Synergistic effects of Cu species and acidity of Cu-ZSM-5 on catalytic performance for selective catalytic oxidation of n-butylamine

In this work, a series of Cu-ZSM-5 catalysts with different SiO₂/Al₂O₃ ratios (25, 50, 100 and 200) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic degradation at 350°C over all Cu-ZSM-5 catalysts. Moreover, Cu-ZSM-5 (25) exhibited the highest selectivity to N₂, exceeding 90% at 350°C. These samples were investigated in detail by several characterizations to illuminate the dependence of the catalytic performance on redox properties, Cu species, and acidity. The characterization results proved that the redox properties and chemisorption oxygen primarily affect n-butylamine conversion. N₂ selectivity was impacted by the Brønsted acidity and the isolated Cu²⁺ species. Meanwhile, the surface acid sites over Cu-ZSM-5 catalysts could influence the formation of Cu species. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra was adopted to explore the reaction mechanism. The Cu-ZSM-5 catalysts are the most prospective catalysts for nitrogen-containing volatile organic compounds removal, and the results in this study could provide new insights into catalysts design for VOC catalytic oxidation.     

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.     

Photodegradation of Hexafluoropropylene Oxide Trimer Acid under UV Irradiation

As a novel alternative to traditional perfluoroalkyl substances (PFASs), including perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), hexafluoroproplyene oxide trimer acid (HFPO-TA) has been detected worldwide in surface water. Moreover, recent researches have demonstrated that HFPO-TA has stronger bioaccumulation potential and higher hepatotoxicity than PFOA. To treat these contaminants e.g. PFOA and PFOS, some photochemical techniques by adding exogenous substances had been reported. However, there is still no report for the behavior of HFPO-TA itself under direct UV irradiation. The current study investigated the photo-transformation of HFPO-TA under UV irradiation in aqueous solution. After 72 hr photoreaction, 75% degradation ratio and 25% defluorination ratio were achieved under ambient condition. Reducing active species, i.e., hydrated electrons and active hydrogen atoms, generated from water splitting played dominant roles in degradation of HFPO-TA, which was confirmed by different effects of reaction atmospheres and quenching experiments. A possible degradation pathway was proposed based on the products identification and theoretical calculations. In general, HFPO-TA would be transformed into shorter-chain PFASs, including hexafluoropropylene oxide dimer acid (HFPO-DA), perfluoropropionic acid (PFA) and trifluoroacetate (TFA). This research provides basic information for HFPO-TA photodegradation process and is essential to develop novel remediation techniques for HFPO-TA and other alternatives with similar structures.     

北京市气温与黑碳和PM2.5对疾病死亡影响的交互效应

通过收集北京市2010~2016年逐日呼吸和心脑血管疾病死亡数据、污染物（BC、PM_2.5、SO₂、O₃和NO₂）日均浓度资料以及同期的气象资料,采用广义相加模型（GAMs）中的主效应模型、非参数二元响应模型和温度分层模型探讨了北京市气温、PM_2.5和BC单效应,以及气温与PM_2.5和BC交互作用分别对呼吸和心脑血管疾病死亡人数的影响.单效应分析结果表明,气温与两种疾病死亡人数的累计暴露-反应关系均呈“J”型分布特征,最适温度为24℃;累计滞后一天情况下PM_2.5和BC的健康效应均最显著,此时PM_2.5和BC浓度每升高四分位间距（IQR）,呼吸系统疾病死亡人数超额增加百分比（ER）分别为2.21%和1.80%,心脑血管疾病死亡人数ER分别为2.02%和1.48%.交互作用的研究结果表明,高温与高浓度的PM_2.5（或BC）对疾病死亡的影响存在协同效应,且高温条件下BC对疾病死亡影响的健康风险大于PM_2.5,当气温大于24℃时,BC和PM_2.5浓度每升高IQR对应的呼吸系统疾病死亡人数ER分别为6.22%和6.17%,心脑血管疾病死亡人数ER分别为5.01%和3.97%.虽然BC只占PM_2.5的一部分,但BC对人群健康的影响不容忽视,应该引起足够的重视.     

贵州农村污水典型抗生素污染水平及生态风险

抗生素残留物是一种新兴的微污染物,广泛存在于各种环境介质及生物样品中,长期暴露在抗生素环境会对人体健康、生态环境产生一定的潜在威胁。由于农村污水排放量逐渐增大、农村地区对抗生素的不合理使用以及受经济、地理地形的限制大部分农村地区都缺乏完整的污水收集管网和污水治理设施,进而导致抗生素通过多种途径进入农村环境,可能会对农村生态环境产生一定的环境风险。为了解贵州农村污水中抗生素的污染水平及处理后污水对环境的影响,作者采用固相萃取—液相色谱—串联质谱(SPE-LC-MS)联用技术,选取贵州省3处典型农村地区,对农村污水治理设施进出水中典型抗生素(包括6种磺胺类、3种四环素类、1种喹诺酮类抗生素)的浓度水平进行分析。结果表明,3处农村污水治理设施进水和出水中均检出不同程度的抗生素,浓度范围分别在ND～417.57 ng/L和ND～253.68 ng/L,其中土霉素浓度最高,进出水的浓度分别为417.57、253.68 ng/L;其次是氧氟沙星,在进出水中的最高浓度分别为278.75、183.73 ng/L。3处农村污水治理设施对抗生素的去除率在-58.32%～45.52%,对目标抗生素的去除率较低。与国内外其他地区农村污水相比,所选地区的进出水中抗生素的浓度较高。通过生态风险评估发现,经处理后的污水中均含有一种RQ≥1的抗生素物质,并且发现氧氟沙星为处理后污水中的高风险污染物,污水的排放会对环境造成一定的生态风险。     

