Competing pathways of cresol formation in toluene photooxidation: OH-toluene adducts react with NO2 or with O2?

Methyl-hydroxy-cyclohexadienyl radicals (OTAs) are the key products of the photooxidation of toluene, with implications for the fate of toluene. Hence, we investigated the photooxidation mechanisms and kinetics of three main OTAs (o-OTA, m-OTA, and p-OTA) with NO₂ using quantum chemical calculations as well as the fate of OTAs under the different concentration ratios of NO₂ and O₂. The mechanism results show that the pathway of H-abstraction by NO₂ to anti-HONO (anti-H-abstraction) is more favorable than the syn-H-abstraction pathway, because the strong interaction between OTAs and NO₂ is formed in the transition states of the anti-H-abstraction pathways. The branching ratios of the anti-H-abstraction pathways are more than 99% in the temperature range of 216−298 K. The total rate constant of the OTA-NO₂ reaction is 9.9 × 10⁻¹² cm³/(molecule∙sec) at 298 K, which is contributed about 90% by o-OTA + NO₂, and the main products are o-cresol and anti-HONO. The half-lives of the OTA-NO₂ reaction in some polluted areas of China are 35 times longer than those of the OTA-O₂ reaction. In the atmosphere, the NO₂- and O₂- initiated reactions of OTAs have the same ability to form cresols as [NO₂] is up to 142.1 ppmV, which is impossible to achieve. It implies that under the experimental condition, the [NO₂]/[O₂] should be controlled to be less than 7.8 × 10⁻⁵ to simulate real atmospheric oxidation of toluene. Our results reveal that for the photooxidation of toluene, the yield of cresol is not affected by the concentration of NO₂ under the atmospheric environment.     

Response of PM2.5-bound elemental species to emission variations and associated health risk assessment during the COVID-19 pandemic in a coastal megacity

The coronavirus (COVID-19) pandemic is disrupting the world from many aspects. In this study, the impact of emission variations on PM_2.5-bound elemental species and health risks associated to inhalation exposure has been analyzed based on real-time measurements at a remote coastal site in Shanghai during the pandemic. Most trace elemental species decreased significantly and displayed almost no diel peaks during the lockdown. After the lockdown, they rebounded rapidly, of which V and Ni even exceeded the levels before the lockdown, suggesting the recovery of both inland and shipping activities. Five sources were identified based on receptor modeling. Coal combustion accounted for more than 70% of the measured elemental concentrations before and during the lockdown. Shipping emissions, fugitive/mineral dust, and waste incineration all showed elevated contributions after the lockdown. The total non-carcinogenic risk (HQ) for the target elements exceeded the risk threshold for both children and adults with chloride as the predominant species contributing to HQ. Whereas, the total carcinogenic risk (TR) for adults was above the acceptable level and much higher than that for children. Waste incineration was the largest contributor to HQ, while manufacture processing and coal combustion were the main sources of TR. Lockdown control measures were beneficial for lowering the carcinogenic risk while unexpectedly increased the non-carcinogenic risk. From the perspective of health effects, priorities of control measures should be given to waste incineration, manufacture processing, and coal combustion. A balanced way should be reached between both lowering the levels of air pollutants and their health risks.     

基于海洋生态影响的液化天然气接收站取排水用海研究

天然气作为优质、绿色清洁的能源得到了高度重视,沿海地区陆续建成多座液化天然气（LNG）接收站,接收站取、排水过程的卷载效应和余氯会对周边海洋生态环境产生一定程度的影响。本研究以全国沿海部分地区的8个拟建或在建液化天然气接收站项目为例,对液化天然气接收站的项目规模、取排水量、取排水设施选址、用海规模、冷排水及余氯影响范围等方面进行了分析。研究认为,当前我国液化天然气接收站取、排水用海的管理存在管理制度不健全、技术标准缺失等问题。针对存在的问题,文章从管理、标准、规划等角度提出了进一步加强液化天然气接收站取、排水用海管理的建议。     

基于STIRPAT模型天津减污降碳协同效应多维度分析

基于STIRPAT模型,从排放总量、减排量和协同效应系数这3个维度定量分析了天津市减污降碳协同效应.结果表明,天津市大气污染物和温室气体的主要排放源均为工业源,大气污染物和温室气体的Pearson相关系数为0.984;人口总数、城镇化率、地区生产总值、能源强度和二氧化碳排放强度是影响天津市减污降碳协同效应的重要因素;天津市2011年和2012年大气污染物和温室气体协同增排,协同效应系数分别为0.18和0.17;2013~2014年和2018~2023年大气污染物减排且温室气体增排,协同效应系数均小于0,减污降碳不具有协同效应;2015~2017年和2024~2060年大气污染物和温室气体同时减排,协同效应系数范围为2.74~8.76.天津市具备在2024年进入减污降碳协同增效阶段的条件,天津市推动减污降碳协同增效最关键的是严格控制温室气体排放总量,持续推动能源强度和二氧化碳排放强度的下降,合理控制人口总数、城镇化率和地区生产总值.     

