The isotopic composition of methane in polar ice cores

Air bubbles in polar ice cores indicate that about 300 years ago the atmospheric mixing ratio of methane began to increase rapidly. Today the mixing ratio is about 1.7 parts per million by volume, and, having doubled once in the past several hundred years, it will double again in the next 60 years if current rates continue. Carbon isotope ratios in methane up to 350 years in age have been measured with as little as 25 kilograms of polar ice recovered in 4-meter-long ice-core segments. The data show that (i) in situ microbiology or chemistry has not altered the ice-core methane concentrations, and (ii) that the carbon-13 to carbon-12 ratio of atmospheric CH(4) in ice from 100 years and 300 years ago was about 2 per mil lower than at present. Atmospheric methane has a rich spectrum of isotopic sources: the ice-core data indicate that anthropogenic burning of the earth's biomass is the principal cause of the recent (13)CH(4) enrichment, although other factors may also contribute.     

Siberian peatlands a net carbon sink and global methane source since the early Holocene

Interpolar methane gradient (IPG) data from ice cores suggest the "switching on" of a major Northern Hemisphere methane source in the early Holocene. Extensive data from Russia's West Siberian Lowland show (i) explosive, widespread peatland establishment between 11.5 and 9 thousand years ago, predating comparable development in North America and synchronous with increased atmospheric methane concentrations and IPGs, (ii) larger carbon stocks than previously thought (70.2 Petagrams, up to approximately 26% of all terrestrial carbon accumulated since the Last Glacial Maximum), and (iii) little evidence for catastrophic oxidation, suggesting the region represents a long-term carbon dioxide sink and global methane source since the early Holocene.     

Recent changes in atmospheric carbon monoxide

Measurements of carbon monoxide (CO) in air samples collected from 27 locations between 71 degrees N and 41 degrees S show that atmospheric levels of this gas have decreased worldwide over the past 2 to 5 years. During this period, CO decreased at nearly a constant rate in the high northern latitudes. In contrast, in the tropics an abrupt decrease occurred beginning at the end of 1991. In the Northern Hemisphere, CO decreased at a spatially and temporally averaged rate of 7.3 (+/-0.9) parts per billion per year (6.1 percent per year) from June 1990 to June 1993, whereas in the Southern Hemisphere, CO decreased 4.2 (+/-0.5) parts per billion per year (7.0 percent per year). This recent change is opposite a long-term trend of a 1 to 2 percent per year increase inferred from measurements made in the Northern Hemisphere during the past 30 years.     

Unexpected changes to the global methane budget over the past 2000 years

We report a 2000-year Antarctic ice-core record of stable carbon isotope measurements in atmospheric methane (delta13CH4). Large delta13CH4 variations indicate that the methane budget varied unexpectedly during the late preindustrial Holocene (circa 0 to 1700 A.D.). During the first thousand years (0 to 1000 A.D.), delta13CH4 was at least 2 per mil enriched compared to expected values, and during the following 700 years, an about 2 per mil depletion occurred. Our modeled methane source partitioning implies that biomass burning emissions were high from 0 to 1000 A.D. but reduced by almost approximately 40% over the next 700 years. We suggest that both human activities and natural climate change influenced preindustrial biomass burning emissions and that these emissions have been previously understated in late preindustrial Holocene methane budget research.     

Freshwater methane emissions offset the continental carbon sink

Inland waters (lakes, reservoirs, streams, and rivers) are often substantial methane (CH(4)) sources in the terrestrial landscape. They are, however, not yet well integrated in global greenhouse gas (GHG) budgets. Data from 474 freshwater ecosystems and the most recent global water area estimates indicate that freshwaters emit at least 103 teragrams of CH(4) year(-1), corresponding to 0.65 petagrams of C as carbon dioxide (CO(2)) equivalents year(-1), offsetting 25% of the estimated land carbon sink. Thus, the continental GHG sink may be considerably overestimated, and freshwaters need to be recognized as important in the global carbon cycle.     

