Screening criteria for long-range transport potential of organic substances in water

Screening of long-range transport potential (LRTP) of organic chemicals in water requires the development of criteria in analogy to the existing LRTP criteria for airborne chemicals. According to the Stockholm Convention, compounds mainly partitioning into air are assumed to be prone to LRTP if they have a half-life in air of more than two days. Using mean flow velocities of European rivers (0.7-1 m/s) and of ocean currents running into the Arctic Ocean (0.28-0.9 m/s), we derived corresponding half-life criteria for freshwater and seawater (10 days and 90 days, respectively). Next, we calculated the characteristic travel distance (CTD) of several thousand chemicals from the Canadian Domestic Substances List (DSL) and all current POPs using the multimedia model ELPOS. This shows that the CTD in water dominates the CTD in air only for chemicals that are characterized by a large half-life in water and a low air-water partition coefficient (about 38% of the nonionic organic substances selected from the DSL). In particular, there are substances that are not classified as persistent compounds in water but exhibit higher CTDs for transport in water than for transport in air. Finally, we evaluated whether the LRTP boundary derived from POP reference chemicals has to be revised if LRTP in water is included and found that this boundary can be applied to all organic chemicals regardless of their transport in air or water.     

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.     

Are there other persistent organic pollutants? A challenge for environmental chemists

The past 5 years have seen some major successes in terms of global measurement and regulation of persistent, bioaccumulative, and toxic (PB&T) chemicals and persistent organic pollutants (POPs). The Stockholm Convention, a global agreement on POPs, came into force in 2004. There has been a major expansion of measurements and risk assessments of new chemical contaminants in the global environment, particularly brominated diphenyl ethers and perfluorinated alkyl acids. However, the list of chemicals measured represents only a small fraction of the approximately 30,000 chemicals widely used in commerce (>1 t/y). The vast majority of existing and new chemical substances in commerce are not monitored in environmental media. Assessment and screening of thousands of existing chemicals in commerce in the United States, Europe, and Canada have yielded lists of potentially persistent and bioaccumulative chemicals. Here we review recent screening and categorization studies of chemicals in commerce and address the question of whether there is now sufficient information to permit a broader array of chemicals to be determined in environmental matrices. For example, Environment Canada's recent categorization of the Domestic (existing) Substances list, using a wide array of quantitative structure activity relationships for PB&T characteristics, has identified about 5.5% of 11,317 substances as meeting P & B criteria. Using data from the Environment Canada categorization, we have listed, for discussion purposes, 30 chemicals with high predicted bioconcentration and low rate of biodegradation and 28 with long range atmospheric transport potential based on predicted atmospheric oxidation half-lives >2 days and log air-water partition coefficients > or =5 and < or =1. These chemicals are a diverse group including halogenated organics, cyclic siloxanes, and substituted aromatics. Some of these chemicals and their transformation products may be candidates for future environmental monitoring. However, to improve these predictions data on emissions from end use are needed to refine environmental fate predictions, and analytical methods may need to be developed.     

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.     

The impact of endocrine disruptors on oocyte competence

To date, approximately 60 chemicals have been identified as endocrine disruptors: exogenous agents that interfere with various aspects of natural hormone physiology. The potential reproductive and health hazards of these environmental chemicals have recently generated concern among the scientific community, policy makers and general public. The present review presents and discusses the available evidence that environmental chemicals are causing ovarian toxicity in various species, with particular attention to farm animals. The impact of chronic exposure to endocrine disruptors via food and drinking water cannot be neglected when studying fertility problems in these species. This review focuses attention on the superfamily of organochlorine chemicals, persistent organic pollutants (POPs), because of their persistence in the environment, ability to concentrate up the food chain, continued detection in environmental matrices and ability to be stored in the adipose tissue of animals and humans. Published data clearly indicate that POPs disrupt mammalian oocyte maturation and follicle physiology in every species studied so far, including farm animals. However, as most of the data available still derive from experiments performed on laboratory species or in vitro models, great care should be taken when extrapolations to other species or environmental situations are attempted.     

The missing piece: sediment records in remote Mountain lakes confirm glaciers being secondary sources of persistent organic pollutants

After atmospheric deposition and storage in the ice, glaciers are temporary reservoirs of persistent organic pollutants (POPs). Recently, the hypothesis that melting glaciers represent secondary sources of these pollutants has been introduced by investigations of the historical trend of POPs in a dated sediment core from the proglacial Alpine Lake Oberaar. Here, the hypothesis is further confirmed by the comparison of sediment data gathered from two Alpine lakes with a glaciated and a nonglaciated hydrological catchment. The two lakes (Lake Engstlen and Lake Stein in the Bernese Alps in Switzerland) are situated only 8 km apart at similar altitude and in the same meteorological catchment. In the nonglacial lake sediment of Lake Engstlen, PCBs and DDT (polychlorinated biphenyls and dichlorodiphenyl trichloroethane) levels culminated with the historic usage of these chemicals some 30-50 years ago. In the glacial Lake Stein, this peak was followed by a reincrease in the 1990s, which goes along with the accelerated melting of the adjacent glacier. This study confirms the hypothesis of glaciers being a secondary source of these pollutants and is in accordance with the earlier findings in Lake Oberaar.     

