Jonathan G. WYNN University of South Florida Geology

USGS-St. Petersburg, FL: Lisa Robbins, Paul Knorr, John Lisle, Kim Yates USF College of Marine Science: Bob Byrne, Xuewe Liu USF-Geology: Bogdan Onac, Paul Knorr LDEO, Columbia Univ.: Taro Takahashi Bedford Inst. Ocean.: Kumiko Azetsu-Scott

§  Establish baseline for pH, pCO2, carbon flux rate and carbonate mineral saturation state ΩCaCO3-min =([Ca2+][CO3

2-]) / ksp-min

§  Compare chemical data (pH and saturation state) to previous work (very sparse prior to 2000’s; Yamamoto-Kawai et al., 2009 documented low Ωaragonite values during 2007 sea ice minimum)

§  Explore mechanisms for change in pH, saturation state

§  Provide basis for mechanistic predictive capability

§  Equilbration with atmospheric CO2

§  Warming/cooling §  Reduction of ice cover

- Dissolution additional of CO2 §  River run-off or direct

snow/rainfall §  Multi-year Ice melt-

§  Dilution of alkalinity

•  Previously 19,000 carbon records/ stations above the Arctic Circle

•  In the last 3 yrs HLY ECS cruises provided over 31,000 more surface records in Canada and Makarov Basins

•  + 25 vertical casts

National Snow and Ice Data Center, Boulder, CO.

Long/Lat.: -156.58 W, 79.91 N (7 sept. 2007)

Long/Lat.: -156.58 W, 79.91 N (12 sept. 2012)

Long/Lat.: -156.07 W, 80.29 N (6 sept. 2007)

Long/Lat.: -156.07 W, 80.29 N (12 sept. 2012)

2012 Nov 30 08:24:49

180˚

!160˚ !140˚

!120˚

70˚ 70˚

80˚ 80˚

0.8 1.0 1.2 1.4 1.6

aragonite!

HLY1002 (2010)2010

2012 Nov 30 08:24:49

180˚

!160˚ !140˚

!120˚

70˚ 70˚

80˚ 80˚

0.8 1.0 1.2 1.4 1.6

aragonite!

HLY1002 (2010)2010

2012 Nov 30 08:24:49

180˚

!160˚ !140˚

!120˚

70˚ 70˚

80˚ 80˚

0.8 1.0 1.2 1.4 1.6

aragonite!

HLY1002 (2010)HLY1102 (2011)

2011

2012 Nov 30 08:24:49

180˚

!160˚ !140˚

!120˚

70˚ 70˚

80˚ 80˚

0.8 1.0 1.2 1.4 1.6

aragonite!

HLY1002 (2010)HLY1102 (2011)HLY1202 (2012)

2012

2010

2011

2012

Underlay shows mean ice coverage during month of cruise

2011

2010

2012

•  Over 20% of Canadian Basin is undersaturated wrt aragonite •  Saturation state is largely due to ice melt (with biological activity and overprint of pCO2)

•  2012 data show migration northward of the changes in carbonate chemistry •  Data can be used to refine global models of ocean acidification and timing when surface

water will become undersaturated

Underlay shows mean ice coverage during month of cruise

2010 2011 2012

Salinity (all surface ~ 8m) NODC World Ocean Atlas Long-term mean 1998, 10m

2010-2012

Giles et al., Nature Geoscience, 2012

Factors contributing to carbonate undersaturation (low Ω):

•  Addition of CO2(g) to atmosphere (anthropogenic CO2), and air-sea equilibrium •  Addition of CO2(aq) to solution (remineralization of organic matter) •  Low temperature (colder water absorbs more CO2)

•  Mixing with freshwater (which has lower alkalinity, DIC) but … there are two sources of freshwater: sea-ice melt, and terrestrial runoff, both with differing degrees of effect on Ω

Red= intensified by global warming and sea-ice melt Blue = diminished by global warming and sea-ice melt

H216O: where 16O is ~99.8% of all oxygen on Earth

H218O: where 18O is ~0.2% of all oxygen on Earth

Natural abundance of the two isotopologues is expressed as a delta value, which describes small deviation in the ratio of 18O/16O from a standard:

16O H H

18O H H

δ 18O =

18O16O( )

SAMPLE18O

16O( )STANDARD(e.g.,SMOW )

−1⎡

⎣

⎢⎢⎢

⎤

⎦

⎥⎥⎥×1000‰

A difference of 20 delta-units ( between δ18O of 0 and –20‰) is: δ18O 18O/16O atomic mass 0‰ 0.0019651 15.99884 –20‰ 0.0020052 15.99892

Tool: an oldie, but a goodie:

Craig & Gordon, 1965

-160

-140

-120

-100

-80

-60

-40

-20

0

-22 -18 -14 -10 -2 2!18O

!D

-26

-200

-180

-220

Spaten Optimator, Munich, Germany

FDO Scratch Amber Lager, Frederick, MD

Home Brew, Tampa, FL

DogFish Head Palo Santo Marron, Milton, DEFosters Premium Ale, Albany, GA

Welch's Sparkling Grape

Yuengling Lager, Tampa, FL?

