不同氯化度的氯化石蜡制备方法研究

通过自行搭建的实验装置（包括回流反应装置、干燥装置、碱液吸收装置和抽真空惰性气体置换保护装置）,将癸烷（decane）与磺酰氯（SO₂Cl₂）试剂在汞灯（10 W, 254 nm）照射下进行自由基取代反应,合成了不同氯化度的碳链长度为10个碳原子的氯化石蜡标准品（C₁₀-chlorinated paraffins, C₁₀-CPs）。合成的粗产品通过硅胶和弗罗里硅土复合柱的净化吸收去除未反应的癸烷,实现反应产物的纯化。将纯化后的氯化石蜡标准品通过气相色谱/质谱进行产物纯度分析和不同单体组成模式分析。结果表明,净化后的标准品中不含癸烷和其他杂质,氯化石蜡单体主要以Cl₇、Cl₈单体为主。光照、温度和反应时间对产物的氯化度有一定的影响,通过计算得到合成产物的纯度在98%以上,氯化度在55.6%~66.9%。结果表明此方法可以用来制备不同氯化度的氯化石蜡标准品。     

环境中氯化石蜡的研究进展

 氯化石蜡是一类具有持久性、生物毒性、生物富集性和长距离迁移性的有机污染物,普遍存在于环境当中。工业上氯化石蜡被广泛用于金属加工润滑液、密封胶添加剂、阻燃剂、聚氯乙烯增塑剂等。作为一类新型污染物,短链氯化石蜡已经被列入斯德哥尔摩公约持久性有机污染物审查范围内,并引起全球的关注。中国是全球氯化石蜡第一大生产国和出口国,但对氯化石蜡的环境研究还处于起步阶段。本文着重综述了国内外大气、土壤、水体、沉积物、生物体等不同环境介质中氯化石蜡的来源、归趋及浓度水平,并对国内氯化石蜡的研究前景进行展望。     

短链氯化石蜡急性暴露对SD雄性大鼠的组织病理学影响

目的：选择短链氯化石蜡含量不同的两种氯化石蜡产品（CPsⅠ,38．22％和CPsⅡ,0．08％）作为模式化合物,比较它们经口连续灌胃暴露14d后对SD雄性大鼠的影响,借以探讨短链氯化石蜡是否存在特殊的毒性效应。方法：CPsⅠ和CPsⅡ的暴露浓度分别为lO、50、100mg／kg（CPsI）和100mg／kg（CPsⅡ）。结果：两种氯化石蜡产品暴露后,对大鼠的摄食、体重无明显影响。CPsⅠ和CPsⅡ急性暴露,均可造成大鼠的肝脏中肝细胞肿胀、水样变性及胞质疏散;肾脏中肾小管肿胀,肾小球萎缩、肾小球玻璃样变;肺部中肺泡隔增厚,炎症细胞浸润等明显的组织病理学改变。结论：氯化石蜡急性暴露对SD雄性大鼠所产生的毒性效应,与样品中短链氯化石蜡的含量并无显著性关联。     

中国短链氯化石蜡排放清单和预测

通过对氯化石蜡(CPs)生产和消费行业的调查和文献调研, 将短链氯化石蜡(SCCPs)的排放按生产、增塑剂、阻燃剂和金属切削液4个行业进行测算, 给出中国SCCPs排放清单和2007?2011年SCCPs年排放 量。中国2011年SCCPs的排放总量为1788.67吨, 其中对大气的排放量达到498.32吨, 对水体的排放达到1290.35吨; 排放量最大的是金属切削液的使用过程。若不采取控制措施, 到2016年SCCPs的年排放量将达到 2562.51吨, 对生态环境和人体健康存在巨大威胁。     

