基于腔衰减相移光谱法的二氧化氮分析仪的设计与应用

基于腔衰减相移光谱法设计了一套二氧化氮在线分析仪,通过优化测量参数,该仪器可长期稳定运行,其时间分辨率为60 s,检出限为0.191 ppb,在0~300 ppb范围内,NO₂气体浓度与相位正切信号值具有较好的二次拟合关系,R²为0.9995.另外,该仪器在泰安站进行了长期外场观测,并与改装后的进口商品化仪器PKU-Thermo 42i-TL进行比对实验,结果表明,两者的测量结果一致性较好,R²=0.9811,表明其具有良好的运行稳定性和测定结果准确性,适用于环境大气二氧化氮浓度的在线监测.外场观测结果表明,春季泰安站二氧化氮浓度均值为12.39 ppb,有明显日变化规律.     

Revealing the changes of bacterial community from water source to consumers tap: A full-scale investigation in eastern city of China

This study profiled the bacterial community variations of water from four water treatment systems, including coagulation, sedimentation, sand filtration, ozonation-biological activated carbon filtration (O₃-BAC), disinfection, and the tap water after the distribution process in eastern China. The results showed that different water treatment processes affected the bacterial community structure in different ways. The traditional treatment processes, including coagulation, sedimentation and sand filtration, reduced the total bacterial count, while they had little effect on the bacterial community structure in the treated water (before disinfection). Compared to the traditional treatment process, O₃-BAC reduced the relative abundance of Sphingomonas in the finished water. In addition, ozonation may play a role in reducing the relative abundance of Mycobacterium. NaClO and ClO₂ had different effects on the bacterial community in the finished water. The relative abundance of some bacteria (e.g. Flavobacterium, Phreatobacter and Porphyrobacter) increased in the finished water after ClO₂ disinfection. The relative abundance of Mycobacterium and Legionella, which have been widely reported as waterborne opportunistic pathogens, increased after NaClO disinfection. In addition, some microorganisms proliferated and grew in the distribution system, which could lead to turbidity increases in the tap water. Compared to those in the finished water, the relative abundance of Sphingomonas, Hyphomicrobium, Phreatobacter, Rheinheimera, Pseudomonas and Acinetobacter increased in the tap water disinfected with NaClO, while the relative abundance of Mycobacterium increased in the tap water disinfected with ClO₂. Overall, this study provided the detailed variation in the bacterial community in the drinking water system.     

Mechanism and catalytic performance for direct dimethyl ether synthesis by CO2 hydrogenation over CuZnZr/ferrierite hybrid catalyst

Direct synthesis of dimethyl ether(DME) by CO_2 hydrogenation has been investigated over three hybrid catalysts prepared by different methods:co-precipitation,sol-gel,and solid grinding to produce mixed Cu,ZnO,ZrO_2 catalysts that were physically mixed with a commercial ferrierite(FER) zeolite.The catalysts were characterized by N_2 physisorption,X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),temperature programmed desorption of CO_2(CO_2-TPD),temperature programmed desorption of NH_3(NH_3-TPD),and temperature programmed H2 reduction(H_2-TPR).The results demonstrate that smaller CuO and Cu crystallite sizes resulting in better dispersion of the active phases,higher surface area,and lower reduction temperature are all favorable for catalytic activity.The reaction mechanism has been studied using in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS).Methanol appears to be formed via the bidentate-formate(b-HCOO) species undergoing stepwise hydrogenation,while DME formation occurs from methanol dehydration and reaction of two surface methoxy groups.     

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.     

Advanced molecular-fingerprinting analysis of dissolved organic sulfur by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry using optimal spray solvent

Molecular level characterization of dissolved organic sulfur (DOS) by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR MS) is necessary for further understanding of the role of DOS in the environment. Here, ESI spray solvent, a key parameter for ion production during ESI process, was investigated for its effect on the molecular characterization of DOS by ESI-FTICR MS. 100% MeOH as spray solvent was found for the first time to remarkably enhance the ionization efficiency of the majority of CHOS-molecules in NOM, which facilitated a total of 1473 CHOS-molecular formulas with one sulfur atom to be detected. The number of CHOS-molecular formulas obtained using 100%MeOH as spray solvent increased notably over 740 in comparison with those using 50% MeOH aqueous solution (731) or 50% ACN aqueous solution (653). Moreover, due to the enhancement of ionization efficiency of DOS during ESI processes, the tandem mass spectra of the NOM CHOS-molecules could be easily obtained using 100% MeOH as spray solvent, which were hardly obtained using 50% MeOH aqueous solution as spray solvent. The results of the tandem mass spectra suggested the first discovery of organosulfates or sulfonic acids in Suwannee River NOM sample. A simple method based on 100% MeOH as ESI spray solvent for advanced molecular characterization of DOS by ESI-FTICR MS was proposed and applied, and the results revealed more molecular information of DOS in sea DOM samples.     

