate change in the model, we have examined the corresponding perturbations in the concentration of POPs in the closed air-soil and air-water systems. Numerical experiments for several POPs have been conducted based on the possible future climate change scenarios. It was found that hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), and a polychlorinated biphenyl (PCBs) congener, PCB-153, exhibit strong response to specified climate change scenarios as shown by their high concentrations perturbations in air. In the air-soil system the coupled model predicts 4-50% increases in the air concentrations of these chemicals corresponding to an increase of 0.05-0.1 K yr(-1) in the air temperature. Based on our simulations, a 20% increase/decrease in precipitation can result in a 53% and 4% decrease/increase in perturbed air concentration of γ-HCH and α-HCH, respectively. Also, the model can be used to determine the direction of air-surface exchange of POP perturbations induced by climate change.     

Oceanic biogeochemical controls on global dynamics of persistent organic pollutants

Understanding and quantifying the global dynamics and sinks of persistent organic pollutants (POPs) is important to assess their environmental impact and fate. Air-surface exchange processes, where temperature plays a central role in controlling volatilization and deposition, are of key importance in controlling global POP dynamics. The present study is an assessment of the role of oceanic biogeochemical processes, notably phytoplankton uptake and vertical fluxes of particles, on the global dynamics of POPs. Field measurements of atmospheric polychlorinated biphenyls (PCBs), polychlorinated dibenzodioxins (PCDDs), and furans (PCDFs) are combined with remote sensing estimations of oceanic temperature, wind speed, and chlorophyll, to model the interactions between air-water exchange, phytoplankton uptake, and export of organic matter and POPs out of the mixed surface ocean layer. Deposition is enhanced in the mid-high latitudes and is driven by sinking marine particulate matter, rather than by a cold condensation effect. However, the relative contribution of the biological pump is a function of the physical-chemical properties of POPs. It is concluded that oceanic biogeochemical processes play a critical role in controlling the global dynamics and the ultimate sink of POPs.     

An arctic terrestrial food-chain bioaccumulation model for persistent organic pollutants

A model representing the bioaccumulation of persistent organic pollutants (POPs) in arctic terrestrial mammalian food-chains is developed, parametrized, tested, and analyzed. The model predicts concentrations of POPs in lichen, caribou (Rangifer tarandus), and wolf (Canis lupus) food-chains of Canada's central and western arctic region from measured concentrations in air and snowpack meltwater. The model accounts for temporal and seasonal variation in diet composition, life-stage, body weight, and fat content over the life-span of the animal. Model predicted concentrations of 25 organic chemicals forecasted for caribou and wolves from Cambridge Bay (69 degrees 07' N 105 degrees 03' W), Inuvik (68 degrees 18' N 133 degrees 29' W) and Bathurst Inlet (64 degrees 15' N 113 degrees 07' W) are shown to be in good agreement with the observed data. The model illustrates a strong relationship between biomagnification factors and chemical K(OA) and illustrates the effect of age, sex, and temperature on POPs bioaccumulation. Model results show that POPs with K(OA)s < 10(5) do not biomagnify in arctic terrestrial food-chains, while substances that exhibit log K(OA)s > 5 and also exhibit a log K(OW) > 2, show significant bioaccumulation in arctic terrestrial food-chains. The model shows that persistent low K(OW) (K(OW)s < 10(5)) but high K(OA) substances such as beta-HCH, 1,2,4,5 tetrachlorobenzene, and beta-endosulfan biomagnify in terrestrial mammals.     

