持久性有机污染物在中国湖库水体中的污染现状及分布特征

持久性有机污染物(POPs)在环境中广泛且持久存在,多数具有致畸、致癌、致突变等危害中国是全球湖泊密度较大的国家之一,湖泊在供水、渔业、维护生态系统多样性等众多方面发挥了重要作用湖泊是POPs的重要归宿之一湖泊水体中的POPs可被水生生物吸收利用并传递,对生态系统及人体健康构成较大危害因此湖泊水体中POPs的分布水平对周围的生态系统及人体健康有非常重要的影响本文收集、分析了2003年至2019年2月公开发表的80篇文献中的中国湖泊水体POPs数据,包括多环芳烃(PAHs)、六六六类农药(HCHs)、滴滴涕类农药(DDX)、多氯联苯(PCBs)、多溴联苯醚(PBDEs)、多氯联苯醚类(PCDEs)、全氟化合物(PFCs)及邻苯二甲酸酯类(PAEs),发现:目前中国已有水体POPs研究数据的湖泊共有49个,涉及19个省、直辖市、自治区,研究区域主要在东部地区(n=32),云贵高原(n=14)和青藏新疆湖区(n=3)少有研究,其它地区鲜有研究; PAHs、HCHs和DDX是研究最多的三类POPs,在中国湖泊水体中平均浓度分别为360.0±433.8 ng/L(n=26)、12.8±23.5 ng/L(n=30)、12.8±24.6 ng/L(n=24);不同湖区间、不同种类POPs以及不同时间相同POPs检出值差距均较大,东部湖区水体POPs浓度高于其它湖区;从时间角度看,虽然这三类POPs各自占总污染物量比例在2010年前后无较大变化,但2010年后的浓度与2010年以前相比有所下降,说明中国履行《关于持久性有机污染物(POPs)的斯德哥尔摩公约》内容以及对PAHs的管控减排已显成效; POPs在中国湖泊水体中的浓度与季节、水体深度(上覆水与间隙水)、采样点位置(入湖口、湖心及出水口)以及人为活动(农业耕作、生活排污、工业污水及码头船只往来等)存在一定关系,但并非完全受这些因素影响,还与POPs种类、所处区域的地理位置等诸多因素有关本文基于大量已发表文献中的研究数据,揭示了中国湖泊水体POPs的污染现状及分布特征,可为中国POPs的污染控制及湖泊保护提供一定的科学依据.     

巢湖悬浮物中有机氯农药的分布、来源与风险

利用GC-MS测定了2010年5月至2011年4月巢湖4个采样点悬浮物中有机氯农药(OCPs)含量,分析了悬浮物中OCPs残留水平的时空变化及其组成特征,探讨了悬浮物中主要OCPs的可能来源与生态风险.结果表明:(1)巢湖悬浮物中共检出17种OCPs,分别为六六六类(HCHs)农药的4种异构体(α-、β-、γ-、δ-HCH)、滴滴涕类(DDTs)农药的两种母体(o,p'-、p,p'-DDT)和3种代谢产物(o,p'-、p,p'-DDE,p,p'-DDD)、六氯苯、七氯、艾氏剂、异艾氏剂、氯丹的两种异构体(α-、γ-chlordane)、硫丹-I和灭蚁灵.(2)巢湖悬浮物中∑OCPs含量为172.7±434.9 ng/g,其中∑HCHs含量为15.1±10.3 ng/g,∑DDTs含量为138.8±407.3 ng/g;DDTs在夏季污染水平达到最高;空间上,污染程度为:东部湖区西部湖区中部湖区.(3)DDTs在总OCPs中占有绝对优势,DDTs比例夏季最高而秋季最低;HCHs仅在秋季为主要污染物.(4)HCHs主要来源于近期林丹的非法使用;而DDT主要来源于工业DDT的使用,在春季可能存在DDT的非法使用;悬浮物中DDT的降解环境主要为有氧环境.(5)巢湖悬浮物中p,p'-DDT和o,p'-DDT会对水生生物产生潜在的不利影响.     

