持久性有机污染物(POPs)的环境问题与研究进展

对持久性有机污染物(persistentorganicpollutants:POPs)的定义、来源和特征进行了介绍。阐述了POPs对环境安全性构成威胁的原因。分析了持久性有机污染物,特别是12类优先控制的"dirtydozen"的环境污染状况,并分析了这些物质在全球大气、水体和土壤中存在的量和来源。这些物质在不同生物体内的浓度存在差异,反映出它们在食物链上的生物累积和放大,也加剧了对环境和人体的毒害作用。总结回顾了有关POPs的相关基础研究,并对将来继续深入研究和对环境监测的指导意义进行了展望。     

Selective extraction of persistent organic pollutants from environmental matrices

An attempt is made to determine the bioavailability of persistent organic pollutants (POP's) in environmental matrices. The approach is based on the use of the Hildebrand Solubility Parameter, and its individual parameters of hydrogen bonding, dispersion and polarity to select weak and strong solvents to extract POP's from soil matrices. The approach has been applied to both spiked soils and certified reference materials. Initial results indicate that it is possible to fractionate POP's from soil matrices based on their ability to be extracted from soil by particular solvents.     

Assessment of health risk associated with persistent organic pollutants in water

This paper presents the results of analyses of water samples taken from water intakes supplying one of the districts located near the city of Wroc?aw. Surprisingly high concentrations of polychlorinated biphenyls and chloroorganic pesticides, classified as persistent organic pollutants (POPs), were detected in the monitored sites. Basing on the analytical and toxicological data, the individual health risks related to carcinogenic effects (excess cancer risk over a lifetime) in humans were assessed, resulting from direct ingestion of community water. Also noncarcinogenic effects resulting from exposure to the examined POPs were determined. The conservative approach to risk assessment, taking into account a safety margin for data incompleteness, was adopted. The carcinogenic risk was found to slightly exceed the unconditionally acceptable risk of 10^?6 in the case of polychlorinated biphenyls and hexachlorocyclohexane, for all the inhabitant populations. The determined values of noncarcinogenic effects expressed by hazard quotient and hazard index indicate that the water pollutants and their concentrations do not cause an increase in noncarcinogenic incidences in the inhabitants using the monitored water sources.     

Penguin colonies as secondary sources of contamination with persistent organic pollutants

Although long-range atmospheric transport has been described as the predominant mechanism for exposing polar regions to persistent organic pollutants (POPs), recent studies have suggested that bird activity can also contribute substantially to contaminant levels in some environments. However, because the species so far reported have all been migratory, it has not been demonstrated conclusively whether locally elevated contamination represents transport from lower latitudes by the migrating birds or, alternatively, redistribution and concentration of contaminants that were already present in the high-latitude environments. The present study demonstrates, for the first time, that several POPs are present in elevated concentrations in an environment frequented by a non-migratory species (Adélie penguins) that spends its entire life in the Antarctic. Levels of POPs, such as p,p'-DDE, hexachlorobenzene (HCB), chlordanes (CHLs) and polychlorinated biphenyls (PCBs), were 10 to 100-fold higher in soil samples from penguin colonies than from reference areas. This significant difference is likely related to local penguin activity, such as a higher abundance of guano and the presence of bird carcasses. This hypothesis is also supported by a higher percentage of persistent congeners (PCB 99, 118, 138 and 153) in the soil from the colonies compared to the reference areas. This profile of PCB congeners closely matched profiles seen in penguin eggs or penguin blood.     

Air monitoring of persistent organic pollutants in the Great Lakes: IADN vs. AEOLOS

When designing a monitoring campaign, one has to consider many factors in the decision to perform a long-term synoptic monitoring program or a short-term intensive study. Each has its own advantages and disadvantages. This paper compares and contrasts the information obtained from two studies conducted on the Laurentian Great Lakes. One, the Integrated Atmospheric Deposition Network (IADN), is a long-term synoptic monitoring study and the other, the Atmospheric Exchange Over Lakes and Oceans (AEOLOS), was a short-term intensive study. The advantages of long-term synoptic monitoring programs are providing greater spatial information, the relative influence of long and short-range transport on the regional background, gross loadings representative of the majority of each lake and long-term temporal trends. Short-term intensive studies provide more information on the processes governing sources, transport and deposition, such as the urban/industrial influence on adjacent large water bodies, specific sources to an urban/industrial area and short-term fluctuations in concentrations due to meteorology, source strength and photochemical reactions. Using information provided by both the IADN and AEOLOS studies, areas of urban influence are predicted for each of the five Great Lakes.     

