兰州市典型企业VOCs排放特征及反应活性分析

基于兰州市大气VOCs排放清单,选取石化厂、乙烯厂、涂料厂3个典型企业采集VOCs样品,分析其无组织排放特征,并采用MIR（最大增量反应活性）法和LOH（·OH反应速率）法综合评价其化学反应活性,识别各企业的VOCs活性优势物种,同时探究不同企业特征VOCs比值.结果表明:不同排放源φ（VOCs）差异较大,范围为20.8×10-9~6 520.3×10-9.从VOCs物种构成上来看,涂料厂芳香烃占比最高,而石化厂、乙烯厂均以烷烃物种最为丰富,石化厂不同工艺VOCs物种构成略有差异.从活性上看,涂料厂VOCs活性最高,其LOH和OFP（臭氧生成潜势）分别为2 676.9 s-1和72 519.0×10-9,约为其他行业的18~1 000倍,间/对-二甲苯、乙苯、邻二甲苯等物种活性较大;其次为石化厂,其LOH和OFP分别为273.2 s-1和4 039.1×10-9,正戊烷、异戊烷、乙烯、丙烯等物种活性贡献率高,其中柴油工艺对石化厂VOCs活性贡献率最大;乙烯厂的OFP最低,其LOH和OFP分别为4.6 s-1和69.7×10-9,其VOCs活性主要来自乙烯、丙烯、正丁烯等烯烃物种.各工业源BTEX（苯、甲苯、乙苯及3种二甲苯异构体的合称）分布具有一定的差异,对于指示不同VOCs来源有一定的参考价值,但不同源比值的重叠性也表明并非全部VOCs来源可以通过特征物种比值来区分.研究显示,控制工业源特别是涂料与石化工业VOCs的排放有助于控制兰州市O₃的生成.      

Enzyme-electrolytic degradation of dichloromethane: Efficiency, kinetics and mechanism

Enzymatic electrolysis cell(EEC) has advantages over microbial electrolysis cell(MEC) due to the needless of microbe inoculation and high-efficiency of enzymatic reaction. In this study, an EEC was first applied to achieve the effective degradation of halogenated organic pollutants and dichloromethane(CH_2Cl_2) was utilized as a model pollutant. The results indicate that the degradation efficiency of CH_2Cl_2 after 2 hr reaction in the EEC was almost100%, which was significantly higher than that with enzyme(51.1%) or current(19.0%). The current induced the continuous regeneration of reduced glutathione(GSH), thus CH_2Cl_2 was degraded under the catalysis of GSH-dependent dehalogenase through stepwise dechlorination, and successively formed monochloromethane(CH_3Cl) and methane(CH_4). The kinetic result shows that with a current of 15 mA, the maximum specific degradation rate of CH_2Cl_2(3.77 × 10~(-3) hr~(-1)) was increased by 5.7 times. The optimum condition for CH_2Cl_2 dechlorination was also obtained with pH, current and temperature of 7.0, 15 mA and 35°C,respectively. Importantly, this study helps to understand the behavior of enzymes and the fate of halogenated organic pollutants with EEC, providing a possible treatment technology for halogenated organic pollutants.     

One-step synthesis of Cu(II) metal–organic gel as recyclable material for rapid, efficient and size selective cationic dyes adsorption

Efficient removal of non-biodegradable and hazardous dyes from wastewater remains a hot research topic. Herein, a rationally designed a Cu(Ⅱ)-based metal–organic gel(Cu-MOG) with a nanoporous 3 D network structure prepared via a simple one-step mixing method was successfully employed for the removal of cationic dyes. The Cu-MOG exhibited high efficiency, with an adsorption capacity of up to 650.32 mg/g, and rapid adsorption efficiency, with the ability to adsorb 80% of Neutral Red within 1 min. The high adsorption efficiency was attributed to its large specific surface area, which enabled it to massively bind cationic dyes through electrostatic interaction, and a nanoporous structure that promoted intra-pore diffusion. Remarkably, the Cu-MOG displayed size-selective adsorption, based on adsorption studies concerning dyes of different sizes as calculated by density functional theory. Additionally, the adsorption performance of the Cu-MOG still maintained removal efficiency of 100% after three regeneration cycles. These results suggested that the Cu-MOG could be expected to be a promising and competitive candidate to conveniently process wastewater.     

