Methane CH4 Greenhouse gas (~20x more powerful than CO2)

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Methane CH4 Greenhouse gas (~20x more powerful than CO2) Formed biologically (methanogenesis) Huge reservoir as methane clathrate hydrate in cold soils and ocean bottom – stable structure at low T, high P

2x1016 kg of C in these deposits What happens if the oceans warm?? ‘Clathrate gun’ hyothesis – warming seas ‘melt’ these clathrates, CH4 released en masse to atmosphere…

Microbes and methane production Methanogenesis – Reduction of CO2 or other organics to form CH4 (also CH4 generation from special fermentative rxns) Only certain groups of Archaea do this, specifically with the Euryachaeota subdivision Called methanogens These organisms do not compete well with other anaerobes for e- donors, thus they thrive where other alternate e- acceptors have been consumed

Methane cycle

Microbial methane oxidation Organisms that can oxidize CH4 are Methanotrophs – mostly bacteria All aerobic methanotrophs use the enzyme methane monooxygenase (MMO) to turn CH4 into methanol (CH3OH) which is subsequently oxidized into formaldehyde (HCHO) on the way to CO2 Anaerobic methane oxidation – use SO42- as the e- acceptor – this was long recognized chemically, but only very recently have these microbes been more positively identified (though not cultured)

Phosphorus cycle P exists in several redox states (-3, 0, +3, +5) but only +5, PO43-, stable in water 1 microbe to date has been shown to grow on PO33- (phosphite, P3+) as a substrate P is a critical nutrient for growth, often a limiting nutrient in rivers and lakes Most P present as the mineral apatite (Ca5(PO4)3(F,Cl,OH)); also vivianite (Fe3(PO4)2*8H2O)

P sorption P strongly sorbs to FeOOH and AlOOH mineral surfaces as well as some clays P mobility thus inherently linked to Fe cycling P sorption to AlOOH is taken advantage of as a treatment of eutrophic lakes with excess P (alum is a form AlOOH) – AlOOH is not affected by microbial reduction as FeOOH can be.

P cycling linked to SRB-IRB-MRB activity Blue Green Algae blooms FeOOH PO43- Org C + SO42- H2S FeS2 Sulfate Reducers

Redox ‘Fronts’ Boundary between oxygen-rich (oxic) and more reduced (anoxic) waters Oxygen consumed by microbes which eat organic material When Oxygen is gone, there are species of microbes that can ‘breathe’ oxidized forms of iron, manganese, and sulfur Anoxic Oxic

St. Albans Bay Sediments Mn2+ + 2e- --> Mn0(Hg) H2O2 + 2e- + 2H+  2H2O O2 + 2e- + 2H+  H2O2 Fe3+ + 1e-  Fe2+ FeS(aq)

Results: Seasonal Work Sediments generally become more reduced as summer progresses Redox fronts move up and down in response to Temperature, wind, biological activity changes

Seasonal Phosphorus mobility Ascorbic acid extractions of Fe, Mn, and P from 10 sediment cores collected in summer 2004 show strong dependence between P and Mn or Fe Further, profiles show overall enrichment of all 3 parameters in upper sections of sediment Fe and Mn would be primarily in the form of Fe and Mn oxyhydroxide minerals  transformation of these minerals is key to P movement

P Loading and sediment deposition Constantly moving redox fronts affect Fe and Mn minerals, mobilize P and turn ideal profile into what we actually see…