大同市空气中多环芳烃与人尿中1-羟基芘的分析

用GC~2/MS和HPLC鉴定出大同市空气中的多环芳烃化合物35种.对大同市不同功能区空气中苯并(a)芘(BaP)和人尿中1-羟基芘同步采样分析.结果表明,不同功能区BaP浓度有显著差别:采暖期浓度急剧增加,城区浓度为对照点的17倍,日均值达330ng/m~3.人尿中1-羟基芘的浓度与空气中BaP的浓度显著相关.采暖期城区尿中1-羟基芘的几何均值为1.86μmol/mol肌酐,非采暖期为1.14μmol/mol肌酐,均较北京市的均值高出五倍多.证明大同市由于直接燃煤,造成空气中多环芳烃的严重污染.     

柳州市大气颗粒物中多环芳烃的分布特征及来源

采用气相色谱/质谱联用技术(GC/MS)检测了柳州市大气颗粒物样品中的PAHs,比较了柳州市各区大气颗粒物中多环芳烃含量的差异以及不同季节对多环芳烃含量的影响,讨论了其分布规律及污染源。     

Bestimmung von Mineralölkohlenwasserstoffen im Boden

The infra-red (IR) and the gas Chromatographic (GC) methods for the determination of mineral oil hydrocarbons in soils were examined in collaborative trials with regard to their accuracy and reproducibility. Natural, homogenized soils and soils spiked with mineral oil were used as standards. The soil matrix was composed relatively simply. The repeatability and reproducibility values obtained were about 5 % und 23 %, respectively. In contrast, the GC method revealed a considerably higher error range, especially by using the split/splitless technique. The degradation of mineral oil hydrocarbons in soils under different temperatures was investigated by IR throughout one year. The degradation rate at room temperature was about 25 %; at lower temperatures no degradation was detected. Thus, the spiked soils may be used as calibration standards for the mineral oil analysis.     

广州某黑臭河涌沉积物中的挥发物质组分

在广州市城区内的猎德涌采集了3个采样点中0~10cm深的表层沉积物,通过DVB/CAR/PDMS固相微萃取(SPME)纤维顶空富集,使用气相色谱/质谱联用仪(GC/MS)对其挥发物进行检测分析。在猎德涌的沉积物中共检测出54种挥发物质,包括36种烷烃、2种环烷烃、1种烯烃、2种硫单体、13种带有发香基团的有机物。在3个采样点分别鉴定出19、49、52种挥发物。在下游河段沉积物中检测出的挥发物种类和峰面积都超过上游。由挥发物质的组成可以判断出其主要污染是来源于交通污染和居民的日常生活污染,其中有3种毒性较大的成分:万山麝香、邻苯二甲酸二异丁酯(DIBP)和2,4-二叔丁基苯酚。     

煤飞灰环境标准参考物中PAHs的表征

本文采用不同提取方法以及不同溶剂对煤飞灰环境标准参考物质样品中PAHs的提取效率进行了考察.采用HPLC,毛细管GC以及GC-MS对飞灰样品中的PAHs进行了分析表征,并对前两种分析方法的精密度、准确性和所得结果的一致性进行了研究.     

Instrument tuning for trace analysis of dioxins and furans for the vg 70s/se gas chromatography/mass spectrometry system using electron impact mode

We present the salient characteristics of tuning procedures that have evolved from our 3 years of experience while producing large amounts of data of the highest quality. Our laboratory routinely analyzes 2,3,7,8‐substituted dioxins and furans at parts per quadrillion levels in 50–100 g of human serum samples using the VG 70S/SE stand‐alone gas chromatography/mass spectrometry (GC/MS) system at 10000 resolution (defined by 5% overlap) in the selected ion recording mode. Trace measurement of dioxins and furans in human biological matrices—for example, whole blood, serum, or adipose tissue‐requires reproducible instrument tuning within day as well as among days for quality results. Additionally, instument‐tuning procedures among operators must be reproducible to minimize operator bias because periodically different operators are used. Instrument tuning is highly subjective and argumentive; therefore, to minimize the ambiguity within our laboratory, we have standardized our technique to reproducibly tune the GC/MS system.     

