Laboratory simulation of SO2 heterogeneous reactions on hematite surface under di erent SO2 concentrations

The variations of sulfate formation and optical coe cients during SO2 heterogeneous reactions on hematite surface under di erent SO2 concentrations were examined using in situ di use reflectance infrared Fourier transform spectroscopy (DRIFTS) and ion chromatograph (IC). Laboratory experiments revealed that within ambient SO2 of 0.51–18.6 ppmv, sulfate product, producing velocity, absorption and backward scattering coe cients showed an increasing trend with SO2 concentration. Under given SO2 concentration, the velocity of sulfate producing performed an evolution of initial increasing, midterm decreasing and final stabilizing. The reactive uptake and Brunauer-Emmett-Teller (BET) uptake coe cients of heterogeneous reactions rose with SO2 and exhibited high reactivities. Considering global warming, this result is important for the knowledge of heterogeneous reactions of SO2 on mineral particle surface in the atmosphere and the assessment of their impacts on radiative forcing.     

大气汞均相和非均相化学反应过程研究进展

作为环境中汞传输的最重要通道,大气在汞的全球生物地球化学循环和传输扩散中起着极其关键的作用.大气环境成分复杂,汞在随大气环境传递过程中会经历复杂的化学反应,并导致不同形态之间相互转化,这也成为影响大气汞远距离传输尺度的关键因素.本文主要对大气汞在不同相界面之间的分配过程和主要影响因素(包括相界面的物理化学性质和外部环境条件等)进行了总结;对大气Hg0主要氧化反应过程(卤族元素氧化和O_3、OH·氧化)进行了阐述;对大气Hg~(2+)还原反应过程,尤其是光致还原反应等进行了梳理.如何综合运用野外监测分析和室内模拟等,利用微观分子表面分析等新技术明确大气汞均相、非均相反应过程,并将反应机理与大气汞传输过程模拟系统融合,将是未来大气汞研究的重要内容之一.     

Homogeneous and heterogeneous reactions of anthracene with selected atmospheric oxidants

The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol (SOA) formations from gas-phase reactions of anthracene with O3 and O3-NO were observed. Meanwhile, the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer (SMPS) during the formation processes. The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr, respectively. The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). Gas chromatograph/mass spectrometer (GC/MS) analyses of oxidation products of anthracene were carried out for assigning the time-of-flight (TOF) mass spectra of products from homogeneous and heterogeneous reactions. Anthrone, anthraquinone, 9,10- dihydroxyanthracene, and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene, while anthrone, anthraquinone, 9-nitroanthracene, and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.     

海盐非均相反应对山东沿海大气O3浓度的影响

通过改进WRF-CMAQ模型中非均相反应模块,定量研究了2017年夏季和冬季海盐与含氮气体非均相反应对我国山东沿海地区大气O₃浓度的影响.模拟结果表明,考虑海盐气溶胶非均相反应后,山东沿海地区夏季O₃小时浓度增加了0.2×10^-9~6.6×10^-9（0.5%~15.5%）,冬季增加了0.8×10^-9~15.3×10^-9（1.7%~27.4%）,ClNO₂在夏季和冬季分别增加了100×10^-12~250×10^-12,300×10^-12~650×10^-12;夏季O₃浓度增加主要集中在山东东部,而冬季O₃的增加则覆盖了山东大部分地区,表明海盐非均相反应对冬季O₃的影响强度及范围均明显高于夏季.海盐非均相反应引起的O₃浓度增加主要发生在日间,特别是8：00~16：00.该反应对渤海及南黄海大气O₃浓度也有影响,且在这些海域生成的O₃可通过4条传输路径影响山东沿海地区,甚至可影响到济南、菏泽等山东中西部地区（距离山东东部海岸线~350km）;海洋大气中O₃的传输可造成山东东部沿海O₃浓度升高0.2×10^-9~15.3×10^-9,山东中西部O₃升高0.3×10^-9~6.2×10^-9.     

光照对SO2在矿质氧化物表面非均相反应的影响

使用原位漫反射红外傅里叶变换光谱(DRIFTS)研究了SO_2在α-Al_2O_3、TiO_2、CaO和α-Fe_2O_3颗粒物表面的非均相反应,考察了紫外光光照(波长约365 nm)对SO_2在不同氧化物表面反应的影响.结果表明,无紫外光照射条件下,SO_2在TiO_2、α-Al_2O_3、CaO颗粒物表面反应的主要产物为亚硫酸盐;有紫外光照射条件下,SO_2在TiO_2、α-Al_2O_3、CaO颗粒物表面反应的主要产物为硫酸盐;但紫外光照射对SO_2在α-Fe_2O_3表面的反应并没有明显的影响.推测机理可能是光照促进了颗粒物表面的亚硫酸盐向硫酸盐的转化.     

