氯化石蜡的环境赋存及转化降解研究进展

氯化石蜡（CPs）是石蜡烃的氯化衍生物,具有良好的阻燃性、电绝缘性等,被广泛用于多种工业产品中。其中短链CPs(SCCPs)于2017年被列入《关于持久性有机污染物的斯德哥尔摩公约》附件A中,受到国内外的广泛关注。目前关于CPs的研究表明,SCCPs和中链CPs在多种环境介质中有普遍检出,且相关研究主要集中在分析方法、环境赋存等方面,对其转化降解的研究报道较少,而极短链CPs和长链CPs的研究数据相对匮乏。文章综述了CPs在不同环境介质中的赋存水平,尤其对其环境转化降解行为进行了梳理总结,相关工作有助于更加全面地了解CPs的环境归趋,为深入开展CPs的污染控制提供科学依据。     

短链氯化石蜡分析方法、环境行为与健康效应的研究进展

氯化石蜡(chlorinated paraffins, CPs)是我国目前广泛应用在工业生产中的阻燃剂和增塑剂,其中短链氯化石蜡(short chain chlorinated paraffins, SCCPs)作为新污染物,因具有持久性、高毒性、长距离迁移特性和生物蓄积性等持久性有机污染物(persistent organic pollutants, POPs)特性引起了国内外的关注,尤其是SCCPs的环境赋存对环境健康的危害亟需进一步研究. 国内对SCCPs的研究集中在分析方法与环境行为等方面,对SCCPs的环境健康效应研究较少. 本文总结了近年来SCCPs分析方法的研究进展,并对其环境健康效应进行了梳理. 结果表明,SCCPs已被证实具有潜在的毒性效应,并且随着时间的推移,SCCPs在环境介质中的暴露浓度越来越高,因此SCCPs的环境外暴露对人体健康的潜在威胁越来越大. 研究显示,我国尚未停止SCCPs的生产与使用,因此在我国“十四五”规划之际,应加快SCCPs分析方法的研究进程,利用高分辨质谱将SCCPs的分析方法规范与标准化,并且在研究SCCPs的环境行为、迁移转化机制与毒性效应的基础上,深入开展SCCPs人体暴露风险与健康效应评估的研究,建立有效的环境健康风险评价模型与机制.      

氯化石蜡产品中短链和中链同系物的指纹分布

使用气相色谱-电子捕获负化学电离质谱（GC-ECNI-MS）,对包含CP-42、CP-52和CP-70三种常见氯含量的22个CPs产品进行了测定,分析了不同氯含量的CPs产品中短链氯化石蜡（SCCPs）和中链氯化石蜡（MCCPs）同系物的分布模式.SCCPs同系物呈现5种分布特征,分别是CP-42型、三类CP-52型和CP-70型,MCCPs同系物呈现4种分布特征,分别是CP-42型和三类CP-52型,CP-70产品中MCCPs同系物未呈现出一致的分布规律.CPs生产原料石蜡中烷烃的成分组成和CPs生产工艺的不同,是造成产品同系物分布模式不一致的原因.通过统计学分析,得到CPs产品中SCCPs和MCCPs同系物的指纹分布,这是开展环境中CPs的源解析、迁移转化、归趋和毒性风险评价等研究的有利工具.     

造纸厂土壤中短链和中链氯化石蜡的污染特征和风险评估

短链氯化石蜡是一类新型持久性有机污染物,氯化石蜡在造纸工业中常用作施胶剂,为了评估造纸厂区土壤中短链及中链氯化石蜡（SCCPs及MCCPs）的污染状况及其潜在风险,采集厂区表层和不同深度的土壤,利用全二维气相色谱-电子捕获负化学离子源-质谱（GC×GC-ECNI-MS）测定土壤中短链及中链氯化石蜡（SCCPs及MCCPs）的含量及同类物分布特征.结果表明,SCCPs和MCCPs在厂区土壤中均有检出,其含量分别为42~3853 ng·g^-1和34~2091 ng·g^-1,氯含量分别为59.9%~61.9%和48.7%~52.8%.不同采样点土壤样品中CPs（ΣSCCPs+ΣMCCPs）含量差异较大,污水处理区及施胶区土壤中SCCPs及MCCPs含量较高.与其他地区相比,厂区土壤中SCCPs及MCCPs处于较高水平.C₁₀Cl_6-7及C_14-15Cl₅是大部分土壤样品的主要同类物.主成分分析表明,厂区土壤中SCCPs及MCCPs可能主要来自于CP52产品的生产和使用.运用风险商值模型（RQ）评价SCCPs及MCCPs在造纸厂区土壤中的潜在风险,发现厂区土壤中SCCPs风险商范围为0.01~0.73,处于中等风险范围,MCCPs风险商范围为0~0.07,处于低等风险范围.儿童和成人人体暴露值低于TDI［10 μg·（kg·d）^-1］,造纸厂区非饮食暴露导致的健康风险较低.     

