Corrigendum to "Fractional release factors of long-lived halogenated organic compounds in the tropical stratosphere" published in Atmos. Chem. Phys., 10, 1093–1103, 2010

We have noted a computational error in the calculation of the averaged Fractional Release Factors (FRFs) relative to the averaged FRF of CFCl3 (CFC-11). ..

Типологічне позиціювання національних організацій в інституціональній структурі громадянського суспільства

У статті пропонуються методологічні підходи до узагальнення та систематизації різних форм громадських організацій етнічного спрямування в контексті з’ясування їх місця в інституціональній структурі громадянського суспільства

High-resolution measurements of atmospheric molecular hydrogen and its isotopic composition at the West African coast of Mauritania

Oceans are a net source of molecular hydrogen (H-2) to the atmosphere, where nitrogen (N-2) fixation is assumed to be the main biological production pathway followed by photochemical production from organic material. The sources can be distinguished using isotope measurements because of clearly differing isotopic signatures of the produced hydrogen. Here we present the first ship-borne measurements of atmospheric molecular H-2 mixing ratio and isotopic composition at the West African coast of Mauritania (16-25 degrees W, 17-24 degrees N). This area is one of the biologically most active regions of the world's oceans with seasonal upwelling events and characterized by strongly differing hydrographical/ biological properties and phytoplankton community structures. The aim of this study was to identify areas of H-2 production and distinguish H-2 sources by isotopic signatures of atmospheric H-2. For this more than 100 air samples were taken during two cruises in February 2007 and 2008. During both cruises a transect from the Cape Verde Islands towards the Mauritanian Coast was sampled to cover differing oceanic regions such as upwelling and oligotrophic regimes. In 2007, additionally, four days were sampled at high resolution of one sample per hour to investigate a possible diurnal cycle of atmospheric H-2. Our results indicate the influence of local sources and suggest the Banc d'Arguin as a pool for precursors for photochemical H-2 production, whereas oceanic N-2 fixation could not be identified as a source for atmospheric H-2 during these two cruises. The variability in diurnal cycles is probably influenced by released precursors for photochemical H-2 production and also affected by a varying origin of air masses. This means for future investigations that only measuring the mixing ratio of H-2 is insufficient to explain the variability of an atmospheric diurnal cycle and support is needed, e.g. by isotopic measurements. Nevertheless, measurements of atmospheric H-2 mixing ratios, which are easy to conduct online during ship cruises, could be a useful indicator of production areas of biological precursors such as volatile organic compounds (VOCs) for further investigations

A consistent molecular hydrogen isotope chemistry scheme based on an independent bond approximation

The isotopic composition of molecular hydrogen (H<sub>2</sub>) produced by photochemical oxidation of methane (CH<sub>4</sub>) and Volatile Organic Compounds (VOCs) is a key quantity in the global isotope budget of (H<sub>2</sub>). The many individual reaction steps involved complicate its investigation. Here we present a simplified structure-activity approach to assign isotope effects to the individual elementary reaction steps in the oxidation sequence of CH<sub>4</sub> and some other VOCs. The approach builds on and extends the work by Gerst and Quay (2001) and Feilberg et al. (2007b). The description is generalized and allows the application, in principle, also to other compounds. The idea is that the C-H and C-D bonds – seen as reactive sites – have similar relative reaction probabilities in isotopically substituted, but otherwise identical molecules. The limitations of this approach are discussed for the reaction CH<sub>4</sub>+Cl. The same approach is applied to VOCs, which are important precursors of H<sub>2</sub> that need to be included into models. Unfortunately, quantitative information on VOC isotope effects and source isotope signatures is very limited and the isotope scheme at this time is limited to a strongly parameterized statistical approach, which neglects kinetic isotope effects. Using these concepts we implement a full hydrogen isotope scheme in a chemical box model and carry out a sensitivity study to identify those reaction steps and conditions that are most critical for the isotope composition of the final H<sub>2</sub> product. The reaction scheme is directly applicable in global chemistry models, which can thus include the isotope pathway of H<sub>2</sub> produced from CH<sub>4</sub> and VOCs in a consistent way

Global modelling of H2 mixing ratios and isotopic compositions with the TM5 model

