石油石化企业温室气体清单编制简析

文章通过简要阐述石油石化企业温室气体清单的编制全过程,确定石油石化企业温室气体排放种类、识别主要温室气体排放源、列举重点生产过程中温室气体排放量的核算方法,为石油石化企业实现温室气体减排和控制工作、为完成国务院规定的到2020年我国单位国内生产总值二氧化碳排放强度比2005年下降40%~45%的约束性指标,奠定数据理论基础。     

环境中总石油烃的气相色谱分析测定

将总石油烃划分为挥发性汽油类(C6～C10)、可萃取柴油和重油类(C10～C40)两部分,分别建立了通过吹扫捕集、液液萃取和超声溶剂萃取分离富集,气相色谱-火焰离子化检测器(GC-FID)测定环境水体和土壤中总石油烃的分析方法。以汽油、柴油、润滑油标准溶液进行外标校正,以色谱出峰总面积进行定量。汽油类(C6～C10)的检出限分别为0.04mg/L和0.42mg/kg,柴油和重油类(C10～C40)的检出限分别为0.06mg/L和4.9mg/kg。方法的精密度和准确度均良好。     

Chemical and ecotoxicological analyses of sediments and elutriates of contaminated rivers due to e-waste recycling activities using a diverse battery of bioassays

A multi-trophic, multi-exposure phase assessment approach was applied to characterize the toxicity of sediments collected from two rivers in Guiyu, China, an e-waste recycling centre. Elutriate toxicity tests (bacterium Vibrio fischeri and microalga Selenastrum capricornutum) and whole sediment toxicity test (crustacean Heterocypris incongruens) showed that most sediments exhibited acute toxicity, due to elevated heavy metals and PAHs levels, and low pH caused by uncontrolled acid discharge. The survival rates of crustaceans were negatively (p < 0.05) correlated with total PAHs in sediments (411-1755 mg kg⁻¹); EC50s of V. fischeri on the elutriates were significantly correlated with elutriate pH (p < 0.01). Significant (p < 0.05) correlations between the induction of hepatic metallothionein in tilapia (Oreochromis mossambicus) and metal concentrations (Cu, Zn, Pb) in sediments were also observed, when fish were fed with diets containing sediment. The results showed that uncontrolled e-waste recycling activities may bring adverse effects to local aquatic ecosystem.     

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。     

石油污染土壤原位生物修复的强化实验研究

为研究添加营养物质和高效降解石油微生物对油污土壤生物修复的作用,通过分层土柱的方法,连续监测了不同条件下不同土层的含水率、石油烃含量、细菌数量及脱氢酶活性。结果表明:添加营养物质同时接种高效微生物可使降解效果明显改善,降解率比在自然条件下提高近50%,而单纯添加营养物质不接种高效微生物可使降解率比在自然条件下提高约25%。降解初期,上层土壤降解效果较好,而到中后期,中下层降解效果好于上层。微生物数量和脱氢酶活性与石油降解率之间存在良好的相关性,脱氢酶活性比微生物数量更能反映修复过程中微生物的存活状态。添加营养物质和高效降解石油微生物对油污土壤原位生物修复具有强化作用。     

Cation exchange in a glacial till drumlin at a road salt storage facility

At a former wood preservation plant severely contaminated with coal tar oil, in situ bulk attenuation and biodegradation rate constants for several monoaromatic (BTEX) and polyaromatic hydrocarbons (PAH) were determined using (1) classical first order decay models, (2) Michaelis–Menten degradation kinetics (MM), and (3) stable carbon isotopes, for o-xylene and naphthalene. The first order bulk attenuation rate constant for o-xylene was calculated to be 0.0025 d^− 1 and a novel stable isotope-based first order model, which also accounted for the respective redox conditions, resulted in a slightly smaller biodegradation rate constant of 0.0019 d^− 1. Based on MM-kinetics, the o-xylene concentration decreased with a maximum rate of k_max = 0.1 µg/L/d. The bulk attenuation rate constant of naphthalene retrieved from the classical first order decay model was 0.0038 d^− 1. The stable isotope-based biodegradation rate constant of 0.0027 d^− 1 was smaller in the reduced zone, while residual naphthalene in the oxic part of the plume further downgradient was degraded at a higher rate of 0.0038 d^− 1. With MM-kinetics a maximum degradation rate of k_max = 12 µg/L/d was determined. Although best fits were obtained by MM-kinetics, we consider the carbon stable isotope-based approach more appropriate as it is specific for biodegradation (not overall attenuation) and at the same time accounts for the dominant electron-accepting process. For o-xylene a field based isotope enrichment factor ε_field of − 1.4 could be determined using the Rayleigh model, which closely matched values from laboratory studies of o-xylene degradation under sulfate-reducing conditions.     

