环境中短链和中链氯化石蜡的来源、污染特征及环境行为研究进展

短链氯化石蜡(SCCPs)是持久性有机污染物,已于2017年5月被正式列入《关于持久性有机污染物的斯德哥尔摩公约》附件A的受控名单.中链氯化石蜡(MCCPs)具有相似的性质.由于氯化石蜡(CPs)大量生产以及广泛应用,其在环境介质中的含量处于较高水平.本文综述了SCCPs和MCCPs的生产和排放,以及2016年以后文献报道的SCCPs和MCCPs在不同环境介质中的研究进展,包括在大气、水体、土壤和沉积物中的赋存、分布特征,探讨了SCCPs和MCCPs的环境行为,同时指出环境中CPs的溯源、界面过程及区域传输是未来的主要研究方向.     

短链氯化石蜡暴露对HepG2细胞代谢的影响

短链氯化石蜡(short-chain chlorinated paraffins,SCCPs)是一组成分复杂的氯代正构烷烃,在环境中普遍存在。然而有关其毒性机理的信息十分有限,限制了对其健康风险的评估。本研究采用液相色谱–串联质谱(LC-MS/MS)分析技术,研究了不同剂量的SCCPs暴露(0、1.0、10.0和100.0μg·L-1;C13-CPs;55.0%Cl)对人体肝癌细胞Hep G2的糖代谢、氨基酸代谢和脂肪酸代谢的影响。通过偏最小二乘判别分析(PLS-DA)鉴别各组代谢产物谱差异,发现3个SCCPs暴露剂量组均能够与对照组完全分开,表明SCCPs短期暴露能够引起细胞代谢活动的显著改变。SCCPs的低剂量暴露可明显刺激Hep G2细胞对氨基酸的吸收。与对照组相比,SCCPs低剂量暴露组(1.0μg·L-1)培养基中谷氨酰胺、色氨酸和丝氨酸的含量显著(P0.05)降低。而高剂量SCCPs(100.0μg·L-1)暴露抑制了细胞对氨基酸和葡萄糖吸收,但促进了乳酸、丙氨酸、半胱氨酸的生成。氨基酸吸收的抑制不可避免地会影响蛋白质的合成。同时,SCCPs的暴露使饱和脂肪酸代谢紊乱,使不饱和脂肪酸水平上调。为确定SCCPs的毒性作用方式,有必要从转录组和蛋白组层面进一步研究其毒性机制。     

短链氯化石蜡(SCCPs)和多环芳烃(PAHs)联合暴露对HepG2细胞抗氧化系统的影响

环境污染物的低剂量、联合毒性效应已经成为毒理学研究中的热点问题。短链氯化石蜡(SCCPs)和多环芳烃(PAHs)都是典型的有机污染物且在人母乳和血液中都以较高的浓度水平存在。为探究PAHs和SCCPs的联合暴露毒性效应,选择了HepG2细胞作为受试模型,测定了PAHs、SCCPs和它们的混合物暴露后细胞增殖活性及抗氧化系统指标。结果表明,PAHs和SCCPs暴露都能引发ROS的产生,两者混合时更加剧了ROS的产生,表现为协同效应。另外,PAHs和SCCPs暴露都能引起过氧化物歧化酶(SOD)活性的降低,因此两者混合时共同抑制SOD酶活性,表现为协同效应。而PAHs引起过氧化氢酶(CAT)活性升高,SCCPs则显著抑制CAT酶活性,两者联合暴露时CAT酶活性仍降低,但表现为拮抗效应。另外,PAHs和SCCPs暴露都引起谷胱甘肽(GSH)含量的轻微下降,只有SCCPs暴露引起丙二醛(MDA)含量显著升高,而两者联合暴露对GSH含量和MDA含量的影响表现为拮抗效应。表明不管是PAHs和SCCPs单独暴露还是联合暴露都能够干扰HepG2细胞内部的抗氧化系统,破坏抗氧化系统和自由基之间的平衡,使细胞氧化性损伤,甚至造成细胞凋亡。     

