我国持久性有机污染物状况及宏观对策

从近几十年来中国POPs的使用情况出发 ,系统分析了典型POPs物质在农产品、土壤、母乳、水体和沉积物等介质中的污染状况。分析了国际上控制POPs的动向以及中国采取的应对策略 ,并对中国控制POPs污染的宏观对策进行探讨。从总体上看 ,目前中国有关POPs的政策法规体系正逐渐与国际接轨 ,但还很不完善 ,缺乏针对性和对污染事故的责任、处罚等明确措施 ,控制POPs对环境的污染与危害 ,制定行之有效的环境监管措施势在必行。     

Linking molecular interactions to consequent effects of persistent organic pollutants (POPs) upon populations

There is great concern about the potential adverse effects of persistent organic pollutants (POPs) on wildlife. Threats come from toxic chemicals with long half lives in the environment that were released worldwide on a large scale in the past, at a time when little was known of their potential effects on the environment. Although the Stockholm Convention (2001) initially targeted 12 POP chemicals--organochlorinated compounds--for the reduction/elimination of releases, the problem can be extended to persistent toxic substances more generally. Therefore, identifying early biomarkers for possible toxic effects to populations in the long term is a challenge for ecotoxicologists. Regional decline in fish, bird and/or invertebrate populations resulting from exposure to POPs, such as DDT (dichlorodiphenyltrichloroethane), PCBs (polychlorinated biphenyls), PCDD (polychlorinated dibenzo-p-dioxins), and TBT (tributyltin) could be related to some biochemical, endocrine and physiological effects in individuals. Examples of known mechanisms of POP ecotoxicity will be illustrated in the first part. The next parts will be devoted to (i) data gaps and limitations to extrapolation from lower to higher levels of biological organization, (ii) confusing factors in field studies and the combined effects of persistent toxic pollutants and (iii) recommendations for the design and interpretation of experimental studies.     

Atmospheric concentrations, occurrence and deposition of persistent organic pollutants (POPs) in a Mediterranean coastal site (Etang de Thau, France)

Atmospheric concentrations and deposition fluxes of PCDD/F and PCB have been evaluated over a 1-year period in a Mediterranean coastal lagoon (Etang de Thau, France). Indicative PBDE air concentrations in the hot season are also reported in this work. ∑2,3,7,8-PCDD/Fs and ∑18PCBs (gas + particulate) air concentrations ranged from 67 to 1700 fg m⁻³ and from 13 to 95 pg m⁻³, respectively whereas ∑8PBDEs (gas + particulate) summer time levels varied from 158 to 230 pg m⁻³. The PCDD/F and PCB atmospheric occurrence over Thau lagoon and subsequent inputs to the surface waters are determined by an assemble of factors, being the seasonality of atmospheric concentration, the air mass origin and meteorological conditions important drivers. Total (wet + dry) ∑2,3,7,8-PCDD/Fs and ∑18PCBs deposition fluxes to Thau Lagoon waters are 117 and 715 pg m⁻² d⁻¹, respectively.     

Serum concentrations of persistent organic pollutants (POPs) in the inhabitants of a Sicilian city

Background

Polychlorinated biphenyls (PCBs) and organochlorine pesticides are common environmental contaminants that have been associated with human health problems.

Objectives

To assess serum concentrations of several organochlorine contaminants in general population living in a city with an ancient agricultural tradition and to identify possible exposure sources in Sicily.

Methods

A cross-sectional study was conducted on 101 individuals. Each participant answered a face-to-face questionnaire submitted by well-trained personnel and provided a serum sample which was analyzed for the concentrations of PCBs, HCB, HCHs and DDTs by using gas-chromatography coupled with mass spectrometry.

Results

HCB, p,p′-DDE, PCB 138, PCB 153 and PCB 180 were detected in more than 80% of the study participants. The ng g⁻¹ lipid median concentrations were: 18.6 for HCB; 175.1 for p,p′-DDE; 22. for PCB 138; 32.5 for PCB 153 and 23.0 for PCB 180. PCB 153 and PCB 138, PCB 138 and PCB 180, PCB 153 and PCB 180, and p,p′-DDE and HCB showed a high correlation each other (p < 0.05). HCB and p,p′-DDE concentrations were significantly higher in subjects >49 years old (adj-p = 0.03 in 50-69 years old and adj-p < 0.001 in >69 years old, respectively) whereas PCB 138, PCB 153 and PCB 180 concentrations were higher in males (adj-p = 0.03), in subjects >69 years old (adj-p = 0.04) and in current smokers (adj-p = 0.04).

