High-resolution glacial and deglacial record of atmospheric methane by continuous-flow and laser spectrometer analysis along the NEEM ice core

The Greenland NEEM (North Greenland Eemian Ice Drilling) operation in 2010 provided the first opportunity to combine trace-gas measurements by laser spectroscopic instruments and continuous-flow analysis along a freshly drilled ice core in a field-based setting. We present the resulting atmospheric methane (CH4) record covering the time period from 107.7 to 9.5 ka b2k (thousand years before 2000 AD). Companion discrete CH4 measurements are required to transfer the laser spectroscopic data from a relative to an absolute scale. However, even on a relative scale, the high-resolution CH4 data set significantly improves our knowledge of past atmospheric methane concentration changes. New significant sub-millennial-scale features appear during interstadials and stadials, generally associated with similar changes in water isotopic ratios of the ice, a proxy for local temperature. In addition to the midpoint of Dansgaard–Oeschger (D/O) CH4 transitions usually used for cross-dating, sharp definition of the start and end of these events brings precise depth markers (with ±20 cm uncertainty) for further cross-dating with other palaeo- or ice core records, e.g. speleothems. The method also provides an estimate of CH4 rates of change. The onsets of D/O events in the methane signal show a more rapid rate of change than their endings. The rate of CH4 increase associated with the onsets of D/O events progressively declines from 1.7 to 0.6 ppbv yr−1 in the course of marine isotope stage 3. The largest observed rate of increase takes place at the onset of D/O event #21 and reaches 2.5 ppbv yr−1.

Evaluating atmospheric methane inversion model results for Pallas, northern Finland

A state-of-the-art inverse model, CarbonTracker Data Assimilation Shell (CTDAS), was used to optimize estimates of methane (CH4) surface fluxes using atmospheric observations of CH4 as a constraint. The model consists of the latest version of the TM5 atmospheric chemistry-transport model and an ensemble Kalman filter based data assimilation system. The model was constrained by atmospheric methane surface concentrations, obtained from the World Data Centre for Greenhouse Gases (WDCGG). Prior methane emissions were specified for five sources: biosphere, anthropogenic, fire, termites and ocean, of which bio-sphere and anthropogenic emissions were optimized. Atmospheric CH 4 mole fractions for 2007 from northern Finland calculated from prior and optimized emissions were compared with observations. It was found that the root mean squared errors of the posterior esti - mates were more than halved. Furthermore, inclusion of NOAA observations of CH 4 from weekly discrete air samples collected at Pallas improved agreement between posterior CH 4 mole fraction estimates and continuous observations, and resulted in reducing optimized biosphere emissions and their uncertainties in northern Finland.

Gas adsorption and desorption effects on cylinders and their importance for long-term gas records

It is well known that gases adsorb on many surfaces, in particular metal surfaces. There are two main forms responsible for these effects (i) physisorption and (ii) chemisorption. Physisorption is associated with lower binding energies in the order of 1–10 kJ mol−¹, compared to chemisorption which ranges from 100 to 1000 kJ mol−¹. Furthermore, chemisorption only forms monolayers, contrasting physisorption that can form multilayer adsorption. The reverse process is called desorption and follows similar mathematical laws; however, it can be influenced by hysteresis effects. In the present experiment, we investigated the adsorption/desorption phenomena on three steel and three aluminium cylinders containing compressed air in our laboratory and under controlled conditions in a climate chamber, respectively. Our observations from completely decanting one steel and two aluminium cylinders are in agreement with the pressure dependence of physisorption for CO₂, CH₄, and H₂O. The CO₂ results for both cylinder types are in excellent agreement with the pressure dependence of a monolayer adsorption model. However, mole fraction changes due to adsorption on aluminium (< 0.05 and 0 ppm for CO₂ and H₂O) were significantly lower than on steel (< 0.41 ppm and about < 2.5 ppm, respectively). The CO₂ amount adsorbed (5.8 × 1019 CO₂ molecules) corresponds to about the fivefold monolayer adsorption, indicating that the effective surface exposed for adsorption is significantly larger than the geometric surface area. Adsorption/desorption effects were minimal for CH₄ and for CO but require further attention since they were only studied on one aluminium cylinder with a very low mole fraction. In the climate chamber, the cylinders were exposed to temperatures between −10 and +50 °C to determine the corresponding temperature coefficients of adsorption. Again, we found distinctly different values for CO₂, ranging from 0.0014 to 0.0184 ppm °C−¹ for steel cylinders and −0.0002 to −0.0003 ppm °C−¹ for aluminium cylinders. The reversed temperature dependence for aluminium cylinders points to significantly lower desorption energies than for steel cylinders and due to the small values, they might at least partly be influenced by temperature, permeation from/to sealing materials, and gas-consumption-induced pressure changes. Temperature coefficients for CH₄, CO, and H₂O adsorption were, within their error bands, insignificant. These results do indicate the need for careful selection and usage of gas cylinders for high-precision calibration purposes such as requested in trace gas applications.

