Levels and bioaccumulation of organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) in fishes from the Pearl River estuary and Daya Bay, South China

Fifty fish samples were collected from the Pearl River estuary (PRE) and Daya Bay, South China and were analyzed for DDTs, HCHs, chlordanes and polybrominated biphenyl ethers (PBDEs). Except the high concentrations of DDT observed in fishes, the concentrations of HCHs, chlordanes and PBDEs were low when compared to other regions. BDE-47 was the predominant PBDE congener and the BDE-209 concentrations were relatively low, despite its high concentration in surface sediments. The absence of significant increase of DDT, HCH, chlordane and PBDE concentrations towards higher delta15N values, as well as the lack of a significant correlation (p<0.1) between log concentrations (lipid normalized) and delta15N, may indicate a weak biomagnification of these chemicals in the food webs. Good agreement was observed between their concentrations and lipid contents of the organisms. Bioconcentration was suggested to be responsible for the accumulation of OCPs and PBDEs in the lower trophic organisms in the studied subtropical waters.     

Organochlorine pesticides and polychlorinated biphenyls in riverine runoff of the Pearl River Delta, China: assessment of mass loading, input source and environmental fate

A large-scale sampling program was conducted to simultaneously collect water samples at the eight major riverine runoff outlets of the Pearl River Delta (PRD), South China to assess the importance of riverine runoff in transporting anthropogenic pollutants from terrestrial sources to the coastal ocean. The concentrations of ∑₂₁OCPs (sum of 21 OCP components) and ∑₂₀PCBs (sum of 20 PCB congeners) were 2.57-41.2 and 0.12-1.47 ng/L, respectively. Compositional distributions of DDTs suggested the possibility of new input sources in the study area, but contributions from dicofol seemed considerably low. The annual inputs of ∑₂₁OCPs and ∑₂₀PCBs were 3090 and 215 kg, with those of total HCHs and DDTs being 1110 and 1020 kg, respectively. A mass balance consideration indicated that riverine runoff is the major mode carrying OCPs from the PRD to the coastal ocean, and the majority of OCPs is further dissipated to open seas.     

北京工业废水和城市污水中有机氯农药残留分析

建立了基于HLB固相萃取柱和气相色谱-电子捕获(GC-ECD)测定水体中有机氯农药的方法,并对方法的回收率、灵敏度进行了评价,同时分析了北京市七类典型污染点源50个采样点位有机氯农药的浓度,检测到的有机氯农药包括γ-六六六、β-六六六、4,4’-滴滴涕、α-六六六、δ-六六六、硫丹Ⅰ、4,4’-滴滴伊、艾氏剂和异狄氏剂,它们的检出率分别为90%、60%、50%、46%、26%、8%、6%、2%和2%。主要有机氯农药污染残留为γ-六六六、β-六六六和4,4’-滴滴涕。检出有机氯农药浓度范围是0.20~76.40ng/L。方法对有机氯农药的回收率达到60.93%~141.50%,方法检测限为0.27~2.90ng/L。     

Levels and source of organochlorine pesticides in surface waters of Qiantang River, China

Qiantang River is a typical river used for drinking water source, flowing through agricultural area in east China. Surface water samples at 45 sampling sites from the river were collected and analyzed for 13 organochlorine pesticides (OCPs) during six surveys in 2 years of 2005–2006. Sediments, soils, farmland runoff water and dry/wet deposition of this region were also measured for their OCPs residue in order to know possible source of OCPs contamination. The total OCPs concentrations in surface water were 7.68–615.2 ng/l. β-HCH, δ-HCH, Aldrin, Heptachlor, Heptachlor epoxide are the major OCPs in water. The maximum levels of OCPs in water were found in July, while significantly lower OCP concentrations were measured in January. Significant linear correlation was found between the concentration of HCH and that of total 13 OCPs in water. The measured OCP concentrations in sediments, soils, farmland runoff water and dry/wet deposition are discussed in relation to concentrations and patterns found in the surface water. Comparison of OCP levels in sediments and soils led to conclusion that erosion of soil contribute significantly to the contamination of water. The OCPs dry and wet deposition to water body was estimated to 0.49 and 0.86 ton/year, respectively. The ratio of α/γ-HCH and (DDE+DDD)/∑DDT in environmental matrix indicated there probably existed new OCPs input of lindane and dicofol into the river.     

椒江口沉积物中有机氯农药的含量及对映体特征

测定了椒江口表层沉积物中滴滴涕(DDTs)和六六六(HCHs)类有机氯农药的含量和对映体分数(EF).结果表明,HCHs、DDTs在所有采样点都有检出,HCHs、DDTs和有机氯农药总量分别为0.65～1.72 ng/g、1.30～34.31 ng/g和1.95～35.07 ng/g,沉积物中的DDTs含量明显高于HC...     

三亚湾沉积柱有机氯农药的垂直分布特征

采用GC-ECD内标法测定了三亚沉积柱状样中有机氯农药的含量,并以210Pb同位素法对柱样定年,探讨了柱样中有机氯农药的垂直分布特征及可能来源.结果表明:沉积物中HCHs和DDTs的含量分别为0.04～1.46和0.01～0.59ng.g-1(以干重计,下同);自20世纪60年代开始大量使用OCPs后,沉积柱中OCPs在1965年、1971年和1975年分别出现了3个峰值;在我国禁止生产和使用OCPs后,柱样中OCPs含量自1986年后略有降低;自1990年起,OCPs含量明显增加,变化幅度较大,其含量变化与三亚发展建设有关.研究区域调查显示,近年来有林丹的输入,HCHs在沉积柱样表层富集较明显;在该偏氧化的沉积环境中,(DDD+DDE)/DDTs的值逐渐变小,且大部分均小于0.5,说明可能有新的DDTs输入.     

