An online monitoring system for atmospheric nitrous acid (HONO) based on stripping coil and ion chromatography

A new instrument for measuring atmospheric nitrous acid(HONO) was developed,consisting of a double-wall glass stripping coil sampler coupled with ion chromatography(SC-IC).SC-IC is featured by small size(50 × 35 × 25 cm) and modular construction,including three independent parts:the sampling unit,the transfer and supporting unit,and the detection unit.High collection efficiency(> 99%) was achieved with 25 μmol/L Na2CO3 as absorption solution even in the presence of highly acidic compounds.This instrument has a detection limit of 8 pptv at 15 min time resolution,with a measurement uncertainty of 7%.Potential interferences from NOx,NO2+SO2,NO2+VOCs,HONO+O3,HNO3,peroxyacetyl nitrite(PAN) and particle nitrite were quantified in laboratory studies and were found to be insignificant under typical atmospheric conditions.Within the framework of the 3C-STAR project,inter-comparison between the SC-IC and LOPAP(long path liquid absorption photometer) was conducted at a rural site in the Pearl River Delta.Good agreement was achieved between the two instruments over three weeks.Both instruments determined a clear diurnal profile of ambient HONO concentrations from 0.1 to 2.5 ppbv.However,deviations were found for low ambient HONO concentrations(i.e.< 0.3 ppbv),which cannot be explained by previous investigated interference species.To accurately determine the HONO budget under illuminated conditions,more intercomparison of HONO measurement techniques is still needed in future studies,especially at low HONO concentrations.     

Perturbations to tropospheric oxidants, 1985–2035: 2. Calculations of hydrogen peroxide in chemically coherent regions

Increasing global emissions of trace gases NO, CH₄, and CO, along with perturbations initiated by changes in stratospheric O₃ and H₂O, may cause tropospheric hydrogen peroxide (H₂O₂) levels to change. Specific scenarios of CH₄CONO emissions and global climate changes are used to predict HO₂ and H₂O₂ changes from 1985 to 2035 in a one-dimensional model that simulates different chemically coherent regions (e.g. urban, non-urban continental and marine mid-latitudes; marine and continental low latitudes).If CH₄ and CO emissions continue to increase throughout the troposphere at current rates (1% yr⁻), there will be large increases in H₂O₂, for example, more than 100% in the urban boundary layer from 1985 to 2035. Globally, H₂O₂ will increase 22% with HO₂ increasing 8% and O₃ increasing 13%. When CH₄, CO and NO emissions are specified on a regionally varying basis and are parameterized for high and low potential growth rates, globally averaged increases in surface concentrations are 12% for H₂O₂ and 18% for O₃. A global warming (with increased H₂O vapor) or stratospheric O₃ depletion superimposed on CH₄, CO and NO emissions changes will cut O₃ increases but add to peroxide, increasing levels as much as 150% above present day in some regions.Both globally uniform and region-specific scenarios predict a 10–15% loss in global OH from 1985 to 2035. Thus, conversion of OH to HO₂ and H₂O₂ in the atmosphere may signify a loss of gaseous oxidizing capacity in the atmosphere and an increase in aqueous-phase oxidizing capacity.     

Fe/Zn-TMS体系吸收去除催化裂化干气中H2S的性能

本研究采用FeCl3·6H2O、ZnCl2和环丁砜(TMS)复配形成的Fe/Zn-TMS体系脱除催化裂化(FCC)干气中的H2S,并用30%H2O2氧化再生Fe/Zn-TMS体系.同时,研究了各活性成分比例、吸收液体积浓度、吸收液pH值等对脱硫效率的影响,以及H2O2用量、吸收富液pH值对Fe2+氧化率的影响.结果表明,n(FeCl3·6H2O)∶n(ZnCl2)∶n(TMS)为0.45∶0.55∶1,吸收液pH为0.75,体积浓度(W)为50%的条件下能长时间高效脱硫,最高脱硫率达99.9%;在n(Fe2+)∶n(H2O2)为2∶1,吸收富液pH为0.65的条件下,Fe2+氧化率达96.7%.体系可循环使用3次,且能耗低、操作简单.     

