Spectroscopic studies of the adsorption and reactions of chlorofluorocarbons (CFC-11 and CFC-12) and hydrochlorofluorocarbon (HCFC-22) on oxide surfaces

Raman and Fourier transform infrared (FT-IR) spectroscopy have been applied to a systematic investigation of the adsorption and decomposition of dichlorodifluoromethane (CCl2F2, CFC-12), fluorotrichloromethane (CCl3F, CFC-11), chlorodifluoromethane (CHClF2, HCFC-22) and molecular chlorine on oxide surfaces. Additionally, the effects of heating and ultraviolet photolysis of the CFC and HCFCs adsorbed on the oxide surfaces have been investigated. Spectral features for these species indicated a small wavenumber shift (1-6 cm-1) associated with the adsorbed phase. Some evidence, specifically the appearance of the Raman band at 507 cm-1, is presented to show that chlorine decomposition species are associated with these oxide surfaces. It was concluded that the new spectral feature (at ca. 507 cm-1) related with the decomposition of the CFC and HCFC molecules was an important indicator of the extent to which the reaction between the adsorbed CFC and HCFC and oxide surface has taken place. The extent of CFC-surface interaction has been quantified in terms of a maximum (Raman) frequency shift parameter (AM). Wavenumber shifts suggest both cation-adsorbate and non-specific adsorption interactions are occurring in the internal channels of the zeolites. Slow decomposition of the adsorbed CFCs under ultraviolet-visible photolysis (at ? > 300 nm) and/or thermal treatment was observed spectroscopically. Using FT-IR spectroscopy, the formation of gas-phase products (CO, CO2, HCl) both onyn photolysis and heating was evident. Results of these measurements are compared with the observed atmospheric reactivity of these compounds.

CFC Alternatives: A Fresh Look

This article examines, through a molecular perspective, the 'ozone-friendly' refrigerants R-134a and R-123 vis-à-vis R-12 and R-11, which are targeted to be phased out under the Montreal Protocol on Substances that Deplete the Ozone Layer, Final Act (1987). It appears that the molecular weight, size parameter, and dipole moment, of R-134a and R-123, may induce a pronounced effect on the chemical equilibrium of ice particles in the polar stratospheric clouds and subsequently influence the photochemical reactions therein. Non-polar, high-molecular-weight perfluoropropane (R-218), could be a better substitute for R-12, while R-134, which is a non-polar HFC of the ethane family, could also be a candidate although its molecular weight is lower than that of R-12. The search for a good substitute for R-11, however, must continue.

关中盆地东部浅层地下水水化学与CFC年龄研究

Hydrochemistry, isotope and CFCs were used to determine groundwater transport in the eastern part of the Guanzhong Basin. In this paper, we systematically collected water samples and measured major ions, 2H-18O and CFCs in surface water and shallow groundwater. Groundwater in this region can be divided into three categories based on total dissolved solids (TDS): fresh water with TDS < 1g/L, brackish water with TDS between 1～3g/L, and saline water with TDS > 3g/L. Saline water is mainly located in the north of the Wei River, and saline groundwater is not in the south. Tributaries in the south of the Wei River and underlain groundwater had similar 2H-18O values, indicating a close hydraulic connection between them. Tributaries in the north of the Wei River characterized certain extent of evaporation, and 2H-18O values deviated to a differing extent between surface water and groundwater, indicating that surface water in the north bank of the Wei River has little hydraulic connection with underlain groundwater. The CFCs age of groundwater from the piedmont recharge area was young, and became older toward the Wei River valley. Vertically, the CFCs age of groundwater increased with well depth. The shallow groundwater is mainly composed of young water with ages < 60 years and old water with ages > 60 years. Young water is in a larger proportion. The NO3-N concentration positively correlates with the CFC-12 concentration in the groundwater, which indicates that young water is subjected to be contaminated. Keyword: Guanzhong Basin , shallow groundwater, isotope, CFC

Analysis of physiological data from the International Clonal Trial (CFC)

A range of physiological parameters (canopy light transmission, canopy shape, leaf size, flowering and flushing intensity) were measured from the International Clone Trial, typically over the course of two years. Data were collected from six locations, these being: Brazil, Ecuador, Trinidad, Venezuela, Côte d’Ivoire and Ghana. Canopy shape varied significantly between clones, although it showed little variation between locations. Genotypic variation in leaf size was differentially affected by the growth location; such differences appeared to underlie a genotype by environment interaction in relation to canopy light transmission. Flushing data were recorded at monthly intervals over the course of a year. Within each location, a significant interaction was observed between genotype and time of year, suggesting that some genotypes respond to a greater extent than others to environmental stimuli. A similar interaction was observed for flowering data, where significant correlations were found between flowering intensity and temperature in Brazil and flowering intensity and rainfall in Côte d’Ivoire. The results demonstrate the need for local evaluation of cocoa clones and also suggest that the management practices for particular planting material may need to be fine-tuned to the location in which they are cultivated.