痕量PBBs/PBDEsGC/MS分析法中PCB及其衍生物干扰消除方法

电子电气产品中痕量阻燃剂聚溴联苯/聚溴联苯醚(PBBs/PBDEs)的检测通常采用气相色谱/质谱(GC-MS)联用法,但该法是建立在持久性污染物多氯化苯/多氯化萘(PCBs/PCNs)基础上,因此此类物质干扰不可避免。为了解决此类问题,提出了2种解决方法:1)阴离子化学电离-气相色谱/质谱联用法(GC/MS-NICI)和电子轰击-气相色谱/质谱联用法(GC/MS-EI)联合使用;2)以YMC ODS-C18为载体,基质固相分散法(MSPD)吸附分离。结果显示,前者可以同时洞察聚溴联苯和联苯醚的分子链断裂后阴离子碎片[Br]-,[HBr2]-和分子链段碎片[M+2]+,[M+4]+,[M+6]+,[M+8]+的滞留峰,增加了对溴系阻燃剂的选择性。后者可以有效分离多种多氯化苯与聚溴联苯醚的色谱峰,这为溴系阻燃剂气相色谱/质谱联用分析法中多氯化苯及其衍生物干扰提供了新的解决方法。采用此方法对8类电子电气产品中10种聚溴联苯醚和多氯化苯进行加标回收实验及精密度分析,回收率在60%～98%,相对误差在9.5%以内,符合国际电工委员会(IEC)对溴系阻燃剂检测精度要求,说明方法具有较高的可靠性,也为我国电子电气业更好遵守...     

First mass measurement of short-lived nuclides at HIRFL-CSR

Recent commissioning of the HIRFL-CSR has demonstrated its ability to perform direct mass measurement for short-lived nuclides. Projectile fragments produced by the 78Kr ions at 481.88 MeV/u were separated with the new radioactive beam line in Lanzhou （RIBLL2）, and injected into and stored in the experimental storage ring （CSRe）. By operating the CSRe as an isochronous mass spectrometry, a typical mass resolution around 2.0×10？5 has been achieved. The masses for 63Ge, 65As and 67Se were measured for the first time. The measured masses are compared with theoretical predictions and the location of the proton drip-line for As isotopes is discussed. The implication of the 65As mass in the astrophysical rapid proton capture process has also been addressed.     

水体中短链氯化石蜡污染研究进展

短链氯化石蜡(SCCPs)拟列入"斯德哥尔摩公约"禁止使用的一类持久性有机污染物,对生态环境和人体健康具有极大的潜在危害,已成为国际环境科学领域的一个研究热点。水体是SCCPs重要的"汇",本文着重综述了水生态系统中沉积物、水、生物体等不同环境介质中SCCPs的含量分布及对水生生物的危害,并对SCCPs的研究重点和前景进行展望。     

角鲨烯软胶囊中角鲨烯的鉴定和分析

用红外光谱和质谱对角鲨烯软胶囊中的角鲨烯进行成分鉴定,用气相色谱-质谱法测定角鲨烯含量。结果表明：所建立的气相色谱-质谱定量分析方法的平均回收率为98.7%,相对标准偏差为5.9%,线性相关系数为0.9999,最低检出限为0.6ng/ml。     

红树蚬与歪红树蚬对短链氯化石蜡胁迫应答的差别

【目的】研究红树蚬Polymesoda erosa与歪红树蚬Polymesoda expansa对短链氯化石蜡(Short-chain Chlorinated Paraffins,SCCPs)胁迫应答的差别。【方法】观察两种蚬血细胞的溶酶体中性红保持时间(Neutral Red Retention Time,NRRT)、总抗氧化活力(Total Antioxidant Capacity,T-AOC)、丙二醛(MDA)含量对不同剂量-时间SCCPs的响应。【结果】在低浓度SCCPs胁迫早期,两种蚬NRRT均表现出"毒物兴奋效应",其中红树蚬表现更为明显;T-AOC值、MDA含量表明歪红树蚬对于逆境的抵抗力更强。中、高浓度SCCPs胁迫下两种蚬对SCCPs响应结果相似。【结论】红树蚬与歪红树蚬对SCCPs胁迫应答随剂量-时间变化总体趋势相似。歪红树蚬对逆境的抵抗力略强。     

二异丙基酮定性定量方法的研究

采用色谱-质谱联用技术对酸-酸化反应制得的二异丙基酮化冷凝液进行系统的定性,并且在色谱仪上利用外标法和面积归一化法对主要组分进行定量方法的比较,得到较好的定性定量结果。     