太湖表层沉积物中有机氯农药残留及遗传毒性初步研究

采用GC-ECD对太湖表层沉积物中的有机氯农药含量进行了定性定量分析.太湖20个采样点均有不同程度的有机氯农药检出,16种有机氯农药总量为4.22-460.99ng/g(dw),北部湖区、潮心区以及沿岸区等均有高值点出现,与沉积物有机质含量、氮磷营养盐含量分布并不一致.检出率最高的有机氯农药组分为DDTs、HCHs.DDTs含量检出顺序为P,P'-DDT>P,P'-DDD>P,P'-DDE,说明环境中可能仍然具有DDT箱入特征;HCHs中?HCH,?HCH检出相当,怃-HCH检出较高,主要为早期残留.结合鼠伤寒沙门氏菌/哺乳动物微粒体酶系(Ames)试验研究太湖典型溯区表层沉积物中有机污染物的遗传毒性,初步确定可能的生态风险因子.     

白洋淀表层沉积物中有机氯农药和全多氯联苯的分布特征及风险评估

为了解白洋淀表层沉积物中有机氯农药(OCPs)和多氯联苯(PCBs)的污染情况,采用改进的GC-μECD方法对白洋淀11处沉积物进行了20种OCPs和全部209种PCB单体的定量检测和分析.结果显示:白洋淀11个沉积物样品共检出10种OCPs和24种PCBs,∑OCPs和∑PCBs的含量范围分别为1.22～52.45 ng/g(DW)和nd～37.61 ng/g,在国内处于中等水平; OCPs组成中以HCHs和Dieldrin(狄氏剂)为主,分别占到∑OCPs的39.9%和31.5%,其中7个采样点的HCHs以林丹输入为主,4个采样点以工业六六六污染为主.DDTs检出率较低,来源主要为历史残留;检出的PCB单体以低氯联苯为主,其中一氯、二氯和三氯联苯占∑PCBs的64.73%;采用沉积物质量标准法进行生态风险评估,结果表明白洋淀地区沉积物中p,p'-DDD和∑PCBs生态风险较低,Dieldrin生态风险尚需关注,γ-HCH生态风险较高,不容忽视.     

近50a中国东部和西部湖区水量空间变化趋势

基于近代湖泊水量(水位、水深和面积)记录,对近50 a中国东部和西部湖区水量的空间变化趋势进行半定量研究.结果表明:整体上看,20世纪80年代以前,东部湖区水量呈现波动变化而西部湖区水量基本趋于减少;80年代以后东部和西部湖区水量均表现为不同程度的增加.其中,20世纪50年代,东部和西部湖区水量状况基本相似,均保持高湖面特征.20世纪60年代,东部湖区水量有所减少但幅度不明显,而西部湖区以中高水量为主.20世纪70年代,不同区域湖泊基本都保持中湖面特征.20世纪80年代,东部湖区水量呈增加趋势而西部湖区水量相对70年代略有减少.20世纪90年代,东部和西部湖区水量均表现为增加趋势.进一步研究发现,最近50 a来中国不同区域湖泊水量发生变化除了气候因素的驱动外,人类活动的影响也是不可忽视的.     

滇东湖泊水生植物和浮游生物碳、氮稳定同位素与元素组成特征

稳定同位素示踪方法是研究生态系统组成与功能的重要手段,有助于认识湖泊食物网的基本组成与生物地球化学循环的主要过程.本研究选择了云南省东部地区营养水平不同的10个湖泊,开展了高等水生植物(沉水植物、漂浮植物)、浮游植物与浮游动物的空间调查,分析了不同生物在碳、氮稳定同位素信号与元素组成上的分布模式.在碳稳定同位素信号的分布上,漂浮植物在4种生物类型中最为偏负且变化幅度最小,为-28.99‰±0.86‰;浮游动物碳稳定同位素(-20.85‰±2.70‰)的分布特征与浮游植物(-21.88‰±2.97‰)显著相似;而沉水植物的碳稳定同位素显著偏正且变化范围较大,平均值为-12.04‰±4.57‰.结果表明,碳源及其传输途径的差异是导致湖泊生物体内碳同位素信号不同的主要驱动过程.在氮稳定同位素信号上,同为初级生产者的沉水植物(5.43‰±5.84‰)、漂浮植物(5.58‰±7.38‰)与浮游植物(7.26‰±3.83‰)较为相似,而浮游动物氮同位素信号(11.02‰±3.18‰)显著高于浮游植物且平均富集约3.46‰,反映了湖泊生物随着营养级的增加出现较为明显的同位素分馏效应.在空间分布上,湖泊生物碳同位素信号受到水温、水深等因素的明显影响,氮同位素信号则随湖泊营养水平的增加而逐渐偏正.与长江中下游等地区相比,云南湖泊生物的碳、氮元素含量总体偏高;同时,代表内源有机质组分的水生植物和浮游生物C/N质量比值都小于20.因此,本研究揭示的生物碳、氮同位素信号与元素组成特征可为评价高原湖泊食物网组成与生物地球化学循环提供重要的科学依据.     