Uptake and bioavailability of persistent organic pollutants by plants grown in contaminated soil

This paper assesses the uptake of persistent organic pollutants (POP's) into plants. In particular, uptake of alpha-endosulfan, beta-endosulfan and endosulfan sulfate from lettuce. The lettuce plants were grown on compost that had previously been contaminated at 10 and 50 microg g(-1) per POP. The soil was slurry spiked by adding the appropriate amount of POP in acetone in an approximate ratio of 1 ratio 2, w/v soil ratio solvent. The solvent was left to evaporate at ambient temperature for 24 hours. Lettuce plants were grown under artificial daylight for 12 hours a day. The influence of soil ageing on the recovery of POP's from spiked soil samples was also assessed. The average recovery of endosulfan compounds from slurry spiked soil (10, 20 and 40 microg g(-1)) was consistent (92.9 +/- 4.4% for n= 9). However, ageing of endosulfan compounds on the slurry spiked soil resulted in lower recoveries (average losses were 12.5% after 14 days ageing of slurry spiked soil). The uptake of POP's was assessed by measuring the amount of endosulfan compounds in roots and leaves from lettuce plants after 10, 20 and 33 days. In addition, control plants grown in uncontaminated soil were monitored and analysed. It was found that endosulfan compounds were present in the roots of all lettuce plants irrespective of soil spike level or age of plant. In the 33 day lettuce plants where the soil was spiked at the highest level (50 microg g(-1)) endosulfan compounds were determined in the leaves. The root to leaf ratio was found to be 3.1 for alpha-endosulfan, 46.0 for beta-endosulfan, and 24.3 for endosulfan sulfate. Spiked lettuce samples were subjected to in vitro gastrointestinal extraction to assess the bioavailability of endosulfan compounds. No detectable endosulfan compounds were determined in the gastric extracts while small quantities (range 0.06-0.12 microg g(-1)) were found in the intestinal extraction. All samples (soil and lettuce) were extracted using pressurised fluid extraction and analysed using gas chromatography with mass selective detection.     

An assessment of persistent organic pollutants in Scottish coastal and offshore marine environments

Concentrations of persistent organic pollutants (POPs), including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were determined in sediment and biota (fish liver) from around Scotland. The concentrations were investigated using assessment criteria developed by OSPAR and ICES. Organic contaminant concentrations, PAHs, PCBs and PBDEs in sediment, and PCBs and PBDEs in fish liver, were significantly higher in the Clyde compared to all other sea areas. This is mainly due to historic industrial inputs. Highest PCB and PAH concentrations were found in the strata furthest up the Clyde estuary, with concentrations of POPs in these strata being at levels such that there is an unacceptable risk of chronic effects occurring in marine species. Furthermore, for PAHs in Clyde sediment there was a significant negative gradient going from north to south towards the open sea. PAH and PCB concentrations in sediment and biota in all other Scottish sea areas (except for PCBs in sediment from East Scotland) were unlikely to give rise to pollution effects, being below relevant assessment criteria. Although no assessment criteria are available for PBDEs, the concentrations observed in Scottish sediments were low with all congeners below the limit of detection (LoD; 0.03 μg kg(-1) dry weight) in 140 out of a total of 307 samples analysed. Where PBDEs were detected, the dominant congeners were BDE47 and BDE99. PBDEs were detected in fish livers, although concentrations were less than 150 μg kg(-1) lipid weight in all sea areas except the Clyde where concentrations ranged between 8.9 and 2202 μg kg(-1) lipid weight. Few trends were detected in contaminant concentrations in biota or sediment at any Scottish site with more than five years data. Downward trends were detected in PAHs in sediment from the Clyde, Irish Sea and Minches and Malin Sea and PCBs in fish liver from the Moray Firth. Rules were developed for the aggregation of the contaminant data across a sea area. An overall assessment for each sea area was then assigned, looking at the frequency of sites or strata within each sea area that were above or below the relevant assessment criteria. Overall the status of the various sea areas, with respect to the assessed POPs, can be considered to be acceptable in that they were below concentrations likely to result in chronic effects for all sea areas except the Clyde.     

