EASC2406 Geochemistry

Hydrosphere-Atmosphere &
Geochemical cycles

Dr. Diane Chung (JL318E)

dianec@hku.hk
Outline

 Composition of seawater
 Earth’s atmosphere
 The cycles of C-H-O-N
Ionic strength in natural water

 Na+, Ca2+, Mg2+,

K+, Cl-, SO42-
and HCO3-
account for
>99% of the
dissolved
constituents.
 Concentration
of ions may vary
by ±10% due
to changes in
salinity.
Composition of modern seawater

 Concentration ratios of dissolved minor and trace elements

show significant variations from place to place.
 E.g. phosphates and nitrates
 Nutrients for plankton
 Reflect the metabolic activities of the organisms
Depth profiles in the North Pacific Ocean

Modified from Broecker and

Peng (1982)
The Principle of Mass Balance
 If the geochemical cycles of the elements are in a steady
state, the total mass of a non-volatile element released by
weathering of igneous rocks must be equal to its mass in
sedimentary rocks and in the oceans.
𝑖 𝑖 𝑖
𝑀𝑖𝑔 𝐶𝑖𝑔 = 𝑀𝑠𝑒𝑑 𝑎𝑗 𝐶𝑠𝑒𝑑 + 𝑀𝑠𝑤 𝐶𝑠𝑤

 𝑀𝑖𝑔 = mass of all igneous rocks in the continental crust that have weathered
𝑖
 𝐶𝑖𝑔 = concentration of elementiin igneous rocks of the crust
 𝑀𝑠𝑒𝑑 = mass of all sedimentary rocks in existence at the present time, including sediment in
the oceans
𝑖
 𝐶𝑠𝑒𝑑 = concentration of element i in sedimentary rocks and sediment in the oceans
 𝑀𝑠𝑤 = mass of water in the oceans
𝑖
 𝐶𝑠𝑤 = concentration of element I in seawater
 𝑎𝑗 = mass fractions of different kinds of sedimentary rocks and sediment in the oceans
Influx of dissolved constituents in seawater

 Rivers are the major sources of dissolved and particulate

materials in the oceans.
Processes modifying the chemistry of
seawater
 Biological processes:
 Synthesis of soft tissues or organic matter
 Secretion of skeletal hard parts
 Bacterial decomposition of organic matter
 Such processes exert major controls on the
concentration of recycled constituents
 Ca2+, HCO3- , SO42-, H4SO4, CO2, O2 , NO3- and PO43-
Processes modifying the chemistry of
seawater
 Seafloor volcanics-seawater interaction
 Both high temperature (200-400∘C) reactions at mid-oceanic
ridge axes and off-axis low temperature reactions.

Source: World Ocean Review

Processes modifying the chemistry of
seawater
 Reaction of seawater with detrital solids transported from
the continents.
 Detrital mineral forming generally a more cation-rich mineral
 Affect only the mineral surface by ion exchange, especially of Ca2+
for Na+.
 Ion exchange is particularly important for trace elements.

silicate/clay minerals

Stow (1994) and Wahsner et al. (1999)

Processes modifying the chemistry of
seawater
 Ocean-to-air transfer of cyclic salts (sea-salt particles
blown from the ocean surface onto the land).
Processes modifying the chemistry of
seawater
 Precipitation of evaporite and sulphide minerals, an
important mechanism for the removal of Na+, Ca2+, Cl-
and SO42- from seawater.

Scruton (1953)
Processes modifying the chemistry of
seawater
 Special processes that
include porewater burial of
Cl- and Na+

 A number of processes
unique to the nitrogen and
phosphorous cycles:
 Nitrification, denitrification,
N2 fixation, adsorption of
phosphate on ferric oxides,
and authigenic apatite
formation
Major processes affecting the concentration of
specific dissolved constituents in seawater

Modified from Berner and Berner (1996)

Mass balance for major elements in the
Ocean
 Primarily by discharge of river water.
 By ion exchange reactions between seawater and
suspended sediment, and between seawater and hot
basalt along mid-ocean ridges.
 At steady state, inputs = outputs for each element.
 Principal outputs of major elements:
 Burial of pore water
 Ion exchange reactions and water-rock interactions
 Diagenesis
 Chemical precipitates (carbonates, sulphides, oxides,
phosphates, silica, sulphates and chlorides)
Inputs of major elements in solution from
river water to oceans

Ion or Total flux Marine salt Anthropogenic Net flux

compound contaminant
Na+ 11.7 2.39 3.39 5.91
K+ 1.36 0.05 0.13 1.17
Mg2+ 5.59 0.29 0.41 4.85
Ca2+ 13.7 0.05 1.18 12.36
Cl- 8.69 2.82 2.63 3.27
SO42- 4.49 0.16 1.29 3.07
HCO3- 33.4 - 1.64 32.09
H4SiO4 6.47 - - 6.47

Drever et al. (1988); Meybeck (1979)

Mass balance for trace elements in the
Ocean

 Trace elements in solution in river water and adsorbed

on suspended particles are deposited in estuaries and on
the continental shelves or accumulate in deep-sea clay.