电子垃圾拆解区氯化石蜡和多氯联苯的分布特征——以广东清远龙塘镇为例

采用GC/MS法测定了广东清远龙塘镇电子垃圾拆解区电子垃圾、电子垃圾焚烧后残渣、当地池塘沉积物和对照区沉积物24种短链氯化石蜡(SCCPs)、24种中链氯化石蜡(MCCPs)和29种多氯联苯(PCBs)的浓度水平.结果显示,氯化石蜡(CPs)和PCBs大量存在于电子垃圾中.电子垃圾、残渣和池塘沉积物SCCPs和MCCPs浓度范围(干重)分别为1.6—46.8μg·g-1和7.3—215μg·g-1,PCBs的浓度范围(干重)为0.15—370.6μg·g-1,明显高于对照区,对周边造成了极大环境风险.SCCPs、MCCPs和PCBs均呈现低碳低氯同系物的相对含量在电子垃圾、电子垃圾焚烧残渣、拆解区池塘沉积物、对照区沉积物中依次递增的现象,表明CPs和PCBs在由电子垃圾向沉积物迁移过程中可能存在脱碳脱氯的降解过程.     

环境空气中短链氯化石蜡研究进展

短链氯化石蜡(SCCPs)是碳链长度为10至13个碳原子的正构烷烃氯代衍生物。SCCPs具有持久性、生物累积性、长距离迁移能力、以及毒性作用。SCCPs已被《关于持久性有机污染物的斯德哥尔摩公约》增列为持久性有机污染物审查范围内,引起了全球关注。SCCPs在环境各介质及生物体内均有检出,近年来,在室内空气和灰尘中也检出了大量SCCPs,其已成为人体暴露的一个重要来源。本文就大气环境及室内空气与灰尘中氯化石蜡(CPs)的采样与分析方法、污染水平与来源,及人体暴露概况进行了综合阐释,以期为我国大气和室内环境中CPs的研究工作提供参考。     

全氟辛烷磺酸对斑马鱼肝脏影响机制的代谢组学研究

为探究全氟辛烷磺酸(PFOS)对水生动物肝脏的慢性毒性毒害机制,寻找其肝脏慢性毒性相关的潜在标志物,运用气相色谱-质谱联用仪代谢组学方法研究暴露于PFOS中斑马鱼肝脏内源性代谢物的变化,寻找显著性差异代谢物及相关通路。实验分为4组:对照组及PFOS浓度分别为10、100、250μg·L~(-1)的实验组,每组20尾斑马鱼,实验时长40 d。结果显示,与对照组相比,PFOS浓度为10μg·L~(-1)的斑马鱼肝脏中筛选出4种发生显著性变化的代谢物,分别为牛磺酸、磷酸乙酰胺、β-D-葡萄糖、油酸,涉及4条代谢通路,即牛磺酸和亚牛磺酸代谢、鞘脂代谢、甘油磷脂代谢、糖酵解或葡萄糖生成。100μg·L~(-1)浓度组的斑马鱼肝脏中筛选出5种,包括牛磺酸、β-D-葡萄糖、棕榈酸、油酸、胆固醇,涉及5条代谢通路,即原代胆汁酸生物合成、牛磺酸和亚牛磺酸代谢、类固醇生物合成、类固醇激素生物合成、糖酵解或葡萄糖生成。250μg·L~(-1)浓度组的斑马鱼肝脏中筛选出5种,即牛磺酸、β-D-葡萄糖、乳酸、甘油-3-磷酸、磷酸乙酰胺,涉及5条代谢通路:牛磺酸和亚牛磺酸代谢、甘油磷脂代谢、甘油脂代谢、鞘脂代谢、糖酵解或葡萄糖生成。根据筛选出的差异代谢物生理功能和其涉及代谢通路分析,推测PFOS主要通过影响牛磺酸和亚牛磺酸代谢、糖酵解或葡萄糖生成及一些脂类代谢从而对斑马鱼肝脏产生毒性效应,其中牛磺酸、葡萄糖与油酸这3种代谢物可作为斑马鱼受PFOS胁迫肝脏代谢异常的潜在标记物。     

淡水环境中短链氯化石蜡的预测无效应浓度及生态风险评估

短链氯化石蜡(short-chain chlorinated paraffins, SCCPs)是《斯德哥尔摩公约》增列的一类持久性有机污染物。搜集筛选出SCCPs对8种淡水生物的慢性毒性数据,构建了物种敏感度分布曲线(SSD),推导出SCCPs的淡水预测无效应浓度(PNECwater)为0.425μg·L~(-1),淡水沉积物预测无效应浓度(PNECsed)为992.5μg·kg-1。搜集了国内外部分淡水河流水体及沉积物中SCCPs环境暴露数据,运用商值法,评估SCCPs的生态风险。结果表明,长江中游和白洋淀水体风险商范围为2.6～154.4和3.7～132.5,处于高风险;国外河流SCCPs污染水平较低,北美地区与日本淡水河流SCCPs风险商小于1,处于低风险。长江中游沉积物的SCCPs的风险商高达400.6,呈现显著风险,欧洲工业区域淡水沉积物中SCCPs存在潜在风险。本研究为SCCPs水质标准制定与环境风险管理提供参考依据。     

