电感耦合等离子体质谱法测定地表水中铊的研究

本研究建立了电感耦合等离子体质谱法(ICP-MS)测定地表水中铊的方法。对仪器工作条件进行了优化,用在线内标校正基体效应的干扰,重点考察了样品测定介质、酸度、共存元素干扰等因素对测定结果的影响。在最佳实验条件下,该方法的检出限可达0.003μg/L,线性相关系数不小于0.999 9,加标回收率为93%~110%。与传统的原子吸收法相比,该方法不需要富集等繁琐的前处理过程,具有检出限低、快速、精密度和准确度高等优点。     

利用SPAMS研究华北乡村站点(曲周)夏季大气单颗粒物老化与混合状态

利用单颗粒气溶胶飞行时间质谱(SPAMS)于2013年6月30日~7月8日对华北地区乡村站点曲周大气单颗粒粒径及其化学组成进行了在线测量,共采集到同时含有正负离子谱图的颗粒230 152个,其粒径主要集中在0.2~2.0μm.结果表明,该地区的大气颗粒物主要分为8类:元素碳(EC,55.5%)、有机碳(OC,10.7%)、钠,钾等碱金属颗粒(alkalis,17.4%)、其他金属颗粒(other metals,1.7%)、富铁颗粒(Fe-rich,6.3%)、富铅颗粒物(Pb-rich,3.1%)、沙尘颗粒(dust,4.8%),other颗粒(0.8%),观测得到的8类气溶胶颗粒中绝大部分包含46NO-2、62NO-3、80SO-3、96SO-4、97HSO-4等二次组分离子,说明这些颗粒都经历了不同的老化过程或与二次组分进行了不同程度的混合.从气溶胶类型的谱分布看,各类型颗粒数浓度峰值基本出现在700~800 nm之间,dust、Fe颗粒主要集中在粗粒径段,EC颗粒子类研究表明随着表面不断吸附NH+4、NO-3、SO2-4等二次组分,EC颗粒逐步演化成老化程度较低的NO-3吸附型EC(ECN)和严重老化的SO2-4吸附型EC(ECS)混合态,两者日变化呈现明显的负相关性,也可能随着二次有机物在EC表面吸附,形成OC/EC混合态.     

土壤溶解性有机质荧光特征及其与铜的络合能力

选取4种不同类型土壤和腐熟鸡粪,透析提取溶解性有机质(DOM),通过凝胶色谱、三维荧光光谱测定并分析了DOM的相对分子质量(M_r)分布、化学结构特征及其与铜的结合能力.结果表明,鸡粪DOM相对分子质量积分面积远高于其他样品,表现出其具有较高的有机物含量,泥炭土次之.暗棕壤、褐土和黑土较低,仅为鸡粪积分面积的4.5%~5%.鸡粪在中分子量段积分面积约占总物质的34.1%,低分子量段和高分子量段分别约占41.7%和24.2%.荧光光谱分析表明,各样品均出现类蛋白荧光峰(E_x/E_m=240~270/300~350 nm),在中、高分子量段(M_r500)暗棕壤存在的荧光峰消失.泥炭土出现了较为独特的可见光区类富里酸荧光峰(E_x/E_m=325/420 nm),该荧光峰和黑土的荧光峰在中、高分子量段(M_r500)都产生了红移现象.鸡粪分别出现了和黑土类似的紫外区类富里酸荧光峰,以及和泥炭土类似的可见光区类富里酸荧光峰,以及一类独特的类蛋白荧光峰(E_x/E_m=280/350 nm),但这种类蛋白荧光峰在中分子量段(500M_r12 000)消失.分析表明泥炭土与Cu的络合常数(lg K)为4.13,其他3种土壤与Cu的络合常数较小且差别不大,集中在2.10~3.10之间.鸡粪与Cu的结合能力最大,络合常数达到6.66.     

2015年石家庄市采暖期一次重污染过程细颗粒物在线来源解析

近年来,我国北方采暖期的大气污染问题备受关注.以2015年11月24日至12月4日石家庄地区一次重污染过程为例,采用大气细颗粒物实时在线源解析技术,对不同时段细颗粒物来源解析结果和各类源粒径分布、重污染期间各类源的质谱特征,结合气象条件进行综合分析.结果表明：重污染期间主要污染物来源为燃煤、工业工艺、机动车尾气和二次无机源;低压、静稳条件和低空传输共同作用下,以燃煤及工业工艺源排放颗粒物为主的细颗粒物严重累积,二次转化加剧,导致此次重污染的发生;来自燃煤源的颗粒物以混合碳为主,工业工艺源以金属为主,机动车尾气源以元素碳和金属锰为主,纯二次无机源以二次无机离子为主,来自扬尘源的颗粒物以铝、钙、铁和硅酸盐为主,生物质燃烧源以左旋葡聚糖LEV为主,餐饮源以有机酸为特征信号;与重污染前后不同,八类源于重污染发生期间在整个粒径段呈现均匀分布状态.     