Covariation of deep Southern Ocean oxygenation and atmospheric CO2 through the last ice age

No single mechanism can account for the full amplitude of past atmospheric carbon dioxide (CO2) concentration variability over glacial–interglacial cycles. A build-up of carbon in the deep ocean has been shown to have occurred during the Last Glacial Maximum. However, the mechanisms responsible for the release of the deeply sequestered carbon to the atmosphere at deglaciation, and the relative importance of deep ocean sequestration in regulating millennial-timescale variations in atmospheric CO2 concentration before the Last Glacial Maximum, have remained unclear. Here we present sedimentary redox-sensitive trace metal records from the Antarctic Zone of the Southern Ocean that provide a reconstruction of transient changes in deep ocean oxygenation and, by inference, respired carbon storage throughout the last glacial cycle. Our data suggest that respired carbon was removed from the abyssal Southern Ocean during the Northern Hemisphere cold phases of the deglaciation, when atmospheric CO2 concentration increased rapidly, reflecting—at least in part— a combination of dwindling iron fertilization by dust and enhanced deep ocean ventilation. Furthermore, our records show that the observed covariation between atmospheric CO2 concentration and abyssal Southern Ocean oxygenation was maintained throughout most of the past 80,000 years. This suggests that on millennial timescales deep ocean circulation and iron fertilization in the Southern Ocean played a consistent role in modifying atmospheric CO2 concentration.

Atmospheric histories and global emissions of halons H-1211 (CBrClF 2 ), H-1301 (CBrF 3 ), and H-2402 (CBrF 2 CBrF 2 )

We report ground-based atmospheric measurements and emission estimates for the halons H-1211 (CBrClF₂), H-1301 (CBrF₃), and H-2402 (CBrF₂CBrF₂) from the AGAGE (Advanced Global Atmospheric Gases Experiment) and the National Oceanic and Atmospheric Administration global networks. We also include results from archived air samples in canisters and from polar firn in both hemispheres, thereby deriving an atmospheric record of nearly nine decades (1930s to present). All three halons were absent from the atmosphere until ~1970, when their atmospheric burdens started to increase rapidly. In recent years H-1211 and H-2402 mole fractions have been declining, but H-1301 has continued to grow. High-frequency observations show continuing emissions of H-1211 and H-1301 near most AGAGE sites. For H-2402 the only emissions detected were derived from the region surrounding the Sea of Japan/East Sea. Based on our observations, we derive global emissions using two different inversion approaches. Emissions for H-1211 declined from a peak of 11 kt yr⁻¹ (late 1990s) to 3.9 kt yr⁻¹ at the end of our record (mean of 2013–2015), for H-1301 from 5.4 kt yr⁻¹ (late 1980s) to 1.6 kt yr⁻¹, and for H-2402 from 1.8 kt yr⁻¹ (late 1980s) to 0.38 kt yr⁻¹. Yearly summed halon emissions have decreased substantially; nevertheless, since 2000 they have accounted for ~30% of the emissions of all major anthropogenic ozone depletion substances, when weighted by ozone depletion potentials.