酸奶中持久性有机污染物残留影响因素浅析

为探究影响酸奶中POPs残留的因素,采用化学提取预富集与GC-ECD相结合的方法,测定了产自北京六个不同区域以及产自中国不同城市相同品牌酸奶中和酸奶及其原料奶中OCPs、PCBs的残留水平。结果显示:北京地区酸奶中OCPs残留水平呈西南>>南部、城区>>东南、东北的分布,PCBs残留呈城区>>西南>南部、东南>>东北的分布;产自不同城市相同品牌酸奶中OCPs、PCBs残留水平与组成因地而异,表明奶源环境是影响酸奶中POPs残留水平的重要因素之一;酸奶中HCHs、DDTs、PCBs残留水平低于其原料奶,原因可能与酸奶生产过程中的加热灭菌环节和微生物发酵过程有关。     

哈尔滨郊区池塘养殖鱼类六六六和滴滴涕残留特征及食用健康风险

目的 明确哈尔滨郊区池塘养殖鱼类六六六(HCHs)和滴滴涕(DDTs)的残留水平及食用安全性。方法 以4种养殖鱼类(鲤、鲢、鲶和草鱼)为研究对象,采用气相色谱-串联质谱法(gas chromatography-tandem mass spectrometry, GC-MS)分析了49份鱼类样品的背肌、腹肌、肝脏、皮和鳃中HCHs和DDTs的残留水平,并对其可食部分进行致癌与非致癌风险评价。结果 HCHs和DDTs在鱼体各组织中残留量分别为0.299~12.881 μg/kg和0.012~1.439 μg/kg,均低于GB 2763—2021《食品安全国家标准 食品中农药最大残留限量》中规定的限量标准(DDTs≤500 μg/kg和HCHs≤100 μg/kg)。在背肌、腹肌和皮中,HCHs和DDTs残留量最高的均是鲶,鲢最低,而且背肌残留水平高于腹肌,HCHs的残留量大于DDTs。鱼体中残留的HCHs异构体组成以γ-六六六为主,贡献率在80.24%~95.82%,其次是α-六六六。食用该养殖鱼类导致的HCHs和DDTs每日摄入量分别为3.433~10.751 ng/(kg·d)和0.213~1.420 ng/(kg·d),均低于参考剂量(reference dose, RfD),致癌风险指数(carcinogenic risk index, CRI)在10-7~10-5,存在一定的潜在致癌风险;非致癌风险指数(non-carcinogenic hazard index, HI)均小于1,在可接受水平。结论 尽管HCHs和DDTs已被禁用多年,仍可在养殖鱼类体内检测到,但其残留水平低于国家限量标准,对人群无明显的食用健康风险。     

杭州湾南岸滩涂沉积物中HCHs与DDTs污染特征分析

摘 要：目的 了解六六六（hexachlorocyclohexanes,HCHs）与滴滴涕(dichloro diphenyl trichloroethanes,DDTs)在杭州湾南岸滩涂沉积物中的污染现状。方法 于2018年4月，采集杭州湾南岸地区4个采样点不同深度（0~80 cm）滩涂沉积物，利用气相色谱-串联质谱法（gas chromatography tandem mass spectrometry, GC-MS/MS）测定了该区域中HCHs与DDTs的含量，对其分布规律进行分析，使用共识沉积物质量基准法对其生态学风险进行了评估。结果 所有样品中均检出，HCHs与DDTs含量分别为4.20~6.24 μg/kg与3.37~4.73 μg/kg，主要以β-HCH、δ-HCH以及DDE为主，其污染主要来源于历史性工业品，整体污染处于较低水平；20.3%的沉积物样品中DDEs含量以及28.1%的样品DDTs总量介于阈值效应浓度(threshold concentration, TECs) 和可能效应浓度(probable effect concentration, PECs)之间。结论 杭州湾南岸沉积物中HCHs与DDTs的污染处于较低水平，具有较小的生态学风险。     

