高锰酸钾凝胶缓释剂的制备及其缓释去除水中三氯乙烯

本研究开发一种结合原位化学氧化和二氧化硅溶胶-凝胶的可控氧化剂释放技术,制备出一种高锰酸钾(KMnO₄)凝胶缓释剂(SRPG).优化SPRG的制备条件和探究影响其在水中缓释效率的因素,并考察其对不同氯代烃的降解效果.结果表明：二氧化硅溶胶的质量分数、KMnO₄的含量及pH对SRPG凝胶化过程有显著的影响;提高缓释剂中KMnO₄的含量和降低二氧化硅溶胶质量分数,可有效提高SRPG中KMnO₄的释放速率,当KMnO₄质量分数为6.51‰,二氧化硅溶胶质量分数为40%,KMnO₄的释放符合拟一阶动力学,释放速率k_obs=0.83 h-1(R²=0.9750),且12 h后KMnO₄释放率为82.7%;SRPG可有效降解水中氯代烃污染物,其中对三氯乙烯(TCE)的去除效果最佳,反应24 h可去除水中98%的TCE.因此,SRPG在原位化学氧化修复土壤和地下水中氯代烃的实际工程中具有良好的应用前景.     

Enhanced carbon tetrachloride degradation by hydroxylamine in ferrous ion activated calcium peroxide in the presence of formic acid

• Complete CT degradation was achieved by employing HA to CP/Fe(II)/FA process. • Quantitative detection of Fe(II) regeneration and HO• production was investigated. • Benzoic acid outcompeted FA for the reaction with HO•. • CO₂•⁻ was the dominant reductive radical for CT removal. • Effects of solution matrix on CT removal were conducted. Hydroxyl radicals (HO•) show low reactivity with perchlorinated hydrocarbons, such as carbon tetrachloride (CT), in conventional Fenton reactions, therefore, the generation of reductive radicals has attracted increasing attention. This study investigated the enhancement of CT degradation by the synergistic effects of hydroxylamine (HA) and formic acid (FA) (initial [CT] = 0.13 mmol/L) in a Fe(II) activated calcium peroxide (CP) Fenton process. CT degradation increased from 56.6% to 99.9% with the addition of 0.78 mmol/L HA to the CP/Fe(II)/FA/CT process in a molar ratio of 12/6/12/1. The results also showed that the presence of HA enhanced the regeneration of Fe(II) from Fe(III), and the production of HO• increased one-fold when employing benzoic acid as the HO• probe. Additionally, FA slightly improves the production of HO•. A study of the mechanism confirmed that the carbon dioxide radical (CO₂•⁻), a strong reductant generated by the reaction between FA and HO•, was the dominant radical responsible for CT degradation. Almost complete CT dechlorination was achieved in the process. The presence of humic acid and chloride ion slightly decreased CT removal, while high doses of bicarbonate and high pH inhibited CT degradation. This study helps us to better understand the synergistic roles of FA and HA for HO• and CO₂•⁻ generation and the removal of perchlorinated hydrocarbons in modified Fenton systems.     

多环芳烃污染土壤的微生物修复技术

对生物修复技术中的微生物进行了分类,并阐述了微生物生物降解土壤中多环芳烃（PAHs）的基本原理。在此基础上,分析了国内外微生物生物修复技术的发展概况,采用图示法重点综述了原位处理技术和非原位处理技术的工艺流程,并列举了相应的工程应用实例。     

AHH activity, tissue dose and DNA damage in different tissues of the scallop Chlamys farreri exposed to benzo[a]pyrene

A collaborative study was performed on scallops (Chlamys farreri) exposed to 0.5, 3 and 10 microg/L benzo[a]pyrene (B[a]P) for 20 days. The levels of aryl hydrocarbon hydroxylase (AHH) activity, B[a]P accumulation and DNA strand break were assayed in the gill and digestive gland. Results showed that AHH activity and B[a]P accumulation were significantly related to B[a]P dose. AHH activity was induced and then became stable gradually. B[a]P accumulation increased first and showed an incoming plateau. DNA strand break levels in the 0.5 and 3 microg/L B[a]P groups remained high and significantly different from control values until day 6, followed by a reduction in the gill and no recovery in the digestive gland. The 10 microg/L B[a]P groups remained significantly lower than control until the end. These results suggested that the application of comprehensive indices may give information on the actual exposure of organisms to pollutants, and also information on toxic effects.     

