海洋沉积物中多氯联苯、多环芳烃和有机氯农药的同时净化与分离

研究了海洋沉积物提取液中28种多氯联苯(PCBs)、16种多环芳烃(PAHs)和21种有机氯农药(OCPs)在硅胶-氧化铝复合净化柱上的同时净化与分离效果,结果表明:在充填4 cm3%去活化氧化铝-6 cm 3%去活化硅胶的8 mm i.d×15 cm固相萃取净化柱上,使用10 mL正己烷作为淋洗PCBs的分割点,可实现PCBs、PAHs和OCPs的满意分离,更有利于PCBs与高环数PAHs、极性较强OCPs的分离。继续用20 mL正己烷-二氯甲烷混合液(体积比1∶1)洗脱,28 PCBs、16种PAHs和21种OCPs均可获得有效回收,回收率分别为75%~110%、76%~115%、75%~130%。经海洋沉积物标准参考物质验证,该方法实用、可靠,流程简单,试剂消耗少,成本低,适用于海洋环境地质调查中基质复杂沉积物样品的定量分析。     

中国西沙海域永兴岛—七连屿海域鱼体内有机污染物含量特征与来源解析及风险评价

环境中的有机污染物对生态系统和人类健康产生严重威胁。有机污染物在全球海域鱼体内普遍检出,且长期食用会对人类造成一定的健康风险。为研究中国西沙海域鱼体内有机污染物污染情况、来源及生态风险,本文利用气相色谱-质谱法(GC-MS)分析测定了永兴岛和七连屿鱼体内有机氯农药(OCPs)、多环芳烃(PAHs)和多氯联苯(PCBs)的含量,采集了包括蜂巢石斑鱼、红裸颊鲷、黑身蓝子鱼在内的17种鱼类共50条。结果表明：鱼体内OCPs、PAHs和PCBs的总含量均值范围分别为2.23～91.57ng/g ww、2.11～31.70ng/g ww和1.55～54.04ng/g ww,平均值分别为32.50ng/g ww、17.29ng/g ww和18.79ng/g ww,中位数分别为16.92ng/g ww、13.34ng/g ww和7.61ng/g ww。双对氯苯基三氯乙烷(DDTs)类农药在美欧沿海鱼体内的含量分别为0.65～107.6ng/g ww和763～5357ng/g lw,中国浙江沿海水域鱼体内PAHs含量为10.4～140ng/g ww,地中海、意大利沿海和美国查尔斯顿港口采集的鱼体内PCBs含量分别为1234～12327ng/g lw、56.8～4791ng/g lw和5.02～232.20ng/g ww,研究区DDTs和PAHs含量水平处于全球海域的低端,推测由于研究区远离污染源。利用DDTs/[双对氯苯基二氯乙烯(DDE)+双对氯苯基二氯乙烷(DDD)]比值来判断DDTs的来源,研究区50%鱼体内DDTs/(DDE+DDD)＞1,表明中国西沙海域有部分新近输入的DDTs,研究区沉积物来源为陆源,推测中国西沙海域DDTs为陆源DDTs和永兴岛农业活动的综合作用。利用蒽(ANT)/[ANT+菲(PHE)]比值＞0.1或该比值＜0.1来判断PAHs的来源是燃烧源还是石油源,研究区88%鱼体内ANT/(ANT+PHE)＞0.1,表明PAHs来源于化石燃料燃烧。风险评价结果显示,鱼体内OCPs和PCBs生态风险低。     

天津高沙岭潮间带表层沉积物中多环芳烃的分布及风险评价

通过对天津海滨浴场南侧潮间带表层沉积物中多环芳烃(PAHs)的定量分析,探讨其分布特征及来源.研究表明,沉积物中∑PAHs含量范围为91.4×10-9～855.4×10-9,从空间上呈现出高潮滩中潮滩低潮滩的分布特征.样品中PAHs二环和三环含量占主导地位,以石油污染输入为主,并混合有化石燃料的不完全燃烧.根据沉积物风险评价标准,萘、芴、菲、蒽超出风险低值,对潮间带生态具有潜在危害,应严格控制PAHs的人为输入,保护潮间带的生态环境.     

