Marine

Geochemical/Biogeochemical
Cycles
Working up to sedimentation
Understanding chemistry of the oceans
Lead to biogenic and chemical sedimentation

Cycles
Dissolved constituents
Particulate- Organic and inorganic
Colloidal material- dissolved? particulate?

Marine Geochemical Cycles

Almost entire periodic table of elements can
be found in the ocean (ions in solution)
Concentrations are not equivalent to riverine
input

Marine Geochemical Cycles

Almost entire periodic table of elements can
be found in the ocean (ions in solution)
Concentrations are not equivalent to riverine
input
Other sources- inputs (hydrothermal, diagenetic)
Must also consider outputs and output rates
(sedimentation, hydrothermal)

Marine Cycles

Open University: MBC, Fig. 2.2

Marine Cycles
P cosmogenic

Air/sea
exchange

DP

G
D

P
DP

D
D

P = particulate inputs D = dissolved inputs G = gas inputs

Open University: MBC, Fig. 2.2

Marine Cycles
Inputs:
Particulate
Terrestrial- riverine, eolian, volcanic
Cosmogenic

Dissolved constituents
Continental weathering (including ground water flux)
Hydrothermal reactions (ocean crust weathering)
Diagenetic reactions (sediment)

Gases
Volcanic
Air/sea exchange
Excess volatiles

Marine Cycles
C

C = internal cycling (recycling)

MBC, Fig. 2.2

Marine Cycles
Cycling
Cyclic salts- from ocean atmosphere
rivers or rainout oceans
Aerosols (Sea spray)

Biological cycling
nutrients

Sediment cycling

Marine Cycles
Air/sea
exchange

O
O

O
O

O = Outputs
MBC, Fig. 2.2

Marine Cycles
Outputs
Sedimentation (biogenic, lithogenic, chemical)

Burial
Reverse weathering
Lithification
Subduction

Diagenetic reactions
Hydrothermal reactions (Seafloor weathering of
basalt)
Gas exchange

Marine Cycles
Removal to sediment
Biogenic precipitation- reverse weathering
Ca2+ + 2HCO3- CaCO3 + CO2 + H2O
Hard parts
Also photosynthesis Organic matter

Adsorption on clays
Important for Fe, Mn and Co cycles

Marine Cycles
Hydrothermal and diagenetic cycles
Both process add and remove cations
Hydrothermal
Mg2+ removed from and Ca2+ added to solutions

Carbonate diagenesis
Ca2+ removed from and Sr2+ and Mg2+ added to
solutions

Marine Cycles
C

Air/sea
exchange

DP

GO

C
O

OD

DO

P
DP

O
C

Open University: MBC, Fig. 2.2

Marine Cycles

OB, Fig. 7.2

Marine Cycles

Process approach
Global cycle- includes passage through
oceans
1) Weathering
2) Removal to sediments
3) Cycling through hydrothermal systems or
marine sediments
4) Uplift or burial/metamorphism

Marine Cycles
Weathering
Carbonate weathering

CaCO3 + CO2 + H2O Ca2+ + 2HCO3carbonic acid

Silicate weathering

in solution

CaSiO3 + 2CO2 + 2H2O Ca2+ + 2HCO3- + 2SiO2 + H2O

Wollanstonite

in solution
Cations balanced by anions in seawater- Cl- and SO42- = excess volatiles

Marine cycles
To close the loop
From the marine realm back to
continent/atmosphere/(biosphere)
Burial and metamorphism
Uplift
Volcanism

Marine Cycles

OB, Fig. 7.2

Dissolved Constituents
Salinity The sum of all the dissolved salts in seawater
Amount of dissolved inorganic solids
Average 35%o

35g salt in 1000g water (g/kg)

35 ppt
35 per mil (%o)
35 psu (practical salinity units)

Dissolved Constituents
Salts divided into
major constituents (> 1 ppm)
minor constituents (1 ppb 1 ppm)
trace constituents (< 1 ppb)

7 Major constituents account for >99.9% of

the salts
Cl-, Na+, Mg2+, SO4 2-, Ca2+, K+, HCO3(Earths crust- O, Si, Al, Fe, Ca, Na, Mg, K, Ti, H)

Salinity
Major Constituents of Seawater
mmol/kg
Chlorine

Cl-

555

Sodium

Na+

480

Magnesium

Mg2+

54

Sulfate

SO42-

29

Calcium

Ca2+

10.5

Potassium

K+

10

Bicarbonate

HCO3-

Salinity
Law of constant proportions
Salinity will vary with evaporation and
precipitation (add and remove H2O), but the
ratio of the major salts does not change
conservative behavior- not altered by biological or
chemical reactions within the ocean
Mg/Ca ~ 5
- Throughout the oceans

Dissolved Constituents
Conservative Behavior (mostly major elements)
Altered only by processes at the boundaries
Within the ocean only altered by mixing
Examples major elements; salinity, potential
temperature and pressure

Non-conservative Behavior (most minor and trace)

Altered by physical, chemical or biological
processes within the ocean
Examples- nutrients, silica, dissolved oxygen

Conservative - Non-conservative
Non-conservative

OC, Fig. 2.1

Conservative

Ca2+?
HCO3-?
SiO2?

