A technique for atmospheric measurements of stable carbon isotope ratios of isoprene,methacrolein, and methyl vinyl ketone

A technique was developed to measure stable carbon isotope ratios (¹³C/¹²C) of light volatile organic compounds (VOCs) such as isoprene, methacrolein (MACR) and methyl vinyl ketone (MVK) using gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS). An automated sampling and cryofocussing system allowed for the extraction of VOCs from air samples of up to 140 L of air collected over 3 h, and the subsequent ¹³C/¹²C analysis of the VOCs by GCC-IRMS. Chromatography using selective transfer between two columns was used to improve the separation for selected compounds, increasing peak resolution and attaining less noisy baselines. Still, some target compounds could not be completely separated from co-eluting peaks. To reduce the bias of isotope ratio determinations, which can result from incomplete peak resolution, a peak-fitting procedure has been developed. In cases of overlapping peaks or substantial baseline drift, this peak fitting allows more accurate determination of isotope ratios than conventional integration schemes. Comparisons between off-line IRMS measurements and a peak-evaluation procedure using a prepared VOC gas-phase standard show that isotope ratios derived from large (>1 ng of carbon per peak) and well-resolved peaks have a reproducibility of ±0.3‰. With smaller masses in the range of 0.1–1 ng of carbon, reproducibility decreased to ±(0.5–0.8)‰. For a 140 L sample of air, such small masses of carbon correspond to mixing ratios in the low pptV range. The developed measurement technique was applied to a small set of ambient air samples taken during hot, sunny periods from late May to early August, 2005, at Forschungszentrum Jülich, Germany, a semi-rural area. The range of δ¹³C values determined for isoprene, benzene, and toluene are consistent with those reported in the literature. GCC-IRMS results of δ¹³C for ambient samples of isoprene, MACR, and MVK, measured at mixing ratios of 15–280 pptV, are presented and discussed.     

Observations of the OH Radical in Comet C/1995 O1 (Hale-Bopp) with the Nançay Radio Telescope

We present OH 18-cm observations of comet Hale-Bopp (C/1995 O1) at the Nançay radio telescope. On nucleus and offset position observations allowed us to obtain both OH production rates and quenching radii. The maximum OH production rate was reached around perihelion, at about10³¹ s^-1.     

Urban Atmospheric Chemistry During the PUMA Campaign 2: Radical Budgets for OH,HO<Subscript>2</Subscript> and RO<Subscript>2</Subscript>

A detailed photochemical box model was used to investigate the key reaction pathways between OH, HO₂ and RO₂ radicals during the summer and winter PUMA field campaigns in the urban city-centre of Birmingham in the UK. The model employed the most recent version of the Master Chemical Mechanism and was constrained to 15-minute average measurements of long-lived species determined in situ at the site. The results showed that in the summer, OH initiation was dominated by the reactions of ozone with alkenes, nitrous acid (HONO) photolysis and the reaction of excited oxygen atoms atoms with water. In the winter, ozone+alkene reactions were the primary initiation route, with a minor contribution from HONO photolysis. Photolysis of aldehydes was the main initiation route for HO₂, in both summer and winter. RO₂ initiation was dominated by the photolysis of aldehydes in the summer with a smaller contribution from ozone+alkenes, a situation that was reversed in the winter. At night, ozone+alkene reactions were the main radical source. Termination, under all conditions, primarily involved reactions with NO (OH) and NO₂ (OH and RCO₃). These results demonstrate the importance of ozone+alkene reactions in urban atmospheres, particularly when photolysis reactions were less important during winter and at nighttime. The implications for urban atmospheric chemistry are discussed.     

掺杂锡的纳米二氧化钛的合成、表征及光催化性能

以Ti(OC4H9)4和SnCl4.5H2O为原料,乙醇为溶剂,离子液体1-丁基-3-甲基四氟硼酸咪唑盐([Bmim][BF4])为表面活性剂,12%的氨水为沉淀剂,采用共沉淀法合成了不同形态的掺杂锡的二氧化钛。利用X-射线粉末衍射仪(XRD)、场发射扫描电镜(FESEM)、同步热分析仪(TG-DSC)、紫外—可见吸收光谱仪(UV-Vis)、比表面积孔隙度分析仪(BET)和能量色散X射线光谱仪(EDS)表征所合成材料的结构、形貌、热稳定性、光学性能、比表面积。Sn掺杂后各样品在紫外和可见光区的吸收能力均有不同程度地增强。与未掺杂TiO2的吸收带边相比,Sn掺杂TiO2的吸收带边分别红移了约35 nm,从而提高了光催化降解甲基橙的活性。为了评估产品的光催化性能,进行了掺杂锡的纳米二氧化钛对甲基橙的光催化降解实验,实验结果表明在2 mL离子液体中合成掺杂锡为7%的纳米二氧化钛对甲基橙的光降解具有最好的催化作用。光照90 min对甲基橙的降解率就达到了97%以上,大幅度提高了TiO2的可见光催化活性,这是因为有效抑制了光生电子和空穴的复合,也明显降低了TiO2的禁带宽度。     

