Toward a global network for persistent organic pollutants in air: results from the GAPS study

The Global Atmospheric Passive Sampling (GAPS) study aims to demonstrate the feasibility of using passive samplers to assess the spatial distribution of persistent organic pollutants on a worldwide basis. The GAPS network includes more than 40 sites on 7 continents, mainly in background locations, with some representation of urban and agricultural areas. Here we present concentrations of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in polyurethane foam disk samplers, deployed from December 2004 to March 2005. Legacy OCPs such as alpha-HCH (hexachlorocyclohexane), Chlordanes (trans- and cis-Chlordane and trans-Nonachlor), Dieldrin, and dichlorodiphenyltrichloroethane isomers were detected at most sites with some high values that may be related to possible continued use and/or re-emissions related to historic use. Geometric mean (GM) air concentrations (pg/m3) were: 8.5 for sigmaHCH (sum of alpha- and gamma-isomers), 2.6 for sigmaChlordanes, 0.8 for Dieldrin, and 0.8 for p,p'-DDE. Current-use pesticides such as gamma-HCH (lindane) and especially Endosulfan I exhibited more variable and higher concentrations with GMs of 5 and 58, respectively. PCBs and PBDEs were elevated at urban/suburban sites consistent with their historical use pattern. GM concentrations (pg/m3) were 17 for PCBs and 4 for PBDEs. Sampling under GAPS will continue and will eventually allow seasonality effects and longer-term temporal and spatial trends to be evaluated.     

Altitudinal and seasonal variations of persistent organic pollutants in the Bolivian Andes Mountains

Polyurethane foam disk passive air samplers were deployed over four periods of approximately 3 months along an altitudinal gradient (1820, 2600, 4650, and 5200 masl) on the east side of the Andean mountain range in Bolivia. The purpose of the study was to assess the gas-phase concentration and the altitudinal and seasonal trends of organochlorine pesticides and polychlorinated biphenyls (PCBs). Target compounds that were regularly detected included alpha- and gamma-hexachlorocyclohexane (HCH), endosulfans, and select PCB congeners. Endosulfans and HCH concentrations increased with altitude. Enrichment factors (concentration at the highest altitude divided by concentration at the lowest altitude) ranged from 10 to 20 for HCHs and 3 to 10 for endosulfans. Air parcel back trajectory analysis indicated that, in general, the high-altitude sites were exposed to a larger airshed and hence susceptible to long-range atmospheric transport from more distant regions. Seasonal differences were also observed with SigmaHCH concentrations peaking during periods 2 and 3 (March-September 2005). Airsheds (derived from the analysis of back trajectories) for periods 2 and 3 were less oriented along the Andes range (mountain air) with greater input from coastal regions. Endosulfans peaked during periods 1 and 2 (February-June 2005) and also exhibited the highest air concentrations of the target compounds, reaching approximately 1500 pg/m3 at the two highest elevation sites. PCB air concentrations at all sites were generally typical of global background values (<12 pg/m3) and showed no increase with altitude. This is the first study to measure air concentrations of persistent organic pollutants (POPs) in Bolivia and one of only a few studies to investigate altitudinal gradients of POPs.     

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.     

Passive-sampler derived air concentrations of persistent organic pollutants on a north-south transect in Chile

Passive air samplers consisting of polyurethane foam (PUF) disks, were deployed in six locations in Chile along a north-south transect to investigate gas-phase concentrations of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and polybrominated diphenyl ethers (PBDEs). The study provides new information on air concentrations of these persistent organic pollutants (POPs) which is lacking in this region. It also provides insight into potential sources and long-range transport (LRT). The samplers were deployed for a 2-month period in five remote sites and one site in the city of Concepción. Mean concentrations (pg m(-3)) for sigmaPCB were 4.7 +/- 2.7 at remote sites and 53 +/- 13 in Concepción. PCB levels at remote sites were related to proximity to urban source regions and/or air back trajectories. With the exception of endosulfan I, mean concentrations (pg m(-3)) of OCPs at background sites were consistently low: 5.4 +/- 1.4 for alpha-HCH, 7.0 +/- 1.1 for gamma-HCH, 2.5 +/- 0.5 for TC, 2.5 +/- 0.6 for CC, 1.9 +/- 1.2 for dieldrin, and less than 3.5 for toxaphene. Endosulfan I showed a decreasing concentration gradient from 99 to 3.5 pg m(-3) from the north to south of Chile. Concentrations of OCPs in the Concepción City were generally 10-20 times higher than at the background sites suggesting continued usage and/or re-emission from past use. For instance, at remote sites, the alpha/gamma ratio (0.76) was typical of background air, while the ratio in Concepción (0.12) was consistent with fresh use of gamma-HCH. Levels of sigmaPBDEs were below the detection limit of 6 pg m(-3) at all sites.     