Infrared absorption spectra, radiative efficiencies, and global warming potentials of newly-detected halogenated compounds: CFC-113a, CFC-112 and HCFC-133a

CFC-113a (CF3CCl3), CFC-112 (CFCl2CFCl2) and HCFC-133a (CF3CH2Cl) are three newly detected molecules in the atmosphere that are almost certainly emitted as a result of human activity. It is important to characterise the possible contribution of these gases to radiative forcing of climate change and also to provide information on the CO2-equivalence of their emissions. We report new laboratory measurements of absorption cross-sections of these three compounds at a resolution of 0.01 cm−1 for two temperatures 250 K and 295 K in the spectral range of 600–1730 cm−1. These spectra are then used to calculate the radiative efficiencies and global warming potentials (GWP). The radiative efficiencies are found to be between 0.15 and 0.3 W∙m−2∙ppbv−1. The GWP for a 100 year time horizon, relative to carbon dioxide, ranges from 340 for the relatively short-lived HCFC-133a to 3840 for the longer-lived CFC-112. At current (2012) concentrations, these gases make a trivial contribution to total radiative forcing; however, the concentrations of CFC-113a and HCFC-133a are continuing to increase. The 2012 CO2-equivalent emissions, using the GWP (100), are estimated to be about 4% of the current global CO2-equivalent emissions of HFC-134a

The SPARC Data Initiative: comparisons of CFC-11, CFC-12, HF and SF6 climatologies from international satellite limb sounders

A quality assessment of the CFC-11 (CCl3F), CFC-12 (CCl2F2), HF, and SF6 products from limb-viewing satellite instruments is provided by means of a detailed intercomparison. The climatologies in the form of monthly zonal mean time series are obtained from HALOE, MIPAS, ACE-FTS, and HIRDLS within the time period 1991–2010. The intercomparisons focus on the mean biases of the monthly and annual zonal mean fields and aim to identify their vertical, latitudinal and temporal structure. The CFC evaluations (based on MIPAS, ACE-FTS and HIRDLS) reveal that the uncertainty in our knowledge of the atmospheric CFC-11 and CFC-12 mean state, as given by satellite data sets, is smallest in the tropics and mid-latitudes at altitudes below 50 and 20 hPa, respectively, with a 1σ multi-instrument spread of up to ±5 %. For HF, the situation is reversed. The two available data sets (HALOE and ACE-FTS) agree well above 100 hPa, with a spread in this region of ±5 to ±10 %, while at altitudes below 100 hPa the HF annual mean state is less well known, with a spread ±30 % and larger. The atmospheric SF6 annual mean states derived from two satellite data sets (MIPAS and ACE-FTS) show only very small differences with a spread of less than ±5 % and often below ±2.5 %. While the overall agreement among the climatological data sets is very good for large parts of the upper troposphere and lower stratosphere (CFCs, SF6) or middle stratosphere (HF), individual discrepancies have been identified. Pronounced deviations between the instrument climatologies exist for particular atmospheric regions which differ from gas to gas. Notable features are differently shaped isopleths in the subtropics, deviations in the vertical gradients in the lower stratosphere and in the meridional gradients in the upper troposphere, and inconsistencies in the seasonal cycle. Additionally, long-term drifts between the instruments have been identified for the CFC-11 and CFC-12 time series. The evaluations as a whole provide guidance on what data sets are the most reliable for applications such as studies of atmospheric transport and variability, model–measurement comparisons and detection of long-term trends. The data sets will be publicly available from the SPARC Data Centre and through PANGAEA (doi:10.1594/PANGAEA.849223).

Transferência de tecnologia na lavoura arrozeira gaúcha : uma análise do Projeto CFC