Highly catalytic activity of Mn/SBA-15 catalysts for toluene combustion improved by adjusting the morphology of supports

Rod-like, hexagonal and fiber-like SBA-15 mesoporous silicas were synthesized to support MnO_x for toluene oxidation. This study showed that the morphology of the supports greatly influenced the catalytic activity in toluene oxidation. MnO_x supported on rod-like SBA-15(R-SBA-15) displayed the best catalytic activity and the conversion at 230°C reached more than 90%, which was higher than the other two catalysts. MnO_x species consisted of coexisting MnO_2 and Mn_2O_3 on the three kinds of SBA-15 samples. Large amounts of Mn_2O_3 species were formed on the surface and high oxygen mobility was obtained on MnO_x supported on R-SBA-15, according to the H_2 temperature programmed reduction(H_2-TPR)and X-ray photoelectron spectroscopy(XPS) results. The Mn/R-SBA-15 catalyst with greater amounts of Mn_2O_3 species possessed a large amount of surface lattice oxygen, which accelerated the catalytic reaction rate. Therefore, the surface lattice oxygen and high oxygen mobility were critical factors on the catalytic activity of the Mn/R-SBA-15 catalyst.     

Ag/P-g-C3N4复合材料可见光催化降解双酚AF的机理研究

利用简单的热聚合及原位沉淀法制备了一系列不同质量比(1%～10%)的Ag/P-g-C_3N_4复合材料,采用XRD、SEM、TEM、UV-Vis DRS、FTIR、BET和XPS等表征手段对复合材料的形貌结构、光学特性和化学组成进行了表征.利用合成材料光催化降解双酚AF(BPAF),研究了溶液初始pH、溶解性有机质(DOM)对BPAF降解的影响,并对光催化降解机理进行了探讨.结果表明,在pH=7时,5%Ag/P-g-C_3N_4表现出最强的光催化性能,其在90 min内对BPAF的降解率达到100%.DOM在低浓度(0.5 mg·L~(-1))时促进了BPAF的光降解,而在高浓度时(2～10 mg·L~(-1))抑制了BPAF的光降解.活性基团捕获实验结果表明,在Ag/P-g-C_3N_4降解BPAF过程中,h~+和·OH起主要的作用,直接参与了BPAF的降解.相对于P-g-C_3N_4,Ag/P-g-C_3N_4光催化性能的增强主要是因为Ag的负载促进了e~-和h~+的分离,同时Ag单质的SPR效应提高了复合材料对可见光的吸收率,延长了光生载流子的寿命.     

不同类型城市人工湿地水体汞的分布特征

为了解城市人工湿地水体中汞的时空分布及甲基化特征,以便探究其潜在的汞暴露生态风险,在重庆市选择4个不同类型的人工湿地,于2017年3月～2018年3月,按季度采集垂直剖面水样,分析总汞(THg)和甲基汞(MeHg)的分布.结果表明:城市人工湿地由于景观布局、功能设置不同,其汞分布特征有一定差异. 4个湿地水体THg均高于背景水域,但远低于有污染历史的水体;湿地中部水体THg均略高于进、出水口,表明城市湿地对水体THg有截留作用.除彩云湖湿地出水口MeHg浓度高于入水口外,其余3个湿地出水口MeHg均低于入水口;湿地中水体MeHg呈随水深增加而升高的趋势,且MeHg占THg的比例(MeHg/THg)均高于其他水域,说明城市湿地具有净汞甲基化的作用. 4个城市湿地水体THg春秋两季高,夏季略有降低,冬季最低;水体MeHg冬季最低,而其他三季差异不大但远高于冬季,约为冬季的3倍.本研究明晰了城市湿地中汞的时空分布和甲基化规律,探究了人类活动对湿地的干扰程度和湿地的响应特征以及湿地汞对下游流域的影响,从控制潜在汞暴露风险的角度,为人工湿地建设提供建议.     

中国水土资源本底匹配状况研究

论文以中国水资源二级区为基本单元,利用单位面积水资源量法和基尼系数法,以二级区水资源总量和潜在可开垦耕地面积为数据基础,评价中国水土资源本底匹配状况,为中国水土资源优化配置提供科学依据。首先根据适宜农作物耕种的高程、坡度和土壤类型条件,得到中国潜在可开垦耕地分布;然后,计算单位潜在可开垦耕地面积水资源量,评价中国水土资源本底匹配分布状况;最后,绘制水土资源洛伦兹曲线,计算基尼系数,对中国水土资源本底匹配总体状况进行评价。研究结果表明： 1）中国北部区域潜在可开垦耕地较多,西南部和南部沿海区域分布较少,未来具有较大耕地开发潜力的区域主要分布在北方; 2）中国本底水资源和潜在可开垦耕地资源空间分布存在严重错位; 3）较之已有研究成果中依据水资源量和耕地面积计算的基尼系数0.566,论文以本底水资源和潜在耕地为基础数据计算的基尼系数0.712要大很多,表征中国本底水土资源不匹配程度要严重得多,中国80%的水资源服务不到23%的潜在可开垦耕地。     

