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2002
Klatt, O, Roether W, Hoppema M, Bulsiewicz K, Fleischmann U, Rodehacke C, Fahrbach E, Weiss RF, Bullister JL.  2002.  Repeated CFC sections at the Greenwich Meridian in the Weddell Sea. Journal of Geophysical Research-Oceans. 107   10.1029/2000jc000731   AbstractWebsite

[1] Repeated observations of the tracer chlorofluorocarbon-11 (CFC-11) for a section along the Greenwich Meridian from Antarctica (70degreesS) to about 50 S are presented for the period 1984-1998. The CFC sections display a highly persistent pattern. A middepth CFC minimum in the central Weddell Sea is bounded laterally by elevated levels of dissolved CFCs at the southern margin of the Weddell Basin and by a column of elevated CFC concentrations around 55degreesS near to the northern margin. Part of the latter column covers waters of the Antarctic Circumpolar Current, which indicates that a moderate portion of these waters was ventilated in the Weddell Sea. Deep CFC maxima adjoining the southern and northern margins of the Weddell Basin indicate advective cores of recently ventilated waters. The southern core supports previous notions of deep water import into the Weddell Sea from the east. For all deep and bottom waters, the portions ventilated on the CFC timescale (similar to50 years) are small. Effective initial CFC saturations for these portions are estimated to be between 60 and 70%, using in part new data from off the Filchner-Ronne Ice Shelf. For various CFC features along the section (mostly advective cores), ventilated fractions and mean ages of these fractions were obtained (with error limits). The procedure was to fit an age distribution of a prescribed form to CFC-11 time series for these features, constructed from the various realizations of the CFC section. The ages are between 3 and 19 years, and the ventilated fractions range between 6 and 23%, indicating a rather limited ventilation of the interior Weddell Sea subsurface layer waters on the CFC timescale. It is shown that the concurrent CFC-12 data provide little additional information. The work demonstrates a high information content of repeated tracer observations and encourages similar approaches also in other ocean regions.

Weiss, RF.  2002.  Nitrous Oxide. The encyclopedia of global change : environmental change and human society. 2( Goudie AS, Cuff DJ, Eds.).:140-141., Oxford: Oxford University Press Abstract
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Vollmer, MK, Weiss RF, Bootsma HA.  2002.  Ventilation of Lake Malawi/Nyasa. The East African great lakes limnology, palaeolimnology, and biodiversity. ( Odada EO, Olago DO, Eds.).:209-233., Dordrecht; Boston, MA: Kluwer Academic Publishers Abstract
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2001
O'Doherty, S, Simmonds PG, Cunnold DM, Wang HJ, Sturrock GA, Fraser PJ, Ryall D, Derwent RG, Weiss RF, Salameh P, Miller BR, Prinn RG.  2001.  In situ chloroform measurements at Advanced Global Atmospheric Gases Experiment atmospheric research stations from 1994 to 1998. Journal of Geophysical Research-Atmospheres. 106:20429-20444.   10.1029/2000jd900792   AbstractWebsite

Measurements of atmospheric chloroform (CHCl3) by in situ gas chromatography using electron capture detection are reported from the Advanced Global Atmospheric Gases Experiment (AGAGE) network of atmospheric research stations. They are some of the most comprehensive in situ, high-frequency measurements to be reported for CHCl3 and provide valuable information not only on clean "baseline" mixing ratios but also on local and regional sources. Emissions from these sources cause substantial periodic increases in CHCl3 concentrations above their baseline levels, which can be used to identify source strengths. This is particularly the case for measurements made at Mace Head, Ireland. Furthermore, these local sources of CHCl3 emissions are significant in relation to current estimates of global emissions and illustrate that the understanding of competing sources and sinks of CHCl3 is still fragmentary. These observations also show that CHCl3 has a very pronounced seasonal cycle with a summer minimum and winter maximum presumably resulting from enhanced destruction by OH in the summer. The amplitude of the cycle is dependent on sampling location. Over the 57 months of in situ measurements a global average baseline concentration of 8.9 +/-0.1 ppt was determined with no appreciable trend in the baseline detected.

