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Weiss, RF, Van Woy FA, Salameh PK.  1992.  Surface water and atmospheric carbon dioxide and nitrous oxide observations by shipboard automated gas chromatography : results from expeditions between 1977 and 1990. Scripps Institution of Oceanography Reference Series. :144., La Jolla, Calif.: Scripps Institution of Oceanography, University of California, San Diego Abstract
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Muhle, J, Huang J, Weiss RF, Prinn RG, Miller BR, Salameh PK, Harth CM, Fraser PJ, Porter LW, Greally BR, O'Doherty S, Simmonds PG.  2009.  Sulfuryl fluoride in the global atmosphere. Journal of Geophysical Research-Atmospheres. 114   10.1029/2008jd011162   AbstractWebsite

The first calibrated high-frequency, high-precision, in situ atmospheric and archived air measurements of the fumigant sulfuryl fluoride (SO(2)F(2)) have been made as part of the Advanced Global Atmospheric Gas Experiment (AGAGE) program. The global tropospheric background concentration of SO(2)F(2) has increased by 5 +/- 1% per year from similar to 0.3 ppt (parts per trillion, dry air mol fraction) in 1978 to similar to 1.35 ppt in May 2007 in the Southern Hemisphere, and from similar to 1.08 ppt in 1999 to similar to 1.53 ppt in May 2007 in the Northern Hemisphere. The SO(2)F(2) interhemispheric concentration ratio was 1.13 +/- 0.02 from 1999 to 2007. Two-dimensional 12-box model inversions yield global total and global oceanic uptake atmospheric lifetimes of 36 +/- 11 and 40 +/- 13 years, respectively, with hydrolysis in the ocean being the dominant sink, in good agreement with 35 +/- 14 years from a simple oceanic uptake calculation using transfer velocity and solubility. Modeled SO2F2 emissions rose from similar to 0.6 Gg/a in 1978 to similar to 1.9 Gg/a in 2007, but estimated industrial production exceeds these modeled emissions by an average of similar to 50%. This discrepancy cannot be explained with a hypothetical land sink in the model, suggesting that only similar to 2/3 of the manufactured SO(2)F(2) is actually emitted into the atmosphere and that similar to 1/3 may be destroyed during fumigation. With mean SO(2)F(2) tropospheric mixing ratios of similar to 1.4 ppt, its radiative forcing is small and it is probably an insignificant sulfur source to the stratosphere. However, with a high global warming potential similar to CFC-11, and likely increases in its future use, continued atmospheric monitoring of SO(2)F(2) is warranted.

Fraser, PJ, Porter LW, Baly SB, Krummel PB, Dunse BL, Steele LP, Derek N, Langenfelds RL, Levin I, Oram DE, Elkins JW, Vollmer MK, Weiss RF.  2004.  Sulfur hexafluoride at Cape Grim: Long term trends and regional emissions, Baseline 2001-2002. :18-23., Melbourne Abstract
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Nevison, CD, Kinnison DE, Weiss RF.  2004.  Stratospheric influences on the tropospheric seasonal cycles of nitrous oxide and chlorofluorocarbons. Geophysical Research Letters. 31   10.1029/2004gl020398   AbstractWebsite

The stratospheric influence on the tropospheric seasonal cycles of N2O, CFC-11 ( CCl3F), CFC-12 (CCl2F2) and CFC-113 (CCl2FCClF2) is investigated using observations from the AGAGE global trace gas monitoring network and the results of the Whole Atmosphere Community Climate Model (WACCM). WACCM provides the basis for a number of predictions about the relative amplitudes of N2O and CFC seasonal cycles and about the relative magnitude and phasing of seasonal cycles in the northern and southern hemispheres. These predictions are generally consistent with observations, suggesting that the stratosphere exerts a coherent influence on the tropospheric seasonal cycles of trace gases whose primary sinks are in the stratosphere. This stratospheric influence may complicate efforts to validate estimated source distributions of N2O, an important greenhouse gas, in atmospheric transport model studies.

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.

