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Alexander, B, Vollmer MK, Jackson T, Weiss RF, Thiemens MH.  2001.  Stratospheric CO2 isotopic anomalies and SF6 and CFC tracer concentrations in the Arctic polar vortex. Geophysical Research Letters. 28:4103-4106.   10.1029/2001gl013692   AbstractWebsite

Isotopic measurements (delta O-17 and delta O-18) Of CO2 along with concentration measurements of SF6, CC1(3)F (CFC-11), CC1(2)F(2) (CFC-12) and CC1(2)FCC1F(2) (CFC-113) in stratospheric samples collected within the Arctic polar vortex are reported. These are the first simultaneous measurements of the concentration of fluorinated compounds and the complete oxygen isotopic composition Of CO2 in the middle atmosphere. A mass-independent anomaly in the oxygen isotopic composition Of CO2 is observed that arises from isotopic exchange with stratospheric O(D-1) derived from O-3 photolysis. The data exhibit a strong anti-correlation between the Delta O-17 (the degree of the mass-independent anomaly) and molecular tracer concentrations. The potential ability of tl-ris isotopic proxy to trace mesospheric and stratospheric transport is discussed.

Arnold, T, Muhle J, Salameh PK, Harth CM, Ivy DJ, Weiss RF.  2012.  Automated measurement of nitrogen trifluoride in ambient air. Analytical Chemistry. 84:4798-4804.   10.1021/ac300373e   AbstractWebsite

We present an analytical method for the in situ measurement of atmospheric nitrogen trifluoride (NF3), an anthropogenic gas with a 100-year global warming potential of over 16 000. This potent greenhouse gas has a rising atmospheric abundance due to its emission from a growing number of manufacturing processes and an expanding end-use market. Here we present a modified version of the "Medusa" preconcentration gas chromatography/mass spectrometry (GC/MS) system of Miller, B. R.; Weiss, R. F.; Salameh, P. K.; Tanhua, T.; Greally, B. R; Male, J.; Simmonds, P. G. Anal. Chem. 2008, 80 (5), 1536-1545. By altering the techniques of gas separation and chromatography after initial preconcentration, we are now able to make atmospheric measurements of NF3 with relative precision <2% (1 sigma) for current background clean air samples. Importantly, this method augments the currently operational Medusa system, so that the quality of data for species already being measured is not compromised and NF3 is measured from the same preconcentrated sample. We present the first in situ measurements of NF3 from La Jolla, California made 11 times daily, illustrating how global deployment of this technique within the AGAGE (Advanced Global Atmospheric Gases Experiment) network could facilitate estimation of global and regional NF3 emissions over the coming years.

Arnold, T, Harth CM, Mühle J, Manning AJ, Salameh PK, Kim J, Ivy DJ, Steele PL, Petrenko VV, Severinghaus JP, Baggenstos D, Weiss RF.  2013.  Nitrogen trifluoride global emissions estimated from updated atmospheric measurements. Proceedings of the National Academy of Sciences.   10.1073/pnas.1212346110   AbstractWebsite

Nitrogen trifluoride (NF3) has potential to make a growing contribution to the Earth’s radiative budget; however, our understanding of its atmospheric burden and emission rates has been limited. Based on a revision of our previous calibration and using an expanded set of atmospheric measurements together with an atmospheric model and inverse method, we estimate that the global emissions of NF3 in 2011 were 1.18 ± 0.21 Gg⋅y−1, or ∼20 Tg CO2-eq⋅y−1 (carbon dioxide equivalent emissions based on a 100-y global warming potential of 16,600 for NF3). The 2011 global mean tropospheric dry air mole fraction was 0.86 ± 0.04 parts per trillion, resulting from an average emissions growth rate of 0.09 Gg⋅y−2 over the prior decade. In terms of CO2 equivalents, current NF3 emissions represent between 17% and 36% of the emissions of other long-lived fluorinated compounds from electronics manufacture. We also estimate that the emissions benefit of using NF3 over hexafluoroethane (C2F6) in electronics manufacture is significant—emissions of between 53 and 220 Tg CO2-eq⋅y−1 were avoided during 2011. Despite these savings, total NF3 emissions, currently ∼10% of production, are still significantly larger than expected assuming global implementation of ideal industrial practices. As such, there is a continuing need for improvements in NF3 emissions reduction strategies to keep pace with its increasing use and to slow its rising contribution to anthropogenic climate forcing.