 The annual riverine input of a trace element of the

oceans must be equal to the output of that element
associated with marine muds.
Mass balance for trace elements in the
Ocean

 The annual input of trace element i by rivers:

𝑖 +𝑀 𝐶 𝑖
inputi = 𝑀𝑠𝑝 𝐶𝑠𝑝 𝑟𝑤 𝑟𝑤

 𝑀𝑠𝑝 = mass of suspended sediment transported annually by rivers into the

ocean
 𝑀𝑟𝑤 = mass of river water entering the ocean annually
 𝑖 = concentration of element i in suspended particles
𝐶𝑠𝑝
 𝑖 =concentration of element i in river water
𝐶𝑟𝑤
Mass balance for trace elements in the
Ocean
Mass balance of elements

 Entering the ocean by river

discharge
 in solution and in suspended
particles
 Leaving the ocean by deposition
of sediment
 as shale and deep-sea clay
Oxidation state of the oceans

Estimated change in atmospheric O2 levels through geologic time (Kasting et al., 1992)
Composition of the oceans in geologic history

 Hadean eon (4.5 - 3.8Ga):

 Absence of preserved rocks or fossils

 Archean (3.8 - 2.5Ga):

 Significant concentrations of Na+, K+, Ca2+, Mg2+
 Dominant anion in seawater: Cl-
 Similar composition and salinity to present-day seawater
 Dominant carbonate minerals: calcite, aragonite, and dolomite
Composition of the oceans in geologic history

 Proterozoic (2.5Ga - 542Ma):

 Supersaturated with CaCO3, CaMg(CO3)2 and SiO2
 SO42- concentration below the present value
 Bedded marine evaporite deposits in Neoproterozoic age
(900-542Ma)

 Early Cambrian (515Ma)

 Ca-depleted, Na-K-Ca-Mg-Cl composition
 Depleted in SO42- and Mg2+ but enriched in Ca2+
Structure and composition of the atmosphere

Source: www.srh.noaa.gov
Average composition of the Earth’s
atmosphere
Oxygenation of the atmosphere
 Oxidation state of the atmosphere (oxic or anoxic) is a
measure of the balance between the sources and sinks of
oxygen.
 The earliest mechanism of oxygen production in the
atmosphere was photolysis of water vapor and CO2 by
solar UV radiation:

H2O(g) + UV photon →H•(g) + OH•(g)

CO2(g) + UV photon →CO(g) + O(g)
O(g) + OH•(g) →O2(g) + H•(g) (↑)
Oxygenation of the atmosphere
The Great Oxidation Event (GOE)
 The irreversible transition from reducing to oxidizing conditions on the
Earth’s surface at around 2.3Ga (Holland, 1994).
 Resulted in an explosive growth in the diversification of minerals.
 Many elements could occur in more than one oxidation state in minerals
formed in near-surface environments.

Source: uwaterloo.ca
Evidence for the Great Oxidation Event I
 A large number of paleosols older than 2.2-2.3Ga have
lost significant amounts of Fe.
 Paleosols younger than 1.9Ga have retained Fe.
 The Fe-poor paleosols can be explained by weathering
under low oxygen conditions prior to 2.2Ga.
Evidence for the Great Oxidation Event II

 Continental red beds appear for the first time in the rock
record only around 2.2Ga and become abundant after
2Ga.
Evidence for the Great Oxidation Event III
 Detrital uraninite (U4+O2) occurs only in rocks older than
~2.3Ga, as in the uranium deposits hosted by
conglomerates in South Africa and Canada.
 Indicating that the atmospheric O2 was too low during
the weathering of the host rock to oxidize uranitite into
soluble U6+-bearing species.
Evidence for the Great Oxidation Event IV
 BIFs are abundant in the sedimentary record prior to
2.4Ga, but are largely absent between 2.4 and 2.0Ga.

Estimate of relative abundance of BIFs with time

Archean BIF, Buhwa Greenstone Belt,

Zimbabwe Craton (Courtesy: Chris Fedo)
Evidence for the Great Oxidation Event V

The secular trends in the isotopic composition of seawater

sulphate and sulphide minerals (Canfield, 1998)
Evidence for the Great Oxidation Event VI
 Mass-independent fractionation of sulphur isotopes
occurs in sediments of Archean and early Proterozoic age
(>2.45Ga), but not in younger sediments.