The Stakeholder Preference for Best Management Practices in the Three Gorges Reservoir Region

A qualitative analysis of in-depth interviews with 92 farmers and 42 policy managers in Wuxi County, the Three Gorges Reservoir Region, was conducted to identify stakeholder preferences for alternative best management practices (BMPs) and to determine the factors that affect their acceptance. Policy manager support for most of the practices was relatively stronger than support by farmers, except for the grade stabilization structure (GSS), hillside ditch (HD) and constructed wetland alternative, owing to their perceptions of soil benefits, economic advantages and environmental advantages. Farmers opposed those practices that occupied cultivated lands or changed the conventional planting methods, such as field border, conservation tillage (CT) and contour buffer strips. They tended to accept the BMPs with off-farm pollution reduction, such as GSS, riparian forest buffer and HD, and the BMPs associated with soil benefits, such as nutrient management and Terrace. The result that almost all respondents did not accept CT differed from reports in the existing literature. There is a significant correlation between the acceptance of some BMPs and the townships where the farmers lived (P ≤ 0.05). The environmental conditions and social factors would affect farmer support for BMPs, including local soil conditions, farming methods, economic income, education level and age. The economic advantages of the BMPs were the main motivation for farmers to accept the practices. Furthermore, intensive education efforts, financial incentives or economic subsidies may promote the adoption of the BMPs in our study area.     

游离亚硝酸预处理对剩余污泥电解及微生物群落结构的影响

为打破传统厌氧发酵周期长,有机质利用率低等瓶颈,增强污泥的资源利用和能源回收,探讨了游离亚硝酸（FNA）预处理对剩余污泥电解效果及微生物群落的影响.对比分析了FNA预处理前后剩余污泥在微生物电解池（MEC）中的电流和氢气产生、溶解性有机物和挥发酸的释放和利用及功能菌群的变化情况.结果表明,FNA预处理能有效地促进剩余污泥在MEC系统中的水解和酸化,其溶解性糖类、蛋白和挥发酸的含量远高于未预处理组,进而促进了水解发酵菌、产电菌及反硝化菌的生长和富集,最终挥发酸利用率均在97%以上,表现为电流（1.9mA）和氢气（0.86mL/g VSS）的增强,分别是空白组的3.8倍和5.1倍.     

寡养单胞菌对S2-氧化特性及主要代谢途径

以无机硫（S²）^-为目标污染物,从北京东沙河黑臭水体筛选出一株能够高效氧化S^2-的土著硫氧化菌,并对其进行16S rRNA测序及生理生化特性鉴定,结果表明,该菌株属于寡养单胞菌属（Stenotrophomonas）,命名为Stenotrophomonas sp.sp3.菌株sp3在温度25℃,初始pH值7.0,初始葡萄糖浓度0.25%,初始菌浓度1.00g/L时,菌株sp3对S^2-的氧化率最高.在此适宜条件下,反应60h后,菌株sp3对S^2-的最高氧化率达到86.6%.S^2-的浓度在整个氧化过程中持续下降后保持稳定,在此过程中产生了S⁰,S₂O₃^2-,SO₃^2-以及SO₄^2-这4种其它存在形态的硫.随着S^2-被氧化,SO₄^2-的浓度呈缓慢上升的趋势.利用高通量测序技术推测菌株sp3主要是通过副球菌硫氧化途径（PSO）将非稳定态的S^2-逐步转化为稳定态的SO₄^2-.在此代谢途径中,一部分S^2-被氧化为S⁰,另一部分S^2-则直接氧化为SO₃^2-;S⁰与SO₃^2-可自发反应生成S₂O₃^2-,而S₂O₃^2-发生歧化反应再释放出SO₃^2-和S⁰;反应生成的部分SO₃^2-继续直接氧化为SO₄^2-.菌株sp3在黑臭水体的水质净化过程中有一定的应用前景.     

掺氮碳量子点对光合细菌生长过程的影响

以柠檬酸为碳源、乙二胺为修饰剂,一步水热合成了掺氮碳量子点（N-CQDs）.通过分析光合色素、蛋白质和丙二醛等生理指标,研究了N-CQDs对光合细菌Rhodopseudomonas acidophila生长的影响.结果表明N-CQDs抑制了R.acidophila的生长并呈现浓度-效应关系;光合色素分析表明N-CQDs促使R.acidophila菌体的类胡萝卜素含量提高,菌绿素含量降低;光谱分析表明N-CQDs导致了胞内物质（如光合色素、蛋白质等）的泄漏.N-CQDs较强的光诱导电子转移能力导致R.acidophila培养体系中产生过量自由基,自由基引发一系列脂质过氧化反应,进而导致生物膜的破裂、物质外泄和细菌衰亡.光照下N-CQDs对R.acidophila表现出较高的毒性.研究结果对于认识N-CQDs的光致毒性及其生态环境效应具有一定的参考价值.