Arnold, T, Manning AJ, Kim J, Li SL, Webster H, Thomson D, Muhle J, Weiss RF, Park S, O'Doherty S.  2018.  Inverse modelling of CF4 and NF3 emissions in East Asia. Atmospheric Chemistry and Physics. 18:13305-13320.   10.5194/acp-18-13305-2018   AbstractWebsite

Decadal trends in the atmospheric abundances of carbon tetrafluoride (CF4) and nitrogen trifluoride (NF3) have been well characterised and have provided a time series of global total emissions. Information on locations of emissions contributing to the global total, however, is currently poor. We use a unique set of measurements between 2008 and 2015 from the Gosan station, Jeju Island, South Korea (part of the Advanced Global Atmospheric Gases Experiment network), together with an atmospheric transport model, to make spatially disaggregated emission estimates of these gases in East Asia. Due to the poor availability of good prior information for this study, our emission estimates are largely influenced by the atmospheric measurements. Notably, we are able to highlight emission hotspots of NF3 and CF4 in South Korea due to the measurement location. We calculate emissions of CF4 to be quite constant between the years 2008 and 2015 for both China and South Korea, with 2015 emissions calculated at 4.3 +/- 2.7 and 0.36 +/- 0.11 Gg yr(-1), respectively. Emission estimates of NF3 from South Korea could be made with relatively small uncertainty at 0.6 +/- 0.07 Gg yr(-1) in 2015, which equates to similar to 1.6% of the country's CO2 emissions. We also apply our method to calculate emissions of CHF3 (HFC-23) between 2008 and 2012, for which our results find good agreement with other studies and which helps support our choice in methodology for CF4 and NF3.

Arnold, T, Ivy DJ, Harth CM, Vollmer MK, Muhle J, Salameh PK, Steele LP, Krummel PB, Wang RHJ, Young D, Lunder CR, Hermansen O, Rhee TS, Kim J, Reimann S, O'Doherty S, Fraser PJ, Simmonds PG, Prinn RG, Weiss RF.  2014.  HFC-43-10mee atmospheric abundances and global emission estimates. Geophysical Research Letters. 41:2228-2235.   10.1002/2013gl059143   AbstractWebsite

We report in situ atmospheric measurements of hydrofluorocarbon HFC-43-10mee (C5H2F10; 1,1,1,2,2,3,4,5,5,5-decafluoropentane) from seven observatories at various latitudes, together with measurements of archived air samples and recent Antarctic flask air samples. The global mean tropospheric abundance was 0.210.05ppt (parts per trillion, dry air mole fraction) in 2012, rising from 0.040.03ppt in 2000. We combine the measurements with a model and an inverse method to estimate rising global emissionsfrom 0.430.34Ggyr(-1) in 2000 to 1.130.31Ggyr(-1) in 2012 (similar to 1.9TgCO(2)-eqyr(-1) based on a 100year global warming potential of 1660). HFC-43-10meea cleaning solvent used in the electronics industryis currently a minor contributor to global radiative forcing relative to total HFCs; however, our calculated emissions highlight a significant difference from the available reported figures and projected estimates.

Bender, M, Jahnke R, Weiss R, Martin W, Heggie DT, Orchardo J, Sowers T.  1989.  Organic carbon oxidation and benthic nitrogen and silica dynamics in San Clemente Basin, a continental borderland site. Geochimica Et Cosmochimica Acta. 53:685-697.   10.1016/0016-7037(89)90011-2   AbstractWebsite

Organic carbon oxidation rates in San Clemente Basin were determined by benthic chamber experiments using the Bottom Lander, along with studies of pore water chemistry. Non-steady-state diagenetic models are developed for interpreting concentration-time data from the benthic chamber experiments. O2, NO3−, and SO42− are all important oxidants for organic carbon at our study site. Regenerated fixed nitrogen was consumed by NO3− reduction. There is a flux of NO3− into the sediments, and the benthic flux of NH4+ is undetectable. The total rate at which fixed nitrogen is removed from the oceans at this site is about twice the flux of PON to the sea floor. SiO2 fluxes calculated from interfacial pore water gradients are in satisfactory agreement with those determined using the Lander. Most silica dissolution must therefore occur within the sediments, although interstitial profiles show that little dissolution occurs below 1 cm depth.

Bill, M, Rhew RC, Weiss RF, Goldstein AH.  2002.  Carbon isotope ratios of methyl bromide and methyl chloride emitted from a coastal salt marsh. Geophysical Research Letters. 29   10.1029/2001gl012946   AbstractWebsite

[1] Methyl bromide (CH3Br) and methyl chloride (CH3Cl) play important roles in stratospheric ozone depletion, but their atmospheric budgets have large uncertainties. The analysis of stable isotope composition of methyl halides may provide useful independent information for further constraining their budgets. Here we report the first measurements of CH3Br and CH3Cl stable carbon isotope ratios emitted from a biogenic source under in situ conditions. CH3Br and CH3Cl emissions from the salt marsh plant Batis maritima showed a strong diurnal variation in delta(13)C, from -65parts per thousand during the daytime to --12parts per thousand at night. The minimum delta(13)C values were observed at midday, coinciding with the time of greatest emissions and ambient temperature. At night, when the emissions were much smaller, the stable carbon isotopic ratios of CH3Br and CH3Cl became enriched in C-13. The daily mean delta(13)C of CH3Br and CH3Cl emissions, weighted by emission rate, were -43parts per thousand and -62parts per thousand respectively.

