母乳中全氟化合物的污染水平与婴儿暴露评估

为探索北京市产妇母乳中典型全氟化合物的污染水平及婴儿经母乳的外暴露水平及风险.于2011~2012年通过征集母乳捐献志愿者方式采集95份母乳样本,并填写调查表,记录母乳捐献者的人口学特征及居住环境等信息.采用固相萃取结合超高效液相色谱-串联质谱法测定母乳中全氟辛酸及全氟辛烷磺酸的含量,估算婴儿经母乳的每日摄入量并与参考剂量进行比较.结果显示北京市产妇母乳中全氟辛酸含量均值和中位数分别为42和37.4pg/m L,范围在13.4~181.3pg/m L之间.全氟辛烷磺酸含量高于全氟辛酸,均值、中位数和范围分别为66.6、54.5和14~390.3pg/m L,统计分析发现全氟辛酸与体重指数呈正相关但与母乳产出时间呈负相关,而全氟辛烷磺酸则与产妇年龄呈正相关.婴儿经母乳全氟辛酸和全氟辛烷磺酸每日摄入量中值分别为4.67和6.81ng/(kg bw·d),最高值分别为22.66和48.79ng/(kg bw·d),显示部分婴儿经母乳摄入的全氟辛烷磺酸水平超过了参考剂量,健康风险值得关注.     

表面活性剂十二烷基苯磺酸钠（SDBS）和十二烷基磺酸钠（SDS）对安氏伪镖水蚤的急性毒性研究(Acute Toxicity of Sodium Dodecyl Benzene Sulfonate（SDBS）and Sodium Dodecyl Sulfate（SDS）to the Copepod, Pseudodiaptomus annandalei)

为探讨表面活性剂成分对海洋桡足类生物的影响,测定了十二烷基苯磺酸钠(SDBS)和十二烷基磺酸钠(SDS)对安氏伪镖水蚤(Pseudo-diaptomus annandalei Sewell)的急性毒性作用.结果表明,SDBS对安氏伪镖水蚤雌体24h、48h、72h和96h的半致死浓度LC50分别为2.40、1.67、1.59和1.58mg·L-1,而对雄体分别为1.84、1.54、1.41和1.40mg·L-1;SDS对雌体24h、48h、72h和96h的LC50分别为54.33、30.85、25.21和15.85mg·L-1,对雄体分别为18.48、13.55、10.51和8.50mg·L-1;SDBS对雌体和雄体的安全浓度分别为0.24mg·L-1和0.32mg·L-1,而SDS对雌体和雄体的分别为2.98mg·L-1和2.19mg·L-1.结果显示,对安氏伪镖水蚤而言,SDBS比SDS的毒性更强;以半致死浓度LC50为参考依据,安氏伪镖水蚤雄体均比雌体对这两种表面活性剂敏感.     

微乳液对难溶有机物的增溶作用及影响因素

研究了蓖麻油硫酸盐(SCOS)微乳液对1,4-二氯苯(DCB)、1,2,3,-三氯苯(TCB)、联苯(BP)和芘(Py)等难溶有机物的增溶作用.SCOS微乳液较阴离子或非离子表面活性剂胶束溶液具有更强的增溶能力;有机物的表观溶解度与微乳液中SCOS的浓度呈正相关,DCB、TCB、BP和Py在SCOS微乳相与水相间的分配系数(logKem)分别为3.15, 4.03, 3.95和5.01;温度、共存有机物和无机盐影响SCOS微乳液对有机物的增溶作用.     

