汉江水体和沉积物中全氟化合物的风险评估

采集汉江旱季和雨季的水样和沉积物,应用超高效液相色谱–三重四级杆质谱,对其中的11种全氟化合物(PFCs)进行检测,研究该区域全氟化合物的污染状况。结果表明,11种全氟化合物都有不同程度的检出,旱季和雨季水样中∑PFCs浓度分别为0.3~23.04和0.16~19.68 ng/L,沉积物中∑PFCs浓度分别为0~55.1和0.99~85.07 ng/g。水样总浓度的最高值出现在汉江汇入长江处的武汉,且武汉采样点的全氟辛酸(PFOA)浓度最高,旱、雨季分别达到22.52和12.52 ng/L。沉积物中总浓度最高值出现在陶岔,且以全氟庚酸(PFHp A)和全氟己酸(PFHx A)为主,沉积物中组分组成的季节差异不大。采用实际检测到的水样中PFOA、全氟辛烷磺酸盐(PFOS)、全氟壬酸(PFNA)、PFHx A和全氟葵酸(PFDA)的浓度以及沉积物中PFOA和PFOS的浓度,运用熵值法,对汉江流域进行全氟化合物污染的风险评估,结果表明,水体和沉积物中的浓度均未达到对生态环境具有风险的水平。     

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。     

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。     

土壤对全氟化合物的吸附作用

全氟化合物(Perfluoroalkyl substances,PFASs)是一类受到全世界关注的新型污染物,有关其环境行为的研究报道很多,但目前有关PFASs吸附的研究多是针对沉积物或碳质材料,对于其在土壤上的吸附研究较少。因此,本文研究了3种不同性质的土壤对6种PFASs(全氟辛酸、全氟辛烷磺酸、全氟壬酸、全氟癸酸、全氟十一酸和全氟十二酸)的吸附特征。结果表明,PFASs在土壤中吸附1h就达到平衡。6种PFASs均符合Freundlich吸附等温式,土壤-水分配系数随碳氟链增加而增加,且PFASs的分配系数(lgKd)与其辛醇-水分配系数(lgKow)呈显著正相关(p<0.01)。PFASs在土壤上的吸附量随土壤有机碳含量和阳离子交换量的增加而增加,6种PFASs的土壤有机碳标化分配系数范围为102.26~105.07 L/kg。除疏水作用外,氢键作用和静电作用也是PFASs在土壤上吸附的重要机制。     

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.     

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.     

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.     

全氟己酸迁移反应机理的理论研究

全氟羧酸(PFCAs)化合物是自然界广泛存在的一类持久性有机污染物,理论研究发现PFCAs的支链结构较直链结构更稳定,更容易存在,而对自然界水体中直链和支链结构含量的实验测定发现,直链结构含量明显高于对应的支链结构含量,探究其不一致原因具有一定的现实意义。应用DFT方法,采用Gaussian 09计算程序,在B3LYP/6-31G(d, p)计算水平下,探究了直链全氟己酸(PFHxA)通过甲基迁移为支链PFCAs的6种反应路径及能量变化。研究发现,通过双三元环反应机理,PFHxA迁移为2-三氟甲基全氟戊酸的反应,具有相对较低的活化能,是主反应路径,其反应速率常数为1.28×10~(-58)/s。迁移反应速率与温度呈正相关,常温下,该迁移反应很难进行,高温有利于反应的进行。     

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。     

离子液体预富集-火焰原子吸收法测定头发中痕量锂

制备了5种离子液体1-烷基-3-甲基咪唑六氟磷酸盐[CnMIm][PF6](其中n=4,6,8,10,12),用于头发中超痕量锂的预富集.锂(I)在萃取剂磷酸三丁酯(TBP)、协萃剂FeCl3作用下形成LiFeCI4·2TBP配合物而被萃取进入离子液体介质.有机相中加入盐酸分解锂配合物而使锂(I)进入水相,其水溶液直接用于火焰原子吸收法测定锂.最佳萃取条件:V(TBP):V(IL)=9:1;水相酸度(HCl):0.03 mol/L;相比(V(O):V(A))=7:1;n(Fe):n(Li)=2:1.在此条件下,锂的一次萃取率和反萃率达到78%和90%,富集倍数在100倍以上.机理研究表明,Li+与TBP和FeCl3形成极性较小的LiFeCI4·2TBP络合物而被萃取进入有机相,在有机相中加入盐酸因H+极化强于Li+而将Li+置换重新进入水相.预富集结合火焰原子吸收法应用于头发中超痕量锂的测定,检出限为2.5 ng/L,精密度0.05%,结果令人满意.     