短链及中链氯化石蜡在上海市松江区农田土壤中的污染渗透及生态风险

土壤是氯化石蜡重要的"源"和"汇",为了评估上海市松江区某农业区土壤中短链氯化石蜡（SCCPs）及中链氯化石蜡（MCCPs）的污染水平及渗透潜能,利用超声提取-复合硅胶柱一步净化-GC-ECNI-LRMS方法监测农田表层及不同深度（0~15、15~30、30~45 cm）土柱样品中SCCPs及MCCPs的含量水平、组成特征及潜在风险.结果表明:①表层土壤中SCCPs和MCCPs含量范围分别为52.58~237.56和417.21~1 690.82 ng/g,二者对应的氯含量分别为58.98%~63.85%和51.23%~56.50%.SCCPs同系物主要以C₁₀Cl_5~7为主,MCCPs同系物以C₁₄Cl_6~7为主.②单因素方差分析发现,MCCPs含量沿土柱深度变化显著（P < 0.01）,其同系物在上层、中层和深层的占比分别为60.5%、25.4%和14.1%.SCCPs同系物含量沿土柱深度分布均匀,MCCPs同系物含量沿土柱深度呈指数递减趋势.垂直分布曲线表明,低氯化、短碳链的氯化石蜡同系物（CPs）具有更高的土壤渗透潜力.③皮尔逊相关性分析发现,CPs含量和总有机碳（TOC）含量之间不存在显著相关性（P>0.05）.主成分分析表明,研究区土壤中SCCPs和MCCPs的来源不同,可能与环境条件以及不同商业CPs混合物的生产技术、原材料差异等有关.④风险商值法评价表明,土壤SCCPs和MCCPs的风险商（risk quotients,RQ）范围分别为0.01~0.05和0.01~0.06,均处于低风险水平（0.01~0.1）.应用人体暴露模型对儿童和成人的人体暴露值进行估算,两类人群的CPs日均暴露值均低于每日可耐受摄入量（TDI,10 μg/kg）,非饮食暴露导致的健康风险较低.研究显示,上海市松江区农田土壤中CPs污染含量处于中等水平,SCCPs沿土柱的渗透能力较强,该地区土壤生物风险商和人体健康暴露值均较低,产生的生态风险可忽略,但农作物富集造成的潜在健康威胁需要引起注意.      

双公约下短链氯化石蜡协同履约的挑战与应对

正2017年4月24日至5月5日,《关于持久性有机污染物的斯德哥尔摩公约》(简称《斯德哥尔摩公约》)第八次缔约方大会和《关于在国际贸易中对某些危险化学品和农药采用事先知情同意程序的鹿特丹公约》(简称《鹿特丹公约》)第八次缔约方大会在瑞士日内瓦背靠背召开。此次会议中,两个公约首次同时将短链氯化石蜡(SCCPs)增列为工业受控化学品,两个公约增列内容和管控要求不     

海洋环境中短链氯化石蜡的研究综述

短链氯化石蜡(SCCPs)作为《斯德哥尔摩公约》拟增列的持久性有机污染物中的一类化合物,具有典型的长距离迁移能力、持久性、生物蓄积性和生物毒性,已成为国际环境科学领域的一个研究热点。海洋是各种污染物的最终归宿,已有的研究证实SCCPs在海洋环境中广泛存在。本文详细介绍了SCCPs的物理化学性质及其环境特性,综述了SCCPs在海洋环境中的含量分布及其对海洋生物的危害,同时对SCCPs在海洋环境中的研究重点和趋势进行了展望。     

崇明岛土壤中MCCPs的污染水平、组成与来源研究

用GC-ECNI-MS测定了崇明岛土壤中24种中链氯化石蜡(MCCPs)同类物组的含量.目的是了解该地区土壤中MCCPs的污染水平、空间分布、组成特征和来源.结果表明MCCPs在崇明岛土壤中普遍存在,浓度范围为2.56~96.3 ng·g-1,中值为7.32 ng·g-1.聚类分析将所有样品分为两类.大多数土壤样品MCCPs以C14-MCCPs和C15-MCCPs为主要碳同类物组,分别占29.8%和28.9%;Cl5-MCCPs和Cl6-MCCPs为主要氯同类物组,分别占29.9%和23.3%;个别样品中,C14-MCCPs是主要碳同类物组,占68.5%,与CP-52的组成相似.大气沉降和土壤-大气交换可能是崇明岛土壤中MCCPs主要来源,个别点可能受到污水处理厂污泥或其他不明污染源的污染.MCCPs与TOC之间没有显著统计相关性.因子分析表明4种MCCPs的碳同类物组具有相似的来源.与国内外其它研究相比,崇明岛土壤中MCCPs处于较低水平.     