The isotopic composition of molecular hydrogen (H2) contains independent information for constraining the global H2 budget. To explore this, we have implemented hydrogen sources and sinks, including their isotopic composition, into the global chemistry transport model TM5. For the first time, a global model now includes a simplified but explicit isotope reaction scheme for the photochemical production of H2. We present a comparison of modelled results for the H2 mixing ratio and isotope composition with available measurements on the seasonal to inter annual time scales for the years 2001–2007. The base model results agree well with observations for H2 mixing ratios. For dD[H2], modelled values are slightly lower than measurements. A detailed sensitivity study is performed to identify the most important parameters for modelling the isotopic composition of H2. The results show that on the global scale, the discrepancy between model and measurements can be closed by adjusting the default values of the isotope effects in deposition, photochemistry and the stratosphere-troposphere exchange within the known range of uncertainty. However, the available isotope data do not provide sufficient information to uniquely constrain the global isotope budget. Therefore, additional studies focussing on the isotopic composition near the tropopause and on the isotope effects in the photochemistry and deposition are recommended

Observation-based assessment of stratospheric fractional release, lifetimes, and ozone depletion potentials of ten important source gases

Estimates of the recovery time of stratospheric ozone heavily rely on the exact knowledge of the processes that lead to the decomposition of the relevant halogenated source gases. Crucial parameters in this context are fractional release factors (FRFs) as well as stratospheric lifetimes and ozone depletion potentials (ODPs). We here present data from the analysis of air samples collected between 2009 and 2011 on board research aircraft flying in the mid- and high-latitude stratosphere and infer the above-mentioned parameters for ten major source gases: CFCl3 (CFC-11), CF2Cl2 (CFC-12), CF2ClCFCl2 (CFC-113), CCl4 (carbon tetrachloride), CH3CCl3 (methyl chloroform), CHF2Cl (HCFC-22), CH3CFCl2 (HCFC-141b), CH3CF2Cl (HCFC-142b), CF2ClBr (H-1211), and CF3Br (H-1301). The inferred correlations of their FRFs with mean ages of air reveal less decomposition as compared to previous studies for most compounds. When using the calculated set of FRFs to infer equivalent stratospheric chlorine, we find a reduction of more than 20% as compared to the values inferred in the most recent Scientific Assessment of Ozone Depletion by the World Meteorological Organisation (WMO, 2011). We also note that FRFs and their correlations with mean age are not generally time-independent as often assumed. The stratospheric lifetimes were calculated relative to that of CFC-11. Within our uncertainties the ratios between stratospheric lifetimes inferred here agree with the values in recent WMO reports except for CFC-11, CFC-12 and CH3CCl3. Finally, we calculate lower ODPs than recommended by WMO for six out of ten compounds, with changes most pronounced for the three HCFCs. Collectively these newly calculated values may have important implications for the severity and recovery time of stratospheric ozone loss

Fractional release factors of long-lived halogenated organic compounds in the tropical stratosphere

Fractional release factors (FRFs) of organic trace gases are time-independent quantities that influence the calculation of Global Warming Potentials and Ozone Depletion Potentials. We present the first set of vertically resolved FRFs for 15 long-lived halocarbons in the tropical stratosphere up to 34 km altitude. They were calculated from measurements on air samples collected on board balloons and a high altitude aircraft. We compare the derived dependencies of FRFs on the mean stratospheric transit times (the so-called mean ages of air) with similarly derived FRFs originating from measurements at higher latitudes and find significant differences. Moreover a comparison with averaged FRFs currently used by the World Meteorological Organisation revealed the limitations of these measures due to their observed vertical and latitudinal variability. The presented data set could be used to improve future ozone level and climate projections

Extreme 13C depletion of CCl2F2 in firn air samples from NEEM, Greenland

A series of 12 high volume air samples collected from the S2 firn core during the North Greenland Eemian Ice Drilling (NEEM) 2009 campaign have been measured for mixing ratio and stable carbon isotope composition of the chlorofluorocarbon CFC-12 (CCl2F2). While the mixing ratio measurements compare favorably to other firn air studies, the isotope results show extreme 13C depletion at the deepest measurable depth (65 m), to values lower than d13C = -80‰ vs. VPDB (the international stable carbon isotope scale), compared to present day surface tropospheric measurements near -40‰. Firn air modeling was used to interpret these measurements. Reconstructed atmospheric time series indicate even larger depletions (to -120‰) near 1950 AD, with subsequent rapid enrichment of the atmospheric reservoir of the compound to the present day value. Mass-balance calculations show that this change is likely to have been caused by a large change in the isotopic composition of anthropogenic CFC-12 emissions, probably due to technological advances in the CFC production process over the last 80 yr, though direct evidence is lacking

