香格里拉本底站大气CO2浓度及变化特征初步研究

利用基于光腔衰荡光谱(Cavity Ring Down Spectroscopy,CRDS)技术自组装的大气CO2在线观测系统,于2010年9月—2011年8月在云南香格里拉大气本底站对大气CO2进行了初步观测.该站春、夏、秋、冬季CO2平均本底浓度分别为394.78×10-6(物质的量之比,下同)、386.82×10-6、386.46×10-6和390.74×10-6.全年浓度在4—5月最高,7月份最低,全年月均值振幅约12.22×10-6.四季浓度日平均高值出现在上午7∶00左右,最低值出现在14∶00—17∶00.日变化振幅在冬季最小,夏季最大,分别为1.51×10-6和21.82×10-6.四季西南来向的地面风对CO2浓度均有明显的降低作用.通过四季每日整点后向轨迹聚类计算,结合浓度资料分析发现,该站春、夏、秋季来自于西南方向的气团降低了观测的CO2浓度,而在冬季未起到明显的降低作用,主要因该站局地植被生态系统排放减少所致.     

新型CO2和CH4混合标气标校流程及方法

基于光腔衰荡法Picarro G-1301型甚高分辨率分析仪自组装新型CO2和CH4混合标气标校系统,研究建立了简便高效的标校流程和方法.该系统操作简便,运行稳定,工作标气消耗更少,线性好,对环境大气浓度范围的CO2和CH4的分析精度分别优于0.06×10-6 mol·mol-1和0.3×10-9mol·mol-1,准...     

水汽对光腔衰荡光谱系统（CRDS）法测定CH_4的影响

分析了CRDS法测定CH4浓度与水汽含量间的关系,并建立了水汽含量在0.50%—2.45%（体积比,以V/V表示,下同）范围内的有效校正方法.采用CRDS法对水汽含量为0.93%的CH4标气进行多次测量,测量值经校正后与理论值的偏差均小于2.0×10-9（体积比,以V/V表示,下同）,最大偏差1.8×10-9,优于大气本底CH4观测质控标准.校正瓦里关站CRDS系统试运行期间的CH4实测数据（水汽含量为0.50%—2.45%）,与该站气相色谱-氢火焰离子化检测器系统（GC-FID系统,下同）同期测量结果相比,38.48%的数据偏差小于2.0×10-9,说明在系统未配备超低温冷阱除水单元之前,本文研究的校正方法适用于观测数据的校正.     

气相色谱法检测本底大气N2O的单一标气定量方法

提出采用单一标气非线性校正的方式对未知气体的N2O进行定量.以浓度为278.11×10-9(物质的量之比)的单一标气多次分析3瓶接近于环境浓度的N2O样气,结果与多点二次多项式拟合均值差异小于0.1×10-9,精度优于(0.03±0.09)%,表明该方法在用于本底大气中N2O浓度在线观测时,能有效校正采用单点线性拟合可...     

气相色谱-质谱联用法在线观测大气中的三氟化氮(NF_3)

基于气相色谱-质谱联用技术(GC-MS)以及自制吸附解析装置,研发了一套大气中三氟化氮(NF_3)的自动在线监测系统,测试结果表明,系统精度3.9%(1σ),准确度1.2%,检出限0.23×10~(-12),表明该系统适用于大气中NF_3浓度在线观测.2016年9月—2017年5月在北京上甸子本底站进行了在线观测实验,空气样品时间分辨率130 min,获得大气中NF_3的本底和非本底浓度.本底数据百分比53.1%,平均本底浓度为1.72×10~(-12),与同纬度带的爱尔兰Mace Head站和美国Trinidad Head站浓度相当.非本底浓度的中位数2.41×10~(-12),相对平均本底浓度抬升40.1%.     

气相色谱-质谱联用法在线观测大气中的氢氟碳化物和全氟化碳

利用组装的气相色谱-质谱联用系统(GC-MS)同时测定大气中6种氢氟碳化物(HFCs)和4种全氟化碳(PFCs),空气样品采样的时间分辨率120 min,精度范围0.15%—3.11%,准确度范围-1.52%—0.63%.对2011年2月在北京上甸子站的实验观测结果进行分析,获得HFC-23、HFC-32、HFC-134a、HFC-143a、HFC-125、HFC-152a、CF4、PFC-116、PFC-218、PFC-318的本底和非本底浓度,表明该系统适用于大气中HFCs和PFCs浓度在线观测.     

