UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl^? and PO₄^3? of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min^?1 (R²=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO? and H₂O and the oxidation reaction with H₂O₂ were found during the degradation pathway of 5 mg/L TCEP in the UV/H₂O₂ system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H₂O₂ system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.     

Ozone pollution characteristics and sensitivity analysis using an observation-based model in Nanjing, Yangtze River Delta Region of China

Ground-level ozone (O₃) has become a critical pollutant impeding air quality improvement in Yangtze River Delta region of China. In this study, we present O₃ pollution characteristics based on one-year online measurements during 2016 at an urban site in Nanjing, Jiangsu Province. Then, the sensitivity of O₃ to its precursors during 2 O₃ pollution episodes in August was analyzed using a box model based on observation (OBM). The relative incremental reactivity (RIR) of hydrocarbons was larger than other precursors, suggesting that hydrocarbons played the dominant role in O₃ formation. The RIR values for NO_X ranged from –0.41%/% to 0.19%/%. The O₃ sensitivity was also analyzed based on relationship of simulated O₃ production rates with reductions of VOC and NO_X derived from scenario analyses. Simulation results illustrate that O₃ formation was between VOCs-limited and transition regime. Xylenes and light alkenes were found to be key species in O₃ formation according to RIR values, and their sources were determined using the Positive Matrix Factorization (PMF) model. Paints and solvent use was the largest contributor to xylenes (54%), while petrochemical industry was the most important source to propene (82%). Discussions on VOCs and NO_X reduction schemes suggest that the 5% O₃ control goal can be achieved by reducing VOCs by 20%. To obtain 10% O₃ control goal, VOCs need to be reduced by 30% with VOCs/NO_X larger than 3:1.     

Chemical characteristics of road dust PM2.5 fraction in oasis cities at the margin of Tarim Basin

In order to understand the compositions characteristics of particulate matter with aerodynamic diameter less than 2.5 μm (PM_2.5) fraction in road dust (RD_2.5) of oasis cities on the edge of Tarim Basin, 30 road dust (RD) samples were collected in Kashi, Cele, and Yutian in the spring, 2018, and RD_2.5 was collected using the resuspension approach. Eight water-soluble ions, 39 trace elements and 8 fractions of carbon-containing species in PM_2.5 were analyzed. Ca²⁺ and Ca were the most abundant ions and elements in RD_2.5 (7.1% and 9.5%). Cl^- in RD_2.5 was affected not only by attributed to saline-alkali soils in oasis cities of the Tarim Basin and dust from Taklimakan Desert but also by human activities. Moreover, the organic carbon/elemental carbon (OC/EC) ratio indicated that carbon components in RD_2.5 in Cele town mainly come from fossil fuel combustion, while those in Yutian and Kashi mainly come from biomass combustion. It is noteworthy that high Ca in RD_2.5 was seriously affected by anthropogenic emissions, and high Na and K contents in RD_2.5 could be derived from soil and desert dust. It was estimated that Cd, Tl, Sn and Cr were emitted from anthropogenic emissions using the enrichment factor. The coefficients of divergence (COD) result indicated that the influence of local emission on road dust emission is greater than that of long-distance transmission. This study is the first time to comprehensively analyze the chemical characteristics of road dust in oasis cities, and the results provides the sources of road dust at the margin of Tarim Basin.     

长沙市近郊莲花镇土壤重金属生态风险评价

选择长沙市近郊的莲花镇作为研究对象,采集了镇域范围内54个土壤样品,运用综合的生态风险评价方法对Hg、Cd、As、Pb、Cr 5种土壤重金属元素污染程度及对人体的健康危害程度进行评价。结果表明:1)5种重金属元素的污染程度排序为Cd > Hg > Pb > As > Cr,Cd呈现重度污染;Cd和Pb空间变异显著,其来源受人为干扰程度高。2)5种重金属元素的潜在生态危害排序为Cd > Hg > As > Pb > Cr,Cd和Hg处于强生态危害程度,是研究区域土壤重金属污染的主要因子;研究区域综合潜在生态风险达到强生态危害等级。3)"手-口"摄入是土壤重金属暴露的主要途径,儿童的非致癌暴露剂量远大于成人。5种重金属对儿童和成人所产生的非致癌风险商和非致癌风险指数均<1,不存在非致癌健康风险。4)Cr的致癌风险指数>10-4,具有极高的致癌风险;Cd和As的致癌风险指数为10-6~10-4,处于可以接受的风险范围。Cr、As的污染有不断加剧的趋势,成为影响人体健康的主要因子,应引起关注。     