我国主产区油茶持久性有机污染物分布特征及相关性研究

为了明确油茶中持久性有机污染物(POPs)的污染分布特征,利用气相色谱-三重四极杆串联质谱(GC-MS/MS)对我国主产区45个采样点135批次油茶果不同部位及对应油茶林土壤进行16种多环芳烃(PAHs)、18种多氯联苯(PCBs)和21种有机氯(OCPs)污染水平分析。同时分析油茶籽仁和油茶林土壤中主要POPs之间相关性。结果表明:油茶果各部位及油茶林土壤PAHs污染以萘、苊烯、苊萘嵌戊烷、荧蒽等低环PAHs污染较为明显;PCBs污染程度很轻,含量均在1μg/kg以下;OCPs污染主要为狄氏剂、毒杀芬、α-六六六、硫丹、异狄氏剂和艾氏剂。油茶籽仁中荧蒽与菲具有强正相关(R~2=0.90);油茶林土壤中芴与菲,■与苯并(a)蒽、苯并(b)荧蒽、苯并(k)荧蒽、苯并(a)芘和苯并(a)蒽,PCB138与茚并(1,2,3-cd)芘,PCB180与苯并(g,h,i)苝,p,p′-DDE与o,p′-DDT、p,p′-DDD之间均具有较强相关性(R~2=0.81～0.98)。     

我国母乳中持久性有机污染暴露水平及主要来源研究

本文介绍了我国母乳中有机氯农药(OCPs)、二噁英(PCDD/Fs)、多氯联苯(PCBs)、多溴联苯醚(PBDEs)、全氟代烃类化合物(PFCs)等持久性有机污染物(POPs)的污染状况及可能的暴露来源。持久性有机污染物在我国母乳中存在一定的身体负荷,可能对婴儿的健康产生不利影响。     

江西省市售保健食品中有机氯农药的残留特征

为了解江西省市售保健食品中有机氯农药的残留情况。于2009年在江西省市售保健食品中采集34份不同产品(口服液类,胶囊类,含片类),采用填充柱气相色谱法测定保健品中六六六(HCBs)和滴滴涕(DDTs)的含量,并从剂型上分析了其残留特征。结果显示,所测样品中有机氯农药的检出率高达94.1%,总有机氯含量为0.005 mg/kg~0.211 mg/kg,其中HCBs和DDTs的检出率分别为94.1%和23.5%,残留范围分别为0.005 mg/kg~0.159 mg/kg和0.067 mg/kg~0.177 mg/kg。口服液和胶囊类保健食品中有机氯农药的检出率和残留浓度都高于含片类。HCBs的主要残留成分为δ-HCB,其次为γ-HCB,DDTs的主要残留成分为p,p'-DDT。本次抽检的江西省保健食品中有机氯农药残留情况不容乐观,使用纯天然、无污染的原料是保证天然保健食品应用安全的前提,同时需要加大监督管理力度,保障消费者的身体健康。     

QuEChERS-气相色谱分析厦门海域鱼体中有机氯类农药残留特征及风险评价

以厦门海域10种鱼类作为研究对象,利用QuEChERS-气相色谱分析鱼肉中有机氯农药(organochlorine pesticides,OCPs)的残留水平和特征,并探讨其可能的健康风险。样品经V(正己烷)∶V(丙酮)=1∶1提取,经400 mg PSA,150 mg C18和900 mg无水MgSO4净化,采用气相色谱定性和定量分析,结合气相色谱-质谱法确认。各OCPs在1～50μg/L质量浓度范围内线性相关系数均大于0. 998 8,回收率为83. 2%～103. 5%,精密度为4. 8%～12. 1%,检出限0. 01～0. 09μg/kg; 10种鱼类均有OCPs检出,含量在5. 532～22. 174μg/kg之间,带鱼和鳓鱼的OCPs含量最高,分别为22. 174μg/kg和19. 910μg/kg; P’P’-DDD、P’P’-DDE和β-HCH是最主要的OCPs污染物;各异构体的含量水平和组成特征表明该水域的OCPs大部分来自早期农药使用残留,但疑似有三氯杀螨醇引入的DDT污染;估计每日膳食摄入量(estimated daily intake,EDI)均远低于国标规定值。Qu EChERS可以应用于大批量水产品中OCPs的检测分析,厦门海域的水环境近期受OCPs污染较小,食用该水域的鱼类产生OCPs危害的风险较低。     

