玛纳斯河流域水库中PFOS和PFOA的分布及来源解析

为探究新疆玛纳斯河流域水库中全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA)的污染现状,采用固相萃取分离富集与高效液相色谱-质谱联用相结合的方法,针对玛纳斯河主干以及该河流域8个水库的入水口、中心区域、出水口共计21个水样点中PFOS和PFOA含量进行了测定。结果表明:PFOS检出率为86%,PFOA的检出率为100%;在所有检测的水库中,最高值是位于工业区附近的蘑菇湖水库中心水样,PFOS浓度为24.85 ng/L,PFOA为75.33 ng/L;最低值是位于森林绿化区的海子湾水库人口水样,PFOS未检出,PFOA为1.67 ng/L,位于农业种植区的其余水库中PFOS和PFOA的浓度介于其间。经分析,工业生产是PFOS和PFOA污染的最大来源,其次是农业生产活动。     

快速城市化流域全氟化合物的污染特征及生态风险

为探究快速城市化地区城市河流中全氟化合物(PFCs)的污染特征, 于枯水期和丰水期分别采集深圳市观澜河干流的表层水样, 通过固相萃取法处理水样, 并利用超高效液相色谱–三重四级杆串联质谱(UPLCESI-MS/MS)技术分析 11 种PFCs的含量。结果表明, 丰水期和枯水期观澜河干流水体中PFCs的含量分别为179.15~613.68和37.04~103.70 ng/L。其中, 全氟己烷磺酸(PFHxS)、全氟丁烷磺酸(PFBS)、全氟己酸(PFHxA)和全氟辛酸(PFOA)是主要污染物。所采集的样品中, 丰水期PFCs的浓度高于枯水期, 下游采样点PFCs的浓度高于上中游河段。与已报道的其他水体相比, 由于流域的快速城市化, 观澜河水体的PFCs含量水平较高。生态风险评估表明, 水体中检出的PFCs均不会对水体造成生态风险。     

黄河下游水体中全氟及多氟烷基化合物的分布特征

系统地研究黄河下游春秋两季水样和沉积物中50种PFASs的分布特征和生态风险。结果表明, PFASs在春秋两季水样中检出的总浓度范围分别为29.83~54.44和16.18~57.81 ng/L, 春秋两季沉积物中PFASs的含量范围分别为18.12~36.16和13.01~36.78 ng/g。在春秋两季占比最高的3类物质在水相和沉积物中均为全氟烷基羧酸(PFCAs)、全氟烷基磺酸(PFSAs)和n:2氟调聚磺酸(n:2 FTSs)。作为新型PFASs, n:2 FTSs在水相和沉积物中均有较高的检出水平。全氟辛酸(PFOA)在水相和沉积物中的主要替代物为短链PFCAs, 六氟环氧丙烷二聚酸(HFPO-DA)则在沉积物中对PFOA有更高的替代趋势; 全氟辛烷磺酸(PFOS)在水相和沉积物中的主要替代物为6:2 FTS。风险熵值法分析结果表明, 水体中各PFASs目标物均未达到环境生态风险水平。     

上海特征性点源周边环境水体中全氟化合物的环境行为特性

上海市某民用国际机场的飞机大量使用全氟化合物为重要成分的航空液压油,并且在机场内部或周边配套消防站使用的水成膜泡沫灭火剂(aqueous film-forming foams, AFFFs)中,全氟化合物作为重要添加剂被广泛使用.含氟化合物的大量使用会对机场周边的地表水产生氟化物污染.以上海市某机场作为特征潜在点源对象,采集周边的10个地表水样,2个对照采样点,检测样品中的17种全氟化合物(perfluormated compounds, PFCs).结果显示:全氟辛酸(perfluorooctanoic acid, PFOA)在地表水中的质量浓度最高,为37.55～189.05 ng/L,均值为94.05 ng/L;其次为全氟戊酸(perfluoro pentanoic acid, PFPeA)和全氟丁烷磺酸盐(perfluorobutane sulphonate, PFBS),浓度分别为15.15～42.33 ng/L, 5.35～57.27 ng/L; PFoA, PFPeA和PFBS的检出率均为100%.运用风险商数法评价机场周边采样点的环境风险,结果显示水样中PFCs均未达到对生态环境具有风险的水平.     

