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Measurements and Models of Atmospheric Potential Oxygen (APO) M.O. Battle 1 , S. Mikaloff Fletcher 2 , M.L. Bender 3 , R.F. Keeling 4 , A.C. Manning 4,5 , N. Gruber 2 , P.P. Tans 6 , M.B. Hendricks 3 , D.T. Ho 3,7 , C. Si- monds 1,8 , R. Mika 3 and B. Paplawsky 4 References Battle, M., M. Bender, M. Hendricks, D. Ho, R. Mika, G. McKinley, S. Fan, T. Blaine and R. Keeling, Geophys. Res. Lett., 30 (15), 1786, doi:10.1029/2003GL017411,2003 Bender, M., P. Tans, J.T. Ellis, J. Orchardo, and K. Habfast, Geochim. Cosmochim. Acta, 58, 4751-4758, 1994. Bender, N.L., D.T. Ho, M.B. Hendricks, R. Mika, M.O. Battle, P.P. Tans, T.J. Conway, B. Sturtevant, and N. Cassar, Glob. Biogeochem. Cycles, in press. Conway, T., P. Tans, L. Waterman, K. Thoning, D. Kitzis, K. Masarie and N. Zhang, J. Geophys. Res., 99 (D11), 22,831-22,855, 1994. Garcia, H.E., and R.F. Keeling, J. Geophys. Res., 106(C12), 31,155-31,166, 2001. Gruber, N., M. Gloor, S. Fan and J. Sarmiento, Glob. Biogeochem. Cycles 15 (4), 783-803, 2001 Heimann, M., and S. Koerner, The global atmospheric tracer model TM3: Model description and user’s manual, Tech. rep., Max-Planck_Institut fur Biogeochemie, Jena, Germany, 2003. Keeling, R.F., and S. Shertz, Nature, 358, 723-727, 1992. Keeling, R., A. Manning, E. McEvoy, and S. Shertz, J. Geophys. Res., 103(D3), 3381-3397, 1998 Marland, G., R. Andres, T.B.C. Johnston, and A. Brenkert, Data Report ORNL NDP-030, Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, Oak Ridge, Tennessee. Stephens, B., R. Keeling, M. Heimann, K. Six, R. Murnane and K. Caldeira, Glob. Biogeochem. Cycles, 12, 213-230, 1998. Takahashi, T., R. Feely, R. Weiss, R. Wanninkhof, D. Chipman, N. Bates, J. Olafsoson, C. Sabine and S. Sutherland, paper presented at 2nd Int. Symp. on CO 2 in the Oceans, Natl Inst. for Environ. Studies, Tsu- kuba, Japan, 1999. Tans, P., T. Conway and T. Nakazawa, J. Geophys. Res., 94, 5151-5172, 1989. Thoning, K.W., P.P. Tans, and W.D. Kohmyr, J. Geophys. Res., 94(D6), 8549-8565, 1989. SUMMARY Acknowledgements We thank the crew and management of the freighters Brisbane Star and Argentina Star and the NOAA ship Ka’imimoana for their invaluable as- sistance. We also thank the observatory staffs for their careful collections. Support for this work was provided by the National Science Foundation, the NOAA Global Change Research Program and the Princeton/BP Amoco Carbon Mitigation Initiative. The goal: To gain insight into the controls on the oceanic carbon cycle. These controls include ocean circulation, biological activity and nutrient dynamics. Along the way, we may learn more about atmospheric transport and air- sea gas exchange. The approach: Atmospheric Potential Oxygen (APO) provides insight into these processes [Ste- phens et al., 1998]. The spatial structure of APO depends upon the interaction of ocean biology, solubility chemistry and general circulation, fos- sil fuel combustion and atmospheric circulation (including rectifiers). We measure the annual- mean meridional gradient in APO. We then compare this measurement with predictions from empirically based air-sea flux estimates, paired with atmospheric transport models. Examining disagreements sheds light on model weaknesses. The results: We have a multi-year dataset in hand that captures meridional gradients in APO. The two most prominent features are a mod- est interhemispheric gradient (relative to earlier studies) and a prominent equatorial bulge. We conclude that the interhemispheric gradient is evolving over time, and the equatorial bulge is generally