太湖流域滆湖底泥重金属赋存特征及其生物有效性

为了探讨太湖流域滆湖底泥重金属(Cd、Cr、Cu、Zn、Ni和Pb)的赋存特征及其生物有效性,对底泥重金属总量、形态以及生物富集量进行了分析.结果表明,6种重金属含量的空间分布表现为北部湖区最高,其次为南部湖区,中部湖区最低,重金属Ni、Cu、Zn和Pb含量显著高于沉积物背景值,分别是背景值的4.77、3.89、2.96和2.76倍,重金属总量与沉积物中的黏土成分含量具有显著相关性.采用三级四部提取法对重金属形态进行分析表明,6种重金属的生物有效态(弱酸结合态、可还原态和可氧化态之和)含量顺序为CdCuZnPbNiCr,其中Cd、Cu、Zn和Pb的生物有效态含量分别占总量的84.15%、78.47%、76.50%和64.29%.Cu和Zn在铜锈环棱螺中富集含量要显著高于其他金属元素.相关性分析表明,6种重金属中仅Cr和Pb的生物富集量与有效态含量具有显著相关性,这表明,重金属在生物体内的富集不仅与有效态含量有关,还与底泥重金属总量有关.因此,评价滆湖重金属的生态风险时需要综合考虑重金属的总量及生物有效态含量.     

广东新丰江水库XFJ-1孔DDTs和HCHs的沉积记录

以~(210)Pb对广东新丰江水库XFJ-1孔进行了定年,以GC-ECD测定新丰江水库沉积钻孔中DDTs和HCHs的含量,通过对比其剖面变化特征与该类农药在我国的生产、使用历史,探讨了水库中DDT、HCH的历史输入途径.过去30年来,XFJ-1孔平均沉积速率为1.42cm/a,沉积物中HCHs和DDTs的含量分别为1.26-3.90ng/g和1.00-3.96ng/g.DDTs、HCHs含量从20世纪80年代初逐渐下降,总体上与我国1983年开始禁止DDT、HCH的大规模生产和使用这一历史事件相符.DDTs、HCHs及其化合物比值的剖面变化特征均表明:流域内后期土壤侵蚀、搬运的再循环污染物质(即二次污染源)对水库DDT和HCH的贡献不明显;相反,农药历史使用(即一次污染源)是其主要来源,大气沉降是其主要输入途径.此外,γ-HCH、o,p′-DDT和p,p′-DDT含量的垂直变化表明,大规模禁用以后这些化合物仍有少量新的输入,需引起重视.     

南极大型动物粪土层和蛋卵中有机氯污染物分布特征及生态学意义

新近从南极菲尔徳斯半岛和阿德雷岛的海鸟和海豹栖息地粪土层中检出持久性有机氯污染物(POPs)总含量范围: 多氯联苯(PCBs)为0.21~3.85 ng/g; 有机氯农药滴滴涕(ΣDDT)为0.09~2.01ng/g; 六六六(ΣHCH)为0.06~0.76 ng/g, 并以七氯、六氯联苯、P, P-DDE和α-HCH化合物为主体; 在贼鸥和巨海燕、企鹅蛋卵中检出POPs含量各为12.5~294.2和2.0~10.2 ng/g (湿重); 积蓄形式以PCB180, PCB153, P, P’-DDE和HCB和P, P’-DDE为主. 研究表明, 栖息地粪土层POPs含量变化与海鸟不同种群食性以及营巢占域的不同而相异; 对不同种类海鸟卵样的POPs数据进行统计分析, 结果显示不同鸟种POPs积累水平的差异取决于不同鸟种的生态习性, 如活动范围、迁徒距离、觅食习性以及巢址选择等, 最重要是海鸟生态食物链中的位置, 其食谱的宽窄, 同样表明海鸟体内POPs积累通过食物链逐渐加强的结果. 其次还对阿德雷岛地区AD1, AD2短柱粪土地层进行²¹⁰Pb测年, 并进行POPs积累率及分子地层学记录的初步研究.     