Broecker, WS, Peacock SL, Walker S, Weiss R, Fahrbach E, Schroeder M, Mikolajewicz U, Heinze C, Key R, Peng TH, Rubin S.  1998.  How much deep water is formed in the Southern Ocean? Journal of Geophysical Research-Oceans. 103:15833-15843.   10.1029/98jc00248   AbstractWebsite

Three tracers are used to place constraints on the production rate of ventilated deep water in the Southern Ocean. The distribution of the water mass tracer PO4* ("phosphate star") in the deep sea suggests that the amount of ventilated deep water produced in the Southern Ocean is equal to or greater than the outflow of North Atlantic Deep Water from the Atlantic. Radiocarbon distributions yield an export flux of water from the North Atlantic which has averaged about 15 Sv over the last several hundred years. CFC inventories are used as a direct indicator of the current production rate of ventilated deep water in the Southern Ocean. Although coverage is as yet sparse, it appears that the CFC inventory is not inconsistent with the deep water production rate required by the distributions of PO4* and radiocarbon. It has been widely accepted that the major part of the deep water production in the Southern Ocean takes place in the Weddell Sea. However, our estimate of the Southern Ocean ventilated deep water flux is in conflict with previous estimates of the flux of ventilated deep water from the Weddell Sea, which lie in the range 1-5 Sv. Possible reasons for this difference are discussed.

Broecker, WS, Ledwell JR, Takahashi T, Weiss R, Merlivat L, Memery L, Peng TH, Jahne B, Munnich KO.  1986.  Isotopic versus micrometeorologic ocean CO2 fluxes: A serious conflict. Journal of Geophysical Research-Oceans. 91:517-527.   10.1029/JC091iC09p10517   AbstractWebsite

Eddy correlation measurements over the ocean give CO2 fluxes an order of magnitude or more larger than expected from mass balance measurements using radiocarbon and radon 222. In particular, Smith and Jones (1985) reported large upward and downward fluxes in a surf zone at supersaturations of 15% and attributed them to the equilibration of bubbles at elevated pressures. They argue that even on the open ocean such bubble injection may create steady state CO2 supersaturations and that inferences of fluxes based on air-sea pCO2 differences and radon exchange velocities must be made with caution. We defend the global average CO2 exchange rate determined by three independent radioisotopic means: prebomb radiocarbon inventories; global surveys of mixed layer radon deficits; and oceanic uptake of bomb-produced radiocarbon. We argue that laboratory and lake data do not lead one to expect fluxes as large as reported from the eddy correlation technique; that the radon method of determining exchange velocities is indeed useful for estimating CO2 fluxes; that supersaturations of CO2 due to bubble injection on the open ocean are negligible; that the hypothesis that Smith and Jones advance cannot account for the fluxes that they report; and that the pCO2 values reported by Smith and Jones are likely to be systematically much too high. The CO2 fluxes for the ocean measured to date by the micrometeorological method can be reconciled with neither the observed concentrations of radioisotopes of radon and carbon in the oceans nor the tracer experiments carried out in lakes and in wind/wave tunnels.

Bullister, JL, Weiss RF.  1983.  Anthropogenic chlorofluoromethanes in the Greenland and Norwegian Seas. Science. 221:265-268.   10.1126/science.221.4607.265   AbstractWebsite

The concentrations of two industrially produced chlorofluoromethanes, CCl3F(F-11) and CCl2F2(F-12), have been measured in the water column and in the marine atmosphere of the Greenland and Norwegian seas. Measurable concentrations of these two chlorofluoromethanes have penetrated to the deep basins of both of these regions, and the general characteristics of their vertical distributions are similar to those of the bomb-produced radioisotopes injected into the atmosphere on a similar time scale. The data have been fitted to a time-dependent box model based on deep convective mixing in the Greenland Sea and lateral exchange between the deep basins. The model calculations for the two chlorofluoromethanes in the Greenland Sea give similar results, with a time scale for deep convection of about 40 years. The time scale for lateral mixing between the deep Greenland Sea and the deep Norwegian Sea is estimated to be 20 to 30 years, although the agreement between the calculations for the two chlorofluoromethanes is limited by analytical uncertainties at the low concentrations found in the deep Norwegian Sea and by uncertainties in the model assumptions.