well-predicted by our modeling ap- proach. The seasonal cycles of APO show some signs of an excessive seasonal rectifier near the Aleutian Islands in the model, and smaller data- model discrepancies at other sites. Figure 1: The climatological annual average meridional gradient in APO, both predicted (dashed) and observed (solid). Panels 3 & 4 show the dependence of the result on different treatments of the data (see “More Details” at right). Panel 1 shows the size of corrections applied to measured APO values based on concurrent measurements of the atmospheric Ar/N 2 ratio. The corrections are intend- ed to remove site-specific artifact associated with sample collection [Battle et al., 2003]. 1: Dept. of Physics and Astronomy, Bowdoin College, 8800 College Station, Brunswick, ME 04011 [email protected] 2: University of California, Los Angeles, Institute of Geophysics & Planetary Sciences, Box 951567, Los Angeles, CA 90095-1567 3: Dept. of Geosciences, Guyot Hall, Princeton University, Princeton, NJ 08544 4: Scripps Institute of Oceanography, University of California, San Diego La Jolla CA 92093-0236 5: Now at Max Planck Institute for Biogeochemistry, Hans Knöll Straße 10, D-07745, Jena, Germany 6: NOAA/CMDL, 325 Broadway, Boulder, CO 80305 United States 7: Now at Lamont-Doherty Earth Observatory, Columbia University, Pali- sades, NY 10964 8: Now at Adams, Harkness Inc.,99 High Street, 11th floor, Boston MA 02110 Affiliations ALT Alert (Canada) AMS Amsterdam Island (France) BRW Point Barrow, Alaska (USA) CBA Cold Bay, Alaska (USA) CGO Cape Grim, Tasmania (Australia) KUM Cape Kumukahi, Hawaii (USA) LJO La Jolla, California (USA) MAC Macquarie Island (Australia) PSA Palmer Station, Antarctica (USA) SAB Sable Island (Canada) SMO American Samoa (USA) SPO South Pole, Antarctica (USA) SYO Syowa Station, Antarctica (Japan) Figure 2: Locations at which samples comprising this dataset were collected. White text: Princeton Yellow: Scripps Orange: Princeton & Scripps. Abbreviations for the land stations are given at right. Publication: A manuscript entitled “Atmospheric Potential Oxygen: New Observations and Their Im- plications for Some Atmospheric and Oceanic Models of the Global Oxygen and Carbon Dioxide Cy- cles” (Battle et al.) is in press at Global Biogeochemical Cycles - 1 - 0 . 5 0 0 . 5 1 1 9 9 6 . 0 1 9 9 8 . 0 2 0 0 0 . 0 2 0 0 2 . 0 2 0 0 4 . 0 K a 'i m im o a n a B r i s b a n e S t a r A r g e n t i n a S t a r L a n d S t a t i o n s S i n e o f l a t i t u d e C o l l e c t i o n d a t e B R W S A B A M S S M O C G O M A C S Y O S P O P S A K U M LJ O A L T C B A Climatological annual average gradients from sparse data: We begin by removing the secular trend in APO and ef- fectively placing the Princeton and Scripps records on a com- mon scale. To do so, we average the trends [Thoning et al., 1989] for CGO and SMO in the Princeton dataset, and likewise for the Scripps record. These average trends are subtracted from all sta- tions in the respective lab’s datasets. After detrending, we collapse all records into a single climatological year. We then construct an- nual mean gradients using two approaches: latitude-time interpola- tion, and fitting of seasonal cycles. Latitude-time interpolation: We divide the set into time-slices of roughly 2 weeks in duration, yielding a series of meridional transects. We fit each transect using a Butterworth filter [Tans, Conway and Nakazawa, 1989]. Because the data density is not constant through the climatological year, we cannot simply aver- age all transects. Instead, we define periods when APO is roughly static, average