Kristal R. Verhulst

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.

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.

Carbonyl sulfide hydrolysis in Antarctic ice cores and an atmospheric history for the last 8000 years

©2014. American Geophysical Union. All Rights Reserved. Carbonyl sulfide (COS) was measured in Antarctic ice core samples from the Byrd, Siple Dome, Taylor Dome, and West Antarctic Ice Sheet Divide sites covering the last 8000 years of the Holocene. COS levels decrease downcore in most of these ice cores. The magnitude of the downcore trends varies among the different ice cores and is related to the thermal histories of the ice sheet at each site. We hypothesize that this is due to the temperature-dependent hydrolysis of COS that occurs in situ. We use a one-dimensional ice flow and heat flux model to infer temperature histories for the ice core samples from different sites and empirically determine the kinetic parameters for COS hydrolysis. We estimate e-folding lifetimes for COS hydrolysis ranging from 102 years to 106 years over a temperature range of 0°C to -50°C. The reaction kinetics are used to estimate and correct for the in situ COS loss, allowing us to reconstruct paleoatmospheric COS trends during the mid-to-late Holocene. The results suggest a slow, long-term increase in atmospheric COS that may have started as early as 5000 years ago. Given that the largest term in the COS budget is uptake by terrestrial plants, this could indicate a decline in terrestrial productivity during the late Holocene.

Preindustrial atmospheric ethane levels inferred from polar ice cores: A constraint on the geologic sources of atmospheric ethane and methane

© 2016. American Geophysical Union. All Rights Reserved. Ethane levels were measured in air extracted from Greenland and Antarctic ice cores ranging in age from 994 to 1918 Common Era (C.E.) There is good temporal overlap between the two data sets from 1600 to 1750 C.E. with ethane levels stable at 397±28 parts per trillion (ppt) (±2standard error (s.e.)) over Greenland and 103±9ppt over Antarctica. The observed north/south interpolar ratio of ethane (3.9±0.1, 1σ) implies considerably more ethane emissions in the Northern Hemisphere than in the Southern Hemisphere, suggesting geologic ethane sources contribute significantly to the preindustrial ethane budget. Box model simulations based on these data constrain the global geologic emissions of ethane to 2.2-3.5Tgyr-1 and biomass burning emissions to 1.2-2.5Tgyr-1 during the preindustrial era. The results suggest biomass burning emissions likely increased since the preindustrial period. Biomass burning and geologic outgassing are also sources of atmospheric methane. The results place constraints on preindustrial methane emissions from these sources.

Changes in atmospheric carbonyl sulfide over the last 54,000 years inferred from measurements in Antarctic ice cores

We measured carbonyl sulfide (COS) in air extracted from ice core samples from the West Antarctic Ice Sheet (WAIS) Divide, Antarctica, with the deepest sample dated to 54,300 years before present. These are the first ice core COS measurements spanning the Last Glacial Maximum (LGM), the last glacial/interglacial transition, and the early Holocene. The WAIS Divide measurements from the LGM and the last transition are the first COS measurements in air extracted from full clathrate (bubble-free) ice. This study also includes new COS measurements from Taylor Dome, Antarctica, including some in bubbly glacial ice that are concurrent with the WAIS Divide data from clathrate glacial ice. COS hydrolyzes in ice core air bubbles, and the recovery of an atmospheric record requires correcting for this loss. The data presented here suggest that the in situ hydrolysis of COS is significantly slower in clathrate ice than in bubbly ice. The clathrate ice measurements are corrected for the hydrolysis loss during the time spent as bubbly ice only. The corrected WAIS Divide record indicates that atmospheric COS was 250–300 parts per trillion (ppt) during the LGM and declined by 80–100 ppt during the last glacial/interglacial transition to a minimum of 160–210 ppt at the beginning of the Holocene. This decline was likely caused by an increase in the gross primary productivity of terrestrial plants, with a possible contribution from a reduction in ocean sources. COS levels were above 300 ppt in the late Holocene, indicating that large changes in the COS biogeochemical cycle occurred during the Holocene.

Methyl chloride in a deep ice core from Siple Dome, Antarctica

Methyl chloride (CH3Cl) is a naturally occurring ozone-depleting substance and a significant component of the atmospheric chlorine burden. In this study CH3Cl was analyzed in air bubbles from the West Antarctic Siple Dome deep ice core with gas ages ranging from about 65 kyr BP to the Late Holocene. CH3Cl levels were below the modern Antarctic atmospheric level of 530 ppt in glacial ice (456 ± 46 ppt, 33–65 kyr BP) and above it during the early Holocene (650–700 ppt, 10–11 kyr BP). For most of the Holocene, CH3Cl levels were 500–550 ppt, with good agreement between CH3Cl levels in this core and in the Dome Fuji ice core (Saito et al., 2007). Several late Holocene ice core samples (<2 kyr BP), show evidence of enrichment in CH3Cl relative to South Pole ice core samples of overlapping gas age. The Siple Dome record suggests that CH3Cl levels in the glacial Southern Hemisphere atmosphere were about 16% lower than those during the mid-late Holocene.

Methyl chloride variability in the Taylor Dome ice core during the Holocene

Methyl chloride (CH3Cl) is a naturally occurring, ozone-depleting trace gas and one of the most abundant chlorinated compounds in the atmosphere. CH3Cl was measured in air from the Taylor Dome ice core in East Antarctica to reconstruct an atmospheric record for the Holocene (11–0 kyr B.P.) and part of the last glacial period (50–30 kyr B.P.). CH3Cl variability throughout the Holocene is strikingly similar to that of atmospheric methane (CH4), with higher levels in the early and late Holocene, and a well-defined minimum during mid-Holocene. The sources and sinks of atmospheric CH3Cl and CH4 are located primarily in the tropics, and variations in their atmospheric levels likely reflect changes in tropical conditions. CH3Cl also appears to correlate with atmospheric CH4 during the last glacial period (50–30 kyr B.P.), although the temporal resolution of sampling is limited. The Taylor Dome data provide information about the range of natural variability of atmospheric CH3Cl and place a new constraint on the causes of past CH4variability.