Rapid rise of sea level 19,000 years ago and its global implications

Evidence from the Irish Sea basin supports the existence of an abrupt rise in sea level (meltwater pulse) at 19,000 years before the present (B.P.). Climate records indicate a large reduction in the strength of North Atlantic Deep Water formation and attendant cooling of the North Atlantic at this time, indicating a source of the meltwater pulse from one or more Northern Hemisphere ice sheets. Warming of the tropical Atlantic and Pacific oceans and the Southern Hemisphere also began at 19,000 years B.P. These responses identify mechanisms responsible for the propagation of deglacial climate signals to the Southern Hemisphere and tropics while maintaining a cold climate in the Northern Hemisphere.     

Atmospheric CO2 concentrations over the last glacial termination

A record of atmospheric carbon dioxide (CO2) concentration during the transition from the Last Glacial Maximum to the Holocene, obtained from the Dome Concordia, Antarctica, ice core, reveals that an increase of 76 parts per million by volume occurred over a period of 6000 years in four clearly distinguishable intervals. The close correlation between CO2 concentration and Antarctic temperature indicates that the Southern Ocean played an important role in causing the CO2 increase. However, the similarity of changes in CO2 concentration and variations of atmospheric methane concentration suggests that processes in the tropics and in the Northern Hemisphere, where the main sources for methane are located, also had substantial effects on atmospheric CO2 concentrations.     

A Large Northern Hemisphere Terrestrial CO2 Sink Indicated by the 13C/12C Ratio of Atmospheric CO2

Measurements of the concentrations and carbon-13/carbon-12 isotope ratios of atmospheric carbon dioxide can be used to quantify the net removal of carbon dioxide from the atmosphere by the oceans and terrestrial plants. A study of weekly samples from a global network of 43 sites defined the latitudinal and temporal patterns of the two carbon sinks. A strong terrestrial biospheric sink was found in the temperate latitudes of the Northern Hemisphere in 1992 and 1993, the magnitude of which is roughly half that of the global fossil fuel burning emissions for those years. The challenge now is to identify those processes that would cause the terrestrial biosphere to absorb carbon dioxide in such large quantities.     

Atmospheric methane and nitrous oxide of the Late Pleistocene from Antarctic ice cores

The European Project for Ice Coring in Antarctica Dome C ice core enables us to extend existing records of atmospheric methane (CH4) and nitrous oxide (N2O) back to 650,000 years before the present. A combined record of CH4 measured along the Dome C and the Vostok ice cores demonstrates, within the resolution of our measurements, that preindustrial concentrations over Antarctica have not exceeded 773 +/- 15 ppbv (parts per billion by volume) during the past 650,000 years. Before 420,000 years ago, when interglacials were cooler, maximum CH4 concentrations were only about 600 ppbv, similar to lower Holocene values. In contrast, the N2O record shows maximum concentrations of 278 +/- 7 ppbv, slightly higher than early Holocene values.     

Patagonian glacier response during the late glacial-Holocene transition

Whether cooling occurred in the Southern Hemisphere during the Younger Dryas (YD) is key to understanding mechanisms of millennial climate change. Although Southern Hemisphere records do not reveal a distinct climate reversal during the late glacial period, many mountain glaciers readvanced. We show that the Puerto Bandera moraine (50 degrees S), which records a readvance of the Southern Patagonian Icefield (SPI), formed at, or shortly after, the end of the YD. The exposure age (10.8 +/- 0.5 thousand years ago) is contemporaneous with the highest shoreline of Lago Cardiel (49 degrees S), which records peak precipitation east of the Andes since 13 thousand years ago. Absent similar moraines west of the Andes, these data indicate an SPI response to increased amounts of easterly-sourced precipitation-reflecting changes in the Southern Westerly circulation-rather than regional cooling.     

Ice record of delta13C for atmospheric CH4 across the Younger Dryas-Preboreal transition

We report atmospheric methane carbon isotope ratios (delta13CH4) from the Western Greenland ice margin spanning the Younger Dryas-to-Preboreal (YD-PB) transition. Over the recorded approximately 800 years, delta13CH4 was around -46 per mil (per thousand); that is, approximately 1 per thousand higher than in the modern atmosphere and approximately 5.5 per thousand higher than would be expected from budgets without 13C-rich anthropogenic emissions. This requires higher natural 13C-rich emissions or stronger sink fractionation than conventionally assumed. Constant delta13CH4 during the rise in methane concentration at the YD-PB transition is consistent with additional emissions from tropical wetlands, or aerobic plant CH4 production, or with a multisource scenario. A marine clathrate source is unlikely.     