NO2在高岭石表面的非均相反应研究

高岭石是典型的1∶1型层状结构的硅铝酸盐,研究其非均相反应对于了解粘土类矿物的非均相反应具有重要的意义.因此,试验以原位漫反射红外傅里叶变换光谱（DRIFTS）为研究手段,对NO2在高岭石表面的非均相反应进行了系统的研究.结果表明,NO2在高岭石表面发生歧化反应生成NO3-和NO2-.相对湿度对非均相反应具有重要影响,有水汽存在时会增加反应的持续能力,但相对湿度的增加会使摄取系数降低.在干态和湿态条件下,NO2在高岭石表面的反应机理不同,干态下为二级反应,湿态下为一级反应.     

Heterogeneous reaction of NO2 on the surface of montmorillonite particles

The studies on heterogeneous reactions over montmorillonite, which is a typical 2:1 layered aluminosilicate, will benefit to the understanding of heterogeneous reactions on clay minerals. Montmorillonite can be classified as sodium montmorillonite or calcium montmorillonite depending on the cation presented between the different layers. Using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), the heterogeneous reaction mechanism of NO₂ on the surface of montmorillonite was firstly investigated. Results showed that the reaction of NO₂ on the surface of sodium and calcium montmorillonite fit a first-order kinetics, and the reaction duration of calcium montmorillonite was longer than that of sodium montmorillonite under the dry condition. For either sodium or calcium montmorillonite, the uptake coefficient decreased as humidity increased.     

非均相活化剂磁性纳米CoFe2O4的制备及其活性评价

采用溶胶-凝胶法制备了磁性纳米铁酸钴（CoFe₂O₄）固体颗粒,并采用扫描电镜（SEM）,X射线衍射仪（XRD）,傅里叶变换红外光谱仪（FT-IR）和振动样品磁强计对样品进行表征分析.以磁性纳米CoFe₂O₄颗粒活化过硫酸盐氧化去除水中四环素为探针反应,评价CoFe₂O₄颗粒的活化性能.结果表明,600℃焙烧温度下制备出的固体颗粒,其活性较高,颗粒表面金属离子浸出率较低;优化温度下制备的CoFe₂O₄颗粒在较宽的pH值范围（4.4~9.0）内均具有较高活性;控制实验条件PDS₀ 1g/L,CoFe₂O₄ 1g/L,TCH₀ 50mg/L,20℃,pH₀ 4.4,反应4h后TCH去除率达到82.0%.CoFe₂O₄颗粒循环重复利用10次后仍保持较高的活性和结构稳定性,而且因其特殊的磁性能便于回收利用.     

蒸汽相变促进可溶PM2.5凝结增长的数值分析

为利用蒸汽相变原理促进氨法脱硫系统排放细颗粒物(PM2.5)的脱除,建立多分散颗粒的凝结增长动力学模型,利用数值模拟方法研究了可溶硫酸铵颗粒的凝结增长规律,并将典型粒径可溶与不可溶颗粒的凝结增长过程进行对比分析.结果表明:不同粒径硫酸铵颗粒的增长速率相近,等温系统的凝结增长效果优于绝热系统;对于同一初始粒径分布下的可溶和不可溶颗粒,微米尺度可溶颗粒的增长速率始终大于不可溶颗粒,亚微米尺度可溶颗粒的增长速率先大于而后小于不可溶颗粒,使得二者的增长曲线存在一个交叉点;蒸汽饱和度增大能显著促进硫酸铵颗粒的增长;等温系统中温度对硫酸铵颗粒的增长影响显著,绝热系统中温度的影响较弱.     

光助-电解锰渣/H2O2非均相体系氧化降解双酚S

以电解锰渣作为光催化剂构建非均相类光Fenton体系,采用双酚S为模型化合物,研究了该反应体系中双酚S氧化降解的降解机制及影响因素,并建立了·OH的生成速率模型以及溶解性有机质（DOM）影响的预测模型.结果表明,电解锰渣中具有催化效果的铁和锰的质量含量分别为1.49%和2.28%;相比UV、UV/电解锰渣、UV/H₂O₂和电解锰渣/H₂O₂体系,电解锰渣/UV/H₂O₂光Fenton体系对双酚S具有更好的氧化降解效果,双酚S的降解效果与电解锰渣投加量、H₂O₂浓度呈正相关,与pH值、双酚S初始浓度呈负相关;溶液中析出的Fe和Mn的浓度与pH值呈负相关,且电解锰渣/UV/H₂O₂氧化体系反应浸出的共存活性金属组分不利于双酚S降解;电子自旋共振和自由基淬灭实验发现电解锰渣/UV/H₂O₂体系中氧化降解双酚的主要活性物种是·OH.采用异丙醇构建了该体系中·OH的生成速率模型,计算可得·OH的生成速率R·^f_OH在3.22×10^-9~1.1×10^-8mol/（L·s）之间,与硝基苯拟合计算出的R·^f_OH（6.5×10^-9mol/（L·s））一致.双酚S降解效率随着DOM浓度的增加而降低.基于自由基稳态动力学理论建立了DOM存在下电解锰渣/UV/H₂O₂体系中双酚S降解的动力学预测模型,发现模型的预测值与实验值较好符合,说明DOM主要通过淬灭体系中的·OH影响双酚S的降解.     