Perfluoroalkyl substances in the blood samples from a male population of Sweden

Temporal trends of perfluoroalkyl substances （PFASs） have been determined in the blood samples from several countries globally including a female population in Sweden recently, yet little is known about the time trends in the blood levels of these compounds in Swedish male populations over recent years. In this study, the fourteen target PFASs consisted of four perfluorosulfonates （PFSAs） and ten perfluorocarboxylates （PFCAs） in the whole blood samples, collected from 153 Swedish elderly men during the period between 2008 and 2010, were analyzed via ultra-performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS）. As the dominant PFASs contaminants in the blood samples, perfluorooctane sulfo- nate （PFOS） showed the highest geometric mean （GM） at 8.5 ng/mL, ranging from 1.7 to 29 ng/mL, while blood perfluorooctanoic acid （PFOA） contained the GM of 1.8 ng/mL, ranging from 0.35 to 6.4 ng/mL. Both the levels of these two compounds were lower than those determined in the blood samples of Swedish elderly pop- ulations derived from the late 1990s. According to the temporal trend analysis, over the three years, the blood levels of PFOS in Swedish male populations declined 16 % per annum, while those of perfluoroundecanoic acid （PFUnDA） increased 6.1% per annum, which were con- sistent with those reported previously for the populations from other countries.     

Occurrence of perfluoroalkyl acids in precipitation from Shenyang, China

Perfluorosulfonates （PFSAs） and perfluorocarboxylates （PFCAs） in precipitation collected from Shenyang, China were determined. Snow samples were collected in the snow event on March 4, 2007 from 34 sites involving both the urban and suburban areas in Shenyang. The snowmelt was preconcentrated by solid phase extraction and analyzed using LC-MS method. Measurable amounts of perfluoroalkyl acids （PFAS） were found in precipitation samples from Shenyang, demonstrating that wet deposition is one possible pathway for the removing of the selected PFAS chemicals from atmosphere. Major PFAS detected were PFOS （〈0.38-51 ng/L）, PFOA （0.82-13 ng/L） and PFHpA （0.76-11 ng/L）, with their mean concentration of 5.4, 3.3 and 2.9 ng/L, respectively. Other PFSAs and PFCAs were detected at much lower frequency or below the limit of detection in all the samples. The work presented here offers some basis for the investigation on the environmental behavior and the evaluation of human exposure to PFAS.     

长江源区重金属分布特征及生态风险评价

于2017年6月在长江源区12个采样点采集表层水样和沉积物样品,测定重金属含量,并结合地累积指数、水质指数和潜在风险指数等,评价长江源重金属污染和生态风险.结果表明,水体中Mn,Ni,Cu,Zn,Cd,Pb 和 Cr 的浓度范围为 ND～4.21,0.609～3.71,0.033～5.01,ND～34.86,ND～0....     

Meta-Analysis on the associations between Prenatal Perfluoroalkyl Substances Exposure and Adverse Birth Outcomes