An assessment of the bioavailability of persistent organic pollutants from contaminated soil

A procedure to assess the bioavailability of persistent organic pollutants (POPs) from soil samples has been developed. The procedure is based on the use of simulated in vitro gastrointestinal extraction to remove POPs from soil matrices. The level of recovery, using this approach, is assessed following liquid-liquid extraction (LLE) and analysis by gas chromatography-mass selective detection (GC-MSD). The remaining soil residue is then extracted using pressurised fluid extraction (PFE) followed by GC-MSD analysis to assess the residual fraction. The residual fraction is monitored to determine the unavailable fraction i.e. not available for absorption in the gastrointestinal tract of humans. The procedure was applied to four soil samples i.e. an aged, spiked soil and three certified reference materials (CRMs) contaminated with POPs. Recoveries of pesticides (lindane, endosulfan I, endrin, DDE, DDD and endosulfan II), phenols (cresol, TCP and PCP), and base neutral compounds (hexachloroethane, acenaphthene, dibenzofuran, fluorene and hexachlorobenzene) from aged, spiked soil following extraction with gastric fluid ranged from 0.8 to 8.3% while following intestinal extraction ranged from 5.5 to 13.5%, irrespective of POP. Recoveries of pesticides (lindane, endosulfan I, endrin, DDE, DDD and endosulfan II) from CRM 805-050 following extraction with gastric fluid were below the limit of detection while following intestinal extraction ranged from 5.3 to 12.8%. Recoveries of phenols (cresol, TCP and PCP) from CRM 401-225 following extraction with gastric fluid ranged from 1.6 to 2.0% while following intestinal extraction ranged from 4.1 to 5.4%. Recoveries of base neutral acid analytes (hexachloroethane, acenaphthene, dibenzofuran, fluorene and hexachlorobenzene) from CRM 107-100 following extraction with gastric fluid ranged from 1.4 to 4.0% while following intestinal extraction ranged from 6.6 to 12.7%. It has been found that the majority of POPs present i.e. >75%, would be excreted if consumed and not be absorbed in the gastrointestinal tract of humans.     

Occupational and indoor air exposure to persistent organic pollutants: a review of passive sampling techniques and needs

Exposure to persistent organic pollutants (POPs) and related compounds such as PCBs, brominated flame retardants, organochlorine pesticides and PAHs is regarded as an important environmental risk factor for humans. Recently concerns about POPs resulted in the international protocol called the Stockholm Convention on POPs. Air quality standards (indoor, outdoor and occupational) for PAHs and other POPs will also be applied in the EU in the future. This will bring requirements for monitoring, to check for compliance and to reduce human exposures to POPs. This can occur from point sources and in various microenvironments, indoors, outdoors and in workplaces. Monitoring can be undertaken either by an active (pumped) method or using a passive (diffusive) air sampling (PAS) device. To date, PAS for POPs have mainly been used as integrating (long-term) samplers for ambient (outdoor) air. However, there are several reasons to develop PAS for monitoring of POPs in occupational and indoor environments. We discuss the potential advantages, limitations and developments needed, so that PAS can be used reliably and routinely indoors and in occupational settings for POPs.     