Desorption of polycyclic aromatic hydrocarbons from field-contaminated soil to a two-dimensional hydrophobic surface before and after bioremediation

This study investigated environmental distributions and production mechanisms of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) in the sediments from some tidal flats located in Asia. Cl-PAHs were found in sediments taken from Arao tidal flat, Kikuchigawa River and Shirakawa River. The range of ∑Cl-PAHs was from 25.5 to 483 pg g⁻¹ for Kikuchigawa River and Arao tidal flat, respectively.Concentrations of PAHs and Cl-PAHs showed no significant correlations (r = 0.134). This result suggests that the origins of these compounds differ. In the identified Cl-PAH isomers, the most abundant Cl-PAH isomer was 9,10-dichloroanthracene (9,10-di-Cl-ANT) in the three sites. In general, concentrations of Cl-ANTs in the coastal environment are about 3-5 orders of magnitude lower than those of anthracene (ANT). However, concentration ratios between Cl-ANTs and ANT (Cl-ANTs/ANT) in the sediments ranged from 4.1% to 24.6%. This result indicated that Cl-PAHs were not generated under industrial processes but the high concentration ratios have resulted from the contribution of photochemical production of Cl-ANTs in the sediments because ANT is known to have high photochemical reactivity.For examining this phenomenon, ANT adsorbed onto glass beads was irradiated with UV under the mimicked field conditions of tidal flats. As a result, it was noticed that, while chlorinated derivatives were negligible in a light-controlled group, production of 2-Cl-ANT, 9-Cl-ANT and 9,10-diCl-ANT on the irradiated surface were found in this study. These results suggest that photochemical reaction of PAHs can be a potential source of the occurrence of Cl-PAHs in the coastal environment.     

西安市大气中多环芳烃的季节变化及健康风险评价

对西安市2009年6月-2010年5月空气中的总悬浮颗粒（TSP）和气态样品进行了连续采样，利用GC—MS对16种PAHs进行分析。∑PAHs浓度（气相＋颗粒相）范围为39．93～1032．46ng／m^3，平均值为197．34ng／m^3；其中，冬季大气中∑PAHs浓度最大，相对浓度的范围为31．21％～72．98％，而夏季的浓度最小；检测出16种2～6环的PAHs，其中以3—4环为主。利用特征分子比值法和因子分析进行源解析，发现研究区PAHs的主要来源为燃煤和机动车尾气排放。通过苯并（a）芘（BaP）等效毒性（BEQ）和苯并（a）芘等效致癌浓度（BaPE）进行健康风险评价，结果显示，西安大气中PAHs的毒性具有明显的季节差异，特别是秋季和冬季大气中PAHs对人类的健康存在较大的潜在威胁。     

Assessment of honey contamination with polycyclic aromatic hydrocarbons

The aim of this study was to assess honey contamination by polycyclic aromatic hydrocarbons. Six species of honey were examined, as well as rape blossom and soil from villages P?czerzyno and Przybys?aw in West Pomerania, Poland. The instrumental analysis was performed using a HP 6890 gas chromatograph coupled to a HP 5973 mass spectrometer with selected ion monitoring (SIM). Quantification was done by gas chromatography-mass spectrometry (GC-MS) using perdeuterated internal standards. Both soil samples showed high levels of all 23 PAHs, whereas honey contained mostly non-carcinogenic PAHs of low molecular weight. The most contaminated honey from P?czerzyno contained 0.24 μg kg-1 benzo[a]pyrene. Moreover, despite low contamination of honey, a positive correlation was found between PAH content in honey, blossom and soil.     

白腐真菌修复多环芳烃污染土壤及其降解机理的研究进展

介绍了白腐真菌对多环芳烃(PAHs)的代谢途径、降解机理,阐述了白腐真菌修复PAHs污染土壤的影响因素和生态效应,并提出了提高白腐真菌修复效率的措施.白腐真菌主要通过分泌木质素降解酶系(木质家过氧化物酶、锰过氧化物酶和漆酶)来降解PAHs,这些胞外酶可通过开环作用把PAHs代谢成为水溶性较强的醌类中间产物,再由其他微生物降解这些中间产物直至矿化.在白腐真菌的培养过程中.通过对环境因素及营养条件(如温度、pH值、C/N比、微量元素和转速)的优化可提高胞外酶产量.在修复PAHs污染土壤过程中,生物竞争、营养条件和环境因素等均会影响白腐真菌的修复效果.同时,归纳总结了改善白腐真菌修复效果的一些措施,如真菌-细菌联合修复、添加适当的培养基质、添加表面活性剂、直接施用酶制剂和改善营养条件等.