上海食用鱼中短链氯化石蜡的污染特征

为了解长三角地区食用鱼中短链氯化石蜡(SCCPs)的污染特征,根据当地人的食鱼习惯,在上海采集了不同营养级的食用鱼8种,共计68尾,测定了肌肉中SCCPs含量并分析了其同族体的分布模式.结果表明,食用鱼肌肉中SCCPs的含量(干重,dw)范围为36～801 ng.g-1;同族体分布以C10-和C11-SCCPs为主,随着碳链长度的增加,SCCPs同族体含量所占比例随之降低,并且均以低氯(Cl6～Cl8)取代的SCCPs为主要组成部分,相对丰度之和占总丰度的61.46%～82.50%.上海食用鱼中SCCPs的含量在世界范围内处于中等水平,其分布模式与国内外研究一致.     

HRGC/ECNI-LRMS测定大辽河入海口表层沉积物中短链氯化石蜡

联合使用酸化硅胶层析柱和中性氧化铝层析柱净化处理沉积物样品中的短链氯化石蜡(SCCPs),并对净化条件进行优化,在此基础上,建立了沉积物中SCCPs的高分辨气相色谱/电子捕获负离子化-低分辨质谱(HRGC/ECNI-LRMS)分析方法.应用该方法分析研究了大辽河入海口表层沉积物中SCCPs的含量和各同系物组分的分布模式.结果表明,大辽河入海口表层沉积物中SCCPs以C10-SCCPs和C11-SCCPs为主,含量在64.9～407.0 ng/g之间,且随着向海洋方向延伸,SCCPs含量呈现下降趋势.     

Addressing the environmental risk of persistent organic pollutants in China

The Stockholm Convention on persistent organic pollutants (POPs) was adopted in 2001. This year is the 10th anniversary of the adoption of the Convention. Until now, 22 chemicals or chemical categories have been listed as POPs in the Stockholm Convention. The POPs Research Center was established in Tsinghua University in the same year when the Convention was adopted. In the last ten years, much work has been done by Chinese researchers to understand the environmental risk of POPs in China. This article aims to review the recent research progress of our POPs Research Center and some other Chinese researchers’ studies in addressing the environmental risk of POPs, including the priority screening and inventory study of POPs, monitoring and modeling of POPs pollution and exposure, and environmental risk assessment and modeling of POPs. Although great advances in addressing the environmental risk of POPs have been made in recent years, we are still facing quite a few problems, such as data scarcity and uncertainty in environmental risk assessment of POPs. The study on the effect of POPs mixtures is in its infancy and currently POPs are usually assessed from legal perspective by risk assessment of single chemicals. These problems should be well addressed by further efforts. Further studies should also be taken in future to study environment risk of POPs by considering aspects of coupled dynamics between climate processes and POPs. Such sound scientific, riskbased information can support decision-making aiming to effectively minimize the risk level of POPs.     

广东省新型POPs监测防控体系建设研究

2009年和2011年斯德哥尔摩公约新纳入的9种和1种持久性有机污染物（POPs）的研究是目前国际上环境领域研究的热点之一,所引起的环境污染和人体健康问题也逐步得到中国环保部门的关注.随着国际斯德哥尔摩公约履约活动的不断深入,中国正面临着履行公约以及削减与控制持久性有机污染物的巨大挑战.本文总结了广东省新型持久性有机污染物监测防控体系建设的必要性和意义,阐述了国内外在该领域的研究现状以及对解决新型POPs问题的作用.     

生产三氯杀螨醇的滴滴涕环境风险及其控制途径研究

滴滴涕是《关于持久性有机污染物（POPs）的斯德哥尔摩公约》中首批受控物质。本文调查了国内传统三氯杀螨醇生产工艺情况,分析了生产过程和产品使用过程中滴滴涕环境排放途径及环境风险,结合公约中有关滴滴涕风险控制的相关要求,分析了有限场地封闭体系三氯杀螨醇生产的基本要素,提出了生产过程中的环境排放限值建议,明确了控制环境排放和环境风险的有效途径。为相关生产企业开展技术改造和实施自我考核以及相关部门开展监督管理工作提供建议。     

我国POPs污染场地的环境管理基础与完善对策研究

固体废物不恰当处理处置是造成场地污染的原因之一,也是今后需要引起关注的环境问题.在POPs公约中,POPs污染场地和POPs废物一样有着明确的无害化管理要求,作为该公约的缔约国,我国将认真履行公约的义务,消除POPs引起的污染.根据调查,我国POPs引起的场地污染比较严重,现有的环境管理法律法规、标准和制度政策是POPs污染场地管理的基础,但这种基础还比较薄弱,尚不能完全满足环境无害化管理的要求.因此,我们在充分利用现有环境管理体系的基础上,还应该继续改进和完善现有法规和标准体系,建立相关的环境风险评价程序和资金筹集机制,加强污染场地环境管理和监督管理能力建设.     