Bullister, JL, Weiss RF.  1988.  Determination of CCl3F and CCl2F2 in seawater and air. Deep-Sea Research Part a-Oceanographic Research Papers. 35:839-853.   10.1016/0198-0149(88)90033-7   AbstractWebsite

An improved analytical technique has been developed for the rapid and accurate shipboard measurement of two anthropogenically produced chlorofluorocarbons (CFCs), CCl3F (F-11) and CCl2F2 (F-12) in air and seawater. Gas samples (dry air or standard) are injected into a stream of purified gas and then concentrated in a low temperature trap. Seawater samples collected in oceanographic Niskin bottles are transferred into glass syringes for storage until analysis. An aliquot of approximately 30 cm3 of seawater is introduced into a glass stripping chamber where the dissolved gases are purged with purified gas, and the evolved CFCs are concentrated in the same cold trap. The trap is subsequently isolated and heated, and the CFCs are automatically transferred by a stream of carrier gas into a precolumn and then a chromatographic separating column. The CCl3F and CCl2F2 peaks are detected by an electron capture detector (ECD) and their areas are integrated digitally. CFC amounts are calculated using fitted calibration curves, generated by injection of various multiple aliquots of gas standard containing known concentrations of CFCs. Preliminary concentration values for these compounds are printed at the completion of each analysis. Total analysis time for air and water samples is < 10 min, allowing detailed vertical profiles of the concentrations of these compounds in the water column and concentrations in the overlying atmosphere to be determined within a few hours of the completion of a hydrographic station. Typical relative standard deviations for analyses of CCl3F and CCl2F2 in near-surface seawater containing equilibrium levels of these compounds are approximately 1%. Limits of detection for both compounds in 30 cm3 seawater samples are about 0.005 × 10−12 mol kg−1.

Carmack, EC, Weiss RF.  1991.  Convection in Lake Baikal: an example of thermobaric instability. Deep Convection and Deep Water Formation in the Oceans. ( Chu PC, Gascard JC, Eds.).:215-228., Burlington: Elsevier Abstract

This book contains articles presenting current knowledge about the formation and renewal of deep waters in the ocean. These articles were presented at an international workshop at the Naval Postgraduate School in Monterey in March 1990.

Chan, LH, Edmond JM, Stallard RF, Broecker WS, Chung YC, Weiss RF, Ku TL.  1976.  Radium and barium at Geosecs stations in Atlantic and Pacific. Earth and Planetary Science Letters. 32:258-267.   10.1016/0012-821x(76)90066-2   AbstractWebsite

Ra and Ba show a general linear correlation in the oceanic water column within the uncertainties of the data: the slope of the line is about 4.6 nanomoles (nmoles) Ra/mole Ba, the intercept being at about 4 nmoles Ba/kg. This demonstrates the usefulness of Ba as a “chemical analogue” of Ra. Box-model calculations indicate that the average deep-water excess of Ra over Ba should be about 10% relative to the surface. This is consistent with the observations outside the deep northeast Pacific. However, the uncertainties in the data are such that the regional variation in the primary input cannot be resolved. In the deep waters of the North Pacific there is in fact a large excess of Ra relative to Ba. The one detailed profile presently available (204) can be explained consistently by a simple vertical advection-diffusion model.

Chipperfield, MP, Liang Q, Rigby M, Hossaini R, Montzka SA, Dhomse S, Feng WH, Prinn RG, Weiss RF, Harth CM, Salameh PK, Muhle J, O'Doherty S, Young D, Simmonds PG, Krummel PB, Fraser PJ, Steele LP, Happell JD, Rhew RC, Butler J, Yvon-Lewis SA, Hall B, Nance D, Moore F, Miller BR, Elkins J, Harrison JJ, Boone CD, Atlas EL, Mahieu E.  2016.  Model sensitivity studies of the decrease in atmospheric carbon tetrachloride. Atmospheric Chemistry and Physics. 16:15741-15754.   10.5194/acp-16-15741-2016   AbstractWebsite