Spatial distribution and source identification of persistent pollutants in marine sediments of Hong Kong

A data matrix, obtained during a 3-year monitoring period (2007–2009) from 45 sampling sites in Hong Kong marine, was subjected to determine the spatial characterization and identify the sources of main pollutants. Indicator analyses indicated that polycyclic aromatic hydrocarbons (PAHs), nickel, manganese, and arsenic (As) were at safe levels. Five heavy metals (zinc, lead, cupper, cadmium, chromium (Cr)) were moderate to severe enrichment at some sites. Inner Deep Bay and Victoria Harbor were considered as hot spots for PAHs and the heavy metals, while Tolo Harbor was highly polluted by the heavy metals. Cluster analysis classified the 45 sampling sites into three groups, representing different pollution levels. Principal component analysis/factor analysis identified four principal components (PCs) and explained 84.9 % of the total variances, standing for persistent pollution, N factor, P and Cr factor, and As factor, respectively. Group A was highly polluted by persistent pollution, group B was the less polluted group, and subgroup B1 was less affected by PC3 and PC4 than subgroup B2. Group C, considered as the moderately polluted group, was greatly affected by N factor or persistent pollution, while subgroup C2 received more N pollution than subgroup C1.     

持久性有机污染物在中国的环境监测现状

论述了持久性有机污染物在中国的监测现状,包括检测方法、标准值以及污染现状等,内容涉及空气、水、沉积物、土壤和生物等介质。提出了中国在此领域存在的问题和发展方向。     

Levels of persistent organic pollutants (POPs) in a coastal northern Norwegian population with high fish-liver intake

Recent research has again raised the issue regarding the potential health effects of long term exposure to persistent organic pollutants (POPs) in the context of a risk-benefit analysis. There remains clear evidence of the beneficial effects of fish consumption on public health and in particular fatty fish with its essential fatty acids. In addition to providing fatty acids, fish fat constitutes an essential source to vitamin D for the northern Norwegian population. Norwegian Food Control Authorities have recommended that children and women of childbearing age should not consume fish liver due to the risk associated with high intake of POPs. The aim of this study was to assess the influence of fish liver intake on the levels of PCBs and chlorinated pesticides in a rural coastal community (n = 31) in northern Norway, applying a cross-sectional design. The geometric mean plasma levels of sum of PCBs (14 congeners) and p,p'-DDE was found to be 558 microg kg(-1) lipids and 179 microg kg(-1) lipids, respectively. These levels were not significantly affected by the reported intake of fish liver, when age and gender were considered. Age in particular, but also gender were significant predictors for most compounds. When merging the dataset with an urban population with considerable lower intake of fish liver, the intake of cod liver still did not significantly affect the levels of PCBs and p,p'-DDE when adjusted for age and gender. Age and gender remain the strongest predictors of plasma levels of POPs in this study whereas fish liver intake was not significantly associated with the POPs.     

The levels and composition of persistent organic pollutants in alluvial agriculture soils affected by flooding

The concentrations and composition of persistent organic pollutants (POPs) were determined in alluvial soils subjected to heavy flooding in a rural region of Poland. Soil samples (n?=?30) were collected from the upper soil layer from a 70-km² area. Chemical determinations included basic physicochemical properties and the contents of polychlorinated biphenyls (PCBs), hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs) and polycyclic aromatic hydrocarbons (PAHs, 16 compounds). The median concentrations of Σ7PCB (PCB28?+?PCB52?+?PCB101?+?PCB118?+?PCB138?+?PCB153?+?PCB180), Σ3HCH (α-HCH?+?β-HCH?+?γ-HCH) and Σ3pp′(DDT?+?DDE?+?DDD) were 1.60?±?1.03, 0.22?±?0.13 and 25.18?±?82.70 μg kg^?1, respectively. The median concentrations of the most abundant PAHs, phenanthrene, fluoranthene, pyrene, benzo[b]fluoranthene and benzo[a]pyrene were 50?±?37, 38?±?27, 29?±?30, 45?±?36 and 24?±?22 μg kg^?1, respectively. Compared with elsewhere in the world, the overall level of contamination with POPs was low and similar to the levels in agricultural soils from neighbouring countries, except for benzo[a]pyrene and DDT. There was no evidence that flooding affected the levels of POPs in the studied soils. The patterns observed for PAHs and PCBs indicate that atmospheric deposition is the most important long-term source of these contaminants. DDTs were the dominant organochlorine pesticides (up to 99 %), and the contribution of the parent pp′ isomer was up to 50 % of the ΣDDT, which indicates the advantage of aged contamination. A high pp′DDE/pp′DDD ratio suggests the prevalence of aerobic transformations of parent DDT. Dominance of the γ isomer in the HCHs implies historical use of lindane in the area. The effect of soil properties on the POP concentrations was rather weak, although statistically significant links with the content of the <0.02-mm fraction, C_total or N_total were observed for some individual compounds in the PCB group.     

