BIOGEOCHEMICAL ASPECTS OF AQUATIC ECOSYSTEM

Aquatic Ecology: lecture 4

Review
oxidation levels C(+IV): CO2, HCO3- , CO 32C(0) : C, CH2O C(-IV) : CH4 N(+V) : NO3N(+III): NO2N(0) : N2 N(-III) : NH3, NH4+, -NH2

oxidation1

What are the oxidation levels of the following elements? S: SO42-, Fe: Fe 2O3, Fe: FeO

Review
oxidation 1. Uptake of oxygen 2. Removal of hydrogen 3. Removal of an electron 1. Uptake of hydrogen 2. Removal of oxygen 3. Uptake of an electron
removal of hydrogen removal of electron (electron donor)

Oxidation2

reduction

H2S Fe 2+

S 2- + 2H+ Fe 3+ + e -

oxidation of organic substrate [CH2O]n + nH2O nCO 2 + 4ne - + 4nH+ ( electon donor )

Redox potential1

Availability of transferable electrons relative to the availability of electrons in hydrogen gas

Redox potential (Eernst equation) EH = E 0 + 2.3 [RT/nF] log[{ox}/{red}] E0: potential of reference (mV) R: gas constant(=81.987 cal/(deg.mol)) T: temperature (K) n: number of moles of electron transferred F: Faraday consatnt (=23061 cal/mole-volt) {ox}: oxidants {red}: reductants

Redox potential2

Eh: standardized to a pH=7 (E7) Eh decreases 58mV for each increase of one pH unit. Theoretical redox potential of water saturated with oxygen at pH=7 and 25C: 800mV Oxygen rich epilimnetic water 400-600mV Sediment -200mV

Redox potential3
400-600mV: aerobic oxidation O 2 + 4e - +4H+ 250mV: reduction of NO32NO 3 + 10e - + 12H + N 2 + 6H2O 225mV: manganic compounds to manganous compounds MnO 2 + 2e - + 4H+ Mn 2+ + 2H2O +100mV - -100mV: ferric to ferrous compounds Fe(OH) 3 + e - + 3H+ Fe 2+ + 2H2O -100mV - -200mV: sulfates to sulfides SO 42- + 8e - + 9H+ below -200mV CO 2 + 8e - + 8H+ HS - + 4H2O CH 4 + 2H2O 2H 2O

CO2 photosynthesis

CO2, CH4 efflux through plant vascular system

CH4

Carbon cycle in wetland

CO2 diffusion

precipitation

photosynthesis respiration

H2CO3 CO2 HCO3CO32outflow

POC DOC

respiration CO2 H2CO3 carbonate system

sulfate reduction fermentation DOC (ethanol, lactic acid)

metanogenisis

CH4

atmosphere

Nitrogen cycle

N2O NO2- anoxic denitrification

N2

N2-fixation

NO3NO2oxic nitrification N2O

phytoplankton zooplankton fish excretion NH4+ anoxia sediments

detritus

streams, rivers, rainfall

N2 O NO2NO3NO2N2 O

N2

Oxidation level

NH4+

What are the oxidation level of the above substances?

Depthwise distribution

NO3

epilimnion

NO3

NO2

thermocline

NH4

hypolimnion

NO2 NH4 oligotrophic lake

eutrophic lake

Nitrification denitrification
NO3

NH4

N2

oxic organic-N NH4 low O 2 <0.2mg/liter anoxic denitrification zone

diffusion

NO3 diffusion N2

Nitrogen cycle in wetland N2

N2 NH3 volatilization NH3 N2 fixation organic N inflow oxidized layer organic N SON NH4 nitrification
+

N2 N2 fixation algae NH4+ NO2NO3outflow

SON

NO2-

NO3diffusion NO3NO2-

organic N reduced layer

SON

NH4+

uptake by rooted plant

denitrification

N2O, N 2

Phosphorus cycle

steams, rivers

sewage

particulate-P in organic detritus PO4 erosion soluble organic-P anoxic O2 inorganic sediment

phytoplankton zooplankton fish

organic sediment

Sediment interaction

PO 43plant /microbial uptake inflow SOP participate organic P participate organic P PO43adsorption precipitation particulate inorganic P FePO 4 Ca 3(PO4)2
3-

SOP

PO 43diffusion

SOP

PO4

anaerobic release of P

uptake by rooted plant

average summer chlorophyll-a (m g/liter) 1000

Total phosphorusChlorophyll-a

100

10

0.1 1 10 100 1000 early spring TP mg/liter

Zooplankton excretion

many zooplankton phytoplankton

phytoplankton

few zooplankton continue to grow grow until depletion of P regulated by zooplankton

zooplankton excretion: 10% of body /day 50% phosphate

Vertical migration

daytime night time PO 43phosphorus cycle zooplanton migration

air polution, volcanoes, sea spray H2S sulfate emission SO 42atmospheric deposition

Sulfur cycle
SO 2

emission

sulfate oxidation S H2S

surface inflow SO 42-

sulfate oxidation organic S H2S S SO 42diffusion organic S reduced layer dimethyl sulfide (DMS) uptake by plants H2S S sulfate reduction SO 24 absorption clay

oxidized layer soil minerals

FeS 2, FeS

leaching