沙棘酸奶挥发性风味物质的GC-IMS表征

为探究沙棘酸奶中的挥发性风味物质，明确复配沙棘进行发酵对酸奶感官和风味物质的影响，通过感官评价与顶空-固相微萃取-气相色谱-离子迁移谱法(HS-SPME-GC-IMS)结合多元统计分析方法对发酵沙棘酸奶的挥发性化合物进行分析，实现特征挥发性化合物的表征。结果表明，沙棘酸奶产生了多种挥发性物质，酯类、酮类和醛类为主要挥发性物质来源。发酵过程减弱了沙棘原浆带来的酸涩味道，使滋味更加柔和，香气更加浓郁、典型。主成分分析筛选出了对香气贡献较大的化合物，聚类分析将挥发性化合物分成三类。其中2, 2, 4, 6, 6-五甲基庚烷、乙酸乙酯(单体)、2-甲基丁酸乙酯、丁酸丙酯、甲酸丁酯(二聚体)、糠硫醇、甲酸异戊酯、乙酸乙酯(二聚体)和甲酸丁酯(单体)为发酵沙棘酸奶的主要风味物质。本研究为复合酸奶的风味物质分析提供了研究思路，研究结果为沙棘酸奶后期的风味提升提供一定理论基础。     

磁固相萃取法研究某场区地下水中有机氯农药

利用磁性多孔碳材料作为吸附剂,借助三重四级杆气质联用仪(GC-MS/MS)多反应检测模式(MRM),通过磁固相萃取(MSPE)的前处理方法,对日照某垃圾填埋场区地下水中的有机氯农药进行分析检测。此分析方法具有采样量小,节省分析试剂,省时省力等明显优越性。采取该区14个地下水样,进行检测结果表明:垃圾填埋场周边的地下水中有机氯农药污染率达100%,其中六六六(HCHs)含量远大于滴滴涕(DDTs),从而说明地下水环境中仍存在有机氯残留。     

宁波海产品中多氯联苯的残留与风险评估

为探讨多氯联苯(PCBs)污染物在宁波市售海产品中的组成规律及季节变化特征,按不同季节采集10种宁波居民主要食用海产鱼类,采用气相色谱法检测其中7种指示性多氯联苯残留量,并进行人体健康风险评价。结果表明,PCBs的残留质量分数为0.06~3.98μg/kg,其中PCB-52和PCB-153为主要组分。PCBs含量分布特征为秋季最高,冬季次之,夏季最低。宁波市售海产品中多氯联苯残留量水平在可接受的范围内。食用上层鱼的健康风险CV值小于食用下层鱼,PCBs监测是风险评估需要控制的关键因素。     

Human health risk of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in edible fish from Huairou Reservoir and Gaobeidian Lake in Beijing,China

Organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) were measured by a gas chromatography–mass spectometry (GC–MS) in some edible fish from Huairou Reservoir and Gaobeidian Lake in Beijing, China. The concentrations of OCPs and PCBs were higher in fish (except Misgurnus anguillicaudatus) from Gaobeidian Lake than in those from Huairou Reservoir. The average concentrations of HCHs, DDTs and PCBs in fish ranged from 0.58 to 8.48, 7.54 to 88.3, below limit of detection (nd) to 22.7 ng/g wet weight, respectively. β-HCH, p,p′-DDE and PCB153 were the most abundant compounds among HCHs, DDTs and PCBs, respectively. Risk assessments of OCPs and PCBs for humans were estimated according to three different guidelines. The results indicated that fish intake would not pose a health risk to humans with a consumption of 7.4 ± 8.6 g/person day according to the acceptable daily intake (ADI) and minimal risk level (MRL) in the two environments. However, the hazardous ratio of the 95th percentile for PCBs in fish from Gaobeidian Lake exceeded 1, which suggested that daily exposure to PCBs had a lifetime cancer risk of greater than 1 in 1,000,000.     