联用色谱和化学计量学方法分析赤芍挥发性成分

采用气相色谱-质谱(GC-MS)检测,通过直观推导式演进特征投影法(HELP)对二维色谱／质谱数据进行解析,得到各组分的纯色谱曲线和质谱,从而实现对赤芍挥发性成分的定性和定量分析。根据色谱保留时间和质谱,在质谱库中进行相似检索,实现对组分的定性分析,然后用归一化法进行定量分析。研究结果表明:从赤芍挥发性成分中共分辨出57个色谱峰,通过质谱库对分辨的纯组分进行检索,鉴定其中36个成分,占挥发性成分总含量的95．21％;赤芍主要挥发成分为水杨醛、正十六碳酸和(Z,Z)-9,12-十八碳二烯酸。     

Laser mass spectrometry for high sensitive and multi-com- ponent analysis of exhaust gas from vehicles

Laser mass spectrometry is a newly developed method for pollutant detection. It combines resonance-en- hanced multiphoton ionization (REMPI) and time-of-flight mass spectro- metry (TOF-MS). It may detect pollutants with high sensitivity, high selectivity and in a multi-com- ponent way. In this note, laser mass spectrometry was used to detect the pollutants in exhaust gases from vehicles. With one-color REMPI (at 266 nm), several aromatic hydrocarbons, including benzene, toluene, xylene, C_3-benzene, etc., were detected. These substances were selectively ionized by (1+1) REMPI and their mass resolution was detected by a TOF mass spectrometer. And a quantitative analysis was achieved.     

Status of persistent organic pollutants and heavy metals in surface water of Arctic region

Trace pollutants in the surface water of the Arctic region have been analyzed by the capillary gas chromatography with the micro-electron capture detector(GCμECD),the gas chromatography-mass spectrometry(GCMS)and the inductively coupled plasmas-mass spectrometry(ICP-MS).Compared with previously reported studies,concentrations of OCPs in these regions are much lower than those in the last decades.The ratio of α/γ-HCH indicates the different pesticide composition between these two regions and is the potential marker for the source of the OCPs.Many other OCPs with different residue patterns have also been found for the first time in the two regions.No heavy metal contaminant was found in the investigation regions.     

<Emphasis Type="Italic">In situ</Emphasis> boron isotope measurements of natural geological materials by LA-MC-ICP-MS

There are two main methods to determine boron isotopic composition. One is the solution method, in which boron is purified after the samples are dissolved in solution and the boron isotope ratios are determined by thermal ionization mass spectrometry (P-TIMS and N-TIMS) or multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). The other is an in-situ analysis method, in which the in-situ boron isotopic ratios in minerals are analyzed directly using secondary ion mass spectrometry (SIMS) or laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). In the in-situ analysis method for boron isotopes, the multifarious chemical purification and separation processes of the solution method are avoided, with increased work efficiency. In addition, the microzones and microbeddings of minerals can be analyzed in-situ to reveal the fine processes and conditions of mineral formation. In this study, using the standard-sample-bracketing (SSB) method, mass bias of the instrument and the fractionation of isotopes were calibrated, and the in-situ determination method of LA-MC-ICP-MS for boron isotopes was established. Through detailed analyses on a series of boron isotope standards and samples, a matrix effect was assessed but not detected, and the analysis results were in accordance with the formerly reported values or P-TIMS determined values, within the error range. The analytical results for IAEA B4 and IMR RB1 with relatively high boron contents were δ¹¹B = –(8.36±0.58)‰ (2σ, n=50) and δ¹¹B = –(12.96±0.97)‰ (2σ, n=57), respectively; the analytical result for IAEA B6 with relatively low boron content was δ¹¹B = –(3.29±1.12)‰ (2σ, n=35). In-situ measurements for B isotopes were performed on geological samples such as tourmaline, ulexite, ludwigite, inyoite and ascharite, with the results consistent with those determined by P-TIMS, within the error range.     