珠江口海水养殖区水体、沉积物及水产品中抗生素的分布

采用超声波萃取结合超高效液相色谱串联质谱(UPLC-MS/MS)法, 研究珠江口(珠海和大亚湾)海水养殖区的水样、沉积物以及水产品(鱼类和贝类)中22种抗生素的污染状况。结果表明, 珠江口海水养殖区的主要污染物是喹诺酮类的诺氟沙星、氧氟沙星、环丙沙星和氟甲喹等。珠海沉积物和水样中抗生素污染程度略高于大亚湾。水样中抗生素的浓度范围为0.13 (磺胺甲恶唑)~4.68 (奇霉素) ng/L, 浓度水平受降水影响显著。沉积物中抗生素的浓度范围为0.02 (金霉素)~8.77 (奇霉素) ng/g (干重), 表现出时间累积性。水产品中抗生素浓度范围为0.06 (磺胺甲基嘧啶)~46.75 (诺氟沙星) ng/g (干重), 贝类和鱼类样品中抗生素污染程度接近, 差异性不显著。相关性分析结果表明, 沉积物样品间的污染程度类似, 水产品样品间污染的相似性也较显著, 而不同水样间的污染成分及污染水平差异性较大。     

Serum levels of perfluorinated compounds in the general population in Shenzhen, China

Perfluorinated compounds (PFCs) have been detected in many environmental matrices, biota, and nonoccupationally exposed populations in China recently. However, little is known about the distribution and levels of various PFCs in the general population living in areas where there is PFC exposure. In the present study, the levels and prevalence of ten target PFCs were determined in 227 serum samples from a population of nonoccupationally exposed individuals in Shenzhen, China. Results indicated that human exposure to PFCs was prevalent in Shenzhen. Perfluorooctanoate (PFOA) was the dominant PFC contaminant in the serum samples, with a median concentration of 6.72 ng/mL, followed by perfluorooctane sulfonate (PFOS) with a median concentration of 2.07 ng/mL. Other PFCs were detected at much lower concentrations, with median concentrations ranging from 0.02 to 0.87 ng/mL. Statistically, no significant (P>0.05) gender differences were observed for any of the PFCs. Significant (P<0.01) positive correlations were found between age and serum concentrations of the target PFCs, except for perfluorobutane sulfonate (R = 0.16, P = 0.01), perfluorohexanoic acid (R = 0.08, P = 0.22), and perfluoroheptanoic acid (R = 0.11, P = 0.10). Based on the one-compartment pharmacokinetic model, the total daily intakes of PFOA and PFOS for the general population in Shenzhen were calculated as 0.63 and 0.20 ng/kg body weight/day, respectively.     

PFCs在水和底泥中的分布、毒性和去除

近年来,全氟化合物(perfluorinated compounds,PFCs)已经在各大河流、海洋和人类血清中被检出,引起世界范围内环境工作者的注意,成为环境领域的又一研究热点.鉴于人体对PFCs的暴露途径主要通过饮用水、饮食和空气/灰尘等方式,对国内外不同环境介质中全氟化合物的分布状况、毒性及去除工艺研究现状进行了简要介绍,讨论了目前存在的问题,为PFCs环境污染研究提供相应参考.     

全氟辛酸在松花江水体多介质环境中迁移、归趋和风险研究

为探究全氟辛酸(perfluorooctanoic acid,PFOA)在松花江水体多介质环境中的迁移和归趋行为,评估其在松花江水体的环境风险,采用Ⅲ级逸度模型模拟估算了松花江流域大气、江水、颗粒物和沉积物中PFOA的含量及其分布规律,计算了PFOA在不同环境介质的迁移通量,采用风险特征比率法评估了PFOA在松花江水体的环境风险.结果表明:PFOA在松花江流域大气、江水、颗粒物、沉积物中的模拟含量分别为1496.03 pg/m3,0.0103 ng/L,15.27μg/kg,19.98μg/kg,PFOA几乎全部进入了颗粒物和沉积物中.PFOA由江水向悬浮颗粒物的迁移、沉积物向江水的迁移分别占相间总迁移通量的84.63％ 和15.12％,为PFOA的主要相迁移路径.由估算结果计算的水和沉积物的风险特征比率(risk characteristic ratios)均远小于1,表明PFOA对松花江水生生物的危害概率较低.     

