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.

Chlorofluorocarbons and noble gas measured on water bottle samples during three POLARSTERN cruises

We use a 27 year long time series of repeated transient tracer observations to investigate the evolution of the ventilation time scales and the related content of anthropogenic carbon (Cant) in deep and bottom water in the Weddell Sea. This time series consists of chlorofluorocarbon (CFC) observations from 1984 to 2008 together with first combined CFC and sulphur hexafluoride (SF6) measurements from 2010/2011 along the Prime Meridian in the Antarctic Ocean and across the Weddell Sea. Applying the Transit Time Distribution (TTD) method we find that all deep water masses in the Weddell Sea have been continually growing older and getting less ventilated during the last 27 years. The decline of the ventilation rate of Weddell Sea Bottom Water (WSBW) and Weddell Sea Deep Water (WSDW) along the Prime Meridian is in the order of 15-21%; the Warm Deep Water (WDW) ventilation rate declined much faster by 33%. About 88-94% of the age increase in WSBW near its source regions (1.8-2.4 years per year) is explained by the age increase of WDW (4.5 years per year). As a consequence of the aging, the Cant increase in the deep and bottom water formed in the Weddell Sea slowed down by 14-21% over the period of observations.

Chlorofluorocarbons (CFC) recovery and source reduction study : interim report /

""ILENR/RE-PA-90/04."

Chlorofluorocarbons, helium, and neon measured on water bottle samples during POLARSTERN cruise ANT-XXII/2 (ISPOL)

During Ice Station POLarstern (ISPOL; R.V. Polarstern cruise ANT XXII/2, November 2004-January 2005), hydrographic and tracer observations were obtained in the western Weddell Sea while drifting closely in front of the Larsen Ice Shelf. These observations indicate recently formed Weddell Sea Bottom Water, which contains significant contributions of glacial melt water in its upper part, and High-Salinity Shelf Water in its lower layer. The formation of this bottom water cannot be related to the known sources in the south, the Filchner-Ronne Ice Shelf. We show that this bottom water is formed in the western Weddell Sea, most likely in interaction with the Larsen C Ice Shelf. By applying an Optimum Multiparameter Analysis (OMP) using temperature, salinity, and noble gas observations (helium isotopes and neon), we obtained mean glacial melt-water fractions of about 0.1% in the bottom water. On sections across the Weddell Gyre farther north, melt-water fractions are still on the order of 0.04%. Using chlorofluorocarbons (CFCs) as age tracers, we deduced a mean transit time between the western source and the bottom water found on the slope toward the north (9±3 years). This transit time is larger and the inferred transport rate is small in comparison to previous findings. But accounting for a loss of the initially formed bottom water volume due to mixing and renewal of Weddell Sea Deep Water, a formation rate of 1.1±0.5 Sv in the western Weddell Sea is plausible. This implies a basal melt rate of 35±19 Gt/year or 0.35±0.19 m/year at the Larsen Ice Shelf. This bottom water is shallow enough that it could leave the Weddell Basin through the gaps in the South Scotia Ridge to supply Antarctic Bottom Water. These findings emphasize the role of the western Weddell Sea in deep- and bottom-water formation, particularly in view of changing environmental conditions due to climate variability, which might induce enhanced melting or even decay of ice shelves.