Yadav, V, Duren R, Mueller K, Verhulst KR, Nehrkorn T, Kim J, Weiss RF, Keeling R, Sander S, Fischer ML, Newman S, Falk M, Kuwayama T, Hopkins F, Rafiq T, Whetstone J, Miller C.  2019.  Spatio-temporally resolved methane fluxes from the Los Angeles megacity. Journal of Geophysical Research-Atmospheres. 124:5131-5148.   10.1029/2018jd030062   AbstractWebsite

We combine sustained observations from a network of atmospheric monitoring stations with inverse modeling to uniquely obtain spatiotemporal (3-km, 4-day) estimates of methane emissions from the Los Angeles megacity and the broader South Coast Air Basin for 2015-2016. Our inversions use customized and validated high-fidelity meteorological output from Weather Research Forecasting and Stochastic Time-Inverted Lagrangian model for South Coast Air Basin and innovatively employ a model resolution matrix-based metric to disentangle the spatiotemporal information content of observations as manifested through estimated fluxes. We partially track and constrain fluxes from the Aliso Canyon natural gas leak and detect closure of the Puente Hills landfill, with no prior information. Our annually aggregated fluxes and their uncertainty excluding the Aliso Canyon leak period lie within the uncertainty bounds of the fluxes reported by the previous studies. Spatially, major sources of CH4 emissions in the basin were correlated with CH4-emitting infrastructure. Temporally, our findings show large seasonal variations in CH4 fluxes with significantly higher fluxes in winter in comparison to summer months, which is consistent with natural gas demand and anticorrelated with air temperature. Overall, this is the first study that utilizes inversions to detect both enhancement (Aliso Canyon leak) and reduction (Puente Hills) in CH4 fluxes due to the unintended events and policy decisions and thereby demonstrates the utility of inverse modeling for identifying variations in fluxes at fine spatiotemporal resolution.

Nevison, CD, Keeling RF, Weiss RF, Popp BN, Jin X, Fraser PJ, Porter LW, Hess PG.  2005.  Southern Ocean ventilation inferred from seasonal cycles of atmospheric N2O and O2/N2 at Cape Grim, Tasmania. Tellus Series B-Chemical and Physical Meteorology. 57:218-229.   10.1111/j.1600-0889.2005.00143.x   AbstractWebsite

The seasonal cycle of atmospheric N(2)O is derived from a 10-yr observational record at Cape Grim, Tasmania (41 degrees S, 145 degrees E). After correcting for thermal and stratospheric influences, the observed atmospheric seasonal cycle is consistent with the seasonal outgassing of microbially produced N(2)O from the Southern Ocean, as predicted by an ocean biogeochemistry model coupled to an atmospheric transport model (ATM). The model-observation comparison suggests a Southern Ocean N(2)O source of similar to 0.9 Tg N yr(-1) and is the first study to reproduce observed atmospheric seasonal cycles in N(2)O using specified surface sources in forward ATM runs. However, these results are sensitive to the thermal and stratospheric corrections applied to the atmospheric N(2)O data. The correlation in subsurface waters between apparent oxygen utilization (AOU) and N(2)O production (approximated as the concentration in excess of atmospheric equilibrium Delta N(2)O) is exploited to infer the atmospheric seasonal cycle in O(2)/N(2) due to ventilation of O(2)-depleted subsurface waters. Subtracting this cycle from the observed, thermally corrected seasonal cycle in atmospheric O(2)/N(2) allows the residual O(2)/N(2) signal from surface net community production to be inferred. Because N(2)O is only produced in subsurface ocean waters, where it is correlated to O(2) consumption, atmospheric N(2)O observations provide a methodology for distinguishing the surface production and subsurface ventilation signals in atmospheric O(2)/N(2), which have previously been inseparable.

Weiss, RF.  1993.  South Atlantic Ventilation Experiment : SIO chlorofluorocarbon measurements. Scripps Institution of Oceanography Reference Series. :466., La Jolla, CA: Scripps Institution of Oceanography, University of California, San Diego Abstract
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Weiss, RF.  1970.  The solubility of nitrogen, oxygen and argon in water and seawater. Deep-Sea Research. 17:721-735.   10.1016/0011-7471(70)90037-9   AbstractWebsite

Recent precise data on the solubilities of nitrogen, oxygen and argon in distilled water and seawater are fitted to thermodynamically consistent equations by the method of least squares. The temperature dependence of the Bunsen solubility coefficient is treated using the integrated van't Hoff equation. It is shown that the Setchénow relation gives an adequate representation of the salting-out effect. Equations expressing the solubilities of these gases, as a function of temperature and salinity, in units of the Bunsen coefficient, ml/l., and ml/kg are given along with solubility tables in each of these units.