Comparison of H2O2 and O3 content in atmospheric samples in the San Bernardino mountains,Southern California

Concentrations of atmospheric H₂O₂ were measured in air, rain, cloud and dew samples in forested areas of the San Bernardino Mountains, southern California, from spring through fall of 1987–1990 O₃ measurements in air were also conducted for comparison. Typical ranges of H₂O₂ concentrations measured were 1–3 ppb in air, 10–90 μM in rain and cloud water, and < μM in dew. The results show that gas-phase H₂O₂ concentrations were slightly higher at nighttime than at daytime or nearly constant throughout a 24-hr period, whereas O₃ concentrations were highest during the afternoon, when polluted air masses from Los Angeles carried by daily sea breezes reached the mountain region. Afternoon concentrations of gaseous H₂O₂ and O₃ in the mountain region were compared with those measured in Los Angeles urban sites to elucidate the regional variation of these oxidants. The results show that ambient concentrations of H₂O₂ and O₃ were about 50–100% higher at the mountains sites than at the Los Angeles sites.     

双氧水协同生化法强化处理印染废水

传统生化法对印染废水的处理有一定的局限性.本文研究了双氧水协同水解酸化-接触氧化系统,对印染废水进行强化处理.采用污泥挂膜、生化系统启动、双氧水协同启动的方法,将双氧水投加到水解酸化时的条件严格控制为:投加3m L·L~(-1)、投加量100.0 m L、流速0.67 m L·min-1、投加频率1次·d-1,可使整个系统成功启动与稳定运行.实验结果表明,双氧水协同水解酸化-接触氧化可对印染废水中的特征污染物进行有效强化处理.其中,COD平均去除率为89.8%,氨氮平均去除率为96.7%,PVA平均去除率为87.4%,废水平均脱色率为92.1%.采用16S rDNA宏基因组高通量测序技术,对比分析了接种种泥、水解酸化污泥和接触氧化污泥微生物的群落结构.结果表明,经过驯化,水解酸化和接触氧化微生物群落均发现了显著变化.其中,水解酸化污泥优势菌门主要为变形菌门Proteobacteria、拟杆菌门Bacteroidetes和疣微菌门Verrucomicrobia;接触氧化污泥优势菌门主要为浮霉菌门Planctomycetes、变形菌门Proteobacteria和酸杆菌门Acidobacteria.该实验从宏观和微观角度,均证实双氧水协同生化法强化处理印染废水具有技术可行性.     

NitroMAC: An instrument for the measurement of HONO and intercomparison with a long-path absorption photometer

NitroMAC (French acronym for continuous atmospheric measurements of nitrogenous compounds) is an instrument which has been developed for the semi-continuous measurement of atmospheric nitrous acid (HONO). This instrument relies on wet chemical sampling and detection using high performance liquid chromatography (HPLC)-visible absorption at 540 nm. Sampling proceeds by dissolution of gaseous HONO in a phosphate buffer solution followed by derivatization with sulfanilamide/N-(1-naphthyl)-ethylenediamine. The performance of this instrument was found to be as follows: a detection limit of around 3 ppt with measurement uncertainty of 10% over an analysis time of 10 min. Intercomparison was made between the instrument and a long-path absorption photometer (LOPAP) during two experiments in different environments. First, air was sampled in a smog chamber with concentrations up to 18 ppb of nitrous acid. NitroMAC and LOPAP measurements showed very good agreement. Then, in a second experiment, ambient air with HONO concentrations below 250 ppt was sampled. While NitroMAC showed its capability of measuring HONO in moderate and highly polluted environments, the intercomparison results in ambient air highlighted that corrections must be made for minor interferences when low concentrations are measured.     

