Speciation and quantitation of degradation products of silicones (Silane/Siloxane Diols) by gas chromatography—mass spectrometry and stability of dimethylsilanediol

Gas chromatography-mass spectrometry (GC-MS) methodology was developed to speciate and quantitate several degradation products of polydimethylsiloxane (PDMS) in soil. We have demonstrated that the major degradation product,viz., dimethylsilanediol, can be readily analyzed by GC-MS without derivatization as commonly practiced in analyzing such materials. A mixture of linear siloxane diols (n = 1–5, wheren is the number of Me₂SiO units), and cyclic dimethylsiloxanes (n = 4–6) was resolved by GC-MS. We also found that peak identity of various diols required that GC-MS is done in the chemical ionization (CI) mode, since the electron impact (EI) ionization mode produced similar mass fragmentation patterns for diols and cyclics containing the same number of silicon atoms. For siloxane diols, detection limits ranged from 100 pg (forn = 1) to 1 ng (for n = 5). For cyclics, the detection limit was about 1 pg. Dimethylsilanediol, known to be unstable even in the solid state, was shown by NMR techniques to be stable in aqueous solution at <0.1% concentration. A 100-ppm solution was stable for over a year. Purity check for dimethylsilanediol is best carried out by Si-29 solid-state NMR technique.     

垂序商陆叶细胞壁结合锰机制研究

垂序商陆是一种典型的锰超积累植物,细胞壁在其累积解毒锰的过程中起了一定的作用.通过细胞壁吸附实验,研究不同p H和不同锰浓度对细胞壁吸附锰的影响,并采用傅立叶红外光谱及同步辐射X-射线吸收光谱技术探讨了其吸附机制.结果表明,垂序商陆叶细胞壁吸附锰的最适p H值为5~6;其吸附行为可用Langmuir模型较好地描述(R2=0.978 5),并计算得其最大吸附量为62.50μmol·g-1.细胞壁上的羟基(—OH)和羰基(—CO)是结合锰的主要位点;锰周围第一配层为氧原子,其配位数为6.3,Mn—O键长为0.216 nm,细胞壁与锰主要以内配层模式相结合.     

三峡库区典型农业小流域土壤溶解性有机质的紫外-可见及荧光特征

以三峡库区典型农业小流域土壤溶解性有机质(DOM)为研究对象,利用紫外-可见和荧光光谱,分析和讨论了不同土地利用类型(包括林地、田地、菜地和民用地)对土壤DOM地化特征的影响.结果表明,不同土地利用条件下DOM性质差异明显,以林地DOM的芳香性程度较高,腐殖化特征最强,其次为田地;尽管居民用地和菜地溶解性有机碳(DOC)含量高(均值分别为0.81 g·kg-1和0.89 g·kg-1),但是芳香化程度低,DOM中非生色组分对高DOC含量的贡献明显.所有样本荧光指数(FI)介于自生源特征(FI=1.9)和陆源特征(FI=1.4)之间,自生源(类蛋白组分)和异生源(类腐殖组分)对DOM均有贡献.大部分样本r(T/C)都大于2.0,说明该农业小流域土壤DOM受外来因素尤其是人类活动影响较大,尤以菜地为代表.另外,不同特征光谱参数对不同土地利用条件下DOM结构和性质差异性的灵敏程度不同,光谱斜率比值(SR)和腐殖化指数(HIX)不能反映DOM地化特征的差异性,因此单一光谱指标并不能全面提供DOM的特征信息,建议两种光谱分析方法联用.     

