Firn Research Articles

A revised 1000 year atmospheric δ13C‐CO2 record from Law Dome and South Pole, Antarctica

We present new measurements of δ13C of CO2 extracted from a high‐resolution ice core from Law Dome (East Antarctica), together with firn measurements performed at Law Dome and South Pole, covering the last 150 years. Our analysis is motivated by the need to better understand the role and feedback of the carbon (C) cycle in climate change, by advances in measurement methods, and by apparent anomalies when comparing ice core and firn air δ13C records from Law Dome and South Pole. We demonstrate improved consistency between Law Dome ice, South Pole firn, and the Cape Grim (Tasmania) atmospheric δ13C data, providing evidence that our new record reliably extends direct atmospheric measurements back in time. We also show a revised version of early δ13C measurements covering the last 1000 years, with a mean preindustrial level of −6.50‰. Finally, we use a Kalman Filter Double Deconvolution to infer net natural CO2 fluxes between atmosphere, ocean, and land, which cause small δ13C deviations from the predominant anthropogenically induced δ13C decrease. The main features found from the previous δ13C record are confirmed, including the ocean as the dominant cause for the 1940 A.D. CO2 leveling. Our new record provides a solid basis for future investigation of the causes of decadal to centennial variations of the preindustrial atmospheric CO2 concentration. Those causes are of potential significance for predicting future CO2 levels and when attempting atmospheric verification of recent and future global carbon emission mitigation measures through Coupled Climate Carbon Cycle Models.

A 60 yr record of atmospheric carbon monoxide reconstructed from Greenland firn air

Abstract. We present the first reconstruction of the Northern Hemisphere (NH) high latitude atmospheric carbon monoxide (CO) mole fraction from Greenland firn air. Firn air samples were collected at three deep ice core sites in Greenland (NGRIP in 2001, Summit in 2006 and NEEM in 2008). CO records from the three sites agree well with each other as well as with recent atmospheric measurements, indicating that CO is well preserved in the firn at these sites. CO atmospheric history was reconstructed back to the year 1950 from the measurements using a combination of two forward models of gas transport in firn and an inverse model. The reconstructed history suggests that Arctic CO in 1950 was 140–150 nmol mol−1, which is higher than today's values. CO mole fractions rose by 10–15 nmol mol−1 from 1950 to the 1970s and peaked in the 1970s or early 1980s, followed by a ≈ 30 nmol mol−1 decline to today's levels. We compare the CO history with the atmospheric histories of methane, light hydrocarbons, molecular hydrogen, CO stable isotopes and hydroxyl radicals (OH), as well as with published CO emission inventories and results of a historical run from a chemistry-transport model. We find that the reconstructed Greenland CO history cannot be reconciled with available emission inventories unless unrealistically large changes in OH are assumed. We argue that the available CO emission inventories strongly underestimate historical NH emissions, and fail to capture the emission decline starting in the late 1970s, which was most likely due to reduced emissions from road transportation in North America and Europe.

Can the carbon isotopic composition of methane be reconstructed from multi-site firn air measurements?

Abstract. Methane is a strong greenhouse gas and large uncertainties exist concerning the future evolution of its atmospheric abundance. Analyzing methane atmospheric mixing and stable isotope ratios in air trapped in polar ice sheets helps in reconstructing the evolution of its sources and sinks in the past. This is important to improve predictions of atmospheric CH4 mixing ratios in the future under the influence of a changing climate. The aim of this study is to assess whether past atmospheric δ13C(CH4) variations can be reliably reconstructed from firn air measurements. Isotope reconstructions obtained with a state of the art firn model from different individual sites show unexpectedly large discrepancies and are mutually inconsistent. We show that small changes in the diffusivity profiles at individual sites lead to strong differences in the firn fractionation, which can explain a large part of these discrepancies. Using slightly modified diffusivities for some sites, and neglecting samples for which the firn fractionation signals are strongest, a combined multi-site inversion can be performed, which returns an isotope reconstruction that is consistent with firn data. However, the isotope trends are lower than what has been concluded from Southern Hemisphere (SH) archived air samples and high-accumulation ice core data. We conclude that with the current datasets and understanding of firn air transport, a high precision reconstruction of δ13C of CH4 from firn air samples is not possible, because reconstructed atmospheric trends over the last 50 yr of 0.3–1.5 ‰ are of the same magnitude as inherent uncertainties in the method, which are the firn fractionation correction (up to ~2 ‰ at individual sites), the Kr isobaric interference (up to ~0.8 ‰, system dependent), inter-laboratory calibration offsets (~0.2 ‰) and uncertainties in past CH4 levels (~0.5 ‰).