Carbon tetrachloride (CCl4) is an ozone-depleting substance, which is controlled by the Montreal Protocol and for which the atmospheric abundance is decreasing. However, the current observed rate of this decrease is known to be slower than expected based on reported CCl4 emissions and its estimated overall atmospheric lifetime. Here we use a three-dimensional (3-D) chemical transport model to investigate the impact on its predicted decay of uncertainties in the rates at which CCl4 is removed from the atmosphere by photolysis, by ocean uptake and by degradation in soils. The largest sink is atmospheric photolysis (74% of total), but a reported 10% uncertainty in its combined photolysis cross section and quantum yield has only a modest impact on the modelled rate of CCl4 decay. This is partly due to the limiting effect of the rate of transport of CCl4 from the main tropospheric reservoir to the stratosphere, where photolytic loss occurs. The model suggests large interannual variability in the magnitude of this stratospheric photolysis sink caused by variations in transport. The impact of uncertainty in the minor soil sink (9% of total) is also relatively small. In contrast, the model shows that uncertainty in ocean loss (17% of total) has the largest impact on modelled CCl4 decay due to its sizeable contribution to CCl4 loss and large lifetime uncertainty range (147 to 241 years). With an assumed CCl4 emission rate of 39 Gg year(-1), the reference simulation with the best estimate of loss processes still underestimates the observed CCl4 (overestimates the decay) over the past 2 decades but to a smaller extent than previous studies. Changes to the rate of CCl4 loss processes, in line with known uncertainties, could bring the model into agreement with in situ surface and remote-sensing measurements, as could an increase in emissions to around 47 Gg year(-1). Further progress in constraining the CCl4 budget is partly limited by systematic biases between observational datasets. For example, surface observations from the National Oceanic and Atmospheric Administration (NOAA) network are larger than from the Advanced Global Atmospheric Gases Experiment (AGAGE) network but have shown a steeper decreasing trend over the past 2 decades. These differences imply a difference in emissions which is significant relative to uncertainties in the magnitudes of the CCl4 sinks.

Chirkov, M, Stiller GP, Laeng A, Kellmann S, von Clarmann T, Boone CD, Elkins JW, Engel A, Glatthor N, Grabowski U, Harth CM, Kiefer M, Kolonjari F, Krummel PB, Linden A, Lunder CR, Miller BR, Montzka SA, Mühle J, O'Doherty S, Orphal J, Prinn RG, Toon G, Vollmer MK, Walker KA, Weiss RF, Wiegele A, Young D.  2016.  Global HCFC-22 measurements with MIPAS: retrieval, validation, global distribution and its evolution over 2005–2012. Atmos. Chem. Phys.. 16:3345-3368.: Copernicus Publications   10.5194/acp-16-3345-2016   AbstractWebsite

We report on HCFC-22 data acquired by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) in the reduced spectral resolution nominal observation mode. The data cover the period from January 2005 to April 2012 and the altitude range from the upper troposphere (above cloud top altitude) to about 50 km. The profile retrieval was performed by constrained nonlinear least squares fitting of modelled spectra to the measured limb spectral radiances. The spectral ν4-band at 816.5 ± 13 cm−1 was used for the retrieval. A Tikhonov-type smoothing constraint was applied to stabilise the retrieval. In the lower stratosphere, we find a global volume mixing ratio of HCFC-22 of about 185 pptv in January 2005. The rate of linear growth in the lower latitudes lower stratosphere was about 6 to 7 pptv year−1 in the period 2005–2012. The profiles obtained were compared with ACE-FTS satellite data v3.5, as well as with MkIV balloon profiles and cryosampler balloon measurements. Between 13 and 22 km, average agreement within −3 to +5 pptv (MIPAS – ACE) with ACE-FTS v3.5 profiles is demonstrated. Agreement with MkIV solar occultation balloon-borne measurements is within 10–20 pptv below 30 km and worse above, while in situ cryosampler balloon measurements are systematically lower over their full altitude range by 15–50 pptv below 24 km and less than 10 pptv above 28 km. MIPAS HCFC-22 time series below 10 km altitude are shown to agree mostly well to corresponding time series of near-surface abundances from the NOAA/ESRL and AGAGE networks, although a more pronounced seasonal cycle is obvious in the satellite data. This is attributed to tropopause altitude fluctuations and subsidence of polar winter stratospheric air into the troposphere. A parametric model consisting of constant, linear, quasi-biennial oscillation (QBO) and several sine and cosine terms with different periods has been fitted to the temporal variation of stratospheric HCFC-22 for all 10°-latitude/1-to-2-km-altitude bins. The relative linear variation was always positive, with relative increases of 40–70 % decade−1 in the tropics and global lower stratosphere, and up to 120 % decade−1 in the upper stratosphere of the northern polar region and the southern extratropical hemisphere. Asian HCFC-22 emissions have become the major source of global upper tropospheric HCFC-22. In the upper troposphere, monsoon air, rich in HCFC-22, is instantaneously mixed into the tropics. In the middle stratosphere, between 20 and 30 km, the observed trend is inconsistent with the trend at the surface (corrected for the age of stratospheric air), hinting at circulation changes. There exists a stronger positive trend in HCFC-22 in the Southern Hemisphere and a more muted positive trend in the Northern Hemisphere, implying a potential change in the stratospheric circulation over the observation period.