all fits within each period, and then average the pe- riods together (weighted by duration) to form an annual average. Results of this method are shown in Panels 2 & 3 of Figure 1. Offsets of seasonal cycles: At each land based station, and each of 8 distinct shipboard latitudes, we fit the climatological seasonal cycle with a function of the form APO = α + β sin(2πt + φ) where α is the “offset” and gives the climatological annual mean value of APO at that stations. Results of this method are shown in Panel 4 of Figure 1. The model: The model results presented here (Panels 3 and 4 of Figure 1) come from an approach described by Gru- ber et al. [2001]. Briefly stated, an OGCM is used to in- fer oceanic oxygen fluxes by scaling predicted ocean oxygen concentrations (more precisely, O 2 *, defined as O 2 * = O 2 - r O 2 : PO 4 PO 4 ) to match observations of this property. These inferred fluxes of O 2 , along with air-sea CO 2 fluxes from Takahashi et al. [1999], seasonal O 2 fluxes from Garcia and Keeling [2001], and fossil fuel CO 2 fluxes from Marland et al. [1998], were used as a lower boundary condition for an atmospheric tracer transport model (TM3 [Heimann and Koerner, 2003]). Model output was processed in a fashion identical to the data. In particular, we sam- pled the modeled fields with the same spatial and temporal sparse- ness present in the observations. What is APO? As defined by Stephens et al. [1998], Atmospher- ic Potential Oxygen (APO) is an atmospheric tracer that is con- servative with respect to terrestrial biological activity. Changes in APO result from fluxes of carbon and oxygen to and from the oceans, and to a lesser extent, combustion of fossil fuels. APO is defined as: APO (per meg) = δ(O 2 /N 2 ) + 1.1 * 4.8 * [CO 2 ] where “per meg” denotes a fractional change of 1 part in10 6 rela- tive to a standard gas [Keeling and Shertz, 1992]. The factor of 1.1 ensures that CO 2 and O 2 fluxes to/from the terrestrial biota do not change APO. The factor of 4.8 converts from [CO 2 ] in ppm, to per meg. Our dataset: Atmospheric samples are collected periodically in paired glass flasks at the locations shown in Figure 2. The sam- ples are analyzed for δO 2 /N 2 and δAr/N 2 at Princeton Universi- ty [Bender et al., 1994, Bender et al. In press.] and the Scripps Institution for Oceanography [Keeling et al., 1998] and for CO 2 at Scripps and NOAA/ CMDL-CCGG [Conway et al., 1994]. Due to logistical and technical limitations, data density and qual- ity varies over the period of study. Data availability is summarized in Figure 3. Figure 3: Time and latitude of collections comprising this data- set. See Figure 2 for station abbreviations. Each point represents a pair of flasks. Poster #137 Presenter: Mark Battle MORE DETAILS -20 -15 -10 -5 0 5 10 15 APO (per meg) -1.0 -0.5 0.0 0.5 1.0 Sine of Latitude -20 -10 0 10 20 -8 -4 0 4 -8 -4 0 4 8 APO (per meg) SPO SYO PSA CGO AMS 30° S 20° S SMO 10° S 0-10° S 0-10° N 10° N KUM 20° N 30° N LJO SAB CBA BRW ALT Panel 3: Annual mean APO values derived from interpolation Data: Land stations Fit to all Model: Land stations Fit to all Panel 4: Annual mean APO values derived from seasonal cycles Data Model Panel 1: Ar/N 2 -based correction to APO Panel 2: Difference in APO between conventional avg. and interpolated avg. -1 -0.5 0 0.5 1 1996.0 1998.0 2000.0 2002.0 2004.0 Ka'imimoana Brisbane Star Argentina Star Land Stations S ine of latitude C ollection date BRW SAB AMS SMO CGO MAC SYO SPO PSA KUM LJO ALT CBA KUM NOAA ship Ka'imimoana BRW SYO AMS CGO MAC SMO SAB Brisbane Star & Argentina Star (ships) CBA ALT PSA LJO SPO

