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Redox and natural waters

Organic carbon is the major control of redox conditions


- OC generated during photosynthesis
- Decomposed during respiration
Photosynthesis
Reaction that converts CO2 to organic matter and O2
- Process driven by energy from the sun
- ll oxygen !ould be consumed if no photosynthesis
- e"g" #volution of photosynthetic algae
Other elements involved besides C and O
- $itrogen% Phosphorous and trace elements
- Photosynthesis occurs until essential nutrient depleted
- generally phosphate is limiting nutrient
- occasionally nitrate is limiting
Redfield ratio&
- approximate composition of organic matter
C'()*2)+O''($')P'
,ore complex reaction better represents photosynthesis&
Reflects importance of P in C-O balance
- C-P molar ratio is '()
- $-P molar ratio is ')
- O-P molar ratio is '+.
'
Respiration and Decay
/hen oxygen present% O, decays in reverse of photosynthesis&
0y products include
- nitrate
- phosphate
- CO2 1 decreases p*
Note: most decay reactions microbially mediated
- e"g" apple in lvin
Oxidation of organic carbon essentially generates electrons&
2here are no free electrons% so there must be corresponding compound that is reduced
- e"g" oxygen reduced to *2O
Other dissolved solutes can oxidi3e the organic matter once oxygen is used up"
- each reactant occurs at lo!er pe levels
- each reaction has a different terminal electron acceptor&
4n other !ords&
- terminal electron acceptors are oxidi3ing agents 5they become reduced6"
2hese are very important reactions&
5'6 $itrate reduction&
- denitrification& final product is molecular nitrogen&
- represents conversion of essential nutrient to inert molecule
2
- reduction to $itrite&
- reduction to ammonia&
mmonia also released from decomposition of amino acids in proteins 5part of organic
matter6
mmonia can raise p* by generation of ammonium&
5'6 7erric iron 5and ,n6 reduction&
- more common in ground !ater !here metal oxides more concentrated" 8ittle in
surface !ater
- 7e
29
generally precipitates as carbonate or sulfide depending on solution
chemistry
5+6 :ulfate reduction
2he product is generally sulfide"
:ulfate-reducing bacteria generally can use only small molecules ; 2( C% e"g"
formate&
acetate&
lactate&
4mplications of these reactions&
- sulfides commonly toxic
- can be used by oxidi3ing bacteria for chemosynthesis
- sediment color change as mineral change from oxides to sulfides
- important for metal chemistry
< some adsorbed to surface are released
+
< others precipitate as sulfides
7ermentation and methanogenesis
- essentially the brea=do!n of complex carbohydrates to simpler molecules
- products often used by sulfate reducing bacteria
e"g"&
#ach group of reactions re>uires specific bacteria
0acteria derive energy from reactions
- essentially cataly3e brea=do!n of unstable to stable system
- reactions occur in approximate succession !ith depth in the sediment
:uccession&
?
Redox Buffering
pe can be buffered just li=e p*
- depends on the electron receptor present
- example of surface !ater
/ith oxygen presents various reactions could control pe&
#ach reaction =eeps pe at particularly value until all reactant consumed
/hen all oxygen consumed% sulfate reduction becomes important&
- pe obtains value for sulfate reduction reaction&
2he pe of !aters !ould be in one of the buffered ranges
- can be determined on basis of presence-absence of oxygen and sulfate
2he buffering of pore !ater !ould differ
- buffering could include solid phases
#xample profiles
- #>uatorial tlantic& slo! sedimentation% little organic matter
- $earshore $C& fast sedimentation% high organic matter
Lakes
4n temperate climates% la=es are vertically stratified&
- #pilimnion 1 !arm% lo! density !ater% !ell-mixed from !inds"
- ,etalimnion 5thermocline6 1 rapid decrease in 2 !ith depth
- *ypolimnion 1 uniformly cold !ater at base of la=e"
2he stratification is stable& there is little mixing bet!een *ypolimnion and epilimnion
t end of summer% epilimnion reaches temperatures same as or lo!er than hypolimnion"
- metalimnion brea=s do!n
- !ind completely mixes !ater column
- called 7all 2urnover
t temperatures @ ?AC% stable stratification occurs again 5e"g" ice6
B
/ith !arming temperatures in spring additional mixing occurs& :pring 2urnover
Dimictic& turn over t!ice a year
,onomictic& turn over once a year
Oxygen content 5redox conditions6 depend on turnover
- Oxygen in hypolimnion decreases as organic matter falls from surface 3one and
is oxidi3ed
- 2he amount of oxygen used depends on production on photic 3one
- 2he production depends on nutrients% usually phosphate
mount of nutrients determines la=e type&
- Oligotrophic& lo! supply of nutrients% !ater oxygenated at all depths
- #utrophic& high supply of nutrients% hypolimnion can be anaerobic"
Pollution can convert oligotrophic la=es to eutrophic ones 5e"g" 8a=e pop=a% 7lorida6
- Difficult to reverse process
- $utrients 5P6 buried in sediments because adsorbed to 7e-oxides
- /hen buried 7e-oxides reduced and form 7e 5446 and 7e-carbonates and sulfides
- Released P returns to la=e
he !cean
2he ocean continually turn over
- 0roec=erCs Dconveyer beltE
- $utrient distribution controlled by decay in !ater column and circulations
- 58a=es& nutrients mostly from input !ater6
Oxygen profiles controlled by settling organic matter
:illed basins
- Cariaco 0asin 1 Fene3uela
- :anich 4nlet 1 0"C"
- :anta 0arbara 0asin% California
8ittle deep !ater circulation
- oxygen rapidly depleted
- may go to sulfate reduction in !ater column
- :ediments affected
< 0lac= 5sulfides6
< 8aminated 5no bioturbation6
)
G
,echanisms controlling redox in sediments
- sedimentation rate
- organic matter content
:edimentation rate particularly important
- controls depth of diffusion from oxygenated !ater
- i"e" time in high pe !ater
"round #ater
Difficult to generali3e about controls on redox reactions
$onetheless% most important controls appear to be&
5'6 Oxygen content of recharge !ater
< enter through fractures 5sin=holes6 - aerobic
< percolate through soils 5carbon rich6 1
anaerobic
526 Distribution of reactive carbon
- a>uifers vary in amount of organic carbon
- D>ualityE of carbon variable% usually refractory
- refractory because a6 old% b6 subject to heat
5+6 Distribution of redox buffers
- a>uifers may have large amounts of ,n and 7e oxides
5?6 Circulation of ground !ater
- flo! rates% transit times% residence times
- longer residence times generally mean lo!er pe
.