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Dissolved

Gases

Important Gases
6 important gases are
dissolved in water systems
(Ex: Ocean)
Nitrogen
Oxygen
Carbon dioxide
Methane
Hydrogen sulde
Ammonia
All have important
funcGons, but dier in
behavior, origin

Air Provides Some Gases


Atmosphere has
enough nitrogen (78%),
oxygen (21%), and
carbon dioxide (0.03%)
to serve as primary
source
Others present only in
trace amounts in
atmosphere

Other Gas Sources


Methane - anaerobic
breakdown of plants/
animals
Hydrogen sulde -
chemical/bacterial
transformaGons
Ammonia - breakdown
of nitrogenous
materials by bacteria,
some animals

How much gas is dissolved in water


at any given Gme?

Dependent on several
factors:
Solubility factor
Pressure
Temperature
Salinity

Gases in Seawater

5-6

The solubility and saturaGon value for gases in sea water


increase as temperature and salinity decrease and as pressure
increases.

Solubility is the ability of something to be dissolved and go into soluGon.


SaturaGon value is the equilibrium amount of gas dissolved in water at an exisGng
temperature, salinity and pressure.
Water is undersaturated when under exisGng condiGons it has the capacity to dissolve more gas.
Gas content is below the saturaGon value.
Water is saturated when under exisGng condiGons it contains as much dissolved gas as it can hold
in equilibrium. Gas content is at saturaGon value.
Water is supersaturated when under exisGng condiGons it contains more dissolved gas than it can
hold in equilibrium. Gas content is above saturaGon value and excess gas will come out of soluGon.

The surface layer is usually saturated in atmospheric gases because of direct exchange with
the atmosphere.
Below the surface layer, gas content reects relaGve importance of respiraGon,
photosynthesis, decay and gases released from volcanic vents.

Solubility Factor
Not all gases dissolve
in water to same
extent
Some gases dissolve
very easily in water,
some dissolve very
li^le

Pressure (atmosphere)
Amount of gas
absorbed by water is
proporGonal to its
par6al pressure in the
atmosphere
AlGtude decreases
saturaGon level by
~1.4% per 100 m

Temperature
Solubility of gas in
water decreases as
temperature rises
GeneralizaGon - cold
water can hold more
gas in soluGon than
warm water
Nearly linear
relaGonship within
normal range of natural
water temperatures

Salinity
Presence of various
minerals in soluGon
lowers the solubility of
gases
Generally disregarded in
limnology because
freshwaters have
salinity near zero

Salinity
Oceans (salinity of
3.5%) have reduced gas
saturaGon values of
~18-20%
Saline pools/lakes can
have much higher
saliniGes (5-6 X ocean
values)
Important consideraGon
here for gas solubiliGes

Oxygen
Abundant and dissolves readily in water
Needed for respiraGon by organisms and for
complete breakdown of organic ma^er
RelaGvely easy to measure

Oxygen
1/4 as abundant as nitrogen in atmosphere, but
twice as soluble
Solubility of oxygen increases as temp. decreases,
salinity decreases, and pressure increases

Oxygen
Two sources for oxygen
in lakes
Atmosphere
Photosynthesis

Atmosphere
Diusion across air-water
interface and down into
water column
Years to reach depth of 5 m
Wind-driven waves and
currents distribute oxygen
to lower levels
Too much agitaGon can
prevent water from
becoming supersaturated

Photosynthesis
Most oxygen in standing
waters is by-product of
photosynthesis
Phytoplankton
contribute most
Rooted macrophytes,
a^ached algae, benthic
algae mats are chief
producers in shallow
lakes, lake margins

Photosynthesis: Your one-stop shop for


all of your oxygen needs!
Solar energy + 6CO2 + 6H2O C6H12O6 + 6O2

Happy Rays of
Sunshine

Carbon
Dioxide
(from air)

Oxygen (to
Carbohydrate
(plant material)

air)

Water (from ground)


Aquatic plants and phytoplankton (single


cell floating plants) release oxygen into
the water as a product of photosynthesis

Happy Rays of
Sunshine

CO2

O2

Phytoplankton (single cell plants) are the base of the aquatic food
web and provide most of the aquatic oxygen.

Submerged aquatic plants can provide shelter for young fish as


well as house an abundant food supply.

Habitat ClassicaGon Based on DO


ConcentraGon

> 2 mg/L

Normoxic

0.2 2 mg/L

Hypoxic

0 0.2 mg/L

Anoxic

Most fish need oxygen levels > 2.0 mg/L


AbioGc Factors That Aect DO


ConcentraGon
Temperature
Water Clarity
Current Velocity
(Flow)

Wind

Temperature

The warmer water is, the less DO it can


hold

100% Saturation Lavel

Think about opening a coke bo^le aher it sat a


few hours on the dash of your car.
100% DO Saturation

20
18
16
14
12
10
8
6
4
2
0

10



Temperature (C)

15

20

25

30

Excess DO evaporates into the atmosphere!


35

Wind
Stirs in atmospheric oxygen

Oxygen Can Diffuse Out of or Into the


Water Column

Atmosphere

Oxygen diffuses out of
water column

Oxygen diffuses into


water column

Oxygen > 100%


Saturation

Oxygen < 100%


Saturation

Water Column

Current Velocity
The faster water ows, the more atmospheric oxygen is
mixed into the water.

Water Clarity
Amount of Sunlight Reaching Plants

The muddier the water is, the less light reaches the plants!