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  • Measurements and Models of Atmospheric Potential Oxygen (APO)M.O. Battle1, S. Mikaloff Fletcher2, M.L. Bender3, R.F. Keeling4, A.C. Manning4,5, N. Gruber2, P.P. Tans6, M.B. Hendricks3, D.T. Ho3,7, C. Si-monds1,8, R. Mika3 and B. Paplawsky4

    References

    Battle, M., M. Bender, M. Hendricks, D. Ho, R. Mika, G. McKinley, S. Fan, T. Blaine and R. Keeling, Geophys. Res. Lett., 30 (15), 1786, doi:10.1029/2003GL017411,2003 Bender, M., P. Tans, J.T. Ellis, J. Orchardo, and K. Habfast, Geochim. Cosmochim. Acta, 58, 4751-4758, 1994. Bender, N.L., D.T. Ho, M.B. Hendricks, R. Mika, M.O. Battle, P.P. Tans, T.J. Conway, B. Sturtevant, and N. Cassar, Glob. Biogeochem. Cycles, in press.Conway, T., P. Tans, L. Waterman, K. Thoning, D. Kitzis, K. Masarie and N. Zhang, J. Geophys. Res., 99 (D11), 22,831-22,855, 1994.Garcia, H.E., and R.F. Keeling, J. Geophys. Res., 106(C12), 31,155-31,166, 2001.Gruber, N., M. Gloor, S. Fan and J. Sarmiento, Glob. Biogeochem. Cycles 15 (4), 783-803, 2001 Heimann, M., and S. Koerner, The global atmospheric tracer model TM3: Model description and user’s manual, Tech. rep., Max-Planck_Institut fur Biogeochemie, Jena, Germany, 2003.Keeling, R.F., and S. Shertz, Nature, 358, 723-727, 1992. Keeling, R., A. Manning, E. McEvoy, and S. Shertz, J. Geophys. Res., 103(D3), 3381-3397, 1998Marland, G., R. Andres, T.B.C. Johnston, and A. Brenkert, Data Report ORNL NDP-030, Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, Oak Ridge, Tennessee.Stephens, B., R. Keeling, M. Heimann, K. Six, R. Murnane and K. Caldeira, Glob. Biogeochem. Cycles, 12, 213-230, 1998. Takahashi, T., R. Feely, R. Weiss, R. Wanninkhof, D. Chipman, N. Bates, J. Olafsoson, C. Sabine and S. Sutherland, paper presented at 2nd Int. Symp. on CO2 in the Oceans, Natl Inst. for Environ. Studies, Tsu-kuba, Japan, 1999. Tans, P., T. Conway and T. Nakazawa, J. Geophys. Res., 94, 5151-5172, 1989.Thoning, K.W., P.P. Tans, and W.D. Kohmyr, J. Geophys. Res., 94(D6), 8549-8565, 1989.

    SUMMARY

    Acknowledgements We thank the crew and management of the freighters Brisbane Star and Argentina Star and the NOAA ship Ka’imimoana for their invaluable as-sistance. We also thank the observatory staffs for their careful collections. Support for this work was provided by the National Science Foundation, the NOAA Global Change Research Program and the Princeton/BP Amoco Carbon Mitigation Initiative.

    The goal: To gain insight into the controls on the oceanic carbon cycle. These controls include ocean circulation, biological activity and nutrient dynamics. Along the way, we may learn more about atmospheric transport and air-sea gas exchange.

    The approach: Atmospheric Potential Oxygen (APO) provides insight into these processes [Ste-phens et al., 1998]. The spatial structure of APO depends upon the interaction of ocean biology, solubility chemistry and general circulation, fos-sil fuel combustion and atmospheric circulation (including rectifi ers). We measure the annual-mean meridional gradient in APO. We then compare this measurement with predictions from empirically based air-sea fl ux estimates, paired with atmospheric transport models. Examining disagreements sheds light on model weaknesses.