矿山排水污染稻田土壤胶体对砷的吸附研究

为研究矿山排水污染土壤胶体对砷的吸附影响,文章以高砷污染区和背景区土壤的胶体在不同的pH、离子强度以及好氧/厌氧淹水条件下对As(Ⅴ)的吸附进行对比试验。结果表明:土壤胶体对As(Ⅴ)的吸附量随pH的增大而减少,且污染区胶体比背景区胶体对As(Ⅴ)的吸附量大;离子强度越大,胶体对As(Ⅴ)的吸附量越大,Ca(NO_3)_2浓度从0.001 mol/L增至0.1 mol/L时,污染区与背景区胶体对As(Ⅴ)的吸附量分别增加了30.57%、50.25%;厌氧淹水后的胶体对As(Ⅴ)的吸附量低于好氧条件下的胶体,解吸量较高,且厌氧淹水后污染区胶体与背景区胶体相比无明显吸附优势,而好氧条件下污染区胶体的解吸率低于背景区胶体,说明厌氧淹水后的胶体不易吸附且易释放As(Ⅴ)。因此,低p H和高离子强度以及好氧的条件有利于土壤胶体对砷的吸附。     

Effect of TiO2 nanoparticle aggregation on marine microalgae Isochrysis galbana

TiO_2 nanoparticles(NPs) could adversely impact aquatic ecosystems. However, the aggregation of these NPs could attenuate this effect. In this work, the biological effects of TiO_2 NPs on a marine microalgae Isochrysis galbana were investigated. The aggregation kinetics of TiO_2 NPs under different conditions was also investigated to determine and understand these effects. Results showed that, though TiO_2 NPs had no obvious impact on the size and reproducibility of algal cells under testing conditions, they caused a negative effect on algal chlorophyll, which led to a reduction in photosynthesis. Furthermore, fast aggregation of TiO_2 NPs occurred under all conditions, especially at the pH close to the p Hzpc. Increasing ionic strength and NP concentration also enhanced the aggregation rate.The aggregation and the following sedimentation of TiO_2 NPs reduced their adverse effects on I. galbana.     

Regionalization based on spatial and seasonal variation in ground-level ozone concentrations across China

Owing to the vast territory of China and strong regional characteristic of ozone pollution,it's desirable for policy makers to have a targeted and prioritized regulation and ozone pollution control strategy in China based on scientific evidences. It's important to assess its current pollution status as well as spatial and temporal variation patterns across China.Recent advances of national monitoring networks provide an opportunity to insight the actions of ozone pollution. Here, we present rotated empirical orthogonal function(REOF)analysis that was used on studying the spatiotemporal characteristics of daily ozone concentrations. Based on results of REOF analysis in pollution seasons for 3 years' observations, twelve regions with clear patterns were identified in China. The patterns of temporal variation of ozone in each region were separated well and different from each other, reflecting local meteorological, photochemical or pollution features. A rising trend in annual averaged Eight-hour Average Ozone Concentrations(O_3-8 hr) from 2014 to 2016 was observed for all regions, except for the Tibetan Plateau. The mean values of annual and 90 percentile concentrations for all 338 cities were 82.6 ± 14.6 and 133.9 ± 25.8 μg/m~3,respectively, in 2015. The regionalization results of ozone were found to be influenced greatly by terrain features, indicating significant terrain and landform effects on ozone spatial correlations. Among 12 regions, North China Plain, Huanghuai Plain, Central Yangtze River Plain, Pearl River Delta and Sichuan Basin were realized as priority regions for mitigation strategies, due to their higher ozone concentrations and dense population.     

基于短时傅里叶变换的干扰信号识别方法

目的提高无线电引信识别欺骗式干扰的能力。方法根据炮弹弹体自旋的特点,使得采用连续波线极化天线的无线电引信所收到的干扰信号呈现出有别于地面回波的周期性幅度调制特征,通过对此特征进行短时傅里叶变换后进行识别,可以作为无线电引信是否受到欺骗式干扰的判断依据。结果通过仿真和试验对方法的可行性进行了验证,表明该识别方法可以很好地提高连续波无线电引信的识别欺骗式干扰的能力。结论基于短时傅里叶变换检测旋转调制的对地旋转弹无线电引信欺骗干扰识别的方法可以对干扰信号特征进行识别,算法处理时间短,能够作为引信是否受到干扰的一种判断依据。     

基于环境保护大数据的监测与智能诊断研究

为了提高环境保护的智能监测能力,采用大数据分析方法进行环境监测和诊断分析,提出一种基于环保大数据关联特征挖掘的环境保护智能监测与诊断技术。构建环境监测的约束参量模型,以土壤监测数据、空间污染排放量以及水资源监测数据为原始统计数据,采用关联规则特征提取方法进行环保大数据的有用信息挖掘,结合模糊C均值聚类算法实现对环保大数据的分类处理,根据分类结果进行环保监测和智能诊断分析。仿真结果表明,采用该方法进行环保大数据挖掘的准确性较好,对各种污染信息的分类精度较高,提高了环保监测和诊断的有效性与实时性。