Effect of substituents in hydroxyl radical-mediated degradation of azo pyridone dyes: Theoretical approaches on the reaction mechanism

Understanding the degradation behavior of azo dyes in photocatalytic wastewater treatment is of fundamental and practical importance for their application in textile-processing and other coloration industries. In this study, quantum chemistry, as density functional theory, was used to elucidate different degradation pathways of azo pyridone dyes in a hydroxyl radical (HO^?)-initiated photocatalytic system. A series of substituted azo pyridone dyes were synthesized by changing the substituent group in the para position of the benzene moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The effect of dye molecular structure on the photocatalytic degradation reaction mechanism was analyzed and quantification of substituent effects on the thermodynamic and kinetics parameters was performed. Potential energy surface analysis revealed the most susceptible reaction site for the HO^? attack. The calculated reaction barriers are found to be strongly affected by the nature of substituent group with a good correlation using Hammett σ_p constants and experimentally determined reaction rates. The stability of pre-reaction complexes and transition state complexes were analyzed applying the distortion-interaction model. The increased stability of the transition state complexes with the distancing from the substituent group has been established.     

Coupling mechanism of activated carbon mixed with dust for flue gas desulfurization and denitrification

To clarify the effect of coking dust, sintering dust and fly ash on the activity of activated carbon for various industrial flue gas desulfurization and denitrification, the coupling mechanism of the mixed activated carbon and dust was investigated to provide theoretical reference for the stable operation. The results show that coking dust had 34% desulfurization efficiency and 10% denitrification efficiency; correspondingly, sintering dust and fly ash had no obvious desulfurization and denitrification activities. For the mixture of activated carbon and dust, the coking dust reduced the desulfurization and denitrification efficiencies by blocking the pores of activated carbon, and its inhibiting effect on activated carbon was larger than its own desulfurization and denitrification activity. The sintering dust also reduced the desulfurization efficiency on the activated carbon while enhancing the denitrification efficiency. Fly ash blocked the pores of activated carbon and reduced its reaction activity. The reaction activity of coking dust mainly came from the surface functional groups, similar to that of activated carbon. The reaction activity of sintering dust mainly came from the oxidative property of Fe₂O₃, which oxidized NO to NO₂ and promoted the fast selectively catalytic reduction (SCR) of NO to form N₂. Sintering dust was activated by the joint action of activated carbon, and both had a coupling function. Sintering dust enhanced the adsorption and oxidation of NO, and activated carbon further promoted the reduction of NO_x by NH₃; thus, the denitrification efficiency increased by 5%-7% on the activated carbon.     

2019年10~12月京津冀及周边“2+26”城市重污染减排效果评估

为评估京津冀及周边区域重污染过程期间应急减排措施的效果,基于情景模拟的方法,采用NAQPMS模式和多种观测资料,分析了2019年10~12月期间京津冀及周边区域环境空气质量、重污染过程和气象条件概况,评估了模式24、72和144 h的PM_2.5预报效果,并对应急减排措施的效果和不确定性进行了讨论.结果表明,2019年10~12月京津冀及周边"2+26"城市PM_2.5平均浓度64 μg ·m^-3,同比降低了10 μg ·m^-3;区域性重污染过程4次,受影响城市重污染过程期间PM_2.5平均浓度156 μg ·m^-3."2+26"城市PM_2.5气象条件评估指数（EMI）变化值范围为-15.6%~16.8%,EMI显示北京、天津和石家庄等12个城市气象条件与同期相比变差,变差程度范围为3.2%~16.8%.减排情景模拟分析显示应急减排措施有效减少了区域性重污染过程的发生,污染物峰值浓度降幅明显,未出现区域性严重污染过程.典型重污染期间,北京、石家庄、保定和唐山等城市PM_2.5日均浓度削减2%~9%.区域应急减排措施促使"2+26"城市PM_2.5季度均值分别降低1~3 μg ·m^-3左右,区域性减排效果明显.     