O Projeto CFC é uma iniciativa de transferência de tecnologia em lavouras de arroz irrigado e está sendo executado simultaneamente no Rio Grande do Sul e na Venezuela. Seu principal propósito é o aumento de produtividade, diminuindo a lacuna de rendimento existente entre as lavouras atuais e o potencial produtivo da cultura obtido em áreas experimentais. Para tanto, está se usando um sistema híbrido de transferência de tecnologia de manejo para altas produtividades. Este sistema inclui o trabalho em grupos de produtores, o estabelecimento de parcelas demonstrativas e a flexibilidade no manejo. As instituições envolvidas são o IRGA (Instituto Riograndense do Arroz) e o FLAR (Fundo Latinoamericano para Arroz Irrigado) na condição de executores, e o CFC (Fundo Comum para Commodities) na condição de principal agente financiador. A presente dissertação, além de caracterizar e contextualizar o Projeto CFC, tem como objetivo analisar o referido Projeto, indicando alguns de seus impactos iniciais e potenciais à lavoura arrozeira gaúcha. Nesse sentido, foi aplicado um questionário visando captar a percepção de produtores, bem como foram construídos alguns cenários a partir dos resultados das parcelas demonstrativas instaladas na safra 2003/2004. Adicionalmente, foi feita uma análise em nível setorial, abordando alguns fatores determinantes da competitividade da produção orizícola. Por fim, além de impactos iniciais e potenciais do Projeto CFC, foi possível perceber indicativos de sua eficácia como método de transferência de tecnologia.

Controlled foreign companies (CFC) e delocalizzazione delle attività economiche nel diritto interno e nell'ordinamento europeo

Le ragioni della delocalizzazione sono molteplici e di differente natura. Si delocalizza, in primo luogo, per ragioni di stampo economico, finanziario eccetera, ma questa spinta naturale alla delocalizzazione è controbilanciata, sul piano strettamente tributario, dall’esigenza di preservare il gettito e da quella di controllare la genuinità della delocalizzazione medesima. E’ dunque sul rapporto tra “spinte delocalizzative” dell’impresa, da un lato, ed esigenze “conservative” del gettito pubblico, dall’altro, che si intende incentrare il presente lavoro. Ciò alla luce del fatto che gli strumenti messi in campo dallo Stato al fine di contrastare la delocalizzazione (più o meno) artificiosa delle attività economiche devono fare i conti con i principi comunitari introdotti con il Trattato di Roma e tratteggiati negli anni dalla giurisprudenza della Corte di Giustizia. In quest’ottica, la disciplina delle CFC costituisce un ottimo punto di partenza per guardare ai fenomeni di produzione transnazionale della ricchezza e agli schemi di ordine normativo preposti alla tassazione di codesta ricchezza. Ed infatti, le norme sulle CFC non fanno altro che omogeneizzare un sistema che, altrimenti, sarebbe lasciato alla libera iniziativa degli uffici fiscali. Tale “normalizzazione”, peraltro, giustifica le esigenze di apertura che sono incanalate nella disciplina degli interpelli disapplicativi. Con specifico riferimento alla normativa CFC, assumono particolare rilievo la libertà di stabilimento ed il principio di proporzionalità anche nella prospettiva del divieto di abuso del diritto. L’analisi dunque verterà sulla normativa CFC italiana con l’intento di comprendere se codesta normativa, nelle sue diverse sfaccettature, possa determinare situazioni di contrasto con i principi comunitari. Ciò anche alla luce delle recenti modifiche introdotte dal legislatore con il d.l. 78/2009 in un quadro normativo sempre più orientato a combattere le delocalizzazioni meramente fittizie.

Analisi di tendenza per ozono e CFC-11 nella serie decennale delle misure di MIPAS in stratosfera e alta troposfera

Lo strumento MIPAS, operativo a bordo del satellite polare ENVISAT negli anni dal 2002 al 2012, ha misurato spettri di emissione nel medio infrarosso utilizzando la tecnica di scansione del lembo atmosferico. L'Agenzia Spaziale Europea (ESA), mediante un algoritmo di inversione ottimizzato, ha ricavato dagli spettri di MIPAS la distribuzione verticale di diversi composti chimici minoritari in stratosfera e alta troposfera. Tra questi composti figurano l'ozono (O3) e il CFC-11. Lo strato di ozono stratosferico svolge una funzione fondamentale come schermo della radiazione ultravioletta solare, altrimenti dannosa per gli esseri viventi sulla terra. D'altra parte, da alcuni decenni i cosiddetti cloro-fluoro carburi (CFC), tra cui la molecola di CCl3F (indicata sinteticamente con la sigla CFC-11) sono ritenuti responsabili della diminuzione generale dell'ozono stratosferico. Per questo motivo nel 1987 a Montreal è stato siglato un accordo internazionale per limitare l'immissione dei CFC in atmosfera. A partire dalla fine degli anni '80, in base a questo accordo, ci si aspetta quindi una progressiva riduzione dei CFC e un conseguente graduale recupero della concentrazione di ozono. Le misure di MIPAS, con copertura geografica globale, offrono una possibilità assai interessante per la verifica di queste tendenze attese. In questo lavoro di tesi, i profili verticali di frazione volumetrica (VMR) di ozono e CFC-11 ricavati dal processore di ESA versione 6.0 sono stati interpolati a livelli di pressione costante, raggruppati per bande di latitudine e mediati su intervalli di tempo mensili. Abbiamo quindi sviluppato un modello di tendenza parametrico che include un termine costante, uno lineare, due termini dell'oscillazione quasi biennale (QBO), un termine di flusso solare radio e diversi termini armonici in seno e coseno con periodo diverso. Il modello è stato quindi adattato mediante un algoritmo di minimizzazione di Levenberg-Marquardt alle medie mensili ottenute dalle misure di MIPAS per tutto il periodo che va da luglio 2002 ad aprile 2012. Le stime di tendenza ottenute per ozono e CFC-11 sono statisticamente significative e, a seconda della latitudine e del livello di pressione considerato, assumono una gamma di valori che va da -0.15 ppmv/decade a +0.44 ppmv/decade per l'ozono e una gamma di valori che va da -50.2 pptv/decade a +6.5 pptv/decade per il CFC-11. Abbiamo ottenuto tendenze per la maggior parte leggermente positive per l'ozono e quasi ovunque fortemente negative per il CFC-11, risultato in accordo con le disposizioni emanate a seguito del Protocollo di Montreal e in buon accordo anche con lavori precedentemente pubblicati in letteratura. Infine abbiamo stimato l'errore sistematico sulle tendenze ricavate, causato dalla deriva strumentale dovuta alla non-linearità della risposta dei rivelatori, che varia a seguito dell'invecchiamento dei rivelatori stessi.

