Biogeochemical cycling of dissolved organic C and nutrients. Figure by MIT OCW.

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1 Biogeochemical cycling of dissolved organic C and nutrients Figure by MIT OCW.

2 The profile of [DOC] With depth in the ocean 1. Measured by HTCO or wet chemical oxidation 2. Surface values are 60-80µM C deep sea values are 40 µm C 3. Deep sea values are nearly constant (implies some tight feedback/control) 4. Global inventory is 680 GT C. Most Resides in the deep ocean!

3 Why 40 µm C? What processes set the global inventory of marine organic carbon? Solar Variability Cosmic Rays Geomagnetic Field Intensity 14 C Cycle C Production CO 2 Distribution among C reservoirs Figure removed due to copyrite restrictions. Source Unknown. Atm Bio/Soils Surf Surf CaCO 3 Seds Deep Deep Figure by MIT OCW.

4 Pioneered by Pete Williams At SIO. Contamination is a big problem!!! Does UV get it all? Pre AMS 1g C (1m3) Now about 1mg C (1L)

5 Radiocarbon in DOC and DIC CO2->DIC->POC->DOC DOC DIC DOC is depleted (older) than DIC at all depths There is a source of new DOC in the surface ocean The 14 C between DIC and DOC is not the same at all depths (greater at the Surface)

6 Radiocarbon in the Atlantic and Pacific Oceans DIC 14 C has the same Value in the Atl and Pac 14 C of DIC and DOC is about the same in the deep Atl and Pac oceans Deep ocean values are equal to a RC age of Several 1000 s years Either there is a source of old DOC, or DOC lasts for several ocean mixing cycles

7 Why is DOC old in surface water?

8 Why is DOC old in surface water?

9 Why is DOC old in surface water? Old DOC 14 C = DOC (deep) New DOC 14 C=DIC

10 Why is DOC old in surface water? Atlantic surface water 14 C calc = C obs = -127 Old DOC 14 C = DOC (deep) New DOC 14 C=DIC Pacific surface water 14 C calc = C obs = -148

11 What flux of carbon is needed to maintain the marine DOC reservoir? Global inventory/residence time = annual flux 680 GT C/ yr = GT C/yr!!! How does this compare with other C fluxes?

12

13 What is the source of Marine DOC? Stable C isotopes Marine C -21 Terrestrial C C3 plants -27 C4 plants -15

14 Hard problems in oceanography- what is DOC and why is it so old?? DOC = humic substances

15 Sampling DOC is hard to do DOC= 1mg/L C Salt = 35g/L Separation based on size Cross Flow Filtration High Pressure 1 nm 1 kd Selects for HMW fraction about 30-35% TOC Low Pressure Membrane effects what Is collected Figure by MIT OCW. Some salts collected too!

16 13 C Nuclear Magnetic Resonance Spectrum of high molecular weight dissolved organic matter C/N = 15+3

17 13 C Nuclear Magnetic Resonance Spectrum of high molecular weight dissolved organic matter OCO (12%) HCOH (55%) COOH CONH (10%) CH x (10%)

18 1 HNMR of high molecular weight DOC HCOH CH x CH 3 COaromatic OCO

19 HMWDOC, what could it be? From our knowledge of cell biochemicals Proteins C/N = 4, CH x (O):CON = 3:1 Carbohydrates C only? OCO:HCOH 1:5 Lipids C only CH x COOH CH x COH..looks to be mostly (50-70%) carbohydrate!

20 280 µm C µm C

21 Relative abundance of major biochemcials in HMWDOC

22 HMWDOC in freshwater and marine environments

23 Polysaccharide Analysis O O Fructose, Glucose 3 Sucrose O H + hydrolysis Minutes Figure by MIT OCW.

24 Relative abundance of sugars in HMWDOC Relative %

25 HMWDOC monosaccharides in rivers,lakes, and seawater Image removed due to copyright restrictions. Locations of sampling: Eel River Lake Superior Nobska Pond Delaware River Mississippi River BUT..yields of sugars are only 5-15% HMWDOC

26 1 HNMR of high molecular weight DOC HCOH CH 3 CO-? CH x aromatic OCO

27 15 N-NMR of HMWDOC. Is HMWDON from protiens or from amino sugars? Amide (RCON) (90-100%) amino sugars O CH 3 CONH Free amine (R-NH2) (0-10%) RC(O)NC(R)C(O)

28 Is a large fraction of HMWDOC and HMWDON from amino sugars or proteins? proteins RC(O)NC(R)C(O) RC(NH 2 )COOH (amino acids) X amino sugars O CH 3 CONH O CH 3 CONH

29 Is a large fraction of HMWDOC and HMWDON from amino sugars? O CH 3 CONH H + O X HNH CH 3 COOH X

30 What is the lipid in HMWDOC? HCOH CH3CON CH x Lipid CH 3 (CH 2 ) n COH CH 3 (CH 2 ) n COOH Deoxy sugars OCO H 2 COH O CH 3 O

31 There are really two types of lipid in HMWDOC CH 3 COOH CH x

32 The effect of periodate on HMWDOC Is the lipid really lipid? HCOH CH3CON Lipid RCOH No Reaction CH x Deoxy sugars OCO CH 3 O CH 3 COOH

33 Periodate oxidation of HMWDOC NaIO 4 80 o C

34 HMWDOC composition summary Direct chemical analyses show that HMWDOC is 50-70% carbohydrate, 5-6% acetamide, and 5-6% lipid Chemical hydrolyses techniques show HMWDOC to be 15% carbohydrate, 3-5% protein, and <1% lipid Indirect chemical analyses show that an additional 25% Is amino sugars, and 25% is deoxysugars. However, There is no direct confirmation of this. A good portion of >25% remains uncharcterized. Much more at the molecular level.

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