巢湖表层水体中DDTs农药的残留特征、来源解析与风险评价

2009年8月采集了巢湖河流及湖泊表层水体共15个样点,利用固相萃取-气相色谱-电子捕获检测器(SPE-GC-ECD)方法测定滴滴涕类(DDTs)农药的含量,分析了其残留特征、来源及风险.结果表明:1)巢湖丰水期DDTs含量范围为1.52-21.79ng/L,平均含量为9.98±4.73ng/L.2)DDT残留主要来自...     

Persistent organochlorine pollutants in Korean offshore waters: Squid (Todarodes pacificus) as a biomonitor

Persistent organochlorine pollutants (POPs) such as polychlorinated biphenyls (PCBs), dichlorodiphenyl trichloroethane and its metabolites (DDTs), chlordane compounds (CHLs), and hexachlorocyclohexanes (HCHs) were determined in Japanese common squid collected from the offshore waters of Korea. Liver accumulated higher levels of contaminants than mantle. The sums of DDTs, PCBs, CHLs and HCHs in liver were in the ranges of 164-4430 ng g⁻¹, 95-1030 ng g⁻¹, 15-121 ng g⁻¹, and 13-98 ng g⁻¹ on a lipid weight basis, respectively. Among the POPs, DDTs showed distinct regional difference in concentration levels and composition between the western and eastern offshore of Korea. One of the highest concentrations of DDTs so far recorded in the western offshore of Korea, that is Yellow Sea. This implies ongoing fresh input of technical DDT to this regional sea. HCHs were relatively high in the Yellow Sea as well, with an enhanced signal of γ-HCH indicating recent input of lindane. In contrast, CHLs showed higher level in the eastern offshore of Korea, that is East Sea, but PCBs showed an even distribution in both regions. Squid could be a useful bio-indicator for monitoring offshore water contamination by POPs.     

Contamination status of POPs and BFRs and relationship with parasitic infection in finless porpoises (Neophocaena phocaenoides) from Seto Inland Sea and Omura Bay,Japan

Contamination status of brominated flame retardants (BFRs) and persistent organic pollutants (POPs) in blubber of finless porpoises (Neophocaena phocaenoides) stranded along the coasts of Seto Inland Sea and Omura Bay in Japan were investigated. Levels of PCBs, DDTs and CHLs were significantly higher than those of HCHs, HCB, PBDEs and HBCDs. Concentrations of PBDEs and HBCDs, as well as organochlorine compounds in males increased with body length (p < 0.05). Among 14 PBDE congeners analyzed, BDE-47 was the predominant, which is similar to those generally reported in biota. PBDEs, HBCDs and PCBs showed no obvious temporal trend in concentrations during the study period, suggesting continuous environmental release of these chemicals. On the other hand, levels of DDT, CHLs and HCHs have decreased. Concentrations of PCBs in liver trematode infected individuals were significantly higher than those in not infected individuals, implying there could be a relationship between contaminant levels and parasitic infection.     

Contamination status of POPs and BFRs and relationship with parasitic infection in finless porpoises (Neophocaena phocaenoides) from Seto Inland Sea and Omura Bay, Japan

Contamination status of brominated flame retardants (BFRs) and persistent organic pollutants (POPs) in blubber of finless porpoises (Neophocaena phocaenoides) stranded along the coasts of Seto Inland Sea and Omura Bay in Japan were investigated. Levels of PCBs, DDTs and CHLs were significantly higher than those of HCHs, HCB, PBDEs and HBCDs. Concentrations of PBDEs and HBCDs, as well as organochlorine compounds in males increased with body length (p<0.05). Among 14 PBDE congeners analyzed, BDE-47 was the predominant, which is similar to those generally reported in biota. PBDEs, HBCDs and PCBs showed no obvious temporal trend in concentrations during the study period, suggesting continuous environmental release of these chemicals. On the other hand, levels of DDT, CHLs and HCHs have decreased. Concentrations of PCBs in liver trematode infected individuals were significantly higher than those in not infected individuals, implying there could be a relationship between contaminant levels and parasitic infection.     

