David Wilbur

The isotopic composition of atmospheric methane

Measurements of the 13C/12C, D/H and 14C composition of atmospheric methane (CH4) between 1988 and 1995 are presented. The 13C/12C measurements represent the first global data set with time series records presented for Point Barrow, Alaska (71°N), Olympic Peninsula, Washington (48°N), Mauna Loa, Hawaii (20°N), American Samoa (14°S), Cape Grim, Australia (41°S), and Baring Head, New Zealand (41°S). North-south trends of the 13C/12C and D/H of atmospheric CH4 from air samples collected during oceanographic research cruises in the Pacific Ocean are also presented. The mean annual δ13C increased southward from about −47.7 ‰ at 71°N to −41.2 ‰ at 41°S. The amplitude of the seasonal cycle in δ13C ranged from about 0.4 ‰ at 71°N to 0.1 ‰ at 14°S. The seasonal δ13C cycle at sites in tropical latitudes could be explained by CH4 loss via reaction with OH radical, whereas at temperate and polar latitudes in the northern hemisphere seasonal changes in the δ13C of the CH4 source were needed to explain the seasonal cycle. The higher δ13C value in the southern (−47.2 ‰) versus northern (−47.4 ‰) hemisphere was a result of interhemispheric transport of CH4. A slight interannual δ13C increase of 0.02±0.005 ‰ yr−1 was measured at all sites between 1990 and 1995. The mean δD of atmospheric CH4 was −86±3 ‰ between 1989 and 1995 with a 10 ‰ depletion in the northern versus southern hemisphere. The 14C content of CH4 measured at 48°N increased from 122 to 128 percent modern between 1987 and 1995. The proportion of CH4 released from fossil sources was 18±9% in the early 1990s as derived from the 14C content of CH4.

Carbon isotopic composition of atmospheric CH4: Fossil and biomass burning source strengths

The 13C/12C of atmospheric methane (CH4) was measured at Point Barrow (71°N, 156°W), Olympic Peninsula (48°N, 126°W), Mauna Loa (19°N, 155°W), and Cape Grim (41°S, 144°E) between 1987 and 1989. The global average δ13CPDB from these measurements (n = 208) was −47.20 ± 0.13%o. The lowest mean annual δ13C value of-47.61 ± 0.14‰ was measured at Point Barrow with values increasing to -47.03 ± 0.14‰ at Cape Grim. The seasonal cycle in the δ13C of CH4 was greatest at Point Barrow, with an amplitude of 0.5‰, and varied inversely with concentration. The isotopic fractionation during CH4 oxidation is calculated to be 0.993 ± 0.002 based on the measured CH4 concentration and δ13C values. The 14C content of atmospheric CH4, measured at monthly intervals at the Olympic Peninsula site between 1987 and 1989, is increasing at 1.4 ± 0.5 pM yr−1, primarily owing to 14CH4 release from nuclear reactors. The global average 14C content of 122 pM for CH4 implies a fossil methane source strength that is 16% of the total source. The global mean δ13C of −47.2‰, when coupled with the 14C results, implies that ∼11% of the total CH4 release rate is derived from biomass burning. These results indicate for a total CH4 source of ∼550 Tg yr−1 that natural gas release accounts for ∼90 Tg yr−1 and biomass burning yields ∼60 Tg yr−1. Preliminary analyses of the δ13C data using a three-dimensional chemical tracer model indicate that the observed meridional gradients in the annual average δ13C and concentration of CH4 are most closely matched with a CH4 source scenario in which 11% of the CH4 is derived from biomass burning.

