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.     

Adsorption mechanisms of PFOA onto activated carbon anchored with quaternary ammonium/epoxide-forming compounds: A combination of experiment and model studies

When wood-based activated carbon was tailored with quaternary ammonium/epoxide (QAE) forming compounds (QAE-AC), this tailoring dramatically improved the carbon's effectiveness for removing perfluorooctanoic acid (PFOA) from groundwater. With favorable tailoring, QAE-AC removed PFOA from groundwater for 118,000 bed volumes before half-breakthrough in rapid small scale column tests, while the influent PFOA concentration was 200 ng/L. The tailoring involved pre-dosing QAE at an array of proportions onto this carbon, and then monitoring bed life for PFOA removal. When pre-dosing with 1 mL QAE, this PFOA bed life reached an interim peak, whereas bed life was less following 3 mL QAE pre-dosing, then PFOA bed life exhibited a steady rise for yet subsequently higher QAE pre-dosing levels. Large-scale atomistic modelling was used herein to provide new insight into the mechanism of PFOA removal by QAE-AC. Based on experimental results and modelling, the authors perceived that the QAE's epoxide functionalities cross-linked with phenolics that were present along the activated carbon's graphene edge sites, in a manner that created mesopores within macroporous regions or created micropores within mesopores regions. Also, the QAE could react with hydroxyls outside of these pore, including the hydroxyls of both graphene edge sites and other QAE molecules. This latter reaction formed new pore-like structures that were external to the activated carbon grains. Adsorption of PFOA could occur via either charge balance between negatively charged PFOA with positively charged QAE, or by van der Waals forces between PFOA's fluoro-carbon tail and the graphene or QAE carbon surfaces.     

天然沸石合成A型分子筛的吸附与再生特性

针对污水厂尾水深度脱氮问题,以某地产天然沸石为原料,采用水热合成法制备了纯度较高、晶型规整、大小均一、吸附量大的A型分子筛.系统考察了其对氨氮的吸附及再生特性,并结合Zeta电位、FTIR以及XRD对其氨氮吸附与再生机理进行了分析.结果表明：准一级和准二级反应动力学均能较好地反映A型分子筛吸附氨氮过程,等温吸附过程符合Langmuir等温吸附模型,对氨氮的最大饱和吸附量为41.68mg/g;吸附饱和的分子筛再生利用方法简便易行,经2mol/L NaCl溶液解吸后能够恢复其吸附能力,5次吸附-解吸再生率均在95%以上;其吸附与再生过程均为Na⁺与NH₄⁺的离子交换反应,吸附与再生互为可逆过程.该方法为污水厂深度脱氮提供了一条经济可行的新思路.     

炭基-Co3O4复合材料活化过一硫酸盐降解阿特拉津

利用水热浸渍法制备了生物炭基-Co₃O₄复合材料（Co-OB）,采用扫描电子显微镜（SEM）、X射线衍射仪（XRD）、傅里叶变换衰减全反射红外光谱仪（ATR-IR）等手段对Co-OB进行表征,并研究了其活化过一硫酸盐（PMS）降解阿特拉津（ATZ）的性能,探究了PMS投加量、腐殖酸（HA）和Cl^-对ATZ降解的影响.结果表明,在Co-OB活化投加量0.025g/L,PMS浓度200μmol/L,ATZ浓度20μmol/L,室温条件下10min内ATZ的去除率为86.3%,与生物炭（OB）和Co₃O₄相比,其去除率为后两者之和的2.2倍.随着PMS浓度增加,ATZ去除率显著提高.Cl^-、HA的存在抑制了ATZ的降解,且随Cl^-、HA浓度增加,抑制程度增大.自由基猝灭实验表明·OH和SO₄·^-是ATZ降解的主要活性物种.通过液相色谱-质谱联用仪（LC-MS）分析出6种中间产物,并推测出ATZ的降解途径.稳定性实验表明Co-OB具有重复使用性及低Co²⁺溶出.     

重轨钢腐蚀的研究进展

钢轨的腐蚀关乎铁路运营效益和运输系统的安全等重大问题,重轨钢的耐腐蚀性同强度、硬度、耐磨性一样重要,应高度重视对重轨钢耐腐蚀性能的研究。介绍了国内外重轨钢的研究,主要概述在重轨钢加入Cr、Nb、Cu、Si、Mn、Ti、Al、Cr或Ni等不同合金元素,对重轨钢耐腐蚀性能的影响。介绍不同组织(珠光体、贝氏体、马氏体、奥氏体)的重轨钢,以及这些组织对重轨钢耐腐蚀性能的影响,并说明了不同的热处理或加工工艺对重轨钢耐腐蚀性能好坏的影响。最后结合重轨钢腐蚀机理、锈层形成机理和电化学过程以及影响金属大气环境腐蚀的主要因素,提出了几点提高重轨钢耐腐蚀性的研究方向。     