Review on the applications of Tropospheric Emissions Spectrometer to air-quality research: Perspectives for China

The Tropospheric Emissions Spectrometer (TES) aboard the National Aeronautics and Space Administration’s (NASA’s) Aura satellite launched in July 2004 is the first satellite instrument to provide simultaneous retrievals of ozone (O₃) and carbon monoxide (CO) throughout the Earth’s lower atmosphere. This paper briefly reviews the TES instrument, the retrieval of O₃ and CO profiles, and the validation of the retrievals. The applications of TES O₃ and CO products include mapping the vertical and horizontal distribution of tropospheric O₃ and CO and their correlations, examining the regional and continental outflow, and analyzing the variability of the two species associated with certain weather and climatic conditions, such as El Ni?o and the Asian monsoon. TES retrievals of O₃ and CO offer an important new source of satellite data over China with good spatial and temporal coverage that can provide evaluation and constraints on the performance of chemical transport models in simulating the general features of ozone pollution over China. Special observations have been conducted and requests may be submitted to the TES team to make geographically focused observations of O₃ and CO over China.     

水合氧化铝负载的磁性核/壳结构Fe3O4@SiO2纳米颗粒对水中磷的去除及再利用

在磁铁矿纳米颗粒表面包被硅壳后再包被水合氧化铝,制备了具备核壳结构的磁性纳米颗粒除磷吸附剂(磁性氧化铝),通过XRD、TEM、VSM、BET比表面积测定进行了表征.XRD和TEM结果显示了核壳结构的存在,其饱和磁化强度达56.00 emu·g~(-1),比表面积达47.27 m~2·g~(-1).Langmuir模型计算的磷最大吸附量为12.90 mg·g~(-1),且在25℃和50℃下均保持稳定,反应快速,40min磷去除率达96%以上.磁性纳米吸附剂对磷的吸附与pH关系密切,在p H为5~9时磷去除率达90%以上.采用实际污水实验,最佳投量为1.25 kg·t~(-1).吸附-脱附-再生实验结果表明,磷吸附率随循环次数增加稍有下降,吸附的磷可以通过1 mol·L~(-1)的NaOH脱附,脱附率为90%左右,且吸附剂可以进行再生,具有反复利用和回收磷资源的潜力.     

Effect of CeO2 and Al2O3 on the activity of Pd/Co_3O_4/cordierite catalyst in the three-way catalysis reactions (CO/NO/CnHm)

The present article studies the effect of CeO₂ and Al₂O₃ on the activity of Pd/Co₃O₄/cordierite catalyst in conversion of NO, CO, C_nH_m. The catalysts were characterized by temperature programmed reduction with hydrogen, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. It is shown that the effect of CeO₂ on the properties of Pd/Co₃O₄/cordierite catalyst depends on preparation method. The catalyst obtained by co-deposition of cerium and cobalt oxides has higher activity in CO oxidation (CO + O₂ and CO + NO) and total hexane oxidation (C₆H₁₄ + O₂). Such phenomenon is probably caused by more than stoichiometric amount of formed oxygen vacancies, an increase in both mobility of surface oxygen and dispersity of components in the catalytic composition. It is demonstrated that CeO₂ addition promotes the SO₂ resistance of Pd/Co₃O₄/cordierite. The second support decreases the activity of Pd/Co₃O₄/cordierite catalyst in the reactions of CO and C₆H₁₄ with oxygen because of CoAl₂O₄ formation.     

Oxidation of diesel soot on binary oxide CuCr(Co)-based monoliths

Binary oxide systems (CuCr₂O₄, CuCo₂O₄), deposited onto cordierite monoliths of honeycomb structure with a second support (finely dispersed Al₂O₃), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine's gas exhausts (O₂, NO_x, H₂O, CO₂) and O³ as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO₂. Oxidants used can be arranged with reference to decreasing their activity in a following series: O₃ >> NO₂ > H₂O > NO > O₂ > CO₂. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O₃ occurs intensively (in the presence of copper chromite based catalyst) even at closing to ambient temperatures. Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the "cold start" problem.     

