1. CO 2 Exchange Over Sea Ice: Questions and Answers After 6 years of Observation Tim Papakyriakou CEOS, Faculty of Environment, Earth and Resources University of Manitoba Winnipeg MB, Canada papakyri@cc.umanitob.ca 09/09/10Los Alamos: Sea Ice Salinity Workshop1

2. Collaborators: Lisa Miller (DFO, Victoria) Jean-Louis Tison (ULB) Bruno Delille (U. Liège) Graduate Students

3. Outline Background and motivation for work Overview of methods Observed fluxes: Chambers Controlling Factors Observed fluxes: Micrometeorological Summary and final comments 09/09/10Los Alamos: Sea Ice Salinity Workshop3

4. Motivation Winter and fall sea ice maxima are between 18 and 28 million km 2 Uncertainty of the space/time dimensions of CO 2 exchange over sea ice, or whether significant fluxes exist Gosink et al. (1976) demonstrate that warm ice (>-7) is reasonably permeable to CO 2 diffusion No established physically-based methodology to represent CO 2 exchange over sea ice, or in ice dominated waters Incomplete understanding of carbon budgets and the atmosphere’s role in the carbon dynamics of polar marine ecosystems 09/09/10Los Alamos: Sea Ice Salinity Workshop4 Takahashi et al (2009) Krembs et al. (2002) Mundy et al. (2007)

5. Motivation 09/09/10Los Alamos: Sea Ice Salinity Workshop5 Drobot et al., 2008

6. Scales of Ice Concentration

7. Open Water pCO 2sw pCO 2air S k Current Practice Scaled according to ice concentration pCO 2sw pCO 2air “ice capping” A Vast majority of air-surface exchange studies. (e.g., Bates et al., 2006, GRL)

8. Immediate Objectives Assess the validity of the ice-capping assumption; Develop an strong understanding air - sea ice CO 2 exchange; – seasonality? – consistently among regions? – parameterizations? Subsequent Activity – Assess an alternative: flux – aggregation? (Lüpkes and Birnbaum, 2005, B-L Meteor 2005)

9. Methods: CO 2 Flux Net ecosystem exchange vs. net accumulation 09/09/10Los Alamos: Sea Ice Salinity Workshop9

10. Methods: CO 2 Flux Net ecosystem exchange vs. net accumulation – cumulative measure of flux – open- and closed-path eddy covariance (micrometeorological) – chamber 09/09/10Los Alamos: Sea Ice Salinity Workshop10

11. Methods: CO 2 Flux Net ecosystem exchange vs. net accumulation – cumulative measure of flux – open- and closed-path eddy covariance (micrometeorological) – chamber – box model - monitor change in system carbon stock (organic and inorganic) over a period of time 09/09/10Los Alamos: Sea Ice Salinity Workshop11

12. Methods: Chambers Flux is calculated using the time rate of change of gas concentration in the chamber Introduces bias errors, including perturbations of local pressure, wind and CO 2 concentration fields valuable information on feature efflux/uptake characteristics 09/09/10Los Alamos: Sea Ice Salinity Workshop12

13. Methods: Eddy Covariance Technique Simultaneous measurement of the high frequency (10 Hz to 20 Hz) fluctuations in vertical wind velocity and CO 2 concentration from above the surface; Time-averaged covariance is directly proportional to the flux; Sensor height to upwind fetch ratio of between approximately 1/100 to 1/300 Good measure of ecosystem exchange (10% to 20% accuracy), but little information on surface sources or sinks 09/09/10Los Alamos: Sea Ice Salinity Workshop13

14. Methods: Open- and Closed Path Systems Difference relates to the style of infrared gas analyzer (IRGA): – open path measurements measures across an ‘open’ optical path – air is drawn through a tube into a ‘closed’ cell for measurement in closed systems – both measure molar density Corrections: (i) ‘spectral loss’ for both systems; (ii) dilution (open path) & sensor heating (open path) 09/09/10Los Alamos: Sea Ice Salinity Workshop14

15. Overview of Chamber Measurements 09/09/10Los Alamos: Sea Ice Salinity Workshop15 April – June 2008 First year sea ice Oct. 2007 First year pack ice Nov. – Dec. 2004 First and multi year pack ice AA03 V1 cruise Sept. - Oct. 2003 First year pack ice IPY BASICS