Rhew, RC, Miller BR, Vollmer MK, Weiss RF.  2001.  Shrubland fluxes of methyl bromide and methyl chloride. Journal of Geophysical Research-Atmospheres. 106:20875-20882.   10.1029/2001jd000413   AbstractWebsite

Flux measurements in coastal sage scrub, chamise chaparral, and creosote bush scrub environments show that methyl bromide (CH(3)Br) and methyl chloride (CH(3)Cl), compounds that are involved in stratospheric ozone depletion, are both produced and consumed by southern California shrubland ecosystems. CH(3)Br and CH(3)Cl are produced in association with a variety of plants and are consumed by the soils, although there is a large variability in the fluxes, depending on predominant vegetation and environmental conditions. At sites with a net uptake of both compounds the fluxes of CH(3)Cl and CH(3)Br show a strong correlation, with a molar ratio of roughly 40:1, pointing to a similar mechanism of consumption. In contrast, the net production rates of these compounds show no apparent correlation with each other. The average observed net CH(3)Br uptake rates are an order of magnitude smaller than the previously reported average soil consumption rates assigned to shrublands. Extrapolations from our field measurements suggest that shrublands globally have a maximum net consumption of <1 Gg yr(-1) for CH(3)Br and < 20 Gg yr(-1) for CH(3)Cl and may, in fact, be net sources for these compounds. Consequently, the measured net fluxes from shrubland ecosystems can account for part of the present imbalance in the CH(3)Br budget by adding a new source term and potentially reducing the soil sink term. These results also suggest that while shrubland soil consumption of CH(3)Cl may be small, soils in general may be a globally significant sink for CH(3)Cl.

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.

Prinn, RG, Huang J, Weiss RF, Cunnold DM, Fraser PJ, Simmonds PG, McCulloch A, Harth C, Salameh P, O'Doherty S, Wang RHJ, Porter L, Miller BR.  2001.  Evidence for substantial variations of atmospheric hydroxyl radicals in the past two decades. Science. 292:1882-1888.   10.1126/science.1058673   AbstractWebsite

The hydroxyl radical (OH) is the dominant oxidizing chemical in the atmosphere. It destroys most air pollutants and many gases involved in ozone depletion and the greenhouse effect. Global measurements of 1,1,1-trichloroethane (CH3CCl3, methyl chloroform) provide an accurate method for determining the global and hemispheric behavior of OH. Measurements show that CH3CCl3 Levels rose steadily from 1978 to reach a maximum in 1992 and then decreased rapidly to levels in 2000 that were Lower than the levels when measurements began in 1978. Analysis of these observations shows that global OH Levels were growing between 1978 and 1988, but the growth rate was decreasing at a rate of 0.23 +/- 0.18% year(-2), so that OH Levels began declining after 1988. Overall, the global average OH trend between 1978 and 2000 was -0.64 +/- 0.60% year(-1). These variations imply important and unexpected gaps in current understanding of the capability of the atmosphere to cleanse itself.

2000
Walker, SJ, Weiss RF, Salameh PK.  2000.  Reconstructed histories of the annual mean atmospheric mole fractions for the halocarbons CFC-11, CFC-12, CFC-113, and carbon tetrachloride. Journal of Geophysical Research-Oceans. 105:14285-14296.   10.1029/1999jc900273   AbstractWebsite