Clerbaux, C, Cunnold DM, Anderson J, Engel AEJ, Fraser PJ, Mahieu E, Manning A, Miller J, Montzka SA, Nassar R, Prinn R, Reimann S, Rinsland CP, Simmonds P, Verdonik D, Weiss R, Wuebbles D, Yokouchi K.  2007.  Long-lived compounds. Scientific assessment of ozone depletion, 2006 (World Meteorological Organization, Global Ozone Research and Monitoring Project, Report 50). :83., Geneva, Switzerland: World Meteorological Organization Abstract
Craig, H, Weiss RF.  1968.  Argon concentrations in the ocean: A discussion. Earth and Planetary Science Letters. 5:175-&.   10.1016/s0012-821x(68)80036-6   AbstractWebsite

Because of the importance of argon as a conservative gas tracer in the oceans and as the only rare gas measured both by mass spectrometry and gas chromatography, critical evaluation and comparison of data measured by the two methods is essential. The use of isotope dilution methods in the mass-spectrometric analyses has produced essentially identical precision and accuracy as have been obtained by gas chromatography and the latest Pacific data are in good agreement, especially below 1000 meters depth. The recent data of Bieri et al. provide significant new evidence for the processes we have proposed as responsible for extrema in the saturation anomalies. The data are also consistent with calculations of diffusional losses of the rare gases in northward flowing bottom water in the Pacific.

Craig, H, Weiss RF.  1971.  Dissolved gas saturation anomalies and excess helium in the ocean. Earth and Planetary Science Letters. 10:289-296.   10.1016/0012-821x(71)90033-1   AbstractWebsite

New solubility measurements have been made for helium and neon in seawater; the results (published elsewhere) show that neon is actually supersaturated in the ocean, rather than generally undersaturated as indicated by previous data. The pattern of He-Ne-Ar saturation anomalies, based on the new solubility data, shows the presence of an injected “atmospheric component” in Atlantic surface and deep waters and in Pacific deep waters, ranging from 0.5 to 1 ml of air (STP)/kg seawater. Nitrogen-argon relationships in the deep Pacific are also consistent with this effect. In addition to T and P, a third parameter is thus required for the study of saturation anomalies. The magnitude of the injected air fraction accounts for all of the “excess He” in Atlantic Deep Water and about 60% of the excess in the Pacific. The non-atmospheric excess He in the Pacific corresponds to an anomaly of 3%, presumably radiogenic and primordial helium.

Craig, H, Weiss RF, Clarke WB.  1967.  Dissolved gases in Equatorial and South Pacific Ocean. Journal of Geophysical Research. 72:6165-&.   10.1029/JZ072i024p06165   AbstractWebsite

The nitrogen, oxygen, and argon in Pacific samples from two expeditions have been measured by gas chromatography, and the neon and helium by mass spectrometry. Nitrogen is systematically about 2% supersaturated and argon about 1.5% undersaturated, relative to the solubility data of Douglas for a moisture saturated atmosphere at 1013-mb total pressure. N2/Ar ratios are in precise agreement with the solubility ratios of Benson and Parker. The range and covariance of N2 and Ar variations are consistent with atmospheric pressure variations over the sea. Oxygen values are systematically higher than the ‘classical’ Winkler values by 3.7%. No evidence was found for the large supersaturation of argon reported by Bieri, Koide, and Goldberg in 1966 and the Ar-T-S relationships are inconsistent with their vertical mixing model. Small increases in a saturation anomaly are core properties of water types formed by subsurface mixing and are associated with T-S slope changes; these effects were found in Antarctic and North Pacific Intermediate water. An upper limit of 8.7% excess helium was found at a depth of 1000 meters at 33°S latitude.

Craig, H, Weiss RF.  1970.  The GEOSECS 1969 Intercalibration Station: Introduction, hydrographic features, and total CO2-O2 relationships. Journal of Geophysical Research. 75:7641-7647., Washington, DC, United States (USA): American Geophysical Union, Washington, DC   10.1029/JC075i036p07641   AbstractWebsite

The temperature, salinity, dissolved oxygen, and shipboard chromatograph ΣCO2 data from the 1969 Geosecs station are summarized. Vertical diffusion-advection model parameters calculated from the ΣCO2 and O2 data, by using the mixing parameters obtained from temperature and salinity, give approximately equal mean CO2 production and O2 consumption rates over the deep-water column.