石化罐区挥发性有机物源强反演技术的研究

石化企业是国民经济的支柱,亦是重大的污染排放源,其中大气污染以VOCs为主,而石化罐区是石化企业最常用的生产装置,研究石化罐区VOCs的核算具有重要的意义。同时,遥感傅里叶变换红外光谱技术以独特的优势,被广泛地应用于大气环境监测中,国内外一些研究学者试图将遥感傅里叶红外光谱技术与VOCs源强反演技术相结合,开发一条VOCs源强核算的新路。基于我国石化罐区的实际情况,提出了一种以遥感傅里叶变换红外光谱技术为监测手段,以石化罐区VOCs源强反演技术-扩散模式反推法为理论基础的石化罐区无组织排放VOCs源强反演的新方法,并介绍了其相关的研究理论、研究方法、研究进展,以及目前所存在的问题,为VOCs源强反演提供了一种新思路。     

Effects of duckweed (Spriodela polyrrhiza) remediation on the composition of dissolved organic matter in effluent of scale pig farms

The swine effluent studied was collected from scale pig farms, located in Yujiang County of Jiangxi Province, China, and duckweed (Spriodela polyrrhiza) was selected to dispose the effluent. The purpose of this study was to elucidate the effects of duckweed growth on the dissolved organic matter composition in swine effluent. Throughout the experiment period, the concentrations of organic matter were determined regularly, and the excitation–emission matrix (3DEEM) spectroscopy was used to characterize the fluorescence component. Compared with no-duckweed treatments (controls), the specific ultra-violet absorbance at 254 nm (SUVA₂₅₄) was increased by a final average of 34.4% as the phytoremediation using duckweed, and the removal rate of DOC was increased by a final average of 28.0%. In swine effluent, four fluorescence components were identified, including two protein-like (tryptophan, tyrosine) and two humic-like (fulvic acids, humic acids) components. For all treatments, the concentrations of protein-like components decreased by a final average of 69.0%. As the growth of duckweed, the concentrations of humic-like components were increased by a final average of 123.5% than controls. Significant and positive correlations were observed between SUVA₂₅₄ and humic-like components. Compared with the controls, the humification index (HIX) increased by a final average of 9.0% for duckweed treatments. Meanwhile, the duckweed growth leaded to a lower biological index (BIX) and a higher proportion of microbial-derived fulvic acids than controls. In conclusion, the duckweed remediation not only enhanced the removal rate of organic matter in swine effluent, but also increased the percent of humic substances.     

Characterization of dissolved organic matter fractions from Lake Hongfeng, Southwestern China Plateau

With XAD-series and ion exchange resins, dissolved organic matter (DOM) from Lake Hongfeng in Southwestern China Plateau was isolated into 6 fractions, i.e., humic acid (HA), fulvic acid (FA), hydrophobic neutrals (HON), hydrophilic acids (HIA), hydrophilic bases (HIB) and hydrophilic neutrals (HIN). Those fractions were characterized by high performance size exclusion chromatography, fluorescence spectroscopy and UV absorbance. Among the 6 fractions, FA was predominant and accounted for 51% of the total DOM. The weight-average (M_w) and number-averaged (M_n) molecular weight of these fractions ranged from 1688 to 2355 Da and from 1338 to 1928 Da, respectively. A strong correlation was observed between specific UV absorbance at 280 nm, E₂/E₃ (absorbance at 250 nm to 365 nm), and the molecular weight for DOM fractions. UV-Vis fulvic-like fluorescence peaks were found in all fractions. Protein-like fluorescence peaks existed in HON may indicate that microbial activity was severely in Lake Hongfeng. There was a significant relationship between fluorescence intensities and specific UV absorbance at 254 nm for those DOM fractions, suggesting their similar luminescence characteristics. The values of fluorescence index (f_450/500) indicated that hydrophobic fractions may derive from terrestrial sources, and the hydrophilic fractions from microbial and terrestrial origins. Those results suggest that there were inter-relationships between molecular weight, fluorescence and absorbance characteristics, and also subtle consistencies between the hydrophilic and hydrophobic properties and the sources for these 6 fractions from Lake Hongfeng.     