Annual mean mixing ratios for the halocarbons CFC-11 (CCl3F), CFC-12 (CCl2F2), CFC-113 (CClF2CCl2F), and carbon tetrachloride (CCl4) have been determined from their first year of industrial production through 1998. From the late 1970s (in the case of CFC-11 and CFC-12) or early 1980s tin the case of CFC-113 and carbon tetrachloride) the reported mixing ratios have been determined from experimental observations made by the Atmospheric Lifetime Experiment/Global Atmospheric Gases Experiment/Advanced Global Atmospheric Gases Experiment program. For years prior to these times we have used estimates of industrial emissions and atmospheric lifetimes to calculate historic concentrations. The likely error bounds of the annual mean values are also reported here. Errors in the annual mean mixing ratio may primarily be a result of incorrect industrial emissions data, an incorrect atmospheric lifetime,or uncertainty in the ALE/GAGE/AGAGE observations. Each of these possible sources of error has been considered separately. These results show that atmospheric concentrations for each of these compounds have experienced a rapid rise in the early part of their production. Tt is only within the past decade that rise rates have decreased sharply and (except in the case of CFC-12) in the past few years that atmospheric concentrations have begun to decrease. The uncertainties in the reconstructed histories are a similar proportion for each of the chlorofluorocarbons (<4% for most of the history). However, uncertainty in the history of carbon tetrachloride is much greater (up to 12%, and this is mainly the result of poor knowledge of CCl4 emissions.

Prinn, RG, Weiss RF, Fraser PJ, Simmonds PG, Cunnold DM, Alyea FN, O'Doherty S, Salameh P, Miller BR, Huang J, Wang RHJ, Hartley DE, Harth C, Steele LP, Sturrock G, Midgley PM, McCulloch A.  2000.  A history of chemically and radiatively important gases in air deduced from ALE/GAGE/AGAGE. Journal of Geophysical Research-Atmospheres. 105:17751-17792.   10.1029/2000jd900141   AbstractWebsite

We describe in detail the instrumentation and calibrations used in the Atmospheric Lifetime Experiment (ALE), the Global Atmospheric Cases Experiment (GAGE), and the Advanced Global Atmospheric Gases Experiment (AGAGE) and present a history of the majority of the anthropogenic ozone-depleting and climate-forcing gases in air based on these experiments. Beginning in 1978, these three successive automated high-frequency in situ experiments have documented the long-term behavior of the measured concentrations of these gases over the past 20 years, and show both the evolution of latitudinal gradients and the high-frequency variability due to sources and circulation. We provide estimates of the long-term trends in total chlorine contained in long-lived halocarbons involved in ozone depletion. We summarize interpretations of these measurements using inverse methods to determine trace gas lifetimes and emissions. Finally, we provide a combined observational and modeled reconstruction of the evolution of chlorocarbons by latitude in the atmosphere over the past 60 years which can be used as boundary conditions for interpreting trapped air in glaciers and oceanic measurements of chlorocarbon tracers of the deep oceanic circulation. Some specific conclusions are as follows: (1) International compliance with the Montreal Protocol is so far resulting in chlorofluorocarbon and chlorocarbon mole fractions comparable to target levels; (2) mole fractions of total chlorine contained in long-lived halocarbons (CCl2F2, CCl3F, CH3CCl3, CCl4, CHClF2, CCl2FCClF2, CH3Cl, CH2Cl2, CHCl3, CCl2=CCl2) in the lower troposphere reached maximum values of about 3.6 ppb in 1993 and are beginning to slowly decrease in the global lower atmosphere; (3) the chlorofluorocarbons have atmospheric lifetimes consistent with destruction in the stratosphere being their principal removal mechanism; (4) multiannual variations in chlorofluorocarbon and chlorocarbon emissions deduced from ALE/GAGE/AGAGE data are consistent approximately with variations estimated independently from industrial production and sales data where available (CCl2F2 (CFC-12) and CCl2FCClF2 (CFC-113) show the greatest discrepancies); (5) the mole fractions of the hydrochlorofluorocarbons and hydrofluorocarbons, which are replacing the regulated halocarbons, are rising very rapidly in the atmosphere, but with the exception of the much longer manufactured CHClF2 (HCFC-22), they are not yet at levels sufficient to contribute significantly to atmospheric chlorine loading. These replacement species could in the future provide independent estimates of the global weighted-average OH concentration provided their industrial emissions are accurately documented; (6) in the future, analysis of pollution events measured using high-frequency in situ measurements of chlorofluorocarbons and their replacements may enable emission estimates at the regional level, which, together with industrial end-use data, are of sufficient accuracy to he capable of identifying regional noncompliance with the Montreal Protocol.