环境污染物PFOS可致人脑微血管内皮细胞骨架蛋白改变

目的:探讨全氟辛烷磺酰基化合物(PFOS)引起的人脑微血管内皮细胞(HBMEC)骨架蛋白(F-actin)排列变化.方法:培养正常的人脑毛细血管内皮细胞,不同浓度PFOS作用30分钟,利用免疫荧光染色的方法检测细胞骨架蛋白F-actin的变化.结果:PFOS可使细胞骨架蛋白F-actin发生重排,这与PFOS的浓度有关.     

TiO2光催化臭氧氧化降解全氟辛酸的研究

TiO_2光催化臭氧氧化可以有效降解全氟辛酸(PFOA),反应4 h后的脱氟率达到44.3%.考察了PO_4~(3-)、PFOA初始浓度、反应温度对PFOA脱氟率的影响.结果表明,TiO_2光催化臭氧氧化降解PFOA过程发生在催化剂表面,PFOA和O_3在TiO_2表面的吸附是降解反应发生的必要条件;反应过程的前半段温度占主导因素,脱氟率随温度升高而升高,反应过程的后半段吸附作用影响更大,温度越低脱氟率反而越高;降解过程中产生的中间产物主要是5种短链全氟羧酸化合物,包括C_6F_(13)C_OOH、C_5F_(11)C_OOH、C_4F_9C_OOH、C_3F_7C_OOH和C_2F_5C_OOH.TiO_2光催化臭氧氧化降解PFOA的机理类似于Photo-Kolbe反应.     

Perfluorooctane sulfonate （PFOS） and related fluorochemicals in chicken egg in China

The ubiquitous occurrence of perfluorinated compounds （PFCs） in environmental samples has drawn much attention. Recent human exposure studies found relatively high perfluorooctane sulfonate （PFOS） concentrations in blood samples from several cities in China when compared with other countries. The objectives of the present study were： （1） to measure PFC concentrations and compositions in chicken egg samples from local markets in China; and （2） to conduct a preliminary human health risk assessment of egg consumption. Eight pooled egg samples from eight locations were analyzed for 11 PFCs. The results showed that close to 100% of the PFOS in the egg was distributed in egg yolk and PFOS was not detected in egg white （〈0.08 ng/g wet weight, w/w）. Of the perfluoroalkylsulfonates, only PFOS was detected in all egg samples, while of the perfluoroalkylcarboxylates, perfluoroundecanoic acid （PFUnDA） was detected in all samples, followed by perfluorooctanoate （PFOA） （75% occurrence） and perfluorodecanoic acid （PFDA） （50% occurrence）. PFOS concentrations in egg ranged from 45.0 to 86.9 ng/g w/w. The results suggested that current concentrations of PFOS in domestic chicken eggs are unlikely to cause immediate harm to Chinese populations.     

Perfluorooctane sulfonate and perfluorooctanoic acid in the fingernails of urban and rural children

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are two typical perfluorinated compounds (PFCs), found in a wide range of environmental media and organisms, including humans. Human biomonitoring studies of body fluids have revealed that in many areas of the world the general population has been exposed to background levels of PFOS and PFOA. Fingernail has been suggested as a promising biopsy material for assessment of PFCs environmental exposure. In the present study, PFOS and PFOA were quantified using high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) in fingernails of urban and rural children (N=93) aged 6–12 years. A questionnaire was conducted to determine factors that could influence the PFOS and PFOA levels in the children. The levels of PFOS in urban children were significantly higher (geometric mean (GM)=328 ng/g) than those in rural children (GM=27 ng/g). In contrast, PFOA levels were significantly lower in the urban children compared with the rural children. Significant positive correlation (R=0.53, P<0.05 for urban areas; R=0.71; P<0.001 for rural areas) between the PFOS and PFOA concentrations indicated they had similar sources. The PFOS and PFOA levels were higher in fingernail samples from children aged <9 years than in children aged ⩾9 years. In addition, females had higher PFOA levels than males, in both regions. Other factors that significantly influenced PFOS and PFOA levels were dietary habits and socio-economic background. The results of this study indicate fingernails are a suitable material for biomonitoring of PFCs environmental exposure. However, the levels determined in the fingernail samples need to be first evaluated with regard to the levels determined in other samples, such as human serum.     