Visualizing different uranium oxidation states during the surface alteration of uraninite and uranium tetrachloride

Low-temperature alteration reactions on uranium phases may lead to the mobilization of uranium and thereby poses a potential threat to humans living close to uranium-contaminated sites. In this study, the surface alteration of uraninite (UO₂) and uranium tetrachloride (UCl₄) in air atmosphere was studied by confocal laser scanning microscopy (CLSM) and laser-induced fluorescence spectroscopy using an excitation wavelength of 408 nm. It was found that within minutes the oxidation state on the surface of the uraninite and the uranium tetrachloride changed. During the surface alteration process U(IV) atoms on the uraninite and uranium tetrachloride surface became stepwise oxidized by a one-electron step at first to U(V) and then further to U(VI). These observed changes in the oxidation states of the uraninite surface were microscopically visualized and spectroscopically identified on the basis of their fluorescence emission signal. A fluorescence signal in the wavelength range of 415–475 nm was indicative for metastable uranium(V), and a fluorescence signal in the range of 480–560 nm was identified as uranium(VI). In addition, the oxidation process of tetravalent uranium in aqueous solution at pH 0.3 was visualized by CLSM and U(V) was fluorescence spectroscopically identified. The combination of microscopy and fluorescence spectroscopy provided a very convincing visualization of the brief presence of U(V) as a metastable reaction intermediate and of the simultaneous coexistence of the three states U(IV), U(V), and U(VI). These results have a significant importance for fundamental uranium redox chemistry and should contribute to a better understanding of the geochemical behavior of uranium in nature. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

环境微界面过程的原位和在线研究方法

环境微界面过程是污染物在各环境要素中迁移转化的基本过程,也是研究污染控制方法的基础.发展原位和在线研究方法,对于揭示污染物在环境微界面的迁移转化规律和进行污染控制过程的研究具有重要意义.本文基于环境微界面过程的基本特征,在针对多相环境催化的原位研究方法基础上,分析了用于环境微界面过程的原位和在线研究方法所面临的挑战和相应对策,主要介绍了红外光谱、拉曼光谱和质谱等技术在气固环境微界面过程原位研究中的应用,提出了发展环境微界面过程原位和在线研究方法体系的构想.     

铝合金在NaCl溶液中的电化学腐蚀行为

采用极化曲线法和交流阻抗法,分析了ZL102和LF6铝合金在不同pH的3%NaCl溶液中的腐蚀特性,并用金相显微镜观察了铝合金的微观组织。结果表明,2种铝合金的自腐蚀电位都随着pH的升高变得愈负;除pH=9.5的情形之外,ZL102铝合金的腐蚀速率均小于LF6铝合金;LF6铝合金结构的不均匀性与其加入的合金化元素是导致其耐蚀性能较ZL102铝合金差的主要原因。     

二级处理出水中溶解性有机物的荧光特性

为研究二级处理出水中溶解性有机物的荧光特性,以沈阳市B污水处理厂为研究对象,利用XAD树脂对二级处理出水中的溶解性有机物(DOM)进行分级分离。按照DOM在不同树脂上的吸附特性将其分为5个部分:疏水性有机酸(HPO-A)、疏水性中性有机物(HPO-N)、过渡亲水性有机酸(TPI-A)、过渡亲水性中性有机物(TPI-N)和亲水性有机物(HPI)。研究结果表明,DOM组分中含有类腐植酸荧光团、类富里酸荧光团、类芳香族蛋白质荧光团和类溶解性微生物代谢产物荧光团,此外,还含有具有多环芳香结构的荧光物质。DOM中的荧光物质主要集中在HPO-N和TPI-N中。类腐植酸荧光团、类富里酸荧光团和类溶解性微生物代谢产物荧光团在TPI-N中的含量最高,而类芳香族蛋白质荧光团在HPO-N中的含量最高。对于HPO-A、TPI-A和TPI-N来说,类富里酸荧光峰的强度最高;类芳香族蛋白质荧光峰是HPO-N的最强峰;类溶解性微生物代谢产物荧光峰是HPI的最强峰。