Methyl chloride (CH₃Cl) is a naturally occurring ozone-depleting gas with a complex biogeochemical cycle involving tropical vegetation, soils, biomass burning and the oceans. This study presents CH₃Cl measurements in air extracted from a 300 m ice core from South Pole, Antarctica, covering the time period from 160 BC to 1860 AD. The data exhibit an increasing trend of 3 ppt (parts per trillion) over 100 years and higher frequency variations that appear to be climate-related. CH₃Cl levels were elevated from 900–1300 AD by about 50 ppt relative to the previous 1000 years, coincident with the warm Medieval Climate Anomaly (MCA). CH₃Cl levels decreased to a minimum during the Little Ice Age cooling (1650–1800 AD), before rising again to the modern atmospheric level of 550 ppt. These variations most likely reflect changes in tropical and subtropical conditions, and raise the possibility that a warmer future climate may result in higher tropospheric CH₃Cl levels.

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.

This study reports measurements of methyl bromide (CH₃Br) in air bubbles from a South Pole ice core, with gas ages covering the past two millennia. The air was extracted by mechanical shredding of the core under vacuum and the evolved gases were analyzed by gas chromatography with high resolution mass spectrometry and isotope dilution. These samples had estimated mean gas ages ranging from 160 BCE to 1860 CE. The mean CH₃Br mixing ratio in the ice core samples was 5.39 ±.06 ppt (1s.e., n = 113). The CH₃Br measurements from this core agree with those from a Siple Dome ice core for mean gas ages between 1671 and 1860 CE, where there is overlap between the cores. The data show no linear trend over the 2000 year period prior to industrialization. Together, Antarctic ice core and firn air measurements clearly demonstrate that the increase in atmospheric CH₃Br during the twentieth century exceeds natural variability during the past 2000 years. There is evidence of centennial-scale variability in CH₃Br on the order of ±10–20% that may indicate a natural climate sensitivity of the atmospheric levels of this ozone depleting substance. The analysis of CH₃Br in additional Antarctic ice cores will be needed to confirm that the centennial-scale variability observed in this core represents a southern hemisphere atmospheric history.

The concentration of carbonyl sulfide (OCS) has been determined in several preindustrial air samples extracted from a shallow ice core from Siple Dome, West Antarctica. The extraction of the air was carried out by shredding the core under vacuum, followed by analysis by gas chromatography with mass spectrometric detection. 11 ice core samples were analyzed, ranging in depth from 82.3 to 90.7 m. The ages assigned to OCS in the ice core samples range from 1616 to 1694 AD. The observed OCS mixing ratios range from 322.6 pptv to 442.3 pptv with a mean of 372.8 ± 37.2 pptv. These levels are significantly lower than the present day atmospheric mixing ratio of 500 pptv and suggest that the anthropogenic sources comprise approximately 25% of the present day OCS budget.

Acetylene is a short-lived trace gas produced during combustion of fossil fuels, biomass, and biofuels. Biomass burning is likely the only major source of acetylene in the preindustrial atmosphere, making ice core acetylene a powerful tool for reconstructing paleofire emissions. Here we present a 2,000-year atmospheric record of acetylene reconstructed from analysis of air bubbles trapped in Greenland and Antarctic ice cores and infer pyrogenic acetylene emissions using a chemistry transport model. From 0 to 1500 CE, Antarctic acetylene averages 36 ± 1 pmol mol−1 (mean ± 1 SE), roughly double the annual mean over Antarctica today. Antarctic acetylene declines during the Little Ice Age by over 50% to 17 ± 2 pmol mol−1 from 1650 to 1750 CE. Acetylene over Greenland declines less dramatically over the same period. Modeling results suggest that pyrogenic acetylene emissions during 1000–1500 CE were sustained at rates significantly greater than modern day and declined by over 50% during the 1650–1750 CE period.