Persistent halogenated hydrocarbons in consumer fish of China: regional and global implications for human exposure

Concentrations of persistent halogenated hydrocarbons (PHHs) were determined in 13 consumer fish species (a total of 390 individuals) collected from a major fish-farming region of China. The potential health risks of PHHs associated with consumption of fish from China was also systematically assessed regionally and globally. In all fish samples, DDTs, HCHs, PCBs, and PBDEs were the predominant PHH residues, with the median levels (ranges) being 6.0 (0.14-698.9), 0.50 (0.13-24.06), 0.10 (< 0.02-7.65), and 0.15 (< 0.0012-3.85) ng/g wet weight, respectively. The upper-bound (90th percentile) values of estimated daily intakes of DDT, HCHs, PCBs, and PBDEs via fish consumption were 45.5, 1.35, 0.46, and 0.30 ng/kg bw/d (urban), and 15.9, 0.47, 0.16, and 0.10 ng/kg bw/d (rural). Globally, the upper-bound outflows via fishery exportation of DDT, HCHs, PCBs, and PBDEs were 185, 5.51, 1.86, and 1.22 kg, respectively, in 2005. Japan was the largest recipient of PHHs, followed by Korea and the United States. Fish consumption assessments indicated that consumption of freshwater farmed and wild marine fish generally does not subject consumers to significant health risk as far as PHHs are concerned, while limited consumption of seawater farmed fish is advised.     

Asian Mussel Watch Program: contamination status of polybrominated diphenyl ethers and organochlorines in coastal waters of Asian countries

Mussel samples were used in this study to measure the levels of polybrominated diphenyl ethers (PBDEs) and organochlorines (OCs) in the coastal waters of Asian countries like Cambodia, China, Hong Kong, India, Indonesia, Japan, Korea, Malaysia, the Philippines, and Vietnam. PBDEs were detected in all the samples analyzed, and the concentrations ranged from 0.66 to 440 ng/g lipid wt. Apparently higher concentrations of PBDEs were found in mussels from the coastal waters of Korea, Hong Kong, China, and the Philippines, which suggests that significant sources of these chemicals exist in and around this region. With regard to the composition of PBDE congeners, BDE-47, BDE-99, and BDE-100 were the dominant congeners in most of the samples. Among the OCs analyzed, concentrations of DDTs were the highest followed by PCBs > CHLs > HCHs > HCB. Total concentrations of DDTs, PCBs, CHLs, and HCHs in mussel samples ranged from 21 to 58 000, 3.8 to 2000, 0.93 to 900, and 0.90 to 230 ng/g lipid wt., respectively. High levels of DDTs were found in mussels from Hong Kong, Vietnam, and China; PCBs were found in Japan, Hong Kong, and industrialized/urbanized locations in Korea, Indonesia, the Philippines, and India; CHLs were found in Japan and Hong Kong; HCHs were found in India and China. These countries seem to play a role as probable emission sources of corresponding contaminants in Asia and, in turn, may influence their global distribution.     

Temperature and organic matter dependence of the distribution of organochlorine compounds in mountain soils from the subtropical Atlantic (Teide,Tenerife Island)

Surface soil samples from Teide mountain (Canary Islands) have been analyzed for polychlorobiphenyls (PCBs), DDTs, hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB), and pentachlorobenzene. The samples were situated between 10 and 3400 m above sea level being distributed below, at, and above the permanent inversion layer system characteristic of the subtropical Atlantic. All OC concentrations were, in general, low when compared with the data from urban, agricultural, or woodland soils reported elsewhere. Typical ranges were 0.04-9.2, 0.01-40, 0.001-1, or 0.01-3.2 ng x g(-1) dry weight for total PCBs, DDTs, HCHs, or HCB, respectively. These compounds exhibited a high dependence from the soil total organic carbon (TOC), showing high coefficients in the log(OC) versus log(TOC) correlations. The slopes of the curve fitted straight lines were, in turn, highly correlated to the log-transformed octanol-air coefficients of the compounds. This overall OC distribution points to steady-state conditions for the concentrations of these compounds in these mountain soils, in equilibrium with TOC. The equilibrium conditions are reached, despite the restrictions to convective air movement associated to the permanent atmospheric inversion layer at these latitudes. In addition, the log-transformed TOC-normalized concentrations of most PCBs, HCB, and pentachlorobenzene exhibit a good correlation with the reciprocal of average annual atmospheric temperatures also showing a temperature dependence for their distribution in the high mountain system. The calculated pseudo-enthalpies for this dependence, 120-160 kJ x mol(-1), exhibit higher values than those of octanol-air phase change calculated from laboratory experiments in previous studies, 66-93 kJ x mol(-1). The difference suggests a higher affinity of OC to soils than that corresponding to simple adsorption mechanisms.     

