lecture 9 – what controls the composition of seawater seawater is salty! why? how is the...
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Lecture 9 – What Controls the Composition of Seawater
Seawater is salty! Why?
How is the composition of river water different from seawater?What controls the composition of riverwater?What happens when you evaporate riverwater?
What controls the composition of seawater?Could Chemical Equilibrium reactions control the composition of the Ocean?What is meant by the Kinetic Model of Seawater?How does the Mass Balance Control work?
Sources - Rivers, Mid-Ocean Ridges (MOR)Sinks – Sediments, MOR
Observed Mean Ocean Concentrations – large range
log10c = x
c = 10x
Logarithmetic:
Could seawater originate by evaporation of river water?
River Water ≠ Sea Water
Mainly Ca2+/HCO3- Mainly Na+/Cl-
Both the composition and key ratios are differentppm = mg kg-1
What Controls the Composition of Rivers?
Weathering of limestone is considered a congruent reaction (all solid dissolves)CaCO3(s) + CO2(g) + H2O = Ca2+ + 2 HCO3
-
1 2Weathering of alumino-silicate minerals to clay minerals are examples
of incongruent reactions (solid partially dissolves)
silicate minerals + CO2(g) + H2O == clay minerals + HCO3- + 2 H4SiO4 + cation
1 1 2
A specific reaction written in terms of CO2(g)
KAlSi3O8(s) + CO2(g) + 1 1/2H2O = 1/2 Al2Si2O5(OH)4(s) + K+ + HCO3
- + 2H4SiO4
* With these reactions you could calculate how much CO2(g) is consumed by weathering
Weathering of rocks
(orthoclase feldspar) (kaolinite)
Variability in Erosion Among Continents
Europe, North Americaand Asia are more calcareous continents.
Most of variability dueto Ca2+ and HCO3
- whichcome from weathering ofcarbonate rock
SO42- and Cl- come
from aerosols and weathering of evaporite rocks (e.g. Salt or NaCl).
Na+, K+, Mg2+, SiO2
come from weatheringsilicate rocks
Evaporation of River water
pH = -log (H+)
Examples:Mono Lake, CASoap Lake, WA
Makes a Na, HCO3, CO3 brine. pH is very basic.
Mono Lake, California
Tufa Towers
Equilibrium approaches – Some History
Goldschmidt (1933)igneous rock (0.6kg) + volatiles (1kg) === seawater (1 L) + sediments (0.6kg) + air (3 L)
Sillen (1959, 1961)Sources - Weathering reactionsSinks - Reverse weathering reactions
Organizational framework:Gibbs Phase Rule
f = c + 2 – p f = degrees of freedom (variables like T,P, concentrations, e.g. Na+, Cl-, Ca2+, SO4
2-)
c = components (ingredients, e.g., HCl, NaOH, MgO))p = phases at equilibrium (domains of uniform composition, e.g. gas, liquid, pure solids)
Sillen: Nine component model (C = 9) Acids: HCl, H2O, CO2 Bases: KOH, CaO, SiO2, NaOH, MgO, Al(OH)3
The ocean chemistry results from a giant acid-base titration. Acids fromthe volcanoes and bases from the rocks.
Sillen suggested that the following phases were at equilibrium.
If these phases at equilibrium at constant T and Cl, then the SW composition is fixedand it could only change if temperature or Cl- changed. Equilibrium constants not known.
Kaolinite, illite, chlorite, montmorillonite and phillipsite are types of clay minerals
Mass Balance approaches
Mackenzie and Garrels 1966 proposed that the input from riverswas balanced by removal to sediments but they had to invokea reverse weathering hypothesis for which there was (and still is) little evidence.
The river inputs are given below (total amount for 108 y).For a steady state ocean, these have to be removed.
Mackenzie and Garrels (1966) American Journal of Science, 264, 507-525
Mackenzie and Garrels (1966) A Chemical Mass Balance for Seawater
Still need to remove:15% of Na90% of Mg100% of K90% of SiO2
42% of HCO3
Specific reverse weathering type reactions proposed to remove excess ions.
Newly formed clays would equal 7% of sedimentary mass.
Most clays are detrital-reflecting continental sources
chlorite in deep-sea sediments
detrital = particles of rock derived from pre-existing rock by weathering and erosion
illite in deep-sea sediments
So, an equilibrium approach doesn’t work.
The composition of seawater has changed in the pastandThe phases suggested do not appear to be at equilibrium
But there is some evidence that such reactions do occur – especially in near shore sediments
So reverse weathering not totally eliminated!But maybe not for an equilibrium ocean.
