Greenhouse Gas and

Ocean Acidification
A Case of Chemistry
in The Disturbed
Environment
Ocean acidification
• What is it?
• Why does it matter?
• What can be done?
What is ocean acidification (OA)?
“A reduction in ocean pH due to the uptake of anthropogenic CO2.”
(Hofmann et al. 2010)
What is ocean acidification (OA)?
“A reduction in ocean pH due to the uptake of anthropogenic CO2.”
(Hofmann et al. 2010)
Four key concepts:
1. The amount of CO2 in the atmosphere is increasing.
2. The chemistry of the ocean is dependent on the chemistry of the
atmosphere.
3. Water becomes acidic (lower pH) the more CO2 it contains.
4. Increased ocean acidity impacts marine organisms’ abilities to make and
keep their hard parts.
 Key concepts:
1. The amount of CO2 in the atmosphere is increasing

Mauna Loa , Hawaii (13,677 ft = 4169 m)

 Key concepts:
1. The amount of CO2 in the atmosphere is increasing

Currently 30%
higher than since
last 650,000 years

Mauna Loa , Hawaii (13,677 ft = 4169 m)

Key concepts:
2. The chemistry of the ocean is dependent on the chemistry of the atmosphere
Key concepts:
2. The chemistry of the ocean is dependent on the chemistry of the atmosphere
• Water naturally absorbs CO2 from the air
• The more atmospheric CO2, the more the ocean absorbs
Key concepts:
3. Water becomes more acidic the more CO2 it contains.
Key concepts:
3. Water becomes more acidic the more CO2 it contains.
CO2 reacts with H20 to produce:
bicarbonate (HCO3)
hydrogen (H)
Key concepts:
3. Water becomes more acidic the more CO2 it contains.
CO2 reacts with H20 to produce:
bicarbonate (HCO3)
hydrogen (H): makes ocean more acidic
Key concepts:
4. Increased ocean acidity affects marine organisms’ abilities to make and keep
their hard parts. Hard parts = calcium carbonate (CaCO3) shells, skeletons, etc.
Key concepts:
4. Increased ocean acidity affects marine organisms’ abilities to make and keep
their hard parts. Hard parts = calcium carbonate (CaCO3) shells, skeletons, etc.
Many marine organisms have CaCO3 hard parts
• They use their ATP (energy) to make their hard parts using calcium
(Ca) and carbonate (CO3) they get from the sea water
Key concepts:
4. Increased ocean acidity affects marine organisms’ abilities to make and keep
their hard parts. Hard parts = calcium carbonate (CaCO3) shells, skeletons, etc.
Many marine organisms have CaCO3 hard parts
• They use their ATP (energy) to make their hard parts using calcium
(Ca) and carbonate (CO3) they get from the sea water
BUT, hydrogen also naturally reacts with CO3
Key concepts:
4. Increased ocean acidity affects marine organisms’ abilities to make and keep
their hard parts. Hard parts = calcium carbonate (CaCO3) shells, skeletons, etc.
Many marine organisms have CaCO3 hard parts
• They use their ATP (energy) to make their hard parts using calcium
(Ca) and carbonate (CO3) they get from the sea water
BUT, hydrogen also naturally reacts with CO3
• The more acidic the ocean, the more CO3 reacts with hydrogen, and
the LESS CO3 left for marine organisms to convert into their hard parts
Key concepts:
4. Increased ocean acidity affects marine organisms’ abilities to make and keep
their hard parts. Hard parts = calcium carbonate (CaCO3) shells, skeletons, etc.
Many marine organisms have CaCO3 hard parts
• They use their ATP (energy) to make their hard parts using calcium
(Ca) and carbonate (CO3) they get from the sea water
BUT, hydrogen also naturally reacts with CO3
• The more acidic the ocean, the more CO3 reacts with hydrogen, and
the LESS CO3 left for marine organisms to convert into their hard parts

“Battle” for carbonate!

Key concepts:
4. Increased ocean acidity affects marine organisms’ abilities to make and keep
their hard parts. Hard parts = calcium carbonate (CaCO3) shells, skeletons, etc.
Many marine organisms have CaCO3 hard parts
• They use their ATP (energy) to make their hard parts using calcium
(Ca) and carbonate (CO3) they get from the sea water
BUT, hydrogen also naturally reacts with CO3
• The more acidic the ocean, the more CO3 reacts with hydrogen, and
the LESS CO3 left for marine organisms to convert into their hard parts

“Battle” for carbonate!

