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1) Organic carbon produced through photosynthesis controls redox conditions in natural waters. Photosynthesis converts carbon dioxide and water into organic matter and oxygen using energy from the sun. (2) Respiration and decay reverse photosynthesis, producing carbon dioxide and using different electron acceptors as oxygen is depleted, including nitrate, ferric iron, sulfate, and eventually methanogenesis. (3) The succession of electron acceptors used maintains buffered redox zones in waters and sediments depending on the availability of each reactant.
1) Organic carbon produced through photosynthesis controls redox conditions in natural waters. Photosynthesis converts carbon dioxide and water into organic matter and oxygen using energy from the sun. (2) Respiration and decay reverse photosynthesis, producing carbon dioxide and using different electron acceptors as oxygen is depleted, including nitrate, ferric iron, sulfate, and eventually methanogenesis. (3) The succession of electron acceptors used maintains buffered redox zones in waters and sediments depending on the availability of each reactant.
1) Organic carbon produced through photosynthesis controls redox conditions in natural waters. Photosynthesis converts carbon dioxide and water into organic matter and oxygen using energy from the sun. (2) Respiration and decay reverse photosynthesis, producing carbon dioxide and using different electron acceptors as oxygen is depleted, including nitrate, ferric iron, sulfate, and eventually methanogenesis. (3) The succession of electron acceptors used maintains buffered redox zones in waters and sediments depending on the availability of each reactant.
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 .