分子光谱技术在水体微塑料监测中的应用

水域、陆地和空气中的微塑料污染不仅对人们赖以生存的生态系统有潜在危害,而且对人类的身体健康存在持续性危害。针对这些污染问题开展研究的首要任务之一就是需要鉴定微塑料的成分,从而明确可能产生污染的源头以及引起污染的途径。分子光谱技术是鉴别微塑料最常用的分析方法之一,尤其是红外光谱法和拉曼光谱法。建立了基于分子光谱技术的水体微塑料检测方法,可实现对水体中1～5 000μm尺寸范围内的微塑料的自动化测试。其中,尺寸大于10μm的微塑料颗粒物可以通过显微红外光谱仪进行检测,尺寸大于1μm的微塑料颗粒物可以通过显微拉曼光谱仪进行检测。该方法操作简单、检测速度快、结果呈现直观,可作为微塑料检测的有力工具。     

X射线光电子能谱在HTPB推进剂老化机理研究中的应用

采用X射线光电子能谱（XPS）法研究了HTPB推进剂在80℃热空气烘箱内分别老化0周、13周和24周的元素组成、化学价态及含量变化。通过拟合C,O,N,Cl等元素的XPS谱图,推测该推进剂在常温（25℃）贮存老化初期应是氧化交联,后期则出现降解断链,并认为NH4ClO4缓慢分解,攻击C C不饱和双键,使得C C双键含量降低是HTPB推进剂老化失效的主要原因。Al粉被包裹在推进剂粘合剂内部,XPS法未能检出Al粉。由于Al粉比较稳定,不参与推进剂老化过程,故XPS仍可用于HTPB推进剂老化机理研究。     

单光子/光电子在线质谱实时分析聚氯乙烯热分解/燃烧产物

实验室研制了低能光电子磁场增强电离(MEPEI)和单光子电离(SPI)复合电离源,该电离源具有电离化合物范围宽、碎片离子少、质谱图简单等优点,结合飞行时间质谱(TOF-MS)实现了聚氯乙烯(PVC)热分解/燃烧产物的在线分析.针对不同的目标化合物,MEPEI/SPI复合电离源通过调节电离区电场强度,可以快速在SPI和SPI-MEPEI之间切换.PVC热分解/燃烧产物中电离能大于光子能量(10.60 eV)的HCl和CO2(12.74 eV、13.77 eV)利用MEPEI模式电离;而烯烃、二氯乙烯、苯系物、氯苯、苯乙烯、茚满及萘系物等可通过SPI-MEPEI复合模式电离.通过实时监测PVC主要燃烧产物的信号强度随温度的变化趋势可推断出,PVC燃烧产物主要是通过两种机制生成:①250～370℃时,PVC发生脱氯及分子内环化反应,产生大量的HCl、苯和萘;②380～510℃时,PVC发生分子间交联反应,生成烷基芳烃,如甲苯和二甲苯/乙苯等.实验结果表明,SPI/SPI-MEPEI复合离子源TOF-MS分析速度快,应用范围广,在在线分析中具有广泛的应用前景.     

Genotoxicity removal of reclaimed water during ozonation

Genotoxicity in wastewater and reclaimed water now is gaining increased attention because of genotoxins' potential damage to the ecosystem and human health. The effect of ozonation on genotoxicity in reclaimed water was investigated. It was found that ozonation decreased the genotoxicy dramatically in three tertiary treatment plants. In the further batch ozonation experiment in laboratory,secondary effluent sample used exhibited the genotoxicity of(41.1 ± 4.1) μg 4NQO/L. Ozonation with a dose of 10 mg O3/L completely removed the genotoxicity in secondary effluent. However,after ozonation, the dissolved organic carbonvalue of the sample didn't change much but the specific ultraviolet absorbance(SUVA) value dropped sharply. With the help of Fourier transform infrared spectroscopy, ozonation was found to change chemical aliphatic carbon and C–O of the dissolved arganic matter, which might be the reason of the significant decreases of SUVA and genotoxicity.     

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.     