Monitoring glacier zones and snow/firn line changes in the Qinghai–Tibetan Plateau using C-band SAR imagery

Small glaciers and ice caps in mountainous areas are often sensitive indicators of local and global climate change. In this paper, typical continental glaciers, the Dongkemadi and its neighbouring glaciers in the central area of the Qinghai–Tibetan Plateau, are monitored using multi-sensor C-band synthetic aperture radar (SAR) imagery. The study includes analysis of the alternating processes of ablation and freezing, the glacier zones detected on SAR images, and the changing snow/firn line across different days, seasons, and years. Experiments show that in late summer the wet snow-/firn-ice boundary, which is termed the late summer wet snow/firn line (WSFL) is easily detected on SAR images and it is relatively stable over multiple days. Also, the detected late summer WSFL, and the recorded yearly equilibrium line which reflects glacier mass balance, are close in a positive mass balance year, but the detected late summer WSFL is lower than the equilibrium line in a negative mass balance year. By combining pit and SAR observations it was found that the firn can be divided into two parts on the glaciers; the thick firn that lies in the neve basin is distinct on SAR images in winter, but the firn surrounding the basin with thickness ranging from 0 to 20cm is difficult to recognize. The thick firn line (the lower boundary of neve basin) is stable in observations eight years apart. Based on the C-band VV polarization SAR image experiments, field work, and existing records, the spatiotemporal backscatter signature specific to the typical continental glacier is identified. The spatiotemporal backscatter signature helps to understand mass balance proxies and surface melt patterns of the glaciers in SAR images.

Continuous monitoring of summer surface water vapor isotopic composition above the Greenland Ice Sheet

Abstract. We present here surface water vapor isotopic measurements conducted from June to August 2010 at the NEEM (North Greenland Eemian Drilling Project) camp, NW Greenland (77.45° N, 51.05° W, 2484 m a.s.l.). Measurements were conducted at 9 different heights from 0.1 m to 13.5 m above the snow surface using two different types of cavity-enhanced near-infrared absorption spectroscopy analyzers. For each instrument specific protocols were developed for calibration and drift corrections. The inter-comparison of corrected results from different instruments reveals excellent reproducibility, stability, and precision with a standard deviations of ~ 0.23‰ for δ18O and ~ 1.4‰ for δD. Diurnal and intraseasonal variations show strong relationships between changes in local surface humidity and water vapor isotopic composition, and with local and synoptic weather conditions. This variability probably results from the interplay between local moisture fluxes, linked with firn–air exchanges, boundary layer dynamics, and large-scale moisture advection. Particularly remarkable are several episodes characterized by high (> 40‰) surface water vapor deuterium excess. Air mass back-trajectory calculations from atmospheric analyses and water tagging in the LMDZiso (Laboratory of Meteorology Dynamics Zoom-isotopic) atmospheric model reveal that these events are associated with predominant Arctic air mass origin. The analysis suggests that high deuterium excess levels are a result of strong kinetic fractionation during evaporation at the sea-ice margin.

Decadal time series of tropospheric abundance of N2O isotopomers and isotopologues in the Northern Hemisphere obtained by the long‐term observation at Hateruma Island, Japan

Decadal time series and short‐term temporal variations in mixing ratio of atmospheric nitrous oxide (N2O) and abundance of its isotopomers (14N15N16O and 15N14N16O) and isotopologue (14N14N18O) relative to 14N14N16O have been observed for the first time in the Northern Hemisphere at Hateruma Island (HAT), Japan during 1999–2010 by monthly air sampling. Results show that the bulk nitrogen isotope ratio δ15Nbulk decreased at the rate of −0.023 ± 0.006‰ yr−1, although the N2O mixing ratio increased at the rate of about 0.7 nmol mol−1 yr−1 (ppb yr−1) during the period. Isotope budget calculation with the δ15Nbulk trend supports the earlier estimates showing that the isotopically light sources such as agriculture and industry contribute to the increase of atmospheric N2O. However, the rate of decrease of δ15Nbulk is slightly smaller in magnitude than the rates obtained virtually for the 20th century from firn air in polar regions and surface air in the Southern Hemisphere (Tasmania and Antarctica), which suggests greater contribution of 15 N‐enriched N2O sources in recent years or in the extra‐polar Northern Hemisphere. In contrast, the oxygen isotope ratio (δ18O) and intramolecular 15N site preference (SP, difference between isotope ratios at central and terminal nitrogen atoms) of N2O showed no significant trends, contrary to previous reports. Results show that no significant seasonal variation exists in δ15Nbulk, δ18O, and SP of N2O at HAT in the past decade within the limits of our sampling frequency and analytical precision.

