A chemiluminescence-based continuous flow aqueous ozone analyzer using photoactivated chromotropic acid

Ozone has become the oxidant of choice for water disinfection, especially in large water treatment facilities. This paper describes a fast and sensitive method for the determination of ozone content by reaction with photoactivated chromotropic acid (CA, 4,5-dihydroxynaphthalene-2,7-disulfonic acid), which results in intense chemiluminescence (CL). Freshly ozonated water from a recirculating ozonizer/reservoir is injected into a carrier stream of deionized water in the flow-injection mode. This flow mixes with a stream of photoactivated CA solution in a spiral cell placed directly on top of an inexpensive miniature (8 mm diameter active area) photomultiplier tube (PMT). Alkaline CA is photoactivated by passing it through a FEP-Teflon^® coil (residence time ∼ 50 s) wrapped around a 1 W UV lamp emitting at 254 nm; without photoactivation, the signal is ∼70-fold lower. The S/N = 3 limit of detection for aqueous ozone is 3 μg l⁻¹ and good response slope is obtained up to an ozone concentration of 1.4 mg l⁻¹, the highest that could be made in this study. The response obeyed a quadratic equation with r² = 0.9984. No interference from permanganate ion is observed. The proposed system was applied to the monitoring of ozonation status of a playa lake water that exhibited significant ozone demand.     

Phthalocyanine-based field-effect transistors as gas sensors

In this review molecular field-effect transistors are described and compared with their gate-modified inorganic counterparts. The different processes involved in gas sensing are summarized. The advantages of transistors on resistors are demonstrated. The sensitivity of molecular field-effect transistors to strong oxidizing species, for example ozone, is detailed and compared with their sensitivity to humidity and volatile organic compounds. Application to ozone monitoring in urban atmospheres is also described.     

Cosmic-ray-driven electron-induced reactions of halogenated molecules adsorbed on ice surfaces: Implications for atmospheric ozone depletion and global climate change

The cosmic-ray-driven electron-induced reaction of halogenated molecules adsorbed on ice surfaces has been proposed as a new mechanism for the formation of the polar ozone hole. Here, experimental findings of dissociative electron transfer reactions of halogenated molecules on ice surfaces in electron stimulated desorption, electron trapping and femtosecond time-resolved laser spectroscopic measurements are reviewed. This is followed by a review of the evidence from recent satellite observations of this new mechanism for the Antarctic ozone hole, and all other possible physical mechanisms are discussed. Moreover, new observations of the 11-year cyclic variations of both polar ozone loss and stratospheric cooling and the seasonal variations of CFCs and CH₄ in the polar stratosphere are presented, and quantitative predictions of the Antarctic ozone hole in the future are given. Finally, a new observation of the effects of CFCs and cosmic-ray-driven ozone depletion on global climate change is also presented and discussed.     

A brief introduction and some background to the article JQSRT 1998;60:1025-31 and its companion

This note provides a short introduction, some background information and relevant history related to reprint of the article “Atmospheric remote-sensing reference data from GOME: Part 1. Temperature-dependent absorption cross-sections of NO₂ in the 231-794 nm range” (JQSRT 1998;60:1025-31). The article and its companion “Atmospheric remote-sensing reference data from GOME: 2. Temperature-dependent absorption cross sections of O₃ in the 231-794 nm range” (JQSRT 1999;61:509-17) provided timely and unique data sets of the absorption cross sections of Nitrogen dioxide, NO₂, and ozone, O₃. The reported absorption cross sections have a spectral resolution sufficient to distinguish the electronic vibrational and rotational features of NO₂ and O₃ and were made in the temperature range of relevance to the earth's atmosphere, viz. 200-300 K, over a wide spectral range. These species are two of the most important trace gases in earth's atmosphere, and play key roles in determining the chemistry and dynamics of the earth's atmosphere and the conditions at the earth's surface experienced by the biosphere. Whilst providing valuable information about the electronic states of NO₂ and O₃, these spectra were determined primarily for their exploitation in the retrieval of trace gases from measurements of solar back scattered radiation by ground based and space borne instrumentation. These yield the local and global amounts and distributions of NO₂ and O₃, thereby constraining our knowledge about atmospheric chemistry and dynamics and the impact of pollution from the local to the global scale. The measurement, publication and use of these spectral sets are among many important milestones in the development of atmospheric remote sensing.     