Steelhead Extra Stout, Blue Lake, CA

Newcastle Brown Ale, Tadcaster, England

Moose Druel Brown Ale,Missoula, MT

Okocim Premium Lager, Warszawa, Poland

Great Divide Fresh Hops, Denver, CO

Great Divide Hibernation Ale, Denver, CO

Grand Teton Bitch Creek, Victor, ID

Great Divide Samurai, Denver, CO

Heinekin Dark Lager,Zoeterwoude, Netherlands

Paulaner Lager, Munich, Germany

Samuel Smiths Nut Brown AleTadcaster, England

Zywiec Lager, Zywiec, Poland

North Coast Brewery Dry StoutFort Bragg, CA

Golden Pheasant Lager, Burbanovo, Slovakia

Ambo, Ethiopia

Italy

Covasna, Romania

Izvor Tosorog, Romania Poiana Vinullui, Romania

Parma, Italy

Eifel, Germany

Harghita, Romania

Denmark

Lipova, Romania

Parma, Italy

Vergeze, France

Poiana Negri, Romania

Covasna, Romania

San Pellegrino, Italy Piacenza, Italy

Tusnad, Romania

Italy

Minunilor, Romania

Antiche Terme dei Gracchi, Italy

-6

Dead Sea, Israel

Eklutna Glacier Lake, AK

Hyder, AK Lindon, UT

PeruCusco, Peru

Mt Shasta, CA Denver, CO

Icebergs, Atlantic Aspen, CO

Konisääjo, Finland Rääveli Lake, Finland

Arequipa, Peru Las Vegas, NV

Carlsbad, CA

Ulvik, Norway Austrian Alps

Borsec, Romania

Saratoga, NY Blue River, OR

Minami Alps, Japan Evian les Bains, France

RomaniaHokuto, Japan Jalisco, Mexico

Munti Dognicei, Romania

Kilauea, HI Rosewell Ck, BC

Bizusa, Romania Tosrog, Romania

Iveland, Norway Connecticut

Mexico Poland Spring, ME Speyside, Scotland

Pittston, PA Botthel, WA

The Maltings, Scotland Denmark

Iceland Volvic, France Auvergne, France

Perthshire, Scotland Ayolo Hills, Italy

Vosges, France New York

Florence, Italy Hampshire, England Fiuggi Italy

Florence, Italy Borrisoleigh, Ireland Fiji India

Bethania, Wales

Umbria, Italy

Cape Grim, Australia

Piney Spring, TX

Ethiopia

Oconee, SC

Knoxville, TN

Addis Ababa, Ethiopia

Dominican RepublicFlorida

Bahamas Puerto Rico Ethiopia

Honolulu, HI Dominican Republic

Addis Ababa, Ethiopia

Puerto Rico

Alemgena, Ethiopia

Tampa Tapwater

Trinidad

Vancouver, BC

Dead Sea, Israel

Snowfall, hoar frost on decks

Sea-ice core

Total Runoff = 3200 km3 yr-1

= 0.1 Sv

Net Precipitation (P-ET) 2000 km3 yr-1

Cooper et al., 2005

!20

!16

!12

!8

!4

0

0 4 8 12 16 20 24 28 32!20

!16

!12

!8

!4

0

0 4 8 12 16 20 24 28 32

SWSIM

MW

! O

[‰]

18

Salinity [psu]

Atlantic-derived seawater

(i.e., like SMOW) Sea-ice meltwater

meteoric water (Arctic rivers, also

precipitation)

Net sea-ice melting

Net sea-ice formation

Mass and isotope balance if you don’t like equations:

(some of it) ± (a little bit more of it) + (the rest of it) = (all of it)

Mass and isotope balance for accountants:

fSIM + fMW + fSE =1fSIM SSIM( )+ fMW SMW( )+ fSE SSE( ) = Sobserved

fSIM δSIM( )+ fMW δMW( )+ fSE δSE( ) = δobserved

...