食品中PCDD/Fs和dlPCBs的检测方法研究进展

二恶英化合物是典型的高毒性持久性有机污染物,可在食物链中不断累积,最终引发食品安全问题,严重威胁人类健康。近年来,食品中二恶英类化合物的分析筛选和监测控制等问题一直是人们研究的重点。本文综述了二恶英类化合物的致毒机制和几种用于分析检测二恶英类化合物方法的基本原理和优缺点,以及国内外分析检测的最新研究进展,并对我国开展二恶英分析监测提出了建议和展望。     

Potential contamination of shipboard air samples by diffusive emissions of PCBs and other organic pollutants: implications and solutions

Air samples were taken onboard the RRS Bransfield on an Atlantic cruise from the United Kingdom to Halley, Antarctica, from October to December 1998, with the aim of establishing PCB oceanic background air concentrations and assessing their latitudinal distribution. Great care was taken to minimize pre- and post-collection contamination of the samples, which was validated through stringent QA/QC procedures. However, there is evidence that onboard contamination of the air samples occurred,following insidious, diffusive emissions on the ship. Other data (for PCBs and other persistent organic pollutants (POPs)) and examples of shipboard contamination are presented. The implications of these findings for past and future studies of global POPs distribution are discussed. Recommendations are made to help critically appraise and minimize the problems of insidious/diffusive shipboard contamination.     

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.     

Has the burden and distribution of PCBs and PBDEs changed in European background soils between 1998 and 2008? Implications for sources and processes

Background soils were collected from 70 locations on a latitudinal transect in the United Kingdom and Norway in 2008, ten years after they had first been sampled in 1998. The soils were analyzed for polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCs), to see whether there had been any change in the loadings or distributions of these persistent organic pollutants (POPs). The same transect has also been used to sample air between the mid-1990s and the present, so the air and soil spatial and temporal trends provide information on air-soil transfers, source-receptor relationships, long-range atmospheric transport (LRAT), and recycling phenomena. Comparisons of the 2008 and 1998 data sets show a general decline for PBDEs in surface soil, and a smaller averaged net decline of PCBs. Changes between the years were observed for total POP concentrations in soil and also for correlations with site and sample characteristics assumed to affect those concentrations. POP concentrations were correlated to distance and strength of possible sources, a relationship that became weaker in the 2008 data. Fractionation, a commonly discussed process for the global cycling of POPs was also lost in the 2008 data. As in 1998, soil organic matter content continues to have a strong influence on the loadings of POPs in surface soils, but changes in the PCB loads were noted. These factors indicate an approach to air-surface soil equilibrium and a lessening of the influence of primary sources on POP concentrations in soil between 1998 and 2008.     

Predicting long-range transport: a systematic evaluation of two multimedia transport models

The United Nations Environment Program has recently developed criteria to identify and restrict chemicals with a potential for persistence and long-range transport (persistent organic pollutants or POPs). There are many stakeholders involved, and the issues are not only scientific but also include social, economic, and political factors. This work focuses on one aspect of the POPs debate, the criteria for determining the potential for long-range transport (LRT). Our goal is to determine if current models are reliable enough to support decisions that classify a chemical based on the LRT potential. We examine the robustness of two multimedia fate models for determining the relative ranking and absolute spatial range of various chemicals in the environment. We also consider the effect of parameter uncertainties and the model uncertainty associated with the selection of an algorithm for gas-particle partitioning on the model results. Given the same chemical properties, both models give virtually the same ranking. However, when chemical parameter uncertainties and model uncertainties such as particle partitioning are considered, the spatial range distributions obtained for the individual chemicals overlap, preventing a distinct rank order. The absolute values obtained for the predicted spatial range or travel distance differ significantly between the two models for the uncertainties evaluated. We find that to evaluate a chemical when large and unresolved uncertainties exist, it is more informative to use two or more models and include multiple types of uncertainty. Model differences and uncertainties must be explicitly confronted to determine how the limitations of scientific knowledge impact predictions in the decision-making process.     

