Mineral surface area, reactive metals and the saturation of mineral-associated carbon

What limits how much organic carbon minerals can hold: specific surface area, reactive iron, aluminium and calcium, a layered binding structure and a finite capacity, plus the processes that release bound carbon.

Boundary: where this process starts

Starts with: Mineral surface area sets binding sites: smectite about 600-800 m2/g, ferrihydrite 200-700, kaolinite 5-20

Boundary: where it ends

Ends after: Mineral-associated carbon turns over in centuries to millennia, versus years to decades for particulate organic matter; Released dissolved organic carbon re-adsorbs on fresh surfaces deeper in the profile, so mineral subsoil acts as a filter

PARTICIPANTSRESOURCESMineralsurfacesIron oxidesDissolvedorganic matterAluminiumoxidesClay mineralsOtherparticipantsCarbonIron oxidesClay mineralsDissolvedorganic carbonAluminiumImpact +3 of 5. Click for details and evidence.Impact +3 of 5. Click for details and evidence.Impact +3 of 5. Click for details and evidence.Impact +3 of 5. Click for details and evidence.Impact +3 of 5. Click for details and evidence.Impact +3 of 5. Click for details and evidence.Impact +4 of 5. Click for details and evidence.Impact +4 of 5. Click for details and evidence.Impact +4 of 5. Click for details and evidence.Impact -3 of 5. Click for details and evidence.Impact -3 of 5. Click for details and evidence.Impact +3 of 5. Click for details and evidence.Impact +3 of 5. Click for details and evidence.Impact +2 of 5. Click for details and evidence.Impact +3 of 5. Click for details and evidence.↻ balances · moderate · 0.3 Released carbon Mineral surface area sets binding sites: smectite about 600-800 m2/g, ferrihydrite 200-700, kaolinite 5-20: uses Iron oxidesMineral surface area sets binding sites: smectite about 600-800 m2/g, ferrihydrite 200-700, kaolinite 5-20: uses Clay mineralsOrganic carbon on mineral surfaces clusters near a monolayer-equivalent loading of 0.5-1.0 mg C per m2: uses CarbonIn acidic humid soils reactive Fe and Al phases (short-range-order oxides, Al-humus complexes) dominate retention by ligand exchange, and radiocarbon turnover times correlate with their content: uses CarbonIn acidic humid soils reactive Fe and Al phases (short-range-order oxides, Al-humus complexes) dominate retention by ligand exchange, and radiocarbon turnover times correlate with their content: uses Iron oxidesIn acidic humid soils reactive Fe and Al phases (short-range-order oxides, Al-humus complexes) dominate retention by ligand exchange, and radiocarbon turnover times correlate with their content: uses AluminiumIn neutral to alkaline soils exchangeable calcium and clay matter more than clay content alone, while reactive Al and Fe explain most variation in acidic soils: uses CarbonIn neutral to alkaline soils exchangeable calcium and clay matter more than clay content alone, while reactive Al and Fe explain most variation in acidic soils: uses Clay mineralsZonal structure: a strongly bound nitrogen-rich contact zone, a hydrophobic zone, and an outer kinetic zone that exchanges with solution in days to weeks: uses CarbonSaturation: the mineral-bound pool approaches a ceiling set by clay plus silt and reactive metals, so extra inputs accumulate as particulate organic matter or are respired: uses CarbonSaturation: the mineral-bound pool approaches a ceiling set by clay plus silt and reactive metals, so extra inputs accumulate as particulate organic matter or are respired: uses Clay mineralsMineral-associated carbon turns over in centuries to millennia, versus years to decades for particulate organic matter: uses CarbonRoot exudates such as oxalic acid dissolve Fe-bound carbon: in experiments oxalic acid released mineral-bound carbon and raised microbial decomposition: makes CarbonmakesRoot exudates such as oxalic acid dissolve Fe-bound carbon: in experiments oxalic acid released mineral-bound carbon and raised microbial decomposition: uses up Iron oxidesuses upWet-soil iron reduction dissolves Fe-organic associations and releases dissolved organic carbon; elevated moisture released protected carbon: uses up Iron oxidesuses upWet-soil iron reduction dissolves Fe-organic associations and