Cunnold, DM, Steele LP, Fraser PJ, Simmonds PG, Prinn RG, Weiss RF, Porter LW, O'Doherty S, Langenfelds RL, Krummel PB, Wang HJ, Emmons L, Tie XX, Dlugokencky EJ.  2002.  In situ measurements of atmospheric methane at GAGE/AGAGE sites during 1985-2000 and resulting source inferences. Journal of Geophysical Research-Atmospheres. 107   10.1029/2001jd001226   AbstractWebsite

[1] Continuous measurements of methane since 1986 at the Global Atmospherics Gases Experiment/Advanced Global Atmospherics Gases Experiment (GAGE/AGAGE) surface sites are described. The precisions range from approximately 10 ppb at Mace Head, Ireland, during GAGE to better than 2 ppb at Cape Grim, Tasmania, during AGAGE (i.e., since 1993). The measurements exhibit good agreement with coincident measurements of air samples from the same locations analyzed by Climate Monitoring and Diagnostics Laboratory (CMDL) except for differences of approximately 5 ppb before 1989 (GAGE lower) and about 4 ppb from 1991 to 1995 (GAGE higher). These results are obtained before applying a factor of 1.0119 to the GAGE/AGAGE values to place them on the Tohoku University scale. The measurements combined with a 12-box atmospheric model and an assumed atmospheric lifetime of 9.1 years indicates net annual emissions (emissions minus soil sinks) of 545 Tg CH4 with a variability of only +/-20 Tg from 1985 to 1997 but an increase in the emissions in 1998 of 37 +/- 10 Tg. The effect of OH changes inferred by Prinn et al. [2001] is to increase the estimated methane emissions by approximately 20 Tg in the mid-1980s and to reduce them by 20 Tg in 1997 and by more thereafter. Using a two-dimensional (2-D), 12-box model with transport constrained by the GAGE/AGAGE chlorofluorocarbon measurements, we calculate that the proportion of the emissions coming from the Northern Hemisphere is between 73 and 81%, depending on the OH distribution used. However, this result includes an adjustment of 5% derived from a simulation of the 2-D estimation procedure using the 3-D MOZART model. This adjustment is needed because of the very different spatial emission distributions of the chlorofluorocarbons and methane which makes chlorofluorocarbons derived transport rates inaccurate for the 2-D simulation of methane. The 2-D model combined with the annual cycle in OH from Spivakovsky et al. [2000] provide an acceptable fit to the observed 12-month cycles in methane. The trend in the amplitude of the annual cycle of methane at Cape Grim is used to infer a trend in OH in 30degrees-90degreesS of 0 +/- 5% per decade from 1985 to 2000, in qualitative agreement with Prinn et al. [2001] for the Southern Hemisphere.

Cunnold, DM, Weiss RF, Prinn RG, Hartley D, Simmonds PG, Fraser PJ, Miller B, Alyea FN, Porter L.  1997.  GAGE/AGAGE measurements indicating reductions in global emissions of CCl3F and CCl2F2 in 1992-1994. Journal of Geophysical Research-Atmospheres. 102:1259-1269.   10.1029/96jd02973   AbstractWebsite

Global Atmospheric Gases Experiment/Advanced GAGE (GAGE/AGAGE) observations of CCl3F indicate that global concentrations of this compound reached a maximum in 1993 and decayed slightly in 1994; CCl2F2 concentrations increased approximately 7 ppt in both 1993 and 1994. The observations suggest that world emissions in these two years were smaller than industry production figures would suggest and have decreased faster than expected under the Montreal Protocol and its amendments. An analysis of regional pollution events at the Mace Head site suggest that industry may be underestimating the decline of emissions in Europe. It is argued, however, that the decline in European emissions is not biasing the background Mace Head measurements (or the GAGE global averages). Combining the chlorofluorocarbon measurements, including CCl2FCClF2, with GAGE/AGAGE measured global decreases in CH3CCl3 and CCl4 after 1992 and with Cape Grim archived air measurements of CHClF2, the measurements suggest that anthropogenic atmospheric chlorine loading from these six gases maximized in 1992 at 2.95 +/- 0.04 ppb and that it had decreased by 0.02 +/- 0.01 ppb by the beginning of 1995.

Cunnold, DM, Fraser PJ, Weiss RF, Prinn RG, Simmonds PG, Miller BR, Alyea FN, Crawford AJ.  1994.  Global trends and annual releases of CCl3F and CCl2F2 estimated from ALE/GAGE and other measurements from July 1978 to June 1991. Journal of Geophysical Research-Atmospheres. 99:1107-1126.   10.1029/93jd02715   AbstractWebsite

