Outline of Topics
Background
Acids and bases
pH ranges in the hydrosphere
Biological effects of acid pollution
Resisting Acidification
pH buffers
Dissolved inorganic carbon in natural waters
Measuring buffering capacity
Homogeneous and heterogeneous buffering
Lecture Questions
What is an acid? What is a base?
What is pH?
Explain the difference between strong and weak acids/bases.
Questions
What pollutants cause acidification of natural waters, and how?
What human activities generate these pollutants?
Acute effects
Interferes with osmoregulation
Mobilization of toxic metals (Al, Mg, Zn)
Effects on Soil
Overall process
7
15
FeS2 ( s ) H 2O(l ) O 2 ( g ) Fe(OH)3 ( s ) 2H 2SO 4 (aq)
2
4
Direct oxidation of S22- by O2 is too slow; instead it is oxidized by something else, usually Fe3+ that is present naturally in the environment:
7
14Fe2 O 2 14H 14Fe3 7H 2O
2
Most acidity in the mine drainage is due to oxidation of disulfide anion to sulfuric acid, but some
is due to hydrolysis by FeIII, for example:
oxidation of disulfide
produces acidity
14 Fe3+
16 H +
14 Fe 2+
Thiobacillus Ferrooxidans
regeneration of Fe3+
14 H +
Oxidation of disulfide is catalyzed by Fe3+: regeneration of catalyst is necessary
Each cycle generates 2 protons of acidity
Abiotic oxidation of Fe2+ by O2 is fairly slow ( = 1000d)
Fe2+ oxidation is biologically mediated by bacteria who derive energy from the
reaction; they are acidophiles who thrive in low pH environments. Reaction is
106 times faster when they are present.
Imagine a water body (lake, river, etc) in equilibrium with both calcite (the most common
carbonate mineral) and the atmosphere.
CO 2 ( g ) 2 CO 2 ( aq)
Dissolution/evolution of
gaseous carbon dioxide
Hydration of CO2
CO 2 (aq ) H 2O H 2CO3 ( aq)
Dissolved carbon dioxide reacts
to give carbonic acid.
H O
Acid-Base Reaction
H 2CO3 ( aq) CO32- ( aq) 2HCO 3- ( aq)
Carbonic acid from the air reacts with
carbonate (a base) from mineral dissolution
to give bicarbonate!
Ocean Acidification
What is ocean acidificaton?
pH has decreased from 8.24 to 8.13 over the last 250 years.
Why?
Carbonate chemistry! Atmospheric CO2 has increased since 1750.
Some of the CO2 dissolves in the oceans and reacts with carbonate.
So what?
Represents an increase of almost 30% in H+ concentration.
Remember that pH is a logarithmic scale.
2.0
10
bicarbonate
buffer region
1.5
pH
buffer
intensity
1.0
6
0.5
4
0.0
2
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
12
10
bicarbonate
buffering
H+ buffering
0.1
0.01
2
pH
10
11
Common mechanisms:
Evolution/dissolution of gaseous CO 2
HCO3 ( aq) H CO 2 ( g ) H 2O
Precipitation/dissolution of calcite mineral
CO 2 ( g ) Ca 2 + H 2O
Carbonaceous waters
The carbonate system (ie, DIC, carbonate minerals, and carbon dioxide)
provides buffering in most natural water bodies
Carbonate buffering occurs whenever water is in contact with air and
with carbonate minerals
Homogeneous buffering due to DIC is the immediate response to
acidification
Heterogeneous buffering provides long-term buffering
Long-term acidification
Would eventually overwhelm the carbonate system
No more homogeneous/heterogeneous buffering involving the carbonate
system
All carbonate minerals would dissolve (weather)
Then all carbonate and bicarbonate would be transformed to carbonic acid
and CO2