石油厌氧降解促进CO2的CH4转化

CO2是主要的温室气体,利用油藏进行CO2封存,并结合原油厌氧生物降解产生的H2对其进行CH4转化,将提高原油采收率,减少封存CO2长久潜在的危害.本研究以高矿化度的青海油田油井采出液为研究对象,添加碳酸氢盐进行厌氧培养,以研究其中CO2进行CH4转化的可能性.结果显示,厌氧培养体系中检测到CH4产生.且在培养过程中,碳酸氢盐添加体系内CO2相对含量降低,甲烷相对产量升高,沥青质和芳香烃组分的相对含量降低,表明青海油田油藏中存在产甲烷菌及与产甲烷过程相关的菌群,同时CO2封存利于增强原油的流动性、提高采收率.定量PCR分析表明,碳酸氢盐的添加抑制了部分微生物的生长但古菌在整个体系生命活动中的作用并未减弱,且产甲烷古菌占古菌的相对丰度明显升高.因此,在青海油田利用油藏微生物进行CO2封存并产生新甲烷能源,同时提高原油采收率具有可能性.     

红壤丘陵区冬闲稻田CH4和N2O排放通量的研究

CH4和N2O是与全球气候变化密切相关的2种主要温室气体,其排放规律以及减排措施已成为当前研究的热点。休闲期抛荒稻田普遍存在于我国西南和南方地区,而对于其CH4和N2O排放规律的研究还比较少。本实验选取江西红壤丘陵区进行观测,于稻田休闲期采用静态箱-气相色谱法进行原位观测,旨在探讨休闲期CH4和N2O的排放规律,可为制定减排措施提供一定的依据。研究结果表明:红壤丘陵区冬闲稻田CH4和N2O平均排放通量(以CH4和N2O-N计)分别为0.03mg.m-2.h-1和3.27μg.m-2.h-1。冬闲期CH4和N2O平均排放通量与土温、降雨量无明显线性关系(P>0.05)。冬闲稻田排放CH4和N2O的综合温室效应(以CO2-eq计)为7.58 g.m-2,其中,CH4和N2O产生的温室效应(以CO2-eq计)分别为2.33和5.25 g.m-2。N2O排放量是冬闲稻田温室气体观测中不可忽视的部分。     

珠江三角洲四种森林类型土壤CO2通量特征研究

采用开路式土壤CO2通量测量系统Li-8100&Li-8150对珠江三角洲地区尾叶桉(Eucalyptus urophylla)人工林、乡土树种恢复林、针阔叶混交林和常绿阔叶林4种林型的土壤CO2通量进行了观测。结果表明:4种森林类型年均土壤CO2通量为尾叶桉人工林(3.35μmol.m-2.s-1)>针阔叶混交林(2.66μmol.m-2.s-1)>乡土树种恢复林(2.09μmol.m-2.s-1)>常绿阔叶林(1.86μmol.m-2.s-1);旱季土壤CO2通量明显小于雨季。前3种森林类型凋落物呼吸处理表明,旱季对照组土壤CO2通量均小于相应的去除凋落物组、雨季则相反,全年的对比结果显示,3种森林类型的凋落物呼吸贡献分别达到1.3%、7.1%和10.8%。土壤CO2通量与10 cm土壤温度呈显著指数相关,且土壤CO2通量温度敏感指数表现为针阔叶混交林Q10最大(3.49),尾叶桉人工林Q10最小(1.95)。     

气相色谱-电子捕获检测法在线观测12种卤代温室气体

利用自组装的气相色谱仪-电子捕获检测器系统(GC-ECD)测定大气中12种卤代温室气体,空气样品采样的时间分辨率80min,分析精度0.16%—4.87%,准确度-1.64%—3.05%.对2007年4月6日—2007年4月16日在北京上甸子站的观测结果进行分析,获得12种卤代温室气体的本底和非本底浓度,表明该系统适用于大气中卤代温室气体浓度在线观测。     

SO2-4/TiO2对SO2-C7H16-TiO2复相光化学反应的影响

研究了TiO2与SO2,C7H16复相光化学反应的光催化活性.在SO2-C7H16-O2-TiO2光催化反应过程中,TiO2表面可形成SO2-4/TiO2结构,它的存在可提高庚烷的光催化氧化速率,利用IR和XPS研究了反应过程中TiO2表面形成的SO2-4/TiO2结构.     