双重净化-气相色谱法同时测定蛋及蛋制品中六六六、滴滴涕和指示性多氯联苯

建立同时测定蛋及蛋制品中六六六、滴滴涕和指示性多氯联苯残留量的双重净化-气相色谱法。样品经乙腈提取,浓硫酸和焙烧型水滑石双重净化后采用气相色谱分析和外标法定量。结果表明：与传统的磺化法相比,采用浓硫酸和焙烧型水滑石双重净化的效果更好,干扰物质少,且目标物提取更充分。在10～200 μg/L的添加水平内4 种六六六、2 种滴滴涕和7 种指示性多氯联苯的线性关系良好,相关系数均大于0.999。方法的检出限（RSN=3）范围为1.12～3.89 μg/kg,定量限（RSN=10）范围为3.73～12.97 μg/kg。添加10、20、100 μg/kg 3 个水平的4 种六六六、2 种滴滴涕和7 种指示性多氯联苯于鸡蛋液、咸蛋及皮蛋空白样品中,加标回收率范围为78.04%～105.05%,相对标准偏差范围为1.28%～7.55%。该方法操作简便快速、准确、灵敏,适用于蛋及蛋制品中六六六、滴滴涕和指示性多氯联苯残留量的快速测定。     

湖北省水产品中持久性有机污染物残留状况分析

目的了解湖北省居民日常消费的水产品中持久性有机污染物的残留情况。方法采集水产品品种39种共285批次,采用气相色谱-质谱法测定水产品中的16种多环芳烃、15种有机氯农药及相关降解产物和31种多氯联苯单体残留,并进行统计分析。结果3环化合物检出率为46%,4环化合物检出率为36%,水产样品中检出的多环芳烃类目标物以3环、4环为主,为中、低环化合物,6环化合物在所有样品中均未检出。各品种鱼体内多环芳烃总量排序为:鲫鱼>鳊鱼、刁子鱼>草鱼、财鱼、桂鱼、鲶鱼、鲢鱼>龙虾、泥鳅、黄鳝、黄颡鱼,多环芳烃总量最高的为鲫鱼,检出含量为85.34μg/kg。结论在湖北省养殖环节和流通环节的水产品中,多环芳烃类化合物残留主要为蒽、芴、萘、菲,均为3环、4环化合物;未检出多氯联苯类化合物;水产样品中有机氯农药残留主要为滴滴涕、氧氯丹、六氯苯。     

Polychlorinated biphenyls and organochlorine pesticides in seafood from the Gulf of Naples (Italy)

Seven target polychlorinated biphenyls (PCBs; IUPAC nos. 28, 52, 101, 118, 138, 153, and 180) and the organochlorine pesticides (OCPs) hexachlorobenzene (HCB) and dichlorodiphenyltrichloroethane (DDT) and its related metabolites (p,p'-DDT, p,p'-DDE, and p,p'-DDD) were quantified in edible tissues from seven marine species (European hake, red mullet, blue whiting, Atlantic mackerel, blue and red shrimp, European flying squid, and Mediterranean mussel) from the Gulf of Naples in the southern Tyrrhenian Sea (Italy). PCBs 118, 138, and 153 were the dominant congeners in all the species examined. The concentrations of all PCBs (from not detectable to 15,427 ng g(-1) fat weight) exceeded those of all the DDTs (from not detectable to 1,769 ng g(-1) fat weight) and HCB (not detectable to 150.60 ng g(-1) fat weight) in the samples analyzed. The OCP concentrations were below the maximum residue limits established for fish and aquatic products by the Decreto Ministerale 13 May 2005 in all the samples analyzed; therefore the OCPs in the southern Tyrrhenian Sea species are unlikely to be a significant health hazard. Conversely, the mean concentrations of PCBs exceeded (greatly in some cases) the current limits (200 ng(-1) fat weight) set by the European Union for terrestrial foods. Although the manufacture and use of PCBs are banned or highly restricted, these compounds still are important persistent chemical contaminants in the Gulf of Naples.     