4种短链全氟化合物替代物在城市污水处理厂的污染特征研究

全氟辛烷羧酸(perfluorooctanoic acid,PFOA)和全氟辛烷磺酸(perfluorooctyl sulfonate,PFOS)等长链全氟化合物(perfluorinated compounds,PFCs)具有持久性、生物累积性和毒性,近年来发现一些短链PFCs具有相对较短的半衰期,可以成为PFOA和PFOS的替代品,这些物质包括C4和C6结构的PFCs,如全氟丁烷羧酸(perfluorobutanoic acid,PFBA)、全氟己烷羧酸(perfluorohexanoic acid,PFHx A)、全氟丁烷磺酸(perfluorobutyl sulfonate,PFBS)和全氟己烷磺酸(perfluorohexyl sulfonate,PFHx S)。为解析我国城市污水厂短链PFCs污染水平和地域分布特征,本研究调查了我国不同地区17座城市污水处理厂的进水、二沉出水和污泥中4种短链PFCs的分布和浓度水平。结果表明4种短链PFCs、PFOA和PFOS在17座污水厂进水中检出率均为100%(6种目标物单体浓度范围:0.19~274.72 ng·L-1);污泥中PFOS和PFOA检出率为100%(PFOS:2.08~72.31 ng·g-1,PFOA:1.03~24.81 ng·g-1),PFBA、PFHx A检出率为100%(0.60~3.33 ng·g-1),PFBS和PFHx S的检出率分别为42.11%和63.16%。在污水厂进水中,将PFOA和PFOS与其同类的短链PFCs浓度进行比较,发现短链PFCs分别相对于PFOA和PFOS的比例最高可达93.47%和94.57%。4种短链PFCs、PFOA和PFOS的地域分布差异明显,总浓度呈现出华东、华南地区高于西北、东北、华北地区的趋势,其中华东地区调查的污水处理厂浓度最高。污水厂4种短链替代物主要通过污水排放,不同污水厂的日排放总量(污泥和出水)为0.25~273.07 g·d-1,万吨水排放量范围为0.04~1.37 g。研究将为我国全氟化合物替代物污染和控制提供数据基础和科学依据。     

超声辐射Fenton试剂耦合法降解直链十二烷基苯磺酸钠的研究

对超声辐射Fenton试剂耦合法降解水中直链十二烷基苯磺酸钠进行了研究。采用单因子法考察了硫酸亚铁用量，氧化剂H2O2用量，超声辐射反应温度和初始溶液pH值等因素对降解率的影响；采用正交试验法优化降解条件，得出了各因素影响的显著性次序。在环境压力下，超声辐射频率40kHz，超声辐射功率500W，反应时间15min，反应温度95℃，溶液起始pH值3，降解物起始质量浓度200mg／L，硫酸亚铁与双氧水质量浓度分别为O．65g／L和1．2g／L的最佳降解条件下，十二烷基苯磺酸钠的降解率可达99．31％。研究结果表明：超声波辐射Fenton试剂耦合法是一种有效的降解十二烷基苯磺酸钠的方法。与Fenton试剂氧化催化法相比，能够显著地缩短反应时间，提高降解率。     

Influence of water hardness on the bioavailability and toxicity of linear alkylbenzene sulphonate (LAS)

In the present work, the influence of Ca²⁺ concentration on the toxicity of single cut linear alkylbenzene sulfonate (LAS) homologues was studied. Precipitation boundary diagrams for each homologue were obtained, indicating turbid and clear zones depending on the LAS and Ca²⁺ concentrations. The separation between transparent and turbid zones is given by the so-called precipitation line. LAS toxicity to Daphnia magna was determined at concentrations close to this precipitation line. It was observed that when Ca(LAS)₂ precipitation progresses, LAS bioavailability decreases for test animals, and the toxicity diminishes even at high nominal LAS concentrations. According to the “free ion activity model” (FIAM), the toxicity of a given chemical compound is mainly due to the ionic species (Ca²⁺–LAS⁻) and not due to the precipitated molecule, Ca(LAS)₂. The significance of the present study is in connection with the assessment of LAS sorption/precipitation studies in soils and sediments, where in situ toxicity is strongly influenced by Ca²⁺/Mg²⁺ ions, according to the results presented in this work.     