fSE = Sobs − fSIM (SSIM )SSE

fMW =δobserved − fSIM δSIM( )−δSE

Sobserved − fSIM SSIM( )SSE

⎡

⎣⎢

⎤

⎦⎥

δMW

fSIM =1− δobserved

δMW

− Sobserved

SSE

+ δSESobserved

SSEδMW

⎛⎝⎜

⎞⎠⎟

1− δSIM

δMW

+ SSIMδSE

SSEδMW

− SSIM

SSE

⎛⎝⎜

⎞⎠⎟

!20

!16

!12

!8

!4

0

0 4 8 12 16 20 24 28 32!20

!16

!12

!8

!4

0

0 4 8 12 16 20 24 28 32

SWSIM

MW

! O

[‰]

18

Salinity [psu]

Meteoric

-seaw

ater m

ixing

0.0 0.1 0.2

f(SIM)

Deep Atlantic-derived seawater (i.e., like

SMOW) Sea-ice

meltwater

meteoric water (Arctic rivers, also

precipitation)

Net sea-ice melting

Net sea-ice formation

! O

[‰]

18

Salinity [psu]

0.0 0.1 0.2

f(SIM)

!8

!6

!4

!2

0

18 20 22 24 26 28 30 32 34

HLY1002 (2010)HLY1102 (2011)

180˚

−160˚ −140˚

−120˚

70˚ 70˚

80˚ 80˚

0.0 0.1 0.2f(MW)

… fMW 2003-5

Yamamoto-Kawai et al., 2008

2006

2008

2010-2011

180˚

−160˚ −140˚

−120˚

70˚ 70˚

80˚ 80˚

0.0 0.1 0.2f(SIM)

… fSIM 2003-5

Yamamoto-Kawai et al., 2008

2006

2008

2010-2011

fSIM fSIM

Underlay shows mean ice coverage during month of cruise

0.2 0.2 0 0

2010 2011

0.0 0.1 0.2arag

onite

fSIM

remainder of Canada Basin

Makarov BasinSever Spur region

undersaturated

supersaturated

fMW

0.5

1.0

1.5

2.0

0.0 0.1 0.2 0.3 0.4 0.5

0.0 0.1 0.2 0.3 0.4 0.5

0.5

1.0

1.5

2.0

0.0 0.1 0.2 0.3 0.4 0.5

0.0 0.1 0.2 0.3 0.4 0.5

0.5

1.0

1.5

2.0

0.0 0.1 0.2 0.3 0.4 0.5

0.0 0.1 0.2 0.3 0.4 0.5

0.5

1.0

1.5

2.0

0.0 0.1 0.2 0.3 0.4 0.5

0.0 0.1 0.2 0.3 0.4 0.5

0.5

1.0

1.5

2.0

0.0 0.1 0.2 0.3 0.4 0.5

0.0 0.1 0.2 0.3 0.4 0.5

0.5

1.0

1.5

2.0

0.0 0.1 0.2 0.3 0.4 0.5

0.1 0.2 0.3 0.4 0.5

0.5

1.0

1.5

2.0

0.0 0.1 0.2 0.3 0.4 0.5

0.1 0.2 0.3 0.4 0.5

fSIM

arag

onite

coastal Beaufort Sea

2010-2011

0.0 0.1 0.2arag

onite

fMW

remainder of Canada Basin

Makarov BasinSever Spur region

fSIM

fMW

arag

onite

coastal Beaufort Sea

undersaturated

supersaturated

0.5

1.0

1.5

2.0

0.0 0.1 0.2 0.3 0.4 0.5

0.0 0.1 0.2 0.3 0.4 0.5

0.5

1.0

1.5

2.0

0.0 0.1 0.2 0.3 0.4 0.5

0.0 0.1 0.2 0.3 0.4 0.5

0.5

1.0

1.5

2.0

0.0 0.1 0.2 0.3 0.4 0.5

0.0 0.1 0.2 0.3 0.4 0.5

0.5

1.0

1.5

2.0

0.0 0.1 0.2 0.3 0.4 0.5

0.0 0.1 0.2 0.3 0.4 0.5

0.5

1.0

1.5

2.0

0.0 0.1 0.2 0.3 0.4 0.5

0.0 0.1 0.2 0.3 0.4 0.5

0.5

1.0

1.5

2.0

0.0 0.1 0.2 0.3 0.4 0.5

0.0 0.1 0.2 0.3 0.4 0.5

0.5

1.0

1.5

2.0

0.0 0.1 0.2 0.3 0.4 0.5

0.0 0.1 0.2 0.3 0.4 0.5

2010-2011

USGS-USF team: Robbins, Knorr, Onac, Buzcowski Chief cruise scientists: Mayer Armstrong, Calder

State Dept: Moore

Science support: Chayes, Roberts. Other researchers: Clemente-Colon, Hall, etc

Captain and crew of the USCGC Healy

USCGC (Icebreaker): HEALY