生物炭纳米复合材料去除环境中有机污染物研究进展

近年来,生物炭在环境修复、固碳、土壤改良等方面的得到广泛应用,与纳米材料联合制备的新型生物炭纳米复合材料使原生生物炭的比表面积、孔隙结构、官能团、催化降解能力等方面都有了较大改善,具有更好的可持续性和高效性,对环境中有机污染物具有良好的去除能力。本文介绍了生物炭纳米复合材料的不同制备工艺,重点阐述了生物炭纳米复合材料对不同环境介质中有机污染物的去除机理及应用,为后续生物炭纳米复合材料在环境修复应用的工程化和商业化提供理论依据和技术参考。     

水生植物对淡水生态系统温室气体排放的影响研究进展

淡水生态系统温室气体(CO_2、CH_4、N_2O)排放是全球气候变化背景下的研究热点。水生植物作为淡水生态系统重要的组成部分,对水体生源要素的生物地球化学循环过程具有重要影响,进而影响水体温室气体产生与排放。本研究基于目前水生植物与水体温室气体排放关系的研究,探讨了水生植物对淡水生态系统温室气体排放动力学过程的影响,提出水生植物分布区可能是温室气体排放热点;水生植物种类、生活型的多样性增加了水体温室气体排放的变异性和不确定性,对监测和估算方法的准确性产生一定影响;进一步总结了水生植物对淡水生态系统温室气体排放的影响机制:1)机械作用,包括气体传输通道作用和浮叶植物的滞留作用; 2)水生植物光合/呼吸作用参与水体碳循环,同时水生植物凋落物分解为水体代谢提供新鲜碳、氮源,提高温室气体产生速率; 3)改变根际厌氧环境,影响根际CH_4和N_2O产生与排放; 4)水生植物群落改变水体生态因子分配格局,影响水体异养代谢等。基于当前研究现状,本文提出要进一步开展不同尺度或不同生境条件下水生植物种类、生活型和生长代谢等对水体温室气体排放动力学的影响研究,并从水生植物群落尺度构建温室气体排放动力学模型,优化监测方法与估算模型,为推进我国淡水生态系统温室气体排放研究提供理论基础。     

MnO_2基材料常温催化降解甲醛研究进展

甲醛(HCHO)是室内空气中的主要污染物之一,已被世界卫生组织确定为致癌和致畸形物质,对人体健康构成了极大威胁。常温催化技术在室温下即可将甲醛降解为无毒无害的CO_2和H2O,能耗低,具有较好的应用前景。二氧化锰(MnO_2)具有价格低廉、环境友好等优势,且晶型种类多,表现出优异的甲醛催化性能,具有较大的实际应用价值而被广泛研究。本文综述了MnO_2基催化剂,包括离子掺杂MnO_2、MnO_2固溶体和负载型MnO_2的甲醛催化活性及其制备方法,并探讨了其活性影响因素、常温催化反应机理,分析了其研究现状及发展趋势。     

氧化环境中FeS修复重金属的稳定性变化与机制

硫化亚铁(FeS)是良好的重金属修复剂,但它对氧化环境敏感.当环境氧气浓度升高时,FeS对重金属的固定效果可能发生改变.本研究考察了氧化环境中FeS与重铬酸根、铅和镉离子的反应规律和结合机制变化.结果表明,环境氧气浓度升高可促进Fe~(2+)的释放,且增加FeS表面S(-II)氧化态的比例(与Pb~(2+)反应:从24%增加到44%,与Cd~(2+)反应:从60%增加到78%).延长反应时间至30 d,虽然PbS和CdS结晶度提高,但两者表面出现Pb—O和Cd—O氧化形态,预示着重金属再释放的风险.有氧干燥条件下FeS表面矿物相转变为纤铁矿,对Cr(VI)的还原能力大幅下降.与未干燥FeS(FeS-Cr-3h)相比,当有氧干燥的FeS与Cr(VI)反应时,总铬的去除量下降约96%(由约100 mg·g~(-1)降至(3.74±1.12) mg·g~(-1)),Cr(VI)去除量下降约57%(由约100 mg·g~(-1)降至(43.28±0.46) mg·g~(-1)).FeS及重金属硫化物的氧化显然不利于重金属的长期稳定.如何延缓或抑制FeS与重金属硫化物的氧化因此成为未来研究需回答的问题.     

乙醇型发酵过程优化及代谢调控分子机制

乙醇型发酵是3种主要厌氧产酸发酵类型之一.乙醇型发酵细菌具有高产氢效率、耐酸性、自凝集生长和发酵产物可直接被产甲烷利用等优势,因此被广泛关注和研究.近年来,在乙醇型发酵产氢过程优化和代谢途径研究方面取得了大量进展.本文对乙醇型发酵产氢反应器优化和运行控制、高效产氢细菌分离和代谢调控分子机制,以及耦合系统强化能源回收等研究进展进行了综述.此外,本文提出了乙醇型发酵的可持续高效产氢及代谢产物的定向回收梯级利用的思路,探讨了乙醇型发酵制氢技术的发展趋势和未来应用中存在的问题.