Radiation-induced defects in quartz. III. Single-crystal EPR,ENDOR and ESEEM study of a peroxy radical

The X- and W-band single-crystal electron paramagnetic resonance spectra of an electron-irradiated natural quartz permit quantitative analysis of a ²⁹Si hyperfine structure (A ~12.6 MHz) and an ²⁷Al hyperfine structure (A ≤ 0.8 MHz) for a previously reported hole-like center. The ²⁹Si hyperfine structure arises from interaction with two equivalent Si atoms and is characterized by the direction of the unique A axis close to a Si–O bond direction. The ²⁷Al hyperfine structure, confirmed by pulsed electron nuclear double resonance and electron spin echo envelope modulation spectra, is characterized by the unique A axis approximately along a twofold symmetry axis. These ²⁹Si and ²⁷Al hyperfine data, together with published theoretical results on peroxy radicals in SiO₂ as well as our own density functional theory (DFT) calculations on model peroxy centers, suggest this hole-like center to have the unpaired spin on a pair of oxygen atoms linked to two symmetrically equivalent Si atoms and a substitutional Al³⁺ ion across the c-axis channel, a first peroxy radical in quartz. The nuclear quadrupole matrix P also suggests that the Al³⁺ ion corresponds closely to the diamagnetic precursor to the [AlO₄]⁰ center. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

基于采样分布式估计器的多无人艇轨迹跟踪控制

提出了一种级联控制算法解决多无人艇（USVs）系统的分布式轨迹跟踪问题.这种控制算法可以分为两层：第一层是基于采样信息的分布式估计器,主要用于估计领航者的期望轨迹;第二层是每个无人艇的本地控制器,主要是结合滑模控制与神经网络径向基函数,在系统具有欠驱动、参数不确定性和扰动等因素的情况下,使其状态跟踪期望轨迹的本地估计值.为了求解上述跟踪控制问题,基于李雅普诺夫理论与级联系统理论,推导得到了所有无人艇位置状态收敛到期望轨迹的充分条件,并通过仿真结果验证了所提出控制方法的有效性与正确性.     

大气中粘性效应对三维地形波及其波动阻力的影响

采用两层大气模式, 通过引入瑞利摩擦系数来定性描述大气中粘性机制, 讨论了粘性效应对三维简单地形波及其波动阻力的影响。结果表明,无论低层大气为稳定层结还是不稳定层结, 大气中粘性的存在将减弱地形波的强度, 减小其产生的波动阻力     

羟基在海洋有害生物污染防治的应用研究

利用高气压强电离放电方法制取高比值浓度的羟基溶液,应用于压载水外来有害生物入侵性传播,赤潮生物污染等领域的防治。论文详细介绍了羟基产生的等离子体过程,在进行的20t／h压载水中试试验和杀灭赤潮微生物的围隔实验中,微生物致死率分别达到100％和99．89％,并且在很大程度上改善了海水水质。结果表明羟基是治理海洋有害生物污染行之有效的方法。     

The influence of light intensity,SO2, NOx and C3H6 on sulfate aerosol formation

The photochemical oxidation of SO₂ in the presence of NO and C₃H₆ was studied in a 18.2 liter pyrex reactor. When light intensity, irradiation time and SO₂ concentration were constant, SO₄ ^2- concentration, derived from the total volume of aerosol produced, peaked when [C₃H₆]/[NO] was approximately 6.0. Another increase im SO₄ ^2- formation was reached at very high ratios (>50). The experimental observations are consistent with the two SO₂ oxidation mechanisms. At low [C₃H₆]/[NO] ratios, the processes proceed via the HO–SO₂ reaction, while at high ratios the O₃–C₃H₆ adduct is assumed to oxidize SO₂ to produce SO₄ ^2- aerosols.