Characterization of a new smog chamber for evaluating SAPRC gas-phase chemical mechanism

A new state-of-the-art indoor smog chamber facility (CAPS-ZJU) has been constructed and characterized at Zhejiang University, which is designed for chemical mechanism evaluation under well-controlled conditions. A series of characterization experiments were performed to validate the well-established experimental protocols, including temperature variation pattern, light spectrum and equivalent intensity (J_NO2), injection and mixing performance, as well as gases and particle wall loss. In addition, based on some characterization experiments, the auxiliary wall mechanism has been setup and examined. Fifty chamber experiments were performed across a broad range of experimental scenarios, and we demonstrated the ability to utilize these chamber data for evaluating SAPRC chemical mechanism. It was found that the SAPRC-11 can well predict the O₃ formation and NO oxidation for almost all propene runs, with 6 hr Δ(O₃ – NO) model error of –3% ± 7%, while the final O₃ was underestimated by ~20% for isoprene experiments. As for toluene and p-xylene experiments, it was confirmed that SAPRC-11 has significant improvement on aromatic chemistry than earlier version of SAPRC-07, although the aromatic decay rate was still underestimated to some extent. The model sensitivity test has been carried out, and the most sensitive parameters identified are the initial concentrations of reactants and the light intensity as well as HONO offgasing rate and O₃ wall loss rate. All of which demonstrated that CAPS-ZJU smog chamber could derive high quality experimental data, and could provide insights on chamber studies and chemical mechanism development.     

Exposure to polycyclic aromatic hydrocarbons and risk for premature ovarian failure and reproductive hormones imbalance

Polycyclic aromatic hydrocarbons (PAHs) are a typical class of persistent organic pollutants that is ubiquitous worldwide. Previous animal studies suggested that PAHs had adverse effects on female reproduction. However, the human data regarding relationship of PAHs exposure with women reproductive health, such as ovarian dysfunction, are scarce. In this case-control study, the associations of serum levels of PAHs with the risk of premature ovarian failure (POF) and reproductive hormones in Chinese women were investigated, with recruiting 157 POF patients and 217 healthy women. The serum levels of 12 types of PAHs, as well as reproductive hormones, including follicle-stimulating hormone, luteinizing hormone and anti-mullerian hormone, were determined. In the logistic regression models, most individual PAH congeners showed significantly positive correlations with the risk of POF (p < 0.05), except for fluorine and pyrene. Benzo(a)pyrene (BaP), as the most carcinogenic PAH congener, was observed to be significantly positively associated with the risk of POF. After adjustment for age, body mass index, educational levels and household income, per one-unit increase in the log-transformed BaP concentration was significantly correlated with 2.191-fold increased risk of POF (OR = 2.191, 95%CI: 1.634–2.938, p < 0.05). To the best of our knowledge, this is the first study to report an association between internal exposure levels of PAHs and the increased risk of POF in women.     

Catalytic ozonation treatment of papermaking wastewater by Ag-doped NiFe2O4: Performance and mechanism

The catalytic ozonation treatment of secondary biochemical effluent for papermaking wastewater by Ag-doped nickel ferrite was investigated. Ag-doped catalysts prepared by sol-gel method were characterized, illustrating that Ag entirely entered the crystalline of NiFe₂O₄ and changed the surface properties. The addition of catalyst enhanced the removal efficiency of chemical oxygen demand and total organic carbon. The results of gas chromatography-mass spectrometer, ultraviolet light absorbance at 254 nm and three-dimensional fluorescence excitation-emission matrix suggested that aromatic compounds were efficiently degraded and toxic substances, such as dibutyl phthalate. In addition, the radical scavenging experiments confirmed the hydroxyl radicals acted as the main reactive oxygen species and the surface properties of catalysts played an important role in the reaction. Overall, this work validated potential applications of Ag-doped NiFe₂O₄ catalyzed ozonation process of biologically recalcitrant wastewater.     

持久性有机污染物(POPs)超临界水修复技术的发展与展望

持久性有机污染物（POPs）具有持久性生物累积性、半挥发性和长距离迁移的性质,广泛位于土壤、废水和污泥中。我国目前面临的POPs污染问题日益严峻。由于超临界水修复技术具有快速、高效、无毒等优点,在POPs修复方面具有较好的应用前景。从超临界水特性、国内外超临界水修复技术等方面系统分析了国内外超临界水修复的研究现状、超临界水修复技术的优缺点和适用性,提出了超临界水修复关键技术及装备系统,以期为其发展和提升提供参考。     

Negative emissions of carbon dioxide through chemical-looping combustion (CLC) and gasification (CLG) using oxygen carriers based on manganese and iron