Study on the optical property and surface morphology of N doped TiO2 film deposited with different N2 flow rates by DCPMS

N doped TiO₂ films were deposited by direct current pulse magnetron sputtering system at room temperature. By using UV-Vis spectrophotometer and atomic force microscope, we studied the influence of N₂ flow rate on the optical property and surface morphology of films. The results indicate that the optical property and surface morphology of N doped TiO₂ film was dominated by the N₂ flow rate. The mean absorbency in visible range of pure TiO₂ films is near to 0%, which means that the pure TiO₂ could hardly display the photocatalytic property in visible range. When N₂ flow rate is 2 sccm, the mean absorbency in visible range of N doped TiO₂ film could reach at 24%. In this case, the film could be used as photocatalyst induced by visible light. While with increasing N₂ flow rate, the mean absorbency in visible range of N doped TiO₂ film decreased abruptly. Especially when N₂ flow rate exceeded 8 sccm, the mean absorbency in visible range of N doped TiO₂ film decreased to about 0%, which is like pure TiO₂ fimls.     

NOx和/或NH3气氛下SO2在高岭土表面非均相转化的实验研究

利用自制气溶胶反应器研究了NO_x和/或NH_3气氛下SO_2在高岭土表面的非均相转化过程,应用扫描电镜(SEM)对高岭土颗粒物形貌进行了表征.结果表明:高岭土颗粒表面的SO_2非均相转化致使其成分和形貌产生了较大变化.相同实验条件下,SO_2转化的协同作用程度由高到低依次为NH_3、NO_x/NH_3和NO_x气氛,相对湿度40%、有光照条件下,SO_2转化量增幅最高可分别达125%、75%和50%.所有气氛下,协同作用在无光照时在高相对湿度(40%~70%)区间更为突出,有光照时其显著性则体现在低相对湿度(20%~40%)区间.SO_2、NO_x、NH_3三者共存时,在高岭土颗粒表面发生的非均相反应过程既有协同作用又存在竞争反应.     

COD/SO_4~(2-)值对硫酸盐废水厌氧消化的影响

采用间歇试验方式,研究了COD/SO_4~(2-)值对硫酸盐废水厌氧消化的影响。试验结果表明,COD/SO_4~(2-)值是影响厌氧消化处理效果的主要参数。本试验中,COD/SO_4~(2-)>15,硫酸盐还原作用对厌氧反应器影响甚微;COD/SO_4~(2-)=5—15时,硫酸盐还原作用对厌氧反应器产生轻度抑制,相对产甲烷率为79.2％—94.7％;COD/SO_4~(2-)=0.5—5时,反应器受中度抑制,相对产甲烷率为61.6％—79.2％;COD/SO_4~(2-)<0.5时,反应器受严重抑制。COD/SO_4~(2-)≥1时,相对产甲烷率与COD/SO_4~(2-)值之间有很好的线性关系。     

不同浓度和形态磷模拟调控浮游植物群落演替实验

为研究水体浮游植物对不同浓度和不同形态磷的利用能力差异,采集福建九龙江江东库区冬季的水样,设置培养温度为20℃,分别进行原位水(TP=0.11mgL-1)、低浓度有机磷(单磷酸胞苷(5'-CMP)和无机磷(0.01mg·L-1)、高浓度的有机磷(单磷酸胞苷5'-CMP)和无机磷(1.00 mg·L-1)调控模拟实验.比...     

粉煤灰非均相催化H2O2氧化S2-的研究

研究了利用电厂粉煤灰作为过氧化氢催化氧化S^2-的非均相催化剂，试验了各种因素对S^2-去除率的影响。结果表明粉煤灰具有良好的催化活性；常温下，当硫化钠和过氧化氢的起始浓度分别为0．26和0．23mol/L时，粉煤灰的用量仅为4％（质量分数，％）就可使S^2-的去除率提高40％左右；与新灰相比，旧灰的活性下降了约20％。     

流化床燃烧温度下N2O与石油焦焦炭多相反应动力学的热重研究

采用升温热重方法研究了流化床温度条件下N2O与石油焦焦炭的多相反应动力学特性,实验中设置升温范围为973～1273K,升温速率为5K·min-1.估算及灰色关联分析的结果表明,在流化床工况下,N2O与石油焦焦炭间的多相反应由内扩散过程控制,尤其是气体在石油焦焦炭中孔中的扩散对于多相反应的进行具有重要作用.同时,采用Coats-Redfern法对升温热重数据进行了分析,得到了4种不同石油焦焦炭(JM char、ZH char、WH char和GH char)的动力学机理及动力学参数,JM char、ZH char、WH char和GH char的活化能分别为128.9、113.8、154.1和127.3 kJ·mol-1.     