基于CSGD的排放清单处理工具研究

CSGD（crowd sourcing geographic data,众源地理数据）是通过互联网向大众或相关机构提供的一种开放地理空间数据,具有易获取、时效性好、准确性高等特点,在排放清单时空分配方面具有应用潜力.然而,现有排放清单处理工具不支持CSGD数据直接输入且难以满足排放清单空间分配和空气质量模式所需清单格式,因此,亟待开发一套可以拓展该类数据在排放清单领域应用的工具.以CSGD中的POI（城市设施兴趣点）数据为主要研究对象,基于QGIS平台、C++语言及Python语言,开发了在Windows系统下的ISAT（inventory spatial allocate tool,排放清单空间分配工具）工具及在Windows或Linux系统下的ISAT.M工具.结果表明:ISAT工具以POI数据为基础制作出的空间分配结果与排放源排放强度的空间分布特征的一致性较好;ISAT.M工具输出的inline清单可以作为CMAQ空气质量模式及其DDM敏感性分析模块的输入文件并开展模拟,通过与SMOKE模型的关闭源法模拟结果对比发现,二者在数据及空间分布上呈较好的一致性.研究显示,CSGD数据应用于排放清单空间分配可较好地反映排放源空间分布特征,同时由于此类数据存在信息冗杂、近郊区数据缺失等问题,在应用过程中应注意数据清洗及数据种类的选取工作.      

石家庄某制药企业污水处理过程中NH3排放研究

为了解污水处理过程中各处理单元NH₃的排放特征,采集石家庄某制药企业各污水处理单元以及经过废气治理后排放的样品,计算各采样点NH₃浓度及排放量。结果表明:各污水处理单元中,水解酸化池NH₃浓度和单位体积污水NH₃排放量均为最高,分别为62.89和3 360 mg∕m ³。各污水处理单元NH₃总排放量为0.97 kg∕h,单位体积污水NH₃排放量为9 312 mg∕m ³;经废气治理后,排入环境的NH₃为0.25 kg∕h,单位体积污水NH₃排放量为2 400 mg∕m ³,去除率为74.2%,经治理后NH₃排放量明显降低。南区、北区废气治理采用碱洗+氧化+水洗工艺,NH₃去除率分别为93.3%和83.1%;生物区废气治理采用生物滴滤床工艺,NH₃去除率为39.1%,碱洗+氧化+水洗工艺对NH₃的去除效果好于生物滴滤床工艺。     

酰胺基两性分子对二硫化钨吸附铀容量的影响机制

含铀废水中铀的回收主要是基于材料与[UO₂(H₂O)₅]²⁺中UO₂ ²⁺之间的络合,但H₂O的电偶极矩对络合有显著弱化作用。采用酰胺基两性分子N,N-二甲基-9-癸烯酰胺（NADA）氢键作用与[UO₂(H₂O)₅]²⁺形成UO₂[(H₂O)_xC₁₂H₂₃NO]_n ^*（x<5,UO₂-Coordination Compound,简称UO₂-CC）,选取惰性物质WS₂为吸附材料,通过静态吸附试验（不同pH、接触时间、浓度和温度）分别研究其对UO₂ ²⁺和UO₂-CC的吸附量。动力学拟合结果表明,二者的吸附反应是化学吸附过程,UO₂ ²⁺经NADA重构后,吸附时间从240 min缩短至180 min,准二级动力学吸附常数提高1.35倍。等温吸附研究结果表明,WS₂与UO₂-CC络合过程符合Langmuir吸附等温模型,且NADA的加入使吸附由自发吸热过程转变为自发放热过程,吸附反应过程有序度增加。NADA原位重构[UO₂(H₂O)₅]²⁺后,WS₂对UO₂ ²⁺的平衡吸附量由45.03 mg/g（WS₂/UO₂ ²⁺体系）提高到122.14 mg/g（WS₂/UO₂-CC体系）。采用光谱分析（X射线光电子能谱法）从分子水平深入研究NADA原位重构[UO₂(H₂O)₅]²⁺后在WS₂上的吸附机制,揭示静电、氢键和U—S共价键等作用力对吸附的贡献,特别是NADA的氢键作用。