releases dissolved organic carbon; elevated moisture released protected carbon: makes Dissolved organic carbonmakesReleased dissolved organic carbon re-adsorbs on fresh surfaces deeper in the profile, so mineral subsoil acts as a filter: uses Iron oxidesReleased dissolved organic carbon re-adsorbs on fresh surfaces deeper in the profile, so mineral subsoil acts as a filter: uses up Dissolved organic carbonuses upprovide binding sites byareaIron oxides: provide binding sites by areaprovide binding sites byareaClay minerals: provide binding sites by areaclusters at monolayerloadingCarbon: clusters at monolayer loadingturnover linked toreactive metalsCarbon: turnover linked to reactive metalsretain carbon by ligandexchangeIron oxides: retain carbon by ligand exchangeretains carbon by ligandexchangeAluminium: retains carbon by ligand exchangeretained more by calciumCarbon: retained more by calciummatter more than claycontent aloneClay minerals: matter more than clay content aloneheld in strongly boundcontact zoneCarbon: held in strongly bound contact zonesaturates themineral-bound poolCarbon: saturates the mineral-bound poolsets the saturationceilingClay minerals: sets the saturation ceilingturns over overcenturiesCarbon: turns over over centuriesreleased, boostingdecompositionCarbon: released, boosting decompositiondissolved, releasingbound carbonIron oxides: dissolved, releasing bound carbonreduced and dissolved inwet soilIron oxides: reduced and dissolved in wet soilreleased from Fe-organicbondsDissolved organic carbon: released from Fe-organic bondsfresh surfaces adsorbcarbonIron oxides: fresh surfaces adsorb carbonre-adsorbs deeper in theprofileDissolved organic carbon: re-adsorbs deeper in the profileStart: Mineral surfacearea, reactive metalsand the saturation …STARTStart: Mineral surface area, reactive metals and the saturation of mineral-associated carbonEnd: Mineral surfacearea, reactive metalsand the saturation …ENDEnd: Mineral surface area, reactive metals and the saturation of mineral-associated carbonMineral surface areasets binding sites:smectite about 600-8…📄1Mineral surface area sets binding sites: smectite about 600-800 m2/g, ferrihydrite 200-700, kaolinite 5-20Organic carbon onmineral surfacesclusters near…👍1📄1Organic carbon on mineral surfaces clusters near a monolayer-equivalent loading of 0.5-1.0 mg C per m2In acidic humid soilsreactive Fe and Alphas…📄1In acidic humid soils reactive Fe and Al phases (short-range-order oxides, Al-humus complexes) dominate retention by ligand exchange, and radiocarbon turnover times correlate with their contentIn neutral to alkalinesoils exchangeablecalcium and clay matt…📄1In neutral to alkaline soils exchangeable calcium and clay matter more than clay content alone, while reactive Al and Fe explain most variation in acidic soilsZonal structure: astrongly boundnitrogen-rich conta…📄1Zonal structure: a strongly bound nitrogen-rich contact zone, a hydrophobic zone, and an outer kinetic zone that exchanges with solution in days to weeksSaturation: themineral-bound poolapproaches a ceili…📄1Saturation: the mineral-bound pool approaches a ceiling set by clay plus silt and reactive metals, so extra inputs accumulate as particulate organic matter or are respiredMineral-associatedcarbon turns over incenturies to millenni…👍1📄1Mineral-associated carbon turns over in centuries to millennia, versus years to decades for particulate organic matterRoot exudates such asoxalic acid dissolveFe-bound carbon: …📄1 ↗1Root exudates such as oxalic acid dissolve Fe-bound carbon: in experiments oxalic acid released mineral-bound carbon and raised microbial decompositionWet-soil iron reductiondissolves Fe-organicassociations a…📄1Wet-soil iron reduction dissolves Fe-organic associations and releases dissolved organic carbon; elevated moisture released protected carbonReleased dissolvedorganic carbonre-adsorbs on fre…📄1Released dissolved organic carbon re-adsorbs on fresh surfaces deeper in the profile, so mineral subsoil acts as a filter
Line thickness = size of impact (1 to 5)% on a line = chance a fork takes that branch📄 = pieces of evidence on a stepNegative effectLoops backHypothesisResource used up (arrow into the step)Resource used, not used upResource made or released (arrow out of the step)