Determination of phenol,cresols and xylenols in workplace air using XAD‐2 sorbent cartridges

A method for sampling and analysis of phenolic compounds in workplace atmospheres using Amberlite XAD‐2 sorbent tubes has been laboratory and field tested. After extraction of the adsorbed phenols with methylene chloride, the concentrated extract was analyzed by capillary column gas chromatography coupled with a flame ionization detector or a mass spectrometer. For a 3L air sample, the method has a detection limit for phenol, cresols, alkyl‐substituted phenols and xylenols of 0.3 mg/m³ using gas chromatography with flame ionization detection (GC/FID) analysis and 0.07 mg/m³ using gas chromatography mass spectroscopy/selected ion monitoring GC‐MS/SIM. Evaluation tests conducted in the laboratory indicated recoveries >85% for a wide range of phenols, cresols, xylenols and other alkyl‐substituted phenols and resorcinol. Sampling conditions were established to ensure that no breakthrough occurred for a predetermined sample volume of three (3) liters even in humid atmospheres. Stability tests indicated that for storage of up to 2 weeks at 4°C, only resorcinol showed a significant reduction in sample recovery. The proposed method and NIOSH Method 3502 were compared for the determination of phenol concentrations in air samples collected at a plant processing phenolic resins. Phenol was positively identified in the XAD sample using GC‐MS/SIM and was detected at concentrations of 40–50% of the total phenols detected using NIOSH Method 3502. This difference is attributed to the airborne paniculate matter which is known to contain bisphenols that will contribute to the total phenolic content sampled in Method 3502, but not on the XAD sample.     

二氧化硫与1—己烯的光化学反应动力学

利用ＧＣ／ＭＳ方法研究了ＳＯ２与１－己烯在无氧和有氧体系中光化学反应动力学，确定了ＳＯ２与１－己烯光化学反应的级数，给出了２９３－３３３Ｋ温度范围内总的反应速度常数Ｋ，以及Ｋ与温度的关系、反应的活化能和指前因子。另外，对反应物己醛和２－己酮的生成反应速度常数及其活化能也进行了计算和讨论。     

二氧化硫与环己烷的光化学反应

本文研究了ＳＯ２与环己烷在无氧及有氧体系中的光化学反应，观察到了白色烟雾有生成并凝聚，利用ＧＣ和ＧＣ／ＭＳ法确定了部分反应产物－环烯烃、醇、酮、二元酸酯、呋喃衍生物以及硫酸二甲酯等有机化合物，探讨了影响光化学反应的几种因素及反应机理。     

Determination of pentachlorophenol in human urine using solid phase extraction and GC‐MS analysis with stable isotope dilution

A method for the determination of pentachlorophenol (PCP) in human urine was developed. Urine samples were fortified with ¹³C₆‐IabeIed PCP and hydrolyzed with sulfuric acid prior to extraction. The urine samples were then passed through preconditioned solid phase extraction cartridges containing octadecylsilane adsorbent. The PCP was subsequently eluted from the cartridge with ethyl acetate and converted to pentachloroanisole prior to GC‐MS analysis. GC‐MS quantitation was performed using the technique of stable isotope dilution. Percent recoveries averaging 100, 97, and 111% were obtained for replicate urine samples fortified with approximately 2, 20, and 200 ng/mL of PCP, respectively. The method detection limit was estimated to be 0.2 ng/mL.     