Conclusions

The present study shows that serum concentrations of organochlorine compounds detected in subjects living in a small Sicilian city with ancient agricultural tradition are similar to those found in subjects living in urban areas of other countries. However, further investigations are needed to compare data from rural/urban areas in the same country, assessing correlations between serum concentrations of several chemical compounds and potential health effects in general population.     

Fourth WHO-coordinated survey of human milk for persistent organic pollutants (POPs): Belgian results

Persistent organic pollutants (POPs) are chemicals that accumulate in the food chain and are toxic to humans and wildlife. The fourth World Health Organization (WHO) survey on POP levels in human milk (2006-2009) aims to provide baseline and trend information on human exposure to POPs. So far Belgium participated in all three previous rounds (1988, 1992, 2001). Whereas the first three rounds focused on determination of dioxins and PCBs in pooled (mixed) samples, the fourth survey comprised the analyses of individual milk samples for nine "basic POPs" (chlorinated pesticides and indicator PCBs) and of pooled milk samples for "basic POPs", "advanced POPs" (dioxins and dioxin-like PCBs) and "optional POPs" (polybrominated diphenylethers [PBDEs], polybrominated dioxins and dibenzofurans [PBrDD/F], mixed halogenated dioxins and dibenzofurans [PXDD/F] and hexabromocyclododecane [HBCD]). For the Belgian participation human milk samples were collected during the summer of 2006 from 197 women between 18 and 30 years old distributed over all Belgian provinces. The individual samples were analyzed in a Belgian Laboratory for "basic" POPs. A pooled sample was made from 178 individual samples and analyzed by the WHO Reference Laboratory for the "basic, advanced and optional" POPs. The results indicate that most organochlorinated pesticides banned 25-30 years ago were below or around detection limits in Belgian human milk samples although DDE was still found at low levels in all samples. Over the last five years the levels of marker PCBs and PCDD/Fs in Belgian human milk decreased, respectively, by 58% and 39%. For some of the other emerging or older compounds recent international data are needed to allow comparison. This shows the importance of international studies as run by WHO.     

Global-scale environmental transport of persistent organic pollutants

In order to realistically simulate both chemistry and transport of atmospheric organic pollutants, it is indispensable that the applied models explicitly include coupling between different components of the global environment such as atmosphere, hydrosphere, cryosphere and soil system. A model with such properties is presented.

The atmospheric part of the model is based on the equations in a general contravariant form which permits easy changes of the coordinate system by redefining the metric tensor of a specifically employed coordinate system. Considering a need to include explicitly the terrain effects, the terrain following spherical coordinate system is chosen from among many possible coordinate systems. This particular system is a combination of the Gal-Chen coordinates, commonly employed in mesoscale meteorological models, and the spherical coordinates, typical for global atmospheric models.

In addition to atmospheric transport, the model also simulates the exchange between air and different types of underlying surfaces such as water, soil, snow, and ice. This approach permits a realistic representation of absorption and delayed re-emission of pollutants from the surface to the atmosphere and, consequently, allows to capture hysteresis-like effects of the exchange between the atmosphere and the other components of the system. In this model, the most comprehensive numerical representation of the exchange is that for soil. In particular, the model includes a realistic soil module which simulates both diffusion and convection of a tracer driven by evaporation from the soil, precipitation, and gravity.

The model is applied to a long-term simulation of the transport of pesticides (hexachlorocyclohexanes in particular). Emission fluxes from the soil are rigorously computed on the basis of the realistic data of the agricultural application. All four modelled systems, i.e. atmosphere, soil, hydrosphere and cryosphere, are driven by objectively analysed meteorological data supplemented, when necessary, by climatological information. Therefore, the verification against the observed data is possible. The comparison of the model results and the observations taken at remote stations in the Arctic indicates that the presented global modelling system is able to capture both trends and short-term components in the observed time series of the concentrations, and therefore, provides a useful tool for the evaluation of the source–receptor relationships.     