Detection of hazardous pollutants in chrome-tanned leather using locally developed laser-induced breakdown spectrometer

K?z?l?rmak River has been used as Ankara??s drinking water source for approximately 1.5?years. Therefore, this region??s water, sediment, and fish samples are measured for detecting the heavy metals. This is important for the current situation as well as the future in terms of potential impact. The amount of heavy metals in drinking water should be within the limited values; otherwise, the accumulation of heavy metals will cause many problems to living organisms. Especially high levels of arsenic, cadmium, nickel, mercury, etc. are very dangerous to freshwater ecosystems as for human if the water is being use as drinking water. In this study, water, sediment samples, muscle, and gills of three fish species (Capoeta tinca, Capoeta capoeta, Leuciscus cephalus) were analyzed for the presence of heavy metals such as (Al, Fe, As, Cd, Ni, Mn, Se, Si) to determine present accumulation levels and possible toxic effect. The accumulation pattern of heavy metals in the water, sediment, and fish tissue follows the sequence: Si > Fe > Al > Mn > As > Ni > Se > Cd, Fe > Al > Mn > Ni > As > Se > Cd, and Fe > Al > Mn > As > Ni > Si > Cd. In addition, the detected concentrations of heavy metals in the K?z?l?rmak and Delice Rivers are compared with other heavy metal studies in the other main rivers and lakes in Turkey.     

A complex investigation of the extent of pollution in sediments of the Sava River: part 2: persistent organic pollutants

Sediment pollution of the biggest Danube tributary, the Sava River, was investigated within the sixth framework European Union project “Sava River Basin: Sustainable Use, Management and Protection of Resources” (SARIB). The extent of pollution was estimated by determining the amount of inorganic and persistent organic pollutants in sediment samples at 20 selected sampling sites along the Sava River. For the purpose of clarity, the findings are presented and published separately (part I: selected elements and part II: persistent organic pollutants). This study presents an investigation into the presence of organic pollutants in the Sava River sediment. According to the Water Framework Directive, the following persistent organic pollutants were investigated: polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB), selected chlorinated pesticides and organotin compounds. The results reveal that PAHs were present in moderate concentrations (sum of 16 PAHs: up to 4,000 ng g^???1) and their concentrations increased downstream. Concen trations of PCB were low (sum of seven indicator PCBs: below 4 ng g^???1) and among the pesticides analyzed only p,p-dichlorodiphenyltrichloroethane was found in moderate concentrations at two sampling sites in Croatia (up to 3 ng g^???1) and hexachlorobenzene was found in a high concentration in the city of Belgrade (91 ng g^???1), although the use of these persistent pesticides has been banned for decades. Repeated sampling at the same location revealed point pollution near Belgrade. Among the organic pollutants surveyed, organotin compounds were not detected. Overall results reveal the presence of persistent organic pollutants in 20 of the Sava River sediments tested that is, in general, comparable or lower than the levels in the Danube River and other moderately polluted European rivers.     

Screening for Stockholm Convention persistent organic pollutants in the Bosna River (Bosnia and Herzogovina)

The Stockholm Convention, which aspires to manage persistent organic pollutants (POPs) at the international level, was recently ratified in Bosnia and Herzegovina (BiH). Despite this fact, there is in general a paucity of data regarding the levels of POPs in the environment in BiH. In the present study, screening for POPs was conducted in one of the country’s major rivers, the Bosna. A two-pronged approach was applied using passive samplers to detect the freely dissolved and bioavailable concentrations in the water phase and sediment analysis to provide an integrated measure of historical contamination. At several places along the river, the concentrations of polycyclic aromatic hydrocarbons (PAH) were high and exhibited potential for both chronic and acute effects to biota. River water also showed elevated concentrations of PAH, up to 480 ng L^?1 near the city of Doboj, and diagnostic ratios suggested combustion sources for the contamination present in both types of sample. The levels of the other contaminants measured—polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers—were generally low in the water phase. However, PCBs and some OCPs were present in river sediments at levels which breach the international criteria and thus suggest potential for ecological damage. Additionally, the levels of heptachlor breached these criteria in many of the sites investigated. This study presents the first screening data for some of these Stockholm Convention relevant compounds in BiH and reveals both low concentrations of some chemical groups, but significant point sources and historic contamination for others.     

