Screening of transformation products in soils contaminated with unsymmetrical dimethylhydrazine using headspace SPME and GC-MS

The paper describes a novel SPME-based approach for sampling and analysis of transformation products of highly reactive and toxic unsymmetrical dimethylhydrazine (UDMH) which is used as a fuel in many Russian, European, Indian, and Chinese heavy cargo carrier rockets. The effects of several parameters were studied to optimize analyte recovery. It was found that the 85 μm Carboxen/polydimethylsiloxane fiber coating provides the highest selectivity for selected UDMH transformation products. Optimal sampling/sample preparation parameters were determined to be 1-h soil headspace sampling time at 40 °C. The GC inlet temperature was optimized to 170 °C held for 0.1 min, then 1 °C s⁻¹ ramp to 250 °C where it was held for 40 min. Temperature programing resulted in a fast desorption along with minimal chemical transformation in the GC inlet. SPME was very effective extracting UDMH transformation products from soil samples contaminated with rocket fuel. The use of SPME resulted in high sensitivity, speed, small labor consumption due to an automation and simplicity of use. It was shown that water addition to soil leads to a significant decrease of recovery of almost all target transformation products of UDMH. The use of SPME for sampling and sample preparation resulted in detection of the total of 21 new compounds that are relevant to the UDMH transformation in soils. In addition, the number of confirmed transformation products of UDMH increased from 15 to 27. This sampling/sample preparation approach can be recommended for environmental assessment of soil samples from areas affected by space rocket activity.     

固相微萃取和气质联用分析测定土壤中13种挥发性芳香烃

建立了固相微萃取(SPME)-气相色谱质谱法(GC-MS)测定土壤中13种挥发性芳香烃的方法.用SPME萃取土壤中的挥发性芳香烃,利用安捷伦5977A气相色谱-质谱进行分离检测,选用土壤基质修改液提高了目标化合物的回收率.13种芳香烃组分在5.0、10、20、40、50μg/kg土壤中质量浓度范围内呈线性关系,相关系数r2大于0.995,方法检测限小于1.0μg/kg,完全满足检测要求.     

固相微萃取/气相色谱-质谱联用法测定橡胶密封材料中N-亚硝胺

建立了固相微萃取/气相色谱-质谱联用法(SPME/GC-MS)测定橡胶密封材料中N-亚硝基-N-甲基苯胺(NMPh A)、N-亚硝基-N-乙基苯胺(NEPh A)和N-亚硝基二苯基胺(NDPhe A)3种N-亚硝胺化合物含量的方法。样品参考国标GB/T 24153-2009进行预处理后,采用固相微萃取进行提取,对影响固相微萃取效率的纤维涂覆种类、萃取时间、搅拌速度和萃取温度等条件进行优化。在优化条件下,方法的线性范围为5~500μg/L,相关系数(r)均大于0.99,检出限为0.5μg/kg,回收率为77%~92%,相对标准偏差(RSD,n=6)为3.8%~7.7%。     

SPME/GC-MS对桑蚕叶中特丁硫磷农药残留的测定

2005年5月广西壮族自治区横县发生农户养殖的桑蚕食用桑叶后大批中毒死亡的案件,惊动全区.对桑叶进行毒物分析,结果表明桑叶中含有特丁硫磷农药.特丁硫磷常用作农田杀虫剂,其被桑叶吸附后,混合在叶绿素中,给分离工作带来困难.     

GC-MS characterization and quantification of sterols and cholesterol oxidation products

Summary A GC-MS method has been studied for characterization and quantification of phytosterols, cholesterol and cholesterol oxidation products. Baseline separations have been achieved between cholesterol, cholesterol 5-6-epoxide, 5-cholestene-3-ol-7one (7-keto-cholesterol), cholestene-3-5-6-triol, 5-cholestene-3-25-diol (25-hydroxycholesterol), 5-cholestene-3-20-diol (20-hydroxycholesterol), 5-cholestene-3-7-diol (7-hydroxycholesterol) and 5-cholestene-3-19-diol (19-hydroxycholesterol) as well as between -cholestane, cholesterol, stigmasterol, campesterol and -sitosterol. Excellent linearity of response has been obtained permitting reliable quantification. The characterization of each derivatized sterol has been performed by mass-spectrometry. The results confirm the utility of combined gas chromatography-mass spectrometry in the analysis and characterization of sterols and cholesterol oxidation products.     

Determination of nitrogen mustard hydrolysis products in rat urine samples using GC-MS

A gas chromatographic-mass spectrometric method was developed, validated and demonstrated by measuring the levels of nitrogen mustard hydrolysis products in the urine collected from dosed rats. The recovery values for trimethylsilyl derivatives of EDEA and MDEA are between 82-95% and 88-112%, respectively. In vivo studies performed by using three different doses (0.5 mg/kg, 1.0 mg/kg, and 2.0 mg/kg) of HN2 base of nitrogen mustard. MDEA concentrations were between 43.1-232.2 ng/mL. The limit of detection (S/N = 3) values are 2.5 ng/mL and 1.6 ng/mL for EDEA and MDEA, respectively, and the precision of the method in terms of RSD is between 5-8%.     

