基于可拓学石化装置失效后果严重度评估方法研究

石化企业中,石化装置的安全运行对保证企业的安全生产起到关键作用,其一旦失效发生事故,将导致巨大的人员伤亡及财产损失。因此,开展石化装置失效后果严重性的评价研究,对保证石化企业的安全生产具有重要意义。本文根据物元可拓性理论,结合石化装置失效后果的严重性情况,运用可拓评判方法建立石化装置失效后果严重度的综合评判模型,给出了评价步骤,最终确定设备失效后果的严重程度。研究结果表明,该方法可应用于多层次的工程风险评价问题,从而为石化工程项目风险管理提供了一种有效的分析方法。     

关天经济区农户农地流转行为研究

农地流转是现阶段实现农地规模经营的必经之路。本文基于关天经济区622份调查问卷,建立了农地流转的农户模型,利用Heckman两阶段模型研究了交易成本认知和农户禀赋对农户参与农地流转(转出)、农地流转率的影响。研究结果表明:(1)关天经济区农户参与农地流转的积极性不高,样本农户参与农地流转的仅为23%,农地流转率均值为11%;(2)流转价格了解程度、农地流转组织形式、农地流转合约期限和对外交通便利情况影响农户是否参与农地流转决策,而农地流转率仅受流转价格了解程度和农地流转契约形式影响;(3)劳动力和土地禀赋正向影响农户转出土地,农地流转率随农业生产能力增强而降低;(4)文化程度与农户是否参与农地流转、农地流转率呈现显著的负相关关系,与天水的农户相比,关中地区的农户更倾向于参与农地流转。因此,要促进农户参与农地流转、提升农地流转率,首先要加强农地流转政策的宣传力度,提高农户整体认知水平,增强农户农地流转政策的理解程度和接受能力;其次,深化农村土地产权改革,加快农地确权颁证,提升农户产权的稳定性和可预期性;再次,建立健全农地流转市场,完善市场在农地流转过程中的信号生成机制和传递功能,降低农地流转过程中的交易成本;第四,采取相应的激励政策提高农户土地、劳动力的利用程度,提升农户农业生产能力,避免农户在农地流转市场中的逆向选择行为;最后,建立有效的农地"经营权退出机制",将束缚在农业生产上的低效劳动力和土地释放出来,实现资源的最优化配置。     

自动化前处理-气相色谱串联质谱法测定淡水鱼体中的有机磷阻燃剂

应用自动化前处理设备和气相色谱串联四级杆质谱仪建立了淡水鱼体中10种有机磷阻燃剂的检测方法。该方法先采用自动索氏提取仪进行样品的提取,再应用凝胶渗透色谱净化仪和florisil柱对提取液进行两级净化,最后用气相色谱串联四级杆质谱法(多反应监测模式)对样品中的有机磷阻燃剂(OPFRs)定性定量。实验表明,凝胶渗透色谱净化系统在以乙酸乙酯∶环己烷(1∶1,V/V)为流动相,流速为5.0 m L·min-1的条件下,收集OPFRs的最佳时间为900~1 680 s;方法的检出限为0.002~0.192 ng·g~(-1)湿重,加标水平为5.000 ng·g~(-1)湿重时,平均加标回收率为48.7%~122%,相对偏差除磷酸三乙酯(TEP)(17.7%)和磷酸三(1,3-二氯异丙基)酯(TDCP)(11.9%)外均小于10%。应用该方法测定采集于东江某污水处理厂入河排污口的鱼类样品时,回收率指示物(d27-TBP)的回收率为82.4%~114%,鱼类样品中∑OPFRs的浓度范围为nd~6.41 ng·g~(-1)湿重。     

Corynebacterium glutamicum as an indicator for environmental cobalt and silver stress–A proteome analysis

Cobalt and silver are toxic for cells, but mechanisms of this toxicity are largely unknown. Analysis of Corynebacterium glutamicum proteome from cells grown in control and cobalt or silver enriched media was performed by two dimensional gel electrophoresis (2DE) followed by mass spectrometry. Our results indicate that the cell adapted to cobalt stress by inducing five defense mechanisms: Scavenging of free radicals, promotion of the generation of energy, reparation of DNA, reparation and biogenesis of Fe-S cluster proteins and supporting and reparation of cell wall. In response to the detoxification of Ag⁺ many proteins were up-regulated, which involved reparation of damaged DNA, minimizing the toxic effect of reactive oxygen species (ROS) and energy generation. Overexpression of proteins involved in cell wall biosynthesis (1,4-alpha-glucan branching enzyme and nucleoside-diphosphate-sugar epimerase) upon cobalt stress and induction of proteins involved in energy metabolism (2-methylcitrate dehydratase and 1, 2-methylcitrate synthase) upon silver demonstrate the potential of these enzymes as biomarkers of sub-lethal Ag⁺ and Co toxicity.     