北大港湿地东部多环芳烃沉积记录与来源分析

利用GC/MS法分析研究了北大港湿地东部沼泽水域沉积物岩芯样中16种多环芳烃(PAHs)含量与组成的垂向分布特征,并对其来源进行了分析。结果表明,沉积物岩芯中PAHs含量在(18.1～821)×10^-9之间,岩芯上段PAHs以5～6环高分子量组分为主,中段和下段则以2～3环组分为主。20世纪50年代以来,北大港湿地PAHs含量显著升高,峰值出现在20世纪50年代中期至60年代中期,比国内多数地区峰值出现时间更早,而20世纪80年代以后PAHs含量再次处于增长态势。根据成分组成和产业发展分析当地不同时期PAHs的来源,20世纪50年代以前,PAHs主要来自于长距离输送和薪柴的低温燃烧,此后则是以湿地周边化石燃料的不完全燃烧为主。北大港湿地的PAHs污染明显受到20世纪50年代以来人类生产活动的影响,化石燃料的不完全燃烧是主要来源,大港油田开采泄漏的影响则不显著。     

废旧电容器封存点土壤中多氯联苯的残留特征

利用气相色谱-质谱联用法(GC-MS)研究了长江三角洲某废旧电容器封存点土壤中多氯联苯(PCBs)的残留特征。利用GC-MS的选择离子监测模式(SIM)对包括7种指示性PCBs和12种类二噁英PCBs共19种PCBs进行分析。统计结果显示,该封存点土壤中19种PCBs含量为2.01～5201.20 ng/g,平均含量为229.38ng/g,明显高于国内一般土壤,但低于国内某些封存点土壤。土壤中19种PCBs同系物以低氯代(3～5氯)为主,三者占同系物总量的85.43%,尤以三氯代-PCB 28、四氯代-PCB 52和五氯代-PCB 118残留量最高。通过对比分析得出,封存点土壤PCBs以Aroclor 1242、Aroclor 1248为主,并含少量的Aroclor 1254。封存点土壤中PCBs残留量虽未超过控制值,但已呈现污染迹象,应及时采取控制措施,阻止污染趋势进一步扩大。     

新疆开都河流域不同环境介质中的有机氯农药和多环芳烃残留及分布特征

为探讨新疆开都河流域水不同介质的来源及分布特征,检测了开都河流域水、土壤和表层沉积物样品中20种有机氯农药(OCPs)和16种多环芳烃(PAHs)的含量。结果显示,OCPs和PAHs在水中的含量分别为42.5~62.5ng/L和29.4~454.3ng/L,在土壤中的含量分别为8.8~12.4ng/g和6.6~128.2ng/g,在表层沉积物中的含量分别为6.6~13.7ng/g和20.8~491.0ng/g。空间分布上,开都河中游污染相对严重的土壤对应的周边河流沉积物也具有较高浓度的污染物,这种分布明显受人类活动影响,沿河道上游呈递增趋势,但总体上低于入湖口沉积物中的含量,表明博斯腾湖蓄积了来自周边的污染物。来源分析表明,开都河流域的六六六(HCHs)和滴滴涕(DDTs)主要是历史残留,而入湖口区水体和表层沉积物中新的DDTs,可能与湖泊沉积物被扰动引起的再悬浮释放有关。PAHs以低分子量组分为主,其高含量主要来自于木柴、煤等中低温燃烧。风险评价结果表明,开都河流域土壤和沉积物中的OCPs和PAHs不存在显著的生态风险。     

广西岩溶区某地下河系统多种介质中多环芳烃的分布特征

为了研究岩溶地下河系统内多种介质中多环芳烃(PAHs)的浓度、组成和分布特征,以广西某典型岩溶地下河为例,利用2013-2014年同期的空气、地下河水、沉积物和土壤样品测试数据,对不同环境介质中16种多环芳烃(PAHs)的浓度、组成和分布特征进行对比分析。结果表明,空气和地下河水以2~3环PAHs为主,其中空气的2~3环PAHs比例为71.66%,地下河水的2~3环PAHs比例为54.84%;沉积物和土壤以4~6环PAHs为主,其中沉积物的4~6环PAHs比例为54.26%,土壤的4~6环PAHs比例为65.06%;环境介质中PAHs的浓度变化为：上游<中游<下游,这与污染源排放、吸附作用等相关;同一区域不同介质的2~3环PAHs百分比为：地下河水>沉积物>土壤,而4~6环PAHs百分比则相反。     