In this study, vanillic acid was measured in the Tunu ice core from northeastern Greenland in samples covering the past 1700 years. Vanillic acid is an aerosol-borne aromatic methoxy acid, produced by the combustion of lignin during biomass burning. Air mass trajectory analysis indicates that North American boreal forests are likely the major source region for biomass burning aerosols deposited to the ice core site. Vanillic acid levels in the Tunu ice core range from < 0.005 to 0.08 ppb. Tunu vanillic acid exhibits centennial-scale variability in pre-industrial ice, with elevated levels during the warm climates of the Roman Warm Period and Medieval Climate Anomaly, and lower levels during the cooler climates of the Late Antique Little Ice Age and the Little Ice Age. Analysis using a peak detection method revealed a positive correlation between vanillic acid in the Tunu ice core and both ammonium and black carbon in the North Greenland Eemian Ice Drilling (NEEM) project ice core from 600 to 1200 CE. The data provide multiproxy evidence of centennial-scale variability in North American high-latitude fire during this time period.

This study presents vanillic acid and parahydroxybenzoic acid levels in an Arctic ice core from Lomonosovfonna, Svalbard covering the past 800 years. These aromatic acids are likely derived from lignin combustion in wildfires and long-range aerosol transport. Vanillic and para-hydroxybenzoic acid are present throughout the ice core, confirming that these compounds are preserved on millennial timescales. Vanillic and para-hydroxybenzoic acid concentrations in the Lomonosovfonna ice core ranged from below the limits of detection to 0.2 and 0.07 ppb, respectively (1 ppb =1000 ng L-1). Vanillic acid levels are high (maximum of 0.1 ppb) from 1200 to 1400 CE, then gradually decline into the twentieth century. The largest peak in the vanillic acid in the record occurs from 2000 to 2008 CE. In the para-hydrobenzoic acid record, there are three centennialscale peaks around 1300, 1550, and 1650 CE superimposed on a long-term decline in the baseline levels throughout the record. Ten-day air mass back trajectories for a decade of fire seasons (March-November, 2006-2015) indicate that Siberia and Europe are the principle modern source regions for wildfire emissions reaching the Lomonosovfonna site. The Lomonosovfonna data are similar to those from the Eurasian Arctic Akademii Nauk ice core during the early part of the record (1220-1400 CE), but the two ice cores diverge markedly after 1400 CE. This coincides with a shift in North Atlantic climate marked by a change of the North Atlantic Oscillation from a positive to a more negative state.

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.

Biomass burning drives changes in greenhouse gases, climate-forcing aerosols, and global atmospheric chemistry. There is controversy about the magnitude and timing of changes in biomass burning emissions on millennial time scales from preindustrial to present and about the relative importance of climate change and human activities as the underlying cause. Biomass burning is one of two notable sources of ethane in the preindustrial atmosphere. Here, we present ice core ethane measurements from Antarctica and Greenland that contain information about changes in biomass burning emissions since 1000 CE (Common Era). The biomass burning emissions of ethane during the Medieval Period (1000-1500 CE) were higher than present day and declined sharply to a minimum during the cooler Little Ice Age (1600-1800 CE). Assuming that preindustrial atmospheric reactivity and transport were the same as in the modern atmosphere, we estimate that biomass burning emissions decreased by 30 to 45% from the Medieval Period to the Little Ice Age. The timing and magnitude of this decline in biomass burning emissions is consistent with that inferred from ice core methane stable carbon isotope ratios but inconsistent with histories based on sedimentary charcoal and ice core carbon monoxide measurements. This study demonstrates that biomass burning emissions have exceeded modern levels in the past and may be highly sensitive to changes in climate.

Biomass burning is an important component of the Earth system in terms of global biogeochemistry, atmospheric composition, climate, terrestrial ecology, and land use. This study examines published ice core trace gas measurements of acetylene, ethane, and methane, which have been used as proxies for paleofire emissions. We investigate the consistency of these records for the past 1,000 years in terms of (1) temporal trends in global fire emissions and (2) quantitative estimates for changes in global burning (dry matter burned per year). Three-dimensional transport and box models were used to construct emissions scenarios for the trace gases consistent with each ice core record. Burning histories were inferred from trace gas emissions by accounting for biome-specific emission factors for each trace gas. The temporal trends in fire inferred from the trace gases are in reasonable agreement, with a large decline in biomass burning emissions from the Medieval Period (MP: 1000–1500 CE) to the Little Ice Age (LIA: 1650–1750 CE). However, the three trace gas ice core records do not yield a consistent fire history, even assuming dramatic (and unrealistic) changes in the spatial distribution of fire and biomes. Substantial changes in other factors such as meteorological transport or atmospheric photochemical lifetimes appear to be required to reconcile the trace gas records.