• Organisms must use more energy or
make less hard part material
Key concepts:
4. Increased ocean acidity affects marine organisms’ abilities to make and keep
their hard parts. Hard parts = calcium carbonate (CaCO3) shells, skeletons, etc.
Many marine organisms have CaCO3 hard parts
• They use their ATP (energy) to make their hard parts using calcium
(Ca) and carbonate (CO3) they get from the sea water
BUT, hydrogen also naturally reacts with CO3
• The more acidic the ocean, the more CO3 reacts with hydrogen, and
the LESS CO3 left for marine organisms to convert into their hard parts

“Battle” for carbonate!

• Organisms must use more energy or
make less hard part material
• Existing hard parts dissolve (chemical
reaction goes “the wrong way”)
Organism Calcium carbonate part

Stony coral Coral skeleton

Sea urchins Skeleton & test

Pteropods Shell

Coralline algae Component of fronds

Fish Ear bones and other structures

Ocean acidification
•Demonstration
1. Seawater absorbs CO2 and becomes
more acidic
2. When seawater is made acidic it
dissolves CaCO3 hard parts

Cuttlefish
Ocean acidification
• What is it?
• Why does it matter?
• Impacts on individual organisms
• Impacts on ecological communities
• What can be done?
 Ocean acidification: Impacts on individual marine organisms
Thinner, smaller and weaker shells in shellfish
• Especially larval stages, which already have thin shells

Mussels

Mussel
larva

Normal Really
acidic
Acidic
Gaylord et al. 2011
 Ocean acidification: Impacts on individual marine organisms
Thinner, smaller and weaker shells in shellfish
• Especially larval stages, which already have thin shells
• Fitness effect: Lower survival due to
• increased crushing and drilling by predators,
• increased risk of desiccation during low tide

Mussels

Mussel
larva

Normal Really
acidic
Acidic
Gaylord et al. 2011
 Ocean acidification: Impacts on individual marine organisms
Reduced fertilization of gametes in corals and other marine organisms
• Deformed flagellum in sperm that impacts their swimming

Natural range in the ocean

Albright et al. 2010

 Ocean acidification: Impacts on individual marine organisms
Reduced fertilization of gametes in corals and other marine organisms
• Deformed flagellum in sperm that impacts their swimming
• Fitness effect: lower population growth
Natural range in the ocean

Albright et al. 2010

 Ocean acidification: Impacts on individual marine organisms
Reduced hearing ability in anemone fish (clown fish) larvae

Simpson et al. 2011

 Ocean acidification: Impacts on individual marine organisms
Reduced hearing ability in anemone fish (clown fish) larvae

Normal

Simpson et al. 2011

 Ocean acidification: Impacts on individual marine organisms
Reduced hearing ability in anemone fish (clown fish) larvae

Normal Acidic

Simpson et al. 2011

 Ocean acidification: Impacts on individual marine organisms
Reduced hearing ability in anemone fish (clown fish) larvae
• Deformed morphology of CaCO3 fish ear bones (otoliths)?
• Disruption of acid-base balance in neuro-sensory system?

• Fitness effect: lower survival due to higher predation.

Normal Acidic

Simpson et al. 2011

Ocean acidification: Impacts on individual marine organisms
Non-calcifying marine algae:
 Ocean acidification: Impacts on individual marine organisms
Non-calcifying marine algae: Increased photosynthesis
• Lower pH means more dissolved CO2 for photosynthesis
Photosynthesis
Chen & Durbin 1994

Lots Little

Amount of dissolved carbon

 Ocean acidification: Impacts on individual marine organisms
Non-calcifying marine algae: Increased photosynthesis and growth
• Lower pH means more dissolved CO2 for photosynthesis to fuel growth
Photosynthesis

Growth
Chen & Durbin 1994

Lots Little Lots Little

Amount of dissolved carbon

 Ocean acidification: Impacts on individual marine organisms
Non-calcifying marine algae: Increased photosynthesis and growth
• Lower pH means more dissolved CO2 for photosynthesis to fuel growth
• Fitness effect: higher survival and pop’n growth
Photosynthesis

Growth
Chen & Durbin 1994

Lots Little Lots Little

Amount of dissolved carbon

Ocean acidification
• What is it?
• Why does it matter?
• Impacts on individual organisms
• Impacts on ecological communities
• What can be done?
Ocean acidification: Impacts on ecological communities
A natural experiment in the Mediterranean Sea:
• Volcanic CO2 vents (acidic water!)

pH

Far Close
Hall-Spencer et al 2008
Ocean acidification: Impacts on ecological communities
A natural experiment in the Mediterranean Sea:
• Volcanic CO2 vents (acidic water!)
• Shift to ecological community dominated by marine organisms
that do not have CaCO3 hard parts

pH

Calcareous algae
% Cover
Hall-Spencer et al 2008

Non-calcareous algae

Far Close
 Ocean acidification: Impacts on ecological communities
Tropical Oceans Predictions:
• Corals will become increasingly rare
• Algae will become more abundant
• Because coral reefs support so many animals,
biodiversity will decline