Steady State
Steady State
Inputs = outputs
Chemical budget is balanced

Believed to be true in a gross sense for major

constituents and many minor/trace for the
Phanerozoic
Sediment/organisms havent changed
Fluid inclusions

Permian/Triassic Evaporites

Ruddiman, 5-15

Steady State
Balanced cycles
Example- Mg cycle
If HT circulation decreases (less seafloor
spreading)
Less Mg uptake at the ridge
Increased Mg uptake elsewhere (carbonates,
evaporites)
Related to distribution coefficient
KD = conc in solid/conc in seawater

Mg and Ca
Seas

Ridgewell and Zeebe. 2005

Residence Time
If elements are in steady state, it is possible
to determine how long they stay in
dissolved form- the residence time
Reactivity of an element
(yrs) =

Abundance (total number of moles)

Flux (input or output rate)

moles
moles/yr

Residence Time
Sr Example
=

(87 m) * (1.37 x 1021 l)

(3 + 1.2 + 0.3) x 10 mol/yr
10

riv

HT

= 2.6 m.y.

diag

Mixing time of the ocean = 1500 yrs

Well mixed

Residence Time
Major constituents tend to have long
residence times
Element

Conc (mM)
(millimoles/l)

Residence time
(m.y.)

Na+
Mg2+
Ca2+
K+
ClSO42-

480
54
10.5
10
555
29

193
15
1.2
8.2
305
22

HCO3-

0.088

Particulate Fluxes
Most of the organic matter and particulate cycles
takes place in the upper water column

Photic zone ~ 100-200 m

Phytoplankton photosynthesize (most of the biomass)
Zooplankton eat phytoplankton (fecal pellets)
Bacteria consume and decompose small particles and
pellets
Input of eolian material

Particle Scavenging
Metal ions and ionic complexes are
adsorbed on particles and transferred to the
seafloor
Adsorption = ionic attraction
Bacteria- small size, large surface area sites
of adsorption
Clays- charged surfaces

Elements that are commonly scavenged

Th, Pb, Co
Have short residence times (<100 1000 yrs)

Particle Scavenging
concentration

depth

Typical Scavenged
Element Profile
(Th, Pb, Fe)

Particulate Fluxes
Transfer to the seafloor
Settle at ~ 1m/hr, 166 days to reach seafloor

Yet sediment on seafloor reflects particles in

overlying water column
Packaged as:
Fecal pellets (~100-200m/day)
Marine snow (aggregates)

Marine Flux

Marine snow
Sediment trap material

WHOI website

Fecal pellet

Nutrient Cycles
Biological Pump
Downward movement of nutrients out of the
photic zone as particles
Release into deeper waters by decay
Combines particle and dissolved fluxes

Biological Pump- Nutrient Cycles

2 box model
Photosynthesis
Biological Pump

Respiration
Regeneration
Remineralization
(Decay)

106 CO2 + 16 HNO3 + H3PO4

+ 122 H2O
(CH2O)106(NH3)16(H3PO4) +
138 O2
Redfield Ratio (marine organic matter)
C:N:P:
106:16:1

Biological Particle Formation

organic matter
recycled in
upper 1000 m
(above the
thermocline)
1% of sinking
organic matter
(0.05 units)
makes it to the
seafloor
(repacked
multiple times)
OC, Fig. 2.3

Biological Particle Formation

Of the 5 units Corg that
sink below the photic
zone (~100 m)
- 3-4 recycled above
the thermocline
-only 0.05 makes it to
the seafloor
Skeletal/organic
matter increases
with depth
Organic matter is rare
in the deep sea!
MBC Fig. 2.3

Vertical Fluxes and Cycling of Dissolved

and Particulate Constituents

photosynthesis

Mixed layer

Straight arrows
= dissolved
fluxes

Thermocline

Wavy arrows =
particle fluxes

Deep Ocean

Biological Pump
MBC, Fig. 2.20

Nutrient Profiles
Micromoles per liter

Hard part profile

See Fig. 2.10 MBC

Can be zero at the surface (limiting)- consumed

P and N- mid depth maxima = oldest water
Si- maximum slightly deeper, high at seafloor- dissolution
from sediment

Nutrient Profiles

Dont always consume all nutrients at the surface

Preformed nutrients- can be advected into deep ocean
Broecker and Peng, Fig. 7-14

Nutrient Profiles

Chester, Marine Geochemistry, Fig. 9.3

Preformed Nutrients
Preformed nutrients- Nutrients that are
advected into the deep ocean rather than
produced by decay
PO4 meas = PO4 preformed + PO4 ox (recycled)

Common in Southern Ocean (HNLC areas)

Low light levels
Lack of biolimiting trace elements- Fe?

High Nutrient-Low Chlorophyll

Regions

Levitus World Ocean Atlas 1994

Preformed Nutrients
PO4* (Broecker) ~ initial phosphate (related
to preformed phosphate)
Distinct value for NCW and SCW
SCW >NCW
Conservative property
PO4* = PO4 + O2/175 1.95 m/kg
Increase in PO4 due to oxidation of organic matter
Balanced by decrease in O2/175

2 box model

O2 added

O2 removed

O2 Profiles
* air/sea exchange
* photosynthesis

regeneration of nutrients

Apparent Oxygen Utilization

(AOU)
~ Know dissolved oxygen content of water when
it sinks
That value decreases through oxidation of organic
matter
Difference between expected value at saturation
and observed value = amount used for oxidation
AOU = O2 sat O 2 meas
Used to calculate preformed nutrients

Dissolved
O2
Supersaturation in
surface waters:
Photosynthesis
Waves/bubbles

Broecker and Peng, Fig. 3-6 and Fig. 2.27- MBC

AOU

Broecker and Peng, Fig. 3-8

Surface= supersaturated

O2 Profile
O2 minimum
corresponds to
nutrient maximum
Combination of
biological pump +
circulation (age- time
away from surface)
MBC, Fig. 2.28- North Pacific

Dissolved Profiles- Summary

MBC, Fig. 2.17