典型涂料制造企业VOCs排放量核算与排放特征分析

采集了上海地区8家不同类型的涂料制造企业中不同生产环节有组织排放的废气样本,分析其VOCs组分特征和活性VOCs物种,并应用3种实际排放量核算方法计算企业的VOCs年排放量,分析了其与排污许可排放量的关系。结果表明：1)涂料制造行业排放废气的特征组分为芳香烃、OVOCs、卤代烃,占全部VOCs质量浓度的56.2%~99.1%,乙酸乙酯、乙酸丁酯、4-乙基甲苯、间/对二甲苯、甲苯、甲乙酮是涂料制造行业VOCs排放的典型物种;2)基于MIR值法的计算结果,芳香烃和OVOCs是涂料制造行业排放VOCs的主要活性组分,累计OFP贡献率达36.0%~99.8%,其中,4-乙基甲苯(52.1%)、氯乙烯(48.1%)、乙酸丁酯(47.9%)、乙酸乙酯(42.6%)、间/对二甲苯(41.3%)是各类涂料工艺废气中OFP贡献率最高的物质,除苯系物、乙酸酯类化合物外,氯乙烯、甲乙酮、四氢呋喃也是涂料制造过程中值得关注的活性物质;3)涂料制造企业车间的有组织废气VOCs排放量占全厂VOCs排放量的75.0%以上,其次是实验室废气,VOCs排放量为3.5%~16.8%。在VOCs实际排放量核算中,使用实测法的核算结果与物料衡算法接近,且计算简便,在正常运行时均低于许可排放限值;而产污系数法所核算数值较许可排放限值更高,在现阶段可作为一项惩罚性计算方法。     

基于微滤技术供水厂的臭氧预氧化前置工艺中臭氧投加量的优化

通过臭氧预氧化降解水体中溶解性有机物(DOM)对DOM的氧化效果以及微滤(MF)膜污染的缓和效应进行了研究,并分析了臭氧氧化过程中光谱参数变化的规律,进而提出一种通过多目标优化模型确定最佳臭氧投加量的方法。结果表明,臭氧预氧化技术能够将中等分子质量的芳香类DOM转化为低分子质量的有机化合物,对应的UV₂₅₄去除率最高可达90.34%,从而显著改变了MF进水的光谱特性。此外,臭氧预氧化还显著缓解了DOM造成的膜污染,膜污染指数(FI)最多可降低51.49%。根据上述结果可建立多目标优化模型,并用于确定臭氧预氧化-膜过滤工艺最佳臭氧投加量。根据层次分析法,对SUVA₂₅₄、FI和臭氧利用率3个客观指标分配不同的权重,以满足不同饮用水厂的需求。此外,模型分析中可用光谱斜率作为SUVA₂₅₄的替代参数,特别是S_275~295 (R²=0.979 7),用UV₂₅₄作为FI的替代参数(R²=0.879 9),进而简化模型系数的获取。以上研究结果可为水厂在实际应用中优化臭氧投加量、综合提高水处理效果、缓解膜污染并降低运行成本提供参考。     

重庆市夏秋季VOCs对臭氧和二次有机气溶胶生成潜势的估算

为估算重庆市夏秋季VOCs（挥发性有机物）对O₃和SOA（二次有机气溶胶）的生成潜势,利用在线GC-MS/FID在2015年8月22日-9月23日对重庆市区点和郊区点VOCs开展了为期一个月的实时观测,获得市区点和郊区点$ \varphi $（TVOCs）（总挥发性有机物）分别为41.35×10-9和22.72×10-9,其中市区点以烷烃（35.2%）和烯炔烃（25.2%）为主,郊区点以含氧挥发性有机物（oxygenated volatile organic compounds,OVOCs）（30.6%）和烷烃（26.0%）为主.结合最大增量反应活性量化市区点和郊区点VOCs的OFPs（臭氧生成潜势）分别为149.11×10-9和71.09×10-9,市区点OFPs最大的是乙烯、丙烯、甲苯、C8和C9的芳香烃等,郊区点OFPs最大的VOCs是丙烯醛、异戊二烯和甲基乙烯基酮.结合气溶胶生成系数量化郊区点和市区点VOCs对SOA的生成贡献分别为0.36和1.26 μg/m3,相比国内其余城市VOCs的SOAP（二次有机气溶胶生成潜势）较小,主要以甲基环己烷、正壬烷、正葵烷和十一烷等高碳烷烃,以及甲苯、苯、二甲苯和乙苯等芳香烃的SOAP为主.研究显示,控制烯炔烃和芳香烃的浓度有助于控制重庆市O₃的生成,控制高碳烷烃和芳香烃则有助于控制重庆市SOA的生成.      

