Oxygen and Carbon in Lakes

1. How do temperature, thermal stratification and biological activity influence oxygen profiles in lakes? 2. What are the major chemical reactions involved in the inorganic carbon complex?

3. How is DIC related to pH?

6 CO2 + 6 H2O

C6H12O6 + 6 O2

Why care about oxygen in lakes?

Required for respiration

Toxic to anaerobic organisms

Influences chemical processes (Redox)

Why care about dissolved inorganic carbon (DIC)?

1. It influences pH

2. It determines the amount of inorganic carbon available for photosynthesis

3. Inorganic carbon complexes are major anions in fresh water

Oxygen flux:

O2

Diffusion

photosynthesis

O2

respiration

Respiration includes bacterial respiration associated with decomposition

Diffusion across the air-water boundary depends on the concentration gradient and turbulence

Turbulence increases the surface area of the water

With more surface area, more potential for diffusion

How much oxygen the water holds is determined by:

Henrys Law:

Cs = KP
Where: Cs = the saturation concentration of a gas K = the solubility constant P = partial pressure

Saturationthe amount of a gas that can be held by water in equilibrium with the atmosphere at a given temperature, pressure and salinity Subsaturationthe condition where the water holds less than the saturation concentration of a particular gas Supersaturationthe condition where the water holds more than the saturation concentration of a particular gas

Solubility of oxygen in pure water 16 14 12

Oxygen (mg/L)

10 8 6 4 2 0 0 10 20 30 40 50 Temperature (C)

Supersaturation occurs during periods of intense photosynthesis Can have flux of oxygen out of water (by diffusion) if water is supersaturated

Can result in strong changes in oxygen concentration in a 24 hour period

The distribution of oxygen in lakes is influenced by: Temperature

Mixing pattern

Productivity

Morphometry

Productivity Productiona flux of mass or energy over time.

Measured in mass/area/time (e.g. g/m2/day)

Primary productionthe increase of new organic matter created by photosynthesis

Lakes are classified based on productivity: Oligotrophic low productivity and clear water Eutrophic high productivity and green water

In oligotrophic lakes, oxygen concentrations are strongly influenced by temperature In eutrophic lakes, oxygen concentrations are modified by photosynthesis and decomposition

Wetzel 2001

Oligotrophic lakes often exhibit an orthograde oxygen curve during midsummer

Hypolimnion temperatures are colder, can hold more oxygen

Eutrophic lakes often exhibit a clinograde oxygen curve by midsummer

Decomposition in the hypolimnion depletes the oxygen

Meromictic lakes have extreme clinograde curves

Never any oxygen in the monimolimnion

Heterograde oxygen curve peak at an intermediate depth

Oxygen (m g/L) 0 0 2 4 6 8 10 12 14
0 0 2 4

Oxygen (m g/L) 6 8 10 12

10

Accumulation of algae at the thermocline

Depth (m)

10

Depth (m)

15

15

Accumulation of decomposing organisms at thermocline

20

20

25

25

30

Metalimnetic oxygen maximum

30

35

35

Metalimnetic oxygen minima

Morphometry
What are the volumes of the epilimnion and hypolimnion?

Dead organisms fall into the hypolimnion where they decompose This decomposition removes oxygen

All else being equal, the hypolimnion of a deeper lake will have more total oxygen because there is more water

Hence, the hypolimnion of a shallow lake will become anoxic faster

Lakes become anoxic from the bottom up:

Most fish cannot survive at oxygen concentrations < 2 mg/L

Winterkillsnow and ice block out sunlight. No photosynthesis but continued respiration

Summmerkillin late summer, macrophytes die and begin to decompose. Most common in shallow basins.

Oneida Lake, NY Surface Area = 207 km2 Maximum fetch = 33 km

0 0 5

22 August 1993

Te mpe r a t ur e ( C) 10 15 20 25 30

Oneida Lake is eutrophic, but does not stratify thermally.

Depth (m)

What do you expect the mid-summer oxygen profile to look like?

10

12

Flux of carbon dioxide (CO2)

CO2

Diffusion

photosynthesis respiration

CO2

Carbon dioxide not only dissolves in water, it reacts with it.

Inorganic carbon occurs in several forms in addition to CO2

Many plants and phytoplankton can only use CO2 for photosynthesis

There is normally much more carbon dioxide in water than expected by Henrys Law. --most lakes are supersaturated with CO2 --like oxygen, CO2 is less soluble in warm water

CO2 H2CO3

Carbon dioxide Carbonic acid

CO32HCO3Ca(HCO3)2 CaCO3 H+ OH-

Carbonate
Bicarbonate Calcium bicarbonate Calcium carbonate Hydrogen ion Hydroxyl ion

When carbon dioxide enters the water:

CO2 (air)

CO2 (dissolved) + H2O

Some of the dissolved CO2 hydrates (reacts with water) to from carbonic acid:

CO2 + H2O

H2CO3

Carbonic acid will dissociate:

H2CO3

HCO3- + H+

Forming bicarbonate and a free hydrogen ion

Bicarbonate further dissociates:

HCO3-

CO32- + H+

to carbonate and a free hydrogen ion

These reaction equations illustrate why the carbon cycle is tied to pH

Free H+ ions produce acidity

Free H+ ions will also react with free OH- ions (when available) to form water

Review: Measure acidity as concentration of H+

pH = - log [H+]
pH ranges from <1 to 14 7 = neutral < 7 = acidic (lots of H+ ions) > 7 = alkaline (lots of OH- ions)

CO2 input (produces H+, decreases pH, more acidic)

Carbonic Acid

Bicarbonate

Carbonate

CO2 + H2O

H2CO3

HCO3- + H+

CO32- +2 H+

CO2 removal by photosynthesis (removes H+, increases pH)

These reactions get a bit more complicated: Also have reactions that result in the formation of the hydroxyl ion

Bicarbonate

Carbonic acid

HCO3- + H2O
Carbonate

H2CO3 + OHBicarbonate

CO32- + H2O

HCO3- + OH-

Which form of carbon will dominate?

depends on the pH

Changes in pH can change the dominant form of carbon in water

If change the dominant form of carbon, can change the pH

Also get DIC from the watershed

Dissolution of limestone (calcium carbonate): CaCO3

Calcium bicarbonate (Ca(HCO3)2) is very soluble

Calcium carbonate is not, so forms a precipitate

At high pH (> ~8.5), calcium carbonate can reprecipitate due to high photosynthesis in the epilimnion Usually happens in late summer (warm temperatures, recall relationship between solubility and temperature)
Ca(HCO3)2 CaCO3 (Solid) + H2O + CO2

This precipitate can accumulate at lake edges, called marl

Can remain in suspension and cause the lakes to look milky, called whiting

Can coat macrophytes, make them look and feel crusty

http://earthobservatory.nasa.gov/Newsroom/NewImages/Images/seawifs_lake_mich_2001_tn.jpg

The Buffer System Lakes that have a lot of carbonate can resist changes in pH with the addition of acids

Ability to resist changes in pH with respect to the addition of acid is called Alkalinity or Acid neutralizing capacity-ANC

ANC is measured by titrating with acid until the pH changes to 4.5

The more acid needed to reach 4.5, the more buffered a lake is against changes in pH

Lakes in limestone regions have high buffering capacity and are therefore not as impacted by Acid Rain. Lakes on granite are highly impacted.

Terms to Know
pH DIC Henrys Law saturation supersaturation subsaturation solubility productivity/production oligotrophic eutrophic othograde clinograde heterograde anoxic/anoxia winterkill summerkill marl alkalinity/ANC