Chemical Oceanography

Lecture 1: Primary Production

Lecture 2: Marine Bio-geochemistry
and Sedimentation
 Lecture 2: Marine Bio-geochemistry
and Sedimentation
• Distribution of Marine Sediments
• Carbonate Equilibrium and the CCD
• Organic Carbon and Sediments
• Bacterial Respiration and Subsurface Redox
Zonation
• Fe/Mn Nodule Formation
 Three Main Sediment Types
• Lithogenic – Physically supplied by weathering of
sediments from continents, e.g. ice rafted
sediment, terrigenous sands and muds, aeolian
dust, sediments become finer away from source,
• Biogenic – Biological inputs - mineral tests and
shells, organic carbon, form oozes
• Chemical (Authigenic) – diagenetic alteration of
sediments, precipitation and dissolution of
different minerals. e.g. dissolution of carbonate
• In reality many sediments made up of mix of
lithogenic, biogenic and chemical components
 Lithogenic sediments
• lithogenic particles are produced by weathering of
rock and minerals from land
• Transported by rivers, glaciers, and wind. Results
in thickest seds at continental margins
• Transport downslope by gravity-slumps and
turbidity currents
• Windblown (Aeolian) and volcanic Dust)
Components-quartz 2-10 microns-deserts.
Important in open ocean.
• Ice-rafting- up to 2000km from Antarctica, N
Atlantic and Arctic
 Biogenic sediments
• Made up of shells (skeletal material produced
by biogenic activity)
•Calcium carbonate shells as corals, algae,
molluscs, foraminifera (zooplankton /benthic),
Coccoliths (algae), pteropods, gastrops (1cm)
•Silica (opal) as diatoms (algae), radiolarians
(animals, zooplankton), sponges.
•Most microscopic and referred to as oozes.
deposition rates of 1-6 cm/1000yrs
•Found in most open ocean seafloor
 Dissolution of Carbonate at Depth
• Chemical processes modify biological (biogenic)
sediments through the dissolution of CaCO3 and
opal silica in deep water.
• Temperature and pressure play a role in increasing
the corrosiveness of deep waters
• The other major control on carbonate dissolution
is due to the creation of CO2 by the oxidation of
organic matter
• This creates bicarbonate ions at the expense of
carbonate ions thereby driving the dissolution of
carbonate tests.
• CO2 (aq)+ CO32-(s) + H2O  2HCO3-(aq)
 Carbonate dissolution and the CCD
• Carbonate content of
deep sea sediments
decreases with increasing
water depth.
• – lysocline, where the
proportion of solution-
resistant tests increases
abruptly
• – calcite compensation
depth (CCD) which is the
boundary between
carbonate-bearing and
carbonate-free sediments
 The Depth of the CCD in Oceans
• CCD normally at 5Km depth but can vary depending on
local conditions
Global Distribution of Marine Sediments
 Organic Carbon Supply to Sediments
• Organic Carbon supply is very important in
sediments – food for bacterial respiration
• Most (99%) organic mater is recycled in water
column – aerobic respiration
• On average only 1% stored in sediments
• Open ocean, long water column (1000’s m), low
primary production, low organic matter supply –
Oxic sediments
• Near land, short water column (100’s m), high
primary production, High organic matter supply –
Anoxic sediments
 Bacterial Respiration and Subsurface
Redox Zonation
• Where primary production is high, or mixing of
oxygen is low (e.g. in enclosed basins, Black Sea),
oxygen is consumed before all available organic
matter – Aerobic respiration stops
• A large number of bacterial species have evolved
to utilise other anaerobic processes to extracting
energy from organic mater to live, grow and
reproduce.
• Main species utilised are: Nitrate, Mn(IV) oxides,
Fe(III) oxides, sulphate and methanogenesis
 Sedimentary REDOX Processes
• Process that transfer electrons, resulting in
oxidation of organic carbon, (oxidation is
loss of electrons)
CH2O (reduced) – e-  CO2 (oxidised) + H2O
• And reduction (reduction is gain of
elections)
X (oxidised) + e-  X (reduced)
• And energy is released
(E.g. aerobic respiration, CH2O + O2  CO2 + H2O)
 Nitrate Reduction (Denitrification)
• Uses nitrate in place of oxygen
• Nitrate Reduced to N2 gas
• Produces CO2

CH2O + NO3-  CO2 + H2O + N2

 Fe/Mn oxide reduction
• Uses solid metal oxides in place of oxygen
• Metal oxides are dissolved,
• Sediment colour changes, brown Fe(III) – green
Fe(II)
• Produces CO2

CH2O + Mn(IV)O2 (s)  CO2 + Mn2+ (aq)

CH2O + Fe(III)OOH (s)  CO2 + Fe2+(aq)
 Sulphate Reduction
• Uses Sulphate in place of oxygen
• Produces toxic hydrogen sulfide
• Produces HCO3- alkalinity
• HS- and Fe2+ (from Fe(III) reduction) combine to
produce FeS minerals (sediments turn black)
• Burial of FeS an important S removal process

CH2O + SO42- + H+  HCO3- + H2O + H2S

 Methanogenesis

• methanogenesis uses CO2, H2 (from fermentation

of organic mater) etc. and organic matter directly
to extract energy
• Produces methane
• Some e.g.
CH2O  CH4 +CO2
CO2 + H2  CH4 + H2O
 Energy Yield and Physical Separation of
Redox Process
• Energy yield is different Aerobic 3190 KJ/Mole
respiration
for each process
Denitrification 3030KJ/Mole
• When a energetically
favourable can occur, it
Mn-reduction 2920-3090
will occur – to the KJ/Mole
exclusive of all other Fe-reduction 1330-1410
processes KJ/Mole
• Leads to a physical Sulphate- 380 KJ/Mole
separation of processes – reduction

vertical succession Methanogenesis 350 KJ/Mole

 Solid and Aqueous phase distribution
Physical separation of anaerobic process, and
changes in sediment colour
 Effect of Environments on Redox Process
• Where supply of Org C is low, no anaerobic
process may occur
• Ocean nitrate concentrations are low - Fe
and Sulphate reduction more important
• In freshwater environments sulphate is
absent - early methanogenesis,
landfill/marsh gas, willow-the-wisp.
 Fe/Mn nodules

• Fe.Mn Nodules Can be litter sea bed, most common near

MOR where supply of Fe/Mn is greatest (Hydrothermal)
• Slow Growth, characteristic banding ~1mm/million years
Biogeochemical cycling of Fe and Mn
• Diagenetic cycling
Fe/Mn Nodule Distribution
 Fe/Mn nodules as a resource
Nodules very rich in metals,
potentially a ore deposit
manganese (29.40 %);
iron (6 %);
nickel (1.34 %);
copper (1.25 %);
cobalt (0.25 %);
titanium (0.6 %);
aluminum (2.9 %)
sodium, magnesium,
silicium, zinc, oxygen and
hydrogen (32.16 %).