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 .