神经毒剂沙林的破坏机理研究

采用VAMP和密度泛函程序DMol3计算了沙林的生成热,并用VAMP-PM3/UHF半经验方法对沙林裂解的过渡态进行了优化计算,共发现9种过渡态,据此判断化学键断裂的难易顺序为P=O＞P-F＞P-O＞C-O＞P-C＞C-C＞C-H; C-H键断裂的活化能最小,可能与氢原子迁移到氧原子上有关.活化能小于相应的键解离能,计算结果能解释沙林的质谱数据.计算结果对使用低当量小型核武器破坏沙林等生化武器(核除剂)的可行性提供了能量上的参考,即试图通过计算得出有效的原位破坏沙林等生化战剂所需的最低能量,进而研究使用低当量小型核武器破坏沙林等生化武器的可行性.     

A Comparison of the Precipitation Chemistry Measurements Obtained by the CAPMoN and NADP/NTN Networks

Precipitation chemistry measurementsobtained by the Canadian Air and PrecipitationMonitoring Network (CAPMoN) and the U.S. NationalAtmospheric Deposition Program/National Trends Network(NADP/NTN) have been examined using more than 7 yrof collocated data from two sites, namely, Sutton,Quebec, Canada and State College, Pennsylvania, U.S.A.In the case of the CAPMoN data, weeklyprecipitation-weighted mean concentrations, totalsample depths and total standard gauge depths werecomputed from daily data and compared to thecorresponding weekly sampling data of the NADP/NTNnetwork. Seasonal and annual precipitation-weightedmean concentrations and deposition values were alsocomputed for both networks and compared. Statisticallysignificant between-network biases were found to existin the weekly results for most of the measuredvariables, particularly standard gauge depth, sampledepth, pH, H⁺, NO₃ ^-,NH₄ ⁺,Na⁺; the NADP/NTN values were consistently lowerthan those of CAPMoN with the exception of pH andNa⁺. The magnitude of the biases was less than35% of the median CAPMoN weekly value for the 7 yr. For most of the measured parameters, thevariability of the between-network differencesrepresented less than 20% of the median CAPMoN weeklyvalue. Both the between-network biases andvariabilities were functions of several physicalparameters, the most dominant being the sample depthand the ionic concentration. For seasonal and annualdeposition values, statistically significantbetween-network biases were found for H⁺,SO₄ ^2-, NO₃ ^-,Ca²⁺,NH₄ ⁺ for both periods; for Mg²⁺ andK⁺ for seasonal data; and Cl^- for yearlydata, with the NADP/NTN deposition values being lowerthan those of CAPMoN. The relative biases ranged from7 to 37%. Part of the between-network bias in thedeposition estimates was directly attributable to astrong bias in the standard gauge depths of the two networks.     

原油稳定装置的风险评价

运用美国道化学公司的火灾爆炸危险指数评价方法,对大庆油田天然气分公司正压原油稳定装置的火灾爆炸危险性进行了定量计算和评价,介绍了火灾爆炸指数评价法的评价程序和计算步骤,定量计算火灾爆炸可能导致的危害程度和最大可能财产损失,根据实际情况确定了单元的危险系数和安全措施补偿系数,最后得出单元危险分析的安全评价结果.     

赤水河中下游冬季河水化学空间分布特征分析

通过在枯水期对赤水河中下游干流及其支流共25个河水样品进行水化学采样,水化学分析结果表明:在阴阳离子组成中,Ca2+为主要阳离子,占总阳离子的64%以上;阴离子以HCO3-和SO42-为主,占总阴离子75%~91%,其中HCO3-占51%以上。Gibbs图研究区河水化学组成受岩石风化作用控制,阴阳离子三角图、水化学比值分析表明研究区河水化学组成主要受碳酸盐岩风化作用影响,在下游部分支流存在一定硅酸盐岩风化作用。水化学时空分布的对比分析表明,人为活动的对赤水河流域岩石风化速率和水化学组成产生了一定的影响。     

典型油田多环芳烃污染对土壤反硝化微生物群落结构的影响

油田区土壤具有潜在的PAHs(polycyclic aromatic hydrocarbons)污染风险,而以硝酸根为电子受体的反硝化作用可能在PAHs的厌氧代谢中起到重要作用.以具有50多年历史的江汉油田区域为对象,从该油田的油井口附近采集了9个土壤样品,编号为JH-1~JH-9,以反硝化相关的nir K(Cu-亚硝酸还原酶基因)和nirS(细胞色素cd1-亚硝酸还原酶基因)为分子标识,通过定量PCR及克隆文库结合T-RFLP(terminal-restriction fragment length polymorphism)的方法,研究典型油田区土壤反硝化微生物的群落结构,并探讨其与土壤环境因子之间的关系.结果表明,该油田区土壤中nirK基因的丰度高于nirS基因,PAHs含量最高的土壤样品(JH-4)中反硝化功能基因nir K和nir S的丰度均最低,相关性分析表明,土壤nir K及nirS基因的丰度均与土壤PAHs含量呈显著负相关(nirK:R2=0.54,P0.05;nirS:R~2=0.58,P0.05).克隆文库及T-RFLP的结果则表明,该油田土壤中nirK基因的群落组成在不同样品间的变异较大,且PAHs含量最高的JH-4中该基因的群落组成与其它各样品有明显的不同,RDA(redundancy analysis)的分析结果进一步表明除有效氮、有效磷外,土壤PAHs含量也是影响nirK型反硝化微生物群落组成的重要因子.相较于nirK,该油田区土壤中nirS基因的群落组成在不同样品间的差异较小,但发现nirS型假单胞菌的丰度与土壤PAHs含量呈正相关,表明具备较强有机污染物降解能力的假单胞菌属可能在该区域土壤PAHs的反硝化代谢中起到重要作用.     