Loss of Oxygen
Physical - change in temperature,
pressure
Biological - most important - respiraGon
by plants, animals, bacteria (decay
processes)
Other - methane bubbles rising from
sediments through water column

Daily variaGon in oxygen


concentraGons

O2 rises during day, declines at night


The greater the plant biomass, the greater the
magnitude of the cycle

Daily AquaGc Oxygen Cycle


Sunshine

Moonshine

Dissolved Oxygen

Moonshine

Midnight

Sunrise

Noon

Sunset

Midnight

Seasonal variaGon in oxygen


concentraGons

O2 high during summer growing season, low in


late-summer when plants die
May produce anoxia and die-os of animals
(summer kill)

Seasonal variaGon in oxygen


concentraGons

O2 also may be low during winter in ice-


covered lakes
Reduced light transmission, respiraGon only -
Winterkill of animals

5-6
Gases in Seawater: O
2

Oxygen tends to be abundant in the surface layer and deep


layer bo^om, but lowest in the pycnocline.
Surface layer is rich in oxygen because of photosynthesis and contact with the
atmosphere.
Oxygen minimum layer occurs at about 150 to 1500m below the surface and
coincides with the pycnocline.
Sinking food parGcles se^le into this layer and become suspended in place
because of the greater density of the water below.
The food draws large numbers of organisms which respire, consuming oxygen.
Decay of uneaten material consumes addiGonal oxygen.
Density dierence prevents mixing downward of oxygen-rich water from the
surface or upwards from the deep layer.
The deep layer is rich in oxygen because its water is derived from the cold surface
waters which sank (convect) to the bo^om. ConsumpGon is low because there are
fewer organisms and less decay consuming oxygen.
Anoxic waters contain no oxygen and are inhabited by anaerobic organisms
(bacteria).

Carbon Dioxide
CO2 increasing in concentraGon in atmosphere
High solubility - 200 X > O2
Follows solubility laws (pressure, temp.)
Many sources other than atmosphere:
rainwater, runo, groundwater, respiraGon,
decomposiGon in sediments

Oceanic carbon cycle


Solubility of CaCO3 dependent on pressure, temperature and mineral type

Solubility at larger depths and lower temperatures


Carbon Dioxide
CO2 behaves much dierently than other gases
once it dissolves in water
Exists in equilibrium with many addiGonal
forms of carbon

CO2 + H2O = H2CO3


Carbonic acid

H2CO3 = HCO3- + H+

bicarbonate

HCO3- = CO32- + H+

carbonate

CO2 + H2O = H2CO3


= HCO3- + H+
= CO32- + 2H+

Sensitive to changes in pH

Low pH - left side dominates

High pH - right side dominates

CO2 + H2O = H2CO3


= HCO3- + H+
= CO32- + 2H+

Addition of CO2 via respiration pushes



equilibrium to right and lowers pH

Removal of CO2 via photosynthesis pulls

equilibrium to left and raises pH

CO2+H2OH2CO3H++HCO3-2H++CO3-

An increase in CO2 causes an increase in H+


Sunshine

Moonshine

pH Level

Moonshine

pH

Midnight

Sunrise

Noon

Sunset

Midnight

CO2 + H2O = H2CO3


= HCO3- + H+
= CO32- + 2H+

Oceanic carbon cycle

Below saturation levels: 


- CaCO3 decreases due to dissolution
- increases due to settling

Depth at which CaCO3 is not preserved:








CCD (Carbonate Compensation Depth)

5-6

Gases in Seawater

Carbon dioxide is of major importance in controlling


acidity in the sea water.
Major sources of carbon dioxide are
respiraGon and decay.
Major sinks are photosynthesis and
construcGon of carbonate shells.
Carbon dioxide controls the acidity of sea
water.

A soluGon is acid if it has excess H+


(hydrogen) ions and is a base if it has
excess OH- (hydroxyl) ions.

Gases in Seawater

5-6

pH is related to the amount of CO2 dissolved in


water because it combines with the water to
produce carbonic acid which releases H+ ions.
CO2 + H2O H2CO3 H+ + HCO3- H+ +
CO3-2

H2CO3 is carbonic acid, HCO3- is the bicarbonate


ion and CO3-2 is the carbonate ion.
Changing the amount of CO2 shihs the reacGon
to either the right or leh of the equaGon.
Adding CO2 shihs the reacGon to the right and produces more H
+ ions making the water more acid.
Removing CO2 shihs the reacGon to the leh, combining H+ ions
with carbonate and bicarbonate ions reducing the acidity.

ConGnue
Dissolved CO2 in water acts as a buer, a
substance that prevents large shihs in pH.
DissoluGon of carbonate shells in deep water
results because cold water under great pressure
has a high saturaGon value for CO2 and the
addiGonal CO2 releases more H+ ions making the
water acid.
Warm, shallow water is under low pressure,
contains less dissolved CO2 and is less acidic.
Carbonate sediments are stable and do not
dissolve.

Take your Gme


h^p://vimeo.com/65512340

Relevance: Oceans play key role in carbon cycling


Ocean-CO2 = 50-60 *
atmospheric-CO2

Surface ocean pH is already 0.1 lower than


preindustrial values. How many magnitude the
increasing [H+] ??
By the end of century pH 0.3 0.4 units
lower

Phytoplankton (single cell plants) Acidification


Hypoxia in the Gulf of Mexico

Hypoxic

waters

Image from Jacques Descloitres, MODIS Land Rapid Response Team, NASA/GSFC,
January 2003

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