The epidemiological associations between the prenatal perfluoroalkyl substances(PFASs) exposure and the reproductive outcomes remain controversial. A continuous evaluation is needed to combine the inconsistent results. In this study, we explored the associations between PFASs exposure and the low birth weight(LBW), preterm birth and small for gestational age(SGA). The quality of selected literature, quantitative estimates, publication bias and subgroup analysis were performed on the basis of 17 retrieved articles published before December 2020. The results showed a significant positive association between the perfluorooctane sulfonate(PFOS) exposure and the risk of LBW [Odds ratio(OR)=1.17; 95% confidence interval(CI): 1.01, 1.36; heterogeneity: P=0.30, I~2=17%]. The positive association was also observed between the PFOS and the risk of preterm birth(OR=1.19; 95% CI: 1.01, 1.39, P=0.007; I~2=62%). There was a paucity of evidence regarding the negative effects of perfluorooctanoic acid(PFOA), perfluorohexanesulfonic acid(PFHxS) and perfluorononanoic acid(PFNA) on the pregnancy outcomes. The findings from the subgroup analysis(the sampling period, the birth gender and biologic specimens) did not substantially altered the results of the overall pooled estimate ORs. The increased prevalence of negative birth outcomes with gestational PFASs exposure warrants further explorations from biological process perspective.     

条子河中多环芳烃和有机氯农药的时空分布及来源解析

以辽河支流条子河中的多环芳烃（PAHs）和有机氯农药（OCPs）为目标物, 分别于春汛期、 丰水期、 平水期和枯水期采集水样及表层沉积物样品, 分析样品中PAHs和OCPs的赋存状态及污染物在该区域的分布和来源. 结果表明： 条子河水中总PAHs的质量浓度为658.1~3 096.6 ng/L, 均值（算术平均值, 下同）为
1 522.1 ng/L; 沉积物中总PAHs的质量比为775.7~2 835.4 ng/g, 均值为1 374.0 ng/g; 条子河水中总α,β,γ HCHs（六六六）的质量浓度为5.36~16.57 ng/L, 均值为10.93 ng/L; 滴滴涕（DDTs)未检出; 沉积物中总HCHs的质量比为2.87~5.56 ng/g, 均值为4.34 ng/g; 条子河水和沉积物中PAHs的含量均为自上游至下游递减, 且枯水期>平水期>春汛期>丰水期; 条子河水中HCHs的质量浓度自上游至下游递增, 且丰水期>春汛期>平水期>枯水期, 沉积物中HCHs的质量比自上游至下游递减, 且枯水期>平水期>春汛期>丰水期; 条子河中的PAHs主要来源于煤炭燃烧和交通燃烧, HCHs主要来源于农药林丹的使用.     

北京市北小河公园绿地生态保健功能效应研究

选取北京市典型社区示范北小河公园内4种绿地结构类型及12种不同配置模式为研究对象,开展了对公园绿地的空气负离子、人体舒适度(温度、湿度、风速)、PM_2.5、减噪效果的四种主要生态保键因子的单项及综合保键效应定量研究与评价,结果表明：北小河公园春夏两季各样地的负离子浓度日变化均呈早晚低中午高的单峰趋势 ,秋冬两季变化趋势没有明显的规律。四季负离子浓度大小排序为：夏季>春季>秋季>冬季,各样地中夏季最高平均值为1492.59个.cm_-3,冬季最低平均值为380.76个.cm_-3; PM_2.5浓度日变化除春季外,其他三季的均呈早晚高、中午低的日变化趋势;各样地消减能力排序为：春季>夏季>秋季>冬季,消减率范围为0.75%～13.65%;各类型绿地在春夏两季均有提高气候舒适性的作用,尤其在夏季作用较明显;各种绿地类型均有减噪效果最佳的宽度,其净衰率范围为0.17%～7.56%;以典型夏季数据进行的综合保健效果评价,最好的绿地结构类型为乔-灌-草和乔-草,灌-草和纯草类型次之。     

Concentrations and source identification of organochlorine pesticides (OCPs) in soils from Wolong Natural Reserve

In order to understand the distribution profile, composition characteristics and sources of OCPs, soil samples collected from Wolong Natural Reserve (WNR) in spring and autumn in 2005 were analyzed using gas chromatography coupled with electron capture detector (GC-ECD). Results showed that all OCPs concentrations were in the range of 10?2 ng/g―10?1 ng/g, representing the background level in those remote sites. Generally, their concentrations were slightly higher in spring than in autumn, which could be exp...     

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.