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当前使用农药和卤代阻燃剂在渤海区域的时空分布特征研究
Alternative TitleSpatial distribution and seasonal variation of current-use pesticides (CUPs) and halogenated flame retardants (HFRs) in the Bohai Sea
刘琳
Subtype硕士
Thesis Advisor唐建辉
2018-05-15
Training institution中国科学院烟台海岸带研究所
Degree Grantor中国科学院大学
Place of Conferral中国科学院烟台海岸带研究所
Degree Name工程硕士
Degree Discipline环境工程
Keyword当前使用农药 渤海 气-水交换 入海河流 Current-use pesticides the Bohai Sea Air-sea exchange River
Abstract部分传统使用的农药(historical-use pesticides,HUPs)和卤代阻燃剂(halogenated flame retardants,HFRs)因其生物累积性、生物毒性、难降解性以及长距离迁移特性在全球范围内被禁用或限制使用。随着传统农药和阻燃剂的淘汰或大幅减产,一些新型农药(如氟乐灵、百菌清、三氯杀螨醇等)和新型阻燃剂(如十溴二苯乙烷(DBDPE)、1,2-二(2,4,6-三溴苯氧基)乙烷(TBE)等)被广泛使用。然而,这些当前使用的农药(current-use pesticides,CUPs)和新型卤代阻燃剂(novel halogenated flame retardants,NHFRs)不仅仅在使用区域,如:城市和乡村的大气及水环境中被检测到,还在未曾使用的偏远地区,如:高山、极地和偏远海区被检出。这说明它们同样具有长距离大气传输的能力,会对环境造成污染。目前对于这些新型持久性有机污染物关注较少,CUPs和NHFRs在中国北方海域更是鲜有报道。 本文以渤海为研究区域,以四种当前使用的农药(CUPs)(氟乐灵、百菌清、毒死蜱和三氯杀螨醇)和卤系阻燃剂(HFRs)为主要研究对象,分别在2016年8月,2016年12月和2017年2月采集渤海表层海水和低层大气样品,研究其在海水和大气中的时空分布特征,并对其来源做简单探究。 氟乐灵、百菌清、毒死蜱和三氯杀螨醇虽然都属于疏水性化合物,但在大气气相和海水溶解相中具有较高的检出率和浓度。大气气相中毒死蜱为浓度最高的化合物(59.06 ± 126.94 pg m-3),海水溶解相中,三氯杀螨醇有最高浓度(115.94 ± 123.16 pg L-3)。CUPs在大气和海水中浓度的季节变化特征为春、夏季高,冬季低。春、夏季农药的大量使用是影响其环境浓度的主要原因,夏季高温加剧农药挥发也是影响因素之一。渤海区域CUPs的重污染区在莱州湾和渤海湾附近,一是由于两大海湾沿岸有许多生产农药的工厂,化工生产带来的废气、废水、废渣等能够通过各种途径进入渤海,二是黄河、海河等河流的输入可能会加剧莱州湾和渤海湾的农药污染。通过CUPs的气-水交换特征显示:渤海既能够成为百菌清污染的“汇”,也能成为大气中氟乐灵和毒死蜱污染的二次源。 BDE209是传统阻燃剂PBDEs中主要的检出物质,而在新型阻燃剂中,DBDPE是主要的检出物质。BDE209和DBDPE在海水和大气中都呈现显著相关,说明DBDPE作为BDE209的替代物,由于相似的结构和化学性质使得它们在环境中的行为、排放方式、排放源都具有一致性。DPs在大气和表层海水中也有一定量的检出,其浓度分别为0.39 ± 0.62 pg m-3和1.29 ± 1.89 pg L-1。由f(syn)=syn-DP/(syn-DP + anti-DP)可以得到DPs的排放类型接近工业产品,但比工业产品的比值稍低,可能是anti-DP的稳定性较高,syn-DP在排放的过程中发生了一定程度的转化。BDE209、DBDPE和DPs都在莱州湾和渤海湾附近有着较高的浓度。莱州湾是我国BFRs的最大产区,化工生产过程中产生的污染物通过大气传输、沉降、河流输入、直接排放等途径进入渤海,从而造成污染。三类物质浓度的季节变化呈现冬季高于夏季的现象,一是冬季颗粒物增加,且温度降低,增加了污染物吸附在颗粒物上的比例,二是冬季由西北陆地吹向东部海洋的风会将污染物带到渤海上空,沉降入海;当然,夏季强降水的冲刷也是导致颗粒物减少,污染浓度降低的重要因素。 总的来说,CUPs和HFRs都属于新型有机污染物,具有明显的POPs属性,目前在中国北方海域研究较少。陆源污染是POPs的主要污染类型,大气和海洋是半挥发性有机物的主要蓄积库,环渤海区域作为两类化合物在我国重要的生产和使用源区,经研究发现,渤海表层海水及上空大气中都有不同程度的目标物检出。CUPs在气相和溶解相中检出比例较高,说明易随气流或洋流迁移到达偏远地区和海区;而HFRs主要存在于颗粒相中,说明易在迁移过程中发生沉降进入土壤或沉积物,形成污染物浓度的积累。因此,研究CUPs和HFRs在渤海区域的浓度和时空分布特征,能够为不同类型的新型POPs在海水和大气中的行为提供借鉴,为渤海区域海洋环境管理和环渤海地区人类健康做出指导。
Other AbstractSome historical-use pesticides (HUPs) and halogenated flame retardants (HFRs) are prohibited or strictly restricted for their bioaccumulative, toxic to organism, persistent in environment and potential for long-range atmospheric transport (LRAT) properties. With the elimination and phased out of traditional pesticides and flame retardants, some of their substitutes or alternatives, such as trifluralin, chlorothalonil, DBDPE and TBE, have been widely used globally. These current-use pesticides (CUPs) and novel halogenated flame retardants (NHFRs) have been detected in areas where they were using, such as the atmosphere and water in urban and rural areas. In addition, they were also found in remote areas like high mountains, polar regions, and pelagic zones. It indicates that they have the ability of long range transport and pollute the environment. Up to now, very limited data are available about the environmental fates of CUPs and NHFRs, especially in the Bohai Sea, North China. CUPs (trifluralin, chlorothalonil, chlorpyrifos and dicofol) and HFRs (PBDEs, NBFRs and DPs) in the low atmosphere and surface seawater were taken during research cruises on the Bohai Sea in August and December 2016 and February 2017. Spatial distribution and seasonal variation in atmosphere and seawater were studied, and their sources are briefly explored. Trifluralin, chlorothalonil, chlorpyrifos and dicofol are hydrophobic compounds, but they have high detection rates and concentrations in the gas