An improved technique to measure firn diffusivity

Gas diffusivity in snow and firn is a basic transport parameter that is important for snow-air exchange processes and for ice core interpretation of past atmospheric composition. Firn is snow that is more than one year old, and it exists over many thousands of kilometers of the polar ice sheets, comprising approximately the upper 60–120m of the ice sheet. Because use of firn air for climate and environmental investigations is a relatively new science, and because of the difficulties in working with firn as a temperature-dependent porous material, few direct measurements of the gas diffusivity through the firn column have been made. This paper describes the development, testing, validation, and initial use of a diffusion chamber specifically designed to measure inert gas diffusivity on firn cores. A brief review of previous methods for determining gas diffusivity for various porous media is discussed. The new technique and apparatus are described. Results of validation of the technique on multiple sizes of glass beads are presented, including comparison to experimental and theoretical results from the literature. After this verification, initial results obtained from using the technique to measure the SF6 gas diffusivity of firn samples from Summit, Greenland are presented; results ranged from 0.005cm2/s to 0.033cm2/s. This set of measurements is compared to the diffusivity of other natural porous media and also to the few previous measurements of gas diffusivity of firn. The improved technique offers a more direct measurement of the transport parameter than other techniques previously used, and offers good potential for future investigations aimed at understanding processes of firnification and gas trapping for ice core climate change research.

How well do different tracers constrain the firn diffusivity profile?

Abstract. Firn air transport models are used to interpret measurements of the composition of air in firn and bubbles trapped in ice in order to reconstruct past atmospheric composition. The diffusivity profile in the firn is usually calibrated by comparing modelled and measured concentrations for tracers with known atmospheric history. However, in most cases this is an under-determined inverse problem, often with multiple solutions giving an adequate fit to the data (this is known as equifinality). Here we describe a method to estimate the firn diffusivity profile that allows multiple solutions to be identified, in order to quantify the uncertainty in diffusivity due to equifinality. We then look at how well different combinations of tracers constrain the firn diffusivity profile. Tracers with rapid atmospheric variations like CH3CCl3, HFCs and 14CO2 are most useful for constraining molecular diffusivity, while &delta:15N2 is useful for constraining parameters related to convective mixing near the surface. When errors in the observations are small and Gaussian, three carefully selected tracers are able to constrain the molecular diffusivity profile well with minimal equifinality. However, with realistic data errors or additional processes to constrain, there is benefit to including as many tracers as possible to reduce the uncertainties. We calculate CO2 age distributions and their spectral widths with uncertainties for five firn sites (NEEM, DE08-2, DSSW20K, South Pole 1995 and South Pole 2001) with quite different characteristics and tracers available for calibration. We recommend moving away from the use of a firn model with one calibrated parameter set to infer atmospheric histories, and instead suggest using multiple parameter sets, preferably with multiple representations of uncertain processes, to assist in quantification of the uncertainties.

Extreme <sup>13</sup>C depletion of CCl<sub>2</sub>F<sub>2</sub> in firn air samples from NEEM, Greenland

Abstract. 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 δ13C = −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.

Spatial patterns of snow accumulation across Belcher Glacier, Devon Ice Cap, Nunavut, Canada

AbstractGround-penetrating radar (GPR) surveys at a center frequency of 500 MHz were used to determine winter (2007/08) and net annual (2005–07) snow water equivalent (SWE) patterns across the upper parts of Belcher Glacier, Devon Ice Cap, Nunavut, Canada. The GPR measurements were validated against snow depths determined from avalanche probe measurements, and converted to SWE values using densities measured with a down-borehole neutron density probe and in shallow snow pits. Distinct internal reflection horizons (IRHs) in the GPR record were formed during warm summers in 2007 and 2005, and a large rain event in summer 2006 which caused ice to accumulate above the 2005 melt surface. Elevation provides the dominant control on winter SWE distribution across the basin, with surface topography (e.g. gullies) also being locally important. Based on the location where IRHs intersected the ice-cap surface, the basin-wide firn line occurred at an altitude of 1260–1300 m over the period 2005–08. Net mass balance across the accumulation area of Belcher Glacier averaged 0.24 m w.e. a−1 over the period 2005–07, mainly dependent on altitude. This is a little higher than most previous estimates for the period since the 1960s, although the differences lie within error limits.