短链氯化石蜡在台州电子拆解地区的分布特征

以峰江为中心,采集了台州电子垃圾拆解区域的26个表层土壤样品,调查台州地区短链氯化石蜡(SCCPs)的污染状况、空间分布和单体构成情况.结果表明,SCCPs在所有土壤样品中均有检出,其浓度水平介于47.95—1298 ng·g-1干重,平均值为276.7 ng·g-1干重.C10和Cl6—7为土壤中SCCPs最主要的碳原子和氯原子同族体.空间分布表明短链氯化石蜡的浓度水平总体呈现随距采样点中心峰江距离增加而减少的趋势,说明电子垃圾拆解活动可能是SCCPs的一个潜在释放源.     

土壤中短链氯化石蜡的气相色谱-电子捕获负化学电离-质谱分析方法

通过考察层析柱对测定短链氯化石蜡(SCCPs)干扰物去除效果的影响,结合实际土壤样品的净化需求,建立了一套适合分析土壤中SCCPs的前处理方法.土壤样品使用索氏抽提,采用硅胶复合柱和弗罗里硅土柱净化,运用气相色谱-质谱(ECNI源)检测SCCPs.SCCPs的仪器定量限为100—600 pg.μL-1.空白加标和基质加标中SCCPs的回收率分别为130%±8.50%和108%±17.8%(SD,n=3).利用该方法分析了采自广州市郊区的6个土壤样品,其SCCPs的含量范围为12.9—34.5 ng.g-1,平均值为26.1 ng.g-1.     

辽东湾海域短链氯化石蜡的生物累积特征

为了解短链氯化石蜡(SCCPs)在我国海域的污染现状,于2009年采集了渤海辽东湾海域的浮游动物、8种底栖动物(虾、蟹、蛤、扇贝和螺)和6种鱼类,采用高分辨气相色谱/电子捕获负离子化-低分辨质谱(HRGC/ECNI-LRMS)分析了其中的SCCPs.结果表明,渤海辽东湾海域水生动物体中SCCPs的含量变化范围为O.66...     

不同耐铝型小麦品种苹果酸分泌差异与有机酸代谢关系研究

铝胁迫下不同耐铝型植物有机酸分泌存在显著差异,有机酸主要在三羧酸循环途径中产生,但目前有机酸分泌差异与有机酸代谢关系还不是很清楚。以耐铝型小麦Triticum aestivum L.品种ET8和铝敏感型小麦品种ES8为材料,研究了铝胁迫对不同耐铝小麦品种根内源苹果酸含量及磷酸烯醇式丙酮酸脱氢酶（PEPC）,柠檬酸合成酶（CS）和苹果酸脱氢酶（MDH）等酶活性的影响。结果表明：铝处理（0、25、50、100μmol.L-1）对内源苹果酸含量无显著影响,相同处理条件下ET8和ES8间亦无显著差异,分别为每根尖（0.48±0.01）、（0.46±0.03）、（0.57±0.02）、（0.52±0.02）nmol和（0.45±0.02）、（0.51±0.09）、（0.51±0.11）、（0.54±0.04）nmol;同无铝处理相比,50或100μmol.L-1铝处理显著促进ET8和ES8根尖细胞PEPC活性升高,但各铝浓度处理对CS和MDH活性无显著影响;相同处理条件下ET8和ES8根尖细胞PEPC,CS和MDH 3种酶活性均无显著差异。综上所述,铝胁迫下不同耐铝小麦品种根苹果酸分泌差异与内源苹果酸含量及有机酸代谢无关。     

Untargeted metabolomic analysis of pregnant women exposure to perfluorooctanoic acid at different degrees