湟水河西宁段水体和沉积物中氮素转化关键过程与影响因素分析

于丰水期(2018年7月)和枯水期(2019年4月)分别在湟水河西宁段典型断面采集水体和沉积物样品共58个,枯水期同时采集污水处理厂出水样6个。利用实时荧光定量PCR方法,对12种氮转化功能基因进行定量分析。结果表明,湟水河平均总氮浓度为3.06±1.23 (1.308～6.51) mg/L。水体和沉积物中相对丰度较高的氮转化功能基因是narG,nirS和nosZ。氮转化功能基因的丰度和组成在沉积物中存在明显的季节差异,在水体中无明显季节差异。关键氮素转化过程是反硝化,对水体和沉积物氮素的去除贡献率分别为88%和98%。水体氮素转化主要受pH值、总氮及NO₃^--N调控,其中,氨氧化与NO₃^--N浓度负相关,反硝化与pH负相关。沉积物氮素转化与水体氮素浓度、沉积物pH值、总氮、总磷和有机碳等相关,其中,氨氧化与水体氮素浓度负相关,而反硝化主要受沉积物性质影响。进一步的分析结果表明,污水处理厂排放会显著降低水体中AOA-amoA, CMX-amo A, nir S, nxr B, napA, nar G...     

珠江广州河段沉积物中典型抗生素的污染特征

采用乙腈/柠檬酸缓冲液超声提取沉积物中的抗生素,并以固相萃取法富集和净化萃取物,以高分离度快速液相色谱/质谱(SPE-RRLC-MS/MS)进行测定,研究了珠江广州河段13个采样点41种目标抗生素的质量分数水平和时空分布特征. 结果表明,珠江广州河段沉积物在枯水期或丰水期共有24种抗生素被检出,枯水期和丰水期质量分数范围分别为ND（未检出）~54.800 g/g和ND~3.433 g/g,两季质量分数最高的抗生素均为氧四环素;沉积物中氟喹诺酮类和四环素类抗生素占比较高;在枯水期总抗生素质量分数整体上高于丰水期,抗生素的质量分数在珠江广州河段沉积物中空间分布整体上呈现人口密集城区河涌人口密集城区航道航道中下游航道上游,与广州市区产污排污的分布状况基本一致.     

柳江流域大型底栖动物群落结构及其与水质因子的关系

以柳江流域23个点位为例,研究了不同水文季节(3月和6月)水质因子(DO、COD_Mn、NH₃-N、As、Hg、Cd、Pb)对底栖动物群落结构的影响,2次调查共鉴定出底栖动物4门7纲16目54科68属(种),种类相似系数为83.76%,物种丰富度表现为枯水期略高于丰水期,底栖动物优势种在枯、丰水期分别有4种和2种,具有明显的季节演替. DCA和TWINSPAN分析结果显示:柳江流域底栖动物群落结构在时空分布上存在一定差异,主要表现为枯、丰水期均有3个不同的底栖动物类群大致依次分布在该流域干流及支流的源头、中上游及下游,群落内指示物种呈现出由清洁种逐渐过渡到耐污种的变化. 指示物种分析结果(ISA)显示:在枯水期,共有8种底栖动物能作为柳江源头和大环江上游群落的指示种,分别为四节蜉属(Baetis sp.)、锯形蜉(Serratella sp.)、溪泥甲一属(Zaitzevia sp.)、短脉纹石娥属(Cheumatopsyche sp.)、蜗虫(Dugesia sp.)、朝大蚊属(Antocha)、摇蚊属(Chironomus sp.)和细蜉属(Caenis sp.),其他类群无显著指示种;在丰水期,共有5种底栖动物能作为群落划分的指示种,其中,方格短沟蜷(Semisulcospira cancellata)、钉螺(Oncomelania sp.)是柳江中上游的指示种,汉森安春蜓(Amphigomphus hansoni)、河蚬(Corbicula fluminea)、卷扁螺(Gyraulus compressus)是柳江下游的指示种. CCA分析结果显示:COD_Mn和DO是枯、丰水期均对柳江流域底栖动物群落分布有重要影响的水质驱动因子,而重金属因子(Cd、Pb、Hg)在枯水期对底栖动物分布影响较大, NH₃-N在丰水期对底栖动物分布影响较大.     