Determination of oxidation products in transformer oils using FT-IR spectroscopy

Transformer oils are subject to a lot of control checks in the process of their exploitation, because the presence of oxidized products causes damages in the electrical equipment. In the process of exploitation of transformer oils anti-oxidation additives get exhausted and products of oxidation are formed. This paper describes the development method for study of oxidation transformer oils by Fourier transform infrared (FT-IR) spectroscopy. The aim of this paper is to determine the main products of oxidation of transformer oils and to increase the sensitivity of FT-IR analysis by the extraction method. The method which we suggest to register all oxidized products is of great interest. The problem is the detection limit of routine apparatus. For this reason we have developed an extraction method, which can identify precisely all oxidized products qualitatively and quantitatively in the region 1800-1650 cm⁻¹. Thus a manifold increase of the FT-IR analysis is achieved, combined with increased sensitivity, precision and the possibilities for registering micro-amounts otherwise beyond the routine technique. FT-IR spectroscopy is a powerful method with great practical significance for investigation of carbonyl- and carboxylic degradation products from transformer oils.     

用SPME/GC-MS方法检验涉火案件中痕量汽油残留物成分

在纵火、爆炸、凶杀等刑事案件中,经常会遇到痕量汽油残留组分的检验与认定。汽油主要由C12以前的烷烃、烯烃、环烷烃和芳香烃化合物组成。由于涉火案件现场中燃烧介质及其中所含汽油的燃烧时间和燃烧程度都不尽相同,那么残留在介质中的汽油组分多少及轻重组分相对含量会产生较     

固相微萃取法测定负压体系中的微量挥发性有机物

通过固相微萃取气相色谱质谱法定性或定量检测负压体系中十二种微量挥发性有机物,如乙醇、二氯甲烷、乙酸乙酯、正己烷、甲苯等,检出范围1.6 ×l0-3 μg.L-1 ～1.7 μg.L-1.     

A kinetic model for limonene oxidation

The kinetic regularities of the autooxidation of R(+)−limonene (LH) were experimentally studied at various temperatures. A kinetic model including the main elementary reactions and the corresponding rate constants was developed. The degenerate chain branching during limonene oxidation proceeds via bimolecular reactions and involves hydroperoxide LOOH + LH → L· + LO· + H₂O and LOOH + LOOH → LO· + LO₂ · + H₂O. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 80–86, January, 2008.     

Kinetic characteristics of initiated oxidation of limonene

The kinetics of oxygen absorption .n the process of limonen (4-isopropenyl- l-methulcyclohex-1-ene) oxidation was studied in chlorobenzene solution at 40–80 °C. The values of the kinetic parameters of oxidation and the activation energy (38.1 kJ mol^–1) have been determined. The nonlinear dependence of the rate of the oxidation of limonene on its concentration has been established, The rate constants of the chain termination reactions were estimated by chemiluminescence techniques.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1676–1681, July, 1996.     

Effect of cationic surfactants on limonene oxidation

Kinetic regularities of free radical formation during limonene oxidation with molecular oxygen in a chlorobenzene solution at 60 °C were studied by the inhibitor method under autooxidation conditions and with additives of surfactants (cetyltrimethylammonium chloride and bromide) using dimer 2,2′-bis[2-(p-dimethylaminophenyl)indane-1,3-dione] and α-tocopherol as acceptors of radicals. In the presence of the surfactants, the rates of radical generation and oxidation increase sharply. The catalytic activity of cetyltrimethylammonium chloride is much higher than that of the corresponding bromide.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2110–2113, October, 2004.     

SPME/GC-MS测定水中芥子砜

日本遗弃在华化学武器中的化学战剂芥子气和芥子亚砜氧化均生成芥子砜,芥子砜有糜烂性[1],所以建立灵敏、快速的监测环境样品中芥子砜的分析方法具有重要意义.本文采用固相微萃取法(SPME)[2]/气相色谱-质谱(GC-MS)监测技术,对水中痕量芥子砜进行了测定,结果表明,本法完全满足水中芥子砜的监测要求.     

Simultaneous Determination of Phytohormones in Plant Extracts using SPME and HPLC

Solid-phase microextraction followed by HPLC was used for the determination of indole-3-acetic acid (IAA), abscisic acid (ABA), indole-3-butyric acid (IBA) and 1-naphthylacetic acid (NAA) in plant samples. Parameters influencing performance, including pH, salinity, extraction time, fiber coating and temperature, were optimized. A Carbowax-coated fiber was chosen for determination due to much higher extraction efficiency compared to polyacrylate fibers. The dynamic ranges spanned over three orders of magnitude. The LOD/(LOQ) values of the target compounds in pure water were 0.149(0.497), 0.442(1.472), 0.121(0.403), 0.058(0.193) μg L⁻¹ for IAA, ABA, IBA and NAA respectively. The method was successfully applied to the analysis of xylem fluid from Musa basjoo stem obtaining recoveries of 98.85% (IAA), 94% (IBA) and 94.30% (NAA). The method was also successfully applied to the analysis of these four target compounds in the hyperaccumulating plant, Viola baoshanensis. The results matched quite well with ones obtained by solid phase extraction followed by HPLC. The method developed was superior when applied to liquid samples because matrix effects could be eliminated.     