● Metabolome can distinguish pregnant women exposure to PFOA at different degrees. ● Metabolome can reveal the metabolic changes of pregnant women exposure to PFOA. ● PFOA exposure degrees could affect the GSH metabolism of pregnant women. ● PFOA exposure degrees could change the microbiota metabolism of pregnant women. Perfluorooctanoic acid (PFOA) is a novel type of persistent synthetic organic pollutant, and its exposure on pregnant women can cause some adverse effects, such as pregnancy-induced hypertension, gestational diabetes mellitus, and preeclampsia. Therefore, understanding the metabolic changes caused by PFOA exposure is of great significance to protect pregnant women from its adverse effects. In this study, the metabolomes from the urine samples of pregnant women exposure to PFOA at different degrees were analyzed by GC-MS and LC-MS. The samples in different groups were distinguished and the differential metabolites were screened based on the VIP value, FC, and P-value of each comparison group through multivariate statistical analysis. The pathways related to differential metabolites were searched to reveal the effects of PFOA exposure on metabolic changes in pregnant women at different degrees. Finally, the ROC of differential metabolites was performed, and the differential metabolites with large area under the curve (AUC) values were selected and compared to identify the mutually differential metabolites. Meanwhile, these metabolites were fitted with a multivariable to explore if they could be used to distinguish different groups. The quantitative comparison of mutually differential metabolites revealed that the levels of L-cysteine, glycine, and 5-aminovaleric acid were positively correlated with the degree of PFOA exposure, indicating that different degrees of PFOA exposure could affect the synthesis or degradation of GSH and change the metabolism of oral or intestinal microbiota. Additionally, they may cause oxidative stress and abnormal fat metabolism in pregnant women.     

乙酰辅酶A羧化酶:脂肪酸代谢的关键酶及其基因克隆研究进展

乙酰辅酶A羧化酶(Acetyl-CoA carboxylase,ACC)在脂肪酸合成和分解代谢中发挥着重要作用.系统介绍了该酶的结构与分类、生物学作用与应用、抑制剂的类型与作用机理以及基因克隆4个方面的进展.ACC在大多数原核生物中为多亚基型酶,而在大多数真核生物中为多功能型单亚基酶,在天蓝色链霉菌和古菌勤奋金属球菌中为另外两种特殊类型;但都具备3个关键的功能域,即生物素羧化酶(BC)、生物素羧基载体蛋白(BCCP)和羧基转移酶(CT).CT功能域作为潜在的靶标广泛应用于植物除草剂的筛选和哺乳动物肥胖、糖尿病等代谢疾病的药物设计中.ACC基因也成为转基因油料作物和生物柴油研究中重要的靶标基因.研究表明,植物质体中的β-CT亚基是多亚基型ACC的限制因子,而BCCP是脂肪酸合成的负调控因子.油脂的合成代谢十分复杂,且存在反馈抑制机制,因此克隆和表达ACC基因可以提高宿主中ACC的活性,但不一定能显著促进脂肪酸的积累.图2参52     

Soil and plant biodegradation of chlorpyrifos in fields of cauliflower and brussels sprouts crops

For the protection of early and summer cauliflower and brussels sprouts crops against root fly, the insecticide chlorpyrifos was applied at planting onto soil around the stem of the plant, or in the planting line. In the soil, chlorpyrifos (1) was transformed into the insecticide metabolites oxon, 0,0‐diethyl‐0‐(3,5,6‐tri‐chloro‐2‐pyridinyl) phosphate (2), and 3,5,6‐trichloro‐2‐pyridinol (3). The soil half life time of chlorpyrifos could be 2.8 times greater (42 days relative to 15 days) when the field history as to cauliflower monoculture and insecticide treatments was short (1 year), than when it was long (8 years). Rains and season also had cumulative effects on the chlorpyrifos soil half life times. In the leaves of cabbage, chlorpyrifos and compound 3 were observed at concentrations which were higher, especially when their soil concentrations were high. Chlorpyrifos and compounds 2 and 3 however were not detected in the “flower” of cauliflower, nor in the brussels sprouts itself, the limit of sensitivity being 0.02 ppm of fresh weight.     

