EOS 260 Part II Flashcards
OILRIG
oxidation is loss, reduction is gain
geochemical oxidation states
doesn’t work to think of electron gain/loss in terms of reservoirs, must think of oxidation state in terms of compounds in them
Oxidation states of H
Reference species- H2O
Reduced- H2
oxidation states of C
reference species- CO2
reduced- CH4, CO
oxidations states of S
reference species- SO2
Reduced- S8
Oxidized- SO4 (2-)
fugacity
pressure value needed at a given temperature to make the properties of a non-ideal gas satisfy the equation for an ideal gas
used to infer oxygen fugacity from stable minerals
mineral redox buffers (ex. hematite-magnetite), in equilibrium at given oxidation state
oxidation states of iron
Fe (2+)- Ferrous, reduced, ex. mineral- wustite, FeO, soluble in water; Fe (3+)- Ferric, oxidized iron, ex mineralogy- hematite, Fe2O3, insoluble in water
magnetite
Fe3O4- mixed valence
i.e. FeO•Fe2O3
In a reducing atmosphere
lots of CH4, CO (reduced molecules)
evidence for redox state
geological indicators: reduced/oxidized minerals
modern geochemical evidence
geological indicators of redox state
redbeds
banded iron formations
certain detrital minerals
minerals in palaeosols
modern geochemical evidence of redox state
sulphur isotopes
trace metal abundances ex. (Mo)
Cr isotopes
Redbeds
detrital sed. rocks (lots of sandstone), with ferric (oxidized) Fe, form through subaerial alteration- deposited in air with lots of O2 available
Redbeds occur
only after ~2.3Ga
BIFs
alternating layers of magnetite/hematite and chert, deposited in anoxic H2O column, sedimentary rock
BIF sedimentation
ferrous Fe released at MOR– dissolved, transported in anoxic ocean– ferric precipitates where oxidation occurs; form major iron ores
indicator of oxygen
redbeds
anoxic oxidation
4Fe(2+) + CO2 + 11H2O +hv —- 4Fe(OH)3 + CH2O + 8H+
reducing power transferred from Fe(2+) to CH2O
BIF occurrences
frequency vs. years ago
1.5-4bya, mostly Precambrian (Archean), some proterozoic
Hamersley BIF
2.69-2.44Ga
deposition- 5x10^11 mol Fe/yr
1.25x10^11 mol O2 equiv. /yr
globally may have been 6X this
detrital uraninite
Archean U ores commonly detrital, imply anoxic event- UO2 would have oxidized and dissolved
detrital
deposited by rivers
mass-independent fractionation of S isotopes
requires photolysis by UV, which requires lack of ozone layer, which means lack of O2
S weird behaviour
δ33S, δ34S, different behaviours, increased weird behaviour ~2.5Ga, large increase in Δ33S ~2.5Ga
Ga =
billion years
S escape pathways
S8, SO2– need to get both forms out of atmosphere
most important geochemical change in history
anoxic- oxic atmosphere
reducing- oxidizing
oxygen level vs. age (Ga)
up to 2.5Ga- oxygen ~1ppb, MIF constraints, ~2Ga significant increase in O2 levels
present oxygen atmosphere
21% O2
3.7x10^19 mol O2
moles in atmosphere
1.8x10^20 mol
reserving oxygenic photosynthesis
respiration:
H2O + CO2– CH2O + O2
how to get O2 into atmosphere
Bury organic carbon in rocks- net oxygen source
marine productivity
103PgC/yr
burial flux
0.1PgC/yr
~10^13 mol/yr
total BOC
~10^21 mol, 25X the O2 in the atmosphere
accounting for oxidation
oxidants: in sediments (0.5), excess Fe3+ in igneous rocks (2.5)
reductants: reduced C in crust (~1.5), missing reductant (~1.5)
where is the rest of the O2
hydrogen escape
Hydrogen escape
H light- escapes atmosphere– oxygen source (splitting water)
photolysis of H2O
2H2O + hv — 4H(to space) + O2
hydrogen escape from H2O rich atmosphere
excess H2O in upper atmos. + energy source– hydrodynamic escape
energy limited
loose ocean worth of H in few hundred million years
hydrodynamic escape
hydrogen literally flows out
energy source for hydrodynamic escape
EUV- extreme UV radiation
limits rate of escape
hydrogen escape from normal atmosphere
H2O cold trapped at tropopause, diffusion limited, CH4 major H-bearing species, rate is small
normal atmosphere, ‘diffusion limited’
- total hydrogen mixing ratio: fH_total = 2fH2O + 4fCH4 +… very small
- buoyancy of light atoms above homopause
hydrogen escape rate from normal atmosphere
~10^10 mol O2/ yr
The Great Oxidation
~2.4Ga, reducing-oxidizing atmosphere, ~1ppmv-1% O2, biggest chemical transition in Earth history, changes in glaciation
bad hypotheses
- GO followed oxygenic photosynthesis (2.7Ga)
- there has always been high O2 in atmosphere
great oxidation box model
atmos/ocean reservoir of O2, CH4 flux between organic carbon
also—> hydrogen escape = constant x CH4
also<— volcanic gases, reduced Fe from mantle
conceptual model of the environment, pre-GO
anoxic atmos./ocean, stromatolite reefs– oxygenic photosyn.– sinking organic matter (requires decay path)
anoxic decay path for organic matter
fermentation followed by methanogenesis (methane formation)
2CH2O — CH4 + CO2
processes
- Primary Productivity
2i. Aerobic respiration
2ii. Methanogenesis - Atmospheric chemistry- methane oxidation
Methane oxidation
Net rxn: 2O2 + CH4 — 2H2O + CO2
methane oxidation rate constant
depends on OH availability
OH availability
produced by footless of H2O by UV
mostly deep in troposphere
depend on UV penetration to troposphere