KMnO4/H2SO4引发制备淀粉改性絮凝剂的研究

以高锰酸钾为引发剂,制备淀粉-丙烯酰胺接枝共聚物.研究酸浓度、引发剂浓度、单体浓度、温度和加料方式对接枝反应的影响.结果表明,少量KMnO4(0.45mmol·l-1)和H2SO4(0.8mmol·l-1)可有效引发淀粉-丙烯酰胺接枝共聚反应,接枝效率达到90%以上,分子量大大提高,对高岭土的絮凝效果较好.     

包膜尿素对水田土壤排放NH3、NOx、CO2影响的研究

为了研究包膜尿素对水田土壤排放NH3、NOx和CO2的影响,采用水稻盆栽的方法,探讨了在水稻不同生育期内不同种类包膜尿素对水田土壤排放NH3、NOx和CO2的影响。结果表明,包膜尿素处理对水田土壤排放NH3、NOx和CO2均具有抑制作用,与普通尿素相比,包膜尿素LP40、LPSS、BB、SC60 NH3的挥发总量降低了5.4%~19.3%,NOx的挥发总量降低了8.1%~23.4%,CO2的挥发总量降低了1.6%~13.0%;施用包膜尿素能够抑制水田土壤NH3、NOx和CO2的排放。     

Simultaneous removal of NOx and chlorobenzene on V2O5/TiO2 granular catalyst: Kinetic study and performance prediction

• A V₂O₅/TiO₂ granular catalyst for simultaneous removal of NO and chlorobenzene. • Catalyst synthesized by vanadyl acetylacetonate showed good activity and stability. • The kinetic model was established and the synergetic activity was predicted. • Both chlorobenzene oxidation and SCR of NO follow pseudo-first-order kinetics. • The work is of much value to design of multi-pollutants emission control system. The synergetic abatement of multi-pollutants is one of the development trends of flue gas pollution control technology, which is still in the initial stage and facing many challenges. We developed a V₂O₅/TiO₂ granular catalyst and established the kinetic model for the simultaneous removal of NO and chlorobenzene (i.e., an important precursor of dioxins). The granular catalyst synthesized using vanadyl acetylacetonate precursor showed good synergistic catalytic performance and stability. Although the SCR reaction of NO and the oxidation reaction of chlorobenzene mutually inhibited, the reaction order of each reaction was not considerably affected, and the pseudo-first-order reaction kinetics was still followed. The performance prediction of this work is of much value to the understanding and reasonable design of a catalytic system for multi-pollutants (i.e., NO and dioxins) emission control.     

Catalytic ozonation of organic compounds in water over the catalyst of RuO2/ZrO2-CeO2

This research investigates the performances of RuO₂/ZrO₂-CeO₂ in catalytic ozonation for water treatment. The results show that RuO₂/ZrO₂-CeO₂ was active for the catalytic ozonation of oxalic acid and possessed higher stability than RuO₂/Al₂O₃ and Ru/AC. In the catalytic ozonation of dimethyl phthalate (DMP), RuO₂/ZrO₂-CeO₂ did not enhance the DMP degradation rate but significantly improved the total organic carbon (TOC) removal rate. The TOC removal in catalytic ozonation was 56% more than that in noncatalytic ozonation. However this does not mean the catalyst was very active because the contribution of catalysis to the overall TOC removal was only 30%. The adsorption of the intermediates on RuO₂/ZrO₂-CeO₂ played an important role on the overall TOC removal while the adsorption of DMP on it was negligible. This adsorption difference was due to their different ozonation rates. In the catalytic ozonation of disinfection byproduct precursors with RuO₂/ZrO₂-CeO₂, the reductions of the haloacetic acid and trihalomethane formation potentials (HAAFPs and THMFPs) for the natural water samples were 38%–57% and 50%–64%, respectively. The catalyst significantly promoted the reduction of HAAFPs but insignificantly improved the reduction of THMFPs as ozone reacts fast with the THMs precursors. These results illustrate the good promise of RuO₂/ZrO₂-CeO₂ in catalytic ozonation for water treatment.     