Infrared absolute intensities of ozone in the 10 and 5 μm spectral range: New investigations

Infrared high resolution spectra of ozone ¹⁶O₃ have been recorded in the 10 and 5 μm spectral ranges in order to derive their absolute intensities with a best achievable accuracy. Spectra have been recorded with the home made stepping mode FTS of GSMA (Reims). In the two spectral regions, we use UV-IR crossed beam cell. The quantification of ozone is achieved using UV cross section at 253.65 nm. A check of this UV calibration is also performed using direct pressure measurements of quasi-pure samples of O₃. The intensities are derived from infrared spectra using multifit procedure already tested. In the 10 μm range, where 12 different spectra have been recorded, 65 well selected lines led to a good agreement (better than 0.3%) with the HITRAN 2008 (or 2004) values, confirming our previous work [De Backer-Barilly MR, Barbe A. Absolute intensities of the 10 μm bands of ¹⁶O₃. J Mol Spectrosc 305:2001;43-53]. In the 5 μm range, where 18 transitions are selected, we also note a correct agreement with HITRAN 2008, despite a slightly larger averaged value between (1.9%) experimental and theoretical (HITRAN). As conclusion, authors suggest the use of current HITRAN 2008 data for atmospheric retrievals.     

Structure elucidation of cyclohexene (9Z)-octadec-9-enyl ethers isolated from the leaves of Uvaria cherrevensis (Annonaceae)

The phytochemical investigation of the leaf extract of Uvaria cherrevensis (Annonaceae) yielded three new cyclohexene (9Z)-octadec-9-enyl ethers, cherrevenols M-O (1–3), and a known fatty ester derivative (4). The structures of the isolated compounds were elucidated by spectroscopic and computer-aided molecular modelling methods. Ozone Induced Dissociation (OzID) mass spectrometry was employed to determine the C-9 position of the side chain olefinic double bonds, while ¹³C NMR spectroscopy indicated their (Z)-configurations. All isolated compounds were evaluated for their antimalarial and cytotoxic activities; all were inactive.     

Sequential Injection Chemiluminescence Methodology for Ozone Evaluation

A sequential injection methodology with chemiluminescence detection for the evaluation of residual ozone in waters is presented. The procedure is based on the reaction between luminol and ozone without catalysts.

Linear calibration plots were obtained for ozone concentrations between 0.05 and 2.0 mg L^?1, with a detection limit of 0.04 mg L^?1.

The developed methodology was applied to the determination of residual ozone in ozonized waters and the results complied with those furnished by the spectrophotometric reference procedure (relative deviations < 6.3%). The method exhibited good precision (RSD < 3.5%) and the sampling rate was about 140 determinations per hour.     

Intercomparison of ozone profiles measurements by a differential absorption lidar system and satellite instruments at Buenos Aires, Argentina

A ground-based DIfferential Absorption Lidar (DIAL) system has been implemented at CEILAP (CITEFA-CONICET) laboratory (34°33′S, 58°30′W), located in the Buenos Aires industrial suburbs. The goal is to perform measurements of the stratospheric ozone layer. Systematic measurements of ozone concentration profiles from 18 to 35 km altitude are performed since early 1999. Our measurements are carried out in 5 h in average during the night and in cloudless conditions. The DIAL system allows us to calculate directly the ozone profile from the lidar backscattering radiation since it is a self-calibrating technique. The signal processing takes into account the influence of the temperature profile on the ozone cross section. The temperature data are obtained from the radiosondes measurements performed at Ezeiza International Airport (34°30′S, 58°18′W), 27 km from DIAL station. The evolution of the stratospheric ozone profile is studied for different months. Results are compared with the data obtained by different satellites SAGE II, HALOE and GOME. The comparisons between our DIAL system and the satellite measurements show an agreement better than 20% for 20–35 km altitude range.     

臭氧与二乙胺和三乙胺气相反应的速率常数

利用自制的烟雾箱系统研究了臭氧与二乙胺和三乙胺的气相反应动力学. 实验过程中保证二乙胺和三乙胺浓度远远大于臭氧浓度, 使得实验在准一级条件下进行. 加入环己烷以消除实验过程中可能产生的OH自由基对反应的影响. 在(298±1) K和1.01×105 Pa条件下, 测得臭氧与二乙胺和三乙胺反应的绝对速率常数值分别为(1.33±0.15)×10^-17和(8.20±1.01)×10^-17 cm³·molecule^-1·s^-1. 与文献中已有的其它胺类的臭氧反应数据比较后发现, 臭氧与胺的反应可以用亲电反应机制来解释. 另外, 通过对比发现, 臭氧与三取代的烷基胺类的反应速率要远远大于其与二取代的烷基胺类的反应速率. 这在一定程度上可有助于解释外场观测到的气溶胶相中二烷基胺盐较多的事实. 利用测得的速率常数和大气中臭氧浓度, 还估算了二乙胺和三乙胺与臭氧反应的大气寿命. 结果显示, 与臭氧的反应是二乙胺和三乙胺在大气中的一种重要的消除途径, 尤其是在污染严重地区.