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Mineral surface area sets binding sites: smectite about 600-800 m2/g, ferrihydrite 200-700, kaolinite 5-20
Evidence (1) · added by Fern-C
  • Brady & Weil, The Nature and Properties of Soils, 15th ed., ch. 8; Cornell & Schwertmann 2003, The Iron Oxides, Wiley-VCH: Specific surface of smectite is 600-800 m2/g, of kaolinite 5-20 m2/g, and of ferrihydrite several hundred m2/g. (confidence 0.7)
Organic carbon on mineral surfaces clusters near a monolayer-equivalent loading of 0.5-1.0 mg C per m2
Evidence (1) · added by Fern-C
  • Mayer 1994, Geochimica et Cosmochimica Acta 58:1271-1284, Surface area control of organic carbon accumulation in continental shelf sediments: Most sedimentary organic carbon sits at 0.5-1.0 mg C per m2 of mineral surface, a monolayer-equivalent level (marine sediments; soils likely similar but less tested). (confidence 0.65)
In acidic humid soils reactive Fe and Al phases (short-range-order oxides, Al-humus complexes) dominate retention by ligand exchange, and radiocarbon turnover times correlate with their content
Evidence (1) · added by Fern-C
  • Torn, Trumbore, Chadwick, Vitousek & Hendricks 1997, Nature 389:170-173; Kramer & Chadwick 2018, Nature Climate Change 8:1104-1108: Across Hawaiian soils the 14C-derived turnover of soil carbon tracked short-range-order mineral content; reactive minerals control carbon retention in humid climates. (confidence 0.75)
In neutral to alkaline soils exchangeable calcium and clay matter more than clay content alone, while reactive Al and Fe explain most variation in acidic soils
Evidence (1) · added by Fern-C
  • Rasmussen et al. 2018, Biogeochemistry 137:297-306, Beyond clay: Exchangeable Ca and reactive metals predicted soil carbon better than clay alone in a multi-site analysis. (confidence 0.7)
Zonal structure: a strongly bound nitrogen-rich contact zone, a hydrophobic zone, and an outer kinetic zone that exchanges with solution in days to weeks
Evidence (1) · added by Fern-C
  • Kleber, Sollins & Sutton 2007, Biogeochemistry 85:9-24: Proposed contact, hydrophobic and kinetic zones with decreasing binding strength outward. (confidence 0.8)
Saturation: the mineral-bound pool approaches a ceiling set by clay plus silt and reactive metals, so extra inputs accumulate as particulate organic matter or are respired
Evidence (1) · added by Fern-C
  • Six, Conant, Paul & Paustian 2002, Plant and Soil 241:155-176; Hassink 1997, Plant and Soil 191:77-87: Soils have a finite capacity to stabilise carbon in the fine fraction; inputs beyond it do not raise the protected pool. (confidence 0.7)
Mineral-associated carbon turns over in centuries to millennia, versus years to decades for particulate organic matter
Evidence (1) · added by Fern-C
  • Trumbore 2000, Ecological Applications 10:399-411, Age of soil organic matter and soil respiration: Radiocarbon shows mineral-protected fractions have mean residence times of hundreds to thousands of years. (confidence 0.8)
Root exudates such as oxalic acid dissolve Fe-bound carbon: in experiments oxalic acid released mineral-bound carbon and raised microbial decomposition
Evidence (1) · added by Fern-C
  • Keiluweit et al. 2015, Nature Climate Change 5:588-595, Mineral protection of soil carbon counteracted by root exudates: Oxalic acid mobilised mineral-associated carbon and stimulated its decomposition in incubations. (confidence 0.8)
Wet-soil iron reduction dissolves Fe-organic associations and releases dissolved organic carbon; elevated moisture released protected carbon
Evidence (1) · added by Fern-C
  • Huang & Hall 2017, Nature Communications 8:1774, Elevated moisture stimulates carbon loss from mineral soils by releasing protected organic matter: Increased moisture raised carbon loss via release of mineral-protected organic matter linked to iron reduction. (confidence 0.65)
Released dissolved organic carbon re-adsorbs on fresh surfaces deeper in the profile, so mineral subsoil acts as a filter
Evidence (1) · added by Fern-C
  • Kaiser & Guggenberger 2000, Organic Geochemistry 31:711-725: Sorption of dissolved organic matter to subsoil minerals removes much of it from percolating water. (confidence 0.75)