and dissolved phases. Chlorpyrifos was the most abundant CUPs in the gas phase (59.06 ± 126.94 pg m-3) and dicofol had the highest concentration in dissolved phase in the seawater (115.94 ± 123.16 pg L-3). Seasonal variations of CUPs showed higher concentrations in spring and summer than those in winter. It is partially attributed to their using seasons, and partially to volatilization caused by high temperature. High levels were detected in the Bohai Bay (BB) and Laizhou Bay (LB). On the one hand, there are many factories along the two bays, which produce large amount of pesticides; on the other hand, the input from the rivers, such as the Yellow River and the Haihe River, aggravate the CUPs pollution in the LB and BB. Air-seawater exchange showed that atmospheric deposition was a significant input pathway of chlorothalonil into the Bohai Sea, whiles volatilization was the secondary source of trifluralin and chlorpyrifos from the seawater to the atmosphere. BDE209 and DBDPE were the predominant compounds of PBDEs and NBFRs, respectively, and their showed significant correlation. As a substitute for BDE209, DBDPE was assumed to has common behaviors and sources with BDE 209 due to similar structure and physio-chemical properties. DPs were commonly detected in the atmosphere and surface water, with the mean values of 0.39 ± 0.62 pg m-3 and 1.29 ± 1.89 pg L-1, respectively. The ratio f(syn)=syn-DP/(syn-DP + anti-DP) can be used to identify the sources of DPs. As indicated by the results, f(syn) is close to industrial mixture in our study. The slightly lower ratio might attribute to the translation of syn-DP during the transport process. LB is the largest production area of BFRs in China. and the waste water, exhaust gas and residue produced in the process of manufacturing may enter the Bohai Sea through atmospheric transport and deposition, river discharge, and waste water pipeline, etc., and resulted in the high levels of HFRs in the LB. Seasonal variations of HFRs presents a higher values in winter than in summer. This is partially due to the increase of particulates and the decrease of temperature in winter. The pollutants are prone to be adsorbed in the particles. Another reason is that the northerly and north-westerly winds from land to south-easterly ocean in winter will bring pollutants to atmosphere above the Bohai Sea. Additionally, the scavenge effects of strong precipitation in summer is also an important factor in the reduction of particles and decrease of pollution concentrations. In general, CUPs and HFRs belong to emerging persistent organic pollutants (POPs), and have obvious POPs attributes. Land-based pollution is the main source of POPs, atmosphere and ocean are the primary container of semi-volatile organic compounds (SVOCs). Bohai rim is the important source area of the two kinds of targets in our country. It is found that there are different detection rates of targets in the seawater and atmosphere in the Bohai Sea. CUPs are easily detected in the gas and dissolved phase, indicating that it is easy to transfer to the remote area with the airflow or ocean current. HFRs mainly exists in the particle phase, which indicates the deposition into soil or sediment during the process of migration, and the accumulation of pollutants. Therefore, our study about the spatial distribution and seasonal variation can provide reference for the behavior of emerging persistent organic pollutants, and guide environmental management and human health of the Bohai Rim.
Subject Area环境工程
Pages83
Language中文
Document Type学位论文
Identifierhttp://ir.yic.ac.cn/handle/133337/25261
Collection中科院烟台海岸带研究所知识产出_学位论文
Recommended Citation
GB/T 7714
刘琳. 当前使用农药和卤代阻燃剂在渤海区域的时空分布特征研究[D]. 中国科学院烟台海岸带研究所. 中国科学院大学,2018.
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