Weiss, RF, Kyser TK.  1978.  Solubility of krypton in water and seawater. Journal of Chemical and Engineering Data. 23:69-72.   10.1021/je60076a014   AbstractWebsite
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Weiss, RF.  1971.  Solubility of helium and neon in water and seawater. Journal of Chemical and Engineering Data. 16:235-241.   10.1021/je60049a019   AbstractWebsite

Sulfur hexafluoride (SF6) has been measured at Cape Grim since 1978 via a combination of in situ and flask measurements, including measurements on the Cape Grim air archive. The long-term growth rate of SF6 as observed at Cape Grim has increased from 0.1 ppt yr-1 in the late 1970s to 0.24 ppt yr-1 in the mid-1990s. Since then the growth rate has remained relatively constant at 0.23±0.02 ppt yr-1, indicating relatively constant global emissions (±10 %) since 1995. Pollution episodes at Cape Grim have been used to estimate regional (Melbourne and environs) and Australian emissions of SF6 at 3±1.5 and 15±7.5 tonnes yr-1 during 2001-2003.

Warner, MJ, Weiss RF.  1985.  Solubilities of chlorofluorocarbons 11 and 12 in water and seawater. Deep-Sea Research Part a-Oceanographic Research Papers. 32:1485-1497.   10.1016/0198-0149(85)90099-8   AbstractWebsite

The solubilities of dilute mixtures of the chlorofluorocarbons CCl3F (CFC-11) and CCl2F2 (CFC-12) in pure water and seawater over the temperature range 0 to 40°C have been measured by gas chromatography. The data have been fitted to equations in temperature and salinity of the form used previously to fit the solubilities of other gases. The fitted values have an estimated accuracy of ∼1.5% and a relative precision of ∼0.7% for both chlorofluorocarbons. The nonideal behavior of these compounds in dilute air mixtures is discussed, and their solubilities from a water-saturated atmosphere are presented in parametric form.

Vollmer, MK, Weiss RF.  2002.  Simultaneous determination of sulfur hexafluoride and three chlorofluorocarbons in water and air. Marine Chemistry. 78:137-148.   10.1016/s0304-4203(02)00015-4   AbstractWebsite

We have developed an analytical technique for the simultaneous measurement of the four trace gases sulfur hexafluoride (SF(6)) and the chlorofluorocarbons CCl(2)F(2) (CFC-12), CCl(3)F (CFC-11) and CCl(2)FCClF(2) (CFC-113) in water and air. Water samples are flame sealed into 350-ml glass ampoules which allow storage and sampling in locations where field measurements are not practical. For analysis, these ampoules are stripped of dissolved gases after their stems are cracked in an enclosed chamber such that the headspace fraction in the ampoule is included in the measurement. The extracted gases are then trapped cryogenically and are separated on packed columns. CFC-11 and CFC-113 are measured on one electron capture detector (ECD), while SF(6) and CFC-12 are cryofocussed on a second trap and analyzed on a second ECD. Detection limits for seawater samples are about 0.015 fmol kg(-1) for SF(6), 0.010 pmol kg(-1) for CFC-12, 0.014 pmol kg(-1) for CFC-11, and 0.024 pmol kg(-1) for CFC-113. This analytical technique also allows for analysis of air samples with low concentrations or at low pressures. Results from a profile in the northeastern Pacific Ocean show that SF6 partial pressure ages are consistent with those of CFC-11 and CFC-12 over the age range covered by this profile. From this, we infer that SF6 is useful for the dating of recently ventilated waters, thus complementing the dating of older waters using CFCs. Earlier reports of the degradation of CFC-113 in oxygenated water are supported by our results for samples stored in ampoules. (C) 2002 Elsevier Science B.V All rights reserved.