加油站的烃类VOCs污染及其治理技术

加油站因储运轻质油品而产生的烃类VOCs对健康、环境、安全以及油品质量等带来了一系列负面影响.发达国家的常规治理措施主要是进行密闭卸油和密闭发油,对加油站的设备安装、管线布置、运营管理等都有一些具体要求;进入21世纪后美国又提出了强化加油站油气回收处理的观点,相应的技术、设备及法规也都日益健全.国内目前对加油站烃类VOCs污染的治理工作与发达国家相比差距很大,应该尽快从烃类VOCs回收处理的专用膜分离装置入手进行相关研究和产品开发.     

江苏天目湖表层沉积物中多环芳烃污染特征与来源

区别于长江三角洲地区众多的大型天然浅水湖泊，江苏天目湖是一个较深的水库型湖泊，也是重要的城乡生活及工农业水源地之一。为了解天目湖表层沉积物中多环芳烃（PAHs）污染状况， 2006年在天目湖全湖采集7个点位的表层沉积物样品，利用GC/MS分析了16种优控PAHs。结果表明：天目湖表层沉积物中16种优控PAHs总量介于28750~71393 ng/g（干重），平均值为45852 ng/g；在空间分布上，北部受污染程度高于南部，主要是北部旅游业快速发展导致污染物排放的影响；沉积物中总有机碳含量与PAHs总量呈显著相关；利用特征化合物指数对PAHs的来源进行判别，指示天目湖表层沉积物中PAHs的主要来源是木材、煤的不完全燃烧。与不同地区水体沉积物PAHs含量对比表明，天目湖PAHs污染处于一个低至中等程度。基于沉积物中多环芳烃的环境质量标准，仅有1个样点芴浓度超过风险效应低值，但远小于毒性风险效应中值，因此沉积物中多环芳烃的生态风险较小。然而天目湖表层沉积物中的PAHs的污染程度已超过南水北调东线所经过的南四湖，而且天目湖湖水较深，湖水交换周期比较长，其PAHs污染应引起重视，需制定切实措施保护江苏“最后一泓净水”。     

土壤中可萃取性石油烃的程序升温进样气相色谱法

与恒温进样气相色谱法相比,程序升温进样具有适用范围广、分析速度快、分离度高等优点。应用程序升温进样气相色谱法,建立了以正己烷为溶剂,C₅-C₄₄正构烃混合物为沸点定性校准物质,柴油-润滑油(体积比为1∶1)混合物为定量标准物质,可对污染土壤中C₁₀-C₄₀可萃取性石油烃同时进行定性和定量的分析方法。该方法还可以快速直观地确定出各石油烃组分在土壤中所占的比例。对不同进样方式的测定结果进行比较发现,在使用分流/不分流进样口的不分流模式对馏分油进行检测时,存在分流歧视现象,定量结果偏差最高可达28.6%;而使用程序升温进样口的程序升温不分流模式,不存在分流歧视现象,在测定所含组分沸程较宽、浓度差别较大的馏分油以及污染土壤时,都具有较高的精密度和准确性。     

两种修复模式下CAHs污染地下水的原位对照

为探究氯代脂肪烃（CAHs）污染地下水原位修复的长效性及环境的长期响应，选择华北某废弃化工厂污染区，开展了生物刺激、零价铁（ZVI）-生物刺激耦合中试对照试验，系统对比了2种修复模式下CAHs的降解效率及地下水生物化学参数的动态变化规律.结果表明，修复后长达4~5a内总CAHs含量均降至50 μg/L以下，耦合修复策略提高了CAHs的整体降解效率且未出现浓度反弹，同时可更快速地改善地下环境，为潜在降解菌的生长提供有利条件.两种修复方式对地下水细菌多样性的长期影响基本一致，均有利于向脱硫菌门Desulfobacterota和绿弯菌门Chloroflexi演化.最终生物刺激区总细菌数量高于耦合修复区约1个数量级，但后者地下水中的脱卤球菌属Dehalococcoidia数量（2.1~35）×10³copies/mL反而高于前者（8.3~9.1）×10³copies/mL，这更有利于CAHs的彻底脱氯.     

活动式大罐收气装置及油气混输新工艺的应用

为了解决东营地区油罐每天都向大气排放工业废气，对环境造成污染的问题，研制了“活动式大罐收气装置”新工艺，用于回收联合站储油罐挥发气。该装置通过玻璃钢管线与油罐连接，油罐挥发气沿玻璃钢管线输至机房内气液分离器，分离出气中的水和轻质油，由天然气压缩机加压，经流量计计量后进入油田天然气气管网。该工艺推广后，经监测结果表明，所有采样点总烃含量低于国家标准２．０ｍｇ／ｍ３。目前全油田３０个联合站安装了此设施，每年回收天然气５１２５万ｍ３，轻质油７０００ｔ。