What is the origin of seawater’s composition?SourcesRivers??Mid-Ocean Ridges??Other?? Aerosols
SinksSediments??Mid-Ocean Ridges??Other?? Aerosols
Kinetic Model of Seawater - A Mass Balance Approach
Residence Time
= mass / input or removal flux = M / Q = M / S
Q = input rate (e.g. moles y-1)S = output rate (e.g. moles y-1)[M] = total dissolved mass in the box (moles)
Mass Balance Model – Modern Version.Includes ridge crest processes.
How about mid-ocean ridges??
350ºC vents have no Mg2+, SO42- or alkalinity (HCO3
-). What’s left is Cl-, Na+, Ca2+, K+, Fe2+
Sites of Hydrothermal Vents on Mid-Ocean Ridges
Hydrothermal End-Member (350°C)(from Von Damm et al (1985)
from site at 21° N (Hanging Garden)
Kinetic model of seawater – mass balance model
Main input and removal fluxes for major ions in seawater (from McDuff and Morel, 1980)
Note: Vr = 4.55 x 1016 L y-1 Vr/Vhydro = 300 Volume of ocean = 1.37 x 1021 L
Group Ia – Cl
short term cycle = aerosols and riversmain sink over geological time = evaporites = controlled by tectonics, geometry of marginal seasresidence time is so long (~100 My) that changes are hard to see.
Group Ib – Mg, SO4, probably K
input from rivers ; main sink through ocean crustThus control is mass balance: VrCr = Vhydro (Csw – Cexit fluid)
for Mg2+ , Cexit fluid = 0thus: Csw = ( Vr / Vhydro ) Cr
= 300 Cr
The dominant control is Vhydro, thus tectonics.
Group II (e.g. Ca, Na) (e.g. the remaining cations with long residence times)
Consider the charge balance for seawater:2[Ca2+] + [Na+] + 2[Mg2+] + [K+] = [HCO3
-] + [Cl-] + 2[SO4 2-]
or rearranged:2[Ca2+] + [Na+] - [HCO3
-] = [Cl-] + 2[SO42-] - 2[Mg2+] - [K+]
This side is controlled by tectonics
Therefore this sum is also controlled by tectonics
The controls on the relative proportions of elements on the left hand side are complicated but include:
a) Ca/Na ion exchange in estuariesb) Ca/HCO3 regulation by calcium carbonate equilibria
Three Categories of Hydrothermal Flow•350°C Black Smokers - 0.5 x 1013 kg y-1
•10°C Axial - 440 x 1013 kg y-1
•10°C Off Axis - 630 x 1013 kg y-1
•River Flux (Global) - 3500 x 1013 kg y-1
from Emerson and Hedges (p. 55)
But – the problem with this approach is that not all HT flow is 350°C!
Group III (e.g. nutrients (Si, P, C, N) and trace metals
Internal cycling can be described by the simple 2-box ocean modelThe main balance is input from rivers and removal as biological debris to sediments
Input from rivers = removal to sedimentsVrCr = f B
where f is the fractionof biogenic flux that is buried (escapes remineralization)
Summary
Salinity of seawater is determined by the major elements.
Early ideas were that the major composition was controlled by equilibrium chemistry.
Modern view is of a kinetic ocean controlled by sources and sinks.
River water is main source – composition from weathering reactions.Evaporation of river water does not make seawater.
Reverse weathering was proposed – but the evidence is weak.
Sediments are a major sink. Hydrothermal reactions are a major sink.Still difficult to quantify!
Pore Water Gradients in Marine Sediments
South Atlantic-Sayles (1979)
But if fluxes are real therewould be more solid phase Mgthan observed!
The long-term global carbon balance
2HCO3- + Ca2+ = CaCO3(s) + CO2(g) + H2O
CaCO3(s) + CO2(g) + H2O = 2HCO3- + Ca2+
H4SiO4 vs Mg in a “Black Smoker” at 21°N
Used to obtain end-member concentrations for 350°C vents
Weathering SusceptibilitiesMinerals Weather at Different Rates
Chemical Weathering and the Geological Carbon Cycle
1. CO2 is removed by weathering of silicate and carbonate rocks on land.2. The weathering products are transported to the ocean by rivers where they are removed to the sediments.3. When these sediments are subducted and metamorphosed at high T and P, 4. CO2 is returned to the atmosphere.
Ittekkot (2003) Science 301, 56
For more detail see Berner (2004) The Phanerozoic Carbon Cycle: CO2 and O2. Oxford Press, 150pp.
Mg
Alk
East Pacific Rise , from Von Damm et al., (1985)
East Pacific Rise, continued
SO4
350C vents have no Mg, SO4 or HCO3. What’s left is Cl, Na, Ca, K, Fe
Hydrothermal Vent Compositions – German and Von Damm (2004) Treatise on Geochemistry, Vol. 6, The Oceans and Marine Geochemistry, Elsevier