Biogeochemical processes of methane emission in addition to uptake Edward Hornibrook Bristo

Biogeochemical processes of methane emission in addition to uptake Edward Hornibrook Bristo www.phwiki.com

Biogeochemical processes of methane emission in addition to uptake Edward Hornibrook Bristo

Hansen, Ben, Executive Editor has reference to this Academic Journal, PHwiki organized this Journal Biogeochemical processes of methane emission in addition to uptake Edward Hornibrook Bristol Biogeochemistry Research Centre Department of Earth Sciences University of Bristol Outline 1. Methanogenesis & methanotrophy 2. Anaerobic C mineralisation in wetl in addition to s – uncertainties 3. Stable isotopes & methane 4. Current BBRC research Aless in addition to ro Volta (1776) “Combustible Air” Wolfe (1993)

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Universal Phylogenetic Tree of Life (16S & 18S RNA) Madigan et al (2003) C6H12O6 + 6 O2 6 CO2 + 6 H2O DG0 = -2870 kJ/mol C6H12O6 3 CO2 + 3 CH4 DG0 = -418 kJ/mol Methanogenic Substrates II. Methyl substrates Methanol, CH3OH Methylamine, CH3NH3+ Dimethylamine, (CH3)2NH2+ Trimethylamine, (CH3)3NH+ Methylmercaptan, CH3SH Dimethylsulphide, (CH3)2S

Diversity of methanogenic Archaea Methanobacteriales 5 Genera & 25 species; Substrates: mainly H2 + CO2, as long as mate; Methanosphaera + methanol, Methanothermus + reduction of S0 Methanococcales 5 Genera & 9 species; Substrates: mainly H2 + CO2, as long as mate; Methanococcus + pyruvate Methanomicrobiales 8 Genera & 22 species; Substrates: mainly H2 + CO2, as long as mate; Methanocorpusculum, Methanoculleus & Methanolacinia + alcohols Methanopyrales 1 Genera & 1 species: Methanopyrus; hyperthermophile (110°C) Substrates: H2 + CO2 Anaerobic Chain of Decay complex organics (cellulose, hemicellulose) homoacetogenic bacteria The importance of syntrophy 4 H2 + 2 HCO3- + H+ CH3COO- + 4 H2O -105 DG typical in situ abundance of reactants & products: VFAs 1 mM; HCO3- 5 mM; glucose 10 mM; CH4 0.6 atm; H2 10-4 atm Madigan et al (2003)

Methanotrophic Bacteria Aerobic methane oxidation (Proteobacteria) Low affinity methanotrophs (culturable) High affinity methanotrophs (no isolates to date) 2. Anaerobic methane oxidation Marine environments Methanogen/ sulphate-reducer consortia Substrates used by methylotrophs & methanotrophs Methane, CH4 Methanol, CH3OH Methylamine, CH3NH3+ Dimethylamine, (CH3)2NH2+ Trimethylamine, (CH3)3NH+ Tetramethylammonium, (CH3)4N+ Trimethylamine N-oxide, (CH3)3NO Trimethylsulphonium, (CH3)3S+ Formate, HCOO- Formamide, HCONH2 Carbon monoxide, CO Dimethyl ether, (CH3)2O Dimethyl ether, (CH3)2O Dimethyl carbonate, CH3OCOOCH3 Dimethyl sulphoxide, (CH3)2SO Dimethylsulphide, (CH3)2S Methanotrophic Bacteria Type I (Ribulose monophosphate C-assimilation pathway) Methylomonas, Methylomicrobium, Methylobacter, Methylococcus Type II (Serine C-assimilation pathway) Methylosinus, Methylocystis, Methylocella, Methylocapsa acidophiles isolated from peat bogs (Dedysh et al. 2000; 2002)