Characterization of polymer coated glass as a passive air sampler for persistent organic pollutants

The use of thin-film polymer-coated glass surfaces or POGs as passive air samplers was investigated during an uptake experiment in an indoor environment with high levels of gas-phase polychlorinated biphenyls (PCBs). POGs consisted of a micron thick layer of ethylene vinyl acetate (EVA) coated onto glass cylinders. The uptake was initially linear with time and governed by the air-side mass transfer coefficient and surface area of the sampler. This was followed by a curvilinear region and finally a constant phase when equilibrium was established between air and EVA. The high surface area-to-volume ratio of the POGs allowed rapid equilibrium with gas-phase PCBs; equilibration times were on the order of hours for the low molecular weight congeners. The equilibrium concentration was dependent on the EVA-air partition coefficient, K(EVA-A), which was shown to be very well correlated to the octanol-air partition coefficient, K(OA). When POGs of varying thickness were equilibrated with air, the amount of PCB accumulated increased with increasing thickness of the EVA, indicating that uptake was by absorption into the entire polymer matrix. A wind field of 4 m s(-1) resulted in an increased uptake rate by a factor of approximately six compared to uptake in relatively still air. This wind speed effect was diminished, however, when POGs were housed in deployment chambers consisting of inverted stainless steel bowls. Relationships based on the air-side mass transfer coefficient and K(EVA-A) were developed for PCBs that describe the entire uptake profile and allow air concentrations to be determined from the amount of chemical accumulated in the POG. It is believed that these relationships are also valid when POGs are used to detect other classes of persistent organic pollutants.     

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.     

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.     

Evidence for dynamic air-water coupling and cycling of persistent organic pollutants over the open Atlantic Ocean

Ship-board air samples collected between The Netherlands and South Africa in January-February 2001 were analyzed for PCBs and selected organochlorine compounds. Broad latitudinal trends in compound concentrations were influenced by proximity to source areas, land, and air mass origin. Lowest concentrations were observed in the remote south Atlantic (1-32 degrees S), where sigma7PCB concentrations were approximately 10 pg m(-3). Here, a diurnal cycle was noted for some PCB congeners, with the daytime concentrations higher than the nighttime concentrations, typically by a factor of 1.5-2.5. The data are consistent with a close coupling of air-open ocean concentrations, which has important implications for future rates of POP removal from the global "recyclable pool". The observations are discussed in the context of the potential controlling variables. Interactions between the phytoplankton and the dissolved phase are implicated in controlling the observations made here and a hypothesis to explain the cycling trends is presented. However, the precise mechanisms remain unclear; further studies are urgently required to elucidate them.     

Effects of wind and air trajectory directions on atmospheric concentrations of persistent organic pollutants near the Great Lakes

Three different regression models involving air temperature, time, and either wind direction or parametric or nonparametric air trajectory direction were used with concentrations of four representative persistent organic pollutants to quantitate the atmospheric transport of these compounds to the Great Lakes. The local wind and parametric trajectory models predicted an optimal source direction for each compound, whereas the nonparametric trajectory model was based on a hypothesized source region. All three regressions were used to calculate the factor by which the partial pressures of each compound measured at five sampling sites increased when the air came from a particular source direction. Dieldrin, chlordane, polychlorinated biphenyl, and polycyclic aromatic hydrocarbon partial pressures were used with each of these regressions, and the correlation coefficients (r2) were evaluated for each model, for each compound, and for each regression term. In general, with the exception of polycyclic aromatic hydrocarbons at some sites, the explanatory powers of the regressions were not improved by the inclusion of any of these directional terms.     

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.     

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.     