Global pilot study for persistent organic pollutants (POPs) using PUF disk passive air samplers

Polyurethane foam (PUF) disks were deployed at global background sites, to test logistical issues associated with a global monitoring network for persistent organic pollutants (POPs). alpha-HCH, exhibited relatively high and uniform concentrations (17-150 pg/m3) at temperate and arctic sites with elevated concentrations associated with trans-Pacific inflow. Concentrations were much lower (<5 pg/m3) in Bermuda, Chile and Cape Grim. Concentrations for gamma-HCH, the main component of lindane, were spatially similar to the alpha-HCH pattern but lower in magnitude (typically, <10 pg/m3). Chlordane concentrations (sum of cis-chlordane, trans-chlordane and trans-nonachlor) were also low (<10 pg/m3). Dieldrin concentrations were in the range 2-25 pg/m3 at most sites but elevated in Bermuda. Back trajectories suggest that advection from Africa and the US may contribute. Endosulfan, a popular current-use pesticide, exhibited highest concentrations ranging from tens to hundreds of pg/m3. There was good agreement between duplicate samplers at each site and PUF disk-derived air concentrations agreed with high volume data. Few logistical/analytical problems were encountered in this pilot study.     

Endocrine effects of sublethal exposure to persistent organic pollutants (POPs) on silver carp (Hypophthalmichthys molitrix)

Silver carp (Hypophthalmichthys molitrix) samples were collected from five selected sites that represent diverse levels of downgraded persistent organic pollutants (POPs) contamination in Ya-Er Lake in October 1999. Hepatic ethoxyresorufin-O-deethylase (EROD) and UDP glucuronosyltransferase (UDPGT) activities, hepatosomatic index (HSI), hepatic retinoids, serum thyroid hormones were measured. It was found that hepatic retinol and serum free 3,5,3'- tetraiodothyronine (FT3) significantly increased (P < 0.01) when both hepatic EROD and UDPGT activities significantly declined (P < 0.01) from pond 1 to 5 with decrease in the degree of pollution. This significant negative correlation (P < 0.01) suggests that the persistent organochlorinated contaminants could induce hepatic EROD and UDPGT activities, alter retinoid and thyroid hormone homeostasis, and finally lead to the reduction of retinol and FT3, the two biologically active forms of retinoids and thyroid hormone in silver carp of Ya-Er Lake.     

Partitioning of persistent organic pollutants (POPs) between human serum and breast milk: A literature review

The literature was reviewed to assess the relationship between the lipid adjusted concentration in human serum and breast milk (expressed as the serum/milk ratio) of a broad range of POPs in paired samples. Thirteen studies were identified, including seven studies that reported serum/milk ratios for polychlorinated dibenzo-dioxins and -furans (PCDD/Fs), ten for polychlorinated biphenyls (PCBs), five for polybrominated diphenyl ethers (PBDEs), and five for organochlorine pesticides (OCPs). Mean serum/milk ratios ranged between 0.7 and 25 depending on the compound and congener. For PCDD/Fs, PCBs and PBDEs, a clear trend of increasing mean serum/milk ratio by increasing molar volume, hydrophobicity and number of halogen substitutes was observed. The mean serum/milk ratios reported by the 13 studies summarized here will aid comparison between human POPs exposure studies using either serum or milk samples. More studies are needed to allow a valid comparison between data obtained from analysis of breast milk and serum samples for a broader range of POPs. Furthermore such studies may shed light on compound specific factors as well as other determinants that may affect the partitioning and partition kinetics of POPs between serum and breast milk.     

Low levels of persistent organic pollutants (POPs) in New Zealand eels reflect isolation from atmospheric sources

Polychlorinated biphenyls (PCBs) and organic pesticides (i.e., DDTs) were measured in long finned eels (Anguilla dieffenbachii) in 17 streams on the west coast of South Island, New Zealand. Very low levels of PCBs and low levels of ppDDE were found. The concentrations of PCBs and ppDDE were not correlated within sites indicating that different processes determined the levels of the two pollutants in New Zealand eels. The PCBs probably originate from atmospheric transport, ppDDE levels are determined by land use and are higher in agriculture areas. The low contamination level of these aquatic systems seems to be a function of a low input from both long and short-range transport as well as few local point sources. No correlation could be found between lipid content and persistent organic pollutants (POPs) concentration (as shown in previous studies) in the eels which could be explained by low and irregular intake of the pollutants.     