Occurrence of persistent organic pollutants in marine fish from the Natuna Island,South China Sea

Five marine fish species were collected from the Natuna Island, South China Sea to investigate the occurrence of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs). Concentrations of PBDEs, PCBs, and DDTs in marine fish ranged from 2.85 to 7.82, 14.3 to 48.1, and 7.99 to 40.3 ng/g lipid weight, respectively. Higher concentrations of PBDEs, PCBs, and DDTs were observed in Snakefish (Trachinocephalus myops), which might be attributed to their different feeding and living habits. PCBs were the predominant POPs in all marine fish, followed by DDTs and PBDEs. BDE 47 and PCB 153 were the predominant congener of PBDEs and PCBs, respectively. Compositional distribution of DDTs indicated the possible presence of fresh input sources around the Natuna Island. The ratios of o,p′-DDT/p,p′-DDT being less than 1 in fish samples suggested that DDT contributions from dicofol seemed considerably low. New input sources of DDT in South China Sea are worth further research.     

Distribution and bioaccumulation of polychlorinated biphenyls and organochlorine pesticides residues in sediments and Manila clams (Ruditapes philippinarum) from along the Mid-Western coast of Korea

The distribution and bioaccumulation features of PCBs, DDTs, and HCHs were investigated in the sediments and Manila clams collected from along the Mid-Western coast of Korea. The measured concentrations of ΣPCBs, ΣDDTs and ΣHCHs were 1.08–3.5, 0.12–0.35 and 0.090–0.30 ng g⁻¹ dw in sediment, and 33–390, 7.4–46 and 6.3–27 ng g⁻¹ lipid in Manila clam, respectively. Their levels were found to be relatively lower than those of other contaminated areas and the consumption of Manila clam from these areas seems to be safe for human health according to calculated lifetime cancer risk and hazard indices. The ΣPCBs and ΣDDTs concentrations in sediments showed a significant relationship to those in clams. The significant correlation was observed between BSAF in clams and K_ow for each PCB congeners and DDT metabolites. These findings support that the PCBs and DDTs levels, which are highly hydrophobic chemicals, in clam reflect the sediment pollution through bioaccumulation.     

Measurement of persistent organic pollutants (POPs) in plastic resin pellets from remote islands: toward establishment of background concentrations for International Pellet Watch

Plastic resin pellets collected from remote islands in the Pacific, Atlantic, and Indian Oceans and the Caribbean Sea were analyzed for polychlorinated biphenyls (PCBs), dichloro-diphenyltrichloroethane and its degradation products (DDTs), and hexachlorocyclohexanes (HCHs). Concentrations of PCBs (sum of 13 congeners) in the pellets were 0.1-9.9 ng/g-pellet. These were 1-3 orders of magnitude smaller than those observed in pellets from industrialized coastal shores. Concentrations of DDTs in the pellets were 0.8-4.1 ng/g-pellet. HCH concentrations were 0.6-1.7 ng/g-pellet, except for 19.3 ng/g-pellet on St. Helena, where current use of lindane is likely influence. This study provides background levels of POPs (PCBs<10 ng/g-pellet, DDTs <4 ng/g-pellet, HCHs <2 ng/g-pellet) for International Pellet Watch. Sporadic large concentrations of POPs were found in some pellet samples from remote islands and should be considered in future assessments of pollutants on plastic debris.     

