Kiel Oxygen Projects GLIDERS Aanderaa oxygen optode (models 3830 & 3835) FLOATS Webb Slocum Glider NEMO, Optimare, Germany MOORINGS Provcarbon, Martec, France Provor CTS3 DO, Martec, France APEX Float, Webb, USA Custom-made optode logger (also suitable for Pirata moorings) McLane Moored Profiler
Oxygen optode: Long-term stability 296.5 296.0 O 2 = 295.0 ± 0.7 µmol/l Oxygen In-situ density 36.08 36.07 Oxygen concentration (µmol L -1 ) 295.5 295.0 294.5 294.0 293.5 36.06 36.05 36.04 36.03 36.02 36.01 σ S,T,p (kg m -3 ) 293.0 p = 1799.2 ± 0.2 dbar High long-term stability 36.00 292.5 35.99 0 100 200 300 400 500 600 Day Tengberg, Körtzinger et al. (2006). Evaluation of a life time based optode to measure oxygen in aquatic systems. Limnol. Oceanogr. Methods 4, 7-17.
Oxygen at 1900 m, float #4900494 Denis Gilbert et al., Argo Science Workshop 3, Hangzhou, China, March 27, 2009 300 W MOID 4900494 Oxygen concentration ( µmol kg -1 ) 295 290 285 280 275 270 265 4-year float record 260 2004 2005 2006 2007 2008 2009
Oxygen optode: Long-term stability Float #1900650 1800 dbar readings Float #1900651 1800 dbar readings APEX-O 2 Floats
Oxygen optode: Long-term stability Still no sign of significant optode drift Float #1900650 Float #1900651 Oxygen data not yet post-calibrated
Oxygen optode: Atmospheric measurements as drift check 440 430 Sensor in air Drift check possible through air measurements 10 9 420 410 8 Oxygen [µm] 400 390 380 370 360 Oxygen, measured Oxygen, calculated Temperature 7 6 5 4 Temperature [ C] 350 3 340 1 21 41 61 81 101 121 141 161 181 Number of datapoint 2 Körtzinger et al. (2005). High-quality oxygen measurements from profiling floats: A promising new technique. J. Atm. Ocean. Techn. 22, 302-308.
Denis Gilbert et al., Argo Science Workshop 3, Hangzhou, China, March 27, 2009 Need better characterization of optode measurements in air O2 concentration ( µm) O2 saturation (%) 500 400 300 200 120 110 100 90 80 In air surface drift optode data from float 4900494 2005 2006 2007 2008 2009 2005 2006 2007 2008 2009 2005 2006 2007 2008 2009 30 20 10 0 Air temperature ( C)
Oxygen optode: Results from moored profiler (McLane MMP) hysteresis of optode temperature sensor use CTD instead of optode temperature small correction (except in strong gradients) Oxygen Difference Optode temperature measurements inadequate Brandt & Körtzinger, unpubl.
Oxygen optode: Results from moored profiler (McLane MMP) hysteresis of optode oxygen measurement in-situ time constant of ~50 s (obtained by minimizing difference between paired profiles) large correction in strong gradients Optode time constant is an issue in profiling applications Brandt & Körtzinger, unpubl.
Oxygen optode: Results from calibration casts on CTD-O 2 system Optodes with individual loggers mounted on CTD-rosette 2-minute stops during upcast for optode equilibration, discrete sampling for S, O 2 CTD-O 2 casts (SBE 43) calibrated for entire cruise using discrete S and O 2 (Winkler) data CTD and optode readings are matched in time and averaged for each bottle stop Multi-linear regressions of O 2 (CTD) on O 2 (opt) are calculated: In-situ calibrations in Oxygen Minimum Zone of eastern tropical North Atlantic to <1 µmol/kg Brandt & Körtzinger, unpubl.
Oxygen optode: Individual sensor laboratory calibration (at Bjerknes Centre, Bergen/Norway) Vessel is vented through a 1 meter tube. Head space inside the vessel is kept to a minimum. Sparge air controller selects cylinders of pre-mixed air or can make any N 2 /O 2 blend with mass flow controllers. Sparge frit sits just below water surface (not visible). Temperature control via outer jacket is stable to 0.01 C. Mechanical mixer Neill & Brown, unpubl. Tap for taking Winkler samples. Triplicate samples at each calibration point provide the reference.
Oxygen optode: Individual sensor laboratory calibration (at Bjerknes Centre, Bergen/Norway) Calibrations done in freshwater 6 x 6 matrix (temperature x oxygen; since 2009: 6 x 8) po 2 is calculated from Winkler-O 2 and fit as function of B Phase and temperature (5 th degree polynomial with 21 terms, since 2009: 3 rd in temp. and 5 th in B phase) Calibration tests in seawater -0.8 calibration residuals umol/liter optode 1 optode 2 optode 3 optode 4 optode 5 Temperature O2 conc. salt error 0.8 error error error error 0.16 252.07 32.096 0.9 0.6 0.9 0.6 1.1-1.3 0.17 395.9 32.062 0.2 1.3 0.7 0.6-2.4 0.4 19.58 290.61 0-1.6 0.0-1.1-0.4 21.06 164.91 32.532 0.7 1.4 1.2 1.4 0.2 21.07 256.07 32.514 0.8 2.0 1.6 2.2 7.14 218.13 32.445 1.1 1.7 1.5 1.8-1.9 7.13 336.8 32.71 1.3 2.9 2.2 2.7-2.9-0.2-1.81 269.41 32.445 1.6 2.0 Laboratory 1.5 calibration 1.6 0.0 0 0 100 200 300 400 500-1.51 270.57 32.53 0.7-0.4 1.7 1.0 1.5-1.79 411.28 32.096-0.3 0.9 0.5-0.5-1.8-0.6-1.52 416.49 32.527 0.9 3.0 1.7 1.5 mean absolute errors 0.9 1.6 1.2 1.4 1.7 mean error for negative temps only 0.9 1.9 1.2 1.3 0.9 Neill & Brown, unpubl. to <2 µmol/kg
New features of optode 4330 New processor, 25 khz (older model 5 khz), Sinusoidal excitation gives lover noise (older model squared pulse), Optimized optics (better geometry), Temperature sensor closer to foil and faster response time (less than 2 s), Introduction of red reference LED. Reduced risk of electronic drift. Possible to use transparent foils. Fast response, less than 8 s, 90 % response. Possibility to offer better calibrations. 30-point and Winkler-checked. Yields accuracies of around 1 %. Output CAN bus & RS232.
