2017年春季常州HONO观测及对大气氧化能力影响的评估

本研究于2017年4月在江苏省常州市环境监测中心使用一套基于湿化学法的仪器对大气中的HONO进行了实时在线观测,HONO浓度范围在0.2～13.9μg·m~(-3)之间,平均值为(2.9±2.3)μg·m~(-3);同时,对O_3、 HCHO、 VOCs、光解频率以及气象参数进行了同步监测.利用MCM箱体模式模拟得到白天·OH浓度最大值范围在1.0×10~6～1.4×10~7个·cm~(-3)之间.同时结合观测结果与模式模拟结果计算了HONO、 O_3、 HCHO和H_2O_2的光解以及烯烃臭氧化反应对·OH的生成速率,定量表征大气氧化性,揭示了这5种来源对大气氧化能力的影响:整体上O_3光解(46.4%)HONO光解(41.1%)烯烃臭氧化反应(10.9%)HCHO光解(1.5%)H_2O_2光解(0.1%);清晨时HONO光解对·OH生成起主要作用,之后随着O_3浓度的增加,O_3光解对·OH的贡献占主导地位;在17:00之后,由于太阳光解频率显著降低,烯烃臭氧化反应对·OH生成有主要贡献;甲醛与过氧化氢的光解对·OH的贡献可忽略.     

Impact of meteorological condition changes on air quality and particulate chemical composition during the COVID-19 lockdown

Stringent quarantine measures during the Coronavirus Disease 2019 (COVID-19) lockdown period (January 23, 2020 to March 15, 2020) have resulted in a distinct decrease in anthropogenic source emissions in North China Plain compared to the paralleled period of 2019. Particularly, 22.7% decrease in NO₂ and 3.0% increase of O₃ was observed in Tianjin, nonlinear relationship between O₃ generation and NO₂ implied that synergetic control of NO_x and VOCs is needed. Deteriorating meteorological condition during the COVID-19 lockdown obscured the actual PM_2.5 reduction. Fireworks transport in 2020 Spring Festival (SF) triggered regional haze pollution. PM_2.5 during the COVID-19 lockdown only reduced by 5.6% in Tianjin. Here we used the dispersion coefficient to normalize the measured PM_2.5 (DN-PM_2.5), aiming to eliminate the adverse meteorological impact and roughly estimate the actual PM_2.5 reduction, which reduced by 17.7% during the COVID-19 lockdown. In terms of PM_2.5 chemical composition, significant NO₃^? increase was observed during the COVID-19 lockdown. However, as a tracer of atmospheric oxidation capacity, odd oxygen (O_x = NO₂ + O₃) was observed to reduce during the COVID-19 lockdown, whereas relative humidity (RH), specific humidity and aerosol liquid water content (ALWC) were observed with noticeable enhancement. Nitrogen oxidation rate (NOR) was observed to increase at higher specific humidity and ALWC, especially in the haze episode occurred during 2020SF, high air humidity and obvious nitrate generation was observed. Anomalously enhanced air humidity may response for the nitrate increase during the COVID-19 lockdown period.     

Electrochemical reduction of Cr(VI) in the presence of sodium alginate and its application in water purification

Chromium (Cr) is used in many manufacturing processes, and its release into natural waters is a major environmental problem today. Low concentrations of Cr(VI) are toxic to human health and living organisms due to the carcinogenic and mutagenic nature of this mineral. This work examined the conversion of Cr(VI) to Cr(III) via electrochemical reduction using gold electrode in an acidic sodium alginate (SA) solution and subsequent removal of the produced Cr(III)-SA by the polymer-enhanced ultrafiltration (PEUF) technique. A solution of SA in nitric acid was used both as an electrolytic medium during the voltammetric measurements and bulk electrolysis and as an extracting agent during the PEUF technique. The electroanalysis of Cr(VI) was performed by linear sweep voltammetry in the presence of acidic SA solution to study its voltammetric behavior as a function of the Cr(VI) concentration, pH, presence of Cr(III), SA concentration and scan rate. In addition, the quantitative reduction of Cr(VI) to Cr(III) was studied through the bulk electrolysis technique.The results showed efficient reduction with well-defined peaks at approximately 0.3 V vs. Ag/AgCl, using a gold working electrode. As the pH increased, the reduction signal strongly decreased until its disappearance. The optimum SA concentration was 10 mmol/L, and it was observed that the presence of Cr(III) did not interfere in the Cr(VI) electroanalysis. Through the quantitative reduction by bulk electrolysis in the presence of acidic SA solution, it was possible to reduce all Cr(VI) to Cr(III) followed by its removal via PEUF.     