Organochlorine and butyltin residues in deep-sea organisms collected from the western North Pacific,off-Tohoku,Japan

Organochlorine (OCs) and butyltin (BTs) residues were determined in deep-sea organisms collected from the western North Pacific, off-Tohoku, Japan. Among OCs, concentrations of polychlorinated biphenyls (PCBs) and DDTs (DDTs and its metabolites) were the highest in deep-sea organisms (maximum concentrations of 6700 and 13,000 ng/g lipid wt, respectively). Chlordane compounds (CHLs) were the next most abundant OCs, and hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB) were the lowest. BTs were also detected at maximum concentrations of 570 ng/g wet wt. Concentrations of PCBs, CHLs and BTs in deep-sea organisms collected from the western North Pacific, off-Tohoku, were generally lower than those in deep-sea and shallow water organisms from Japanese coastal waters. On the other hand, considerable variations in the concentrations of OCs were found among deep-sea organisms analyzed. Several carnivorous fishes such as snubnosed eel, lanternshark and grenadiers accumulated some OCs such as PCBs, DDTs and CHLs at high concentrations of up to a few μg/g levels. In addition, the residue pattern of OCs and BTs in fishes showed a specific trend according to the sampling depth; higher concentrations of PCBs, DDTs and CHLs and lower concentrations of HCHs, HCB and BTs were found in fishes collected from greater depth (1000 m) compared to those from shallower waters. This trend is consistent with the results of our earlier study on mesopelagic myctophid fishes. Results of this study suggest vertical transport of hydrophobic OCs such as PCBs, DDTs and CHLs and its accumulation in benthic deep-sea organisms.     

Organohalogen contaminants in striped dolphins (Stenella coeruleoalba) from Japan: Present contamination status, body distribution and temporal trends (1978-2003)

Organohalogen contaminants including PCBs, DDTs, CHLs, HCHs, HCB, PBDEs and HBCDs were determined in striped dolphins (Stenella coeruleoalba) found stranded at Gogo-shima (n = 6, 2003) and collected from Taiji (n = 15, 1978-1992) in Japan. All target compounds were significantly detected in all the specimens, indicating ubiquitous contamination of oceanic cetaceans in northwest Pacific Ocean. Examination of body distribution of organohalogens in the six specimens from Gogo-shima showed no significant difference in concentrations among the analyzed tissues, except for brain, which had lower levels possibly due to the existence of blood-brain barrier. For evaluating temporal trends, archived blubber samples of adult male stripped dolphins collected in 1978, 1979, 1986 and 1992 were analyzed. Concentrations of PCBs, DDTs and HCHs did not change significantly during 1978-2003. In contrast, remarkable increasing trends of PBDEs and HBCDs were observed, suggesting growing consumption in Japan and surrounding countries in recent years.     

PCBs, PBDEs and organochlorine pesticides in crabs Hepatus pudibundus and Callinectes danae from Santos Bay, State of São Paulo, Brazil

The occurrence of persistent organic pollutants (POPs) as polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDE) in crabs Hepatus pudibundus and Callinectesdanae was assessed from two different places inside of the Santos Bay and Moela Island near one of the most economically important metropolitan areas in Southern Brazil. Among POPs analyzed, ∑PCBs (222-923 ng g(-1)lipid weight) and ∑DDTs (154-410 ng g(-1)lw) exhibited the highest concentrations in the crabs. ∑HCHs ranged from 10.3 to 30.9 ng g(-1)lw and were found in all individuals. Other OCPs found in lower concentration was Mirex (7.6-41.6 ng g(-1)lw) and HCB (5.83-16.9 ng g(-1)lw). ∑PBDEs (24.1 ng g(-1)lw) were only found in one male individual from the species C. danae collected near to the submarine sewage of Santos. Male crabs showed higher POP concentrations than female crabs for those two species.     

Levels and distribution of polybrominated diphenyl ethers and organochlorine compounds in sea turtles from Japan

Three species of sea turtles (green, hawksbill and loggerhead turtles) stranded along the coasts or caught (by-catch) around Ishigaki Island and Kochi, Japan were collected between 1998 and 2006 and analyzed for six organohalogen compounds viz., PBDEs, PCBs, DDTs, CHLs, HCHs and HCB. The present study is the first and foremost to report the occurrence of organohalogen compounds in the sea turtles from Japan. Among the compounds analyzed, concentrations of PCBs, DDTs and CHLs were the highest in all the turtle samples. PBDEs were ubiquitously present in all the turtle species. Comparing with the other two species, concentrations of organohalogens in green turtle were relatively low and decreasing trend in the concentrations were noted with increasing carapace length. Concentrations of OCs in sea turtles from the coasts of Ishigaki Island and Kochi were relatively low as compared to those from other locations in the world.