烟台、日照近海及南四湖沉积物中的多氯联苯

本对南四湖、日照与烟台近海表层沉积物中的36种多氛联苯(PCBs)异构体的含量、分布特征、毒性当量浓度及其来源进行7初步探讨。总PCBs含量以南四湖最高(0．随心g和0．63ng/g)。日照、烟台近海分别为0．27ng/g和0．35ng/g，均落在国内外海洋近岸表层沉积物含量范围的低值区。近海沉积物中多氛联苯主要以低氛代PCBs(一至五氛)为主，而南四湖南、北部沉积物都是以四、五、六氛代PCBs为主要组分，反映了山东内陆湖与沿海多氛联苯的来源有别。烟台近海沉积物中共平面PCBs对总毒性当量浓度的影响高达三分之一，表明有相对较大比例的共平面多氛联苯的输入来源。     

新江湾城开发区表层土壤中有机氯农药和多氯联苯的分布特征

利用电子捕获检测器气相色谱法(GC-ECD)测定新江湾城表层土壤中有机氯农药(OCPs)和多氯联苯(PCBs),六六六类(HCHs)和滴滴涕类(DDTs)化合物均被检出,HCHs含量为0.81~2.84 ng/g,平均1.90 ng/g;DDTs含量为9.37~130.8 ng/g,平均43.9 ng/g。HCHs都未超过国家土壤环境质量标准的一级水平,但是有两个站点的DDTs超过国家土壤环境质量标准的一级水平。7种多氯联苯(7PCBs)含量为1.83~8.46 ng/g,平均3.99 ng/g,以四氯代PCB 52和六氯代PCB 138残留最高。PCBs污染主要集中在火力发电厂处,并向周边蔓延,反映了PCBs污染的来源与电力设备有关,其污染来源很有可能来自历史上变压器油泄漏物的残留及来自工业区的新的PCBs输入。     

长江口启东—崇明岛航道沉积物中多环芳烃分布来源及生态风险评价

近年来我国长江河口有关沉积物中多环芳烃(PAHs)污染的研究主要集中在长江口近海及上海主城区滨岸等区域,而长江口航道则鲜有报道。本文在长江口启东—崇明岛航道区域采集表层(0~20 cm)沉积物样品,利用加速溶剂萃取技术提取,用高效液相色谱-荧光检测器对14种PAHs进行测定,研究其分布特征、环境来源和潜在的生态风险。研究结果显示,PAHs在所有沉积物样品中均有不同程度的检出,浓度范围为83.43~5206.97 ng/g,平均值736.95 ng/g。就PAHs单体而言,含量较高的是2~4环污染物,其中菲的含量最高,占各点位PAHs总量的9.04%~24.06%;其次为荧蒽和芘;具有高致癌性的苯并(a)芘在各个点位均能检出,占PAHs总量的0.94%~10.68%。与国内外类似河口和近海海域相比,本研究区PAHs处于中等污染水平。利用比值法解析PAHs的来源,菲/蒽(Phe/Ant)10且荧蒽/芘(Fla/Pyr)≥1的点位占所有采样点位的56.25%,表明区域内PAHs的主要来源是化石燃料的高温燃烧;位于航运码头附近采样点位的PAHs以石油源为主,部分点位呈化石燃料源和石油源混合污染特征。对照风险效应低值(ERL)和风险效应中值(ERM)进行初步风险评价,表明研究区域部分采样点位的PAHs具有潜在的生态风险。     

Assessment of organic pollutants (PAH and PCB) in surface water: sediments and shallow groundwater of Grombalia watershed in northeast of Tunisia