Natural bitumens versus oil pollution in the Vlasina lake peat

Free and associated bitumens were isolated by sequential extraction from Vlasina lake peat (SE Serbia) and were investigated in order to differentiate between oil pollution and natural bitumens. Four peat samples were collected at different depths, on a peat island. Gas chromatographic (GC) and gas chromatography/mass spectrometry (GC/MS) analysis revealed the presence of three markedly different bitumen fractions. Here we show that the free bitumens are representing the native peat bitumens. The two associated bitumens are mainly the products of bacterial rework of organic substance, which were then trapped by two differing mechanisms. The bitumens characteristics and association features exclude a contribution of oil pollution.Selected article from the Regional Symposium on Chemistry and Environment Krusevac, Serbia, June 2003, organised by Dr. Branimir Jovancicevic.     

Modified Edman degradation applied to hemoglobin for monitoring occupational exposure to alkylating agents

A method that can be used for the monitoring of exposure to alkylating agents in the environment is presented. It is based on the quantification of alkylated N‐terminal valines in hemoglobin, using a modified Edman degradation procedure. The detection limit (GC/electron capture detector or GC/MS) is increased by two magnitudes of ten when using pentafluorophenyl isothiocyanate instead of phenyl isothiocyanate in the derivatization step. As little as one nmole N‐(—2 hydroxyethyl)valine per gram hemoglobin can be detected under practical conditions.     

北京昆明湖水中有机污染物的分析及去除

本文采用GC/MS技术,分析出北京昆明湖水中的63种有机化合物,其中有17种是我国和美国EPA优先控制的"黑名单"成员.经用改性铝土矿粉处理,使COD去除率达88.6%,有44%的有机污染物去除率达70%以上.     

固相萃取/气相色谱质谱法测定灰尘中的氯代多环芳烃

建立了固相萃取(SPE)/气相色谱质谱(GC/MS)联用检测灰尘中氯代多环芳烃(ClPAHs)的方法.以正己烷和二氯甲烷混合液为提取溶剂,索氏提取灰尘样品中的20种ClPAHs,活性硅胶层析柱与活性炭混合硅胶SPE柱协同净化.净化后的提取液采用GC/MS测定,SIM模式扫描,并用质谱特征离子定量分析.结果表明,填充量为0.2 g(W(活性炭)∶W(硅胶)=1∶40)的活性炭混合硅胶SPE小柱能有效地将ClPAHs分离出来,载样后采用反向溶剂洗脱,既提高了回收率又减少了洗脱剂甲苯的用量,净化效果好.处理灰尘样品后检测分析,20种ClPAHs的平均回收率稳定在60.4%—120.1%,相关系数>0.99,检出限为0.04—0.17 ng.g-1,相对标准偏差为1.6%—10.2%.本方法前处理简单,定性、定量准确可靠,可广泛应用于环境介质中氯代多环芳烃的检测.     

Identification of a floral-derived kairomone for currant clearwing, <Emphasis Type="Italic">Synanthedon tipuliformis</Emphasis>

The currant clearwing Synanthedon tipuliformis (Clerck) (Sesiidae) is a worldwide pest of black currants, Ribes nigrum. This moth has been observed to feed on nectar of inflorescences of Canada thistles, Cirsium arvense (L.) Scop. This work was undertaken to identify floral compound(s) produced by Canada thistles inflorescences that mediate the response of the currant clearwing. Floral volatiles were collected during the day and analysed by coupled gas chromatography/electroantennographic detection (GC/EAD) and gas chromatography/mass spectrometry (GC/MS). Three compounds consistently elicited EAD response from moth antennae and were identified by GC/MS as phenylacetaldehyde, methyl salicylate and dimethyl salicylate. When the compounds were tested individually or in various combinations in field trapping experiments, a 3-component blend attracted the largest number of female and male currant clearwings. Subsequent field trapping experiments were conducted to determine the optimal attraction dose for the ternary blend using three loadings of 1, 10 and 100 mg loaded into a polyethylene sachet. The highest catches were in traps baited with the 100 mg loading. In all trials, males and mated females were caught in significant numbers, while very low numbers of virgin females were found in the traps. In recent years the efficacy of mating disruption against currant clearwing has been reported as declining. The new kairomone blend identified in this study can be used with the sex pheromone to provide an effective control option for this important pest.     