石墨双向吸附特性的研究

使用高压匀浆泵制备出具有同时吸附长链正构烷烃和稠环芳烃能力的石墨吸附剂。借助于气相色谱、紫外光谱对吸附剂吸附能力进行了探讨,推导出等温吸附平衡方程,计算了等温吸附的平衡常数K(1400～40250)和标准自由焓变(-17～-26kJ/mol),证明了石墨吸附剂具有双向吸附能力。对影响石墨吸附的因素:吸附时间、温度、固液比、粒度及分散度进行了研究,认为石墨的粒度及分散度是影响石墨吸附的主要因素。     

超标偷排污水溯源的物证分析技术研究

利用电感耦合等离子-质谱（ICP-MS）、离子色谱（IC）、气-质联用(GC-MS)、三维荧光光谱(3D-EEMS)等仪器联用分析手段,分别从涉污企业外排污废水水样中测取具有广泛代表性的无机元素及金属离子、阴离子、有机小分子与有机大分子等信息,从中选出对于污染源溯源有价值的化学指纹。对多种模拟水样进行污染源溯源的实验结果表明,借助上述仪器联用分析技术得到的污废水化学指纹具有一定的普适性及良好的稳定性和可加和线性,其高灵敏度足以满足超排指纹检出的要求;通过超排指纹与涉企指纹比对排查能够顺利锁定污染源,实现对超排者的溯源追责。     

农药残留分析技术新进展(综述)

从样品提取技术及分析检测技术两方面介绍了目前国内外流行的农药残留分析检测技术。在农药残留分析样品提取技术中主要介绍了加速溶剂提取法、超临界流体萃取、微波加热提取法、固相微萃取法。在农药残留分析技术中主要论述了超临界流体色谱技术、气相色谱／质谱联用技术、液相色谱／质谱联用技术、直接光谱分析技术、毛细管区带电泳技术等。     

滇桂艾纳香茎和叶中挥发性化学成分的HS-SPME-GC-MS 分析

 采用固相微萃取法提取中草药滇桂艾纳香茎和叶中挥发性成分,经气相色谱/质谱测定其化学成分和相对含量,共鉴定了98种化学成分,茎和叶中各82种。主要挥发成分及含量为：大叶香烯 D（茎：36.59%;叶：40.87%）、香木兰烯（茎：13.20%;叶：17.00%）、顺 α 没药烯（茎：6.06%;叶：7.48%）、β 荜澄茄油烯（茎：4.83%;叶：5.85%）、γ 依兰油烯（茎：2.18%;叶：2.58%）和1,2,4a,5,6,8a-六氢-4,7-二甲基-1-（1-甲乙基）-萘（茎：2.03%;叶：2.55%）,它们都为倍半萜类化合物。本实验中发现滇桂艾纳香茎和叶的中倍半萜类化合物含量分别占挥发性成分含量的91.75%和94.52%。     

基于胺法的旋流喷淋气液吸收烟气CO2的性能

为了强化CO_2捕集过程的气液传质,设计了一类多级旋流喷淋反应器,实验研究了典型的醇胺(乙醇胺(MEA)、二乙醇胺(DEA))脱除CO_2的分离效率和传质系数,并分析了操作条件的影响.结果表明:在相同的实验条件下,MEA的脱碳效率(最大值95%)大于DEA的脱碳效率(最大值92.3%).与相关研究数据的对比表明,多级旋流喷淋可以有效增强醇胺-CO_2喷淋反应系统的传质过程.醇胺溶液旋流气液吸收烟气CO_2的脱碳效率受操作条件的影响,其随着吸收剂质量分数、吸收剂流量和反应温度的增加而提高,随着烟气中CO_2体积分数和烟气流量的增加而降低.     

Fragmentation study of two brassinolides by ion trap tandem mass spectrometry

The fragmentation pathways of two isomers of brassinosteroids, 28-homobrassinolide (28-h-BL) and 28-epihomobrassinolide (28-eh-BL), have been investigated by tandem mass spectrometry (MSⁿ, n = 1, 2, 3, 4) with the electrospray ionization (ESI) source. The ESI mass spectrometric fragmentation pathways of protonated 28-h-BL and 28-eh-BL were comprehensively elucidated, and the principles revealed in this investigation could potentially be used to identify and distinguish brassinosteroids and their isomers.