我国医疗废物领域履行POPs公约对策研究

文章根据POPs公约对医疗废物管理和处置的总体要求,结合我国目前医疗废物管理和技术应用现状,结合我国医疗废物处置设施污染物排放、工程建设及运行管理状况,从医疗废物处理技术的具体应用实际需要出发对如何推进采用BAT/BEP,推进中国该领域履约进程进行了探讨,并提出了我国医疗废物领域履行POPs公约的管理和技术对策。     

Financing for innovative technologies and best practices to reduce persistent organic pollutants

Persistent Organic Pollutants (POPs) threaten human health and the global environment. Recognizing their dangers many countries began to limit or ban POPs production, use, and release in the 1990s. Eventually the Stockholm Convention on POPs, was adopted in 2001 and entered into force in 2004. The Global Environment Facility (GEF) provides financial support to developing country Parties for the implementation of the Stockholm Convention. The GEF’s POPs investment portfolio focuses on: 1) strengthening the capacity of developing country Parties to implement the Stockholm Convention; 2) establishing and supporting partnerships to develop and implement National Implementation Plans (NIPs), and 3) demonstrating and deploying best technologies and practices to reduce POPs emission, including development of safe alternatives. Since 2001 the GEF has committed US$568.8 million to POPs projects and leveraged some US$1474.5 million in co-financing from partners in the public and private sectors, bringing the total value of the GEF POPs portfolio to over US$2 billion. With GEF support, 108 developing country Parties have developed their NIPs. The GEF also financed 109 projects for the implementation of the Convention. Upon completion, these GEF POPs investments will contribute to the disposal of more than 70,000 tons of Polychlorinated Biphenyls (PCBs) oil, contaminated equipments, and waste, more than 40,000 tons of obsolete POPs pesticides and associated waste, and reducing dioxin/furan and mercury emission by introducing environmentally sound technologies and best practices. This paper summarizes: 1) direct and indirect GEF investments to support the goals of the Stockholm Convention; 2) investment case studies on PCB, DichloroDiphenylTrichloroethane (DDT), chlordane and mirex, medical waste, obsolete POPs and engaging civil society; and 3) lessons learned in terms of GEF financing strategies, best technologies and environmental practices to address POPs.     

Multi-generation health risks of persistent organic pollution in the far north: use of the precautionary approach in the Stockholm Convention

Precautionary regulation of persistent, toxic substances is controversial because of continued and irresolvable uncertainties in ecotoxicology. This is especially an issue for people who eat wild food, still a common practice in the Arctic. Persistent organic pollutants (POPs) have been shown to interfere with hormone function and genetic regulation. In animal studies, myriad dysfunctions can be induced (manifested later in life) by low-dose POPs exposure during development. The ubiquity of POPs in biological tissue makes all organisms subject to developmental exposure. The Arctic, where subsistence living is common, is a sink region for POPs. To curtail bioaccumulation and biomagnification, the United Nations has created the Stockholm Convention in May 2001, which targets 12 chemicals for virtual elimination. Using the precautionary approach, the treaty also enables the listing of new targets as threats are recognized. The “dirty dozen” are well-documented developmental toxics and other POPs are expected to exhibit similar patterns of accumulation and harm. Arctic peoples insist that waiting for irrefutable evidence is poor planning. Nevertheless, the United States, a major signatory, has proved reluctant to ratify the language that would enable this expedient listing of new targets. Such reluctance allows health threats in the Arctic and around the world to grow. This paper reviews the theoretical background for and current evidence regarding the global issues of endocrine disruption and POPs contamination, especially as they relate to wildlife and people in the far north. It is concluded that there is an urgent need for the US to ratify the full text of the Stockholm Convention, including the provision for the listing of new targets.     

我国医疗废物焚烧处置污染控制案例研究

医疗废物处置行业是我国确定的优先控制的无意产生POPs重点行业之一。该行业以二噁英减排为目的开展最佳可行技术的研究及示范推广是《履行<关于持久性有机污染物的斯德哥尔摩公约>国家实施计划》确定的任务之一。本文详细对江西南昌和湖南益阳医疗废物集中处置设施二噁英控制最佳可行技术示范改造的主要技术内容进行了分析,提出未来一段时间医疗废物集中处置设施污染控制管理趋势,以及技术升级改造的主要方向和技术重点。