硫代硫酸钠对排硫硫杆菌固碳能力的影响及其作用机制

通过测定不同浓度Na_2S_2O_3·5H_2O培养时排硫硫杆菌(DSM 505)菌液的总有机碳浓度(TOC),分析Na_2S_2O_3·5H_2O对排硫硫杆菌固碳能力的影响,并结合各浓度Na_2S_2O_3·5H_2O条件下固碳关键酶Rubis CO编码基因cbb的转录特性和胞外游离有机碳浓度(EFOC),阐明Na_2S_2O_3·5H_2O影响排硫硫杆菌固碳能力的作用机制.结果表明,适当范围内增加Na_2S_2O_3·5H_2O的浓度能显著提高排硫硫杆菌的固碳能力,降低胞外游离有机碳在总有机碳中所占的比例.cbb基因转录特性分析结果表明,Na_2S_2O_3·5H_2O浓度对cbb基因的转录效率和表达模式均无显著影响.因此推测Na_2S_2O_3·5H_2O影响排硫硫杆菌固碳能力的作用机制可能是作为电子供体提供能量,促进细胞骨架合成,从而削弱胞外游离有机碳对排硫硫杆菌自养过程的抑制作用,进而增强固碳能力.     

煤粉炉联产贝利特-Q相水泥熟料及其水化性能试验

选用长广煤为试验煤种,分析纯CaO、MgO为添加剂,在两段多相反应实验台开展联产Q相水泥熟料试验.同时,对熟料样品矿物组成进行XRD、SEM和EDS分析,并对联产获得的Q相水泥熟料样品开展水化强度、膨胀性、安定性、凝结时间和水化性能等测试.结果表明,熟料样品矿物组成主要为2CaO·SiO2、Q相和3CaO·3Al2O3.CaSO4等;Q相水泥熟料样品砂浆试样各龄期抗压强度和抗折强度接近于32.5强度等级普通硅酸盐水泥标准,当Q相水泥熟料中掺加30%的硅酸盐水泥熟料时,其砂浆试样各龄期抗压强度和抗折强度达到32.5强度等级普通硅酸盐水泥标准要求;Q相水泥熟料样品膨胀性、安定性和凝结时间符合国家水泥相关标准;除2CaO·SiO2外,联产Q相水泥熟料水化3d就出现2CaO·Al2O3·8H2O、3CaO·Al2O3·3CaSO4·32H2O、xCaO·SiO2·yH2O和Al2O3·3H2O水化产物,且随着水化龄期的延长,2CaO·Al2O3·8H2O、3CaO·Al2O3·CaSO4·12H2O、3CaO·Al2O3·6H2O等水化产物逐渐增多,显示出良好的水化性能.     

过氧化氢存在下HCFC－22光解特性

模拟大气条件研究了ＨＣＦＣ－２２＋Ｈ２Ｏ２在有氧或无氧存在下用低压相进行辐照,在２０ｍ的长光程池中用富里叶红外光仪测量其化学产物,结果表明在没有氧情况下产物为ＣＯＦ２,ＣＯ２,ＨＦ和ＨＣｌ;有氧存在时产物为ＣＯ２,Ｈ２Ｏ,ＨＦ和ＨＣｌ。从这些产物推广其可能的光解机理。     

Electrochemical measurement of carbon monoxide in breath: Interference by hydrogen

The purpose of this study was to determine the concentration of carbon monoxide (CO) in blood (COHb) and breath to demonstrate that breath hydrogen (H₂) can be a significant interferant. For this purpose, we measured blood COHb with CO-oximetry and breath CO with an electrochemical analyzer. In addition, the samples were analyzed by gas chromatography (GC). The concentration of CO in breath, collected with a Priestley tube after a 20 s breath hold, from healthy, nonsmoking adult males (n = 20) and females (n = 10) had a mean ± SD (range) of 2.6 ± 0.4 ppm (2.0–3.9), respectively, when measured by GC. However, these same samples when measured with an electrochemical (EC) analyzer showed elevated CO values of 4.7 ± 2.9 ppm (2.6–17.6). The concentration of H₂, a prominent trace gas in breath known to interfere with EC analyzers, correlated strongly with the observed EC analyzer response [EC (ppm CO) = 0.336 H₂ (ppm) + 1.93, r² = 0.98]. The EC analyzer was linear for H₂ concentrations up to 40 ppm, with a sensitivity of 0.035 V ppm⁻¹. The analyzer sensitivity to CO was 0.10 V ppm ⁻¹. Blood from this population showed COHb concentrations of 0.56 ± 0.11% (0.40–0.97), as measured by GC, but elevated values were found when measured by CO-oximeter (Ciba Corning Diagnostics Corp., Models 2500 and 270), 1.3 ± 0.2% (1.1–1.6) and 1.0 ± 0.3% (0.1–1.6), respectively. When breath CO was compared to blood COHb, only measurements by GC significantly correlated [COHb% = 0.241 CO(ppm) — 0.076, r² = 0.78]. We conclude that, relative to quantitative analysis by GC, (1) EC analyzers are susceptible to H₂ interference that cause falsely elevated CO measurements, and (2) CO-oximeters overestimate COHb concentrations in the range typical for healthy nonsmokers.     

