Week 9 Greenhouse effect and the oceans

Learning Outcomes
At the end of this section, students should be able to:
 Explain the chemistry behind the greenhouse effect is and why only certain gases can
behave as greenhouse gases
 Discuss why the natural greenhouse effect is necessary
 Outline the factors causing the greenhouse effect
 Describe why the oceans absorb carbon dioxide
 Explain the role of marine plankton with respect to the greenhouse effect

Why only certain gases are greenhouse gases?

 A gas molecule absorbs radiation of a given wavelength only if the energy can be used to
increase the internal energy of the molecule.
 The internal energy is quantized in a series of electronic, vibrational and rotational
states.
 An increase in the internal energy is achieved by transition to a higher state.
 Electronic transitions (to higher electronic state) generally require UV radiation (<0.4
m)
 Vibrational transitions require near-IR radiation (0.7-20 m); corresponding to
wavelength range of peak terrestrial radiation
 Rotational transitions require far-IR radiation (>20 m)
 Little absorption takes place in the visible wavelength range (0.4-0.7 m)
 Gases that absorb in the  range 5-50 m, where most terrestrial radiation is emitted are
called greenhouse gases
 More generally, molecules that can acquire a charge asymmetry by stretching or flexing
(CO2, H2O, N2O, O3, hydrocarbons, etc) are greenhouse gases; those that cannot (N2, O2,
H2) are not
 The solar radiation received by earth is predominantly of short wavelength

Refer to Figure 9.1

Self-Test 9.1
Why is it that only certain gases are considered as greenhouse gases?
Figure 9.1 The steady-state radiation budget of the earth.

 30% returned to outer space through reflection by atmospheric gases

 Incoming radiation: 51% absorbed by ocean & land
19% absorbed by atmospheric gases
 Insolation absorbed by ocean & land – eventually lost to outer space as heat or long 
radiation
 Transmission of heat from ocean to atmosphere is via
(i) thermal conduction & convection, or by
(ii) surface evaporation of water & condensation in clouds
 Atmospheric gases retain a significant amount of solar heat
 Emission of this energy as heat warms the atmosphere
 Therefore steady-state temperature of the atmosphere is determined by its gas content
 An increase in gas levels in the atmosphere will mean an increase in the rate at which
solar energy is absorbed by the atmosphere
 This means that the increase in absorption of heat will temporarily exceed its loss to
outer space
 Once the new gases had absorbed their requisite amount of radiation, steady state
would be established but at a higher temperature – termed the GHE
 Without the GHE, the temperature of earth will be around -4oC
 Majority of long wavelength radiation emitted from the earth is in the range 4-80 m (IR
region) – see Figure 9.2

Self-Test 9.2
How does the atmosphere get warm?
Molecular vibrations and the greenhouse effect

Figure 9.2 Absorbance spectrum for infrared radiation. The amount of radiation emitted by
Earth is shown by the dashed line. The amount of radiation absorbed by the atmospheric
gases is shown by the solid line.

 Atmospheric water & CO2 can absorb throughout this range, except from 8-12 m
(“absorption gap”)
 O3 can absorb from 9-10 m but has insignificant contribution due to low concentration
 Despite this “absorption gap”, 71% of the IR emitted from the earth’s surface is
absorbed by one of the atmospheric gases & then is released as heat to the atmosphere
 Atmospheric temperatures would rise if the amount of IR-absorbing gases were
increased
 Name these gases:

Figure 9.3 Contributions to the greenhouse effect in the 1980’s

Self-Test 9.3
What sort of temperature would the earth experience without the greenhouse effect?
Figure 9.4 Total Annual Anthropogenic GHG Emissions by Groups of Gases 1970-2010 (IPCC
2014) [F- fluorinated; FOLU – Forestry & Other Land Use]

Factors causing greenhouse effect

Figure 9.5 Sources contributing to global warming

Absorption of Carbon Dioxide by the Ocean

The ocean has potential to absorb CO2 for 2 reasons:

(i) Gas solubility enhanced by reaction with carbonate:

CO32- + H2O + CO2  2HCO3-
Has large K value, that any CO2 entering the ocean is rapidly converted to HCO3-
(ii) Amount of carbon that can be absorbed by the ocean is greatly augmented by the sinking of
the biogenic POM & CaCO3 into the deep sea (“biological pump”)
As a result, the deep water is enriched in CO2 (i.e., supersaturated by ~30% w.r.t. NAEC).