Thirteen years of Atmospheric Lifetime Experiment/Global Atmospheric Gases Experiment CCl3F and CCl2F2 measurements at five remote, surface, globally distributed sites are analyzed. Comparisons are made against shipboard measurements by the Scripps Institution of Oceanography group and archived air samples collected at Cape Grim, Tasmania, since 1978. CCl3F in the lower troposphere was increasing at an average rate of 9.2 ppt/yr over the period July 1978 to June 1988. CCl2F2 was increasing at an average 17.3 ppt/yr in the lower troposphere over the same period. However, between July 1988 and June 1991 the increases of CCl3F and CCl2F2 in this region have averaged just 7.0 ppt/yr and 15.7 ppt/yr, respectively. The rate of increase has been decreasing 2.4 ppt/yr and 2.9 ppt/yr(2) over this 3-year period. Based on a recent scenario of the global releases of these compounds and using the new calibration scale SIO 1993, the equilibrium lifetimes are estimated to be 44(-10)(+17) and 180(_81)(+820) years for CCl3F and CCl2F2, respectively. Using these lifetime estimates and a two-dimensional model, it is estimated that global releases of these two chlorofluorocarbons in 1990 were 249+/-28 x 10(6) kg for CCl3F and 366+/-30 x 10(6) kg for CCl2F2. It is also estimated that combined releases of these chlorofluorocarbons in 1990 were 21+/-5% less than those in 1986.

Dalsoren, SB, Myhre CL, Myhre G, Gomez-Pelaez AJ, Sovde OA, Isaksen ISA, Weiss RF, Harth CM.  2016.  Atmospheric methane evolution the last 40 years. Atmospheric Chemistry and Physics. 16:3099-3126.   10.5194/acp-16-3099-2016   AbstractWebsite

Observations at surface sites show an increase in global mean surface methane (CH4) of about 180 parts per billion (ppb) (above 10 %) over the period 1984-2012. Over this period there are large fluctuations in the annual growth rate. In this work, we investigate the atmospheric CH4 evolution over the period 1970-2012 with the Oslo CTM3 global chemical transport model (CTM) in a bottom-up approach. We thoroughly assess data from surface measurement sites in international networks and select a subset suited for comparisons with the output from the CTM. We compare model results and observations to understand causes for both long-term trends and short-term variations. Employing Oslo CTM3 we are able to reproduce the seasonal and year-to-year variations and shifts between years with consecutive growth and stagnation, both at global and regional scales. The overall CH4 trend over the period is reproduced, but for some periods the model fails to reproduce the strength of the growth. The model overestimates the observed growth after 2006 in all regions. This seems to be explained by an overly strong increase in anthropogenic emissions in Asia, having global impact. Our findings confirm other studies questioning the timing or strength of the emission changes in Asia in the EDGAR v4.2 emission inventory over recent decades. The evolution of CH4 is not only controlled by changes in sources, but also by changes in the chemical loss in the atmosphere and soil uptake. The atmospheric CH4 lifetime is an indicator of the CH4 loss. In our simulations, the atmospheric CH4 lifetime decreases by more than 8 % from 1970 to 2012, a significant reduction of the residence time of this important greenhouse gas. Changes in CO and NOx emissions, specific humidity, and ozone column drive most of this, and we provide simple prognostic equations for the relations between those and the CH4 lifetime. The reduced lifetime results in substantial growth in the chemical CH4 loss (relative to its burden) and dampens the CH4 growth.

Deeds, DA, Vollmer MK, Kulongoski JT, Miller BR, Muhle J, Harth CM, Izbicki JA, Hilton DR, Weiss RF.  2008.  Evidence for crustal degassing of CF4 and SF6 in Mojave Desert groundwaters. Geochimica Et Cosmochimica Acta. 72:999-1013.   10.1016/j.gca.2007.11.027   AbstractWebsite

Dissolved tetrafluoromethane (CF(4)) and sulfur hexafluoride (SF(6)) concentrations were measured in groundwater samples from the Eastern Morongo Basin (EMB) and Mojave River Basin (MRB) located in the southern Mojave Desert, California. Both CF(4) and SF(6) are supersaturated with respect to equilibrium with the preindustrial atmosphere at the recharge temperatures and elevations of the Mojave Desert. These observations provide the first in situ evidence for a flux of CF(4) from the lithosphere. A gradual basin-wide enhancement in dissolved CF(4) and SF(6) concentrations with groundwater age is consistent with release of these gases during weathering of the surrounding granitic alluvium. Dissolved CF(4) and SF(6) concentrations in these groundwaters also contain a deeper crustal component associated with a lithospheric flux entering the EMB and MRB through the underlying basement. The crustal flux of CF(4), but not of SF(6), is enhanced in the vicinity of local active fault systems due to release of crustal fluids during episodic fracture events driven by local tectonic activity. When fluxes of CF(4) and SF(6) into Mojave Desert groundwaters are extrapolated to the global scale they are consistent, within large uncertainties, with the fluxes required to sustain the preindustrial atmospheric abundances of CF(4) and SF(6). (c) 2007 Elsevier Ltd. All rights reserved.