摘要
持久性有机污染物(Persistent Organic Pollutants, POPs)是一类具有难降解性、生物蓄积性、半挥发性和高毒性的天然或人工合成的有机物,对人体健康和生态环境存在着严重的威胁,POPs排放到环境中后,会在环境中各介质或不同介质之间经历各种迁移转化行为,这些行为过程对POPs的区域环境归趋及其人体暴露风险具有重要的影响作用。
POPs的半挥发性使其易从土壤、水体挥发到大气环境中,并以蒸气形式存在于空气中或吸附于大气颗粒物上；POPs所具有的难降解性,使其一旦排到环境,能在环境介质中滞留较长的时间。POPs的上述两种特性,使其可以在环境中不断地挥发、沉降、再挥发,从而进行长距离迁移,导致其在全球各区域环境介质中的广泛存在。了解人类所处环境受POPs的污染状况、各种环境介质中POPs的污染浓度水平特征和分布规律,分析各种环境介质中POPs的污染来源、迁移过程及迁移能力是当今环境科学领域的热点和难点研究问题。
兰州位于中国半干旱地区,常年有沙尘暴现象发生,且有着特殊的气象和地理条件,典型POPs在兰州地区的环境行为特征还有待揭示。做为典型POPs的有机氯农药(Organochlorine Pesticides, OCPs)曾在兰州地区被大量使用,且近期的研究表明环境介质中还存在这些农药残留。兰州重工业的发展、大量化石燃料的燃烧等都使得兰州地区典型POPs多环芳烃、二恶英等污染物的排放显著增加。本文以几种典型POPs作为目标化合物,研究了其在兰州地区环境中的大气、土壤污染浓度水平、气-土交换特征、长距离迁移和环境总持久性等环境行为,拟为半干旱的兰州地区典型POPs的生态风险评价及污染治理提供科学依据。
研究方法及内容：
采集兰州地区冬、春和夏季的大气样品和不同土地利用类型的表层土壤,分析总悬浮颗粒物(Total Suspended Particulate, TSP)浓度水平、大气和土壤中OCPs六六六(1,2,3,4,5,6-hexachlorocyclohexane, HCH或BHC)的α、β、γ和δ四种异构体以及滴滴涕(2,2-bis (4-Chlorophenyl)-1,1,1-trichloroethane, DDT)的主要异构体及衍生物4,4’-DDE、2,4'-DDT、4,4'-DDD和4,4’-DDT的含量及其季节变化趋势、大气中气态和颗粒态间的分配特征,利用滴滴涕和其主要衍生物之间的比例关系初步解析土壤中滴滴涕的源汇情况,通过与文献资料中的数据比较,分析近年来兰州地区大气和土壤中六六六和滴滴涕浓度水平的变化趋势,并与国内外城市相比该研究区域大气和土壤的污染程度；采用逸度的概念及逸度商和逸度分数的判断标准,初步研究兰州地区六六六和滴滴涕在气-土间的交换状态,并讨论了采用逸度商作为判断标准所存在的不确定性或潜在误差；借助TaPL3模型研究兰州地区典型POPs (2,3,7,8-TCDD、γ-HCH、BaP、HCB和p, p'-DDT)的长距离迁移潜力和环境总持久性及两者之间的关系,并与国外的同类研究结果进行了比较,以2,3,7,8-TCDD为例,对模型的关键参数和输出结果的不确定性进行研究。
研究结论：
(1)兰州地区大气中六六六和滴滴涕的浓度水平与文献数据比较发现,近年有较大幅度降低,与国内其他城市冬季和春季大气中的六六六和滴滴涕含量的比较,兰州市大气中六六六和滴滴涕的污染处于中下等级水平,大气受污染程度较轻。在采集的24个大气样品中,有10个可以满足大气总悬浮颗粒物TSP环境质量2级标准,样品的平均TSP质量浓度为426μg/m3；除了β-HCH外,其它几种污染物六六六及滴滴涕(a-HCH、γ-HCH、δ-HCH、2, 4'-DDT、4,4'-DDE、4,4'-DDD和4,4’-DDT)的气态浓度水平都是随着季节的更替而变化,气态浓度依次按冬季、春季和夏季增大,即随温度的升高而含量增加,表现出大气浓度对温度的依赖性。三个季度大气中六六六和滴滴涕均主要以气态形式存在,气态含量平均占了大气总含量的85%。
(2)兰州地区2009年大部分土壤中六六六和滴滴涕的平均含量满足土壤环境质量标准值的一级,本部校区样点的滴滴涕含量超过一级标准,满足二级标准,说明自禁止使用六六六和滴滴涕以来,土壤中的残留量已经变的较低。其他城市相比,土壤中滴滴涕和六六六的残留量较低。由3月和6月的样品分析结果：土壤中六六六和滴滴涕含量的变化没有很明显的季节性。研究的6个样点中,有3个点的p, p'-DDT/p, p'-DDE比值大于1,其中安宁区河湾村苗圃的p, p'-DDT/p, p'-DDE的比值最大,推断该点可能存在禁用后新施用滴滴涕的可能。2009年兰州地区土壤中六六六的残留量较1982年下降了1-3个数量级,部分污染物较2004年也有所下降。
(3)兰州地区典型POPs气-土交换研究表明：4,4’-DDD表现为从大气中向土壤净沉降,土壤从大气中吸收该污染物；δ-HCH的气-土交换已经达到或接近平衡状态；其余六种污染物(α-HCH、β-HCH、γ-HCH、2,4'-DDT、4,4'-DDE和4,4’-DDT)有明显偏离气-土平衡状态的趋势,推测其气-土交换状态是从土壤向大气中的净挥发,即土壤为源。
(4)兰州地区典型POPs长距离迁移潜力(Long-Range Transport Potential, LRTP)和环境总持久性(Overall Persistence, Pov)研究结果表明：2,3,7,8-TCDD、γ-HCH、BaP、HCB和p, p'-DDT通过大气的特征迁移距离(Characteristic Travel Distance, CTD)分别为126、934、117、13307和122km,在大气中的总停留时间分别为1421、1082、1413、3949和1387d；通过水体的CTD分别为6633、119000、16249、16658和20667km,在水体中的总停留时间分别1584、1551、2711、4428和3988d；污染物的LRTP和Pov没有直接的联系；2,3,7,8-TCDD在大气中的CTD的分布比其在水体中的CTD分布更集中,在大气和水体中的总停留时间的分布则相似。与国外同类结果比较,通过大气的CTD明显偏低,其对应的Pov明显偏大；通过水体的CTD明显偏高,其对应的Pov稍小一些。