Mass concentrations and temporal profiles of PM10, PM2.5 and PM1 near major urban roads in Beijing

Mass concentrations of PM₁₀, PM_2.5 and PM₁ were measured near major roads in Beijing during six periods: summer and winter of 2001, winter of 2007, and periods before, during and after the 2008 Beijing Olympic Games. Since the control efforts for motor vehicles helped offset the increase of emissions from the rapid growth of vehicles, the averaged PM_2.5 concentrations at roadsides during the sampling period between 2001 and 2008 fluctuated over a relatively small range. With the implementation of temporary traffic control measures during the Olympics, a clear “V” shaped curve showing the concentrations of particulate matter and other gaseous air pollutants at roadsides over time was identified. The average concentrations of PM₁₀, PM_2.5, CO and NO decreased by 31.2%, 46.3%, 32.3% and 35.4%, respectively, from June to August; this was followed by a rebound of all air pollutants in December 2008. Daily PM₁₀ concentrations near major roads exceeded the National Ambient Air Quality Standard (Grade II) for 61.2% of the days in the non-Olympic periods, while only for 12.5% during the Olympics. The mean ratio of PM_2.5/PM₁₀ near major roads remained relatively stable at 0.55 (±0.108) on non-Olympic days. The ratio decreased to 0.48 (±0.099) during the Olympics due to a greater decline in fine particles than in coarse-mode PM. The ratios PM₁/PM_2.5 fluctuated over a wide range and were statistically different from each other during the sampling periods. The average ratios of PM₁/PM_2.5 on non-Olympic days were 0.71.     

Catalytic oxidation of CO over Pt/Fe3O4 catalysts: Tuning O2 activation and CO adsorption

• Strong metal-support interaction exists on Pt/Fe₃O₄ catalysts. • Pt metal particles facilitate the formation of oxygen vacancies on Fe₃O₄. • Fe₃O₄ supports enhance the strength of CO adsorption on Pt metal particles. The self-inhibition behavior due to CO poisoning on Pt metal particles strongly impairs the performance of CO oxidation. It is an effective method to use reducible metal oxides for supporting Pt metal particles to avoid self-inhibition and to improve catalytic performance. In this work, we used in situ reductions of chloroplatinic acid on commercial Fe₃O₄ powder to prepare heterogeneous-structured Pt/Fe₃O₄ catalysts in the solution of ethylene glycol. The heterogeneous Pt/Fe₃O₄ catalysts achieved a better catalytic performance of CO oxidation compared with the Fe₃O₄ powder. The temperatures of 50% and 90% CO conversion were achieved above 260°C and 290°C at Pt/Fe₃O₄, respectively. However, they are accomplished on Fe₃O₄ at temperatures higher than 310°C. XRD, XPS, and H₂-TPR results confirmed that the metallic Pt atoms have a strong synergistic interaction with the Fe₃O₄ supports. TGA results and transient DRIFTS results proved that the Pt metal particles facilitate the release of lattice oxygen and the formation of oxygen vacancies on Fe₃O₄. The combined results of O₂-TPD and DRIFTS indicated that the activation step of oxygen molecules at surface oxygen vacancies could potentially be the rate-determining step of the catalytic CO oxidation at Pt/Fe₃O₄ catalysts. The reaction pathway involves a Pt-assisted Mars-van Krevelen (MvK) mechanism.     

A2型高粱细胞质雄性不育系与其保持系的胞质DNA和核DNA差异

以高粱细胞质雄性不育系A2V4（A）及其保持系V4（B）的总DNA为模板，对184个随机引物进行筛选，找到6个其RAPD扩增产物在A／B间存在稳定差异的引物，将该6个引物同时扩增A／B的总DNA、线粒线DNA（mtDNA）及叶绿体DNA（cpDNA），以总DNA为模板时得到12个扩增片段，以mtDNA为模板时得到4个，以cpDNA为板时得到11个，结果分析表明，在这些扩增片段中，有7个仅仅出现在以胞质DNA为模板的扩增中，有5个在以总NDA和胞质DNA为模板时同时出现，即认为这12个片段来自胞质DNA，另有7个片段，在以胞质DNA为模板时未出现，而是仅仅出现在以总DNA为模板的扩增中，认为是来自核DNA，来自核DNA的7个扩增片段中，有5个来自保持系，有2个来自不育系，这表明，不育系与保持系在核DNA上存在差异，对A／B核DNA在CMS中的重要性及研究对策进行了讨论。     