Sodium cyanide-induced modulations in the activities of some oxidative enzymes and metabolites in the fingerlings of Cyprinus carpio (Linnaeus)

Carp fingerlings exposed to a sublethal concentration (0.5?mg?L^?1) of sodium cyanide showed a steady decrement over a 7-day period in respiratory rate, rise in lactate dehydrogenase (LDH), and fall in succinate dehydrogenase (SDH) activities followed by variations in lactic and pyruvate levels. Changes in these enzyme activities might be due to impaired oxidative metabolism and severe cellular damage leading to the release of these enzymes. Decline in the activities of SDH and LDH clearly represents a shift from aerobic to anaerobic metabolism as evidenced by elevated lactate and decline in pyruvate levels. The shift to anaerobic metabolism is also reflected by severe drop in the respiratory rate of the fish. This may be a consequence of the blockage of electron transfer from cytochrome c oxidase to molecular oxygen, thus ceasing cellular respiration and it can lead to cellular hypoxia even in the presence of normal hemoglobin oxygenation. Hence, we indirectly reconfirm the inhibition of oxidative metabolism by sodium cyanide. Alterations in behavioral pattern induced by sublethal sodium cyanide exposure may be due to the combination of cytotoxic hypoxia with lactate acidosis, which depresses the central nervous system (CNS); as the brain is the most sensitive site to anoxia, it results in impaired CNS function.     

硫化物胁迫对日本沼虾呼吸代谢和能量代谢酶的影响

研究了硫化物暴露后日本沼虾细胞色素氧化酶(CCO)、琥珀酸脱氢酶(SDH)、延胡索酸还原酶(FRD)和乳酸脱氢酶(LDH)4种呼吸代谢酶及能量代谢酶-精氨酸激酶(AK)活性的变化规律.将日本沼虾暴露于0.6 mg·L~(-1)、2mg·L~(-1)的2个硫化物质量浓度组和不含硫化物的对照组水体中,暴露后0、2、12、24、48 h和解除暴露后48 h取肝胰腺和肌肉组织进行酶活性分析.结果显示:肝胰腺和肌肉组织SDH和CCO活性随硫化物质量浓度升高或暴露时间延长而显著降低(P<0.05).FRD、LDH和AK活性随硫化物质量浓度升高或暴露时间延长而显著升高(P<0.05).解除硫化物暴露后48 h,各质量浓度组酶活性与对照组无显著差异.上述酶活性还存在组织差异,肝胰腺呼吸代谢酶活性高于肌肉中相应酶活性,而AK活性与此相反.结果表明,硫化物胁迫导致日本沼虾有氧呼吸代谢减弱,无氧呼吸代谢增强,并动用其能量贮存物质磷酸精氨酸,产生更多ATP以适应外界不良环境.     

Ecological network analysis of an urban energy metabolic system: Model development, and a case study of four Chinese cities

Urban metabolism research faces difficulties defining ecological trophic levels and analyzing relationships among the metabolic system's energy components. Here, we propose a new way to perform such research. By integrating throughflow analysis with ecological network utility analysis, we used network flows to analyze the metabolic system's network structure and the ecological relationships within the system. We developed an ecological network model for the system, and used four Chinese cities as examples of how this approach provides insights into the flows within the system at both high and low levels of detail. Using the weight distribution in the network flow matrix, we determined the structure of the urban energy metabolic system and the trophic levels; using the sign distribution in the network utility matrix, we determined the relationships between each pair of the system's compartments and their degrees of mutualism. The model uses compartments based on 17 sectors (energy exploitation; coal-fired power; heat supply; washed coal; coking; oil refinery; gas generation; coal products; agricultural; industrial; construction; communication, storage, and postal service; wholesale, retail, accommodation, and catering; household; other consuming; recovery; and energy stocks). Analyzing the structure and functioning of the urban energy metabolic system revealed ways to optimize its structure by adjusting the relationships among compartments, thereby demonstrating how ecological network analysis can be used in future urban system research.     

臭氧对植物新陈代谢的影响

从气孔反应、膜透性变化、光合作用反应、物质代谢变化和酶活性变化等５个方面系统综述了臭氧对植物新陈代谢的影响。     

农药杀虫双的代谢毒理学研究

杀虫双为我国首创的农用杀虫剂，属沙蚕毒互类农药，以同位素示踪法和现代化学分离技术相结合的手段，进行了杀虫双在动物体内吸收、分布、排泄、转化、动力学以及代谢产物的分离鉴定等一系列研究，杀虫双进入体现人首先转化成沙蚕毒素，胃是主要转化部位，进入体循环，在血液中主要存在于红细胞中，且吸收、分布、排泄迅速，不易蓄积，杀虫双与沙蚕毒素、巴丹、易卫杀的最终代谢产物轮相符，杀虫双中毒死者血液中分离鉴定出沙蚕毒素