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Acid Pollution of Natural Waters

Outline of Topics
Background
Acids and bases
pH ranges in the hydrosphere
Biological effects of acid pollution

Sources of Acid Pollution


Acid deposition
Acid mine drainage

Resisting Acidification

pH buffers
Dissolved inorganic carbon in natural waters
Measuring buffering capacity
Homogeneous and heterogeneous buffering

Acids and Bases

Lecture Questions
What is an acid? What is a base?
What is pH?
Explain the difference between strong and weak acids/bases.

pH Ranges in the Hydrosphere

pH of Natural Waters: Lakes

Sources of Acid Pollution

Questions
What pollutants cause acidification of natural waters, and how?
What human activities generate these pollutants?

SO2 and NOx emissions


Generated by fossil fuel combustion (SO2 especially by coal burning)
Atmospheric oxidation of SO2 leads to sulfuric acid and sulfate aerosol
Atmospheric oxidation of NO leads to nitric acid and nitrate aerosol
Acidification occurs during wet and dry deposition and due to spring
snowmelt

Acid mine drainage


Mining operations generate large quantities of mine waste
Products of the aqueous oxidation of exposed minerals (mostly FeS2) in
the waste leads to acidification of ground and surface water

Effects of Acidification on Aquatic Ecosystems

Acute effects
Interferes with osmoregulation
Mobilization of toxic metals (Al, Mg, Zn)

Chronic effects: reproduction problems


Lowers calcium levels in female fish, hinders ability to produce eggs
Fertilized fish eggs may develop abnormally
Frog and salamander eggs can be greatly affected by spring snowmelt

Aquatic ecosystem effects


Can result in decline and algal species diversity and biomass
May effect ecosystem productivity
May decrease decomposer populations, affecting nutrient cycling and
increasing DOM/POM levels

Effects of Acid Pollution on Terrestrial Ecosystems


Direct Effects
Damage to foliage

Effects on Soil

The nature of soil


Soil pH
Loss of nutrients and other metals
Loss of ability to retain nutrients

Acid Mine Drainage

Picture to the left shows acid mine


drainage in tar creek, OK (at a
superfund site)
Mining operations expose minerals and
mine waste to air and water
Acid mine drainage is mostly due to
the biologically-mediated oxidation of
pyrite, FeS2
Color is due to precipitation of oxidized
iron (eg as Fe(OH)3)

Mechanism of Pyrite Oxidation

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:

S22 14Fe3 8H 2O 2SO 24 14Fe 2 16H

The Fe3+ is regenerated by reaction with dissolved oxygen

The Fe3+ is a catalyst for the generation of acid mine drainage


This is the rate determining step of the entire process; it is an exothermic reaction

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:

Fe3 3H 2 O Fe(OH)3 (s) 3H

Iron Cycling Controls Rate of Acid Generation


S2-2

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.

Carbonate Chemistry in Natural Waters

Why is calcium bicarbonate, Ca(HCO3)2(aq), the dominant solute in most freshwaters


(so-called calcareous waters)?

Imagine a water body (lake, river, etc) in equilibrium with both calcite (the most common
carbonate mineral) and the atmosphere.

Overall process: heterogeneous reaction between an acid and a base

CO2 ( g ) CaCO3 ( s) H 2O(l ) Ca 2+ (aq) 2HCO3 (aq)


Dissolution Processes
H O

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

CaCO3 ( s ) 2 Ca 2+ CO32Dissolution/precipitation of calcite


(or another carbonate mineral)

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!

Water in equilibrium with atmospheric CO2 and CaCO3: pH = 8.3,


[HCO3-] = 1mM, [Ca2+] = 0.5mM (at 25oC).

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.

If it continues unchecked it can greatly affect calcifying


organisms.
These build shells of CaCO3
Their shells can start to dissolve if the oceans become too acidic.
Some scientists predict this could happen on a wide scale in 10-20
years if CO2 emissions go unchecked.

Resisting Acidification: Buffering Acid Pollution


What is a buffer?
A (pH) buffer is a solution that can absorb a large amount of
acid or base with a relatively small change in pH

How do they work?