流溪河水体有机氯农药的生态风险评价

通过检测流溪河水体18个采样点水样中的有机氯农药浓度,构建了淡水生物对有机氯农药的物种敏感性分布,并计算出各类水生生物的HC5(Hazardous Concentration for 5%the Species)值,预测了不同浓度有机氯农药对生物的潜在影响比例(Potential Affected Fraction,PAF),最后采用商值概率分布法对流溪河水体的有机氯农药进行了生态风险评价.结果表明:流溪河水体中的有机氯农药浓度在216.41~389.70 ng·L-1之间,平均值为293.02 ng·L-1;甲体六六六(α-BHC)的HC5值最高,而硫丹硫酸酯和p,p'-滴滴滴(p,p'-DDD)对全部物种的HC5值均低于0.10μg·L-1,对生态系统的影响较大;当污染物的浓度达到0.50μg·L-1时,除甲体六六六、七氯之外,其余9种有机氯农药对全部物种的PAF值均超过了5%的阈值;除硫丹Ⅱ外,其余10种有机氯农药均具有潜在的生态风险;在假定保护95%物种的情况下,硫丹硫酸酯的生态风险最高.     

鲫鱼脑AChE制备及对几种有机磷农药敏感性研究

乙酰胆碱酯酶(AChE)是生物神经兴奋传导中的一种关键性酶。有机磷农药能够磷酰化AChE活性中心的丝氨酸羟基,导致神经传导阻断,因此AChE是有机磷农药残留检测的靶酶。文章选择鲫鱼脑作为酶源,对AChE提取方法进行了研究,并探讨了其对有机磷农药的敏感性。首先粗提AChE,通过正交试验确定了AChE酶活测定的最佳条件,研究了粗酶对几种有机磷农药的敏感性及检测限,之后通过层析方法纯化AChE,得到高活性的目标酶。研究表明AChE活性测定最佳条件为:200mmol/L底物、pH8.0、30℃水浴30min,这些因素对酶得活性影响顺序为:底物浓度pH温度时间,酶剂量对其影响最小;由鲫鱼脑粗提得到的AChE对4种有机磷农药的敏感性为:敌敌畏敌百虫氧乐果三唑磷辛硫磷乙酰甲胺磷;纯化后酶活达到了458.43μmo(lmin·mg),适合用于有机磷农药检测。     

土壤中OCPs残留特征及健康风险评价——以松花江佳木斯段为例

文章利用索氏提取技术,使用气相色谱-电子捕获检测器(GC-ECD)分析方法测定了佳木斯市松花江沿岸土壤中17种有机氯农药(OCPs)残留情况,并探讨该区土壤中OCPs的残留来源,运用健康评价模型对DDTs和HCHs对人体可能存在的健康风险进行了评价。17种OCPs的回收率为69.6%～112.4%,GC-ECD的仪器检出限为0.006～0.021 0 ng/g,方法检出限为2.05～12.83 pg/g,相对标准偏差为3.21%～11.37%,能够满足OCPs痕量分析的要求。研究结果表明,17种OCPs均有不同程度的检出,浓度较高的组分为滴滴涕(DDTs)、六六六(HCHs)和七氯,∑OCPs浓度为167.27～667.54 ng/g。研究区DDTs、HCHs的来源解析表明,DDTs、HCHs主要来自于早期农药的残留及林丹的使用。利用健康风险评价模型对土壤中HCHs、DDTs所致健康风险的评价结果表明,目前研究区土壤中HCHs、DDTs类污染物对人体健康的风险处于较低水平。     

福州城郊冬夏两季大气中HCHs和DDTs分布特征

2010年冬、夏两季,利用大流量采样器采集了福州市大气样品,并用气相色谱-电子捕获检测器(GC-mECD)分析其中六六六(HCHs)和滴滴涕(DDTs)残留水平、分布特征及来源.结果表明,大气ΣHCHs浓度范围为28.04~413.0 pg/m3,总体而言,城区高于郊区,夏季高于冬季,气相高于颗粒相;气相中HCHs浓度夏季高于冬季,颗粒相中则相反;夏季气相中HCHs浓度显著高于颗粒相,而冬季气相与颗粒相中HCHs浓度基本相当.4种HCHs异构体中,气相与颗粒相中均是δ-HCH相对含量最高.大气ΣDDTs浓度范围为146.5~897.8 pg/m3,总体而言,郊区高于城区,冬季高于夏季,颗粒相高于气相;气相中DDTs浓度夏季高于冬季,颗粒相中则相反;冬季颗粒相中DDTs浓度显著高于气相,而夏季颗粒相与气相中DDTs浓度无显著差异.4种DDTs异构体/同系物中,气相中o,p′-DDT的相对含量最高,颗粒相中o,p′-DDT和p,p′-DDT相对含量较高.来源解析表明,福州城郊大气中HCHs非历史污染,存在林丹的使用或输入;大气中可能存在DDTs输入,并可能有大量三氯杀螨醇的输入.