吹扫捕集-气相色谱质谱法分析土壤中54种挥发性有机污染物的方法研究

应用吹扫捕集-气相色谱质谱法分析土壤中卤代烃、氯代苯、苯系物类等54种挥发性有机物,应用选择性离子扫描（SIM）的方式进行分段扫描.与全扫描方式相比,SIM方式对土壤中多组分的定量分析更具有积极作用.采用内标法绘制校正曲线,方法检出限范围在0.20×10^-9~1.20×10^-9之间.基体加标回收率范围在82.0%~112.5%之间,准确度相对于全扫描的方式高出0.1~14.5个百分点.     

4 种经济海藻脂肪酸组成分析

采用改进的Bligh-Dyer法提取脂溶性成分,气相色谱-质谱联用法(GC-MS)进行分离和鉴定,C19:0内标确定总脂及各组分含量,研究了鼠尾藻(Sargassum thunbergii)、浒苔(Enteromorpha prolifera)、龙须菜(Gracilaria lemaneiformis)和红毛菜(Bangia sp.)4种经济海藻的脂肪酸组成及含量。结果表明,4种海藻都检测出C14-C22脂肪酸,总脂含量在12～19 mg/g之间,不饱和脂肪酸为主要组成成分,含量均超过60%。不饱和脂肪酸中以多不饱和脂肪酸(PUFAs)为主,富含n-3和n-6系列PUFAs,n-6与n-3系列PUFAs之比均低于2。比较4种海藻脂肪酸组成特点表明,鼠尾藻以C16、C18和C20为主要组成成分,具褐藻类脂肪酸组成特征;浒苔以C16和C18为主要组成成分,具绿藻类脂肪酸组成特征;龙须菜和红毛菜以C16和C20类脂肪酸为主,具典型红藻类脂肪酸组成特征,同时二者又有不同之处,分别显示真红藻与原始红藻脂肪酸组成的特点。     

Preliminary Study on PAHs Distribution in High-grade Oil Shale and Its Spontaneous Combustion Product in Fushun, Liaoning Province

Spontaneous combustion of oil shale is very common as a result of long-time exposure to the air in the Fushun West Open-Pit Mine and West Dump. The PAHs in the high-grade off shale and its spontaneous combustion product were analyzed semiquantitatively by GC-MS in order to investigate their distribution in different states and their potential negative effects on the environment. Totally 57 and 60 PAHs and their alkyl homologues were identified in the two analyzed samples, among which the alkyl derivatives were predominant, taking up to about 65% in the total PAHs. Those low-molecular mass PAHs （3- or 4-ring） were the main compounds in the two samples. Ten of sixteen USEPA priority pollutant PAHs were detected in two samples, of which phenanthrene was the richest whose contents were 6.93% and 15.03%. Based on comparison of analysis results, the amount and contents of PAHs, except for triaromatic steroid group, were higher in the burning oil shale. So it can be determined that the effects caused by spontaneous combustion of oil shale would be more serious and that the effects of the Fushun oil shale and its spontaneous combustion on the environment should not be ignored in the future work.     

利用鳕鱼皮蛋白制备热反应型肉香调味基料的研究

以复合酶深度水解鳕鱼皮蛋白为主要原料,通过与半胱氨酸和葡萄糖的美拉德反应制得肉香风味,并通过固相微萃取-气相-质谱联用技术检测鉴定出大量的肉香味物质.为鳕鱼皮蛋白水解物制备肉香调味基料提供理论依据.     

龙须菜(Gracilaria lemaneiformis)高温逆境代谢产物的GC-MS 分析

利用固相微萃取(SPME)和气相色谱/质谱联用技术(GC-MS)分析龙须菜在高温逆境中可挥发性代谢产物的变化规律.最优分析条件为样品60℃平衡30min,用聚二甲基硅氧烷.二乙烯基苯纤维头(PDMS/DVB)顶空萃取吸附25min,在210℃下解吸附5min后对解吸物进行GC-MS检测.结果表明,从龙须菜中检测到56个挥发性代谢产物,在高温逆境条件下主要有烯烃(61.67%)、醛(22.47%)、酮(5.98%)、烷烃(1.92%)、卤代物(0.65%)、醇(0.41%)、酯(0.37%)、其它(1.34%).比较了常温和高温逆境培养条件下龙须菜中代谢产物的相对含量变化规律:高温胁迫下E-2-戊烯醛等7种代谢产物含量显著减少,三氯甲烷等4种代谢产物含量显著增加.其中E-2-庚烯醛、E,E-2,4-庚二烯醛、2-正戊基呋喃和三氯甲烷可能与龙须菜高温逆境生理有关.本研究可为龙须菜抗逆生理和抗高温品系选育提供理论依据和指导.     