Mg^2＋配位作用对磺胺嘧啶结构及吸收光谱影响的计算模拟及验证。

以磺胺嘧啶为模型化合物,基于量子化学密度泛函理论（DFT）,通过结构优化及相互作用能的计算,预测Mg^2＋与磺胺嘧啶形成1：1配合物的结构．结果表明,Mg^2＋和磺酰胺基的N和0原子配位,同时结合一个水分子;配合物磺酰胺基的键长、键角和二面角发生明显变化．基于含时密度泛函理论（TD-DFT）方法,计算磺胺嘧啶及其配合物...     

一种基于SDS溶液高效提取土壤残留Bt蛋白的方法

通过对SDS浓度、孵育温度和孵育时间3种提取条件的研究,建立了一种基于SDS溶液的提取土壤中残留Bt蛋白的方法(简称SDS法).在ρ(SDS)为2 g·L-1、孵育温度为50℃、孵育时间≥4 h条件下,采用SDS法可有效地从不同类型土壤样品中提取残留Bt蛋白,提取效果明显好于碳酸盐法、人造蠕虫肠道蛋白提取液法和PBST(phosphate buffer solution with Tween-20)法.     

南海油田开发环境影响实例分析

陆丰22-1是中国第一个正式弃置的海上油田,处于南海330m深水区.分析开发前期、中期及末期油田附近海域表层海水、表层沉积物和底栖甲壳类体内石油烃含量数据,结果表明油田附近海域环境质量较好,油田开发对环境的主要污染影响是表层海水和底栖生物体内石油类污染物质含量有所升高,尚未见生活污水和食品废弃物的排放对环境造成影响的迹...     

南方某氟化学工业园周围环境中全氟化合物的分布研究

南方某氟化学工业园四氟乙烯(TFE)和聚四氟乙烯(PTFE)的年生产量均达万吨以上,大量氟化学品的生产可能对周围环境产生一定的危害.本文以该氟化学工业园为研究对象,对其周边地区的水体、沉积物中的11种全氟化合物(PFASs)含量进行监测,并首次对植物树叶和树皮中PFASs含量进行测定.结果表明,与树皮相比,树叶对环境中PFASs具有更强的富集能力;水、沉积物、树叶和树皮中最主要的PFASs均是全氟辛酸(PFOA).地表水中PFOA浓度均值为675.9 ng·L-1,最高浓度达1503 ng·L-1;沉积物中PFOA浓度均值为1.11 ng·g-1(干重,下同),最高浓度为2.58 ng·g-l;树叶和树皮中的PFOA浓度均值分别为22.18和15.43 ng·g-1,最高浓度分别为168.6和89.67 ng·g-1.     

Rapid removal of polyacrylamide from wastewater by plasma in the gas–liquid interface

Due to the severe restrictions imposed by legislative frameworks, the removal of polyacrylamide(PAM) rapidly and effectively from produced wastewater in offshore oilfields before discharge is becoming an urgent challenge. In this study, a novel advanced oxidation process based on plasma operated in the gas–liquid interface was used to rapidly decompose PAM, and multiple methods including viscometry, flow field-flow fractionation multi-angle light scattering, UV–visible spectroscopy, and attenuated total reflectanceFourier transform infrared spectroscopy were used to characterize the changes of PAM.Under a discharge voltage of 25 kV and pH 7.0, the PAM concentration decreased from 100 to 0 mg/L within 20 min and the total organic carbon(TOC) decreased from 49.57 to1.23 mg/L within 240 min, following zero-order reaction kinetics. Even in the presence of background TOC as high as 152.2 mg/L, complete removal of PAM(100 mg/L) was also achieved within 30 min. The biodegradability of PAM improved following plasma treatment for 120 min. Active species(such as O_3 and H_2O_2) were produced in the plasma. Hydroxyl radical was demonstrated to play an important role in the degradation of PAM due to the inhibitory effect observed after the addition of an ·OH scavenger, Na_2CO_3. Meanwhile, the release of ammonia and nitrate nitrogen confirmed the cleavage of the acylamino group.The results of this study demonstrated that plasma, with its high efficiency and chemicalfree features, is a promising technology for the rapid removal of PAM.