分子模拟方法在爆炸反应机理方面的应用进展

针对爆炸过程反应机理异常复杂,实验检测手段对其认识匮乏的现状,综述了量子化学、反应分子动力学等分子模拟方法的特点及研究进展,分析了分子模拟技术在燃爆机理研究中的应用进展,包括量子化学方法对于燃料热解/燃烧、瓦斯等可燃体系爆炸过程的微观基元反应步骤、反应能垒及热力学参数的计算,以及反应分子动力学(ReaxFF MD)在含能材料、可燃混合气等复杂爆炸体系获取可能的反应路径及中间自由基变化的应用。对分子模拟方法在爆炸领域研究的应用提出了建议及展望,指出ReaxFF MD和密度泛函理论(DFT)相结合是一种研究复杂爆炸体系微观反应机理极具潜力的方法,借助先进的分析检测手段对模拟方法的验证及修正,能获取更准确、全面的微观反应动力学模型。     

Kinetic modeling of microbially-driven redox chemistry of radionuclides in subsurface environments: coupling transport, microbial metabolism and geochemistry

Microbial reactions play an important role in regulating pore water chemistry as well as secondary mineral distribution in many subsurface systems and, therefore, may directly impact radionuclide migration in those systems. This paper presents a general modeling approach to couple microbial metabolism, redox chemistry, and radionuclide transport in a subsurface environment. To account for the likely achievement of quasi-steady state biomass accumulations in subsurface environments, a modification to the traditional microbial growth kinetic equation is proposed. The conditions for using biogeochemical models with or without an explicit representation of biomass growth are clarified. Based on the general approach proposed in this paper, the couplings of uranium reactions with biogeochemical processes are incorporated into computer code BIORXNTRN Version 2.0. The code is then used to simulate a subsurface contaminant migration scenario, in which a water flow containing both uranium and a complexing organic ligand is recharged into an oxic carbonate aquifer. The model simulation shows that Mn and Fe oxyhydroxides may vary significantly along a flow path. The simulation also shows that uranium(VI) can be reduced and therefore immobilized in the anoxic zone created by microbial degradation.     

河套灌区浅层地下水NO3--N时空变化及驱动因素

为探明河套灌区地下水硝酸盐污染现状、时空演变特征和主要影响因素,选择乌拉特灌域为研究区,采用统计分析、 Piper三线图、相关分析和离子比值等方法,探究了该地区地下水硝酸盐质量浓度时空变化格局和主要驱动因素.结果表明,乌拉特灌域地下水氮素主要以NO^-₃-N为主,ρ（NO^-₃-N）存在极高值(60.00 mg·L^-1),超标率达10.50%;时间分布：8月地下水ρ（NO^-₃-N）最高(平均值为6.61 mg·L^-1), 10月(6.22 mg·L^-1)和11月(6.25 mg·L^-1)次之,3月(平均值为1.77 mg·L^-1)最小,土壤中NO^-₃-N在降雨和灌溉驱动作用影响下,下渗至地下水,呈现出丰水期和灌溉集中期高于其它时期的特征;空间分布：灌域西南部(8.87 mg·L^-1)&g...     

Does Soil Acidification Affect Spruce Needle Chemical Composition and Tree Growth?