On-going nitrification in chloraminated drinking water distribution system (DWDS) is conditioned by hydraulics and disinfection strategies

Within the drinking water distribution system (DWDS) using chloramine as disinfectant, nitrification caused by nitrifying bacteria is increasingly becoming a concern as it poses a great challenge for maintaining water quality. To investigate efficient control strategies, operational conditions including hydraulic regimes and disinfectant scenarios were controlled within a flow cell experimental facility. Two test phases were conducted to investigate the effects on the extent of nitrification of three flow rates (Q = 2, 6, and 10 L/min) and four disinfection scenarios (total Cl₂=1 mg/L, Cl₂/NH₃-N=3:1; total Cl₂=1 mg/L, Cl₂/NH₃-N=5:1; total Cl₂=5 mg/L, Cl₂/NH₃-N=3:1; and total Cl₂=5 mg/L, Cl₂/NH₃-N=5:1). Physico-chemical parameters and nitrification indicators were monitored during the tests. The characteristics of biofilm extracellular polymetric substance (EPS) were evaluated after the experiment. The main results from the study indicate that nitrification is affected by hydraulic conditions and the process tends to be severe when the fluid flow transforms from laminar to turbulent (2300<Re<4000). Increasing disinfectant concentration and optimizing Cl₂/NH₃-N mass ratio were found to inhibit nitrification to some extend when the system was running at turbulent condition (Q = 10 L/min, Re = 5535). EPS extracted from biofilm that was established at the flow rate of 6 L/min had greater carbohydrate/protein ratio. Furthermore, several nitrification indicators were evaluated for their prediction efficiency and the results suggest that the change of nitrite, together with total organic carbon (TOC) and turbidity can indicate nitrification potential efficiently.     

Concentrations and chemical compositions of PM10 during hazy and non-hazy days in Beijing

In order to study the concentrations of major components,characteristics and comparison in hazy and non-hazy days of PM_(10) in Beijing,aerosol samples were collected at urban site in Beijing from December 29,2014 to January 22,2015.Heavy metals like Zn,Pb,Mn,Cu,As,V,Cr and Cd were deeply studied considering their toxic effects on human being;nine water-soluble inorganic ions(SO_4~(2-),NO_3~-,NH_4~+,Na~+,K~+,Cl~-,Ca~(2+) and Mg~(2+)) and carbon fractions(OC and EC) were also analyzed.The concentrations of heavy metals were 1.03–1.98 times higher in hazy days than those in non-hazy days,mainly due to biomass burning and coal burning.The trends in total heavy metals concentrations were basically consistent with the trends in PM concentrations except for two obvious periods(12.29–12.30;1.14–1.15);but when air masses accumulated locally or around Beijing,trends in PM concentrations and heavy metals were opposite.The proportion for NO_3~-/SO_4~(2-) indicated that mobile sources such as automobiles were important reasons for haze in Beijing.Correlation between OC and EC during non-hazy days was strong(R~2= 0.95) but it was low(R~2= 0.67) during hazy days,and large variations for OC/EC values occurred in hazy days.The calculated mass concentration of SOC is 2.58 μg/m~3,which only accounted for 10.1% of the OC concentration.When air masses from the far north-west,they decreased PM concentration in Beijing and they were relatively clean;however,those from the near east,south-east and south of the mainland increased PM concentration and they were dirty.     

石期河流域地下水化学特征及物质来源分析

为明确典型岩溶溶丘洼(谷)地区域地下水化学特征及其成因,以石期河流域为研究对象,运用Gibbs图、Piper图、端元分析及离子比例系数等方法,对地下水水化学特征及物质来源进行了定性和定量分析.结果表明,研究区内地下水pH值介于6.06～8.07之间,Ca~(2+)、 Mg~(2+)和HCO~-_3是地下水中的主要离子,其质量浓度范围分别为2.61～108.7、 0.54～27.61和8.1～370.74mg·L~(-1),符合岩溶水高钙弱碱性特征;地下水物质成分中, Ca~(2+)和Mg~(2+)主要受到碳酸参与的灰岩和白云岩风化作用的控制, Na~+主要来源于硅酸盐岩的溶解,同时, Ca~(2+)和Na~+在地下水流动过程中进行阳离子交替吸附作用; K~+、 Cl~-和NO~-_3主要受到农业化肥施放和生活废水排放的影响.此外,大气降水作为该区域地下水的主要补给来源,对当地地下水化学特征和物质来源也有一定的影响.     

典型西南工业城市春冬季PM2.5来源与潜在源区分析——以柳州市为例

为了揭示柳州城区春冬季PM_2.5的来源及其潜在源区分布和贡献,利用2018年24h自动监测数据和气象数据对柳州市大气污染物浓度变化特征进行了分析,并且使用后向轨迹模型（HYSPLIT）对春冬季柳州市PM_2.5逐日72h气流后向轨迹和前向轨迹进行聚类分析,同时结合潜在源贡献因子分析法（WPSCF）和轨迹浓度权重法（WCWT）对其潜在源区和浓度贡献进行了分析.结果显示,（1）在研究期内,不利的主导风向和工业区布局导致研究区PM_2.5在春冬季污染较严重,且工业源和交通源是其主要本地来源;（2）春冬季PM_2.5高值主要来源于西北和东南方向,其中,西北向PM_2.5主要来源于本地排放,且浓度在空间上呈现西高东低的趋势;（3）春季后向轨迹PM_2.5浓度整体大于冬季,春冬季中对柳州市PM_2.5影响最大轨迹均来自东部的短距离输送,而来自西北的气流轨迹输对PM_2.5贡献最低.春冬季柳州市大气PM_2.5通过气流传输对贵州地区大气环境有较大影响;（4）春季,柳州市PM_2.5的主要潜在源区分布在广西东南部、广东中西部、南海沿岸海域、湖南中部、江西西北部、湖北东部及安徽西北部;冬季,主要分布在广西东南部、广东西南部和南海沿岸海域.     

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...