苯和甲苯硝化及磺化反应热危险性分级研究

首先介绍了化工工艺热安全性的内涵,并从反应过程热危险性分析的方法学出发,介绍间隙、半间歇化学反应工艺热危险性分级研究的总体思路及方法。然后,围绕甲苯和苯的硝化、磺化反应,用全自动反应量热仪(RC1e)和加速度量热仪(ARC)测定其反应过程的绝热温升(△Tad)、目标反应所能达到的最高温度(TM)、分解反应最大速率到达时间(θD)等参数。运用风险评价指数矩阵法(方法1)和基于失控过程温度参数的热危险评估法(方法2)分别对其硝化和磺化反应过程的热危险性进行了分级评估。结果表明,这两种方法具有良好的一致性;给定工艺条件下甲苯和苯的一段硝化反应过程的热危险度等级较低;而磺化反应的热危险较高。尽管这两种方法还有一定的局限性,但对于间歇、半间歇合成工艺的本质安全化设计、工艺热危险性的评估具有重要的参考价值和实用意义。     

室内多环芳烃污染源的化学组成特征研究

运用环境舱模拟源排放的方法采集了烹调油烟与环境烟草烟雾的样本,对18种PAHs进行了定量分析.比较了不同食用油与不同品牌香烟产生PAHs组成特征的差异,初步建立了2类室内PAHs来源的化学成分谱.结果表明:烹调油烟中3环以下的PAHs为主体,Fluo,Pyr和Flu相对含量较为稳定;香烟烟雾以3～4环组分为主体,Flu,Phe,InP和BaA较为稳定,Cor含量较烹调油烟而言显著增加.2类源的ρ(BaA)/ρ(Chy),ρ(BeP)/ρ(BaP)与ρ(InP)/ρ(BghiP)稳定且存在显著差异,可以用来解析室内PAHs以及PAHs暴露的来源.运用等效毒理学因子估算了其危害程度,结果表明:每100 g食用油在烹调过程(60 min)中释放产生PAHs的毒理学效应仅为吸烟过程中每g烟草所产生PAHs毒理效应的一半.      

Estimation and comparison of night-time OH levels in the UK urban atmosphere using two different analysis methods

Night-time OH levels have been determined for UK urban surface environments using two methods,the decay and steady state approximation methods.Measurement data from the UK National Environmental Technology Centre archive for four urban sites(Bristol,Harwell,London Eltham and Edinburgh) over the time period of 1996 to 2000 have been used in this study.Three reactive alkenes,namely isoprene,1,3-butadiene and trans-2-pentene were chosen for the calculation of OH levels by the decay method.Hourly measurements o...     

New cytochrome P450 1B1, 1C1, 2Aa, 2Y3, and 2K genes from Chinese rare minnow (Gobiocypris rarus): Molecular characterization,basal expression and response of rare minnow CYP1s and CYP2s mRNA exposed to the AHR agonist benzo[a]pyrene

Cytochrome P450 (CYP450) genes play an important role in catalyzing oxidative metabolism of toxicants. Recently, CYP1 subfamily were discovered and reported in fish, however, little is known regarding the CYP2 isoforms in fish. In the present study, the cDNA fragments of CYP 1B1 and 1C1 and CYP2Aa, 2Y3, and 2K of rare minnow were cloned and exhibited a high amino acid sequence identity compared with their zebrafish orthologs. Basal expression showed CYP1C1 and CYP 2Aa expression were observed in all eight tissues analyzed (liver, gill, intestine, kidney, spleen, brain, skin, and muscle). CYP 1A, and 1B1 expression was found in all tissues except for muscle and skin. However, CYP 2Y3 was expressed in liver, spleen, intestine and muscle whereas CYP 2 K in liver, kidney and intestine. 4 and 100 μg L⁻¹ Benzo[a]pyrene (BaP) induced patterns showed that CYP 1A, 1B1 and 1C1 expression in liver, gill, and intestine was strongly up-regulated (p < 0.05). Furthermore, CYP 2Y3 was strongly induced in liver from BaP treatments (p < 0.05). The high induction on mRNA level of CYP1s and CYP 2Y3 by BaP could be associated with catalyzing detoxification and indicated that CYP2s may also be potential biomarker to screen AHR agonist. The high responsiveness of CYP1 and 2 genes suggested Chinese rare minnow is feasible to screen and assess pollution with AHR agonist.     

The Fate in the Marine Environment of a Minor Diesel Fuel Spill from an Antarctic Research Station

Monitoring was undertaken of the fate in the marine environment of an accidental spill of diesel fuel (1000 litres) from Faraday Research Station, Galindez Island, Antarctica in March 1992. On the day after the incident concentrations in seawater reached a maximum of 540 µg 1-1 for n-alkanes and 222 µg 1-1 for polycyclic aromatic hydrocarbons (PAH). However, concentrations returned to local background levels within one week. The fuel had an immediate toxic effect on intertidal limpets in the local station area, and 100 animals were found dead the day after the spill. Surviving animals had elevated concentrations of both n-alkanes and PAH for over a month after the spill, reaching a maximum of 9960 µg kg-1 for n-alkanes and 90 µg kg-1 for PAH 30 days after the spill occurred. This was the result of accumulation from a residue of the diesel being flushed by rainwater into the littoral zone. Seven months after the spill concentrations of both n-alkanes and PAH in limpets living close to the station were still an order of magnitude greater than those found in animals at an uncontaminated control site. This is because limpets living in the littoral zone were continually exposed to chronic but low-level hydrocarbon contamination from station activities. The diesel spill itself had a very minor, localised and short-term impact on the Antarctic marine environment.     

