Mark Owen Battle

A record of atmospheric halocarbons during the twentieth century from polar firn air

Measurements of trace gases in air trapped in polar firn (unconsolidated snow) demonstrate that natural sources of chlorofluorocarbons, halons, persistent chlorocarbon solvents and sulphur hexafluoride to the atmosphere are minimal or non-existent. Atmospheric concentrations of these gases, reconstructed back to the late nineteenth century, are consistent with atmospheric histories derived from anthropogenic emission rates and known atmospheric lifetimes. The measurements confirm the predominance of human activity in the atmospheric budget of organic chlorine, and allow the estimation of atmospheric histories of halogenated gases of combined anthropogenic and natural origin. The pre-twentieth-century burden of methyl chloride was close to that at present, while the burden of methyl bromide was probably over half of todays value.

Recent decreases in fossil-fuel emissions of ethane and methane derived from firn air

Methane and ethane are the most abundant hydrocarbons in the atmosphere and they affect both atmospheric chemistry and climate. Both gases are emitted from fossil fuels and biomass burning, whereas methane (CH4) alone has large sources from wetlands, agriculture, landfills and waste water. Here we use measurements in firn (perennial snowpack) air from Greenland and Antarctica to reconstruct the atmospheric variability of ethane (C2H6) during the twentieth century. Ethane levels rose from early in the century until the 1980s, when the trend reversed, with a period of decline over the next 20 years. We find that this variability was primarily driven by changes in ethane emissions from fossil fuels; these emissions peaked in the 1960s and 1970s at 14–16 teragrams per year (1 Tg = 1012 g) and dropped to 8–10 Tg yr−1 by the turn of the century. The reduction in fossil-fuel sources is probably related to changes in light hydrocarbon emissions associated with petroleum production and use. The ethane-based fossil-fuel emission history is strikingly different from bottom-up estimates of methane emissions from fossil-fuel use, and implies that the fossil-fuel source of methane started to decline in the 1980s and probably caused the late twentieth century slow-down in the growth rate of atmospheric methane.

Carbon and hydrogen isotopic composition of methane over the last 1000 years

the common era (CE)). The d 13 Co f CH4 data corroborate the record from Law Dome, Antarctica, with high fidelity. The new d Do f CH4 data set covaries with the d 13 Co f CH4 record. Both d 13 Co f CH4 and d Do f CH4 were relatively stable and close to the present-day values from � 1000 to � 1500 CE. Both isotopic ratios decreased to minima around 1700 CE, remained low until the late 18th century, and then rose exponentially to present-day values. Our new d Do f CH4 data provide an additional independent constraint for evaluating possible CH4 source histories. We searched a broad range of source scenarios using a simple box model to identify histories consistent with the constraints of the CH4 concentration and isotope data from 990–1730 CE. Results typically show a decrease over time in the biomass-burning source (found in 85% of acceptable scenarios) and an increase in the agricultural source (found in 77% of acceptable scenarios), indicating preindustrial human influence on atmospheric methane as proposed in previous studies.

Atmospheric O2/N2 changes, 1993–2002: Implications for the partitioning of fossil fuel CO2 sequestration

Improvements made to an established mass spectrometric method for measuring changes in atmospheric O 2 /N 2 are described. With the improvements in sample handling and analysis, sample throughput and analytical precision have both increased. Aliquots from duplicate flasks are repeatedly measured over a period of 2 weeks, with an overall standard error in each flask of 3-4 per meg, corresponding to 0.6-0.8 ppm O 2 in air. Records of changes in O 2 /N 2 from six global sampling stations (Barrow, American Samoa, Cape Grim, Amsterdam Island, Macquarie Island, and Syowa Station) are presented. Combined with measurements of CO 2 from the same sample flasks, land and ocean carbon uptake were calculated from the three sampling stations with the longest records (Barrow, Samoa, and Cape Grim). From 1994-2002, We find the average CO 2 uptake by the ocean and the land biosphere was 1.7 ± 0.5 and 1.0 ± 0.6 GtC yr -1 respectively; these numbers include a correction of 0.3 Gt C yr -1 due to secular outgassing of ocean O 2 . Interannual variability calculated from these data shows a strong land carbon source associated with the 1997-1998 El Nifio event, supporting many previous studies indicating that high atmospheric growth rates observed during most El Nino events reflect diminished land uptake. Calculations of interannual variability in land and ocean uptake are probably confounded by non-zero annual air sea fluxes of O 2 . The origin of these fluxes is not yet understood.

Polar firn air reveals large-scale impact of anthropogenic mercury emissions during the 1970s.

Mercury (Hg) is an extremely toxic pollutant, and its biogeochemical cycle has been perturbed by anthropogenic emissions during recent centuries. In the atmosphere, gaseous elemental mercury (GEM; Hg°) is the predominant form of mercury (up to 95%). Here we report the evolution of atmospheric levels of GEM in mid- to high-northern latitudes inferred from the interstitial air of firn (perennial snowpack) at Summit, Greenland. GEM concentrations increased rapidly after World War II from ≈1.5 ng m−3 reaching a maximum of ≈3 ng m−3 around 1970 and decreased until stabilizing at ≈1.7 ng m−3 around 1995. This reconstruction reproduces real-time measurements available from the Arctic since 1995 and exhibits the same general trend observed in Europe since 1990. Anthropogenic emissions caused a two-fold rise in boreal atmospheric GEM concentrations before the 1970s, which likely contributed to higher deposition of mercury in both industrialized and remotes areas. Once deposited, this toxin becomes available for methylation and, subsequently, the contamination of ecosystems. Implementation of air pollution regulations, however, enabled a large-scale decline in atmospheric mercury levels during the 1980s. The results shown here suggest that potential increases in emissions in the coming decades could have a similar large-scale impact on atmospheric Hg levels.

