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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.

2001
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
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.

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.

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.

1997
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.

1995
Prinn, RG, Weiss RF, Miller BR, Huang J, Alyea FN, Cunnold DM, Fraser PJ, Hartley DE, Simmonds PG.  1995.  Atmospheric trends and lifetime of CH3CCI3 and global OH concentrations . Science. 269:187-192.   10.1126/science.269.5221.187   AbstractWebsite

Determination of the atmospheric concentrations and lifetime of trichloroethane (CH3CCl3) is very important in the context of global change. This halocarbon is involved in depletion of ozone, and the hydroxyl radical (OH) concentrations determined from its lifetime provide estimates of the lifetimes of most other hydrogen-containing gases involved in the ozone layer and climate. Global measurements of trichloroethane indicate rising concentrations before and declining concentrations after late 1991. The lifetime of CH3CCl3 in the total atmosphere is 4.8 +/- 0.3 years, which is substantially lower than previously estimated. The deduced hydroxyl radical concentration, which measures the atmosphere's oxidizing capability, shows little change from 1978 to 1994.

1991
Falkner, KK, Measures CI, Herbelin SE, Edmond JM, Weiss RF.  1991.  The major and minor element geochemistry of Lake Baikal. Limnology and Oceanography. 36:413-423. AbstractWebsite

A comprehensive, joint Soviet-American study of the chemistry of Lake Baikal, the world's deepest (1,632 m) lake, was carried out in July 1988. In this paper, we report the major, minor, and preliminary trace element concentrations for three profiles obtained at or near the deepest and central part of the three major basins of the lake. With the exception of Ba, the distributions of major and minor elements were homogeneous, displaying no variations greater than analytical uncertainties. Average concentrations in mu-mol kg-1 (1 SD) are titration alkalinity = 1,093(6), SO42- = 57.4(1.3), Cl = 12.3(0.7), Ca = 402(7), Mg = 126(1), Na = 155(4), and K = 24.1(1.0); and in nmol kg-1 are Sr = 1,350(30), Li = 296(12), Ba = 74.7(2.6), Rb = 7.10(0.23), and U = 1.77(0.12). Excluding K and Cl, these values compare favorably with previously published results. Although some hydrothermal activity is known to occur within the lake, it does not appear to significantly affect major ion cycling. The residence times of the major ions are 330 yr or the same as that of water in the basin and so are controlled predominantly by their riverine fluxes. There is not yet enough information to assess whether hydrothermal processes affect minor element cycles. Ba concentrations decrease with depth, showing abrupt decreases near the bottom at two stations. It appears to undergo some form of uptake at the sediments, but further study is required to discern the processes governing Ba distribution.

1989
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.

1980
Lupton, JE, Klinkhammer GP, Normark WR, Haymon R, Macdonald KC, Weiss RF, Craig H.  1980.  Helium-3 and manganese at the 21°N East Pacific Rise hydrothermal site. Earth and Planetary Science Letters. 50:115-127.   10.1016/0012-821x(80)90123-5   AbstractWebsite

Water samples collected at the 21°N hydrothermal site on the East Pacific Rise crest, including Deep-Tow and hydrocast samples collected in 1977 and three hot vent water samples collected recently with the submersible “Alvin”, contain significant additions of3He,4He, and Mn. Although the vent water collections were at least 50-fold diluted with ambient seawater, they are up to 53 times enriched in3He and 7.4 times enriched in4He relative to saturated seawater, with concentrations of total dissolvable manganese (TDM) up to 310 μg/kg.3He and4He covary in the vent samples, with3He/4He about 8 times the atmospheric ratio, reflecting a mantle helium source. In contrast to the helium isotopes the Mn/3He ratio in the vent samples is variable, ranging from 4.3 × 104 up to 1.0 × 105 g/cm3. Profiles of3He/4He and TDM in the water column at 21°N show a sharp maximum ofδ(3He) = 47%and TDM= 0.69 μg/kg, much higher than the average values of 34% and 0.2 μg/kg for the deep water in this region. This spike in3He and Mn occurs at 2400 m depth, 200 m above the level of the 21°N vents, and 100 m higher than any local bathymetry, evidence for upward transport of the hydrothermal discharge via rising plumes of hot vent water. Two of the 21°N Deep-Tow samples associated with small (⩽0.010°C) temperature anomalies hadδ(3He) = 38%and TDM= 0.28 and 0.58 μg/kg, also slightly elevated relative to background. The Deep-Tow and hydrocast samples have lower Mn/3He ratios than average vent samples due to Mn removal by scavenging. Comparison of vent samples and water column measurements at 21°N indicate that the pure vent water could be detected using3He and Mn even when diluted ∼105 times with seawater, confirming that these two tracers are extremely sensitive indicators of submarine hydrothermal activity.

1970
Takahashi, T, Weiss RF, Culberson CH, Edmond JM, Hammond DE, Wong CS, Li Y-hui, Bainbridge AE.  1970.  A carbonate chemistry profile at the 1969 GEOSECS intercalibration station in the eastern Pacific Ocean. Journal of Geophysical Research. 75:7648-7666., Washington, DC, United States (USA): American Geophysical Union, Washington, DC   10.1029/JC075i036p07648   AbstractWebsite

To compare and evaluate measurements made by the various laboratories participating in the Geochemical Ocean Section Study (Geosecs), four carbonate chemistry parameters, pH, pCO2, alkalinity, and total dissolved CO2, as well as temperature and salinity were measured for samples collected at the Geosecs intercalibration station, 28°20′±07′N and 121°41′±02′W. The methods for measurement include the glass-calomel electrode pair for pH, the pH and the potentiometric acid titration methods for alkalinity, gas chromatographic, infrared and potentiometric acid titration method for total CO2, and the gas equilibrator-infrared method for pCO2. The alkalinity values measured by the pH method agree with the values measured by the potentiometric acid titration method within 1%, and the total CO2 values measured by the chromatographic method agree with the values measured by the potentiometric acid titration method within 2%. The observed 3 to 5% difference between the total CO2 values measured by the chromatographic and infrared methods is attributed to the biological alteration of the unpoisoned samples used for the infrared methods. When two of the four measured carbonate parameters were used to calculate the remaining two parameters, the calculated values are found to differ systematically from the measured values for those two parameters. Such a discrepancy can be eliminated if a 30% error in the second apparent dissociation constant for carbonic acid (K2′) is assumed.