Influence of dissolved humic substances on the mass transfer of organic compounds across the air-water interface

The effect of dissolved humic substances (DHS) on the rate of water-gas exchange of two volatile organic compounds was studied under various conditions of agitation intensity, solution pH and ionic strength. Mass-transfer coefficients were determined from the rate of depletion of model compounds from an apparatus containing a stirred aqueous solution with continuous purging of the headspace above the solution (dynamic system). Under these conditions, the overall transfer rate is controlled by the mass-transfer resistance on the water side of the water-gas interface. The experimental results show that the presence of DHS hinders the transport of the organic molecules from the water into the gas phase under all investigated conditions. Mass-transfer coefficients were significantly reduced even by low, environmentally relevant concentrations of DHS. The retardation effect increased with increasing DHS concentration. The magnitude of the retardation effect on water-gas exchange was compared for Suwannee River fulvic and humic acids, a commercially available leonardite humic acid and two synthetic surfactants. The observed results are in accordance with the concept of hydrodynamic effects. Surface pressure forces due to surface film formation change the hydrodynamic characteristics of water motion at the water-air interface and thus impede surface renewal.     

The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

采油废水中多环芳烃的生态风险评价

先利用C-18固相萃取小柱富集大港油田港东联合处理站污水处理站的采油废水中16种多环芳烃(PAHs,即萘、苊烯、苊、芴、菲、蒽、荧蒽、芘、、苯并[a]蒽、苯并[b]荧蒽、苯并[k]荧蒽、苯并[a]芘、茚并[1,2,3-cd]芘、二苯并[a,h]蒽和苯并[g,h,i]苝),再用气相色谱/质谱(GC/MS)分析测定其浓度,以评价PAHs的去除率和生态风险。结果表明:(1)采油废水经处理后,COD、石油类去除率分别达到82.27%、91.06%;外排水COD、石油类达到《污水综合排放标准》(GB 8978—1996)一级标准要求,优于中国采油废水处理的一般水平。(2)采油废水主要以2、3环的PAHs为主,约占总量的93%以上。(3)苯并[a]芘超过《地表水环境质量标准》(GB 3838—2002)中限值。(4)处理前的采油废水中蒽、菲和苯并[a]芘具有一定的生态风险;处理后的外排水中萘、蒽、菲、荧蒽、苯并[a]芘的暴露浓度(PEC)/预测无效应浓度(PNEC)均小于1,目前尚未对环境造成威胁。但是8种PAHs(苊烯和苯并类PAHs除外)总和表现出较大的毒性,需要引起重视。     

污泥转移SBR工艺处理低浓度生活污水

污泥转移SBR工艺是一种通过内部污泥回流实现污泥在不同SBR隔室间转移,从而增加污泥利用效率,提高系统除污效能的新工艺。以设计规模为240 m3/d、处理低浓度生活污水的工艺系统为对象,研究了新工艺在不同泥转移量(污泥回流比)下的除污性能,并与系统以传统SBR方式运行的情况进行了对比。结果表明,新工艺可以有效提高SBR反应器的容积利用率;采用30%的污泥回流比进行污泥转移,新工艺的处理能力比传统SBR工艺提高近1/2,除磷效率从46%提升至85%。出水各项水质指标均能达到国家排放标准的要求。     

抗压实验法厌氧颗粒污泥机械强度的测定及影响因素分析

通过首先对厌氧颗粒污泥样品进行筛分,然后测定其机械强度,解决了实际操作过程中现有抗压实验法出现的精确度与重现性较差的问题。通过对不同来源厌氧颗粒污泥样品机械强度的测定、对比分析发现,厌氧颗粒污泥的机械强度大小与反应器的规模、反应器所采用水力负荷存在一定的正相关性,且与其主要金属元素（Ca、Fe和Mg）含量的大小存在着密切的关系。     

Electrochemical oxidation of herbicide bifenox acid in aqueous medium using diamond thin film electrode

The electrochemical oxidation of bifenox acid was studied at a boron-doped diamond thin film by cyclic voltammetry and galvanostatic electrolysis. The course of the electrolysis was monitored by measurement of chemical oxygen demand (COD) and by gas chromatography/mass spectrometry (GC / MS) analysis. It was found that exhaustive electrolysis leads to degradation and, ultimately, to mineralization of the starting herbicide. The degradation intermediates were identified showing that the oxidation process begins with the fragmentation of the molecule followed by reactions involving the hydroxyl radical, which is generated by the discharge of water. The study of the effect of current density and concentration showed that the degradation efficiency increases with decreasing current densities and increasing concentrations. The whole results were interpreted in a mechanistic scheme involving two oxidation pathways, the first is a direct oxidation at the electrode and the second uses hydroxyl radical as mediator of the oxidation. Finally, a kinetic study based on spectrophotometric measurements showed that the degradation process is pseudo first order.