BiOCl/SiO2/Fe3O4复合材料可见光催化去除水中亚甲基蓝

以FeCl_3·6H_2O、FeCl_2·4H_2O、(C_2H_5)_4SiO_4、Bi(NO_3)_3·5H_2O、KCl为主要原料,采用化学共沉淀法和水热法制备了BiOCl/SiO_2/Fe_3O_4光催化剂,并对其进行EDS、TEM、XRD、FT-IR、UV-Vis表征,最后通过亚甲基蓝降解实验,研究了催化剂在合成过程中pH及催化剂投加量对其光催化性能的影响.结果表明,在pH=6、催化剂初始投加量为0.5 g·L~(-1)时,对亚甲基蓝的可见光催化效果最佳,光照120 min后对10 mg·L~(-1)的亚甲基蓝溶液的脱色率达到93.2%.BiOCl/SiO_2/Fe_3O_4经过简单的无水乙醇和水洗后,可高效重复利用4次.综合表明,BiOCl/SiO_2/Fe_3O_4是一种在处理染料废水中具有应用前景的磁性光催化剂.     

纳米Fe3 O4-H2 O2 非均相Fenton反应催化氧化邻苯二酚

由四氧化三铁(Fe3O4)-过氧化氢(H2O2)构成的非均相Fenton体系主要利用H2O2分解产生的羟基自由基氧化去除难降解有机污染物.研究了邻苯二酚在纳米Fe3O4-H2O2构成的非均相Fenton体系中的催化氧化特征,同时对实验室制备的纳米级Fe3O4和商品微米级Fe3O4两种催化剂的催化活性进行比较,并考察了H2O2初始浓度对邻苯二酚的催化氧化的影响.结果表明,自制纳米Fe3O4-H2O2体系较商品Fe3O4-H2O2体系,能更快速地去除溶液中的邻苯二酚和总有机碳(TOC),邻苯二酚的去除率接近100%,同时能迅速催化H2O2分解.邻苯二酚的催化氧化反应遵循准一级反应动力学方程,H2O2的分解反应能用三级反应动力学方程较好拟合.此外,反应过程中铁释放低于0.3 mg.L-1,不足以启动均相Fenton反应,反应机制为由界面反应控制的非均相反应机制.     

不同方法制备Co3O4催化剂CO-SCR性能及机制

氮氧化物(NOx)是造成细颗粒物、近地面臭氧等大气污染问题的重要前体物.随着大气污染治理行动的深入,对工业锅炉/窑炉烟气排放的NOx进行控制十分重要.采用不同方法制备了一系列Co_3O_4催化剂,考察了不同制备方法对CO选择性催化还原NO(CO-SCR)反应活性的影响,通过BET、XRD、Raman、HR-TEM和SEM等技术对该系列催化剂进行了表征.活性测试表明,以硫酸钴为前驱体用固态研磨法制备的Co_3O_4-S催化剂具有更优异的CO-SCR反应活性,且表现出较好的抗水蒸气性能,以醋酸钴为前驱体用固态研磨法制备的Co_3O_4-C催化剂显示出较好的抗水性能. NO氧化结果显示,催化剂的NO氧化效果越好,CO-SCR活性也越好. Raman表征结果显示,Co_3O_4-S表面可能含有更多的Co2+离子,从而有利于形成氧空位. H2-TPR结果表明,Co_3O_4-S催化剂的氧化还原性较好. HR-TEM表征发现Co_3O_4-S和Co_3O_4-O主要暴露(111)和(220)晶面,而更多(220)晶面的暴露可能更有利于反应的进行.     

