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 (-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, respectively. 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 (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 is a compatible scenario. The measurement uncertainty is too high to determine whether the average emission isotope delta 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 system

Radioglaciological studies on Hurd Peninsula glaciers, Livingston Island, Antarctica

We present the results of several radio-echo sounding surveys carried out on Johnsons and Hurd Glaciers, Livingston Island, Antarctica, between the 1999/2000 and 2004/05 austral summer campaigns, which included both radar profiling and common-midpoint measurements with low (20- 25 MHz)- and high (200MHz)-frequency radars. The latter have allowed us to estimate the radio-wave velocity in ice and firn and the corresponding water contents in temperate ice, which vary between 0 and 1.6% depending on the zone. Maximum ice thickness is ~200 m, with a mean value of 93.6 ± 2.5 m. Total ice volume is 0.968 ± 0.026 km3, for an area of 10.34 ± 0.03 km2. The subglacial relief of Johnsons Glacier is quite smooth, while that of Hurd Glacier shows numerous overdeepenings and peaks. The radar records suggest that Hurd Glacier has a polythermal structure, contrary to the usual assumption that glaciers in Livingston Island are temperate. This is also supported by other dynamical and geomorphological evidence

Nitrate stable isotopes and major ions in snow and ice samples from four Svalbard sites

Increasing reactive nitrogen (N-r) deposition in the Arctic may adversely impact N-limited ecosystems. To investigate atmospheric transport of N-r to Svalbard, Norwegian Arctic, snow and firn samples were collected from glaciers and analysed to define spatial and temporal variations (1 10 years) in major ion concentrations and the stable isotope composition (delta N-15 and delta O-18) of nitrate (NO3-) across the archipelago. The delta N-15(NO3-) and delta O-18(NO3-) averaged -4 parts per thousand and 67 parts per thousand in seasonal snow (2010-11) and -9 parts per thousand and 74 parts per thousand in firn accumulated over the decade 2001-2011. East-west zonal gradients were observed across the archipelago for some major ions (non-sea salt sulphate and magnesium) and also for delta N-15(NO3-) and delta O-18(NO3-) in snow, which suggests a different origin for air masses arriving in different sectors of Svalbard. We propose that snowfall associated with long-distance air mass transport over the Arctic Ocean inherits relatively low delta N-15(NO3-) due to in-transport N isotope fractionation. In contrast, faster air mass transport from the north-west Atlantic or northern Europe results in snowfall with higher delta N-15(NO3-) because in-transport fractionation of N is then time-limited

Reflections On the Anomalous ANITA Events: The Antarctic Subsurface as a Possible Explanation

The ANITA balloon experiment was designed to detect radio signals initiated by neutrinos and cosmic ray air showers. These signals are typically discriminated by the polarization and phase inversions of the radio signal. The reflected signal from cosmic rays suffer phase inversion compared to a direct tau neutrino event. In this paper we study sub-surface reflection, which can occur without phase inversion, in the context of the two anomalous up-going events reported by ANITA. We find that subsurface layers and firn density inversions may plausibly account for the events, while ice fabric layers and wind ablation crusts could also play a role. This hypothesis can be tested with radar surveying of the Antarctic region in the vicinity of the anomalous ANITA events. Future experiments should not use phase inversion as a sole criterion to discriminate between downgoing and upgoing events, unless the subsurface reflection properties are well understood.Comment: 4+2 pages, 3 figure