炼化企业VOCs排放现状及治理对策

简要介绍了挥发性有机物(VOCs)的定义及危害,分析了炼化企业的VOCs排放现状,并简要介绍了VOCs有组织和无组织排放的种类。介绍了中国石化济南分公司延迟焦化装置和柴油加氢装置针对有组织排放和无组织排放开展的各种治理措施及LDAR检测开展情况。     

杭州市典型企业废水中挥发性有机物排放特征及其评价

以10家杭州市典型企业进出口废水为调查对象,用顶空气相色谱质谱法测定77种挥发性有机物(VOCs),分析其排放特征,并对监测结果进行评价.结果表明,进口废水共定量检出22种VOCs,检出质量浓度范围为7~3.39×106μg·L-1;出口废水共定量检出14种VOCs,检出质量浓度范围为16~6.82×104μg·L-1.就行业而言,香精香料制造企业进出口废水VOCs检出的质量浓度最高.以《污水综合排放标准》(GB 8978-1996)三级排放标准为评价标准时,1号企业出口废水检出甲苯质量浓度为2.45×103μg·L-1,超过标准限值.以挥发性有机物的水介质排放环境目标值(DMEG WH)为标准时,3号企业出口废水检出的正丁醇、异丙醇、丙酮质量浓度均超过它们各自的水介质排放环境目标值.     

Influence of dissolved organic matter character on mercury incorporation by planktonic organisms：An experimental study using oligotrophic water from Patagonian lakes

Ligands present in dissolved organic matter （DOM） form complexes with inorganic divalent mercury （Hg^2＋） affecting its bioavailability in pelagic food webs. This investigation addresses the influence of a natural gradient of DOM present in Patagonian lakes on the bioaccumulation of Hg^2＋ （the prevailing mercury species in the water column of these lakes） by the algae Cryptomonas erosa and the zooplankters Brachionus calyciflorus and Boeckella antiqua. Hg^2＋ accumulation was studied through laboratory experiments using natural water of four oligotrophic Patagonian lakes amended with^197Hg^2＋. The bioavailability of Hg^2＋ was affected by the concentration and character of DOM. The entrance of Hg^2＋ into pelagic food webs occurs mostly through passive and active accumulation. The incorporation of Hg^2＋ by Cryptomonas, up to 27% of the Hg^2＋ amended, was found to be rapid and dominated by passive adsorption, and was greatest when low molecular weight compounds with protein-like or small phenolic signatures prevailed in the DOM. Conversely, high molecular weight compounds with a humic or fulvic signature kept Hg^2＋ in the dissolved phase, resulting in the lowest Hg^2＋ accumulation in this algae. In Brachionus and Boeckella the direct incorporation of Hg from the aqueous phase was up to 3% of the Hg^2＋ amended. The dietary incorporation of Hg^2＋ by Boeckella exceeded the direct absorption of this metal in natural water, and was remarkably similar to the Hg^2＋ adsorbed in their prey. Overall, DOM concentration and character affected the adsorption of Hg^2＋ by algae through competitive binding, while the incorporation of Hg^2＋ into the zooplankton was dominated by trophic or dietary transfer.     

