Ag/TiO2光电催化降解染料及出水有机质影响机制

本研究以阳极氧化法结合电化学沉积法成功制备的具有高度整齐有序纳米管结构的Ag/TiO₂纳米管阵列（Ag/TNTAs）为阳极,碳/聚四氟乙烯为阴极构建光电催化（PEC）体系.并探究其光电催化降解甲基橙（MO）效能,结果表明,Ag/TNTAs光电催化降解能力（68.2%）远高于光催化（18.9%）、电化学氧化（38.2%）和直接光解;另外在水质净化厂出水有机质（EfOM）参与的光电体系中,当EfOM的初始浓度小于或等于1.0mgC/L时,其对光电催化降解MO起到促进作用,其中当其浓度为0.4mgC/L时促进作用最为明显.而高浓度的EfOM则抑制光电催化活性.此研究表明光电催化体系能高效催化染料降解,且EfOM能在一定阈值范围内促进光电催化降解污染物.     

太原市城区夏季VOCs来源及其对O3生成的贡献

采集太原市城区夏季VOCs样品并分析其浓度特征,使用参数修正法得到VOCs初始浓度,分析其来源及对O₃生成的贡献.结果显示：太原市城区总VOCs平均浓度为48.13 μg/m³,烷烃（25.52 μg/m³）为主要组分.VOCs浓度呈明显日变化特征,在日间（10：00~14：00）光化学产生O₃的关键时段浓度最低.油品挥发、机动车排放、燃煤、植物排放与液化石油气/天燃气（LPG/NG）使用源对修正后环境VOCs的贡献分别为26.89%、25.55%、21.14%、14.99%、11.44%,对O₃生成的贡献分别为21.44%、33.10%、24.07%、13.77%、7.62%.机动车为新鲜排放气团VOCs的重要来源,而油品挥发、燃煤的输送与本地积累是其他（混合、夜间与反应）气团VOCs的重要来源.机动车排放、油品挥发与燃煤为VOCs与O₃生成的重要贡献源,控制此类源排放可减少太原市城区环境VOCs浓度并有效降低O₃生成.     

深圳秋季大气有机气溶胶来源与挥发性研究

使用热扩散管与长飞行时间气溶胶质谱联用系统对2020年深圳市秋季亚微米级气溶胶进行在线测量,获取和分析了气溶胶的化学组成及挥发性特征,并利用正矩阵因子分析法（PMF）对有机气溶胶进行了来源解析.结果显示：观测期间,气溶胶平均质量浓度为（28.3±11.1）μg/m³（9.5~76.8μg/m³）,其中,有机物占比最高,为57.9%,其次为硫酸盐（24.7%）.PMF对有机气溶胶解析结果得到四类源,分别为烃类有机气溶胶（HOA）、餐饮源有关的有机气溶胶（COA）、低氧化性的氧化有机气溶胶（LO-OOA）和高氧化性的氧化有机气溶胶（MO-OOA）.HOA、COA、LO-OOA和MO-OOA平均分别占到总有机物的9.1%、27.2%、31.8%和31.9%.进一步采用NO⁺/NO₂⁺比值法和PMF方法估算有机硝酸酯（ON）浓度,两种方法估算结果相关性良好,ON的平均浓度为0.17~0.25μg/m³,占总有机气溶胶质量的1.5%~9.7%,说明其对深圳大气气溶胶贡献显著.ON与各有机气溶胶因子的相关性比对发现,其与LO-OOA相关性最高（R=0.80）,说明其可能来源于新鲜的二次生成反应.挥发性研究结果得出,深圳市气溶胶主要化学组分挥发性顺序为氯盐≈无机硝酸盐 > 铵盐 > 有机物 > 有机硝酸酯 > 硫酸盐,对于有机气溶胶因子,其挥发性排序为LO-OOA > HOA > COA > MO-OOA,除了LO-OOA,其余因子挥发性与其氧化态排序一致,而LO-OOA从50~70℃组分下降最多,说明其所含组分挥发性差异最为明显.     

Effects of reductive inorganics and NOM on the formation of chlorite in the chlorine dioxide disinfection of drinking water

Chlorine dioxide (ClO₂) disinfection usually does not produce halogenated disinfection by-products, but the formation of the inorganic by-product chlorite (ClO₂^–) is a serious consideration. In this study, the ClO₂^– formation rule in the ClO₂ disinfection of drinking water was investigated in the presence of three representative reductive inorganics and four natural organic matters (NOMs), respectively. Fe²⁺ and S^2– mainly reduced ClO₂ to ClO₂^– at low concentrations. When ClO₂ was consumed, the ClO₂^– would be further reduced by Fe²⁺ and S^2–, leading to the decrease of ClO₂^–. The reaction efficiency of Mn²⁺ with ClO₂ was lower than that of Fe²⁺ and S^2–. It might be the case that MnO₂ generated by the reaction between Mn²⁺ and ClO₂ had adsorption and catalytic oxidation on Mn²⁺. However, Mn²⁺ would not reduce ClO₂^–. Among the four NOMs, humic acid and fulvic acid reacted with ClO₂ actively, followed by bovine serum albumin, while sodium alginate had almost no reaction with ClO₂. The maximum ClO₂^– yields of reductive inorganics (70%) was higher than that of NOM (around 60%). The lower the concentration of reductive substances, the more ClO₂^– could be produced by per unit concentration of reductive substances. The results of the actual water samples showed that both reductive inorganics and NOM played an important role in the formation of ClO₂^– in disinfection.     

