Organic matter in seawater

Fractions of Organic Matter:

Total Organic Matter = Dissolved OM + Particulate OM

TOM = DOM + POM

TOC = DOC + POC

TOP = DOP + POP
TON = DON + PON
NUTRIENT CYCLE
Biological uptake (Particulate)
Dissolved Nutrient  Phytoplankton  Zooplankton
light

Regeneration
(aerobic respiration) Biogenic detritus
(non-living organic matter)

Regeneration

Sinking particles

Sediments
(Burial)
 Chemist’s description of
phytoplankton

Dissolved Particulate
- Inorganic material - Organic material

Redfield Ratio 106C: 16N: 1P: 138O

 Conc of nutrients in seawater changes in relation to fixed conc
ratio in the organism
Total OC = Dissolved OC + Particulate OC
• Dissolved OC = 80%
• Particulate OC = 20%
Organic compounds in seawater
1. Amino acids

- polymerize to form long chain = proteins

- proteins in the form of enzymes catalyze biochemical reactions
- source = extracellular metabolites (phyto and zooplankton)
= result of decomposition of proteins during decay of
organic tissue or excreta
= result from exudation, excretion, decomposition of
dead organisms (source of DOC)
2. Carbohydrates

- polymer of simple sugar (CH2O)n

- two types a) energy storers
b) structural pieces of shells (supporting tissue of phytoplankton)

3. Lipids / Fatty acids

- structure is CH3(CH2)nCOOH n = 3-18

- include: waxes = have a protective function
triglycerides = serves as energy store reserves, buoyancy controls
and thermal or mechanical insulator
sterols = hormonal regulator of growth, respiration, reproduction,
membrane rigidifier
- some lipids used as biomarkers = well preserved in marine sediments
hence record past variations of ocean surface properties
(paleoceanography, paleoclimatology)
- alkenone record past sea surface temp
- alkenes or fatty alcohols record paleo-winds or paleo-productivity of
continental vegetation
 Pigments - fall under lipids
ex. Chlorophyll and carotenoids – used by plants to absorb and
transfer light energy during photosynthesis

4. Hydrocarbon

- structure CH3(CH2)nCH3 n -> 24

- principal hydrocarbons in algae are alkenes, alkanes, branched or cyclic
alkanes

5. Steroids

- used as structural builders

6. Other metabolites
- vitamins, co-enzymes, nucleic acids (ATP, DNA), hormones

7. Man-made components
- insecticides = herbicides
- plastics
- freon = used as water mass tracers
8. Humics
- inert, largely refractory to biological degradation and chemical oxidation
- produced by biodegradation of dead organic matter
- humic acid not single acid, complex mixture of many acids containing
carboxyl, phenolate groups

Role of Humics
CaCO3 and SiO2 are soluble in water so organisms coat themselves with
organic material to protect their shell from dissolving – act as chelator
Humic acids are insoluble in water at acid pH
Fulvic acids are also derived from humic substances ; soluble in water across the full range of pH
Oxidative cross-linking

Hydrolysis
Breakdown of DOC
AMINO CARBOHYDRATES LIPIDS HUMICS
ACID
Open 8% 35% 4% 53%
ocean
Coastal 9% 37% 8% 46%
waters
 Weight Percentages of Major Biochemical Classes in
Selected Organisms

Biochemical Higher plants Higher plants Marine Marine

type Plankton Plankton

Diatoms and
Conifer wood Wheat straw Dinoflagellates Copepods
Carbohydrates 56-65 75 0-36 0-4
Protein (a) 2-5 24-48 71-77
Lignin 28-34 18 0 0
Lipid (b) (b) 2-10 5-19

(a) unreported
(b) trace
Terrestrial – more cellulose and lignin; not much N; difficult to degrade
Marine – more protein and lipids; higher N
Breakdown of POC

Detritus ~82% (non-living)

Phytoplankton ~16%
Zooplankton ~2%
Fish, etc ~0.02%
Origin of OM
 Organic Matter
External
River – POC from soil (plant &
animal source); fluvial pdn of
humic and fulvic acid
Atm – from vegetation, soil, marine
and freshwater biomass, forest
burning
(enter via wet/dry deposition)
Internal
POC
Living - plankton (phyto, zoo,
nano), bacteria
Non-living - detritus, fecal
pellets; aggregation of organic
molecules, flocculation,
adsorption into mineral
phases
DOC – exudation of phyto,
excretion of zoo, post-death
decay process
AOU controlled by in-
situ decomposition of
DOC
 0m

50 m

250 m

700 m

Flux – measure of transfer rate per unit area

 Depth C Flux N Flux P Flux Fluxes as % Surface Atomic Ratios
(m) Prodn
C N P C: N: P C:N

COASTAL, UPWELLING Redfield C:N 6.6

50 36 4.1 0.19 53 39 32 190 2 1 8.8 Closer to
Refiled

250 21 1.8 0.13 30 18 21 160 4 1 12

27% 700 9.6 0.9 0.053 14 8.7 8.5 180 17 1 11
lost

COASTAL, NON-UPWELLING
50 7.6 0.77 0.029 34 23 15 260 27 1 9.9 Near
Redfield

250 4.3 0.43 0.013 19 13 6.3 330 33 1 10

46%
lost
700 4.1 0.28 0.011 18 8.1 4.9 370 25 1 15

OPEN OCEAN
75 5.7 0.41 0.014 50 24 13 410 29 1 14 Far from
Redfield
575 1.2 0.089 0.0026 11 5.2 2.4 460 34 1 15
82% 1050 1 0.034 0.0011 9 2 1.2 910 31 1 29
lost

Average Fluxes in mmoles/m2/d Flux decreases w depth and elemental composition changes
1. Particulate fluxes higher in upwelling area than in open ocean

nutrients primary production particle flux

2. Particulate flux decrease with depth

3. Particles in upwelling area closer to Redfield ratio, this means they

are more intact

4. C:N ratio higher in open ocean, N is more metabolizable

• 1st 4 years – fluxes high during winter and spring, low in late summer and fall
• Flux variation related to seasonal hydrographic changes, seen in oxygen isotopic
composition of the tests of a foram caught in the trap
• G. ruber (protozoa) build calcite skeleton with same oxygen isotopic composition of
surrounding waters
• 18O/16O in skeleton is characteristic of water temperature and salinity, hence it can
determine the temp-salinity regime that prevailed in the env prior to organism’s death and
descent in the water column
• higher flux occurs during low temp (determined from O isotopes)
• Period of low temp coincides with period of greatest mixed layer depth, thus high nutrients
 Heavy

δ18O

Light

0 Temp

Summer – pptn high δ18O lighter (higher temp)

Winter – evapn high δ18O heavier (lower temp)
Halocarbons

CFM – Chlorofluoromethane or Freon

• also known as CFC or chlorofluorocarbon
• F11 (trichlorofluoromethane) and F12 (dichlorofluoromethane)
• used as refrigerant, aerosol propellants, plastic foam blowing agent,
industrial solvent
• man-made, inert, volatile

CCl4 - used in production of CFCs

Atmosphere composed of
troposphere – lowest where weather phenomena and atmospheric
disturbance occurs
stratosphere – UV more intense, where ozone layer is found

Ozone – 3 molecules of O, absorbs light so it prevents harmful UV

radiation from reaching the earth
CFMs is non-toxic in troposphere but can diffuse to stratosphere and act
as catalyst in destruction of ozone layer
Ozone Formation
10 pmol/kg = 1980
4.5 pmol/kg = 1966
1980-1964
=16 years
Ventilation
time or time
for surface
water to sink
to 1000 m