O3/H2O2降解Atrazine效能研究

利用O₃/H²O²降解莠去津,对氧化产物进行了色谱分析,以评价该体系降解莠去津效能.莠去津初始浓度2 mg/L,7.5 mg/L的O₃单独氧化去除率为27.2%;相同O₃投量下,H²O²/O₃摩尔比0.75时,5 min莠去津的去除率最高可达96.5%,表明H²O²/O₃体系对莠去津的去除效果良好,降解速度快.以离子色谱对产物的离子进行分析,莠去津浓度下降的同时,硝酸根和氯离子浓度增高.GC-MS检测的产物和对LC-MS谱图的分析表明,有机产物中存在脱乙基、脱异丙基和脱氯莠去津,说明H²O²/O₃并不能彻底氧化莠去津,因此工程中作为主要去除单元或突发性污染事件的应急手段可能还需要与活性炭等单元联用.     

Advanced oxidation of bromide-containing drinking water：A balance between bromate and trihalomethane formation control

Addition of H2O2 has been employed to repress bromate formation during ozonation of bromide-containing source water. However, the addition of H2O2 will change the oxidation pathways of organic compounds due to the generation of abundant hydroxyl radicals, which could affect the removal efficacy of trihalomethane precursors via the combination of ozone and biological activated carbon （O3-BAC）. In this study, we evaluated the effects of H2O2 addition on bromate formation and trihalomethane formation potential （THMFP） reduction during treatment of bromide-containing （97.6-129.1 μg/L） source water by the O3-BAC process. At an ozone dose of 4.2 mg/L, an H2O2/O3 （g/g） ratio of over 1.0 was required to maintain the bromate concentration below 10.0 μg/L, while a much lower H2O2/O3 ratio was sufficient for a lower ozone dose. An H2O2/O3 （g/g） ratio below 0.3 should be avoided since the bromate concentration will increase with increasing H2O2 dose below this ratio. However, the addition of H2O2 at an ozone dose of 3.2 mg/L and an H2O2/O3 ratio of 1.0 resulted in a 43% decrease in THMFP removal when compared with the O3-BAC process. The optimum H2O2/O3 （g/g） ratio for balancing bromate and trihalomethane control was about 0.7-1.0. Fractionation of organic materials showed that the addition of H2O2 decreased the removal efficacy of the hydrophilic matter fraction of DOC by ozonation and increased the reactivity of the hydrophobic fractions during formation of trihalomethane, which may be the two main reasons responsible for the decrease in THMFP reduction efficacy. Overall, this study clearly demonstrated that it is necessary to balance bromate reduction and THMFP control when adopting an H2O2 addition strategy.     

Evaluation of a number of chemical mechanisms for their application in models describing the formation of photochemical ozone in Europe

A series of 24 chemical mechanisms from the literature are compared against each other using harmonized emissions, photolysis rate coefficients for simple inorganic chemistry and life cycle data for ozone, PAN and H₂O₂. The evaluation sought to understand the impact of parameterizing hydrocarbon oxidation on the peak concentrations of photochemically-generated secondary pollutants. Only seven of the 24 chemical mechanisms gave peak concentrations of ozone, PAN and H₂O₂ simultaneously in their respective central ranges. PAN and H₂O₂ were generally calculated with a much lower precision compared to ozone. Only 11 mechanisms out of 24 gave responses to both 50% hydrocarbons and NO_x emissions controls in their respective central bands. The lack of coordinated ozone, PAN and hydrogen peroxide measurements across Europe currently limits the adequacy of model comparisons and hence the confidence which may be placed in assessments of likely impacts of future control strategies.