Effect of colloid-size copper-based pesticides and wood-preservatives against microbial activities of Gram-positive Bacillus species using five-day biochemical oxygen demand test

Copper-based pesticides and wood preservatives could end up in the environment during production, use, and end-of-life via different pathways that could cause unintended ecological and adverse health effects. This paper provides the effect of colloid-size Cu-based pesticides (CuPRO and Kocide), micronized Cu azole (MCA-1 and MCA-2) and alkaline Cu quaternary (ACQ) treated woods, Cu²⁺, Cu²⁺ spiked untreated wood (UTW), and CuCO₃ solutions against Gram-positive Bacillus species using five-day biochemical oxygen demand (BOD₅) standard test. The total Cu leached from MCA-1, MCA-2, and ACQ in Milli-Q water after 5 days were ~0.1, ~0.11, and ~0.64 g/kg of wood, respectively. However, the form of Cu leached from MCA woods was mostly ionic (> 90%). The total organic carbon (TOC) content of any tested wood (UTW/MCA-1/MCA-2/ACQ) was ~99% of its corresponding total carbon (TC) content, whereas the TOC of any tested wood sawdust exceeded that of its corresponding piece/block by > 300%. The dissolved oxygen (DO) consumption value in the presence of Cu²⁺, CuCO₃, CuPRO, and Kocide solutions was significantly influenced by Cu particles/ions. However, the DO consumption value in the presence of UTW/MCA-1/MCA-2/ACQ woods was significantly influenced by organics leached from woods. On the other hand, the DO consumption of MCA sawdust was greater than (300%) that of MCA pieces/block. The findings of this study provide more insight into how organics leached from woods significantly reduce the toxic effects of Cu ions against Gram-positive Bacillus species.     

A large-scale outdoor atmospheric simulation smog chamber for studying atmospheric photochemical processes: Characterization and preliminary application

Understanding the formation mechanisms of secondary air pollution is very important for the formulation of air pollution control countermeasures in China. Thus, a large-scale outdoor atmospheric simulation smog chamber was constructed at Chinese Research Academy of Environmental Sciences (the CRAES Chamber), which was designed for simulating the atmospheric photochemical processes under the conditions close to the real atmospheric environment. The chamber consisted of a 56-m³ fluorinated ethylene propylene (FEP) Teflon film reactor, an electrically-driven stainless steel alloy shield, an auxiliary system, and multiple detection instrumentations. By performing a series of characterization experiments, we obtained basic parameters of the CRAES chamber, such as the mixing ability, the background reactivity, and the wall loss rates of gaseous compounds (propene, NO, NO₂, ozone) and aerosols (ammonium sulfate). Oxidation experiments were also performed to study the formation of ozone and secondary organic aerosol (SOA), including α-pinene ozonolysis, propene and 1,3,5-trimethylbenzene photooxidation. Temperature and seed effects on the vapor wall loss and SOA yields were obtained in this work: higher temperature and the presence of seed could reduce the vapor wall loss; SOA yield was found to depend inversely on temperature, and the presence of seed could increase SOA yield. The seed was suggested to be used in the chamber to reduce the interaction between the gas phase and chamber walls. The results above showed that the CRAES chamber was reliable and could meet the demands for investigating tropospheric chemistry.     

Application of FeIII-TAML/H2O2 system for treatment of fluoroquinolone antibiotics

Over the recent past, fluoroquinolone antibiotics (FQs) have raised extensive attention due to their potential to induce the formation of resistance genes and “superbugs”, thus various advanced oxidation techniques have been developed to eliminate their release into the environment. In the present study, the prototype tetraamido macrocyclic ligand (Fe^III-TAML)/hydrogen peroxide (H₂O₂) system is employed to degrade FQs (i.e., norfloxacin and ciprofloxacin) over a wide pH range (i.e., pH 6-10), and the reaction rate increases with the increase in pH level. The effect of dosage of Fe^III-TAML and H₂O₂ on the degradation of FQs is evaluated, and the reaction rate is linearly correlated with the added amount of chemicals. Moreover, the impact of natural organic matters (NOM) on the removal of FQs is investigated, and the degradation kinetics show that both NOM type and experimental concentration exhibit negligible influence on the oxidative degradation of selected antibiotics. Based on the results of liquid chromatography-high resolution mass spectrometry and theoretical calculations, the reaction sites and pathways of FQs by Fe^III-TAML/H₂O₂ system are further predicted and elucidated.     