Electrochemical and spectroscopic characteristics of dissolved organic matter in a forest soil profile

Dissolved organic matter （DOM） represents one of the most mobile and reactive organic compounds in ecosystem and plays an important role in the fate and transport of soil organic pollutants, nutrient cycling and more importantly global climate change. Electrochemical methods were first employed to evaluate DOM redox properties, and spectroscopic approaches were utilized to obtain information concerning its composition and structure. DOM was extracted from a forest soil profile with five horizons. Differential pulse voltammetry indicated that there were more redox-active moieties in the DOM from upper horizons than in that from lower horizons. Cyclic voltammetry further showed that these moieties were reversible in electron transfer. Chronoamperometry was employed to quantify the electron transfer capacity of DOM, including electron acceptor capacity and electron donor capacity, both of which decreased sharply with increasing depth. FT-IR, UV-Vis and fluorescence spectra results suggested that DOM from the upper horizons was enriched with aromatic and humic structures while that from the lower horizons was rich in aliphatic carbon, which supported the findings obtained by electrochemical approaches. Electrochemical approaches combined with spectroscopic methods were applied to evaluate the characteristics of DOM extracted along a forest soil profile. The electrochemical properties of DOM, which can be rapidly and simply obtained, provide insight into the migration and transformation of DOM along a soil profile and will aid in better understanding of the biogeochemical role of DOM in natural environments.     

不同聚硅酸硫酸铁去除有机物及膜污染的影响

采用腐植酸、苯胺、海藻酸钠、羟丙基甲基纤维4种有机物分别模拟天然有机物中的疏水酸性、疏水碱性、亲水带电性及亲水中性4种有机物,使用"聚硅酸+Fe3+"、"聚硅酸+聚硫酸铁(PFS)"、"聚硅酸+Fe2++H2O2"3种不同聚合方式的聚硅酸硫酸铁(PFSS)进行水处理,并将絮凝处理后的废水上清液通过微滤膜,考察不同聚合方式PFSS对有机物的去除及膜污染的影响。实验结果表明:4种有机物最难去除的是苯胺和海藻酸钠,羟丙基甲基纤维素其次,腐殖酸最易去除;以"聚硅酸+PFS""、聚硅酸+Fe2++H2O2"方式聚合的絮凝剂与"聚硅酸+Fe3+"方式聚合的絮凝剂相比,去除产生可逆污染的腐植酸的比例相差不大,但去除产生不可逆污染加大的苯胺、海藻酸钠、羟丙基甲基纤维素3种有机物的比例明显增大,膜污染率虽然相对稍大,但更加可逆。     

用GC/MS分析火灾后苯板产生固体废物中的有机物

采用GC/MS方法对某苯板厂火灾后产生的固体废弃物进行检测分析.结果表明,在苯板火灾后产生的固体废弃物中检测出61种化合物,其中被美国EPA列入优先污染物的苯系物、萘和蒽等占总有机物12.2％.     

江苏省人为源挥发性有机物排放清单

掌握VOCs排放特征是研究区域大气复合污染特征和控制策略的前提.对江苏省VOCs人为源进行系统分类,收集活动水平数据,应用国内外排放因子研究成果及江苏省行业调研结果,采用排放因子法建立了江苏省2010年分行业、分城市的人为源VOCs排放清单.结果表明:江苏省人为源VOCs排放总量约为179.20×104t,其中化石燃料燃烧源、生物质燃烧源、工业过程源、溶剂使用源、移动源、油品储运源的排放量分别占排放总量的24.1%、3.3%、22.3%、25.3%、18.4%和6.6%,工业过程源中石油炼制、有机化工、医药制造是重点行业,溶剂使用源中机械装备制造、电子设备制造是重点行业.南京、苏州、无锡、常州、南通5个苏南城市VOCs排放量明显高于苏北和苏中地区,占全省总排放量的60.0%,苏州、南京、无锡排放量居前3位.各城市化石燃料燃烧源和移动源排放所占比例均超过10.0%,其他重点行业差异显著,其中南京市为石油炼制、有机化工,苏州市为有机化工、机械涂装,无锡市为有机化工、电子设备制造.