A Ten Years Monitoring of Chlorofluorocarbons at the Antarctica: Results and Perspectives

Abstract

Chlorofluorocarbons are man-made long lasting atmospheric pollutants of great environmental concern, responsible for important global change phenomena. Recently, they were replaced by hydrogenated halocarbons that, even if less persistent, do not lack in environmental impact. Atmospheric concentrations of these compounds were measured in Antarctica by gas chromatography. The extremely low atmospheric mixing ratios of these compounds require a pre-concentration step of the air sample on suitable adsorbent in order to meet the sensitivity of the analytical method Results obtained analyzing air samples collected in Antarctica since 1988 for the determination of CFC-12 and CFC-11 are reported, together with data concerning the less abundant species.     

Comparison of theoretical methods for assessing the heat of formation of C1 and C2 chlorofluorocarbons and hydrochlorofluorocarbons

The heat of formation of a number of key C₁ and C₂ chlorofluorocarbons and hydrochlorofluorocarbons have been calculated by G3, G3MP2, G3MP2B3 and G3B3 methods. Based on the results of the atomization approach, it was found that the errors are approximately dependent upon the number of C-F or C-Cl bonds. Moreover, the bond additive correction (BAC) procedure and isodesmic reactions approach improved the accuracy and decreased these system errors significantly. The extended comparison between the BAC procedure and isodesmic reaction approaches had been made; the latter yielded the best results and showed broader applicability.     

Simultaneous determination of CFC-11, CFC-12 and CFC-113 in seawater samples using a purge and trap gas-chromatographic system

We have optimized the analytical parameters of a homemade instrument for the simultaneous measurement of the chlorofluorocarbons CCl₂F₂ (CFC-12), CCl₃F (CFC-11) and C₂Cl₃F₃ (CFC-113) in seawater. Seawater samples are flame sealed into 60 ml glass ampoules avoiding any contact with the atmosphere and stored in cold, dark condition until analysis. In the laboratory, after cracking the ampoule in an enclosed chamber filled with ultra-pure nitrogen, the seawater sample is transferred to a stripping chamber, where ultra-pure nitrogen is used to purge the dissolved CFCs from the seawater. The extracted gases are then cryogenically trapped, subsequently the trap is isolated and heated and the CFCs are transferred by a carrier gas stream into a precolumn and then are separated on a gaschromatographic packed column. To separate adequately CFC-12 from N₂O, during the early part of the chromatographic run, the gas stream passes through a molecular sieve, which is then isolated and backflushed. The CFCs are detected on an electron capture detector (⁶³Ni ECD). After a careful choice of the experimental conditions, the performances of the system were evaluated. The detection limits for seawater samples are: 0.0081 pmol kg⁻¹ for CFC-12, 0.0073 pmol kg⁻¹ for CFC-11 and 0.0043 pmol kg⁻¹ for CFC-113. The reproducibility of replicate samples lies within 5% for the three CFCs. The system has been successfully employed for CFC measurements in seawater samples collected in the Ross Sea (Antarctica) in the framework of the Italian Antarctic research project.     

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.     

Hydrogen substitution effect on the solubility of perhalogenated compounds in ionic liquid [bmim][PF6]

Solubility behaviors of binary mixtures of CFCl₃ (R-11), CFCl₂-CF₂Cl (R-113), CHCl₃ (R-20), CDCl₃ (R-20-d), CHCl₂–CF₃ (R-123) with room-temperature ionic liquid [bmim][PF₆] (1-butyl-3-methylimidazolium hexafluorophosphate) have been investigated using the volumetric and cloud-point methods, since all the systems show liquid–liquid equilibria (LLE). Large immiscibility (LLE) gaps of the perhalogenated compounds (R-11 and R-113) in the ionic liquid have been drastically reduced by the addition of only one hydrogen (or deuterium) in these compounds. The R-123 + [bmim][PF₆] binary system belongs to the Type-V fluid behavior. Noticeably large negative values (−2 to −8 cm³ mol⁻¹) of the excess molar volume in the ionic liquid-rich side solution have been observed for all the present systems. Experimental LLE data have been well correlated by the use of the NRTL (non-random two liquid) activity coefficient model.     