After Farquhar and Wing (2003)

Evidence for the Great Oxidation Event VII

 Modeling of the
intensity of organic
carbon burial, the
major source of
atmospheric O2
shows a marked
transition to high
values between 2.4
and 2.2 Ga.
A model for the evolution of the atmosphere

The three-box model of the atmosphere-ocean system pertaining to

atmospheric evolution over geologic time. O = oxidizing, R = reducing.
Walker et al. (1983) and Kasting (1993)
The cycles of C-H-O-N
Volatile and
water-soluble
 Exogenic cycle: elements

 Operates on the Earth’s surface

Weathering of
endogenic rocks
 Endogenic cycle:
 Operates in the Earth’s interior
Non-volatile
 Involves magma, igneous rocks, elements

sedimentary rocks, and

metamorphic rocks.
 The Carbon Cycle

CO2 dissolves in water CO2 enters the biosphere by

photosynthesis and by absorption of
The bicarbonate ions of the
carbonate ions through plant roots
hydrosphere are incorporated into
sediment in the form of CaCO3 Biospheric C is deposited as organic
matter in sediment and soil
Exhaled through volcanoes directly
into the atmosphere as CO2 Sediment composed of
plant debris forms coal
Sediment composed primarily
of CaCO3 forms limestone

C in sedimentary rocks C in sedimentary rocks formed

incorporated into magma into anthracite or graphite by
during partial melting and thermal metamorphism; limestone
enters igneous rocks recrystallizes to form marble

Reduced C enters the crust

by the intrusion of magma
Holser et al. (1988)
Reservoirs and fluxes of the natural carbon
cycle
The Water Cycle
Depends on the presence of water for its existence;
receives and discharges water to the other
Water in the upper atmosphere
reservoirs on the surface of the Earth
dissociates into gases and the H2
subsequently escapes into space

Volcanoes discharge
water vapour

Almost all of it originates

from groundwater and by
hydration of crustal rocks
Volumes and fluxes of water within the
hydrologic cycle

Berner and Berner (1987)

Nitrogen compounds in the major exogenic
reservoirs
Reservoir Amount (mol N) Residence time
Atmosphere N2 2.82 × 1020 44 ×106 year
NH3 1.83 × 1012 3-4 months
NH 0.29 × 1012 2-3 weeks
N2O 91 × 1012 12-13 years (?)
NO 0.22 × 1012 1 month (?)
NO2 0.22 × 1012 1-2 months
HNO3 small 2-3 weeks
Biosphere Continents 5.52 × 1016
Ocean 6.40 × 1016
Hydrosphere Dissolved N2 1.57 × 106
(oceans)
Dissolved organic 2.40 × 1016
Sediment Inorganic N 14.2 × 1018
Organic N 57.2 × 1018 400×106 years

Garrel et al. (1975)

 The nitrate produced by lightning
in the atmosphere is assimilated by

The Nitrogen Cycle plants and enters the biosphere

Biological cycling of N2 : initiated

NH3 is released following the by the formation of nitric oxide
death of the organism during lightning discharge

NO2- and NO3- are assimilated by plants

through their roots and are incorporated Nitrate reduce to N2 by
into cell material as the amino radial NH2 denitrifying bacteria

Hydrolysis of NH3 and then

oxidized to NO2- and NO3-
by nitrifying bacteria

N in plant tissue enters the endogenic

cycle when organic material is
deposited in sedimentary basins
Walker and Drever (1988)
 The Sulphur Cycle

Bacterial reduction of sulphate in

ocean and fresh water

Sulphate salts may be precipitated in

maine and non-marine evaporite basins
S in sedimentary rocks returns
to the hydrosphere in the form
of dissolved sulphate when the
sedimentary rocks are exposed
to chemical weathering.

S from the mantle may enter the

Reduced S is deposited as pyrite in hydrosphere as a result of alteration of basalt
marine and non-marine shales in the ocean, as a result of chemical
weathering of mafic igneous rocks, and by the
emission of SO2 by volcanoes
Principal reservoirs of sulphur in the
geochemical cycles
Reservoir Moles of S Principal form
Ocean 40 × 1018 Sulphate
Atmosphere 56 × 109 SO2
Fresh water 40 × 1015 Sulphate
Sediment
Oceanic 8 × 1018 Sulphide
Continental, reduced 145 × 1018 Sulphide

Continental, oxidized, evaporite 192 × 1018 Sulphate

Oceanic basalt, altered 25 ×1018 Sulphide

Mafic rocks, unaltered 106 ×1018 Sulphide
Igneous and metamorphic rocks 430 ×1018 Sulphide

Holser et al. (1988)