Atmospheric CO2 and climate on millennial time scales during the last glacial period

Reconstructions of ancient atmospheric carbon dioxide (CO2) variations help us better understand how the global carbon cycle and climate are linked. We compared CO2 variations on millennial time scales between 20,000 and 90,000 years ago with an Antarctic temperature proxy and records of abrupt climate change in the Northern Hemisphere. CO2 concentration and Antarctic temperature were positively correlated over millennial-scale climate cycles, implying a strong connection to Southern Ocean processes. Evidence from marine sediment proxies indicates that CO2 concentration rose most rapidly when North Atlantic Deep Water shoaled and stratification in the Southern Ocean was reduced. These increases in CO2 concentration occurred during stadial (cold) periods in the Northern Hemisphere, several thousand years before abrupt warming events in Greenland.     

Deuterated methane observed on saturn

Absorptions for the V(2) band of deuterated methane (CH(3)D) have been observed in the 5-micron spectrum of Saturn, obtained with a Fourier transform spectrometer. Analysis of the band yields a CH(3)D abundance of 2.6 +/- 0.8 centimeter-amagat and a temperature of 175 +/- 30 K for the mean level of spectroscopic line formation. This temperature indicates that a substantial portion of Saturn's flux at 5 microns is due to thermal radiation, and that we are therefore looking fairly deep into its atmosphere, as is the case for the Jupiter 5-micron window. This CH(3)D abundance leads to a deuteriumlhydrogen ratio of about 2 x 10(-5) in Saturn's atmosphere. This ratio is much lower than the terrestrial value but comparable to that determined for Jupiter and may be taken as representative of the deuteriumlhydrogen ratio in the solar system at the time of its formation.     

A mid-brunhes climatic event: long-term changes in global atmosphere and ocean circulation

A long-term climatic change 4.0 x 10(5) to 3.0 x 10(5) years ago is recorded in deep-sea sediments of the Angola and Canary basins in the eastern Atlantic Ocean. In the Angola Basin (Southern Hemisphere) the climatic signal shows a transition to more humid ("interglacial") conditions in equatorial Africa, and in the Canary Basin (Northern Hemisphere) to more "glacial" oceanic conditions. This trend is confirmed by comparison with all well-documented marine and continental records from various latitudes available; in the Northern Hemisphere, in the Atlantic north of 20 degrees N, climate merged into more "glacial" conditions and in equatorial regions and in the Southern Hemisphere to more "interglacial" conditions. The data point to a more northern position of early Brunhes oceanic fronts and to an intensified atmosphere and ocean surface circulation in the Southern Hemisphere during that time, probably accompanied by a more zonal circulation in the Northern Hemisphere. The mid-Brunhes climatic change may have been forced by the orbital eccentricity cycle of 4.13 x 10(5) years.     

Continuing worldwide increase in tropospheric methane, 1978 to 1987

The average worldwide tropospheric mixing ratio of methane has increased by 11% from 1.52 parts per million by volume (ppmv) in January 1978 to 1.684 ppmv in September 1987, for an increment of 0.016 +/- 0.001 ppmv per year. Within the limits of our measurements, the global tropospheric mixing ratio for methane over the past decade is consistent either with a linear growth rate of 0.016 +/- 0.001 ppmv per year or with a slight lessening of the rate of growth over the past 5 years. No indications were found of an effect of the El Ni?o-Southern Oscillation-El Chichon events of 1982-83 on total global methane, although severe reductions were reported in the Pacific Northwest during that time period. The growth in tropospheric methane may have increased the water concentration in the stratosphere by as much as 28% since the 1940s and 45% over the past two centuries and thus could have increased the mass of precipitable water available for formation of polar stratospheric clouds.     

Evolution of the eastern tropical Pacific through Plio-Pleistocene glaciation

A tropical Pacific climate state resembling that of a permanent El Ni?o is hypothesized to have ended as a result of a reorganization of the ocean heat budget approximately 3 million years ago, a time when large ice sheets appeared in the high latitudes of the Northern Hemisphere. We report a high-resolution alkenone reconstruction of conditions in the heart of the eastern equatorial Pacific (EEP) cold tongue that reflects the combined influences of changes in the equatorial thermocline, the properties of the thermocline's source waters, atmospheric greenhouse gas content, and orbital variations on sea surface temperature (SST) and biological productivity over the past 5 million years. Our data indicate that the intensification of Northern Hemisphere glaciation approximately 3 million years ago did not interrupt an almost monotonic cooling of the EEP during the Plio-Pleistocene. SST and productivity in the eastern tropical Pacific varied in phase with global ice volume changes at a dominant 41,000-year (obliquity) frequency throughout this time. Changes in the Southern Hemisphere most likely modulated most of the changes observed.     