Experimental Float Design and Development PSI CO 2 Pro Aanderaa Optode NEMO Float (Optimare, Germany) CO 2 & Oxygen Sensors Design Field Testing SOPRAN, Sub-project 3.5 (Körtzinger & Heimann) Sea-Air fluxes of CO 2 and O 2 in the eastern tropical Atlantic: a combined atmosphere-ocean perspective
First Mission Deployment: 24. Oct. 09 Recovery: 29. Dec. 09 Duration: 56 days of profiling 45 profiles in upper 200 m for T,S,O 2 & CO 2 111 pco 2 measurements, 1800 O 2 measurements No GPS positions for profiles 5 45 (malfunction) SOPRAN, Sub-project 3.5 (Körtzinger & Heimann) Sea-Air fluxes of CO 2 and O 2 in the eastern tropical Atlantic: a combined atmosphere-ocean perspective
Measurement Performance pco 2 data: t t= ( pco2 pco2 ) t= 0 t= ( pco2 pco2 ) ln = k t Fiedler & Körtzinger, unpubl. pco 2 [µatm] shallow Time [sec] pco 2 [µatm] deep Time [sec] SOPRAN, Sub-project 3.5 (Körtzinger & Heimann) Sea-Air fluxes of CO 2 and O 2 in the eastern tropical Atlantic: a combined atmosphere-ocean perspective
Measurement Performance O 2 data: Indication of diel cycle O 2 saturation Winkler reference SOPRAN, Sub-project 3.5 (Körtzinger & Heimann) Sea-Air fluxes of CO 2 and O 2 in the eastern tropical Atlantic: a combined atmosphere-ocean perspective Fiedler & Körtzinger, unpubl.
Honeywell Durafet Ion Sensitive Field Effect Transistor ph sensor a potential float/glider sensor 4 mm Long-term stability months at ±0.006 ph in seawater High temperature stability weeks of cycling 5 to 35 C in equimolar buffers (ph=pk(t)) show >0.01 ph stability Conduction Channel Pressure tolerance is now limiting factor. Reengineering packaging to be pressure tolerant device operating to 2000 dbar pressure routinely in lab. Low power (µws), low weight (grams), fast (<1 s) ph 7.90 7.88 7.86 7.84 7.82 7.80 7.78 7.76 Durafet Spectrophotometric Outliers created by bubbles on conduction channel 12/28/08 1/11/09 1/25/09 2/8/09 2/22/09 3/8/09 3/22/09 4/5/09 MBARI Seawater Test Tank Std. dev. of difference from Spec. ph values is 0.006 over 3+ months (ph going up as tank outgases CO 2 )
Labrador Sea showcase : The ocean taking a deep breath A quasi-stationary float Pressure (dbar) 0 200 400 290 295 300 305 310 315 320 325 B Oxygen (mmol m -3 ) Oxygen inventory 0-1400 m (mol O 2 m -2 ) Oxygen inventory (0-1400 m) [mol O 2 m -2 ] 454 1600 Oxygen inventory 452 Mixed layer depth C 1400 450 1200 448 446 1000 444 800 442 440 600 438 400 436 200 434 432 0 250 270 290 310 330 350 370 5 390 25 410 45 430 65 450 85 105 470 125 490 145 510 165 530 185 550 Julian day 2003 2004 Mixed layer depth (m) 600 800 1000 1200 1400 1600 1800 2000 Oct. 5, 2003 (profile 4) Oct. 26, 2003 (profile 7) Nov. 2, 2003 (profile 8) Dec. 7, 2003 (profile 13) Dec. 28, 2003 (profile 16) Feb. 8, 2004 (profile 22) Feb. 22, 2004 (profile 24) Mar. 21, 2004 (profile 28) Apr. 4, 2004 (profile 30) Apr. 11, 2004 (profile 31) Körtzinger et al. (2004). The ocean takes a deep breath. Science, 306, 1337.
Labrador Sea showcase : more science to come Kihm & Körtzinger, in prep.
Labrador Sea showcase : more science to come - Mixed layer O 2 budget flux - Surface O 2 data disequilibrium - QuikSCAT wind speed Transfer coefficient, k 660 Kihm & Körtzinger, in prep.
Eastern tropical North Atlantic: OMZ and upwelling dynamics Provor CTS3 DO, Martec, France Provcarbon, Martec, France Fiedler, Kihm & Körtzinger, in prep..
Eastern tropical North Atlantic: OMZ and upwelling dynamics Active upwelling (O 2 sat 50-60%) Sub-surface respiration underneath upwelled patch Cape Verde Front separating shadow zone form subtropical gyre Fiedler, Kihm & Körtzinger, in prep..