Perfluorooctane sulfonate (PFOS) and other fluorochemicals in viscera and muscle of farmed pigs and chickens in Beijing,China

Eleven perfluorinated compounds (PFCs) were determined in tissue samples from farmed pigs and chickens (n=143) that were purchased in Beijing in March 2009. The total PFCs mean concentration was the highest in pig liver (3.438 ng g^–1 wet weight (ww)), followed by pig kidney (0.508 ng g^–1 (ww)), pig heart (0.167 ng g^–1 (ww)), chicken liver (0.098 ng g^–1 (ww)), chicken heart (0.050 ng g^–1 (ww)), pork loin (0.018 ng g^–1 (ww)), and chicken breast (0.012 ng g^–1 (ww)). Among the PFCs analyzed, perfluorooctane sulfonate (PFOS) was the predominant compound in viscera and muscle of farmed pigs and chickens. In addition, a strong linear correlation (r = 0.932) was observed between the concentrations of PFOS and perfluoroundecanoic acid (PFUnDA) in pig liver. Our preliminary conclusion is that there is little potential risk of exposure to PFCs via the consumption of these products in Beijing.     

神东煤矿区高氟矿井水季节成因分析及灌溉风险

神东矿区矿井水中氟化物(F-)含量过高,严重威胁着该地区供水安全和生态环境可持续发展。矿井水中F-分布,来源和形成机制已被关注和研究,然而对于季节性变化和灌溉适宜性评价尚不清楚。为此,本文系统采集了丰枯水期各35组矿井水样品,研究了矿井水中F-含量的季节性分布,剖析了其来源和形成机制,并进行了生态用水灌溉适宜性评价。结果表明神东矿区丰水期和枯水期矿井水F-含量分别为0.16-13.96mg/L（均值为4.43mg/L）和0.16-17.60mg/L（均值为4.89mg/L）,枯水期矿井水F-的含量明显高于丰水期。神东矿区丰枯水期矿井水F-均与Ca2+呈显著负相关,与Na+和HCO3?呈正相关。丰枯水期高F-矿井水的形成主要受萤石矿物溶解,离子交换作用和竞争吸附作用控制。 神东矿区丰枯水期分别有100％和66.67％低F-矿井水适宜生态灌溉,而92.00％和96.15％的高F-矿井水则不适宜生态灌溉。     

松花江吉林市段江水与沉积物中多环芳烃的分布、 来源和生态风险

在丰水期、 枯水期和平水期分别采集松花江吉林市段的江水和沉积物样品, 先用气相色谱 质谱联用仪(GC MS)测定其中16种多环芳烃（PAHs）的含量, 再通过比值法对各水期江水和沉积物中的PAHs进行来源识别, 并分别利用商值法和风险效应值法评价江水和沉积物的生态风险. 结果表明: 松花江吉林市段丰水期、 枯水期和平水期江水中PAHs的质量浓度分别为0.917~3.974 μg/L,0.980~3.293 μg/L和0.771~4.127 μg/L; 丰水期和平水期沉积物中PAHs的质量比分别为1 035.5~1 732.0 ng/g和1 188.5~1 632.0 ng/g; 不同水期江水中的PAHs质量浓度变化较大, 沉积物中的PAHs质量比变化较小; PAHs为石油源和燃烧源混合输入所致; 江水中PAHs的生态风险较小, 表层沉积物中的PAHs具有一定的生态风险.