Global cooling?

The world's inhabitants, including Scientists, live primarily in the Northern Hemisphere. It is quite natural to be concerned about events that occur close to home and neglect faraway events. Hence, it is not surprising that so little attention has been given to the Southern Hemisphere. Evidence for global cooling has been based, in large part, on a severe cooling trend at high northern latitudes. This article points out that the Northern Hemisphere cooling trend appears to be out of phase with a warming trend at high latitudes in the Southern Hemisphere. The data are scanty. We cannot be sure that these temperature fluctuations are be not the result of natural causes. How it seems most likely that human activity has already significantly perturbed the atmospheric weather system. The effect of particulate matter pollution should be most severe in the highly populated and industrialized Northern Hemisphere. Because of the rapid diffusion of CO(2) molecules within the atmosphere, both hemispheres will be subject to warming due to the atmospheric (greenhouse) effect as the CO(2) content of the atmosphere builds up from the combustion of fossil fuels. Because of the differential effects of the two major sources of atmospheric pollution, the CO(2) greenhouse effect warming trend should first become evident in the Southern Hemisphere. The socioeconomic and political consequences of climate change are profound. We need an early warning system such as would be provided by a more intensive international world weather watch, particularly at high northern and southern latitudes.     

Anomalous carbon-isotope ratios in nonvolatile organic material

Organic mats are associated with sulfur deposits in Upper Pleistocene sand ridges of the coastal plain of southern Israel; black, brittle, and non-volatile, they show parallel layering but no other apparent cellular structure. Two independent carbon-14 determinations yielded ages of 27,750+/-500 and 31,370+/-1400 years. Four carbon-13:carbon-12 determinations fell within the range deltaC(13) =-82.5 to -89.3 per mille relative to the PDB standard; these appear to be the lowest values yet reported for naturally occurring high-molecular-weight organic material. The origin of the carbon is probably complex; it must have passed through at least one biologic cycle before final deposition.     

Global trends in total atmospheric ozone

Analyses of the mean monthly global distributions of total ozone for the 13-year period from 1957 through 1970 reveal an upward trend of about 7.5 percent per decade in the Northern Hemisphere and about 2.5 percent per decade in the Southern Hemisphere. The increase seems to have started about March 1961 in the Northern Hemisphere and about September 1961 in the Southern Hemisphere. The cause of these trends is at present unknown.     

A mercury-catalyzed, high-yield system for the oxidation of methane to methanol

A homogeneous system for the selective, catalytic oxidation of methane to methanol via methyl bisulfate is reported. The net reaction catalyzed by mercuric ions, Hg(II), is the oxidation of methane by concentrated sulfuric acid to produce methyl bisulfate, water, and sulfur dioxide. The reaction is efficient. At a methane conversion of 50 percent, 85 percent selectivity to methyl bisulfate ( approximately 43 percent yield; the major side product is carbon dioxide) was achieved at a molar productivity of 10(-7) mole per cubic centimeter per second and Hg(II) turnover frequency of 10(-3) per second. Separate hydrolysis of methyl bisulfate and reoxidation of the sulfur dioxide with air provides a potentially practical scheme for the oxidation of methane to methanol with molecular oxygen. The primary steps of the Hg(II)-catalyzed reaction were individually examined and the essential elements of the mechanism were identified. The Hg(II) ion reacts with methane by an electrophilic displacement mechanism to produce an observable species, CH(3)HgOSO(3)H, 1. Under the reaction conditions, 1 readily decomposes to CH(3)OSO(3)H and the reduced mercurous species, Hg(2)(2+) The catalytic cycle is completed by the reoxidation of Hg(2)(2+) with H(2)SO(4) to regenerate Hg(II) and byproducts SO(2) and H(2)O. Thallium(III), palladium(II), and the cations of platinum and gold also oxidize methane to methyl bisulfate in sulfuric acid.