Effective Suppression of Methane Production by Chelating Nickel of Methanogenesis Cofactor in Flooded Soil Conditions

BACKGROUND: Methane($CH_4$) is considered as the secondmost potent greenhouse gas after carbon dioxide ($CO_2$). Methanogenesis is an enzyme-mediated multi-step process by methanogens. In the penultimate step, methylated Co-M is reduced by methyl Co-M reductase (MCR) to $CH_4$ involving a nickel-containing cofactor F430. The activity of MCR enzyme is dependent on the F430 and therefore, the bioavailability of Ni to methanogens is expected to influence MCR activity and $CH_4$ production in soil. In this study, different doses of EDTA(Ethylene Diamine Tetraacetic Acid) were applied in flooded soils to evaluate their suppression effect on methane production by chelating Ni of methanogenesis cofactor. METHODS AND RESULTS: EDTA was selected as chelating agents and added into wetland and rice paddy soil at the rates of 0, 25, 50, 75, and $100mmol\;kg^{-1}$ before 4-weeks incubation test. During the incubation, cumulative $CH_4$ production patterns were characterized. At the end of the experiment, soil samples were removed from their jars to analyze total soil Ni and water-soluble Ni content and methanogen abundance. Methane production from 100 mmol application decreased by 55 and 78% in both soils compared to that from 0 mmol. With increasing application rate of EDTA in both soils, water-soluble Ni concentration significantly increased, but total soil Ni and methanogen activities showed negative relationship during incubation test. CONCLUSION: The decrease in methane production with EDTA application was caused by chelating Ni of coenzyme F430 and inhibiting methanogenesis by methyl coenzyme M reductase. Consequently, EDTA application decreased uptake of Ni into methanogen, subsequently inhibited methanogen activities and reduced methane production in flooded soils.

담수토양에서 메탄생성반응 보효소 니켈의 킬레이팅에 의한 메탄 생산량의 효과적 저감

담수 토양인 논토양과 습지 토양에 킬레이팅 에이전트 EDTA를 처리하고 실내시험을 실시한 결과, 두 토양 모두에서 메탄 생산량이 확연히 감소함을 알 수 있었다. EDTA 처리량을 증가시킴에 따라 토양수 내 니켈이 증가하였으며 메탄생성균의 활성은 저감되었다. 메탄생성균의 활성이 저감됨에 따라 메탄 생산량은 현저히 감소하였으며 메탄생성균의 활성과 메탄생성량은 상당히 유의한 상관관계를 지니고 있었다. 이러한 메탄 저감 효과는 EDTA처리에 따라 coenzyme F430의 Ni이 EDTA와 킬레이팅 화합물을 형성함에 따라 분자크기가 증대하게 됨으로서 methyl coenzyme M reductase (MCR)에 의한 메탄을 생성하는 반응을 억제 시키는 것이 원인으로 판단된다. 결론적으로 담수토양에서 EDTA처리에 의해 니켈은 메탄생성균 체내로의 흡수가 억제되었고 이러한 니켈의 흡수저해는 메탄생성균의 활성을 억제시켜 토양으로부터 메탄 생산성량을 저감시킨 것으로 확인되었다.