Persistent Organic Pollutants (POPs) are organic compounds of natural or anthropogenic origin, which are characterized by hard degradation, bioaccumulation, semi-volatility and high toxicity. As a result, POPs pose a serious threat to human health and the ecological environment In addition, when POPs be emitted to the environment, they can have serious effects on the environmental fate and health exposure risk because of some behaviors and characteristics including transfer and transformation between different environmental media.
Semi-volatile POPs can easily evaporate into air from soil and water, and exist in the vapor phase and absorpt into particles phase or aerosol. Moreover, once the POPs have been discharged into the environment they can stay in the environmental media for a long time due to their characteristic of non-degradation. Because of the two characteristics of semi-volatility and non-degradation of POPs, they can emit into air and,then deposit, futhermore evaporate into air and then deposit again, so they will be transported through atmosphere for a long-range distance and can be found in the global environmental media. Therefore, to study the pollution situation, to know the characteristics of pollutants concentration level and distrubution, and to identify the souces, transfer potential and fate become the hotspot problems in environmental field in recent years.
Lanzhou is located in the semi-arid area of China, in which the sandstorms commonly occur all over the year. Lanzhou city also has special meteorological and geographical conditions, so it is significent to reveal the characteristics of environmental behaviors of POPs in Lanzhou area. Organochlorine pesticides are a kind of tapical POPs and were used as insecticides in large quantities in Lanhou area previously. Recent researches have revealed that there are still some residual in environmental media in Lanzhou area. In addition, the development of heavy industry, the large-volume fossil fuel combustion and other human activities result in the remarkable increase in discharge quantity of poly cyclic aromatic hydrocarbons、dioxin and other pollutants in Lanhou area.This paper tries to chooses several typical POPs as aim compounds and Lanzhou city as study area, and to study their pollution characteristics of air and soil, the air-soil exchange, and the environmental behaviors of long-range transport and overall environmental persistence. Therefore, this study will provide some scientific data for the ecological risk assessment and pollution contron of typical POPs in semi-arid Lanzhou area.