Basically: added protons or hydroxide react with something
instead of just changing pH

Buffering in natural systems


Soils and natural waters are naturally buffered against pH
change (some more so than others)
It is possible to overwhelm temporarily or permanently the
buffering ability of a water body
The carbonate system is the most important buffering
mechanism in natural waters
Carbonate system: all forms of dissolved inorganic carbon (DIC)

Buffering in Natural Waters


Question
How are natural waters buffered against changes in pH?
Some background:
The ability to resist acidification: pH buffering
Soils and natural waters are naturally buffered against pH change
(some more so than others)
It is possible to overwhelm temporarily or permanently the
buffering ability of a water body
The carbonate system is the most important buffering
mechanism in natural waters.

The ability to buffer is quantified by the buffer index.


Determined from titration curves.
Next slide illustrates by showing the titration curve of a carbonate
salt

Quantitative Assessment: Buffer Intensity


2.5

Titration curve for 1L of


1mM carbonate solution

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

mmol added acid

2.5

3.0

3.5

Buffer Intensity, mmol L-1 pH-1

12

Carbonate Buffer Intensity (CT = 1mM)

Buffer Intensity (), mmol L-1 pH-1

10
bicarbonate
buffering

H+ buffering

carbonate & OHbuffering

0.1

0.01
2

pH

10

11

Resisting Acidification: Buffering Acid Pollution

Buffering of natural waters is often specified by measurements of its


alkalinity
Alkalinity: the amount of acid that must be added (per unit volume) to
reach a pH of 4.5 (the pH when all bicarbonate has been protonated)
In a carbonate-only system, alkalinity is determined largely by the
concentration of the dissolved inorganic carbon (DIC)

[alk ] [HCO3 ] 2[CO32 ] [OH ] [H ]

Typical values in natural waters are 1 mmol/L in other words, it


takes 1 mmol of protons to convert all the DIC in a 1L sample
completely to CO2(aq)
The above expression does not consider non-carbonate sources of
alkalinity
Alkalinity measurements typically only measure homogeneous
buffering ability of the natural water

Homogeneous Buffering of Natural Waters


Homogeneous buffering is the neutralization of added
acid/base by dissolved species
Mostly due to the bicarbonate buffer system:

HCO3 (aq ) H H 2CO 3 ( aq)

DIC (alkalinity) is about 1 mM in fresh water and about 2 mM in


marine water.
Borate species (75 M in seawater) provides approximately 10% of
the buffering ability in marine waters
Silicate is widespread in all natural waters (20 M in seawater,
100 M in rivers) and can be an important buffer in low-carbonate
freshwater

Heterogeneous Buffering of Natural Waters

Heterogeneous buffering is buffering due to the dissolution or


evolution/precipitation of a gas or a solid
Slower but more powerful than homogeneous buffering

Common mechanisms:
Evolution/dissolution of gaseous CO 2

HCO3 ( aq) H CO 2 ( g ) H 2O
Precipitation/dissolution of calcite mineral

CaCO3 ( s ) H Ca 2 ( aq) HCO3 ( aq)


Acid weathering of silicates (proton displacement) will occur over longer time
periods. It is primarily important when carbonate minerals have been
intensely weathered (ie, when they start disappearing).

Heterogeneous vs Homogeneous Buffering


Homogeneous is much faster
than heterogeneous buffering
Buffering due to silicate
weathering is slower than due
to calcite and CO2
dissolution/formation
Heterogeneous buffering
ultimately provides a greater
capacity to assimilate protons
(ie, neutralize added acid)
Neutralization of added acid by
carbonate minerals continues
until all dissolve and ultimately
generate CO2:
CaCO3 ( s ) 2H

CO 2 ( g ) Ca 2 + H 2O

Summary: Resisting Acidification

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

Silicate buffering can then occur


But it is slow, and silicate minerals weather too
Eventually transformed to quartz, which does not weather (or buffer) well.

Buffering of Soils (?)

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