Anaerobic C Mineralisation in Wetl in addition to s Tenet 1: Methanogenesis is the terminal step in anaerobic decay of organic matter in freshwater wetl in addition to s. Tenet 2: In most freshwater systems, 2/3 of methanogenesis occurs via acetate fermentation in addition to 1/3 by CO2 reduction (H2). Vile et al. (2003). Global Biogeochem. Cycles 17(2), 1058. anaerobic C mineralisation in freshwater wetl in addition to s along a natural sulphate gradient 36 to 27% SO42- reduction vs. 1% methanogenesis fermentation of organic acids CO2 Bridgham et al. (1998). Ecology 79, 1545-1561. anaerobic C mineralization via methanogenesis: 0.5% in bogs in addition to <2% in fens Wieder & Lang (1988). Biogeochemistry 5, 221-242. anaerobic C mineralisation in West Virginian Sphagnum bog 38 to 64% SO42- reduction vs. 2.8 to 11.7% methanogenesis Decoupling of Terminal Carbon Mineralisation Pathway Hines et al. (2001). Geophys. Res. Lett. 28(22), 4251-4254. northern wetl in addition to s: CH4 derived mainly from CO2/H2 Acetate accumulation to high levels; ultimately degraded aerobically to CO2 contribution to high levels of DOC/ organic acids in ombrotrophic bogs Lansdown et al. (1992). Geochim. Cosmochim. Acta 56(9), 3493-3503. Kings Lake Bog, Washington State (ombrotrophic peatl in addition to ) CH4 derived mainly from CO2/H2; confirmed with 14C tracer experiments Avery et al. (1999) Nov Jan Feb Apr Jun Jul Nov Jan Feb Apr Jun Jul -45 -50 -55 -60 -65 d13C-CH4 (‰) soil (peat) temperature (°C) 20 15 10 5 0 Buck Hollow Bog (Michigan, USA) CR CR AF Duddleston et al. (2002). Geophys. Res. Lett. 28(22), 4251-4254. Turnagain Bog (ombrotrophic peatl in addition to , Anchorage Alaska; pH 4.6 to 5.1) 'Underachieving' northern wetl in addition to s SO42- H2S O2 VFAs CO2 acetate CH4 H2/CO2 CH4 What is the mechanism of acetate production (i) heterotrophic or (ii) autotrophic Possible causes: (i) temperature (ii) pH (iii) vegetation (iv) trophic level CH4 flux & VFAs (Christensen et al. 2003) d-values 0 + D, 13C, 15N, 18O, 34S (‰) - -90 -80 -70 -60 -50 -40 -30 -20 -10 0 +10 13C (‰) Stable Carbon Isotopes after Hoefs (1997) 0 5 10 15 20 25 Methane Flux (% of total) Natural Wetl in addition to s L in addition to fills Freshwater Gas Hydrates Oceans ~ -70±5‰ Ruminants Rice Paddies Termi Environment CO2-reduction d13C-CH4 d13C of CH4 with pathway confirmed with 14C tracers acetate d13C-CH4 Study coastal marine peatl in addition to rice paddy coastal marine freshwater estuary peatl in addition to (May) peatl in addition to (June) Alperin et al. (1992) Lansdown et al. (1992) Sugimoto & Wada (1993) Blair et al. (1993) Avery (1996) Avery et al. (1999) Avery et al. (1999) -62 ‰ -73 ± 4 ‰ -77 to -60 ‰ -62 to -58 ‰ -72 ± 2.2 ‰ -72 ± 1.3 ‰ -71 ± 1.3 ‰ -39 to -37 ‰ n/a -43 to -30 ‰ n/a -43 ± 10 ‰ -43.8 ± 12 ‰ -44.5 ± 5.4 ‰ -10 -20 20 10 0 -30 -30 -40 -50 -60 -70 -80 -90 (r2 = 0.64; n = 55) Sifton Bog: Hornibrook et al. (2000) DC = 86‰ 13C-CH4 (‰) 13C-CO2 (‰) DC = 54‰ DC = 40‰ AF CR intersection: -42.3‰ (CH4) -21.3‰ (CO2) Sugimoto & Wada (1993) C3 compost (soybean meal & rice straw): 13C = -26.5‰ dried rice plants: -39.7‰ -24.4‰ 13C (CH3-) 13C (COOH) dried rice plants: 13C (CH3COOH) = -32.1‰ kudzu (fresh green leaves): 13C (CH3COOH) = -32.9‰ kudzu: -42.9‰ -22.9‰ Hansen, Ben Daily Courier, The Executive Editor www.phwiki.com

-10 -20 20 10 0 -30 -30 -40 -50 -60 -70 -80 -90 13C-CH4 (‰) 13C-CO2 (‰) -40 Other Wetl in addition to s AF CR Hornibrook et al. (2000) -10 -20 20 10 0 -30 -30 -40 -50 -60 -70 -80 -90 13C-CH4 (‰) 13C-CO2 (‰) -40 Other Wetl in addition to s AF CR Aravena et

UK Sites determine CH4 pathway predominance using 14C tracers determine the prevalence of these d13C distributions in different classes of natural wetl in addition to s (SW Engl in addition to & Wales) determine relationship between pore water distribution in addition to d13C signature of CH4 emissions Ms. Helen Bowes (NERC Ph.D. student) Field sites 1.Cors Caron 2.Tor Royal, Dartmoor 3.Llyn Mire 4.Blanket bog, Elan Valley 5.Gors Lywd, Elan Valley 6.Crymlyn Bog 7.Wicken Fen 1 2 4 6 7 3 5 Summary The relative proportions of anaerobic processes in freshwater wetl in addition to s needs to be better characterised. How wide spread is decoupling of terminal stages of anaerobic C mineralisation in northern wetl in addition to s Models Better underst in addition to ing of anaerobic C flow needed to represent microbial activity accurately in process-based models Integrated models of gas abundance/ emission + accurate simulation of stable isotope signatures. What controls decoupling Can systems switch TCM processes Can stable isotope signatures of CH4 be used as an accurate proxy as long as biogeochemical in addition to physical processes

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