16. Chamber Measurements: CFL and Antarctic Sites Measurements over first-year sea ice cleared of snow; Fluxes range between 0.02 μmol m - 2 s -1 and -0.06 μmol m -2 s -1 ; Little flux activity was observed below a surface temperature of - 10°C; Fluxes responded to the air-surface pCO 2 gradient – direction and magnitude; Ice temperature exerted a strong control over sea ice pCO 2. 09/09/10Los Alamos: Sea Ice Salinity Workshop16 black = CFL; blue = Antarctic Geilfus et al., 2010

17. Chamber Measurements over New Ice New ice supported CO 2 efflux SIMBA: flux ranged between 0.03 μmol m -2 s -1 and 0.06 μmol m -2 s -1 with colder ice supporting larger fluxes BASICS: flux ranged between 0.12 μmol m -2 s -1 and 0.5 μmol m -2 s -1 09/09/10Los Alamos: Sea Ice Salinity Workshop17 OLD ICE New ice Snow Frost Flowers ED C B A H i between 25 and 27 cm

18. Role of Snow: Chamber Results Springtime measurements in the Sea of Okhotsk (ice thickness between ~ 42 cm and 45 cm) (Nomura et al. 2010); Observed fluxes ranged between -1.18 μmol m -1 s -1 and -0.37 μmol m -1 s -1 from sea ice without a snow or slush cover and and responded to the air ice surface pCO 2 gradient; Fluxes were suppressed beyond critical snow thickness of ~ 9 cm; Combined snow and slush of < 9 cm reduced the uptake to ~ 50% of snow- free values, while the effect on efflux was less pronounced; Suggested that refreezing of melt water and resulting ice layer impeded the exchange. 09/09/10Los Alamos: Sea Ice Salinity Workshop18

19. Response of Brine pCO2 to ΔT Flux is dictated by the response of brine pCO 2 to changing temperature: – On freezing/melting: increase/decrease in brine pCO 2 within sea ice results from decrease/increase in brine solubility with increasing/decreasing brine salinity. thermal cycling in brine could induce covection 09/09/10Los Alamos: Sea Ice Salinity Workshop19 Thomas et al. (2010) Geilfus et al. (2010) Controls Over Observed Fluxes

20. Response of Brine pCO2 to CaCO 3 Formation On cooling/warming: – possible precipitation/dissolution of CaCO 3 – first salt to precipitate at T=-2.2 – observational evidence of ikaite in both Arctic and Antarctic sea ice (Dieckman et al. 2008; 2010) – thermal cycling in brine could cause CaCO 3 to precipitate and dissociate; 09/09/10Los Alamos: Sea Ice Salinity Workshop20 2 HCO 3 - + Ca 2+ ↔ CaCO 3 + CO 2 CaCO 3 Assur (1960) Controls Over Observed Fluxes

21. 09/09/10Los Alamos: Sea Ice Salinity Workshop21 “Closed system” Precipitation of CaCO 3 and release of CO 2 BUT during the spring – summer: Dissolution of CaCO 3 and CO 2 consumption Balance null during the period “Open System” Precipitation of CaCO 3 IF CaCO 3 and CO 2 are released in the water column Balance null or source if crystal CaCO 3 sink fast and deep IF CaCO 3 stays in the ice and CO 2 is released in the water column and passed below the pycnocline: The system is will be a CO 2 sink. -1.9°C “Surface process” “Open System” Near surface formation in young ice or frost flowers allows CO 2 to be released to the atmosphere → Source 2 HCO 3 - + Ca 2+ ↔ CaCO 3 + CO 2 Courtesy: Tison

22. Role of Biology Primary Production – Sea ice alga typically concentrate within the bottom 20 cm of sea ice; – Production varies regionally within the Arctic and Antarctica; Arctic (mean Cla = 31 mg m -2 ; range between <10 and 300 mg m -2 ); Antarctica (mean Cla=170 ; range betweeen 1000 mg m -2 ). Arrigo et al. (2010) Respiration – bacteria are ubiquitous in sea ice bacterial production can exceed primary production in the fall, winter, and summer; high surface and near surface concentrations can be found in frost flowers associated with young sea ice. Deming (2010) 09/09/10Los Alamos: Sea Ice Salinity Workshop22 Controls Over Observed Fluxes

23. Overview of Eddy Covariance Measurements 1.Semiletov et al. (2004) Spring and summer open- path eddy covariance measurements w/o sensor heating correction; Landfast sea ice Barrow, Alaska; CO 2 fluxes between -1 μmol m -2 s -1 and 0.6 μmol m -2 s -1 ; Fluxes are 2 to 3 larger than measured by chambers; Flux follows decreasing brine pCO 2 concentration with depth. 09/09/10Los Alamos: Sea Ice Salinity Workshop23