Wells, KC, Millet DB, Bousserez N, Henze DK, Chaliyakunnel S, Griffis TJ, Luan Y, Dlugokencky EJ, Prinn RG, O'Doherty S, Weiss RF, Dutton GS, Elkins JW, Krummel PB, Langenfelds R, Steele LP, Kort EA, Wofsy SC, Umezawa T.  2015.  Simulation of atmospheric N2O with GEOS-Chem and its adjoint: evaluation of observational constraints. Geoscientific Model Development. 8:3179-3198.   10.5194/gmd-8-3179-2015   AbstractWebsite

We describe a new 4D-Var inversion framework for nitrous oxide (N2O) based on the GEOS-Chem chemical transport model and its adjoint, and apply it in a series of observing system simulation experiments to assess how well N2O sources and sinks can be constrained by the current global observing network. The employed measurement ensemble includes approximately weekly and quasicontinuous N2O measurements (hourly averages used) from several long-term monitoring networks, N2O measurements collected from discrete air samples onboard a commercial aircraft (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container; CARIBIC), and quasi-continuous measurements from the airborne HIAPER Pole-to-Pole Observations (HIPPO) campaigns. For a 2-year inversion, we find that the surface and HIPPO observations can accurately resolve a uniform bias in emissions during the first year; CARIBIC data provide a somewhat weaker constraint. Variable emission errors are much more difficult to resolve given the long lifetime of N2O, and major parts of the world lack significant constraints on the seasonal cycle of fluxes. Current observations can largely correct a global bias in the stratospheric sink of N2O if emissions are known, but do not provide information on the temporal and spatial distribution of the sink. However, for the more realistic scenario where source and sink are both uncertain, we find that simultaneously optimizing both would require unrealistically small errors in model transport. Regardless, a bias in the magnitude of the N2O sink would not affect the a posteriori N2O emissions for the 2-year timescale used here, given realistic initial conditions, due to the timescale required for stratosphere-troposphere exchange (STE). The same does not apply to model errors in the rate of STE itself, which we show exerts a larger influence on the tropospheric burden of N2O than does the chemical loss rate over short (< 3 year) timescales. We use a stochastic estimate of the inverse Hessian for the inversion to evaluate the spatial resolution of emission constraints provided by the observations, and find that significant, spatially explicit constraints can be achieved in locations near and immediately upwind of surface measurements and the HIPPO flight tracks; however, these are mostly confined to North America, Europe, and Australia. None of the current observing networks are able to provide significant spatial information on tropical N2O emissions. There, averaging kernels (describing the sensitivity of the inversion to emissions in each grid square) are highly smeared spatially and extend even to the midlatitudes, so that tropical emissions risk being conflated with those elsewhere. For global inversions, therefore, the current lack of constraints on the tropics also places an important limit on our ability to understand extratropical emissions. Based on the error reduction statistics from the inverse Hessian, we characterize the atmospheric distribution of unconstrained N2O, and identify regions in and downwind of South America, central Africa, and Southeast Asia where new surface or profile measurements would have the most value for reducing present uncertainty in the global N2O budget.

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.

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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Weiss, RF, Jahnke RA, Keeling CD.  1982.  Seasonal effects of temperature and salinity on the partial pressure of CO2 in seawater. Nature. 300:511-513.   10.1038/300511a0   AbstractWebsite

The exchange of CO2 between the atmosphere and the sea is of major importance to our understanding of the climatic consequences of anthropogenic CO2. Because the solubility of CO2 and the dissociation of carbonic acid in seawater are modulated by temperature and salinity, the detection of long-term changes in the oceanic carbonate system, first requires that the comparatively large short-term variations in the partial pressure of CO2 should be characterized. We present here the first direct observations of seasonal variations in the partial pressure of CO2 in the subtropical gyres of the North and South Pacific Ocean. These variations compare well with the variations predicted from observed changes in temperature and salinity using empirical equations which do not require the determination of alkalinity or total inorganic carbon, and the agreement is improved by the inclusion of air–sea exchange in the model calculations. Thus we predict that specific alkalinity within the two gyres remains extremely constant, which is confirmed by carbonate equilibrium calculations based on our measurements of total inorganic carbon.