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.     

Remediation of preservative ethylparaben in water using natural sphalerite: Kinetics and mechanisms

As a typical class of emerging organic contaminants(EOCs), the environmental transformation and abatement of preservative parabens have raised certain environmental concerns. However, the remediation of parabens-contaminated water using natural matrixes(such as, naturally abundant minerals) is not reported extensively in literature. In this study, the transformation kinetics and the mechanism of ethylparaben using natural sphalerite(NS) were investigated. The results show that around 63% of ethy...     

Seasonal to sub-seasonal variations of the Asian Tropopause Aerosols Layer affected by the deep convection, surface pollutants and precipitation

The Asian Tropopause Aerosols Layer (ATAL) refers to an accumulation of aerosols in the upper troposphere and lower stratosphere during boreal summer over Asia, which has a fundamental impact on the monsoon system and climate change. In this study, we primarily analyze the seasonal to sub-seasonal variations of the ATAL and the factors potentially influencing those variations based on MERRA2 reanalysis. The ability of the reanalysis to reproduce the ATAL is well validated by CALIPSO observations from May to October 2016. The results reveal that the ATAL has a synchronous spatiotemporal pattern with the development and movement of the Asian Summer Monsoon. Significant enhancement of ATAL intensity is found during the prevailing monsoon period of July–August, with two maxima centered over South Asia and the Arabian Peninsula. Owing to the fluctuations of deep convection, the ATAL shows an episodic variation on a timescale of 7–12 days. Attribution analysis indicates that deep convection dominates the variability of the ATAL with a contribution of 62.7%, followed by a contribution of 36.6% from surface pollutants. The impact of precipitation is limited. The ATAL further shows a clear diurnal variation: the peak of ATAL intensity occurs from 17:30 to 23:30 local time (LT), when the deep convection becomes strongest; the minimum ATAL intensity occurs around 8:30 LT owing to the weakened deep convection and photochemical reactions in clouds. The aerosol components of the ATAL show different spatiotemporal patterns and imply that black carbon and organic carbon come mainly from India, whereas sulfate comes mainly from China during the prevailing monsoon period.     

宁波市地表水重金属时空分布特性和健康风险评价

分别在丰水期和枯水期,从宁波市工业区和商业区地表水中采集了120个水样,检测了6种重金属(Cd、 Cr、 Ni、 Pb、 Zn和Fe)的浓度水平,分析了它们的时空分布特征,计算了重金属间的斯皮尔曼相关系数;结合时空特征和斯皮尔曼相关系数推测了主要污染源;通过计算健康风险指数和致癌风险指数评价了地表水中重金属对暴露人群存在的风险.结果表明,宁波市工业区和商业区不同季节地表水重金属的污染特性有很大的差异.工业区丰水期和枯水期重金属浓度平均值的大小顺序分别为：Fe>Zn>Ni>Pb>Cr>Cd和Fe>Zn>Cr>Ni>Pb>Cd,超标的严重性顺序分别为：Cr>Cd?Pb和Pb>Cr=Cd,含重金属工业废水是工业区地表水重金属的主要污染源之一.商业区丰水期和枯水期重金属浓度平均值的大小顺序分别为：Fe>Pb>Ni>Zn>Cd>Cr和Fe>Pb>Ni>Zn>Cr=Cd,丰水期超标的严重性顺序为：Cd>Pb;枯水期仅有Pb超标,超标率60%,公路源污染物是商业区地表水...     

1961～2015年贵州高原≥10℃积温时空变化特征

为揭示贵州高原≥10℃积温精细动态变化,以81个气象站点1961～2015年气温资料及地理信息数据为数据源,采用积温倾向率、累计距平、滑动T检验、小波分析、多元回归分析等统计方法,分析≥10℃的积温整体变化及周期变化,模拟各年代积温带空间变化。结果表明:(1) 1961～2015年≥10℃积温平均值为5 147. 22℃,1997年前后发生由冷到暖的突变,积温变化主周期约为3～5年,8年;(2) 1961～2015年、1961～1996年、1997～2015年≥10℃积温倾向率均值分别为49. 5℃/10a、-28. 1℃/10a、123. 5℃/10a,1961～1996年表现为降温趋势,1997～2015年表现为升温趋势,三个时间段积温倾向率均未通过显著性检验;(3)多元回归拟合≥10℃积温年代际空间分布,复相关系数均高于0. 92,积温空间分布呈现由西向东、由北向南升高的趋势;(4)不同年代际间积温带动态变化差异较大,1980s后约有60%以上区域表现为积温带Ⅱ升为积温带Ⅲ,积温带Ⅲ升为Ⅳ,1990s后降温区域消失。积温资源的增加对受高原气候限制的贵州高原有重要影响,对调整农业气候区划,确定作物种植区域以及最优化利用热量资源更具有针对性。     