CEPT-曝气生物滤池低温下处理模拟灰水的应用研究

实验研究了在冬季低温条件（2～10℃）下，化学温凝预处理曝气生物滤池(CEPT/BAF)工艺处理模拟灰水的效果。考查了混凝预处理效果、BAF的出水水质与滤料高度的关系、水力负荷对出水COD的影响、直链烷烃苯磺酸钠(LAS)对出水NH₃-N等的影响。研究表明：经过预处理(PAC为40 mg/L)后的模拟灰水，BAF的有机负荷去除率达到40%～55%；COD、LAS的去除主要发生在滤料前端1.2 m处，去除率达到70%，去除率与滤料高度近似呈指数关系下降；在COD负荷、水力负荷不变的情况下，当进水LAS从23 mg/L降到9 mg/L时，BAF的NH₃-N的去除率则从41%上升到72%，说明较高浓度的LAS对亚硝化及硝化细菌有一定影响。模拟灰水经过化学混凝/曝气生物滤池处理之后，出水水质NH₃-N、COD和LAS分别在10、40和4 mg/L以下。     

Highly elevated levels of perfluorooctane sulfonate and other perfluorinated acids found in biota and surface water downstream of an international airport, Hamilton, Ontario, Canada

Per- and poly-fluorinated compounds (PFCs), which include perfluorinated carboxylates (PFCAs) and sulfonates (PFSAs) and various precursors, are used in a wide variety of industrial, commercial and domestic products. This includes aqueous film forming foam (AFFF), which is used by military and commercial airports as fire suppressants. In a preliminary assessment prior to this study, very high concentrations (> 1 ppm wet weight) of the PFSA, perfluorooctane sulfonate (PFOS), were discovered in the plasma of snapping turtles (Chelydra serpentina) collected in 2008 from Lake Niapenco in southern Ontario, Canada. We presently report on a suite of C₆ to C₁₅ PFCAs, C₄, C₆, C₈ and C₁₀ PFSAs, several PFC precursors (e.g. perfluorooctane sulfonamide, PFOSA), and a cyclic perfluorinated acid used in aircraft hydraulic fluid, perfluoroethylcyclohexane sulfonate (PFECHS) in surface water from the Welland River and Lake Niapenco, downstream of the John C. Munro International Airport, Hamilton, Ontario, Canada. Amphipods, shrimp, and water were sampled from the Welland River and Lake Niapenco, as well as local references. The same suite of PFCs in turtle plasma from Lake Niapenco was compared to those from other southern Ontario sites. PFOS dominated the sum PFCs in all substrates (e.g., > 99% in plasma of turtles downstream the Hamilton Airport, and 72.1 to 94.1% at all other sites). PFOS averaged 2223 (± 247.1 SE) ng/g in turtle plasma from Lake Niapenco, and ranged from 9.0 to 171.4 elsewhere. Mean PFOS in amphipods and in water were 518.1 (± 83.8) ng/g and 130.3 (± 43.6) ng/L downstream of the airport, and 19.1 (± 2.7) ng/g and 6.8 (± 0.5) ng/L at reference sites, respectively. Concentrations of selected PFCs declined with distance downstream from the airport. Although there was no known spill event or publicly reported use of AFFF associated with a fire event at the Hamilton airport, the airport is a likely major source of PFC contamination in the Welland River.     

Effect of salinity and sediment characteristics on the sorption and desorption of perfluorooctane sulfonate at sediment-water interface

This study investigated the influence of solution salinity, pH and the sediment characteristics on the sorption and desorption of perfluorooctane sulfonate (PFOS). The results showed that the sorption of PFOS onto sediment increased by a factor of 3 as the CaCl₂ concentration increased from 0.005 to 0.5 mol L⁻¹ at pH 7.0, and nearly 6 at pH 8.0. Desorption hysteresis occurred over all salinity. The thermodynamic index of irreversibility (TII) values increased with increasing concentration of CaCl₂. Maximum irreversibility was found in the sorption systems with CaCl₂ in the concentration of 0.5 mol L⁻¹. The results suggested that PFOS can be largely removed from the water with increasing salinity, and get trapped onto sediments irreversibly. These phenomena could be explained by salting-out effect and Ca-bridging effect. Studies also suggested that the content of total organic carbon is the dominant psychochemical properties of sediment controlling the sorption of PFOS.