Assessment of diffusive isotopic fractionation in polar firn, and application to ice core trace gas records

During rapid variations of the atmospheric mixing ratio of a trace gas, diffusive transport in the porous firn layer atop ice sheets and glaciers alters the isotopic composition of that gas relative to the overlying atmosphere. Records of past atmospheric trace gas isotopic composition from ice cores and firn need to be corrected for this diffusive fractionation artifact.We present a novel, semi-empirical method to accurately estimate the magnitude of the diffusive fractionation in the ice core record. Our method (1) consists of a relatively simple analytical calculation; (2) requires only commonly available ice core data; (3) is not subject to the uncertainties inherent to estimating the accumulation rate, temperature, close-off depth and depth–diffusivity relationship back in time; (4) does not require knowledge of the true atmospheric variations, but uses the smoothed records obtained from ice cores; (5) arguably gives more accurate results than a combined firn densification–firn air transport modeling study would.We apply the method to records of CH4, CO2 and N2O mixing ratios, and we find that the correction is particularly important for δ13C–CH4. We apply the correction to δ13C–CH4 records over the last glacial termination and the 8.2ka event. In both cases the diffusive signal exceeds the analytical precision of the data, and has a significant impact on the observed isotopic trends. For the 8.2ka event the corrected data show an isotopic enrichment in δ13C–CH4 for the duration of the event, consistent with reduced wetland emissions.

A new multi-gas constrained model of trace gas non-homogeneous transport in firn: evaluation and behaviour at eleven polar sites

Abstract. Insoluble trace gases are trapped in polar ice at the firn-ice transition, at approximately 50 to 100 m below the surface, depending primarily on the site temperature and snow accumulation. Models of trace gas transport in polar firn are used to relate firn air and ice core records of trace gases to their atmospheric history. We propose a new model based on the following contributions. First, the firn air transport model is revised in a poromechanics framework with emphasis on the non-homogeneous properties and the treatment of gravitational settling. We then derive a nonlinear least square multi-gas optimisation scheme to calculate the effective firn diffusivity (automatic diffusivity tuning). The improvements gained by the multi-gas approach are investigated (up to ten gases for a single site are included in the optimisation process). We apply the model to four Arctic (Devon Island, NEEM, North GRIP, Summit) and seven Antarctic (DE08, Berkner Island, Siple Dome, Dronning Maud Land, South Pole, Dome C, Vostok) sites and calculate their respective depth-dependent diffusivity profiles. Among these different sites, a relationship is inferred between the snow accumulation rate and an increasing thickness of the lock-in zone defined from the isotopic composition of molecular nitrogen in firn air (denoted δ15N). It is associated with a reduced diffusivity value and an increased ratio of advective to diffusive flux in deep firn, which is particularly important at high accumulation rate sites. This has implications for the understanding of δ15N of N2 records in ice cores, in relation with past variations of the snow accumulation rate. As the snow accumulation rate is clearly a primary control on the thickness of the lock-in zone, our new approach that allows for the estimation of the lock-in zone width as a function of accumulation may lead to a better constraint on the age difference between the ice and entrapped gases.