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin. Part I: Drug Residues and other Polar Contaminants in Berlin Surface and Groundwater

Several polar contaminants were found in screening analyses of 30 representative surface water samples collected from rivers, lakes, and canals in Berlin. Residues of pharmaceuticals and N-(phenylsulfonyl)-sarcosine originating from various sewage treatment plants effluents were found at concentrations up to the μg/L-level in the surface water, whereas the concentrations of polar pesticides such as dichlorprop and mecoprop were always below 0.1 μg/L. The pharmaceuticals most frequently detected in the surface water samples include clofibric acid, diclofenac, ibuprofen, propiphenazone, and two other drug metabolites. Additional investigations of groundwater wells of a drinking water plant have shown that polar contaminants such as drug residues or N-(phenylsulfonyl)-sarcosine easily leach through the subsoil into the groundwater aquifers when contaminated surface water is used for groundwater recharge in drinking water production.     

大花细辛挥发油化学成分GC-MS分析

通过对大花细辛(Asarummaximum Hemsl)挥发油化学成分研究,探讨其保健和药用机理,为开发和利用大花细辛提供科学依据。用无水乙醇对大花细辛进行提取,并用GC-MS对提取物进行化学成分和相对含量分析共获得86种化合物,其中主要的并具研究价值的有33种,占总化合物的92.68%。其中5-甲基-1,2,3-三甲氧基苯(C10H14O3)的相对含量最高,为23.00%;其次为2-甲氧基-4-乙烯基苯酚(C9H10O2),为10.54%。     

Characteristics of Hydrogen-rich Coals in Southern China: Implications from Organic Geochemistry and Carbon Isotopic Compositions

The organic geochemical characteristics of hydrogen-rich coal in southern China were investigated synthetically through organic geochemistry and carbon isotope analyses.The results showed that the hydrogen contents of the test samples were more than 5.0% and the H/C atomic ratios were between 0.76-1.06.Samples were found to be composed mostly of Type Ⅱ-Ⅲ℃ kerogen,consistent with good hydrocarbon-generation potential.The R_o(0.54-1.10%)and T_max(430-453℃)values imply that the hydrogen-rich coals were in low maturity to mature stages.Stable carbon isotopic ratios(δ¹³C_org)of the samples used varied from ?24.5‰ to ?23.4‰,the barkinite content ranging from 13.9% to 83.3%,indicating a predominantly terrestrial origin with marine influence during coal formation.Some organic geochemical parameters showed corresponding changes as the hydrogen content increased from 5.0% to 7.0%,however,the source inputs changed significantly when hydrogen content was greater than 6.0%.Terrestrial higher plants gradually become predominant within the coal-forming materials,whereas this dominant position is not apparent at lower hydrogen contents,which is attributable to the strong seawater effect during the hydrogen-rich coal formation process.     

基于SEM-EDS及GC-MS技术研究有机氯分子结构对零价铜脱氯机制的影响

零价铜作为一种廉价金属很少应用于促进氯代有机物脱氯研究,其原因是零价铜的催化还原脱氯活性差,且反应机制复杂。本文采用机械球磨技术制备了Cu-Fe和Cu-Ni合金,研究零价铜在不同微观环境下对对氯苯酚(4-CP)的脱氯行为,旨在考察有机氯分子结构对零价铜脱氯机制的影响。应用扫描电镜-能谱(SEM-EDS)及色相色谱-质谱(GC-MS)分析发现,铜原子的微环境及有机氯分子结构均影响铜的脱氯机制。在Cu-Fe体系中,Cu遵循经典的催化加氢脱氯机制,4-CP的降解产物为苯酚;Cu-Ni体系的还原作用来源于零价铜,其中的镍金属并未起到催化加氢作用,Cu-Ni合金及单独零价铜对4-CP的降解产物是环己酮。零价铜对4-CP的降解率可达70%以上,而Cu-Fe体系的降解率仅为34%,两者对芳香族氯代物的降解效率差距显著。零价铜能够降解化学稳定性高的4-CP和苯酚,但不能降解化学稳定性相对较差的脂肪族氯代有机物(如一氯乙酸和二氯乙酸),因此认为零价铜脱氯机制并非传统的催化加氢机制,而是遵循直接电子传递还原机制,且有机氯分子的苯环结构是零价铜直接电子传递还原的诱因。     

气相色谱质谱联用及电喷雾质谱法分析多棘海盘车的脑苷脂结构

通过硅胶柱层析法分离得到多棘海盘车脑苷脂,并采用气相色谱质谱联用(GC-MS)及电喷雾质谱(ESI-MS)分析鉴定其结构。GC-MS分析表明,多棘海盘车脑苷脂AAC-1、AAC-2的糖基组成相同,均为葡萄糖;长链碱主要由d18∶2、d18∶3以及少量的d22∶1组成;两者结构最主要的差别在脂肪酸部分,AAC-1由C2位不含羟基的脂肪酸组成,而AAC-2则由C2位含1个羟基取代的脂肪酸组成。ESI-MS分析结果表明,AAC-1和AAC-2的分子量范围在740～850amu之间。通过GC-MS和ESI-MS结合使用,可快速推测出多棘海盘车脑苷脂基本结构及单体分子组成,对下一步的构效关系研究具有重要意义。