Distribution and mass inventories of polycyclic aromatic hydrocarbons and organochlorine pesticides in sediments of the Pearl River Estuary and the northern South China Sea

Surface sediment (0-5 cm) samples were collected from the Pearl River Estuary (PRE) and the adjacent northern South China Sea (SCS) in July 2002 and analyzed for 25 polycyclic aromatic hydrocarbons (PAHs) and 8 organochlorine pesticides (OCPs) including dichlorodiphenyltrichloroethanes (DDTs), hexachlorocyclohexanes (HCHs), and heptachlor. The total PAHs and OCPs concentrations were 138-1100 and 0.18-3.57 ng/g dry weight, respectively. Compositional pattern analysis suggested that PAHs in the PRE were derived from both pyrogenic and petrogenic sources, whereas most PAHs in the northern SCS were pyrogenically originated. The concentrations of both PAHs and OCPs were higher in the PRE than in the northern SCS, and a decreasing trend with the distance from the estuary to the open sea was observed. In addition, perylene was a predominant component in all samples and clustered with PAH compounds with high log Kow values (from phenanthrene). These findings indicated that river outflows were the major source of contamination in the offshore sediments. A preliminary assessment suggested that atmospheric deposition contributed only a minor portion of PAHs or OCPs in the sediments of the northern SCS. The sediment (0-5 cm) mass inventories were 126 and 423 metric tons for PAHs and were 0.4 and 1.4 metric tons for OCPs in the PRE and the northern SCS, respectively. Clearly, contaminated sediments of the northern SCS may be a potential source of PAHs and OCPs to the global oceans.     

Investigation of selected persistent organic pollutants in farmed Atlantic salmon (Salmo salar), salmon aquaculture feed,and fish oil components of the feed

There is extensive literature documenting the bioaccumulation of persistent organic pollutants in the marine environment, but relatively little data are available on contamination pathways in aquaculture systems such as that for farmed salmon. In recent years,the salmon industry has grown significantly in Europe. This study reports on the determination of a wide range of polychlorinated biphenyls (PCBs), organochlorine pesticides, and polybrominated diphenyl ethers (PBDEs) in farmed and wild European Atlantic salmon fish, aquaculture feeds, and fish oils used to supplement the feeds. The study confirms previous reports of relatively high concentrations of PCBs and indicates moderate concentrations of organochlorine pesticides and PBDEs in farmed Scottish and European salmon. Concentrations of the selected persistent organic pollutants varied among the samples: PCBs (salmon, 145-460 ng/g lipid; salmon feeds, 76-1153 ng/g lipid; fish oils, 9-253 ng/g lipid), S DDTs (salmon, 5-250 ng/g lipid; salmon feeds, 34-52 ng/g lipid; fish oils, 11-218 ng/g lipid), and PBDEs (salmon, 1-85 ng/g lipid: salmon feeds, 8-24 ng/g lipid; fish oils, ND-13 ng/g lipid). Comparison of the samples for all groups of contaminants, except for HCHs, showed an increase in concentration in the order fish oil < feed < salmon. Homologue profiles were similar, with an increase in contribution of hepta- and octa-PCBs in the fish, and profiles of DDTs were similar in all three types of samples. With a constant contribution to the total PCB content, the ICES 7 PCBs appear to be reliable predictors of the PCB contamination profile through all the samples. For PBDEs, BDE 47 dominated the profiles, with no significant difference in the PBDE profiles for the three matrixes. Samples with higher PCB contents generally showed higher levels of the pesticide residues, but this was not the case with the PBDEs, indicating the existence of different pollution sources.