Comparison of active and passive sampling for the determination of persistent organic pollutants (POPs) in sewage treatment plants

Semipermeable membrane devices (SPMDs) and conventional active sampling methods were used for the sampling of wastewater from the wastewater treatment plant of Thessaloniki, northern Greece. The occurrence of 22 POPs was shown by both sampling methods. The most abundant compounds were heptachlor-exo-epoxide and PCBs-52; -101 and -180. Concentrations of POPs detected by active sampling and those estimated by the SPMDs matched very well in some cases, but significant mismatches were also observed. Regression analysis of the results detected by both methods showed moderate correlations. The highest uptake rate of hydrophobic compounds by SPMDs was observed for analytes with log K(OW) between 5.5 and 6.0. Our data suggest that active and passive sampling are complimentary, and that at least for the outflow of a WWTP, SPMDs could be used for the routine monitoring of compounds that are listed at the Water Framework Directive of the European Commissions.     

Persistent organic pollutants (POPs): state of the science

The environmental chemistry and ecotoxicology of persistent organic pollutants (POPs) are fascinating areas of scientific research. Our objective in this paper is to provide a brief, focussed overview of what constitutes a POP, highlight the harmful effects they may have on biota, make some comments on their environmental sources and analysis, their environmental trends and processes, their movement through foodchains and highlight some important regional-and global-scale environmental transport issues. Finally, we offer some personal thoughts on some current and future areas of scientific enquiry on POPs.     

A comparison of Alpine emissions to forest soil and spruce needle loads for persistent organic pollutants (POPs)

The project MONARPOP analysed the concentrations of semivolatile organic compounds (SVOCs) in two important sink compartments, needles of Norway spruce (Picea abies [L.] Karst.) and forest soil from 40 remote Alpine forest sites in Austria, Germany, Italy, Slovenia and Switzerland.In the present study the load of PCDD/F, PCB, PBDE, PAH, HCB, HCH and DDT in the Alps calculated on the basis of measured data are compared with their estimated emissions in the Alpine region. It comes out that the masses of the studied pollutants stored in the forests are higher than the corresponding emissions in the Alpine area indicating that the Alps are a sink for POPs advected from surrounding areas. It is assumed that local emissions of PCDD/F and PAH deriving from biomass burning are probably underestimated and that the pool of these pollutants in the forests represents the accumulation over some decades.     

Regional dynamics of persistent organic pollutants (POPs) in the Pearl River Delta, China: implications and perspectives

The mass transport budgets of 1,1,1-trichloro-2,2-bis(chlorophenyl)ethane (p,p′-DDT) and decabromodiphenyl ether (BDE-209) in the Pearl River Delta, South China were calculated based on previously collected data. Residual p,p′-DDT, mostly related to historical use, has largely settled into soil (780,000 kg), while the soil BDE-209 inventory (44,000 kg) is considerably smaller. Conversely, large amounts of BDE-209 currently used in numerous commercial products have resulted in a much higher atmospheric depositional flux of BDE-209 (28,100 kg/yr) relative to p,p′-DDT (310 kg/yr). The soil inventory of p,p′-DDT is predicted to decrease to half of its current value after 22 years, and the percent area containing soil p,p′-DDT at levels exceeding the effects range-medium (27 ng/g) will decrease from 40% to 20%. Finally, soil BDE-209 inventory will reach an equilibrium value of 940 tons in ∼60 years, when BDE-209 levels in 50% of soil will be above an equivalent risk guideline value (125 ng/g).     