A 350-year atmospheric history for carbonyl sulfide inferred from Antarctic firn air and air trapped in ice

during 1650–1850 A.D. and increases throughout most of the twentieth century. Measurements of COS in modern air and in the upper layers of the firn at South Pole indicate ambient, annual mean mixing ratios between 480 and 490 ppt with substantial seasonal variations. Peak mixing ratios are observed during austral summer in ambient air at South Pole and Cape Grim, Tasmania (40.41� S). Provided COS is not produced or destroyed in firn, these results also suggest that atmospheric COS mixing ratios have decreased 60–90 ppt (10–16%) since the 1980s in high latitudes of the Southern Hemisphere. The history derived for atmospheric mixing ratios of COS in the Southern Hemisphere since 1850 is closely related to historical anthropogenic sulfur emissions. The fraction of anthropogenic sulfur emissions released as COS (directly or indirectly) needed to explain the secular changes in atmospheric COS over this period is 0.3–0.6%. INDEX TERMS: 0325 Atmospheric Composition and Structure: Evolution of the atmosphere; 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; KEYWORDS: atmosphere composition, carbonyl sulfide, stratosphere sulfate aerosol

Atmospheric variability of methyl chloride during the last 300 years from an Antarctic ice core and firn air

Measurements of methyl chloride (CH3Cl) in Antarctic polar ice and firn air are used to describe the variability of atmospheric CH3Cl during the past 300 years. Firn air results from South Pole and Siple Dome suggest that the atmospheric abundance of CH3Cl increased by about 10% in the 50 years prior to 1990. Ice core measurements from Siple Dome provide evidence for a cyclic natural variability on the order of 10%, with a period of about 110 years in phase with the 20th century rise inferred from firn air. Thus, the CH3Cl increase measured in firn air may largely be a result of natural processes, which may continue to affect the atmospheric CH3Cl burden during the 21st century.

Recent increases in global HFC‐23 emissions

Firn-air and ambient air measurements of CHF3 (HFC-23) from three excursions to Antarctica between 2001 and 2009 are used to construct a consistent Southern Hemisphere (SH) atmospheric history. The results show atmospheric mixing ratios of HFC-23 continuing to increase through 2008. Mean global emissions derived from this data for 2006–2008 are 13.5 ± 2 Gg/yr (200 ± 30 × 1012 gCO2-equivalent/yr, or MtCO2-eq./yr), ∼50% higher than the 8.7 ± 1 Gg/yr (130 ± 15 MtCO2-eq./yr) derived for the 1990s. HFC-23 emissions arise primarily from over-fluorination of chloroform during HCFC-22 production. The recent global emission increases are attributed to rapidly increasing HCFC-22 production in developing countries since reported HFC-23 emissions from developed countries decreased over this period. The emissions inferred here for developing countries during 2006–2008 averaged 11 ± 2 Gg/yr HFC-23 (160 ± 30 MtCO2-eq./yr) and are larger than the ∼6 Gg/yr of HFC-23 destroyed in United Nations Framework Convention on Climate Change Clean Development Mechanism projects during 2007 and 2008.

Measurements and models of the atmospheric Ar/N2 ratio

The Ar/N 2 ratio of air measured at 6 globally distributed sites shows annual cycles with amplitudes of 12 to 37 parts in 10 6 . Summertime maxima reflect the atmospheric Ar enrichment driven by seasonal warming and degassing of the oceans. Paired models of air-sea heat fluxes and atmospheric tracer transport predict seasonal cycles in the Ar/N 2 ratio that agree with observations, within uncertainties.

An improved comparison of atmospheric Ar/N2 time series and paired ocean‐atmosphere model predictions

[1] Ar/N 2 Variations in the atmosphere reflect ocean heat fluxes, air-sea gas exchange, and atmospheric dynamics. Here atmospheric Ar/N 2 time series are compared to paired ocean-atmosphere model predictions. Agreement between Ar/N 2 observations and simulations has improved in comparison to a previous study because of longer time series and the introduction of automated samplers at several of the atmospheric stations, as well as the refinement of the paired ocean-atmosphere models by inclusion of Ar and N 2 as active tracers in the ocean component. Although analytical uncertainties and collection artifacts are likely to be mainly responsible for observed Ar/N 2 outliers, air parcel back-trajectory analysis suggests that some of the variability in Ar/N 2 measurements could be due to the low-altitude history of the air mass collected and, by extension, the local oceanic Ar/N 2 signal. Although the simulated climatological seasonal cycle can currently be evaluated with Ar/N 2 observations, longer time series and additional improvements in the signal-to-noise ratio will be required to test other model predictions such as interannual variability, latitudinal gradients, and the secular increase in atmospheric Ar/N 2 expected to result from ocean warming.