Rhew, RC, Miller BR, Weiss RF.  2000.  Natural methyl bromide and methyl chloride emissions from coastal salt marshes. Nature. 403:292-295.   10.1038/35002043   AbstractWebsite

Atmospheric methyl bromide (CH3Br) and methyl chloride (CH3Cl), compounds that are involved in stratospheric ozone depletion, originate from both natural and anthropogenic sources. Current estimates of CH3Br and CH3Cl emissions from oceanic sources, terrestrial plants and fungi, biomass burning and anthropogenic inputs do not balance their losses owing to oxidation by hydroxyl radicals, oceanic degradation, and consumption in soils, suggesting that additional natural terrestrial sources may be important(1). Here we show that CH3Br and CH3Cl are released to the atmosphere from all vegetation zones of two coastal salt marshes. We see very large fluxes of CH3Br and CH3Cl per unit area: up to 42 and 570 mu mol m(-2) d(-1), respectively. The fluxes show large diurnal, seasonal and spatial variabilities, but there is a strong correlation between the fluxes of CH3Br and those of CH3Cl, with an average molar flux ratio of roughly 1:20. If our measurements are typical of salt marshes globally, they suggest that such ecosystems, even though they constitute less than 0.1% of the global surface area(2), may produce roughly 10% of the total fluxes of atmospheric CH3Br and CH3Cl.

Min, DH, Bullister JL, Weiss RF.  2000.  Constant ventilation age of thermocline water in the eastern subtropical North Pacific Ocean from chlorofluorocarbon measurements over a 12-year period. Geophysical Research Letters. 27:3909-3912.   10.1029/1999gl011318   AbstractWebsite

Northeastern Pacific chlorofluorocarbon (CFC) data collected between 1982 and 1994 near Geochemical Ocean Sections Study (GEOSECS) station 1 (28.5 degreesN, 122.5 degreesW) record decadal timescale ventilation processes of the subtropical thermocline in this region. The CFC-12 concentration age field versus potential density has been remarkably constant over the 12-year period, although CFC concentrations in the upper kilometer of the water column have increased with time. Results from a simple one-dimensional advection-diffusion model are consistent with an advection velocity of ca. 0.8-0.9 cm s(-1) from the source area. The influence of the 1982-83 El Nino is noticeable in the 1983 observations. While the main stream of subarctic source water al,pears to spread southward at a constant rate, during El Nino years the influence of comparatively CFC-free tropical thermocline waters is enhanced in this region, leading to reduced vertical inventories of CFCs, but without changing the apparent CFC ages as functions of potential density. Apparent oxygen utilization rates decrease with increasing CFC age, and also appear not to have changed significantly ol er the 12-year measurement period.

1999
Lefevre, N, Watson AJ, Cooper DJ, Weiss RF, Takahashi T, Sutherland SC.  1999.  Assessing the seasonality of the oceanic sink for CO2 in the northern hemisphere. Global Biogeochemical Cycles. 13:273-286.   10.1029/1999gb900001   AbstractWebsite