Visible-light-driven heterostructured g-C3N4/Bi-TiO2 floating photocatalyst with enhanced charge carrier separation for photocatalytic inactivation of Microcystis aeruginosa

• Bi doping in TiO₂ enhanced the separation of photo-generated electron-hole. • The performance of photocatalytic degradation of MC-LR was improved. • Coexisting substances have no influence on algal removal performance. • The key reactive oxygen species were h⁺ and ^•OH in the photocatalytic process. The increase in occurrence and severity of cyanobacteria blooms is causing increasing concern; moreover, human and animal health is affected by the toxic effects of Microcystin-LR released into the water. In this paper, a floating photocatalyst for the photocatalytic inactivation of the harmful algae Microcystis aeruginosa (M. aeruginosa) was prepared using a simple sol-gel method, i.e., coating g-C₃N₄ coupled with Bi-doped TiO₂ on Al₂O₃-modified expanded perlite (CBTA for short). The impact of different molar ratios of Bi/Ti on CBTA was considered. The results indicated that Bi doping in TiO₂ inhibited photogenerated electron-hole pair recombination. With 6 h of visible light illumination, 75.9% of M. aeruginosa (initial concentration= 2.7 × 10⁶ cells/L) and 83.7% of Microcystin-LR (initial concentration= 100 μg/L) could be removed with the addition of 2 g/L CBTA-1% (i.e., Bi/Ti molar ratio= 1%). The key reactive oxygen species (ROSs) in the photocatalytic inactivation process are h⁺ and ^•OH. The induction of the Bi⁴⁺/Bi³⁺ species by the incorporation of Bi could narrow the bandgap of TiO₂, trap electrons, and enhance the stability of CBTA-1% in the solutions with coexisting environmental substances.     

Highly effective visible-photocatalytic hydrogen evolution and simultaneous organic pollutant degradation over an urchin-like oxygen-doped MoS2/ZnIn2S4 composite

● An urchin-like OMS/ZIS composite was fabricated by a facile solvothermal method. ● The OMS/ZIS exhibits superior photocatalytic H₂ evolution for organics degradation. ● A probable mechanism of dual-functional photocatalysis was proposed in detail. ● This work provides an inspiration for rational design of dual-functional catalysts. Achieving hydrogen production and simultaneous decomposition of organic pollutants through dual-functional photocatalytic reactions has received increasing attention due to the environmentally friendly and cost-effective characteristics of this approach. In this work, an urchin-like oxygen-doped MoS₂/ZnIn₂S₄ (OMS/ZIS) composite was fabricated for the first time using a simple solvothermal method. The unique microstructure with abundant active sites and fast charge transfer channels further shortened the charge migration distance and compressed carrier recombination. The obtained composite exhibited an efficient H₂ evolution reaction rate of 12.8 mmol/g/h under visible light, which was nearly times higher than pristine ZnIn₂S₄, and the apparent quantum efficiency was 14.9% (420 nm). The results of the simultaneous photocatalytic H₂ evolution and organic pollutant decomposition test were satisfactory, resulting in decomposition efficiencies of resorcinol, tetracycline, and bisphenol A that reached 41.5%, 63.5%, and 53.0% after 4 h, respectively, and the highest H₂ evolution rate was 672.7 μmol/g/h for bisphenol A. Furthermore, natural organic matter (NOM) abundantly found in actual water was adopted as an electron donor for H production under simulated sunlight irradiation, indicating the promising practicability of simultaneous hydrogen evolution and NOM decomposition. Moreover, the mechanisms of the dual-purpose photocatalytic reactions, as well as the synergistic effect between the molecular structures of the organic pollutants and the corresponding adsorption behavior on the photocatalyst surface were illustrated in detail. These obtained results may serve as an inspiration for the rational design of highly efficient, dual-functional photocatalysts in the future.