The elaboration of the 'Stockholm convention' on persistent organic pollutants (POPs): a negotiation process fraught with obstacles and opportunities

The conclusion in December 2000 of the negotiations for the 'Stockholm Convention' can clearly be labeled as a success. The Convention text was negotiated in merely five sessions of the Intergovernmental Negotiating Committee (INC) and accomplished after its fifth session despite the fact that numerous controversial issues, such as the inclusion of new substances under the ambit of the Convention, the acknowledgement of the precautionary principle or--clearly most controversial--the financing mechanisms, remained to be resolved. This paper attempts to provide a somewhat impressionistic account of the negotiations leading to the conclusion of the 'Stockholm Convention' as experienced by the members of the Swiss delegation participating in the negotiations of the INC. Besides a brief overview on the 'history' of the negotiations, it will focus on some issues of special interest--and controversy--to the negotiators, and finally attempt to provide an outlook on the future of the work performed by the INC and the implementation of the Convention. Issues of special interest are environmental policy issues, capacity building and financing, trade-related issues, precautionary principles, and technical and scientific issues.     

Further studies on the uptake of persistent organic pollutants (POPs) by polyurethane foam disk passive air samplers

Passive air samplers (PAS) can be used to monitor semi-volatile organic compounds in the atmosphere. Polyurethane foam (PUF) disks are a popular sampling medium because they have a high retention capacity for such compounds. This paper reports a highly time-resolved uptake study, to derive uptake rate data under field conditions, and investigate the effects of using different foam densities on the uptake rate. PUF disks were deployed alongside an active sampler, for periods of up to 12 weeks. The uptake rates were measured for a range of gas- and particle-bound persistent organic pollutants (polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)), of different properties, to explore whether gas–particle partitioning affected uptake rate. Uptake rates for two different densities of foam (0.021 and 0.035 g cm^?3) were not statistically significantly different from each other. Uptake rates of light PCBs averaged ～6.5 m³ day^?1, somewhat higher than in previous studies; higher wind speeds and lower temperatures in this study are the likely reason for this difference. The study showed: i) the uptake rate of the compound with lowest K_OA considered in this study (PCB-28/31) declined in the later weeks, indicating an approach to equilibrium; ii) uptake rates of lighter BDEs and heavier PCBs (compounds of intermediate K_OA in this study) remain similar throughout the study period, indicating that they are not approaching equilibrium during the 12-week-study; iii) uptake rates were typically: ～8 m³ day^?1 for PCB-52; ～9.5 m³ day^?1 for PCB-95; ～11 m³ day^?1 for BDE-28 and ～2 m³ day^?1 BDE-99. The latter compound has an important particle-bound component and this lowers the sampling rate compared to predicted uptake rates for compounds which are in the gas phase only. It is shown that knowledge of gas–particle partitioning is needed to correct for this effect, and to improve predicted uptake rates.     

The global re-cycling of persistent organic pollutants is strongly retarded by soils

'Persistent organic pollutants' (POPs) are semi-volatile, mobile in the environment and bioaccumulate. Their toxicity and propensity for long-range atmospheric transport (LRAT) has led to international bans/restrictions on their use/release. LRAT of POPs may occur by a 'single hop' or repeated temperature-driven air-surface exchange. It has been hypothesised that this will result in global fractionation and distillation-with condensation and accumulation in polar regions. Polychlorinated biphenyls (PCBs)--industrial chemicals banned/restricted in the 1970s--provide a classic illustration of POP behaviour. A latitudinally-segmented global PCB inventory has been produced, which shows that approximately 86% of the 1.3 x 10(6) tonnes produced was used in the temperate industrial zone of the northern hemisphere. A global survey of background surface soils gives evidence for 'fractionation' of PCBs. More significantly, however, very little of the total inventory has 'made the journey' via primary emission and/or air-surface exchange and LRAT out of the heavily populated source regions, in the 70 years since PCBs were first produced. Soils generally occlude PCBs, especially soils with dynamic turnover of C/bioturbation/burial mechanisms. This limits the fraction of PCBs available for repeated air-soil exchange. The forested soils of the northern hemisphere, and other C-rich soils, appear to be playing an important role in 'protecting' the Arctic from the advective supply of POPs. Whilst investigations on POPs in remote environments are important, it is imperative that researchers also seek to better understand their release from sources, persistence in source regions, and the significant loss mechanisms/global sinks of these compounds, if they wish to predict future trends.