土壤有机质组分中多环芳烃分配特征和生态风险

土壤有机质是影响多环芳烃（PAHs）环境行为的一个重要因素,不同有机质组分结合的PAHs生物有效性和环境风险有所不同.本文对6个野外污染土壤中15种优控PAHs的含量和组成及其在土壤轻组（LF）和重组（HF）中的分配特征进行了研究,并采用苯并[a]芘（BaP）毒性当量浓度（TEQ_BaP）评价了全土、LF和HF中PAHs的生态风险.结果表明,6个土样中15种PAHs总量范围为8.31×10²~2.97×10⁴μg/kg,4环PAHs百分含量最高,范围为35.7%~59.6%.6个土样LF中PAHs总量范围为2.38×10⁴~1.17×10⁵μg/kg,HF中PAHs总量范围为3.75×10²~2.12×10⁴μg/kg.虽然土壤中LF质量百分比只有1.0%~9.8%,但其结合的PAHs量却占土壤中PAHs总量的5.9%~60.6%.LF中15种PAHs总TEQ_BaP值范围为2.99×10²~1.68×10⁴μg/kg,分别是全土和HF的2.7~33.2倍和3.6~69.5倍.在PAHs污染土壤修复和生态风险评估中,应重视LF中PAHs.对LF中PAHs量占土壤中PAHs总量百分比较高的土壤,可以通过分离LF的方法来修复污染土壤.     

石油烃在非均质包气带中的吸附作用及迁移规律

为深入分析强非均质性污染场地中石油烃的运移规律,探究石油烃类污染物在场地中的吸附、迁移及其影响因素,选取潮白河上游为典型研究区,受冲洪积扇条件控制,区域内包气带非均质性强,地下水埋深较大.采集污染场地包气带介质样品,分别装填原状土（0~20 mm）、细颗粒（< 2 mm）和粗颗粒（>4 mm）3种介质迁移柱,通过土柱淋滤试验表征石油烃在典型介质中的迁移特性;通过静态吸附试验和微生物降解试验识别石油烃迁移过程的关键影响因素,揭示多要素作用条件下的石油烃迁移规律.结果表明:原状土、细颗粒和粗颗粒这3种介质迁移柱出水中石油烃浓度均呈先下降、后波动上升、最终趋于稳定的趋势.3种介质对石油烃的吸附过程均呈现快吸附和慢吸附两个阶段,快吸附阶段发生在试验0~15 h内,完成了吸附的70%~80%;慢吸附阶段持续时间较长,吸附总量缓慢增加.固液比、温度和pH等要素对3种介质石油烃吸附性能的影响相对较小.微生物降解是慢吸附阶段石油烃浓度呈波动上升的主要原因,且在整个石油烃垂向迁移过程中,吸附作用对石油烃去除的贡献率为80%,微生物降解的贡献率为20%.研究显示,相对于微生物作用而言,强非均匀介质在石油烃类污染场地的污染物吸附和迁移过程中起关键控制作用.      

低碳烃选择性催化还原NOx的研究进展

对报道较多的以低碳烃作为还原荆，选择性催化还原NO的研究进展进行了综述，重点介绍了离子交换分子筛类催化剂、金属与金属氧化物的研究状况，分析了存在问题及今后的研究重点，简要介绍了固体超强酸类催化荆。     

石油烃类降解菌在不同矿化度下的生长规律及去油效果研究

研究了不同盐浓度含油废水中石油烃类降解菌的生长情况以及对原油的去除效果。实验结果表明:在盐浓度低于15%的石油烃废水中,降解菌生长旺盛,且数量大;在盐浓度为15%～25%的石油烃废水中有较多菌量,但数量已明显减少;在盐浓度为30%以上的石油烃废水中几乎无细菌生长。培养时间为13h时,去油率可达到55%;随着培养时间的延长,原油去除率趋于平缓。高盐度石油烃废水中生存的微生物在处理含油废水方面具有很大的应用潜力。     

内酯型槐糖脂修复石油污染土壤的影响因素

采用内酯型槐糖脂(SL50)修复石油污染土壤。通过单因子实验与正交实验,考察了槐糖脂溶液质量浓度、振荡时间、反应体系初始pH、NaCl加入量以及固液比(土壤质量与表面活性剂溶液体积之比)对污染土壤石油烃洗脱率的影响。单因子模型回归分析结果表明,参数变量均符合二次拟合模型,槐糖脂溶液质量浓度、反应体系初始pH以及NaCl加入量的二次模型拟合效果较好。正交实验结果表明,槐糖脂溶液质量浓度和反应体系初始pH是该实验的敏感性因子,最优洗脱条件为槐糖脂溶液质量浓度40 mg/L、反应体系初始pH 9、NaCl加入量6%(w)。