北京市气温与黑碳和PM2.5对疾病死亡影响的交互效应

通过收集北京市2010~2016年逐日呼吸和心脑血管疾病死亡数据、污染物（BC、PM_2.5、SO₂、O₃和NO₂）日均浓度资料以及同期的气象资料,采用广义相加模型（GAMs）中的主效应模型、非参数二元响应模型和温度分层模型探讨了北京市气温、PM_2.5和BC单效应,以及气温与PM_2.5和BC交互作用分别对呼吸和心脑血管疾病死亡人数的影响.单效应分析结果表明,气温与两种疾病死亡人数的累计暴露-反应关系均呈“J”型分布特征,最适温度为24℃;累计滞后一天情况下PM_2.5和BC的健康效应均最显著,此时PM_2.5和BC浓度每升高四分位间距（IQR）,呼吸系统疾病死亡人数超额增加百分比（ER）分别为2.21%和1.80%,心脑血管疾病死亡人数ER分别为2.02%和1.48%.交互作用的研究结果表明,高温与高浓度的PM_2.5（或BC）对疾病死亡的影响存在协同效应,且高温条件下BC对疾病死亡影响的健康风险大于PM_2.5,当气温大于24℃时,BC和PM_2.5浓度每升高IQR对应的呼吸系统疾病死亡人数ER分别为6.22%和6.17%,心脑血管疾病死亡人数ER分别为5.01%和3.97%.虽然BC只占PM_2.5的一部分,但BC对人群健康的影响不容忽视,应该引起足够的重视.     

低温等离子体协同催化降解废气污染物的研究进展

阐述了低温等离子体协同催化工艺流程与反应机理,探讨了反应温度、废气进口组分、废气中水蒸气含量、气体流速、气溶胶等因素对降解效果的影响。分析认为:一段式低温等离子体协同催化可改变低温等离子体特征及催化剂催化特性,但尚未解决尾气臭氧逃逸、副产物产生及放电稳定性等问题;两段式低温等离子体协同催化可提高污染物分子降解效率并减少尾气臭氧逃逸,但未能有效利用等离子体的能量,气体中的水蒸气、粉尘及反应过程中产生的气溶胶均能影响后置催化剂的催化性能;两段式低温等离子体协同催化已具备工程应用条件,还需配套高效预处理单元以降低废气中水蒸气、粉尘等对催化剂的影响。     

南海浮游植物对沙尘和灰霾添加的响应

通过2016年5月~6月在南海3个站位开展的船基围隔培养实验,研究了沙尘和灰霾添加对南海浮游植物生长和群落结构变化的影响.结果发现,沙尘和灰霾添加由于提供了N、P等营养盐,整体上促进了浮游植物的生长,且促进程度与添加量密切相关.通过定量计算营养盐指数和叶绿素a累积浓度,发现培养期间叶绿素a累积浓度与沙尘添加浓度呈显著正相关关系（R²=0.87,P<0.01）;低浓度灰霾添加的作用与沙尘添加类似（R²=0.91,P<0.01）,但当灰霾浓度增大时,叶绿素a累积浓度的增加受到一定程度的抑制,这可能与灰霾中含有较高含量的毒性物质有关.各粒级浮游植物叶绿素a浓度的变化表明,沙尘和低浓度灰霾添加使浮游植物优势种群由超微型向小型和微型转变;在高浓度灰霾添加组,由于营养盐与毒性物质的综合作用,浮游植物粒级结构变化不明显.超微型浮游植物细胞丰度测定结果表明,沙尘对聚球藻、原绿球藻和超微型真核浮游植物均表现出促进作用,高浓度灰霾添加能够抑制聚球藻和超微型真核浮游植物的生长.     