The research methods and contents in this paper are as follows:
The aims of this work are to collect the air and top-soil samples in winter,spring and summe, respectively, in Lanzhou area, to analyse the concentration levels of TSP, four isomers of HCH (α、β、γandδ-HCH),the isomers and metabolite of DDT (4,4'-DDE、2,4'-DD、4, 4'-DDD和4,4'-DDT) from these samples, to identify their variation trends of concentrations with season, to reveal the gas-particle partitioning characteristic in air, and the initially sources and sinks of DDTs in the soil by using the ratio of DDTs and its metabolite, to analyse the variation trends of concentrations of HCH and DDTs in the air and soil samples in recent years, to compare the pollution levels of HCH and DDTs between the Lanzhou city with other cities by refering the relevant literature data, to investigate the states of air-soil exchange of HCH and DDT in soil of Lanzhou area by using the concept of fugacity and the criteria of fugacity quotient and fugacity fraction, to discuss the uncertainties or potential errors by using fugacity quotient as the criteria; to estimate the long-range transport potential (LRTP) and overall persistence (Pov) of typical POPs (2,3,7,8-TCDD、γ-HCH、BaP、HCBand p, p'-DDT) through air and water in semi-arid Lanzhou area by TaPL3 model, to discuss the relationship between the characteristic travel distance (CTD) and Pov, to compare the results with foreign researches, to examine and evaluate the model uncertainties against physical/chemical properties and environmental paramaters by a sensitivity study and the Monte Carlo method for 2,3,7, 8-TCDD.
The conclusions are summarized as follows:
(1) The concentrations of HCHs and DDTs in the atmosphere of Lanzhou tend to decrease largely in recent years by comparing the study data with literature data. The concentration of HCH and DDT in Lanzhou are under intermediate level by comparing the concentrations in air of winter and spring of Lanzhou with the data of other cities, and as a results, the air pollution is lightly in Lanzhou area. In this study, there are ten air samples results can be granted the two-level of The National Ambient Air Quality Standards in all the twenty-four air samples, and the mean TSP concentration is 426μg/m3. For other pollutants, the gaseous concentrations obviously vary with the alternation of season except forβ-HCH, in addition, and the gaseous concentrations showed an increasing trend from larger to small in order of winter、spring and summer, namely the air concentrations increasing depend on the temperature rising. The HCHs and DDTs in the air samples mainly exist in the gas phase with about 85% percent of total air concentrations.
(2) The average concentrations of HCHs and DDTs in soil of Lanzhou area meet the one-level of The National Soil Quality Standards, which reveals that the residual amounts of HCHs and DDTs in soil show relatively low level since they have been banned. The residual amounts of HCHs and DDTs in soil of Lanzhou area are lower compared with that of other cities. The concentrations variations of HCHs and DDTs don't have obvious seasonality according to the monitoring results of samples in March and June. The ratio of p, p'-DDT/p, p'-DDE is more than one in three sampling sites and the highest ratio is p, p'-DDT/p, p'-DDE in Anning sites, which indicate that it is possible that there are new DDTs uses after their prohibition. The residual levels of HCHs and DDTs in soil of Lanzhou area already have been declined to from 1 to 3 orders of magnitude compared with that of 1982, moreover, some pollution levels for other aim compounds have also been declined compared with that of 2004.
(3) The study results of air-soil exchange for tapical POPs in Lanzhou are as follows:4, 4'-DDD is absorbed to soil from air, which indicate that it displays a net deposition from air to soil. Forδ-HCH, the air-soil exchange probably close to the equilibrium. And for other pollutants (α-HCH、β-HCH、γ-HCH、2,4'-DDT、4,4'-DDE和4,4'-DDT), they have obvious deviation trend from air-soil equilibrium, which suggest that the air-soil exchange probably show a net volatilization from soil to air, namely soil is source.
(4) The Simulating results for LRTP and Pov of typical persistent organic pollutants in Lanzhou area suggest that the CTD values of 2,3,7,8-TCDD、γ-HCH、BaP、HCB and p, p'-DDT are 126、934、117、13 307 and 122 km, and the Pov values are 1421、1082、1413、3949 and 1387 d in atmosphere, respectively. Meanwhile, the CTD values of 2,3,7,8-TCDD、γ-HCH、BaP、HCB and p, p'-DDT are 6633、119000、16249、16658 and 20667 km, and the Pov values are 1584、1551、2711、4428 and 3988 d in water, respectively. In addition, there is not obvious relationship between LRTP and Pov, and the distributions of the CTD values in atmosphere of 2,3,7,8-TCDD are more intentionally than those in water, but the distributions of the Pov values of 2,3,7, 8-TCDD in atmosphere are similar to those in water. Futhermore, comparing with study results of foreign researches, the CTD values of 2,3,7,8-TCDD in atmosphere is lower considerably than that in water but the Pov in both air and water are relatively higher.
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