Time trends of selected persistent organic pollutants in lake sediments from Greenland

Sediments from seven lakes in West Greenland were used as natural archives to study past and present levels of PCBs (polychlorinated biphenyls, tri- to decachlorinated), tetra-BDE #47 (2,2',4,4'-bromodiphenyl ether), chlordane (cis- and trans-octachlordane) and HxCBz (hexachlorobenzene). The concentrations found are lower than or comparable to concentrations found in sediments from other Arctic regions and one to 2 orders of magnitude lower than concentrations typically found in sediments at lower latitudes. The observed temporal trends (direct and indirect dating) show a decreasing total PCB concentration. Even though local contamination sources exist, the POP deposition in the studied area is most likely a result from long-range transport. The hypothesis about "cold condensation" suggests a latitudinal fractionation to occur between different volatile compounds during the transport toward the pole. In this study a time delay in the deposition for the low-chlorinated PCBs (tri- and tetrachlorinated), compared to their emission histories and compared to higher chlorinated PCBs, was indicated. Although very low tetra-BDE #47 concentrations are observed in this study, there are indications for an increasing concentration in recent sediment layers that may reflect increasing environmental concentrations at lower latitudes. The investigated pesticides are still in use at lower latitudes, however neither chlordane nor HxCBz show any distinct temporal trend of increasing or decreasing concentration toward the sediment surface.     

肉及肉制品中持久性有机污染物(POPs)的控制及分析

综述了肉及肉制品中POPs的主要特性、控制措施、分析方法等的最新进展。     

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.     

Multivariate data analyses of persistent organic pollutants in maternal adipose tissue in Singapore

Persistent organic pollutants (POPs) were detected in 88 maternal adipose tissue samples collected during year 2004 to 2006, in Singapore. Organochlorine pesticides (OCPs) were the most dominant followed by polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Multivariate data analyses (MVA) including principal component analysis (PCA), partial least-squares regression (PLSR), and partial least-squares discriminant analysis (PLS-DA) were applied to elucidate the relationship between concentrations of POPs in adipose tissues and donors' characteristics. Food consumption played the most significant role in accounting for levels of POPs in adipose tissue. Fish and poultry consumption was the route of PCBs and PBDEs in mothers in Singapore, while beta-HCH came mainly from vegetables. An age-dependent accumulation of POPs was found for beta-HCH and PCB congeners, and lactation and gestation functioned as a decontamination processes for PCBs in adipose tissue. Gestational diabetes mellitus (GDM) may change the profile of POPs in adipose tissue, probably due to an alteration in lipid metabolism. POPs investigated here may not be the cause of antenatal complication in pregnant women, and baby gender was not related to the pattern of contaminants in maternal adipose tissue.     

制浆造纸工业二恶英类持久性有机污染物控制和减排研究

介绍了制浆造纸工业二恶英类持久性有机污染的来源、控制和削减措施。取消氯气漂白工艺,采用无元素氯漂白技术代替氯气漂白技术是将来发展的方向。     

Orographic cold-trapping of persistent organic pollutants by vegetation in mountains of western Canada

Conifer needles from mountain areas of Alberta and British Columbia, Canada, were collected from sites that ranged in altitude from 770 to 2200 masl and were analyzed for polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCs) to determine if they are progressively concentrated in colder, more elevated mountain areas, where temperatures decrease as elevation increases. Concentrations of OCs in needles ranged from 43 to 2430 pg g(-1), 55-17500 pg g(-1), and 11-2930 pg g(-1) (dry weight), for total hexachlorocyclohexanes (HCHs), PCBs, and endosulfans, respectively. The more volatile OCs, with subcooled liquid vapor pressures (PL) > 0.1 Pa at 25 degrees C, increased at higher altitudes, whereas the less volatile OCs were either unrelated or inversely correlated with altitude. These spatial patterns were similar for species of spruce (Picea engelmannii and glauca) and pine (Pinus contorta and albicaulis). Back trajectories revealed that air masses arriving at these sites traveled over Asia and the Pacific Ocean before reaching the Rocky Mountains. Results from this study demonstrate that alpine ecosystems accumulate these chemicals to the same degree that is observed in polar environments that are known to receive contaminants by long-range transport.     

