Improved peak selection strategy for automatically determining minute compositional changes in fuels by gas chromatography-mass spectrometry

During the development of automated computational methods to detect minute compositional changes in fuels, it became apparent that peak selection through the spectral deconvolution of gas chromatography-mass spectrometry (GC-MS) data is limited by the complexity and noise levels inherent in the data. Specifically, current techniques are not capable of detecting minute, chemically relevant compositional differences with sufficient sensitivity. Therefore, an alternative peak selection strategy was developed based on spectral interpretation through interval-oriented parallel factor analysis (PARAFAC). It will be shown that this strategy outperforms the deconvolution-based peak selection strategy as well as two control strategies. Successful application of the PARAFAC-based method to detect minute chemical changes produced during microbiological growth in four different inoculated diesel fuels will be discussed.     

Void formation due to gas evolution during the recycling of Acrylonitrile-Butadiene-Styrene copolymer (ABS) from waste electrical and electronic equipment (WEEE)

During processing of recycled ABS and ABS/HIPS blends, voiding defects can occur within the resulting material which can result in deterioration of mechanical properties. The voids were previously thought to be caused by the evolution of volatile substances during processing. This study investigated the recycling of post-consumer ABS from a variety of types of WEEE. The mechanical properties of the processed material were assessed and a combination of visual observation during processing and optical microscopy was used to identify the extent of voiding. It was found that flexural strength and ductility in particular decreased with increased levels of voids. The gases emitted during heating and processing were analysed using Gas Chromatography with Mass Spectroscopy (GCMS) and were found to be breakdown products of the original polymers. These seem to be present in the WEEE, either as polymerization residuals or as products of degradation during the initial service life rather than degradation products from reprocessing. The amounts of volatiles liberated were quantified, which showed that the volatile emissions from post-consumer material were of a similar magnitude to those seen with virgin material. More intensive or longer processing led to a reduction in the emissions and voiding and an improvement in strength, suggesting that there is a finite potential for volatile liberation, and that the problem could be overcome by the use of suitable processing conditions.     

磁性硫化胶的成分鉴定

用ＦＴ－ＩＲ和ＧＣ－ＭＳ方法分析检测磁性橡胶的热裂解液,结合Ｂｅｉｌｓｔｅｉｎ铜丝实验,对其并用胶成分和助剂进行鉴定。该方法可推广应用于其它并用胶。     

轻中度生物降解作用对原油中烷基萘和烷基菲的影响

研究了辽河盆地冷东油田经生物轻中度降解原油族组分布特征,并根据饱和烃生物标志化合物特征对生物降解程度进行了划分.借助于定量GCMS分析技术,分别研究了萘系列和甲基菲异构体的抗生物降解能力.随着萘系列取代基的增多,其抗生物降解能力逐渐增强.在生物降解程度为四级时,甲基菲4个异构体的含量才出现较大的变化:9-MP的抗生物降解能力最强,3-MP、2-MP和1-MP的抗生物降解能力相当.计算了TMNr,TeMNr,MNR,DNR,TNR-2,TNR-1共6个地化参数,并计算出了相对应的成熟度Ro,Ro值要比实际值(0.25%～0.65%)稍偏高,TMNr与TeMNr、MNR与DNR之间的相关性很差,说明经微生物轻中度降解后的原油的地化参数发生了改变,不能用来计算成熟度.探讨了轻中度生物降解程度原油中甲基菲指数(MPI1和MPI2)的变化情况:在降解程度为三级以前该指数没有明显变化,当降解程度超过三级时呈现变小的趋势,所以使用该参数前要考虑原油是否经历过生物改造.     

超声萃取气相色谱-质谱联用法测定塑料中邻苯二甲酸酯类增塑剂及其不确定度评估

采用超声萃取、气相色谱质谱联用的方法测定塑料中六种邻苯二甲酸酯类增塑剂,通过数理统计证明了该方法与标准的索氏抽提方法没有显著性差异。方法测定各个化合物的相对标准偏差在2.2%和12.0%之间,回收率在85.4%和104.8%之间。采用EURACHEM的不确定度数学模型计算了扩展不确定度,数值为测定结果的7.0%和26%之间。     

诃子与川楝子配伍后挥发油化学成分分析

采用水蒸气蒸馏法将诃子与川楝子按1∶1的质量比配伍后提取挥发油,并用GC-M S联机技术对其化学成分进行研究,分离出249个组分,鉴定了其中的13个,主要成分有单[2-乙基己基]邻苯二甲酸、2,2′-亚甲基叔丁基对甲酚,乙基（2E）-3-[4-甲氧基苯基]-2-丙烯、7-甲基-Z-十四烯-1-醇酯。     

Physical and chemical characteristics of aging pyrolysis oils produced from hardwood and softwood feedstocks

Pyrolysis oils were produced from hardwood or softwood feedstocks in a vacuum batch reactor and trapped at 0 °C. The vacuum process was used to intentionally avoid the presence of entrained char particles. The hardwood feedstock was a pelletized mixture of various Eastern tree species. The softwood samples were de-barked Lodgepole pine (Pinus contorta) and Douglas Fir (Pseudotsuga menziesii) wood cut into the same dimensions as the pellets. The oils’ physical (viscosity) and chemical (speciation) properties were measured as-produced and after aging. The total liquid and char yields ranged from ∼50 to 55% and 25 to 27% respectively. Measured water contents were 30% or more, which are greater typically reported from fast pyrolysis oils produced in fluidized beds. Aging took place in covered glass containers at room temperature over a period of 5 months. Gas chromatography-mass spectrometry (GCMS) was used to characterize the oils’ volatile components. Since bio-oils are mixtures of hundreds of different compounds with wide-ranging molecular weights and polarities, the oils were extracted using benzene followed by methanol. Out of ca. 80 non-polar and 100+ polar compounds GCMS showed a few chemical species present in the freshly produced oils were absent in the aged oils. The oils’ viscosities at shear rates (measured between 1 and 1000 s⁻¹) increased by approximately a factor of 2.5 during aging. To determine if this was due to polymerization reactions during aging or simply water and other volatile material losses, freshly made oils were aged at an accelerated rate by using elevated temperatures (65 °C and 85 °C) in a water-saturated environment between 1 and 7 days. The oils are fairly stable with respect to aging both over long periods of time (months) at room temperature and at elevated temperatures, 65 °C and 85 °C for shorter time periods (days). It is concluded that high water content and char-free characteristics act to slow polymerization reactions.