Iodine emissions from the sea ice of the Weddell Sea

Abstract. Iodine compounds were measured above, below and within the sea ice of the Weddell Sea during a cruise in 2009, to make progress in elucidating the mechanism of local enhancement and volatilisation of iodine. I2 mixing ratios of up to 12.4 pptv were measured 10 m above the sea ice, and up to 31 pptv was observed above surface snow on the nearby Brunt Ice Shelf – large amounts. Atmospheric IO of up to 7 pptv was measured from the ship, and the average sum of HOI and ICl was 1.9 pptv. These measurements confirm the Weddell Sea as an iodine hotspot. Average atmospheric concentrations of CH3I, C2H5I, CH2ICl, 2-C3H7I, CH2IBr and 1-C3H7I were each 0.2 pptv or less. On the Brunt Ice Shelf, enhanced concentrations of CH3I and C2H5I (up to 0.5 and 1 pptv respectively) were observed in firn air, with a diurnal profile that suggests the snow may be a source. In the sea ice brine, iodocarbons concentrations were over 10 times those of the sea water below. The sum of iodide + iodate was depleted in sea ice samples, suggesting some missing iodine chemistry. Flux calculations suggest I2 dominates the iodine atom flux to the atmosphere, but models cannot reconcile the observations and suggest either a missing iodine source or other deficiencies in our understanding of iodine chemistry. The observation of new particle formation, consistent with the model predictions, strongly suggests an iodine source. This combined study of iodine compounds is the first of its kind in this unique region of sea ice rich in biology and rich in iodine chemistry.

ChemInform Abstract: Chemical Signals of Past Climate and Environment from Polar Ice Cores and Firn Air

AbstractReview: 69 refs.

Proof of Concept: Firn Air Facility Cooling at Summit Station, Greenland

AbstractA firn air cooling system that utilized the natural reservoir of cool air at depth in polar ice sheets was tested at Summit Station, Greenland during the summer of 2010. Cooling is required on station to meet the requirements for food safety and scientific core storage. Firn air cooling is a potential replacement for traditional mechanical cooling systems. The system design, installation, and results of several experiments are presented. The system cooled a 27 m3 enclosed, insulated structure from −20 to −25°C using a 10-m borehole and a fan pumping the naturally cool air. The system was easy to install in a short time frame and was low cost from an equipment and operating perspective.

The isotopic record of Northern Hemisphere atmospheric carbon monoxide since 1950: implications for the CO budget

Abstract. We present a 60-year record of the stable isotopes of atmospheric carbon monoxide (CO) from firn air samples collected under the framework of the North Greenland Eemian Ice Drilling (NEEM) project. CO concentration, δ13C, and δ18O of CO were measured by gas chromatography/isotope ratio mass spectrometry (gc-IRMS) from trapped gases in the firn. We applied LGGE-GIPSA firn air models (Witrant et al., 2011) to correlate gas age with firn air depth and then reconstructed the trend of atmospheric CO and its stable isotopic composition at high northern latitudes since 1950. The most probable firn air model scenarios show that δ13C decreased slightly from −25.8‰ in 1950 to −26.4‰ in 2000, then decreased more significantly to −27.2‰ in 2008. δ18O decreased more regularly from 9.8‰ in 1950 to 7.1‰ in 2008. Those same scenarios show CO concentration increased gradually from 1950 and peaked in the late 1970s, followed by a gradual decrease to present day values (Petrenko et al., 2012). Results from an isotope mass balance model indicate that a slight increase, followed by a large reduction, in CO derived from fossil fuel combustion has occurred since 1950. The reduction of CO emission from fossil fuel combustion after the mid-1970s is the most plausible mechanism for the drop of CO concentration during this time. Fossil fuel CO emissions decreased as a result of the implementation of catalytic converters and the relative growth of diesel engines, in spite of the global vehicle fleet size having grown several fold over the same time period.

Stable carbon isotope fractionation in the UV photolysis of CFC-11 and CFC-12

Abstract. The chlorofluorocarbons CFC-11 (CFCl3) and CFC-12 (CF2Cl2) are stable atmospheric compounds that are produced at the earth's surface, but removed only at high altitudes in the stratosphere by photolytic reactions. Their removal liberates atomic chlorine that then catalytically destroys stratospheric ozone. For such long-lived compounds, isotope effects in the stratospheric removal reactions have a large effect on their global isotope budgets. We have demonstrated a photolytic isotope fractionation for stable carbon isotopes of CFC-11 and CFC-12 in laboratory experiments using broadband UV-C (190–230 nm) light. 13C/12C isotope fractionations (ε) range from (−23.8±0.9) to (−17.7±0.4) ‰ for CFC-11 and (−66.2±3.1) to (−51.0±2.9) ‰ for CFC-12 between 203 and 288 K, a temperature range relevant to conditions in the troposphere and stratosphere. These results suggest that CFCs should become strongly enriched in 13C with decreasing mixing ratio in the stratosphere, similar to what has been recently observed for CFC chlorine isotopes. In conjunction with the strong variations in CFC emissions before and after the Montréal Protocol, the stratospheric enrichments should also lead to a significant temporal increase in the 13C content of the CFCs at the surface over the past decades, which should be recorded in atmospheric air archives such as firn air.