吹扫捕集-气相色谱法同时测定海水中的氟氯烃和六氟化硫

氟氯烃(CFCs)和六氟化硫(SF6)都是人工合成的卤代化合物,在海洋科学考察中是非常重要的基础观测参数,在示踪海/气交换、水团交换等一系列重要海洋学过程研究中均有特殊的应用价值;同时,也可以用于估算表观耗氧速率(Apparent oxygen utilization rate,AOUR)以及人为碳(Anthropogenic C02,Cant)等一些重要的物理及生物地球化学过程参量.CFCs,SF6在海水中的浓度非常低,测量难度大,而CFCs和SF6的联合使用对海洋学过程研究具有重大意义.本研究建立了一套吹扫捕集系统以分析海水中CFC-12和SF6,对吹扫捕集系统测定条件进行了优化,最佳的实验条件为:捕集温度-70℃,吹扫时间8min,吹扫压力310 kPa,脱附时间30 s,脱附温度90℃.本方法测定简单、灵敏度高,CFC-12和SF6的检出限分别为0.02 pmol/kg和0.03 fmol/kg,CFC-12和SF6的测定精密度分别为±1.2％和±0.5％.标准工作曲线的线性相关系数均大于0.9995.本方法成功应用于2014年中国第六次北极科学考察航次中采集的海水样品的测定.     

Catalytic hydrolysis of CFC-12 over solid acid Ti(SO_4)_2

Due to increasing enthusiasm for environmental preservation, the synthesis ofchlorofluorocarbons (CFCs) alternatives and the decomposition of existing CFCs havebeen two hot topics since the production and utilization of CFCs are banned by manycountries. The former has been well carried out while the latter was rarely reported inChina. Among a dozen of decomposition approaches. catalytic hydrolysis is verypromising because of simple processes, requiring mild conditions, dioxins free and the…     

Hydrochlorofluorocarbon concentration in exit gas from a heated reactor

Hydrochlorofluorocarbons (HCFCs) have been shown to be harmful to the ozone layer because they provide free chlorine atoms that destroy ozone (O₃). The purpose of this research was to devise a method to decompose hydrochlorofluorocarbon molecules efficiently and inexpensively without producing harmful by-products. Monochlorodifluoromethane (CHClF₂) was selected for this study because it is a synthetic and frequently used refrigerant. A conversion/reactor tank was designed that consisted of four or five layers of sodium oxalate enclosed in the reaction tank, resting on glass wool and aluminum screens. Monochlorodifluoromethane enters above the layers of sodium oxalate and exits after passing through the last layer through a hole placed perpendicular to the entrance hole. Using the Argentometric method for chloride analysis, results showed that this device decomposed the HCFC molecules to chlorides, fluorides, and carbon dioxide. The method was tested under varying temperature, flow rates, and structural design conditions to obtain optimum efficiency.     

Long-term evolution in the tropospheric concentration of chlorofluorocarbon 12 (CCl2F2) derived from high-spectral resolution infrared solar absorption spectra: retrieval and comparison with in situ surface measurements

The average tropospheric volume mixing ratios of chlorofluorocarbon 12 (CCl₂F₂) have been retrieved from high-spectral resolution ground-based infrared solar-absorption spectra recorded from March 1982 to October 2003 with the McMath Fourier transform spectrometer at the US National Solar Observatory facility on Kitt Peak in southern Arizona (31.9°N, 111.6°W, 2.09 km altitude). The retrievals are based on fits to the unresolved ν₈ band Q-branches near using the SFIT2 retrieval algorithm. The annual increase rate was equal to (16.88±1.37) parts per trillion (10^-12) by volume at the beginning of the time series, March 1982, or (4.77±0.04)%, 1 sigma, declining progressively to (2.49±1.24) parts per trillion, by volume at the end, October 2003, or (0.46±0.24)%, 1 sigma. Average tropospheric mixing ratios from the solar spectra have been compared with average surface flask and in situ sampling measurements from the Climate Monitoring and Diagnostics Laboratory (CMDL) station at Niwot Ridge, CO, (USA) (40.0°N, 105.5°W, 3013 m altitude). The average ratio and standard deviation of the monthly means of the retrieved tropospheric mixing ratios relative to the CMDL surface mixing ratios is (1.01±0.03) for the overlapping time period. Both datasets demonstrate the progressive impact of the Montreal protocol and its strengthening amendments on the trend of CCl₂F₂, though a tropospheric decrease has yet to be observed.     

A routine gas chromatographic method for the analysis of chlorofluorocarbons in aerosol cans

Summary A gas chromatographic (GC) method for the routine analysis of fully halogenated chlorofluorocarbons (CFCs) in aerosol cans is described. The identification of CFCs by GC was found to be in full agreement with those by GC-mass-spectrometery. The method has been applied to the analysis of CFCs in 448 aerosol products. The most commonly used fully halogenated CFC propellants in aerosol cans were found to be CFC11, CFC12 and CFC114.