UV photons today
attenuated in stratosphere by O3
bistability in atmospheric oxygen
Balanced (O2 + 1/2CH4) source— fast methane oxidation
or— slow methane oxidation
fast methane oxidation
low oxygen– no ozone– UV to troposphere– OH abundant– fast methane oxidation– low O2
slow methane oxidation
high oxygen– ozone layer– UV blocked— not much OH— slow methane oxidation– high O2 (can accumulate)
bistability graph
oxygen vs. NPP (input)
low O2 level stability– form O3 layer– ‘flip up’ to high O2 stability
instability in middle
closed cycle
production of methane and oxygen — atmospheric chemical destruction
to support reducing atmosphere
need strong flux of reductants (Fe2+) to ‘tip the balance’ (of the closed cycle)
rate of hydrogen escape depends on
fH_total, depends on reductant input; more reducing atmos. = faster planetary oxidation
high oxygen stability
more stable state
once high oxygen is reached, unlikely it will be lost
GO biochemistry
metabolisms, NPP
GO atmospheric chemistry
methane oxidation
GO upper atmosphere physics
hydrogen escape
GO aqueous chemistry
iron solubility
GO sedimentary geology
evidence for oxidation states
FYSP
faint young sun paradox- contradiction between observations of H2O_l early in Earth’s history, and Sun’s output only 70% as intense
Ice cover on Earth since 3Ga
globally- small periods in proterozoic, most of cryogen
regional- mostly Devonian- Permian
before 3.0Ga- not enough records
S 4.5bya
0.7S
Quasi-linear increase through time
feature of main sequence of stellar evolution
Energy deficit
σT^4 = (1-α) S/4
ΔF_s = (1-0.3)(1368/4)(1-0.8) = 50W/m^2
but no record of it being cold.. had to be warmer than today?
neoarchean S =
0.8S_o
deficit in solar forcing balanced with
radiative forcing
CO2
CH4
other GHGs
CO2 radiative forcing vs. concentration
50W/m^2 would require 80,000ppm
paleosols
fossilized soil in contact w/ atmos., look at mineral assemblage to determine if they could have been present w/ different CO2 levels
palaeosols show
10-100pCO2 at 2.5Ga ?
Methane radiative forcing
100ppm of CH4 gives 8-15W/m^2, not enough forcing
CO2 + CH4 forcing
~40W/m^2– need another 10
the missing F
turn up N2– pressure broadening
green line in graphs = 2XN2_atm levels– CO2 has higher forcing
pressure broadening
more molecules = more pressure = more molecular movement (more collisions with radiation)
measuring pressure in past
paleobarometer
methods for measure pressure in past
fossilized rain drop imprints (tell density)
other proposals for ‘the other 10’
mixture of other GHGs- ammonia, OCS, clouds
clouds
high clouds have strongest greenhouse effect– more low clouds? – very unknown
when is the cryogenian
650-750Ma, neo-proterozoic (top of the proterozoic)
importance of Cryogenian
extensive, Snowball Earth glaciations (pole-pole)
lead into second oxidation event
evolution of animals around this time
2 glaciations in cryogenian
- Sturtian (longer)
2. Marinoan
pole-pole glaciation
large ice cap instability (past ~30º)
sturtian timing
onset: 710-720 Ma
termination: 655-655 Ma
duration: 58Myr
Marinoan timing
onset: 640-660Ma
termination: 630-640Ma
duration: 4-14Ma
dating glacial onset/termination
O isotopes- get ‘reset’
U-Pb- volcanic ash right below/above glacial sediment
sedimentary record of a glacier
glaciers erode and deposit
produce variety of sediments/structures
glacial environment
ice– out wash plain
below ice– glacial till
post-glacial environment
till plain– terminal moraine– pitted outwash plain
till
very poorly sorted sediment ranging in size from very fine grained to giant boulders
glacial deposits
till striated clasts glacial pavement dropstones polygonal sand wedges
glacial pavement
striations/grooves/chattermarks in bedrock
chattermark
something in bottom of glacier sticks for a bit then moves.. stick– move–stick–move
dropstone
glacier near body of water– iceberg– iceberg drops debris; warp layered beds; can cause folding (if high force)
glacial deposits
mostly around glacier margins
glacial movement
very dynamic, move all over the place all the time
polygonal sand wedges
freeze/thaw cycles at edge of glacier; ground water– ice– crack sed.– fill w/ sand– propagates; same shape as mud cracks, columnar joint
Importance of glacial deposit present locations
paleogeography, paleomagnetism– determining where continents were– determining if glaciation was low latitude
Paleomagnetism
rocks contain minerals w/ magnetic properties that align themselves w/ Earths dipole magnetic field; which way lines point- which way was up– determine paleo
flow/field lines
parallel to surface at equator
perpendicular to surface at pole
general cryogenian strat section, bottom up
coarse grain clastics– deep water carbonate– shallow water carbonate– fine grained clastic– glacigenic diamictice– DWC– SWC– glycogenic diamictice– DWC– SWC
in between glacial units (glacigenic diamictite)
we see carbonate– implies low latitude
diamictite
sedimentary rock that consists of a wide range of lithified, nonsorted to poorly sorted, terrigenous sediment, i.e. sand or larger size particles that are suspended in a mud matrix