Seasonal CO2 fluxes are estimated from quarterly maps of Delta pCO(2) (difference between the oceanic and atmospheric partial pressure of CO2) and associated error maps. Delta pCO(2) maps were interpolated from pCO(2) measurements in the North Atlantic and the North Pacific Oceans using an objective mapping technique. Negative values correspond to an uptake of CO2 by the ocean. The CO2 flux for the North Atlantic Ocean, between 10 degrees N and 80 degrees N, ranges from -0.69 GtC/yr, for the first quarter (January-March), to -0.19 GtC/yr for the third quarter (July-September) using the gas exchange coefficient of Tans et al. [1990], satellite wind speeds, and a correction for the skin effect. On annual average, the North Atlantic ocean (north of 10 degrees N) is a sink of CO2 ranging from -0.23 +/- 0.08 GtC/yr (gas exchange coefficient of Liss and Merlivat [1986] with Esbensen and Kushnir [1981] wind field) to -0.48 +/- 0.17 GtC/yr (gas exchange coefficient of Tans et al. with satellite wind field). The CO2 flux for the North Pacific, between 15 degrees N and 65 degrees N, ranges from -0.66 GtC/yr from April to June to zero from July to September. For the Atlantic, the errors are generally small, that is, less than 0.19 GtC/yr, but for the Pacific considerably larger uncertainties are generated due to the less extensive data coverage. The northern hemisphere ocean (north of 10 degrees N) is a net sink of CO2 to the atmosphere which is stronger in spring (April-June), due to the biological activity, with an estimate of -1.23 +/- 0.40 GtC/yr averaged over this period. The annual mean northern hemisphere ocean flux is -0.86 +/- 0.61 GtC/yr.

Prinn, RG, Zander R, Cunnold DM, Elkins JW, Engel A, Fraser PJ, Gunson MR, Ko MKW, Mahieu E, Midgley PM, Russel III JM, Volk CM, Weiss RF.  1999.  Long-lived ozone-related compounds. Scientific assessment of ozone depletion, 1998 (World Meteorological Organization, Global Ozone Research and Monitoring Project Report 44). :54., Washington, DC: National Oceanic and Atmospheric Administration Abstract
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Kurylo, MJ, Rodriguez JM, Andreae MO, Atlas EL, Blake DR, Butler JH, Lal S, Lary DJ, Midgley PM, Montzka SA, Novelli PC, Reeves CE, Simmonds PG, Steele LP, Sturges WT, Weiss RF, Yokouchi Y.  1999.  Short-lived ozone-related compounds. Scientific assessment of ozone depletion, 1998 (World Meteorological Organization, Global Ozone Research and Monitoring Project Report 44). :56., Washington, DC: National Oceanic and Atmospheric Administration Abstract
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1998
Miller, BR, Huang J, Weiss RF, Prinn RG, Fraser PJ.  1998.  Atmospheric trend and lifetime of chlorodifluoromethane (HCFC-22) and the global tropospheric OH concentration. Journal of Geophysical Research-Atmospheres. 103:13237-13248.   10.1029/98jd00771   AbstractWebsite

Concentrations of CHClF2 (HCFC-22) in clean background air collected at Cape Grim, Tasmania, over the period 1978-1996, and at La Jolla, California, over the period 1992-1997, have been measured by oxygen-doped electron capture detection gas chromatography. The mid-1996 dry-air mole fractions and trends were 116.7 parts per trillion (ppt) and 6.0 ppt yr(-1) in Cape Grim and 132.4 ppt and 5.5 ppt yr(-1) in California: respectively. These observations, together with estimates of industrial emissions, have been fitted to a two-dimensional global atmospheric model by an optimal estimation inversion technique to yield estimated tropospheric and total atmospheric Lifetimes for chemical destruction of CHClF2 of 9.1(-2.8)(+4.4) years and 10.0(-3.0)(+4.4) years, respectively. These lifetimes Correspond to a temperature- and density-weighed global tropospheric OH abundance of 11.0(-3.6)(+5.0) x 10(5) radical cm(-3), which is in statistical agreement with our recent more accurate estimate of OH abundance based on measurements of CH3CCl3. Our analysis suggests that, compared to current industrial estimates, southern hemisphere emissions are higher, global emissions are larger in earlier years and smaller in later years, and, finally, production by nonreporting companies is less.