    The results: We have a multi-year dataset in hand that captures meridional gradients in APO. The two most prominent features are a mod-est interhemispheric gradient (relative to earlier studies) and a prominent equatorial bulge. We conclude that the interhemispheric gradient is evolving over time, and the equatorial bulge is generally well-predicted by our modeling ap-proach. The seasonal cycles of APO show some signs of an excessive seasonal rectifi er near the Aleutian Islands in the model, and smaller data-model discrepancies at other sites.

    Figure 1: The climatological annual average meridional gradient in APO, both predicted (dashed) and observed (solid). Panels 3 & 4 show the dependence of the result on different treatments of the data (see “More Details” at right). Panel 1 shows the size of corrections applied to measured APO values based on concurrent measurements of the atmospheric Ar/N2 ratio. The corrections are intend-ed to remove site-specifi c artifact associated with sample collection [Battle et al., 2003].

    1: Dept. of Physics and Astronomy, Bowdoin College, 8800 College Station, Brunswick, ME 04011 [email protected]

    2: University of California, Los Angeles, Institute of Geophysics & Planetary Sciences, Box 951567, Los Angeles, CA 90095-1567

    3: Dept. of Geosciences, Guyot Hall, Princeton University, Princeton, NJ 08544

    4: Scripps Institute of Oceanography, University of California, San Diego La Jolla CA 92093-0236

    5: Now at Max Planck Institute for Biogeochemistry, Hans Knöll Straße 10, D-07745, Jena, Germany

    6: NOAA/CMDL, 325 Broadway, Boulder, CO 80305 United States

    7: Now at Lamont-Doherty Earth Observatory, Columbia University, Pali-sades, NY 10964

    8: Now at Adams, Harkness Inc.,99 High Street, 11th fl oor, Boston MA 02110

    Affi liations

    ALT Alert (Canada)AMS Amsterdam Island (France)BRW Point Barrow, Alaska (USA)CBA Cold Bay, Alaska (USA)CGO Cape Grim, Tasmania (Australia)KUM Cape Kumukahi, Hawaii (USA)LJO La Jolla, California (USA)MAC Macquarie Island (Australia)PSA Palmer Station, Antarctica (USA)SAB Sable Island (Canada)SMO American Samoa (USA)SPO South Pole, Antarctica (USA)SYO Syowa Station, Antarctica (Japan)

    Figure 2: Locations at which samples comprising this dataset were collected. White text: Princeton Yellow: Scripps Orange: Princeton & Scripps. Abbreviations for the land stations are given at right.

    Publication: A manuscript entitled “Atmospheric Potential Oxygen: New Observations and Their Im-plications for Some Atmospheric and Oceanic Models of the Global Oxygen and Carbon Dioxide Cy-cles” (Battle et al.) is in press at Global Biogeochemical Cycles

    -1

    -0.5

    0

    0.5

    1

    1996.0 1998.0 2000.0 2002.0 2004.0

    K a'imimoanaB ris bane S tar Argentina S tar L and S tations

    Sin

    eo

    fla

    titu

    de

    C ollection date

    B R W

    S AB

    AMS

    S MO

    C G O

    MAC

    S Y OS P O

    P S A

    K UM

    LJO

    ALT

    C B A Climatological annual average gradients from sparse data: We begin by removing the secular trend in APO and ef-fectively placing the Princeton and Scripps records on a com-mon scale. To do so, we average the trends [Thoning et al., 1989] for CGO and SMO in the Princeton dataset, and likewise for the Scripps record. These average trends are subtracted from all sta-tions in the respective lab’s datasets. After detrending, we collapse all records into a single climatological year. We then construct an-nual mean gradients using two approaches: latitude-time interpola-tion, and fi tting of seasonal cycles.