大气自净能力指数的气候特征与应用研究

为了定量地评估污染气象条件对空气污染的作用并实现对空气污染潜势的预报,本文在城市大气污染数值预报系统（CAPPS）预报原理的基础上,定义了大气自净能力指数,并分别给出了采用气象站观测资料和通过数值模拟计算大气自净能力指数的方法.基于气象站观测资料的全国大气自净能力指数分析计算表明,全国大气自净能力最差的地区分布在四川盆地和新疆塔里木盆地,大气自净能力最强的地区分布在青藏高原、蒙古高原、云贵高原、以及东北平原和三江平原、山东半岛和海南岛;1961~2017年,京津冀、长三角和珠三角地区的大气自净能力指数呈下降的变化趋势,全年低自净能力日数呈上升的变化趋势.采用大气自净能力指数评估2014年北京APEC会议期间大气污染防控效果,表明在11月8~10日极端不利扩散气象条件发生时,减排措施使北京市空气质量AQI平均降低77%,使京津冀平原地区11个城市的空气质量AQI平均降低37%.基于国家气候中心月动力延伸气候预测模式（DERF2.0）的预报产品和中尺度模式（WRF）,建立了可以预测全国未来40d逐日大气自净能力指数的延伸期-月尺度大气污染潜势预测系统,回报实验表明,在大多数情况下可以提前15d预报出大气重污染过程;月尺度的大气重污染过程预报效果更大程度上取决于月动力延伸气候预测模式（DERF2.0）的预报准确率.     

Ecotoxicity evaluation of Cu- and Fe-CNT complexes based on the activity of bacterial bioluminescence and seed germination

The toxic effects of the composites of Fe~0 and Cu~0 with different percentages of CNTs were examined based on the activity of bacterial bioluminescence and seed germination. In terms of the EC_50 values, the toxic effects of Cu~0 on bacterial bioluminescence and seed germination were approximately 2 and 180 times greater than that of Fe~0, respectively. The toxicity increased with increasing CNT content in the Cu-CNT mixtures for both organisms,whereas opposite results were observed with Fe-CNT mixtures. The mean toxic effects of Cu-CNT(6%) were approximately 1.3–1.4 times greater than that of Cu-CNT(0%), whereas the toxic effects of Fe-CNT(6%) were approximately 2.1–2.5 times lower than that of Fe-CNT(0%) for both the bioluminescence activity and seed germination. The causes of this phenomenon are unclear at this point. More research will be needed to elucidate the mechanism of the toxicity of nano-mixture materials and the causes of the different patterns of toxicity with Cu-and Fe-CNT mixtures.     

密封组合形式对结构密封性能影响研究

目的研究密封组合形式对结构密封性能的影响。方法开展密封性能试验,从密封形式、装配形式和涂覆形式的3种组合形式开展试验研究,找出结构密封性能影响因素,筛选密封最优组合形式。结果结构密封3种组成形式分别为有无贴合面的密封形式,干涉装配、湿装配形式,部分涂覆、全涂覆形式。开展2种应力水平下8种密封组合形式的密封性能试验,在保证密封工艺质量条件下,按照飞机结构和受载特点选取合理密封组合形式能有效提高结构密封性能。结论在飞机应力较高、不常拆的密封部位应选择贴合面密封、干涉装配、部分涂覆的密封组合形式,在飞机结构设计要求间隙装配、常拆卸的密封部位选择贴合面密封、湿装配、部分涂覆的密封组合形式。     

电絮凝净化含聚污水影响因素研究

目的为保障油田正常安全生产,促进油田含聚污水的循环利用。方法采用电絮凝技术单因素研究方法开展净化含聚污水的静态实验研究,探讨外加电流密度、极板间距、初始pH及聚合物浓度等因素对净化效果的影响规律。结果当初始pH为7.0,电流密度为4.0 m A/m2,极板间距为1.0 cm,电解16 min时,综合处理效果最佳。此时,含油量与浊度去除率分别为98.85%,99.93%,处理每克油平均消耗为0.0494 g的Al,处理每立方米含聚污水的能耗为0.2895 k Wh。污水中的聚合物浓度越小,净化效果越好。结论中性处理,极板间距为1.0 cm,外加电流密度为4.0 m A/m2,通电16 min是最佳处理条件。