Simmonds, PG, Cunnold DM, Weiss RF, Prinn RG, Fraser PJ, McCulloch A, Alyea FN, O'Doherty S.  1998.  Global trends and emission estimates of CCl4 from in situ background observations from July 1978 to June 1996. Journal of Geophysical Research-Atmospheres. 103:16017-16027.   10.1029/98jd01022   AbstractWebsite

Atmospheric Lifetime Experiment/Global Atmospheric Gases Experiment/Advanced Global Atmospheric Gases Experiment (ALE/GAGE/AGAGE) measurements of CCl4 at five remote surface locations from 1978 to 1996 are reported. The Scripps Institution of Oceanography (SIO) 1993 absolute calibration scale is used, reducing the concentrations by a factor of 0.77 compared to previous ALE/GAGE reports. Atmospheric concentrations of CCl4 reached a peak in 1989-1990 of 104.4 +/-. 3.1 parts per trillion (ppt) and have since been decreasing 0.7 +/-. 0.1 ppt yr(-1). Assuming an atmospheric lifetime of 42 +/- 12 years, the emissions averaged 94(+22)(-11) x 10(6) kg from 1979 to 1988 and 49(+26)(-13) x 10(6) kg from 1991 to 1995. The reduction in the emissions in 1989-1990 coincided with a substantial decrease in the global production of the chlorofluorocarbons (CFCs). The total emission of CCl4 from countries that report annual production is estimated to have declined from 11% in 1972 to 4% in 1995 of the CCl4 needed to produce the CFC amounts reported. This implies that nonreporting countries released substantial amounts of CCl4 into the atmosphere in the 1980s and that their releases have exceeded those from the reporting countries since 1991.

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.

Murphy, PP, Harrison DE, Feely RA, Takahashi T, Weiss RF, Gammon RH.  1998.  Variability of Δ pCO2 in the subarctic North Pacific. A comparison of results from four expeditions. Tellus Series B-Chemical and Physical Meteorology. 50:185-204.   10.1034/j.1600-0889.1998.t01-1-00006.x   AbstractWebsite

Time-space variability of surface seawater pCO(2) is examined over the region (150 degrees W-180 degrees, 46 degrees N-50 degrees N) of the subarctic North Pacific where large meridional gradients of temperature and nutrient concentrations exist. The data were collected during four trans-Pacific expeditions in three different years (1985-1987), but within the same 30-day period of the year (August-September). Systematic measurement differences between the four data sets are estimated as <10 mu atm. The inter-expedition comparison suggests that surface seawater pCO(2) in the study area is quite variable, with mean differences of up to 25 mu atm and local differences up to 60 mu atm. Spatial and interannual variability of surface seawater pCO(2) were found to contribute significant uncertainty to estimates of the mean Delta pCO(2) for the study area. Fluxes were calculated using Delta pCO(2) values from the four expeditions combined with gas exchange coefficients calculated from four different wind fields giving a range of -0.94 to +4.1 mmol CO2 m(-2) d(-1). The range of fluxes from the study area is scaled to a larger area of the North Pacific to address how this variability can translate into uncertainties in basin-wide carbon air-sea exchange fluxes.

Jacobs, SS, Weiss RF.  1998.  Ocean, ice, and atmosphere : interactions at the Antarctic continental margin. Antarctic Research Series. :380., Washington, D.C.: American Geophysical Union Abstract
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1997
Severinghaus, JP, Keeling RF, Miller BR, Weiss RF, Deck B, Broecker WS.  1997.  Feasibility of using sand dunes as archives of old air. Journal of Geophysical Research-Atmospheres. 102:16783-16792.   10.1029/97jd00525   AbstractWebsite