五氯酚及其钠盐中氯代二恶英类分析

采用ＨＰＬＣ和ＧＣ／ＭＳ的方法，对国产ＰＣＰ及其钠盐中的ＰＣＤＤｓ，ＰＣＤＦｓ进行了分析。测定了所有２，３，７，８－取代同系物。此外，还根据各ＣＤＤｓ，ＣＤＦｓ的毒性当量因于ＴＥＦｓ，计算了其毒性当量Ｉ－ＴＥＱｓ，分别为１４２，９２ｎｇ．ｇ＾－１。在前述基础上，仨算了由于ＰＣＰ及其钠盐的应用，引起的ＰＣＤＤｓ，ＰＣＤＦｓ环境输入。约为２４０ｋｇ／ａ。     

Photodegradation of the herbicide goal

Photodegradation products of the herbicide Goal active ingredient were obtained with a xenon lamp and analyzed using direct inlet mass spectrometry, MS/MS and GC/MS. A number of products were identified and their generation pathways were established to be mainly Ar—O bond cleavage, dechlorination and photocyclisation. The latter process gives chlorinated and unchlorinated dibenzofurans some of which may be toxic.     

Effect of natural aquatic humic substances on the photodegradation of bisphenol A

The photochemical degradation of bisphenol A (BPA) was studied in the presence of natural humic substances from different origins under simulated solar irradiation. BPA underwent insignificant direct photolysis in neutral water, but rapid photosensitized degradation in four humic substances solutions via pseudo-first-order reaction occurred. The photo-degradation rate of BPA was insensitive to the different initial BPA concentrations and was inhibited in aerated solution compared with the deoxygenated medium. The reactive oxygen species (ROS) such as ·OH and ¹O₂ produced from excitation of humic substances under irradiation was determined from the quenching kinetic experiment using molecular probe. The five main intermediate photoproducts of BPA in Nordic lake fulvic acid (NOFA) were tentatively identified using gas chromatography/mass spectrometer (GC/MS). Based on the identification of ROS and the analysis of photoproduct formation, the possible phototransformation pathways of BPA were proposed, involving the direct photolysis due to the energy transfer from the triplet state humic substance (³HS*) to BPA molecules and hydroxyl radical addition and oxidation as well.     

攀枝花市大气颗粒物中多环芳烃污染特征分析及来源识别

2007年2月在攀枝花市不同功能区采集了大气PM10样品42个和污染源样品32个,采用超声抽提GC/MS方法测定分析了16种多环芳烃(PAHs)的含量。结果显示攀枝花市PM10颗粒相PAHs单体浓度范围为0.34～416.45ng/m3,总量浓度范围为24.56～2569.66ng/m3;攀枝花市5个采样点中河门口片区PM10多环芳烃单体浓度范围为5.64～416.45ng/m3,污染最严重。源样品测定结果分别为扬尘78.74ug/g,煤烟尘6.12ug/g,钢铁工业尘30.54ug/g,焦化尘3187.42ug/g。应用比值法和化学质量平衡(CMB)模型对污染源进行识别,燃煤和炼焦是攀枝花市PAHs的主要来源,对攀枝花市大气可吸入颗粒物中多环芳烃污染的分担率分别为55.8%、19.9%。     

城市加油站苯系物污染状况

在重庆地区利用苏马罐系统和气相色谱质谱分析方法对加油站及其周边空气中苯系物进行了初步监测。结果发现,几种苯系物均有检出,各监测点苯系物总体浓度介于0.34-11.33 mg/m3之间,其中苯浓度最高,各点浓度为0.07-3.57 mg/m3,二甲苯其次,苯乙烯最低。从不同监测点来看,卸油区和加油区苯系物浓度普遍较高,环境敏感点相对较低。