Continuous-flow IRMS technique for determining the 17O excess of CO2 using complete oxygen isotope exchange with cerium oxide

This paper presents an analytical system for analysis of all single substituted isotopologues (¹²C¹⁶O¹⁷O, ¹²C¹⁶O¹⁸O, ¹³C¹⁶O¹⁶O) in nanomolar quantities of CO₂ extracted from stratospheric air samples. CO₂ is separated from bulk air by gas chromatography and CO₂ isotope ratio measurements (ion masses 45 / 44 and 46 / 44) are performed using isotope ratio mass spectrometry (IRMS). The ¹⁷O excess (Δ¹⁷O) is derived from isotope measurements on two different CO₂ aliquots: unmodified CO₂ and CO₂ after complete oxygen isotope exchange with cerium oxide (CeO₂) at 700 °C. Thus, a single measurement of Δ¹⁷O requires two injections of 1 mL of air with a CO₂ mole fraction of 390 μmol mol⁻¹ at 293 K and 1 bar pressure (corresponding to 16 nmol CO₂ each). The required sample size (including flushing) is 2.7 mL of air. A single analysis (one pair of injections) takes 15 minutes. The analytical system is fully automated for unattended measurements over several days. The standard deviation of the ¹⁷O excess analysis is 1.7‰. Multiple measurements on an air sample reduce the measurement uncertainty, as expected for the statistical standard error. Thus, the uncertainty for a group of 10 measurements is 0.58‰ for Δ ¹⁷O in 2.5 h of analysis. 100 repeat analyses of one air sample decrease the standard error to 0.20‰. The instrument performance was demonstrated by measuring CO₂ on stratospheric air samples obtained during the EU project RECONCILE with the high-altitude aircraft Geophysica. The precision for RECONCILE data is 0.03‰ (1σ) for δ¹³C, 0.07‰ (1σ) for δ¹⁸O and 0.55‰ (1σ) for δ¹⁷O for a sample of 10 measurements. This is sufficient to examine stratospheric enrichments, which at altitude 33 km go up to 12‰ for δ¹⁷O and up to 8‰ for δ¹⁸O with respect to tropospheric CO₂ : δ¹⁷O ~ 21‰ Vienna Standard Mean Ocean Water (VSMOW), δ¹⁸O ~ 41‰ VSMOW (Lämmerzahl et al., 2002). The samples measured with our analytical technique agree with available data for stratospheric CO₂

Isotopic evidence for biogenic molecular hydrogen production in the Atlantic Ocean

Oceans are a net source of molecular hydrogen (H2) to the atmosphere. The production of marine H2 is assumed to be mainly biological by N2 fixation, but photochemical pathways are also discussed. We present measurements of mole fraction and isotopic composition of dissolved and atmospheric H2 from the southern and northern Atlantic between 2008 and 2010. In total almost 400 samples were taken during five cruises along a transect between Punta Arenas (Chile) and Bremerhaven (Germany), as well as at the coast of Mauretania. The isotopic source signatures of dissolved H2 extracted from surface water are highly deuterium-depleted and correlate negatively with temperature, showing δD values of (−629 ± 54) ‰ for water temperatures at (27 ± 3) °C and (−249 ± 88) ‰ below (19 ± 1) °C. The results for warmer water masses are consistent with biological production of H2. This is the first time that marine H2 excess has been directly attributed to biological production by isotope measurements. However, the isotope values obtained in the colder water masses indicate that beside possible biological production a significant different source should be considered. The atmospheric measurements show distinct differences between both hemispheres as well as between seasons. Results from the global chemistry transport model TM5 reproduce the measured H2 mole fractions and isotopic composition well. The climatological global oceanic emissions from the GEMS database are in line with our data and previously published flux calculations. The good agreement between measurements and model results demonstrates that both the magnitude and the isotopic signature of the main components of the marine H2 cycle are in general adequately represented in current atmospheric models despite a proposed source different from biological production or a substantial underestimation of nitrogen fixation by several authors