In 1994, a large survey of soil chemistry was undertaken in thecounty of Värmland in central Sweden (Lundström et al., 1998).The southern part of the county was affected by soilacidification whereas there were no such indications in thenorthern part. To investigate the influence of soil chemistryon the trees at the specific sites, the survey was continued byan analysis of needle chemistry (Norway spruce) which wasundertaken at 150 of the 180 sites, and of tree growth at 65 ofthe 180 sites. Growth was expressed as a ratio between expectedgrowth, estimated with a national, empirical growth model, andthe growth observed in the field. In statistical analyses,using rank correlation, PCA and PLS, there were only weakindications of an influence of soil chemistry on needlechemistry and on tree growth. A moderate correlation betweennitrogen and sulphur in needles was found, which wasinterpreted as an effect of deposition and of processes in thetree canopy. No obvious regional pattern of the growth ratiowas found, in contrast to the clear pattern of soilacidification. The statistical analysis could not with anycertainty point out any of the soil chemistry variables asespecially important for the tree growth ratio.     

CHEMIFOG_V – A Model to Simulate Radiation Fogs and their Interaction with Vegetation and Chemistry

Radiation fog is an important modifier of atmosphericcompounds in the planetary boundary layer. In vegetated areas effects are especially pronounced due to the enlarged surface area. Besides affectingthe lower boundary of atmospheric models fog acts as amulti-phase reaction chamber leading to acid deposition. Here we present the 1-dimensional radiation fog modelCHEMIFOG_V to simulate regional radiation fogevents. The key feature of the fog model is thedetailed microphysics, where the aerosol/dropletspectrum is describedwith a joint 2-dimensional distribution, but also thedynamics, thermodynamics, and radiative transfer are calculated. Toinvestigate the interaction between fog and the biosphere amulti-layer vegetation module, including a soil module as well as a drydeposition module were coupled. Vegetation influences thedynamics, thermodynamics, and the radiation field of the lowestatmospheric layers. With CHEMIFOG_V, numerical case studieson dry and moist deposition processes on vegetation surfaces wereperformed. Hereby multi-phase chemistry and the processing of aerosolswere considered. The results show that the chemical composition of thedeposited fog droplets is mainly determined by the aerosol composition. Dry deposition fluxes are dependent on the incoming radiation and the leaves' surface conditions with respect to water coverage.Due to chemical aerosol processing and deposition, the aerosol spectrumis significantly modified in the planetary boundary layer.     

A study of the atmospheric reaction of CH3S with O3 as a function of temperature

The atmospheric reaction of the methylthiyl radical (CH₃S) with O₃ was investigated as a function of temperature (259–381 K), in the pressure range of 25–300 Torr, using the technique of laser photolysis/laser-induced fluorescence. The resulting Arrhenius expression, with an uncertainty of ±2σ, was k₁(T=259–381 K)=(1.02±0.30)×10⁻¹² exp[(432±77) K/T] cm³ molecule⁻¹ s⁻¹. The obtained rate constant k₁ was independent of pressure over the limited range employed. Our results are compared with the previous studies carried out, at single temperature and as a function of temperature, by different techniques.     

OH自由基降解二英OCDD的反应机理及动力学研究

采用量子化学计算研究了OH自由基降解八氯代二苯并对-二英（OCDD）的微观反应机理,计算分析了微观反应进程,结果表明该反应存在两条途径：①α-氯取代：1,4,6,9位置氯取代,该路径反应活化能较高,反应难以进行,并以中间产物积聚,无法使OCDD的毒性消失;②β-氯取代：2,3,7,8位置氯取代,该路径的反应能相对较低,且能使OCDD的毒性消失,是有效降解OCDD的主要途径.结合过渡态理论,计算获得动力学参数：反应活化能为8.32 kJ·mol^-1（B3LYP/6-311G++（d,g）//B3LYP/6-31G（d））,阿仑尼乌斯表达式为k=1.29×10¹⁴exp（-1049.6/T）（cm³·mole^-1·s^-1）.这与文献实验结果取得了很好的吻合,说明本文对OH自由基降解OCDD的反应机理及动力学研究是合理且可靠的.本文的计算结果可为催化氧化降解二英的进一步研究提供理论参考.