Gas transport in firn: multiple-tracer characterisation and model intercomparison for NEEM, Northern Greenland

Abstract. Air was sampled from the porous firn layer at the NEEM site in Northern Greenland. We use an ensemble of ten reference tracers of known atmospheric history to characterise the transport properties of the site. By analysing uncertainties in both data and the reference gas atmospheric histories, we can objectively assign weights to each of the gases used for the depth-diffusivity reconstruction. We define an objective root mean square criterion that is minimised in the model tuning procedure. Each tracer constrains the firn profile differently through its unique atmospheric history and free air diffusivity, making our multiple-tracer characterisation method a clear improvement over the commonly used single-tracer tuning. Six firn air transport models are tuned to the NEEM site; all models successfully reproduce the data within a 1σ Gaussian distribution. A comparison between two replicate boreholes drilled 64 m apart shows differences in measured mixing ratio profiles that exceed the experimental error. We find evidence that diffusivity does not vanish completely in the lock-in zone, as is commonly assumed. The ice age- gas age difference (Δage) at the firn-ice transition is calculated to be 182+3−9 yr. We further present the first intercomparison study of firn air models, where we introduce diagnostic scenarios designed to probe specific aspects of the model physics. Our results show that there are major differences in the way the models handle advective transport. Furthermore, diffusive fractionation of isotopes in the firn is poorly constrained by the models, which has consequences for attempts to reconstruct the isotopic composition of trace gases back in time using firn air and ice core records.

Continuous measurements of methane mixing ratios from ice cores

Abstract. This work presents a new, field-deployable technique for continuous, high-resolution measurements of methane mixing ratios from ice cores. The technique is based on a continuous flow analysis system, where ice core samples cut along the long axis of an ice core are melted continuously. The past atmospheric air contained in the ice is separated from the melt water stream via a system for continuous gas extraction. The extracted gas is dehumidified and then analyzed by a Wavelength Scanned-Cavity Ring Down Spectrometer for methane mixing ratios. We assess the performance of the new measurement technique in terms of precision (±0.8 ppbv, 1σ), accuracy (±8 ppbv), temporal (ca. 100 s), and spatial resolution (ca. 5 cm). Using a firn air transport model, we compare the resolution of the measurement technique to the resolution of the atmospheric methane signal as preserved in ice cores in Greenland. We conclude that our measurement technique can resolve all climatically relevant variations as preserved in the ice down to an ice depth of at least 1980 m (66 000 yr before present) in the North Greenland Eemian Ice Drilling ice core. Furthermore, we describe the modifications, which are necessary to make a commercially available spectrometer suitable for continuous methane mixing ratio measurements from ice cores.

Distributions, long term trends and emissions of four perfluorocarbons in remote parts of the atmosphere and firn air

Abstract. We report the first data set of atmospheric abundances for the following four perfluoroalkanes: n-decafluorobutane (n-C4F10), n-dodecafluoropentane (n-C5F12), n-tetradecafluorohexane (n-C6F14) and n-hexadecafluoroheptane (n-C7F16). All four compounds could be detected and quantified in air samples from remote locations in the Southern Hemisphere (at Cape Grim, Tasmania, archived samples dating back to 1978) and the upper troposphere (a passenger aircraft flying from Germany to South Africa). Further observations originate from air samples extracted from deep firn in Greenland and allow trends of atmospheric abundances in the earlier 20th century to be inferred. All four compounds were not present in the atmosphere prior to the 1960s. n-C4F10 and n-C5F12 were also measured in samples collected in the stratosphere with the data indicating that they have no significant sinks in this region. Emissions were inferred from these observations and found to be comparable with emissions from the EDGAR database for n-C6F14. However, emissions of n-C4F10, n-C5F12 and n-C7F16 were found to differ by up to five orders of magnitude between our approach and the database. Although the abundances of the four perfluorocarbons reported here are currently small (less than 0.3 parts per trillion) they have strong Global Warming Potentials several thousand times higher than carbon dioxide (on a 100-yr time horizon) and continue to increase in the atmosphere. We estimate that the sum of their cumulative emissions reached 325 million metric tonnes CO2 equivalent at the end of 2009.