大气沉降向华中丘陵区稻田输入硫通量的观测

选取我国华中丘陵区的湖南省长沙县一个典型水稻种植区,对2015与2016年2年雨水样中的SO₄²-S和大气SO₂的沉降量进行监测,分析雨水中SO₄^2-、NO₃^-的关系,解析大气硫沉降的主要来源.结果表明,研究区大气中SO₂-S和雨水中SO₄^2--S的年均浓度分别为8.5 μg/m³和1.1mg/L,大气硫沉降年均总量为26.8kgS/（hm²·a）,其中年均降雨混合沉降量18.2kgS/（hm²·a）,年均干沉降量为8.6kgS/（hm²·a）.研究区域硫素干、混合沉降量存在明显的季节差异,硫素混合沉降春季高于夏、秋、冬季,而硫素干沉降冬季高于春、夏、秋季.雨水中NO₃^-/SO₄^2-的质量比大多小于1,表明研究区大气硫素主要来自固定污染源（燃煤）.华中丘陵区稻田具有较高的硫沉降,但硫沉降量已较21世纪初出现了较大幅度下降,农业生产中需要根据农田硫素收支状况酌情补充硫肥来保证作物高产稳产.     

华北地区沙尘天气垂直气溶胶直接辐射强迫

利用CALIOP数据和SBDART（Santa Barbara DISORT Atmospheric Radiative Transfer）辐射传输模式研究了2013~2016年华北地区8d沙尘天气气溶胶及其直接辐射强迫垂直分布特征,分析了气溶胶垂直分布和光学特性对直接辐射强迫的影响.结果表明,气溶胶集中分布在地表及以上3km范围,其中纯净沙尘型和污染沙尘型气溶胶位于上层,污染大陆型气溶胶和烟雾位于下层.大气层顶、地表和大气层的日均气溶胶直接辐射强迫分别是-38.41~-88.44,-74.03~-225.86,9.06~137.42W/m².0~8km高度范围气溶胶直接辐射强迫是负值,且随着高度的增加绝对值逐渐减小.气溶胶垂直分布对大气层顶、地表和大气层的直接辐射强迫影响较小,但对直接辐射强迫垂直分布影响较大,由气溶胶廓线差异造成的同一高度层气溶胶直接辐射强迫最大差值能达到31.18W/m².气溶胶光学厚度和单次散射反照率对直接辐射强迫影响明显.消光能力相同时,吸收性气溶胶对短波太阳光的衰减作用大于散射性气溶胶,后向散射比例大的气溶胶大于后向散射比例小的气溶胶.     

氮掺杂二氧化钛负载钒磷氧催化氧化NO的实验研究

以VPO为活性组分,N掺杂TiO 2为载体,采用浸渍法制备了VPO/TiN催化剂,基于单因素实验研究了其对NO的选择性催化氧化(SCO)性能以及抗硫抗水性能。研究表明:当P/V为1/5、N/Ti为1、活性组分负载量为10%、焙烧温度为350℃时,催化剂的SCO活性最好,NO氧化率达到61%;光致发光光谱(PL)表征显示N掺杂TiO 2在催化剂表面形成的氧空位可增强催化剂对O 2的吸附;VPO/TiN催化剂抗硫抗水性能较强,反应后的催化剂表面未发现硫酸根的特征峰,水蒸气主要通过与NO竞争吸附占据活性位点来抑制催化剂的SCO活性。     

Heterogeneity in the relationship between carbon emission performance and urbanization: evidence from China

Mitigation and Adaptation Strategies for Global Change - Global change caused by carbon emissions alone has become a common challenge for all countries. However, current debates about urbanization...     

双区静电除尘器的数值模拟研究

采用数模拟的方法研究了双区静电除尘器内流场分布、颗粒荷电及颗粒运动等难以直接测量的物理过程,构建了双区静电除尘过程完整的数值模型.采用泊松方程、电流连续性方程和匀强电场方程描述电场,采用N-S方程和雷诺应力标准湍流模型描述流场,采用拉格朗日法描述颗粒运动轨迹.通过截面风速与颗粒去除率的模拟值与实验值的对比,验证了数值模型在模拟内部流场和颗粒运动时的准确性.数值模拟结果表明：双区静电除尘器内部流场分布对入口风速的变化非常敏感;颗粒荷电方式占比由颗粒粒径决定;荷电区内颗粒向极板的趋近过程由流体曳力和电场力共同完成,收尘区内的趋近过程则由电场力主导;入口流速通过改变颗粒前进速度和内部流场形态来影响颗粒运动轨迹.