Large unaltered samples of the atmosphere covering the past century would complement the history of atmospheric gases obtained from bubbles in ice cores, enabling measurement of geochemically important species such as O-2, (CH4)-C-14, and (CO)-C-14. Sand dunes are a porous media with interstitial air in diffusive contact with the atmosphere, somewhat analogous to the unconsolidated layer of firn atop glaciers. Recent studies have demonstrated the value of firn as an archive of old air [Battle et al., 1996; Bender et al., 1994a]. Unlike firn, sand dunes are incompressible and so remain permeable to greater depths and may extend the firn record into the past century. To evaluate the feasibility of using sand dunes as archives of old air, we drilled 60 m deep test holes in the Algodones Dunes, Imperial Valley, California. The main objective was to see if the air in a sand dune is as old as predicted by a diffusion model, or if the dune is rapidly flushed by advective pumping during windstorms and barometric pressure changes. We dated the air with chlorofluorocarbons and krypton-85, anthropogenic tracers whose atmospheric concentrations are known and have been increasing rapidly in the past half century. These tracer data match the pure diffusion model well, showing that advection in this dune is negligible compared to diffusion as a transport mechanism and that the mean age of the air at 61 m depth is similar to 10 years. Dunes therefore do contain old air. However, dunes appear to suffer from two serious drawbacks as archives. Microbial metabolism is evident in elevated CO2 and N2O and depressed CH4 and O-2 concentrations in this dune, corrupting the signals of interest in this and probably most dunes. Second, isotopic analyses of N-2 and O-2 from the dune show that fractionation of the gases occurs due to diffusion of water vapor, complicating the interpretation of the O-2 signal beyond the point of viability for an air archive. Sand dunes may be useful for relatively inert gases with large atmospheric concentration changes such as chlorofluorocarbons.

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.

Takahashi, T, Feely RA, Weiss RF, Wanninkhof RH, Chipman DW, Sutherland SC, Takahashi TT.  1997.  Global air-sea flux of CO2: An estimate based on measurements of sea-air pCO2 difference. Proceedings of the National Academy of Sciences of the United States of America. 94:8292-8299.   10.1073/pnas.94.16.8292   AbstractWebsite

Approximately 250,000 measurements made for the pCO(2) difference between surface water and the marine atmosphere, Delta pCO(2), have been assembled for the global oceans. Observations made in the equatorial Pacific during El Nine events have been excluded from the data set, These observations are mapped on the global 4 degrees x 5 degrees grid for a single virtual calendar year (chosen arbitrarily to be 1990) representing a non-El Nino year. Monthly global distributions of Delta pCO(2) have been constructed using an interpolation method based on a lateral advection-diffusion transport equation. The net flux of CO2 across the sea surface has been computed using Delta pCO(2) distributions and CO2 gas transfer coefficients across sea surface. The annual net uptake flux of CO2 by the global oceans thus estimated ranges from 0.60 to 1.34 Gt-C.yr(-1) depending on different formulations used for wind speed dependence on the gas transfer coefficient, These estimates;Ire subject to an error of up to 75% resulting from the numerical interpolation method used to estimate the distribution of Delta pCO(2) over the global oceans, Temperate and polar oceans of the both hemispheres are the major sinks for atmospheric CO2, whereas the equatorial oceans are the major sources for CO2. The Atlantic Ocean is the most important CO2 sink, providing about 60% of the global ocean uptake, while the Pacific Ocean is neutral because of its equatorial source flux being balanced by the sink flux of the temperate oceans, The Indian and Southern Oceans take up about 20% each.

1996
Warner, MJ, Bullister JL, Wisegarver DP, Gammon RH, Weiss RF.  1996.  Basin-wide distributions of chlorofluorocarbons CFC-11 and CFC-12 in the north Pacific: 1985-1989. Journal of Geophysical Research-Oceans. 101:20525-20542.   10.1029/96jc01849   AbstractWebsite