Effects of sampling techniques on physical parameters and concentrations of selected persistent organic pollutants in suspended matter

This study focusses on the effect of sampling techniques for suspended matter in stream water on subsequent particle-size distribution and concentrations of total organic carbon and selected persistent organic pollutants. The key questions are whether differences between the sampling techniques are due to the separation principle of the devices or due to the difference between time-proportional versus integral sampling. Several multivariate homogeneity tests were conducted on an extensive set of field-data that covers the period from 2002 to 2007, when up to three different sampling techniques were deployed in parallel at four monitoring stations of the River Rhine. The results indicate homogeneity for polychlorinated biphenyls, but significant effects due to the sampling techniques on particle-size, organic carbon and hexachlorobenzene. The effects can be amplified depending on the site characteristics of the monitoring stations.     

利用Triolein-半渗透膜采样技术测定淮河水中的有毒有机污染物

利用 Triolein 半渗透膜采样技术 ( Triolein SPMD)采集了淮河信阳、淮南断面水样 ,测定了采样器中多氯联苯、多环芳烃、取代苯等有毒有机污染物浓度。污染物在 SPMD酯中高浓度富集 ,使其定性和定量更加容易和准确。根据SPMD酯 水分配平衡理论 ,进一步估算得到目标污染物在水中的平均浓度。本研究证明 Triolein SPMD技术可用于水中多氯联苯、多环芳烃、取代苯等污染物的采集和定量分析 ,可在我国的优先污染物监测、控制工作中发挥作用。     

Estimating overall persistence and long-range transport potential of persistent organic pollutants: a comparison of seven multimedia mass balance models and atmospheric transport models

Two different approaches to modeling the environmental fate of organic chemicals have been developed in recent years. The first approach is applied in multimedia box models, calculating average concentrations in homogeneous boxes which represent the different environmental media, based on intermedia partitioning, transport, and degradation processes. In the second approach, used in atmospheric transport models, the spatially and temporally variable atmospheric dynamics form the basis for calculating the environmental distribution of chemicals, from which also exchange processes to other environmental media are modeled. The main goal of the present study was to investigate if the multimedia mass balance models CliMoChem, SimpleBox, EVn-BETR, G-CIEMS, OECD Tool and the atmospheric transport models MSCE-POP and ADEPT predict the same rankings of the overall persistence (P(ov)) and long-range transport potential (LRTP) of POPs, and to explain differences and similarities between the rankings by the mass distributions and inter-compartment mass flows. The study was performed for a group of 14 reference chemicals. For P(ov), the models yield consistent results, owing to the large influence of phase partitioning parameters and degradation rate constants, which are used similarly by all models. Concerning LRTP, there are larger differences between the models than for P(ov), due to different LRTP calculation methods and spatial model resolutions. Between atmospheric transport models and multimedia fate models, no large differences in mass distributions and inter-compartment flows can be recognized. Deviations in mass flows are mainly caused by the geometrical design of the models.     

Spatial scales of variation in lichens: implications for sampling design in biomonitoring surveys

The variability of biological data is a main constraint affecting the quality and reliability of lichen biomonitoring surveys for estimation of the effects of atmospheric pollution. Although most epiphytic lichen bioindication surveys focus on between-site differences at the landscape level, associated with the large scale effects of atmospheric pollution, current protocols are based on multilevel sampling, thus adding further sources of variation and affecting the error budget. We test the hypothesis that assemblages of lichen communities vary at each spatial scale examined, in order to determine what scales should be included in future monitoring studies. We compared four sites in Italy, along gradients of atmospheric pollution and climate, to test the partitioning of the variance components of lichen diversity across spatial scales (from trunks to landscapes). Despite environmental heterogeneity, we observed comparable spatial variance. However, residuals often overcame between-plot variability, leading to biased estimation of atmospheric pollution effects.