基于卫星遥感的湖南省甲醛时空分布及影响因素分析

利用OMI遥感的甲醛逐日数据、MODIS传感器监测的NDVI数据以及湖南省能源消耗和氮氧化物排放量数据,对2009～2017年湖南省对流层大气中甲醛柱浓度时空变化特征及其影响因素进行了探究。结果表明：湖南省甲醛柱浓度总体空间分布具有西部山区低、北部洞庭湖平原和南部南岭地区高的特征;近九年湖南省甲醛柱浓度时间分布呈先增加后减小的趋势,最高值出现在2012年,最低值出现在2017年;年内甲醛柱浓度值夏季最高,秋季、春季次之,冬季最低,最低值出现在12月,最高值出现于9月;影响因素中地形与风向因素对甲醛柱浓度的空间分布有一定的影响,甲醛柱浓度与温度的相关性较高,降水次之,植被对甲醛的产生有很大的贡献,能源消耗与氮氧化物排放是湖南省甲醛柱浓度变化的重要人为因素。     

大气污染防治综合科学决策支持平台的开发及应用

大气污染防治和环境治理的紧迫性和复杂性需要科学有效的决策,而以费效评估为标志的综合决策评估模型是支撑环境决策和管理的重要工具.当前以ABaCAS（Air Pollution Control Cost-Benefit and Attainment Assessment System,空气污染控制成本效益与达标评估系统）为代表的综合决策评估模型可以实现对特定减排方案的费效评估,然而无法支持开展基于费效的达标路径优化,以及对应不同环境目标下减排策略的优化制定.针对上述问题,建立了大气污染防治综合科学决策支持平台.该平台以ABaCAS的4个核心模块为基础,建立了新的基于环境目标的反算技术（LE-CO）及优化集成运行模式（ABaCAS-OE）,实现了对不同环境目标要求的减排量反算,并对优化的减排策略下的空气质量改善效果、目标可达性、控制成本及健康收益进行快速估算.将大气污染防治综合科学决策支持平台应用到京津冀及周边地区"2+26"城市,反算了2035年达标要求下的减排情景,以及对应减排方案的费用与效益.结果表明,相较于2015年,预测了2035年京津冀及周边地区的PM_2.5、SO₂、NO_x、VOCs、NH₃排放量需分别减排70%~87%、49%~85%、66%~74%、51%~66%、0~40%才可达标,并且该情景可以带来可观的效益,费用-效益比达3.7.未来大气污染防治综合科学决策支持平台的研究将进一步面向多目标、多行业、多组分、多区域的精细化调控技术,实现经济、能源、排放、浓度、成本、健康、生态、气候一体化的综合决策,以全面支撑我国大气污染防治的综合科学决策.      

WLTC循环下汽油车氨排放影响因素分析

为研究WLTC（worldwide light-duty test cycle,全球轻型汽车驾驶循环）循环下常规污染物和行驶工况对汽油车NH₃排放的影响,选定一辆满足国Ⅴ排放标准、配备TWC（three way catalyst,三元催化器）尾气后处理装置的轻型汽油车,测定其在WLTC循环下CO₂、CO、NO_x和NH₃的摩尔排放量.结果表明:CO、NO_x与NH₃排放的线性相关系数分别为0.626和0.321.NH₃高排放的出现除了伴有CO的高排放外,还需车辆具有高速和持续的正向加速度.用配备TWC尾气后处理装置前、后NO_x排放量的差值表示NO_x的转化量发现,NO_x的高转化量并不一定对应NH₃的高排放量,在循环后期大量产生的NO_x会抑制NH₃的排放.由于VSP（vehicle specific power,比功率）能综合反映行驶工况,研究行驶工况对NH₃排放的影响时主要分析VSP与NH₃之间的关系,通过VSP聚类方法将VSP划分为不同区间,得出当VSP Bin（vehicle specific power bin,比功率区间）大于0时,基于CO₂的NH₃排放基本呈随VSP Bin增大而增加的规律,并且基于CO₂的NH₃排放量最大值对应的VSP Bin为持续正向加速工况.研究显示,常规污染物中CO和NO_x对NH₃的排放会产生不同程度的影响,加速度作为行驶工况的表征参数之一会直接或通过影响CO和NO_x的排放间接影响NH₃的生成.      

完全混合式曝气系统运行特性及微生物群落结构解析

利用某污水处理厂完全混合式曝气系统处理生活污水,探讨了系统同步硝化反硝化脱氮过程,解析了系统中污泥微生物群落结构.中试试验结果表明,系统运行稳定,且在无外加碳源的条件下,COD、氨氮和总氮平均去除率分别为93.2%、96.9%和75.2%,出水COD、氨氮和总氮均优于一级A排放标准.系统污泥具有较强的反硝化能力,其脱氮速率是污水处理厂污泥的2.86倍以上.通过对系统污泥周质硝酸盐还原酶聚合酶链式反应(polymerase chain reaction,PCR)扩增和高通量测序结果,发现系统中存在好氧反硝化菌,污泥中优势菌为动胶菌属(Zoogloea)、陶厄氏菌属(Thauera)和Dechloromonas菌属.