Toxic organic compounds in wastewater are serious threats for both human and environment healthy states. This study investigates the potential sources of surface water, sediment and groundwater pollution by polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyl (PCBs) as discharged by wastewater into the River of Oued El bey in northeastern Tunisia. Analysis indicates that the concentration of PAHs and PCBs are high in wastewater and vary from 0.37 to 0.83 mg/L and from 0.28 and 1.18 mg/L, respectively. The spatial distribution of PAHs and PCB in surface water showed a variation between 0.37 to 9.91 mg/L and between 0.1 to 0.47 mg/L, respectively. However, the quality of surface water is changed after wastewater evacuation at Oued Tahouna. The determination of PAH and PCB pollutants in groundwater shows a great interest in the development of water resources. The Concentration of these pollutants varying from 0.0204 to 1.93 mg/L and from 0.0052 to 0.196 mg/L, respectively. For PAH, analysis reveals also that naphtelene, fluorene, anthracene and chrysene are the most detected PAHs compounds in water and sediment samples while benzo[b]fluoranthene and benzo[a]pyrene are less present and in trace level. Higher concentrations of PAHs and PCBs are found in samples taken close to industrial areas of Bouargoub and Soliman, and wastewater discharge locations in Soliman. Analysis of the spatial distribution of PAHs and PCBs clearly link their higher concentration in water and sediments to wastewater and manufacturing discharges in the study area. In surface sediment, the organic pollutants are present. The cluster analysis for organic pollutants in different state and different matrix highlight a relationship between the wastewater evacuation and the water qualities which confirmed the direct response of the pollution sources on the surface water and groundwater organic pollution quality.     

Tidal river sediments in the Washington,D.C. area. II. Distribution and sources of organic contaminants

Concentration of aliphatic, aromatic, and chlorinated hydrocarbons were determined from 33 surface-sediment samples taken from the Tidal Basin, Washington Ship Channel, and the Anacostia and Potomac rivers in Washington, D.C. In conjunction with these samples, selected storm sewers and outfalls also were sampled to help elucidate general sources of contamination to the area. All of the sediments contained detectable concentrations of aliphatic and aromatic hydrocarbons, DDT (total dichlorodiphenyltrichloroethane), DDE (dichlorodiphenyldichloroethene), DDD (dichlorodiphenyldichloroethane), PCBs (total polychlorinated biphenyls) and total chlordanes (oxy-, α-, and γ-chlordane and cis + trans-nonachlor). Sediment concentrations of most contaminants were highest in the Anacostia River just downstream of the Washington Navy Yard, except for total chlordane, which appeared to have upstream sources in addition to storm and combined sewer runoff. This area has the highest number of storm and combined sewer outfalls in the river. Potomac River stations had lower concentrations than other stations. Total hydrocarbons (THC), normalized to the fine-grain fraction (clay + silt, < 63 μm), ranged from 120 μg g^?1 to, 1,900 μg g^?1 fine-grain sediment. The hydrocarbons were dominated by the unresolved complex mixture (UCM), with total polycyclic aromatic hydrocarbons (PAHs) concentrations ranging from 4 μg g^?1 to 33 μg g^?1 fine-grain sediment. Alkyl-substituted compounds (e.g., C1 to C4 methyl groups) of naphthalene, fluorene, phenanthrere + anthracene, and chrysene series dominated the polycyclic aromatic hydrocarbons (PAHs). Polycyclic aromatic hydrocarbons, saturated hydrocarbons, and the unresolved complex mixture (UCM) distributions reflect mixtures of combustion products (i.e., pyrogenic sources) and direct discharges of petroleum products. Total PCB concentrations ranged from 0.075 μg g^?1 to 2.6 μg g^?1 fine-grain sediment, with highest concentrations in the Anacostia River. Four to six C1-substituted biphenyls were the most-prevalent PCBs. Variability in the PCB distribution was observed in different sampling areas, reflecting, differing proportion of Arochlor inputs and degradation. The concentration of all contaminants was generally higher in sediments closer to known sewer outfalls, with concentrations of total hydrocarbon, PAHs, and PCBs as high as 6,900 μg g^?1, 620 μg g^?1, and 20 μg g^?1 fine-grain sediment, respectively. Highest PCB concentrations were found in two outfalls that drain into the Tidal Basin. Concentrations of organic contaminants from sewers draining to the Washington Ship Channel and Anacostia River had higher concentrations than sediments of the mid-channel or river. Sources of PCBs appear to be related to specific outfalls, while hydrocarbon inputs, especially PAHs, are diffuse, and may be related to street runoff. Whereas most point-source contaninant inputs have been regulated, the importance of nonpoint source inputs must be assessed for their potential addition of contaminants to aquatic ecosystems. This study indicates that in large urban areas, nonpoint sources deliver substantial amounts of contaminants to ecosystems through storm and combined sewer systems, and control of these inputs must be addressed.     