Noble gas, CFC and other geochemical evidence for the age and origin of the Bath thermal waters, UK

The city of Bath is a World Heritage site and its thermal waters, the Roman Baths and new spa development rely on undisturbed flow of the springs (45 °C). The current investigations provide an improved understanding of the residence times and flow regime as basis for the source protection. Trace gas indicators including the noble gases (helium, neon, argon, krypton and xenon) and chlorofluorocarbons (CFCs), together with a more comprehensive examination of chemical and stable isotope tracers are used to characterise the sources of the thermal water and any modern components. It is shown conclusively by the use of 39Ar that the bulk of the thermal water has been in circulation within the Carboniferous Limestone for at least 1000 years. Other stable isotope and noble gas measurements confirm previous findings and strongly suggest recharge within the Holocene time period (i.e. the last 12 kyr). Measurements of dissolved 85Kr and chlorofluorocarbons constrain previous indications from tritium that a small proportion (<5%) of the thermal water originates from modern leakage into the spring pipe passing through Mesozoic valley fill underlying Bath. This introduces small amounts of O2 into the system, resulting in the Fe precipitation seen in the King’s Spring. Silica geothermometry indicates that the water is likely to have reached a maximum temperature of between 69–99 °C, indicating a most probable maximum circulation depth of ∼3 km, which is in line with recent geological models. The rise to the surface of the water is sufficiently indirect that a temperature loss of >20 °C is incurred. There is overwhelming evidence that the water has evolved within the Carboniferous Limestone formation, although the chemistry alone cannot pinpoint the geometry of the recharge area or circulation route. For a likely residence time of 1–12 kyr, volumetric calculations imply a large storage volume and circulation pathway if typical porosities of the limestone at depth are used, indicating that much of the Bath-Bristol basin must be involved in the water storage.

Chlorine isotope composition in chlorofluorocarbons CFC-11, CFC-12 and CFC-113 in firn, stratospheric and tropospheric air

The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2, Laube et al., 2010a), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation (ϵapp) for mid- and high-latitude stratospheric samples are respectively −2.4 (0.5) and −2.3 (0.4) ‰ for CFC-11, −12.2 (1.6) and −6.8 (0.8) ‰ for CFC-12 and −3.5 (1.5) and −3.3 (1.2) ‰ for CFC-113, where the number in parentheses is the numerical value of the standard uncertainty expressed in per mil. Assuming a constant isotope composition of emissions, we calculate the expected trends in the tropospheric isotope signature of these gases based on their stratospheric 37Cl enrichment and stratosphere–troposphere exchange. We compare these projections to the long-term δ (37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978–2010) and tropospheric firn air samples from Greenland (North Greenland Eemian Ice Drilling (NEEM) site) and Antarctica (Fletcher Promontory site). From 1970 to the present day, projected trends agree with tropospheric measurements, suggesting that within analytical uncertainties, a constant average emission isotope delta (δ) is a compatible scenario. The measurement uncertainty is too high to determine whether the average emission isotope δ has been affected by changes in CFC manufacturing processes or not. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes (approximately 200 mL), using a single-detector gas chromatography–mass spectrometry (GC–MS) system.