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Learning goals

Know the carbon atom


Where acid rain comes from

Carbonate equilibrium reactions

What is pH and how to calculate


Why important

Alkalinity
Chemical weathering

Learning goals

Climate controls on atmospheric CO2


Ocean acidification

What causes it
Why important
What does the future hold

CARBON

Shells: 2,4
Minimum oxidation
number is 4
Maximum oxidation
number is +4

Carbon Isotopes

C-12
C-13
C-14

Carbon forms

Graphite
Diamond
Buckmisterfullerene
Organic Matter
DOC
Particulate C

Types of carbon compounds

Gas phase

Organic

CO2, methane, volitale organic compounds


(VOCs)
Amino acids, DNA, etc

Water

Dissolved inorganic carbon (DIC)


Dissolved organic carbon (DOC)

DOC in GROUNDWATER

Less than 2 mg/L


Microbial decomposition
Adsorption
Precipitation as solid
> 100 mg/L in polluted ag systems
Increases geochemical weathering

ORGANICS in WATER

Solid phases (peat, anthracite, kerogen


Liquid fuels (LNAPL), solvents (DNAPL)
Gas phases
Dissolved organics (polar and non-polar)

CARBONATE SYSTEM

Carbonate species are necessary for all


biological systems
Aquatic photosynthesis is affected by the
presence of dissolved carbonate species.
Neutralization of strong acids and bases
Effects chemistry of many reactions
Effects global carbon dioxide content

DIPROTIC ACID SYSTEM

Carbonic Acid (H2CO3)

Bicarbonate (HCO3-)

Can donate two protons (a weak acid)


Can donate or accept one proton (can be
either an acid or a base

Carbonate (CO32-)

Can accept two protons (a base)

OPEN SYSTEM

Water is in equilibrium with the partial


pressure of CO2 in the atmosphere

Useful for chemistry of lakes, etc


Carbonate equilibrium reactions are thus
appropriate

PCO2=103.5yieldspH=5.66

Whatis103.5?316ppmCO2
WhatistodaysPCO2?~368ppm=103.43

pH=5.63

Ocean pH and atmospheric CO2

NATURAL ACIDS

Produced from C, N, and S gases in the


atmosphere
H2CO3 Carbonic Acid

HNO3 Nitric Acid

H2SO4 Sulfuric Acid

HCl

Hydrochloric Acid

pH of Global Precipitation

http://www.motherjones.com/tom-philpott/2015/01/noaa-globes-co

OPEN SYSTEM
Water is in equilibrium with the partial
pressure of CO2 in the atmosphere
Useful for chemistry of lakes, etc
Carbonate equilibrium reactions are thus
appropriate

CarbonicacidformswhenCO2dissolves

inandreactswithwater:

CO2(g)+H2O=H2CO3
MostdissolvedCO2occursasaqueousCO2
ratherthanH2CO3,butwewriteitascarbonic
acidforconvenience
Theequilibriumconstantforthereactionis:

Notewehaveagasinthereactionandusepartial
pressureratherthanactivity

Firstdissociation:
H2CO3=HCO3+H+

FIRST REACTION

Seconddissociation:
HCO3=CO32+H+

SECOND REACTION

Variables and Reactions Involved in Understanding


the Carbonate System
Gas
Dissociation of Dissociation Cations Measureequilibria carbonic acid
of water
ments
PCO2
[H2CO3]
[H+]
[Ca2+]
DIC
[HCO3]
[CO32]

[OH]

Alkalinity

Activity of Carbonate Species versus pH

CARBONATE SPECIES and pH

pH controls carbonate species

Increased CO2 (aq) increases H+ and


decreases carbonate ion
Thus increasing atmospheric CO2
increases CO2 (aq) and causes the water
system to become more acidic
However, natural waters have protecting,
buffering or alkalinity

ALKALINITY refers to
water's ability, or inability, to
neutralize acids.
The terms alkalinity and total
alkalinity are often used to
define the same thing.

Alkalinity is routinely measured in natural


water samples. By measuring only two
parameters, such as alkalinity and pH, the
remaining parameters that define the
carbonate chemistry of the solution (P CO2,
[HCO3], [CO32], [H2CO3]) can be
determined.

Totalalkalinitysumofthebases

inequivalentsthataretitratable
withstrongacid(theabilityofa
solutiontoneutralizestrongacids)

Baseswhichcanneutralizeacidsin

naturalwaters:HCO3,CO32,
B(OH)4,H3SiO4,HS,organicacids
(e.g.,acetateCH3COO,formate
HCOO)

Carbonate alkalinity

Alkalinity (HCO3) + 2(CO32)

Reason is that in most natural waters,


ionized silicic acid and organic acids are
present in only small concentrations
If pH around 7, then

Alkalinity HCO3

CLOSED CARBONATE
SYSTEM
Carbon dioxide is not lost or gained to the
atmosphere
Total carbonate species (CT) is constant
regardless of the pH of the system
Occurs when acid-base reactions much
faster than gas dissolution reactions
Equilibrium with atmosphere ignored

TOTAL CARBONATE SPECIES


(CT)

How does [CO32] respond to changes in Alk or DIC?


CT = [H2CO3*] + [ HCO3] + [CO32]
~ [ HCO3] + [CO32]

(an approximation)

Alk = [OH] + [HCO3] + 2[CO32] + [B(OH)4-] [H+]


~ [HCO3] + 2[CO32]

(a.k.a. carbonate alkalinity)

So (roughly):
[CO32] ~ Alk CT
CT , [CO32]

Alk , [CO32]

Diurnal changes in DO and pH


Whats up?