气相色谱法测定地下水中有机氯农药和多氯联苯

建立了地下水中常见有机氯农药和多氯联苯的气相色谱分析方法。有机氯农药检出限均小于2.21ng/L,多氯联苯中PCB1检出限为5.20ng/L,其他目标组分检出限在1.30ng/L以下。两大类待测组分回收率均可以达到63.5%～110.2%,各组分精密度(RSD,n=5)在2.2%～17.3%。除异狄氏剂外,有机氯农药基体加标回收率为87.34%～133.76%。方法稳定性和重现性较好,样品前处理操作简便,适用于实验室分析或进一步改进。     

气相色谱-质谱法同时测定河流沉积物中多环芳烃和有机氯农药

建立了用加速溶剂萃取,气相色谱-质谱法同时测定河流沉积物中16种多环芳烃和19种有机氯农药的分析方法,优化了萃取溶剂、萃取温度和时间、凝胶渗透色谱收集时间、固相萃取洗脱溶剂和洗脱体积等条件。16种多环芳烃的方法检出限在0.15~0.59 ng/g,加标回收率为82%~102%,相对标准偏差(RSD,n=5)为1.1%~4.5%。19种有机氯农药的方法检出限在0.14~2.23 ng/g,加标回收率为71%~108%,相对标准偏差(RSD,n=5)为1.0%~4.5%。实际样品的测定结果表明,该方法分离效果较好,能够满足沉积物样品中多环芳烃和有机氯农药的分析要求。     

赣江流域持久性有机污染物（POPs）沉积记录——OCPs和PCBs分子地层学研究

通过对赣江河漫滩剖面沉积物中持久性有机污染物中OCPs和PCBs沉积记录进行研究,确定赣江流域有机污染历史。根据其浓度变化,进行了分子地层学的划分,其中在26～46 cm层段都存在HCHs、DDTs和PCBs的高浓度残留量,并且DDTs高浓度残留量则延续的更长。整个剖面中OCPs和PCBs残留量属于非污染状态,但应注意其重新被释放到环境中的风险。POPs分子沉积记录与赣江流域使用历史记录相一致,从而具有一定研究近现代沉积物的年代学意义。     

人类世的地球化学标志——沉积物中的持久性有机污染物

确定人类世地层标志物是选取全球层型剖面和点（GSSP）的重要前提。目前水系沉积记录作为人类世GSSP的候选表现出显著优越性。水系沉积物中的持久性有机污染物（POPs）可以连续、高分辨率地反映人类活动影响和强度变化,通过横向对比全球POPs历史变化可以获取潜在标志物的高速增长起点。本次研究收集了3类POPs的69套数据,通过分析数据的时间趋势重建其沉积记录,以求获得全球范围内各类POPs的增长特征。全球沉积记录显示20世纪40~60年代间不同类型的POPs开始展现出不同程度的快速增长,其中多环芳烃（PAHs）和多氯联苯（PCBs）可以作为潜在的标志物指示沉积物中化学地层的界限,有机氯农药（OCPs）中只有滴滴涕（DDTs）具备这种特性。同时,这3类POPs的沉积记录可以反映人类能源消耗、农业生产和工业品商品制造等方面活动,作为标志物体现人类多种活动营力在地球系统中留下的证据。

     

Organic and organometallic compounds in estuarine sediments from the Gulf of Mexico (1993–1994)