Primary and secondary organic aerosol in an urban/industrial site: Sources, health implications and the role of plastic enriched waste burning

PM10 samples were collected from an urban/industrial site nearby Athens, where uncontrolled burning activities occur. PAHs, monocarboxylic, dicarboxylic, hydroxycarboxylic and aromatic acids, tracers from BVOC oxidation, biomass burning tracers and bisphenol A were determined. PAH, monocarboxylic acids, biomass burning tracers and bisphenol A were increased during autumn/winter, while BSOA tracers, dicarboxylic- and hydroxycarboxylic acids during summer. Regarding aromatic acids, different sources and formation mechanisms were indicated as benzoic, phthalic and trimellitic acids were peaked during summer whereas p-toluic, isophthalic and terephthalic were more abundant during autumn/winter. The Benzo[a]pyrene-equivalent carcinogenic power, carcinogenic and mutagenic activities were calculated showing significant (p < 0.05) increases during the colder months. Palmitic, succinic and malic acids were the most abundant monocarboxylic, dicarboxylic and hydrocarboxylic acids during the entire sampling period. Isoprene oxidation was the most significant contributor to BSOA as the isoprene-SOA compounds were two times more abundant than the pinene-SOA (13.4 ± 12.3 and 6.1 ± 2.9 ng/m³, respectively). Ozone has significant impact on the formation of many studied compounds showing significant correlations with: isoprene-SOA (r = 0.77), hydrocarboxylic acids (r = 0.69), pinene-SOA (r = 0.63),dicarboxylic acids (r = 0.58), and the sum of phthalic, benzoic and trimellitic acids (r = 0.44). PCA demonstrated five factors that could explain sources including plastic enriched waste burning (30.8%), oxidation of unsaturated fatty acids (23.0%), vehicle missions and cooking (9.2%), biomass burning (7.7%) and oxidation of VOCs (5.8%). The results highlight the significant contribution of plastic waste uncontrolled burning to the overall air quality degradation.     

Potential applications of porous organic polymers as adsorbent for the adsorption of volatile organic compounds

Volatile organic compounds (VOCs) with high toxicity and carcinogenicity are emitted from kinds of industries, which endanger human health and the environment. Adsorption is a promising method for the treatment of VOCs due to its low cost and high efficiency. In recent years, activated carbons, zeolites, and mesoporous materials are widely used to remove VOCs because of their high specific surface area and abundant porosity. However, the hydrophilic nature and low desorption rate of those materials limit their commercial application. Furthermore, the adsorption capacities of VOCs still need to be improved. Porous organic polymers (POPs) with extremely high porosity, structural diversity, and hydrophobic have been considered as one of the most promising candidates for VOCs adsorption. This review generalized the superiority of POPs for VOCs adsorption compared to other porous materials and summarized the studies of VOCs adsorption on different types of POPs. Moreover, the mechanism of competitive adsorption between water and VOCs on the POPs was discussed. Finally, a concise outlook for utilizing POPs for VOCs adsorption was discussed, noting areas in which further work is needed to develop the next-generation POPs for practical applications.     

城市污水处理过程中溶解性有机物及荧光物质的变化规律

以锦州市W污水处理厂为研究对象,利用三维荧光光谱分析技术和荧光区域积分(FRI)方法考察了城市污水处理过程中溶解性有机物及荧光物质的去除状况.利用XAD树脂将DOM分为5个部分:疏水性有机酸(HPO-A)、疏水性中性有机物(HPO-N)、过渡亲水性有机酸(TPIA)、过渡亲水性中性有机物(TPI-N)和亲水性有机物(HPI).结果表明,HPO-A和HPI是该污水处理厂进水中的主要DOM组分,并且DOM中的荧光物质主要为类芳香族蛋白质荧光物质和类富里酸荧光物质.在该污水处理厂内,生物降解作用是TPI-A和HPI的主要去除机制,HPO-N和TPI-N主要是由深度处理工艺(絮凝-沉淀-过滤)去除的,生物处理工艺和深度处理工艺对HPO-A的去除能力接近,而生物处理工艺和深度处理工艺对TPI-N的去除效果均较差.生物处理工艺对HPO-A、TPI-A和HPI中的荧光物质有较强的去除能力,而对HPO-N和TPI-N中荧光物质的去除效果较差.深度处理工艺能够有效去除HPO-A和HPO-N中的荧光物质,而对TPI-A、TPI-N和HPI中的荧光物质无明显去除作用.