Persistent organic pollutants in fish: biomonitoring and cocktail effect with implications for food safety

The impact of anthropogenic wastes of persistent organic pollutants (POPs) on the marine environment has increased in the last decades. POPs include polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCs). To assess the levels of these POPs in the wild fish population, pelagic and benthopelagic predator fish species were selected as biomonitors. For detection and quantification of POPs in muscular tissues, a simple extraction through Accelerated-Solvent-Extraction (ASE) with an ‘in-line’ clean up purification approach was applied, followed by a GC–MS/MS analysis. Concentrations of sum DDT, sum HCH and endrin correlated with all PCB concentrations. Significant differences among fish species were found for all OCs and all PCBs except PCB 31 and 101. Blackspot seabream had the highest PCB concentrations; OCs were highest in tuna. Due to major concerns regarding fish population losses and the possible human chronic exposure to contaminated fish, studies addressing combined effects of multiple POPs (‘cocktail effect’) should be implemented. Our data motivate further experimental and observational studies in fish to define adequate baseline levels for cumulative human exposure and potential role of these contaminants for food safety.     

可蓄积到食物中的持久性有机污染物及其检测技术研究进展

持久性有机污染物(POPs)可通过大气、水、土壤等介质在环境和人体积累,对人的身体健康和生命安全构成威胁。本文综述了持久性有机污染物的种类、危害和治理技术。详细介绍了目前检测方法的研究进展和热点,对各种方法的优缺点进行了分析。旨在为持久性有机污染物的检测提供参考。     

Plant uptake of non ionic organic chemicals

Plant uptake of organic chemicals is an important process when considering the risks associated with land contamination, the role of vegetation in the global cycling of persistent organic pollutants, and the potential for industrial discharges to contaminate the food chain. There have been some significant advances in our understanding of the processes of plant uptake of organic chemicals in recent years; most notably there is now a better understanding of the air to plant transfer pathway, which may be significant for a number of industrial chemicals. This review identifies the key processes involved in the plant uptake of organic chemicals including those for which there is currently little information, e.g., plant lipid content and plant metabolism. One of the principal findings is that although a number of predictive models exist using established relationships, these require further validation if they are to be considered sufficiently robust for the purposes of contaminated land risk assessment or for prediction of the global cycling of persistent organic pollutants. Finally, a number of processes are identified which should be the focus of future research.     

我国母乳中持久性有机污染物机体负荷研究进展

母乳是世界卫生组织推荐的作为人生物监测的理想基质,也是履行《关于持久性有机污染物的斯德哥尔摩公约》成效评估的主要基质。为评估普通人群持久性有机污染物机体负荷水平及履约成效评估需要,我国自2007年以来连续开展母乳监测工作,重点对多氯代二苯并二噁英和多氯代二苯并呋喃、多氯联苯、多溴二苯醚等典型持久性有机污染物开展相关监测。获得了表征我国普通人群机体负荷水平的代表性数据以及时空分布状况,为我国履约工作提供了有力支撑。     

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).     

持久性有机污染物膳食摄入的研究进展

持久性有机污染物(POPs)在环境中能够普遍存在并且通过食物链能够富集,已经影响到了食品的安全。由于人们通过膳食摄入持久性有机污染物是一个主要的因素,所以人们在日常膳食的过程中持久性有机污染物在一定程度上对人们的健康存在着潜在健康风险。本文综述了近年来国内外有关人们通过膳食摄入不同POPs的膳食暴露情况,包括持久性有机氯农药、二噁英及其类似物、多溴联苯醚、全氟有机化合物等,并且将不同国家和地区的人们对这些化合物膳食摄入量的不同进行了比较和分析。在此基础上,评估了人们对不同POPs膳食摄入的健康风险,希望为进一步开展和健康风险评估相关的研究提供依据。     

ABAM, a model for bioaccumulation of POPs in birds: validation for adult herring gulls and their eggs in Lake Ontario

An Avian BioAccumulation Model (ABAM) of persistent organic pollutant (POP) uptake and elimination in adult life-stage of birds was validated by simulation of concentrations of DDE, dieldrin, mirex, and HCB in herring gull eggs in Lake Ontario for the years 1985, 1990, and 1992. These chemicals represented a range of whole-body half-lives of 82-265 days in the gull. Dietary intake of POPs by a female gull was simulated by a dynamic bioenergetics model which included dependence on temperature, photoperiod, egg production, and feeding chicks. Concentrations in the two main prey fish of the gull in Lake Ontario were used for POP exposure. Clearance from the female was based on a two compartment toxicokinetic model. Egg concentrations were estimated from egg/whole body female concentration ratios. Simulated concentrations were compared to measured concentrations in gull eggs from 4 different colonies in the northern part of Lake Ontario. Simulations using a diet of 81% fish and 19% uncontaminated food resulted in the best fit with least variance among predicted and measured data. The mean ratio of predicted to measured concentrations in eggs was 1.0 +/- 0.27 among chemicals, years, and colonies for this exposure scenario. This result was in excellent agreement with field assessments of herring gull diet composition in Lake Ontario of 80-82% fish. The ability to perform accurate a priorisimulations for the range of test conditions employed in the validation constituted a rigorous test of the soundness of the model's structure and parameterization. With species-specific adjustments, ABAM can be regarded as a general model for lipophilic POPs bioaccumulation in birds.