Hoegh-Guldberg et al. 2007

Ocean acidification: Impacts on ecological communities
• Predators that eat shelled prey may decline in numbers
• Case study: Salmon and pteropods ("sea butterflies")
 Ocean acidification: Impacts on ecological communities
• Predators that eat shelled prey may decline in numbers
• Case study: Salmon and pteropods ("sea butterflies")

Aydin et al. 2005; Comeau et al. 2009

 Ocean acidification: Impacts on ecological communities
• Predators that eat shelled prey may decline in numbers
• Case study: Salmon and pteropods ("sea butterflies")

Normal

Acidic

Aydin et al. 2005; Comeau et al. 2009

 Ocean acidification: Impacts on ecological communities
• Predators that eat shelled prey may decline in numbers
• Case study: Salmon and pteropods ("sea butterflies")

• Prediction: Decline in pteropod populations → Decline in pink

salmon body weight. Reduced salmon population size & viability.

Normal

Acidic

Aydin et al. 2005; Comeau et al. 2009

Ocean acidification
• What is it?
• Why does it matter?
• What can be done?
• Ecological options
• Societal options
What can be done? Ecological options to OA
• Marine species have 4 possible options:
1. Tolerate
2. Adapt
3. Move
4. Local extirpation, or total extinction
What can be done? Ecological options to OA
Tolerate the change through acclimatization
• Acclimatize = change phenotype (traits) in response to OA
What can be done? Ecological options to OA
Tolerate the change through acclimatization
• Acclimatize = change phenotype (traits) in response to OA
• Case study: Urchin fertilization
• Eggs have acid-protecting jelly coating.
• Make more!

Sea urchin
 What can be done? Ecological options to OA
Tolerate the change through acclimatization
• Acclimatize = change phenotype (traits) in response to OA
• Case study: Urchin fertilization
• Eggs have acid-protecting jelly coating.
• Make more!
Cool water
Warm water
Hot water
Sea urchin
Byrne 2011

Normal Acidic
 What can be done? Ecological options to OA
Tolerate the change through acclimatization
• Acclimatize = change phenotype (traits) in response to OA
• Case study: Urchin fertilization
• Eggs have acid-protecting jelly coating.
• Make more! Are there indirect costs?
Cool water
Warm water
Hot water
Sea urchin
Byrne 2011

Normal Acidic
What can be done? Ecological options to OA
Adapt (i.e., change genetically over many generations)
What can be done? Ecological options to OA
Adapt (i.e., change genetically over many generations)
• Species would need a fast generation time relative
to rate of pH change
What can be done? Ecological options to OA
Adapt (i.e., change genetically over many generations)
• Species would need a fast generation time relative
to rate of pH change
• The current rate of ocean acidification is
~100 times faster than has ever happened
for 10s of millions of years. Doh!
What can be done? Ecological options to OA
Adapt (i.e., change genetically over many generations)
• Species would need a fast generation time relative
to rate of pH change
• The current rate of ocean acidification is
~100 times faster than has ever happened
for 10s of millions of years. Doh!
Place your bet
Pteropods: mature in months
Fish: mature in years
What can be done? Ecological options to OA
Adapt (i.e., change genetically over many generations)
• Hypothesis: California species genetically adapted for OA!
 What can be done? Ecological options to OA
Adapt (i.e., change genetically over many generations)
• Hypothesis: California species genetically adapted for OA!
• Why? Due to upwelling, species are used low and
variable pH conditions

Hauri et al.
2009
 What can be done? Ecological options to OA
Adapt (i.e., change genetically over many generations)
• Hypothesis: California species genetically adapted for OA!
• Why? Due to upwelling, species are used low and
variable pH conditions

pH

Hauri et al.
2009
 What can be done? Ecological options to OA
Adapt (i.e., change genetically over many generations)
• Hypothesis: California species genetically adapted for OA!
• Why? Due to upwelling, species are used low and
variable pH conditions
• But, will conditions exceed natural tolerance?

pH

Hauri et al.
2009
What can be done? Ecological options to OA
3. Move (i.e., shift distribution to non-OA waters)
• In Theory, this is possible because
• Larger animals can swim away
• Larvae can drift away
What can be done? Ecological options to OA
3. Move (i.e., shift distribution to non-OA waters)
• In Theory, this is possible because
• Larger animals can swim away
• Larvae can drift away
• BUT, need to stay within physiological limits
What can be done? Ecological options to OA
4. Local extirpation, or total extinction
• A distinct possibility if ocean acidification continues
 What can be done? Ecological options to OA
4. Local extirpation, or total extinction
• A distinct possibility if ocean acidification continues