Photosynthesis is the biochemical process in which plants and algae


harness the energy of sunlight to produce food. Photosynthesis of
aquatic plants and algae in the water occurs when sunlight acts on the
chlorophyll in the plants. Here is the general equation:
6 H20 + 6 CO2 + light energy > C6H12O6 + 6 O2
Note that photosynthesis consumes dissolved CO2 and produces
dissolved oxygen (DO). we can see that a decrease in
dissolved CO2 results in a lower concentration of carbonic acid
(H2CO3), according to:
CO2 + H20 <=> H2CO3 (carbonic acid)
As the concentration of H2CO3 decreases so does the concentration
of H+, and thus the pH increases.

Cellular Respiration
Cellular respiration is the process in which organisms,
including plants, convert the chemical bonds of energy-rich molecules
such as glucose into energy usable for life processes.
The equation for the oxidation of glucose is:
C6H12O6 + 6 O2 > 6 H20 + 6 CO2 + energy
As CO2 increases, so does H+, and pH decreases.
Cellular respiration occurs in plants and algae during the day and night,
whereas photosynthesis occurs only during daylight.

LITHOSPHERE

Linkage between the atmosphere and the


crust
Igneous rocks + acid volatiles =
sedimentary rocks + salty oceans (eq 4.1)

IMPORTANCE OF ROCK
WEATHERING

[1] Bioavailability of nutrients that have no


gaseous form:

P, Ca, K, Fe

Forms the basis of biological diversity,


soil fertility, and agricultural productivity
The quality and quantity of lifeforms and
food is dependent on these nutrients

IMPORTANCE OF ROCK
WEATHERING
[2] Buffering of aquatic systems

-Maintains pH levels
-regulates availability of Al, Fe, PO4

Example: human blood.


-pH highly buffered
-similar to oceans

IMPORTANCE OF ROCK
WEATHERING
[3] Forms soil
[4] Regulates Earths climate
[5] Makes beach sand!

Rock
Cycle

Sedimentary Processes
1) Weathering & erosion
2) Transport &
3) deposition

4) Lithification

Weathering:
decomposition and
disintegration of rock
Product of weathering
is regolith or soil
Regolith or soil that is
transported is called
sediment
Movement of
sediment is called
erosion

Weathering Processes

Mechanical Weathering Disintegration of rock without change in


chemical composition

Chemical WeatheringDecomposition of rock as the result of


chemical attack. Chemical composition
changes.

Mechanical Weathering

Frost wedging
Alternate heating and
cooling

Decompression
causes jointing

Chemical Weathering Processes

Hydrolysis - reaction with water (new minerals


form)
Oxidation - reaction with oxygen (rock rusts)
Dissolution - rock is completely dissolved

Most chemical weathering processes are


promoted by carbonic acid:
H2O +CO2 = H2CO3 (carbonic acid)

CARBONIC ACID

Carbonic acid is produced in rainwater by


Reaction of the water with carbon dioxide
Gas in the atmosphere.

CARBONATE (DISSOLUTION)

All of the mineral is completely


Dissolved by the water.
Congruent weathering.

DEHYDRATION

Removal of water from a mineral.

HYDROLYSIS

H+ replaces an ion in the mineral.


Generally incongruent weathering.

HYDROLYSIS

Silicate rock + acid + water = base cations


+ alkalinity + clay + reactive silicate (SiO 2)

Hydrolysis
Feldspar + carbonic acid
+H2O
= kaolinite (clay)
+ dissolved K (potassium)
ion
+ dissolved bicarbonate
ion
+ dissolved silica
Clay is a soft,
platy mineral,
so the rock
disintegrates

HYDROLYSIS

Base cations are

Ca2+, Mg2+, Na+, K+

Alkalinity = HCO3-

Clay = kaolinite (Al2Si2O5(OH)4)

Si = H4SiO4; no charge, dimer, trimer

OXIDATION

Reaction of minerals with oxidation.


An ion in the mineral is oxidized.

Oxidation

Oxidation can affect any


iron bearing mineral, for
example, ferromagnesian
silicates which react to
form hematite and limonite

Oxidation of pyrite and other sulfide minerals forms


sulfuric acid which acidifies surface water and rain
Pyrite + oxygen + water = sulfuric acid + goethite
(iron sulfide)
(iron oxide)

Products of weathering

Clay minerals further decompose to aluminum


hydroxides and dissolved silica.

Removal of Atmospheric CO2

Slow chemical weathering of continental rocks balances


input of CO2 to atmosphere
Chemical weathering reactions important
Hydrolysis and Dissolution

Atmospheric CO2 Balance

Slow silicate rock weathering balances


long-term build-up of atmospheric CO2

On the 1-100 million-year time scale


Rate of chemical hydrolysis balance rate of
volcanic emissions of CO2

Neither rate was constant with time

Earths long term habitably requires only that


the two are reasonably well balanced

What Controls Weathering Reactions?

Chemical weathering influenced by


Temperature
Weathering rates double with 10C rise
Precipitation
H2O is required for hydrolysis
Increased rainfall increases soil saturation
H2O and CO2 form carbonic acid
Vegetation
Respiration in soils produces CO2
CO in soils 100-1000x higher than atmospheric CO
2
2

Climate Controls Chemical Weathering

Precipitation closely linked with


temperature
Warm air holds more water
than cold air
Vegetation closely linked with
precipitation and temperature
Plants need water
Rates of photosynthesis
correlated with temperature

Chemical Weathering: Earths Thermostat?

Chemical weathering can provide negative feedback that


reduces the intensity of climate warming

Chemical weathering can provide negative feedback that


reduces
the intensity
of climate cooling
Chemical
Weathering:
Earths Thermostat?

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