同源地人工湖水体和底泥中有机物组成及有机结构的分析研究

采用XAD-8大孔吸附树脂对水体和底泥中的有机物进行组分分离,并通过傅里叶变换红外光谱(FTIR)、紫外-可见光谱(UV-Vis)和三维荧光光谱(3DEEMs)对自然水体和底泥中的疏水酸(腐殖酸、富里酸)、疏水碱、疏水中性物质和亲水物质进行表征和对比.结果表明,水体中有机物含量:亲水物质富里酸腐殖酸疏水碱疏水中性物质,底泥中有机物的含量为:腐殖酸富里酸亲水物质疏水碱疏水中性物质.根据红外、紫外、三维荧光光谱可知底泥中有机物的芳香程度、不饱和程度及分子量大小略高于水体有机物.根据荧光指数(FI)和自生源指标(BIX)可知,底泥和水体的腐殖酸和富里酸主要来源于陆生动植物和土壤有机质,而其余物质主要源于细菌和藻类活动.     

采用水解酸化-复合好氧处理制药工业废水的工艺评价

以制药工业综合废水处理为例对其采用的两级水解酸化复合好氧工艺的处理效果进行评估。按常规指标进行评估,该工艺对于制药综合废水的处理效果达到了设计目的,COD去除率可达到78.2%以上,NH+4-N的去除率达到99.3%,出水质量基本满足"污水综合排放标准(GB8978-1996)"二级标准和"辽宁省污水综合排放标准(DB21.1627-2008)";急性毒性的检测表明,经过该工艺处理后出水为低毒性;三维荧光谱分析(EEM)表明,制药综合废水经生物处理后的可溶性有机物中仍然存在难降解物质,建议增加物化处理以提高处理效果;并且制药废水经处理后的出水中的盐度对排入的生态系统存在风险,建议纳入排放标准以加强管理。     

4-硝基苯胺与人血清白蛋白相互作用的研究

通过荧光和紫外光谱法研究了4-硝基苯胺与人血清白蛋白（HSA）的作用.结果表明,4-硝基苯胺对HSA的内源荧光具有强烈的猝灭作用.猝灭机理为静态猝灭,同时伴随有非辐射能量转移的发生.根据双对数方程计算其结合常数和结合位点数.确定4-硝基苯胺与HSA有一类结合部位.根据热力学参数得出4-硝基苯胺与HSA之间的主要作用力为氢键和疏水作用力.同步荧光的结果表明,作用点位靠近色氨酸,并且使色氨酸的疏水环境增强.     

A Monte Carlo study of radon detection in cylindrical diffusion chambers

The functioning of radon diffusion chambers was studied using the Monte Carlo code RAMMX developed here. The alpha particles from radon are assumed randomly produced in the volume of the cylinder, and those from the progeny are assumed to originate randomly at the cylindrical surface. The energy spectrum, the distribution of incident angles, and the distribution of path lengths of the alpha particles on the detector were obtained. These quantities vary depending on input parameters such as initial alpha particle energy, radius and depth of the diffusion chamber, detector size and atmospheric pressure. The calculated energy spectrum for both ²²²Rn and ²²⁰Rn was compared with experiment, permitting the identification of each peak and its origin, and a better understanding of radon monitoring. Three aspects not considered in previous calculations are progeny alphas coming from surfaces of the monitor, taking into account the atmospheric pressure, and including the isotope ²²⁰Rn.     

Binding of polycyclic aromatic hydrocarbons by humic acids formed during composting

Binding of two model polycyclic aromatic hydrocarbons (PAHs), phenanthrene and pyrene, by humic acids (HAs) isolated from an organic substrate at different stages of composting and a soil was investigated using a batch fluorescence quenching method and the modified Freundlich model. With respect to soil HA, the organic substrate HA fractions were characterized by larger binding affinities for both phenanthrene and pyrene. Further, isotherm deviation from linearity was larger for soil HA than for organic substrate HAs, indicating a larger heterogeneity of binding sites in the former. The composting process decreased the binding affinity and increased the heterogeneity of binding sites of HAs. The changes undergone by the HA fraction during composting may be expected to contribute to facilitate microbial accessibility to PAHs. The results obtained also suggest that bioremediation of PAH-contaminated soils with matured compost, rather than with fresh organic amendments, may result in faster and more effective cleanup.