Determination and characterization of the pyrolysis products of isoprocarb by GC-MS

The pyrolysis behavior of isoprocarb (an insecticide with contact and stomach action) is investigated using pyrolysis-gas chromatography-mass spectrometry. The pyrolysis products are separated using an HP-5 column under temperature program with helium as the carrier gas. The total of 80 separated pyrolysis components at 600 degrees C, 750 degrees C, and 900 degrees C under helium atmosphere are identified using a probability-based matching search procedure, combined with the correlation of boiling point (BP) and Lee retention index (RI). Some of the BP values of the tentative components are estimated using the group contributions method because experimental values are not available. The levels of the identified components are estimated by the peak area normalization method from the chromatogram. It is found that isoprocarb decomposes more with the increase of temperature, and a large number of mono aromatics and polycyclic aromatic hydrocarbons and their derivatives are produced when the pyrolysis temperature is higher than 750 degrees C. The content of the decomposition products in the pyrolysate varies from 0.04% to 22.20%.     

Determination of the disproportionation products of limonene used for the catalytic hydrogenation of castor oil

The direct determination by GC-MS analysis of the products from the limonene disproportionation obtained from the catalytic hydrogenation of castor oil is not possible since a transesterification of the oil is required before injection. Therefore, a method for the determination of those products is proposed here: a solid-phase microextraction (SPME) followed by GC-MS. With the optimization of SPME it was possible to isolate a great number of products of the disproportionation of limonene used as hydrogen donor in the catalytic hydrogenation of castor oil by Pd/C. This system also proved to be appropriate to monitor castor oil hydrogenation by following and identifying the limonene disproportionated products.     

Degradation product emission from historic and modern books by headspace SPME/GC-MS: evaluation of lipid oxidation and cellulose hydrolysis

Volatile organic compounds emitted from a several decade series of bound periodicals (1859–1939) printed on ground wood paper, as well as historical books dating from the 1500s to early 1800s made from cotton/linen rag, were studied using an improved headspace SPME/GC–MS method. The headspace over the naturally aging books, stored upright in glass chambers, was monitored over a 24-h period, enabling the identification of a wide range of organic compounds emanating from the whole of the book. The detection of particular straight chain aldehydes, as well as characteristic alcohols, alkenes and ketones is correlated with oxidative degradation of the C₁₈ fatty acid constituency of paper. The relative importance of hydrolytic and oxidative chemistry involved in paper aging in books published between 1560 and 1939 was examined by comparing the relative abundances of furfural (FUR) a known cellulose hydrolysis product, and straight chain aldehydes (SCA) produced from the oxidation of fatty acids in paper. The relative abundance of furfural is shown to increase across the 379-year publication time span. A comparison of relative SCA peak areas across the series of books examined reveals that SCA emission is more important in the cotton/linen rag books than in the ground wood books.     

固相微萃取-气相色谱-质谱法分析常春油麻藤花挥发油成分

利用固相微萃取-气相色谱-质谱(SPME-GC-MS)联用技术对常春油麻藤的挥发油成分进行了分析,共鉴定出52种成分,占挥发油总成分的78.60%。常春油麻藤挥发油主要化学成分是1-辛烯-3-醇(15.38%),n-十六酸(6.01%),壬醛(5.23%),3-辛酮(5.17%),1-辛烯-3-酮(4.19%),2-戊烯醛(3.96%),己醛(3.43%),1-己醇(2.98%)等。     

固相微萃取/气相色谱-质谱研究沉香的特征成分

采用固相微萃取(SPME)富集不同产地天然沉香中的挥发性成分,气相色谱-质谱联用技术(GCMS)分离鉴别其挥发性成分,并根据分析结果对沉香品质进行判断。研究发现不同产地的天然沉香主要由倍半萜、芳香族等化合物组成,但由于产地不同,其化学成分及含量均有很大差别。以沉香的6种特征性有效成分苄基丙酮、对甲氧基苄基丙酮、沉香螺旋醇、沉香呋喃、苍术醇、白木香醛及其含量作为评价沉香品质的主要指标。研究结果显示,老挝沉香的特征成分总含量最高,约为20%;柬埔寨沉香其次,约为17%,而国产沉香(海南、广东东莞)的特征成分含量相对较低。表明老挝沉香的品质最好,柬埔寨沉香次之,但均优于国产沉香。该方法具有样品用量少、特征性强的优点。