Using passive air samplers to assess urban-rural trends for persistent organic pollutants. 1. Polychlorinated biphenyls and organochlorine pesticides

Passive air samplers were used to investigate urban-rural differences of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) over an integrated time period. Samplers consisting of polyurethane foam (PUF) disks and semi-permeable membrane devices (SPMDs) were housed in protective chambers and deployed at six sites for a 4 month duration in the summer of 2000. The sampling transect originated in downtown Toronto and extended approximately 75 km northward into a rural region. Results for the two types of samplers agreed well with one another. Higher blank levels were encountered for the SPMDs, especially for the OCPs, whereas blanks were very low for the PUF disks. Passive sampler-derived air concentrations were consistent with previous measurements of PCBs and OCPs in the region. The largest urban-rural gradient was observed for PCBs (approximately 5-10 times). Chlordanes also showed an urban-rural gradient, possibly reflecting past usage of chlordane on residential lawns and emissions from treated house foundations. Other OCPs exhibited a rural-urban gradient (dieldrin, endosulfan 1, and DDT isomers), which was attributed either to off-gassing from previously treated agricultural soils (dieldrin and DDTs) or to continued usage in agriculture (endosulfan 1). The results of this study demonstrated the feasibility of using such devices to determine air concentrations of persistent organic pollutants (POPs) and to assess their spatial distribution for time-integrated samples. Data such as this is essential for: model validation and for process research and addressing international monitoring strategies on POPs.     

食品中持久性有机污染物现状及对策研究

当前,生态环境持续恶化问题已经引起国际社会的高度重视,从全球范围内看,环境污染问题的加剧,给人类的身体健康带来了极大的威胁,在此背景下,各国政府针对环境污染对人类身体健康所带来的危害与影响问题加大了研究力度,并以专门机构与部门的设置为进一步解决环境问题探寻出路。而持久性有机污染物(POPs)在农药中的运用,使得农产品农药污染问题加剧,并引起了社会的高度重视。本文就食品中持久性有机污染物的现状进行调查与评价,阐述了持久性有机污染的特征,分析了食品中持久性有机污染物的来源与危害,并针对食品中POPs污染现状进行了分析,最后为如何实现对POPs污染物的有效防治提出了对策。     

双壳贝类中的持久性有机污染物生物标志物的研究及其应用

双壳贝类不仅是中国重要的经济水产品种,因其营底栖和滤食的生活习性,常被作为海洋生态系统的指示物种。持久性有机污染物（P0Ps）具有持久性、易蓄积、难降解等特点,对生物造成消极的影响。生物标志物因对污染物响应灵敏,在生物受到严重损害之前即可显示出明显变化,在环境监测领域应用广泛。本文关注了近年来该领域的研究进展,系统介绍了贝类中的POPs生物标志物、主要类型及其相关技术,并对其存在的问题及下一步发展的趋势进行了分析和展望。     

Coupling passive air sampling with emission estimates and chemical fate modeling for persistent organic pollutants (POPs): a feasibility study for Northern Europe

Passive air samplers (polyurethane foam disks) were deployed at 23 background locations along a broadly west-east transect in 8 northern European countries and analyzed for PCBs, PBDEs, PAHs, and a range of organochlorine pesticides (HCB, DDTs, and DDEs). PCBs and PAHs were highest at the center of the transect (Denmark) and lowest in northern Norway. HCB was relatively uniformly distributed, reflecting its persistence and high degree of mixing in air. Higher DDE and DDT levels occurred in Eastern Europe and at several sites in Central Europe. PBDE levels were generally similar at all sites, but lower for some locations in Eastern Europe and Ireland. Emissions information for PCBs, HCB, and PBDEs was used as input for a multi-media chemical fate model, to generate predicted air concentrations and compare with these measured values. Different scenarios were highlighted by this exercise: (i) country and compound combinations where the national inventory gave predicted air concentrations in close agreement with those measured (e.g., PCBs in the UK); (ii) country and compound combinations where predicted concentrations were well below those measured, but where advection of emissions from elsewhere is likely to be important (e.g., PCBs in Norway); (iii) consistent underestimation of compound concentrations by the emissions modeling (i.e., HCB); and (iv) general overestimation of ambient concentrations (i.e., PBDEs). Air mass trajectory analysis showed the likely role of long-range atmospheric transport (LRAT) on national levels. In general, advection from the south and west of Europe appeared to contribute to ambient POPs levels for countries in the center and northeast of the transect. Guidelines are presented as to how countries that want to assess their POPs source inventories can do so with this relatively cheap initial screening approach.     

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.     

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.