Measurement of heterogeneous uptake of NO2 on inorganic particles, sea water and urban grime

Heterogeneous reactions of NO₂ on different surfaces play an important role in atmospheric NO_x removal and HONO formation, having profound impacts on photochemistry in polluted urban areas. Previous studies have suggested that the NO₂ uptake on the ground or aerosol surfaces could be a dominant source for elevated HONO during the daytime. However, the uptake behavior of NO₂ varies with different surfaces, and different uptake coefficients were used or derived in different studies. To obtain a more holistic picture of heterogeneous NO₂ uptake on different surfaces, a series of laboratory experiments using different flow tube reactors was conducted, and the NO₂ uptake coefficients (γ) were determined on inorganic particles, sea water and urban grime. The results showed that heterogeneous reactions on those surfaces were generally weak in dark conditions, with the measured γ varied from <10^?8 to 3.2 × 10^?7 under different humidity. A photo-enhanced uptake of NO₂ on urban grime was observed, with the obvious formation of HONO and NO from the heterogeneous reaction. The photo-enhanced γ was measured to be 1.9 × 10^?6 at 5% relative humidity (RH) and 5.8 × 10^?6 at 70% RH on urban grime, showing a positive RH dependence for both NO₂ uptake and HONO formation. The results demonstrate an important role of urban grime in the daytime NO₂-to-HONO conversion, and could be helpful to explain the unknown daytime HONO source in the polluted urban area.     

不同雨强下黄土裸坡水-沙-氮磷流失耦合模拟

采用室内人工模拟降雨试验研究6种雨强3种坡度下黄土裸露坡面水沙及氮磷养分流失规律.结果表明：1）降雨强度与土壤入渗速率,坡面产流产沙量的线性拟合决定系数均大于0.8,有较好的正相关关系;2）25°黄土坡面下：NO₃^--N初始浓度较高,随降雨历时呈波动性减少,具有明显的初期冲刷效应;NH₄⁺-N初始流失浓度由90mm/h雨强下0.6057mg/L增至120mm/h的1.3076mg/L,但其浓度随降雨历时均不断减小;TN流失浓度在雨强为90,105和120mm/h时分别为0.6056,0.8011和1.3076mg/L,随雨强增大而增大;TP初始流失浓度在105mm/h时最大,90mm/h时最小,且不同雨强下TP流失浓度相互交错,不稳定;3）养分流失与坡面产流量具有较强的线性相关性,与产沙量呈显著的幂函数关系.15°坡面时,氮素流失在6种雨强下均以颗粒态为主,平均约占72%,但在雨强增大过程中,颗粒态所占比例先减少后增加;而磷素流失颗粒态所占比例均大于90%,与降雨强度和坡度均没有直接关系.     

产酸脱硫反应器中碳硫比对群落生态特征的影响

通过产酸脱硫反应器处理高浓度含硫酸盐废水的连续流试验,从群落动态的角度研究碳硫比(COD/SO₄^2-)从4.2降低到2.0的过程中,pH值、氧化还原电位(ORP)、碱度(ALK)和末端产物(VFAs)组成、优势种群分布等群落生态特征的变化规律试验证明,在此过程中ORP和ALK提高,而pH值和VFAs中乙酸的分布比例降低,群落类型由高碳硫比稳定型转化为低碳硫比亚稳定型,但仍未改变乙酸型顶极群落的典型特征.     

Study on the optical property and surface morphology of N doped TiO2 film deposited with different N2 flow rates by DCPMS

N doped TiO₂ films were deposited by direct current pulse magnetron sputtering system at room temperature. By using UV-Vis spectrophotometer and atomic force microscope, we studied the influence of N₂ flow rate on the optical property and surface morphology of films. The results indicate that the optical property and surface morphology of N doped TiO₂ film was dominated by the N₂ flow rate. The mean absorbency in visible range of pure TiO₂ films is near to 0%, which means that the pure TiO₂ could hardly display the photocatalytic property in visible range. When N₂ flow rate is 2 sccm, the mean absorbency in visible range of N doped TiO₂ film could reach at 24%. In this case, the film could be used as photocatalyst induced by visible light. While with increasing N₂ flow rate, the mean absorbency in visible range of N doped TiO₂ film decreased abruptly. Especially when N₂ flow rate exceeded 8 sccm, the mean absorbency in visible range of N doped TiO₂ film decreased to about 0%, which is like pure TiO₂ fimls.