The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

Parental phenols exposure and spontaneous abortion in Chinese population residing in the middle and lower reaches of the Yangtze River

Widespread use of phenols has led to ubiquitous exposure to phenols. In experimental animals, phenols increased resorptions, reduced live litter size and fetal body weights. However, there are limited epidemiological evidences of the relationships between exposure to phenols and pregnancy outcomes. We evaluated the associations between parental urinary levels of various phenols and spontaneous abortion in a Chinese population residing in the middle and lower reaches of the Yangtze River. A case-control study was conducted that included 70 case couples with medically unexplained spontaneous abortion and 180 control couples who did not have a history of spontaneous abortion and had at least one living child. Both parental urinary phenols were measured by ultra-high performance liquid chromatography-tandem mass spectrometry including bisphenol A (BPA), benzophenone-3 (BP-3), 2,3,4-trichlorophenol (2,3,4-TCP), pentachlorophenol (PCP), 4-n-octylphenol (4-n-OP) and 4-n-nonylphenol (4-n-NP). Compared with the low exposure group, there was an increased risk of spontaneous abortion with high paternal urinary PCP concentration [odds ratio (OR) = 2.09, 95% Confidence Interval (CI), 1.05–4.14], and maternal exposure to 4-n-OP and alkylphenol(s) also significantly increased the risk of spontaneous abortion (OR = 2.21, 95% CI, 1.02–4.80; OR = 2.81, 95% CI, 1.39–5.65, respectively). Our study firstly provides the evidence that paternal PCP exposure, maternal 4-n-OP and alkylphenol(s) exposure are associated with spontaneous abortion in humans.     

Comparison of Three Extraction Methods for 17 β-Estradiol in Sand,Bentonite, and Organic-Rich Silt Loam

Extraction is an important procedure for samples that contain soil because other compounds in soil may affect analysis of estrogens. This study was conducted to evaluate three different extraction methods for 17β-estradiol in soil. Sand, bentonite, and organic-rich silt loam were spiked with 1 mg kg^{? 1} of 17β-estradiol as a model compound of estrogens. 17β-estradiol and its metabolites, estrone and estriol, were extracted using (i) a modified Bligh and Dyer extraction, (ii) a pressurized fluid extraction, and (iii) a diethyl ether extraction, and measured by liquid chromatography tandem mass spectrometry. There were significant differences in the extraction efficiency for 17β-estradiol among the extraction methods and the soils: the efficiencies ranged from 10% to 97%. Overall, the diethyl ether extraction method had the largest efficiency of 17β-estradiol with 45% and 57% for bentonite and silt loam, respectively. Transformation of 17β-estradiol to estrone and estriol in the different extraction methods was less than 3.6% during the extraction procedures. This study underlined the importance of sample preparation for estrogen analysis in soil samples.     

Determination of antibiotics in sewage from hospitals, nursery and slaughter house, wastewater treatment plant and source water in Chongqing region of Three Gorge Reservoir in China

Sewage samples from 4 hospitals, 1 nursery, 1 slaughter house, 1 wastewater treatment plant and 5 source water samples of Chongqing region of Three Gorge Reservoir were analyzed for macrolide, lincosamide, trimethoprim, fluorouinolone, sulfonamide and tetracycline antibiotics by online solid-phase extraction and liquid chromatography-tandem mass spectrometry. Results showed that the concentration of ofloxacin (OFX) in hospital was the highest among all water environments ranged from 1.660 μg/L to 4.240 μg/L and norfloxacin (NOR, 0.136-1.620 μg/L), ciproflaxacin (CIP, ranged from 0.011 μg/L to 0.136 μg/L), trimethoprim (TMP, 0.061-0.174 μg/L) were commonly detected. Removal range of antibiotics in the wastewater treatment plant was 18-100% and the removal ratio of tylosin, oxytetracycline and tetracycline were 100%. Relatively higher removal efficiencies were observed for tylosin (TYL), oxytetracycline (OXY) and tetracycline (TET)(100%), while lower removal efficiencies were observed for Trimethoprim (TMP, 1%), Epi-iso-chlorotetracycline (EICIC, 18%) and Erythromycin-H₂O (ERY-H₂O, 24%). Antibiotics were removed more efficiently in primary treatment compared with those in secondary treatment.     

Corynebacterium glutamicum as an indicator for environmental cobalt and silver stress–A proteome analysis

Cobalt and silver are toxic for cells, but mechanisms of this toxicity are largely unknown. Analysis of Corynebacterium glutamicum proteome from cells grown in control and cobalt or silver enriched media was performed by two dimensional gel electrophoresis (2DE) followed by mass spectrometry. Our results indicate that the cell adapted to cobalt stress by inducing five defense mechanisms: Scavenging of free radicals, promotion of the generation of energy, reparation of DNA, reparation and biogenesis of Fe-S cluster proteins and supporting and reparation of cell wall. In response to the detoxification of Ag⁺ many proteins were up-regulated, which involved reparation of damaged DNA, minimizing the toxic effect of reactive oxygen species (ROS) and energy generation. Overexpression of proteins involved in cell wall biosynthesis (1,4-alpha-glucan branching enzyme and nucleoside-diphosphate-sugar epimerase) upon cobalt stress and induction of proteins involved in energy metabolism (2-methylcitrate dehydratase and 1, 2-methylcitrate synthase) upon silver demonstrate the potential of these enzymes as biomarkers of sub-lethal Ag⁺ and Co toxicity.