First
modern
corals

Veron 2008 Million years ago Present

 What can be done? Ecological options to OA
4. Local extirpation, or total extinction
• A distinct possibility if ocean acidification continues

High Earth’s two most recent mass extinction events

coral Both associated with high CO2 levels
growth

First
modern
corals

Veron 2008 Million years ago Present

Ocean acidification
• What is it?
• Why does it matter?
• What can be done?
• Ecological options
• Societal options
What can be done? Societal options to OA
• #1 best action: Reduce fossil fuel emissions
• Support policies to reduce carbon emissions
• Reduce personal carbon footprint
 What can be done? Societal options to OA
• Think globally, act locally
• Freshwater and acidic soils → lower ocean pH

1. Mitigate run-off and erosion

• Riparian buffers, wetlands, etc.

2. Conserve natural pH buffering of coastal soils

• Return crushed old shells (e.g., clams)

Green et al. 2009; Kelly et al. 2011

What can be done? Societal options to OA
• Support marine conservation
• Biodiversity can help marine ecosystems be resilient
to stressful conditions
 Culture larvae under differing
CO2 conditions
Sea urchin larvae

Each bucket
represents a different
CO2 treatment

Dr. Pauline Yu
(UCSB)
ANTARCTIC RESEARCH ON OCEAN ACIDIFICAITON
(Hofmann Lab research, UCSB)
Ocean acidification: So much more to learn

Broadest field study on ocean

acidification to date

Hofmann et al. 2011

 Effects on oceanic chemistry
• Pre-industrial atmospheric [CO2]: 280 ppm
• Today atmospheric [CO2]: 380 ppm
CO2 obeys Henry’s law:
 [CO2](atmosphere)   [CO2](surface oceans)

• Dissolution of CO2 into seawater releases

hydrogen ions and therefore causes ocean
acidification
 In the past 200 years the oceans absorbed 50% of
CO2 emitted by human activities (>500 Gt C02)
 pH decrease of 0,1 units since pre-industrial times
 Effects on oceanic chemistry
Oceanic absorption of atmospheric CO2: relevant processes
Effects on oceanic chemistry
• pH range of seawater:
8,2 ± 0,3 (today)
• Relative proportions
of the 3 main
inorganic forms of
CO2 dissolved in
seawater:
- CO2 (aq) (including
H2CO3): 1%
- HCO3-: 91%
- CO32-: 8%
Effects on calcium carbonate and saturation
horizons
• Solubility of CaCO3  temperature, pressure (depth):
increasing solubility by decreasing temperature and
increasing depth
 Result of these variables: development of natural
boundary in seawater called “saturation horizon”
• Dissolution of CO2 decreases [CO32-], because carbonate
ions react with protons to become bicarbonate (HCO3-)

Equilibrium shifts to the right

(Dissolution)
 Effects on calcium carbonate and
saturation horizons
• Increasing CO2 levels (and resultant lower pH) of
seawater decreases the saturation state of CaCO3
and raises the saturation horizon closer to the
surface
• Two main forms of calcium carbonate: aragonite and
calcite
Aragonite Calcite

Structure orthorhombic trigonal

Solubility high low
Calcifying Corals, Foraminifera, macroalgae,
species pterods, coccolithophores,
macroalgae crustacea
 Saturation horizon of
calcite and aragonite

• Aragonite SH nearer the

surface of the oceans
because higher solubility
than calcite

• Calcifying organisms
producing aragonite form of
CaCO3 are more
vulnerable to changes in
ocean acidity
 Ocean acidification vs. chemistry of
nutrients and toxins
• Metals exist in two forms in seawater: complex
and free dissolved
• pH
- generally increases the proportion of free
dissolved forms (most toxic forms)
- release of bound metals from the sediment to
the water column
- effects on nutrient speciation (phosphate,
ammonia, iron, silicate)
 Ocean acidification: past and future
• Ocean acidification is
essential an irreversible
process during our
lifetimes
• Fastest natural change in
atmospheric CO2 at the
end of the recent ice age:
Δ[CO2]= +80 ppm in 6000
years
Current change occur
100 folder stronger
Changes in ocean pH are outside the range of natural
variability  They could have a substantial affect on biological
processes in the surface oceans
 Source of Presentation
• A sample lecture on ocean acidification at
the undergraduate level, provided by Dr.
Crow White.
http://oceanacidification.msi.ucsb.edu/reso
urces/educators/CrowWhite_OA_Lecture.
ppt/view
• And other websources related to Ocean
Acidification