Latitudinal distribution of persistent organic pollutants in pelagic and demersal marine fish on the Norwegian Coast

The latitudinal distribution of persistent organic pollutants (POPs: legacy organochlorines [OCs], polybrominated diphenyl ethers [PBDEs,] and hexabromocyclododecane [HBCD]) was examined in livers of two species of marine fish, the pelagic saithe (Pollachius virens,n = 40) and the demersal cod (Gadus morhua,n = 40), along a south-north gradient (59°-70°N) on the Norwegian Coast. Cod had in general two to three times higher concentrations of POPs than saithe, probably because of higher exposure in the benthic food chain. The concentrations of heavy halogenated compounds were higher in the southernmost region than further north. Moreover, the POP pattern showed a gradual shift in the compositions from south to north, especially for OCs in cod: i.e. the relative importance of low-chlorinated polychlorinated biphenyl (PCB) congeners and some OC-pesticides (e.g., hexachlorobenzen [HCB]) in the contaminant burdens increased with latitude. The latitudinal fractionation signal was weaker in saithe, possibly due to its pelagic and nomadic behavior. Hence, this study shows not only a strong latitudinal fractionation in the compositional patterns of POPs in marine fish but also the effects of habitat use and fish behavior.     

Bioaccumulation of persistent organic pollutants in lichen-caribou-wolf food chains of Canada's Central and Western Arctic

While biomagnification of persistent organic pollutants (POPs) in aquatic food chains is well documented, there have been few investigations of the trophodynamics of POPs in Arctic terrestrial food chains. This study presents field-collected concentration data and corresponding fugacities of various hydrophobic organic chemicals (ranging in octanol-water partition coefficients or K(OW) from approximately 10(3.8) to 10(9)) in two lichen species (Cladina rangiferina and Cetraria nivalis), willow leaves (Salix glauca), barren-ground caribou (Rangifer tarandus), and wolves (Canis lupus) from Canada's Central and Western Arctic region. The results show that, in contrast to aquatic food chains, persistent substances including beta-hexachlorocyclohexane and 1,2,4,5-tetrachlorobenzene with a K(OW) <10(5) can substantially biomagnify in lichen-caribou-wolf food chains in Canada's Central and Western Arctic. Strong positive correlations between the biomagnification factor and the octanol-air partition coefficients (K(OA)) of nonmetabolizable compounds were observed in wolves. In caribou, the biomagnification factors dropped slightly with increasing K(OA). K(OA) proved to be a better indicator of biomagnification than K(OW). Current management policies that consider only chemicals with K(OW) values >10(5) as bioaccumulative substances fail to identify substances that have the potential to biomagnify in Arctic terrestrial food chains despite a low K(OW) because of a high K(OA).     

Atmospheric dry deposition of persistent organic pollutants to the Atlantic and inferences for the global oceans

Atmospheric deposition to the oceans is a key process affecting the global dynamics and sinks of persistent organic pollutants (POPs). A new methodology that combines aerosol remote sensing measurements with measured POP aerosol-phase concentrations is presented to derive dry particulate depositional fluxes of POPs to the oceans. These fluxes are compared with those due to diffusive air-water exchange. For all polychlorinated biphenyl (PCB) congeners and lower chlorinated dibenzo-p-dioxins and furans (PCDD/Fs), air-water exchange dominates the dry deposition mechanism. However, this tendency reverses in some areas, such as in marine aerosol influenced areas and dust outflow regions, consistent with the important variability encountered for the depositional fluxes. Seasonal variability is mainly found in mid-high latitudes, due to the important influence of wind speed enhancing dry deposition fluxes and temperature as a driver of the gas-particle partitioning of POPs. The average dry aerosol deposition flux of sigmaPCBs and sigmaPCDD/Fs to the Atlantic Ocean is calculated to be in the order of 66 ng m(-2) yr(-1) and 9 ng m(-2)yr(-1) respectively. The total dry aerosol deposition of sigmaPCBs and sigmaPCDD/Fs to the Atlantic Ocean is estimated to be 2200 kg yr(-1) and 500 kg yr(-1), respectively, while the net air-water exchange is higher, 22000 kg sigmaPCBs yr(-1) for PCBs and 1300 kg sigmaPCDD/Fs yr(-1). Furthermore, it is suggested that marine aerosol plays an important role in scavenging atmospheric contaminants.