All of the dissolved chlorofluorocarbon measurements made between 1985 and 1989 along several long zonal and meridional hydrographic sections in the North Pacific are presented in this manuscript. Chlorofluorocarbon (CFC) concentrations are displayed as functions of depth and density along the sections. Over much of the region studied, dissolved CFCs are observed to have penetrated to densities greater than those that outcrop at the surface in the North Pacific (sigma(theta) > 26.8). Maxima in CFC concentration are associated with remnant winter mixed layers and with mode waters. When the observed CFC concentrations from these sections are normalized to a common date and mapped onto five density surfaces in the North Pacific, it becomes apparent that the Sea of Okhotsk is an important location for the ventilation of the intermediate waters of the North Pacific. The CFC observations are used together with hydrographic data to study the pathways and timescales of circulation and ventilation processes in the upper and intermediate waters of the North Pacific. Using models of the increases of these compounds as a function of time, CFC ''apparent ages'' are calculated on these isopycnal surfaces. The CFC apparent ages are used together with observed apparent oxygen utilization to estimate oxygen utilization rates along these sections.

Killworth, PD, Carmack EC, Weiss RF, Matear R.  1996.  Modeling deep-water renewal in Lake Baikal. Limnology and Oceanography. 41:1521-1538. AbstractWebsite

Temperature, dissolved oxygen, nutrients, and chlorofluorocarbon-12 data obtained from Lake Baikal are used to describe deep-water renewal in a deep, temperate-latitude lake. Observations are used to propose the physical mechanism governing convection and to formulate a model of deep ventilation. The key physical mechanism governing deep-water renewal is the so-called thermobaric instability. Because the temperature of maximum density decreases with depth, a lake can become conditionally unstable if the base of the cold mixed layer is displaced to a depth at which its temperature matches the local temperature of maximum density, thereby resulting in sinking plumes. An important consequence of this phenomenon is that deep temperate lakes such as Baikal do not completely mix twice yearly; instead, deep ventilation is episodic. A two-dimensional model of a wind- and buoyancy-driven lake shows many strong mixing events and a fairly realistic seasonal cycle, indicating that the hypothesis is physically realizable. A filling-box model is used to deduce the annually averaged fluxes necessary to produce a steady vertical distribution of tracers as observed. Good fits are obtained to oxygen and chlorofluorocarbon distributions by this model.

Fraser, P, Cunnold D, Alyea F, Weiss R, Prinn R, Simmonds P, Miller B, Langenfelds R.  1996.  Lifetime and emission estimates of 1,1,2-trichlorotrifluorethane (CFC-113) from daily global background observations June 1982 June 1994. Journal of Geophysical Research-Atmospheres. 101:12585-12599.   10.1029/96jd00574   AbstractWebsite

Observations every two hours of CCl2FCClF2 at Mace Head, Ireland (February 1987-June 1994); Cape Meares, Oregon (April 1984-June 1989); Ragged Point, Barbados (October 1985-June 1994); Cape Matatula, Samoa (October 1985-June 1989 and January 1992-June 1994); and Cape Grim, Tasmania (June 1982-June 1994) are reported, The observations from Cape Grim have been extended back to 1978 using archived air samples. The global atmospheric abundance of CCl2FCClF2 is indicated to have been growing exponentially between 1978 and 1987 with an e-folding time of approximately 7.6 years; it has been growing less rapidly since that time. On January 1, 1994, the mean inferred northern hemispheric mixing ratio in the lower troposphere was 84.4 +/- 0.4 ppt and the southern hemispheric value was 80.6 +/- 0.4 ppt; the global growth rate in 1991-1993 is estimated to have averaged approximately 3.1 +/- 0.1 ppt/year. The differences between the northern and southern hemispheric concentrations are calculated to be consistent with the almost entirely northern hemispheric release of this gas. The annual release estimates of CCl2FCClF2 by industry, which include estimates of eastern European emissions, fairly consistently exceed those deduced from the measurements by approximately 10% from 1980 to 1993. The uncertainties in each estimate is approximately 5%. This difference suggests that up to 10% of past production might not yet have been released. The measurements indicate that atmospheric releases of CCl2FCClF2 have been decreasing rapidly since 1989 and in 1993 amounted to 78 +/- 27 x 10(6) kg or 42 +/- 15% of the 1985-1987 emissions.