    Latitude-time interpolation: We divide the set into time-slices of roughly 2 weeks in duration, yielding a series of meridional transects. We fi t each transect using a Butterworth fi lter [Tans, Conway and Nakazawa, 1989]. Because the data density is not constant through the climatological year, we cannot simply aver-age all transects. Instead, we defi ne periods when APO is roughly static, average all fi ts within each period, and then average the pe-riods together (weighted by duration) to form an annual average. Results of this method are shown in Panels 2 & 3 of Figure 1.

    Offsets of seasonal cycles: At each land based station, and each of 8 distinct shipboard latitudes, we fi t the climatological seasonal cycle with a function of the form APO = α + β sin(2πt + φ) where α is the “offset” and gives the climatological annual mean value of APO at that stations. Results of this method are shown in Panel 4 of Figure 1.

    The model: The model results presented here (Panels 3 and 4 of Figure 1) come from an approach described by Gru-ber et al. [2001]. Briefl y stated, an OGCM is used to in-fer oceanic oxygen fl uxes by scaling predicted ocean oxygen concentrations (more precisely, O2*, defi ned as O2* = O2 - rO2:PO4PO4) to match observations of this property. These inferred fl uxes of O2 , along with air-sea CO2 fl uxes from Takahashi et al. [1999], seasonal O2 fl uxes from Garcia and Keeling [2001], and fossil fuel CO2 fl uxes from Marland et al. [1998], were used as a lower boundary condition for an atmospheric tracer transport model (TM3 [Heimann and Koerner, 2003]). Model output was processed in a fashion identical to the data. In particular, we sam-pled the modeled fi elds with the same spatial and temporal sparse-ness present in the observations.

    What is APO? As defi ned by Stephens et al. [1998], Atmospher-ic Potential Oxygen (APO) is an atmospheric tracer that is con-servative with respect to terrestrial biological activity. Changes in APO result from fl uxes of carbon and oxygen to and from the oceans, and to a lesser extent, combustion of fossil fuels. APO is defi ned as:

    APO (per meg) = δ(O2/N2) + 1.1*4.8*[CO2]

    where “per meg” denotes a fractional change of 1 part in106 rela-tive to a standard gas [Keeling and Shertz, 1992]. The factor of 1.1 ensures that CO2 and O2 fl uxes to/from the terrestrial biota do not change APO. The factor of 4.8 converts from [CO2] in ppm, to per meg.

    Our dataset: Atmospheric samples are collected periodically in paired glass fl asks at the locations shown in Figure 2. The sam-ples are analyzed for δO2/N2 and δAr/N2 at Princeton Universi-ty [Bender et al., 1994, Bender et al. In press.] and the Scripps Institution for Oceanography [Keeling et al., 1998] and for CO2 at Scripps and NOAA/ CMDL-CCGG [Conway et al., 1994].

    Due to logistical and technical limitations, data density and qual-ity varies over the period of study. Data availability is summarized in Figure 3.

    Figure 3: Time and latitude of collections comprising this data-set. See Figure 2 for station abbreviations. Each point represents a pair of fl asks.

    Poster #137Presenter: Mark Battle

    MORE DETAILS

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    LT Panel 3: Annual mean APO values derived from interpolation

    Data: Land stations Fit to allModel: Land stations Fit to all

    Panel 4: Annual mean APO values derived from seasonal cycles Data Model

    Panel 1: Ar/N2-based correction to APO

    Panel 2: Difference in APO between conventional avg. and interpolated avg.

    -1

    -0.5

    0

    0.5

    1

    1996.0 1998.0 2000.0 2002.0 2004.0

    K a'imimoanaB ris bane S tar Argentina S tar L and S tations

    Sin

    eo

    fla

    titu

    de

    C ollection date

    B R W

    S AB

    AMS

    S MO

    C G O

    MAC

    S Y OS P O

    P S A

    K UM

    LJO

    ALT

    C B A

    KUMNOAA ship

    Ka'imimoana

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    MAC

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    Brisbane Star &

    Argentina Star

    (ships)

    CBA

    ALT

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    LJO

    SPO