太湖北部流域水化学特征及其控制因素

为了解太湖北部流域主要河网区水质受该流域地质状况、岩石和土壤的化学风化作用以及人类活动的影响等方面,对太湖北部流域河网区主要河道水体中的主要离子进行了采样研究。结果表明：太湖北部流域水体中的TDS平均值为355．74mg·L-1,变化范围为276．08--681．54mg·L-1,其中ca2＋和HCO3-是占绝对优势的离子,分别占阳离子和阴离子总量的46．2％和48．9％;其次是Na＋和SO42-,分别占阳离子和阴离子总量的35．9％和27．5％。进而判断出该流域水化学类型是以碳酸盐岩石和蒸发岩来源为主的HCO3-Ca2＋-Na＋型。再从离子的自然起源和人类活动角度分别对水化学类型的控制因素进行分析,一方面利用吉布斯分布模式投点作图得出结论：其离子自然起源的优势机制是岩石的风化作用,而蒸发一结晶和大气降水的输入作用十分微弱,这与该流域的水文、地理、地质背景相一致;另一方面通过SPSS软件的相关关系分析得出结论：NO3-、SO42-、心、ca2＋和Mg2＋的相关性较强,与cl‘也呈正相关,说明水体中这些主要离子都具有共同的来源,其中NO3-的较高含量（平均值为14．74mg·L-1）反映了该流域受人类影响较大。尤其是NO3-与sO42-的相关性达到0．83,再次说明氮污染对该流域水体的酸化和水质变化有较大影响。     

利用化学沉淀法降低焦化废水氨氮浓度的预处理工艺研究

为了有效净化高浓度氨氮工业废水,采用向废水中投加MgCl2·6H2O和Na3PO4·12H2O生成磷酸氨镁沉淀的方法,以去除其中的高浓度氨氮。结果表明,在pH值为9.0,Mg^2＋、NH4^＋、PO4^3-的摩尔比为1.2：1：0.9,反应温度为25℃,反应时间为20 min,沉淀时间为50 min的条件下,氨氮质量浓度可由3 100 mg/l降低到56mg/l,去除率达到98%以上,为后续生化处理创造了条件。     

Spatially distributed modeling of the long-term carbon balance of a boreal landscape

Spatially and temporally distributed information on the sizes of biomass carbon (C) pools (BCPs) and soil C pools (SCPs) is vital for improving our understanding of biosphere-atmosphere C fluxes. Because the sizes of C pools result from the integrated effects of primary production, age-effects, changes in climate, atmospheric CO₂ concentration, N deposition, and disturbances, a modeling scheme that interactively considers these processes is important. We used the InTEC model, driven by various spatio-temporal datasets to simulate the long-term C-balance in a boreal landscape in eastern Canada. Our results suggested that in this boreal landscape, mature coniferous stands had stabilized their productivity and fluctuated as a weak C-sink or C-source depending on the interannual variations in hydrometeorological factors. Disturbed deciduous stands were larger C-sinks (NEP₂₀₀₄ = 150 gC m⁻² yr⁻¹) than undisturbed coniferous stands (e.g. NEP₂₀₀₄ = 8 gC m⁻² yr⁻¹). Wetlands had lower NPP but showed temporally consistent C accumulation patterns. The simulated spatio-temporal patterns of BCPs and SCPs were unique and reflected the integrated effects of climate, plant growth and atmospheric chemistry besides the inherent properties of the C pool themselves. The simulated BCPs and SCPs generally compared well with the biometric estimates (BCPs: r = 0.86, SCPs: r = 0.84). The largest BCP biases were found in recently disturbed stands and the largest SCP biases were seen in locations where moss necro-masses were abundant. Reconstructing C pools and C fluxes in the ecosystem in such a spatio-temporal manner could help reduce the uncertainties in our understanding of terrestrial C-cycle.     

A review of gas-phase chemical mechanisms commonly used in atmospheric chemistry modelling

The atmospheric chemical mechanism is an essential component of airshed models used for investigating the chemical behaviors and impacts of species. Since the first tropospheric chemical mechanism was proposed in the 1960s, various mechanisms including Master Chemical Mechanism (MCM), Carbon Bond Mechanism (CBM), Statewide Air Pollution Research Center (SAPRC) and Regional Atmospheric Chemistry Mechanism (RACM) have been developed for different research purposes. This work summarizes the development and applications of these mechanisms, introduces their compositions and lumping methods, and compares the ways the mechanisms treat radicals with box model simulations. CBM can reproduce urban pollution events with relatively low cost compared to SAPRC and RACM, whereas the chemical behaviors of radicals and the photochemical production of ozone are described in detail in RACM. The photolysis rates of some oxygenated compounds are low in SAPRC07, which may result in underestimation of radical levels. As an explicit chemical mechanism, MCM describes the chemical processes of primary pollutants and their oxidation products in detail. MCM can be used to investigate certain chemical processes; however, due to its large size, it is rarely used in regional model simulations. A box model case study showed that the chemical behavior of OH and HO₂ radicals and the production of ozone were well described by all mechanisms. CBM and SAPRC underestimated the radical levels for different chemical treatments, leading to low ozone production values in both cases. MCM and RACM are widely used in box model studies, while CBM and SAPRC are often selected in regional simulations.     

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.     

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.