Carbon capture and storage (CCS) is an economically attractive strategy for avoiding carbon dioxide (CO₂) emissions from, e.g., power plants to the atmosphere. The combination of CCS and biomass combustion would result in a reduction of atmospheric CO₂, or net negative emissions, as plant growth is a form of sequestration of atmospheric carbon. Carbon capture can be achieved in a variety of ways, one of which is chemical looping. Chemical-looping combustion (CLC) and chemical looping gasification (CLG) are two promising technologies for conversion of biomass to heat and power or syngas/methane with carbon capture. There have been significant advances made with respect to CLC in the last two decades for all types of fuel, with much less research on the gasification technology. CLG offers some interesting opportunities for production of biofuels together with carbon capture and may have several advantages with respect to the bench mark indirect gasification process or dual-bed fluidized bed (DFBG) in this respect. In CLG, an oxygen carrier is used as a bed material instead of sand, which is common in indirect gasification, and this could have several advantages: (i) all generated CO₂ is present together with the syngas or methane in the fuel reactor outlet stream, thus in a concentrated stream, viable for separation and capture; (ii) the air reactor (or combustion chamber) should largely be free from trace impurities, thus preventing corrosion and fouling in this reactor; and (iii) the highly oxidizing conditions in the fuel reactor together with solid oxide surfaces should be advantageous with respect to limiting formation of tar species. In this study, two manganese ores and an iron-based waste material, LD slag, were investigated with respect to performance in these chemical-looping technologies. The materials were also impregnated with alkali (K) in order to gauge possible catalytic effects and also to establish a better understanding of the general behavior of oxygen carriers with alkali, an important component in biomass and biomass waste streams and often a precursor for high-temperature corrosion. The viability of the oxygen carriers was investigated using a synthetic biogas in a batch fluidized bed reactor. The conversion of CO, H₂, CH₄, and C₂H₄ was investigated in the temperature interval 800–950 °C. The reactivity, or oxygen transfer rate, was highest for the manganese ores, followed by the LD slag. The conversion of C₂H₄ was generally high but could largely be attributed to thermal decomposition. The K-impregnated samples showed enhanced reactivity during combustion conditions, and the Mangagran-K sample was able to achieve full conversion of benzene. The interaction of the solid material with alkali showed widely different behavior. The two manganese ores retained almost all alkali after redox testing, albeit exhibiting different migration patterns inside the particles. LD slag lost most alkali to the gas phase during testing, although some remained, possibly explaining a small difference in reactivity. In summary, the CLC and CLG processes could clearly be interesting for production of heat, power, or biofuel with negative CO₂ emissions. Manganese ores are most promising from this study, as they could absorb alkali, giving a better conversion and perhaps also inhibiting or limiting corrosion mechanisms in a combustor or gasifier.

     

电源模式对ADC12高硅铝合金微弧氧化膜层组织与性能的影响

目的探究三种电源模式对ADC12高硅铝合金微弧氧化膜层性能的影响,从中选择对其微弧氧化膜层性能较优的电源模式。方法在三种不同电源模式(交流电源、单极性脉冲电源和双极性脉冲电源)的条件下,应用微弧氧化(MAO)技术在ADC12高硅铝合金表面制备了陶瓷膜层,并采用扫描电镜(SEM)、X射线衍射仪(XRD)、显微硬度计、摩擦磨损试验机等手段表征ADC12铝合金微弧氧化膜层的显微组织与性能。结果三种电源模式下微弧氧化膜层中都存在α-Al_2O_3、γ-Al_2O_3和Al9Si等物相;双脉冲模式下制备的微弧氧化膜层的致密性最好,厚度为15μm,硬度达到719 HV,摩擦系数为1.2左右,膜层与基体开始脱落的载荷为25.8 N。交流模式下制备的微弧氧化膜层膜厚较低,厚度为9μm,硬度达到698 HV,摩擦系数为1.35左右,膜层与基体开始脱落的载荷为19.5 N。单极性模式下制备的微弧氧化膜层厚度为17μm,但硬度为706 HV,摩擦系数为1.35左右,膜层与基体开始脱落的载荷为13.09 N。结论通过三种电源模式的比较,ADC12高硅铝合金在双极性脉冲电源模式下制得膜层的综合性能较好。     

基于污染气象条件分级的深圳PM2.5污染回顾评价

提出了一种基于地面自动气象站网观测数据的污染气象条件分级标准,基于这套标准对2012—2019年深圳的PM_2.5污染进行了回顾分析.结果表明,2012—2019年深圳PM_2.5年均浓度总体上呈下降趋势,但2013年相对于2012年,以及2017年相对于2016年出现了反弹.其中,2013年PM_2.5浓度相对于2012年反弹的主要原因是污染排放本身的反弹,而2017年相对于2016年的反弹则更主要是由于不利的污染气象条件天数增加造成的.在2012—2019年期间,深圳的地面污染气象条件总体上呈恶化趋势,出现不利于环境改善的污染气象条件天数总体上呈增加趋势,在这种不利情况下,深圳的PM_2.5浓度仍然保持明显的下降趋势,充分说明了深圳市环保工作的成效.     

基于城市化的浙江省湾区经济带碳排放时空分布特征及影响因素分析

基于STIRPAT扩展模型与2003-2017年浙江省湾区经济带面板数据,分析碳排放时空分布特征并应用时空地理加权回归模型（GTWR）实证考察城市化视角下碳排放的驱动机制及其时空异质性。结果表明：（1）浙江省湾区经济带各地市碳排放规模逐年增加但增幅不大,增速放缓,碳排放量差异明显,碳排放强度逐年下降,空间上呈现自西南向东北逐渐加大的趋势;（2）经济发展水平和对外开放程度是碳排放的主导因素,其他依次为能源消费结构、技术进步和城市化;（3）各影响因素呈现较强的时空异质性,不同时间、地区各驱动要素的波动方向和强度并不相同。在此基础上具体分析各地区碳排放驱动因素影响情况,为实现区域差异化碳减排策略提供指导。