24. Overview of Eddy Covariance Measurements 2.Zemmelink et al. 2006 Summertime open-path eddy covariance measurements w/o sensor heating correction; MY sea ice Weddel Sea CO 2 fluxes between -0.35 μmol m - 2 s -1 and 0.1 μmol m -2 s -1 ; Flux was controlled by algae production at a slushy snow ice interface. 09/09/10Los Alamos: Sea Ice Salinity Workshop24

25. Overview of Eddy Covariance Measurements 3.Papakyriakou and Miller (submitted) Springtime (open-path) eddy covariance measurements over first- year sea ice in the Canadian Arctic Archipelago; CO 2 fluxes between -3.0 μmol m -2 s -1 and 1 μmol m -2 s -1 ; CO 2 evasion is in line with Semiletov et al. (2004), but maximum uptake was a factor of 5 greater. 09/09/10Los Alamos: Sea Ice Salinity Workshop25

26. Overview of Eddy Covariance Measurements Early Season Efflux (ave = 0.36 μmol m -2 s -1 ): 09/09/10Los Alamos: Sea Ice Salinity Workshop26 Less confident in results: (i) large contribution by heating correction (over corrected?); (ii) turbulent mixing is weak; CO 2 concentration of ~ two times atmospheric value is required at the snow base to support an average early experiment efflux by diffusion, which is realistic (e.g., Delille et al 2007; Heinesch et al. 2010; Miller et al., submitted); Possible CO 2 sources: bacterial respiration (DOC, EPS), DIC stock in snow and saline upper ice. T (C) Vb (%)

27. Overview of Eddy Covariance Measurements Late Season Uptake: 09/09/10Los Alamos: Sea Ice Salinity Workshop27 Heating correction is a small component of the flux; High wind speed facilitates strong turbulent mixing, ventilates the snow and promotes blowing snow: high surface area to mass ratio; rapid turbulent exchange; Occurs when sea ice is hydrologically ‘open’; Regional sea ice is tremendously productive, approaching between 28 and 55 mg C m -2 day -1 (data from Lavoi et al., 2005) Contribution of atmospheric CO 2 ? T (C) Vb (%)

28. Overview of Eddy Covariance Measurements 09/09/10Los Alamos: Sea Ice Salinity Workshop28 Thermodynamics appears to drive an air-ice pCO2 gradient by affecting brine carbonate speciation, and sea ice permeability; and High wind is necessary to facilitate the exchange

29. Contrast to Closed Path Observations Heinesch et al (2010) report closed- path eddy covariance measurements over landfast sea ice near to Barrow; Winter fluxes ranged between 0 and 0.8 μmol m -2 s -1, while fluxes in the early spring fluxes range between ± 0.2 μmol m -2 s -1 Efflux rates are comparable to Papakyriakou and Miller, however maximum uptake is an order of magnitude smaller; Consistent relationships to thermodynamics. Regional differences in sea ice biogeochemistry, or uncorrected biases associated with the respective systems? 09/09/10Los Alamos: Sea Ice Salinity Workshop29

30. Summary CO 2 fluxes have been measured using difference techniques, in different hemispheres, and appear to respond in direction and magnitude to temperature sensitivity of brine carbonate equilibria Chambers typically show the smallest absolute fluxes. Early eddy covariance measurements tended to show uptake – perhaps because of a missing sensor heating correction. Recent eddy covariance measurements using different systems conform for efflux, but not uptake. Perhaps variation in regional sea ice biogeochemistry can account for part of the discrepancy. Relationships are observed between fluxes and snow sea ice thermodynamics using different EC flux systems. Little is known about the role of saline snow on the carbon exchange dynamics. Measurements suggest that mobile snow may play an important role in CO 2, particularly when sea ice cold and assumed “closed” to brine drainage. 09/09/10Los Alamos: Sea Ice Salinity Workshop30

31. Answers and Questions There appears episodic and sometimes large CO 2 exchange over sea ice. Fluxes appear related to sea ice thermodynamics and temperature-brine relations. Which methodology consistently provides accurate flux measurements, or should they be expected to? How geographically relevant are the fluxes reported here? Can sea ice carbon stocks (organic and inorganic) support observed fluxes, and what exactly is the source of the observed efflux? What is the fate of atmospheric carbon taken into the snow/sea ice layer? 09/09/10Los Alamos: Sea Ice Salinity Workshop31

32. 11/02/09Winnipeg, MB Thank You. Questions?