Sediment samples from 281 estuarine sites in the Gulf of Mexico were collected in 1993–1994 and analyzed for several classes of organic and organometallic compounds as part of the Environmental Monitoring and Assessment Program of the United States Environmental Protection Agency. Polynuclear aromatic hydrocarbons (PAHs) were the contaminant class found most frequently and in the highest concentrations; the sum of 24 congeners (ΣPAHs) ranged from <5 ng g^?1 to 15.500 ng g^?1 (dry wt basis). A low percentage of samples (3.9%) exceeded 2000 ng g^?1 ΣPAHs, and only six samples (2.1%) exceeded 4000 ng g^?1, a level above which adverse biological effects may be expected to occur. Less than 4% of sediments exceeded 20 ng g^?1 for the sum of 20 polychlorinated biphenyls (ΣPCBs) and only four samples (1.4%) exceeded 20 ng g^?1 for the sum of several organochlorine pesticides (ΣOCPs). A sample from Freeport Harbor, Texas, contained 4230 ng g^?1 ΣPAHs, 322 ng g^?1 ΣPCBs, and 49.6 ng g^?1 ΣOCPs. Tributyltin exceeded 100 ng g^?1 in only four samples, all of which were from stations in Corpus Christi Bay or Galveston Bay in Texas. The detection of a suite of organophosphate pesticides was very rare and did not exceed 15 ng g^?1. Sediments from the tidally influenced section of the Mississippi River in Louisiana contained low to moderate levels of all classes of organic compounds. The most contaminated sites were in urban estuaries (e.g., Corpus Christi, Galveston, and Pensacola (Florida bays), underscoring the need to concentrate future monitoring and assessment efforts at the regional and local level.     

PCBs and PAHs in surficial sediments from aquatic environments of Mexico City and the coastal states of Sonora,Sinaloa, Oaxaca and Veracruz (Mexico)

Concentrations of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were measured in 13 surficial sediment samples collected at three lacustrine locations in the surroundings of Mexico City and four coastal areas of the States of Sinaloa, Sonora, Oaxaca and Veracruz. Total PCB concentrations span the interval 3.18–621 ng g⁻¹. The highest values (63.7–621 ng g⁻¹) were found in Mexico City, which is a highly anthropogenically impacted area, whereas low concentrations (3.18–12.9 ng g⁻¹) were characteristic of seven places, some of them subject to intense hydrodynamics. In these latter cases, values increase by 18–73 times if normalised against the fine fraction (silt plus clay) content in sediment. Two samples from Mexico City exceed the ERM (Effect Range Median) guidelines and are likely to cause adverse effects. Samples contain only lower chlorinated PCBs (mainly 2-, 3- and 4-CB), thus suggesting that the most used PCB commercial mixture was Aroclor 1242. The homologue composition of the sample taken close to the nuclear power plant of Laguna Verde is identical to this commercial mixture. PAHs in the same samples have relatively low concentrations (14.9–287 ng g⁻¹), well below ERL (Effect Range Low) guidelines. The composition of PAH mixtures accounts for the influence of both petrogenic and pyrolitic sources, with these latter prevailing at some places in Mexico City.     

土壤和沉积物中22种有机氯农药和8种多氯联苯的气相色谱分析

近年来地下水、土壤和沉积物等介质中有机氯农药和多氯联苯分析方法的改善主要集中在样品前处理和分析测试条件等方面,而探讨布点、采样等方面的整套方法较少。本文建立了一套适用性较广的气相色谱法同时测定土壤和沉积物中22种有机氯农药和8种多氯联苯,方法检出限为0.09~0.48 ng/g,平均空白回收率为58.7%~133.7%。针对布点、采样、运输、保存、提取、净化、浓缩、仪器测试、数据处理和提交报告整个过程阐述了方法的有效性和实用性;并对提取、净化、测试等多个环节提供了两种或更多的选择,使方法具有更大的灵活性。本文提出,布点前应根据踏勘样品和前人资料考虑采集不同深度的样品;样品的布点、采集和制备均需选择样品,它们共同决定了样品的代表性;分析方法要灵活运用,对于很少检出的目标化合物可采用允许共峰但分析快速的方法,如果有检出再采用针对性的方法分别测定;样品的测定序列不应为了节约分析成本而过于简单。