 This disequilibrium is maintained by vertical density stratification that keeps

remineralized CO2 trapped in the cold, deep sea
 CO2 cannot escape to the atmosphere until thermohaline circulation returns the deep
water to the surface
 The efficiency of the “biological pump” can be determined by the type and abundance
of the phytoplankton at the surface
 Once at the surface, a water mass undergoes gas exchange with the atmosphere.
 The direction of exchange is determined by the difference in gas concentration at the
sea surface and the atmosphere
 IF the atmosphere has higher partial pressure of CO2, diffusion will be into the sea
surface
 Net gas uptake will continue until the sea surface acquires its NAEC or sinks below the
mixed layer
 Gas transfer rates are controlled by:
o Difference in partial pressures
o Water temperature
o Wind velocity, and
o Sea state
 Gas transfer across air-sea interface, tends to be slower than other processes that affect
the pp of CO2 in the surface waters
 Thus most surface waters are not in gaseous equilibrium with the atmosphere
 Equatorial waters tend to be supersaturated with CO2

https://www.youtube.com/watch?v=InX6gw5yJc8

 Warming at the surface will cause this water to become supersaturated with CO2 and
CaCO3.
 Thus upwelling: net source of CO2 to the atmosphere
 At high latitudes, horizontal advection supplies warm waters which become
undersaturated upon cooling & hence absorb CO2 from the atmosphere
 The size of this sink is increased by photosynthesis especially in subpolar waters where
nutrient concentrations are relatively high
 Despite regional variations, the ocean as a whole appears to be a net sink for CO2
 Models and calculations suggest that between 25 to 40% of the fossil fuel-produced CO2
has been absorbed by the oceans
 Due to upwelling, equatorial Pacific is the single largest source region; accounts for a
little over half of the CO2 escaping from the oceans
 Most of the absorbed gas is probably contained in the mixed layer
 Self-Test 9.4
How would greenhouse gas emissions harm ocean creatures?

 The limited penetration is the result of strong vertical density stratification at the
latitudes where most of the anthropogenic CO2 has been emitted
 The one exception is where CO2 has been transported to higher latitudes
 At such locations, the sinking of deep water can transport CO2 below the mixed layer
where only a small amount of CO2 would have been absorbed as its rate is limited by
wind transport and the relatively small area in which it occurs
 In contrast, anthropogenic C can be transported into the deep sea at all latitudes by
sinking in the form of biogenic detritus
 In this case, CO2 absorption capacity of the ocean will be limited by two factors: (i)
efficiency of recycling biogenic particles in surface waters, and (ii) nutrient availability
 Therefore on short time scales, most CO2 transfer to the deep ocean would be
accomplished by this “biological pump”
 For longer time scales, (>1000 years), ocean’s capacity to absorb CO2 will be greatly
augmented by dissolution of sedimentary CaCO3
 On these time scales, thermohaline circulation will transport CO2-rich surface waters
into the deep sea, bringing them into contact with the sediments
 Some of the CO2 will react with CaCO3 thereby lowering the partial pressure in the water
mass
 When the water mass returns to the surface it will be able to absorb more CO 2
 Thus a significant amount of time will have to elapse before the ocean realizes its
maximum C-absorbing potential
 Due to this considerable time lag in the ocean’s response to increased atmospheric CO 2
levels, the ratio of DIC (ocean:atmopshere of 60:1) is not likely to be reestablished as
CO2 emission rates are continuing to increase

Self-Test 9.5
Explain what the “biological pump” is.

Marine plankton and the GHE

 Large amounts of DMS (CH3)2S) produced by planktonic organisms
 There is considerable net flux of DMS from sea to air
 In atmosphere, gets oxidized to form sulfuric acid aerosols
 Together with dust & sea salt aerosols provide nuclei for condensation of atmospheric
water vapor into clouds and rain
 Increases in atmospheric CO2 levels means similar increases in oceanic surface waters
resulting in increased marine productivity
 This in turn leads to increased DMS production and hence more cloud formation, aided
by increased evaporation from ocean surface into a warm atmosphere already warmed
by the GHE
  Clouds reflect back solar radiation into outer space
 Whilst there is evidence that cirrus clouds allow UV radiation to pass through and trap
IR, it seems likely that in general the more clouds there are, the less solar radiation will
reach the ocean surface to warm it, i.e., DMS from marine plankton may act to alleviate
the GHE of rising CO2 levels
 Cloud cover is also more extensive over oceanic than continental areas

Summary

In this topic, you have learnt that:

 The greenhouse effect is due to the absorption of radiation by gases in the atmosphere
 Gases that absorb in the range 5-50m are greenhouse gases which correspond with
those that have charge asymmetry
 Anthropogenic sources of greenhouse gases have resulted in the increase in warming
 Oceans absorb CO2 due to its reaction with carbonate and to the biological pump
 Marine plankton produce DMS that eventually leads to formation of clouds which tends
to counter the greenhouse effect
Recommended Readings and Video Links
1. The Greenhouse Effect
https://www.ucar.edu/learn/1_3_1.htm
2. The Biological Pump (video)
https://www.youtube.com/watch?v=U03MUHFuO2o
3. The Biological Pump in a high CO2 world
http://www.int-res.com/articles/theme/m470p249.pdf