O2, Ar, N2, and 222Rn in surface waters of the subarctic Ocean: Net biological O2 production

Distributions of oxygen, argon, nitrogen, and radon in the upper ocean of the subarctic Pacific distinguish the fluxes controlling the oxygen mass balance during the summers of 1987 and 1988. The difference between the net O2 flux (in mmol m−2 d−1) to the atmosphere via gas exchange (32) and the integrated decrease with time (−14) is balanced by biological production (13-17), air injection by bubble entrainment (5), and O2 flux to the thermocline −(0-4). Nitrogen/argon and oxygen/argon ratios reveal that ˜15% of the oxygen supersaturation in summer is produced by air injection and ˜40% by biological production, with the rest induced by surface water warming. Our estimate of biologically induced oxygen production when translated stoichiometrically to nitrogen uptake agrees to within error estimates with both the particulate and dissolved nitrogen mass balances for the upper ocean determined in the SUPER program during the same time period. The oxygen mass balance requires a net carbon production in the euphotic zone of ˜140 mg C m−2 d−1 (PQ=1.5), which is 20–30% of the level of 14C primary production determined by SUPER investigators.

Accurate measurement of O2, N2, and Ar gases in water and the solubility of N2

The degree of atmospheric saturation for O2, Ar, and N2 gases in water can be determined to accuracies of ±0.1–0.3% using mass spectrometry to determine the gas ratios and Winkler titrations for oxygen analysis. We describe methods used to obtain this level of accuracy and precision. Oxygen accuracy of ±0.1% can be obtained by careful attention to standardization using KIO3 standards that have been corrected for impurities. Accurate O2/Ar and O2/N2 gas ratios (±0.1–0.2%) are obtainable by measuring the mass ratios against the atmosphere if the effect of different gas concentrations on the performance of the mass spectrometer are taken into account. Oxygen and argon saturation values have been determined previously to accuracies of less than or equal to ±0.1%, but published estimates of the saturation value for nitrogen differ by more than 1%. We have redetermined the N2 saturation value at 19°C and zero salinity to be 0.92% greater than the results reported in the work of Weiss (1970).

Chemical tracers of productivity and respiration in the subtropical Pacific Ocean

We determine annual rates of net biological oxygen production in the euphotic zone and respiration in the upper thermocline of the subtropical North Pacific ocean using mass balances of oxygen, argon, and nitrogen measured at the U.S. Joint Global Ocean Flux Study time series station ALOHA. Net evasion of nitrogen and argon to the atmosphere caused by warming of surface waters is balanced by supply primarily from cross-isopycnal transport. Mixing rates between the euphotic zone and the top of the permanent thermocline required to balance the inert gas flux are 1–2 cm2 s−1 when transformed to units of an eddy diffusion coefficient. Application of mixing rates derived from the inert gas mass balance to the oxygen field yields a net annual euphotic zone production rate of 1.4±1.0 moles O2 m−2 yr−1, one half of which is lost to the atmosphere, with most of the rest mixed into the top of the thermocline. Since cross-isopycnal gradients of dissolved organic carbon (DOC) are about half to those of oxygen, we estimate that at least one quarter of the carbon flux out of the euphotic zone is via DOC. Because surface ocean dissolved organic matter has a relatively high C/N ratio, the stoichiometry among O2, C, and inorganic N in the upper ocean should be different than that observed in deeper waters.

Kinetic isotopic fractionation during air‐water gas transfer of O2, N2, CH4, and H2

The authors present experimental results that show that the kinetic isotopic fractionation during gas exchange is 0.9972 [plus minus] 0.0002 for oxygen, 0.9992 [plus minus] 0.0002 for methane, 0.9987 [plus minus] 0.0001 for nitrogen and 0.982 [plus minus] 0.002 for hydrogen, and that the equilibrium fractionation between water and gas phases is 1.037 for hydrogen. They show that the isotopic fractionation during gas transfer for these gases is not equal to the square root of their reduced mass in water, as would be predicted by an extension of the kinetic theory of ideal gases to dissolved gases. The use of isotopes as tracers of biogeochemical gases requires knowledge of the fractionation factor for air-water gas transfer; there have been few direct measurements of these factors. 31 refs., 11 figs., 1 tab.