26 1 O 2 oxic zone 2 3 mm O 2 SO 4 2 H 2S 3) CH 4, H 2S, Fe 2+, Mn 2+ O 2 1 O 2 3. 富栄養化内湾堆積物における硫化水素溶出抑制機構 H 2S 3 1. Fe (III) H 2S 2. NO 3 Beggiatoa B

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1 Journal of Environmental Biotechnology Vol. 11, No. 1 2, 25 32, 2011 総説 ( 特集 ) 富栄養化内湾堆積物における硫化水素溶出抑制機構 : 長距離細胞外電子伝達が機能している可能性 Prevention Mechanism of Hydrogen Sulfide Release in Eutrophicated Coastal Marine Sediment: Possible Role of Extracellular Electron Transfer Mikio Sayama TEL: m.sayama@aist.go.jp National Institute of Advanced Industrial Science and Technology (AIST), 16 1 Onogawa, Tsukuba, Ibaraki , Japan キーワード Key words: dead zone, sulfide, sediment, extracellular electron transfer はじめに ΣH 2S=H 2S+HS +S 2 ΣH 2S H 2S H 2S H 2S H 2S H 2S H 2S H 2S H 2S 1) H 2S 2) H 2S 2. 富栄養化内湾堆積物における生物地球化学的物質循環過程 ) ) 1 O 2 NO 3 Mn(IV) Fe (III) SO 4 2 CO 2

2 26 1 O 2 oxic zone 2 3 mm O 2 SO 4 2 H 2S 3) CH 4, H 2S, Fe 2+, Mn 2+ O 2 1 O 2 3. 富栄養化内湾堆積物における硫化水素溶出抑制機構 H 2S 3 1. Fe (III) H 2S 2. NO 3 Beggiatoa Beggiatoa NO 3 H 2S 3. H 2S H 2S 3 3 H 2S 3.1. 東京湾湾央域の水堆積物界面近傍における O 2,H 2 S 及び ph の鉛直微細濃度プロファイル, Beggiatoa 菌体量及び形態別 Fe 含量の季節変化 20 m O 2 H 2S ph Beggiatoa Fe Fe H 2S 4) 1 oxic zone H 2S sulfidic zone O 2 NO O O 2 H 2S ph oxic zone sulfidic zone O 2 H 2S suboxic zone

3 27 1 Fe H 2 S O ppm Step Technique Target phase Iron mineral Reactivity towards dissolved sulfide Electric conductivity 1 Porewater press Porewater dissolved Fe 2+ 2 CaCl 2 (ph 7) extraction Adsorbed Fe(II) for 24 h 3 Ascorbic acid (ph 7.5) extraction for 24 h 4 Cold 0.5 M HCl extraction for 48 h 5 Oxalate (ph 3.0) extraction for 7 d 6 Dithionite (ph 4.8) extraction for 24 h Solid-phase amorphous and poorly crystalline iron oxides Solid-phase amorphous iron sulfide Solid-phase crystalline iron oxides All of the solid-phase crystalline iron oxides except magnetite Ferrihydrite Fe III 5HO 8 4H 2 O highly reactive insulative Lepidocrocite γ-fe III OOH highly reactive semiconductive? Iron sulfide Fe II S semiconductive Magnetite Fe II Fe III 2O 4 poorly reactive conductive Hematite α-fe III 2O 3 poorly reactive semiconductive Goethite α-fe III OOH poorly reactive semiconductive Suboxic zone H 2S oxic zone sulfidic zone O 2 H 2S H 2S O 2 suboxic zone ph 3 6 Sulfidic zone 30 mm mm H 2S Beggiatoa Fe 7 H 2S Beggiatoa Fe magnetite Hematite goethite ferrihydrite lepidocrocite H 2S O 2 H 2S H 2S 3.2. 好気環境期 (1~2 月 ):Fe (III) による H 2 S の化学的酸化 ( 固定 ) H 2S Fe (III) H 2S 2) 8 H 2S Fe (III) ferrihydrite lepidocrocite 4) 1 H 2S Fe (III) FeS FeS 2 suboxic zone 5) H 2S+Fe (III)+H + S 0 +FeS+FeS 2+Fe 2+ +H 2O 1 H + suboxic zone ph Fe (III) suboxic zone Fe (III) FeS FeS 2 Mn(IV) Fe (III) 5) Fe 2+ +MnO 2+H 2O Fe (III)+Mn 2+ +H + 2 H + suboxic zone ph O 2 H 2S Fe (III) ferrihydrite lepidocrocite 4) 1 7 ph suboxic zone H 2S Fe (III) H 2S 嫌気環境から微好気環境への移行期 (9~10 月 ): Beggiatoa による NO 3 を用いた H 2 S の生物学的酸化 H 2S H 2S

4 28 2 O 2 NO 3 oxic zone O 2 penetration depth H 2 S sulfidic zone H 2 S penetration depth O 2 H 2 S ph O 2 H 2 S ph O 2 H 2 S ph O 2 H 2 S ph ) O 2 H 2S O 2 H 2S H 2S O 2 H 2S NO 3 Beggiatoa 2,6) 9 Beggiatoa NO 3 1 μm 1 M sulfidic zone NO 3 H 2S suboxic zone 7) 10 5,7) H 2S+NO 3 +H + S 0 +NH 4 + +H 2O 3 H + suboxic zone sulfidic zone ph S 0 Beggiatoa Beggiatoa oxic zone O 2 5,7)

5 mm H 2 S Beggiatoa Fe 8 H 2 S Fe (III) H 2 S S 0 +O 2+H 2O SO 4 2 +H + 4 H + oxic zone suboxic zone ph NO 3 H 2S suboxic zone Beggiatoa Beggiatoa H 2S 7) NO 3 H 2S 4 7 Fe (III) 7 Beggiatoa 7 Beggiatoa 9 ph oxic zone suboxic zone suboxic zone sulfidic zone H 2S Beggiatoa NO 3 H 2S 微好気環境から好気環境への移行期 (11~12 月 ): 微生物が関与する生物電気化学的過程 ( 長距離細胞外電子伝達 ) による H 2 S の生物学的酸化 1 Geobacter Shewanella extracellular electron transfer, EET 8,9) EET 10)

30 9 NO 3 Beggiatoa 3 11 9 BeggiatoaBeggiatoa filament NO

2S Suboxic zone Mn(IV) Fe (III) Beggiatoa O 2 H 2S ph 11)

ph oxic zone suboxic zone O 2 H + oxic zone suboxic zone O

6 30 9 NO 3 Beggiatoa BeggiatoaBeggiatoa filament NO 3 1 M Beggiatoa 30 mm 10 H 2 S Beggiatoa NO 3 H 2 S EET H 2S Suboxic zone Mn(IV) Fe (III) Beggiatoa O 2 H 2S ph 11) 1. Suboxic zone mm suboxic zone 2. ph oxic zone suboxic zone O 2 H + oxic zone suboxic zone O 2 H + O 2 O 2+4e-+4H + 2H 2O 3. O mm suboxic zone sulfidic zone H 2S 1

7 31 11 H 2 S H 2 S EET O 2 H 2S EET 11) O 2 H 2S 5 7 H 2S Fe (III) ferrihydrite lepidocrocite 4) 1 Beggiatoa 7 Fe (III) magnetite 4) 1 7 ph oxic zone suboxic zone H 2S Fe (III) magnetite EET H 2S 11 Beggiatoa EET H 2S O 2 NO 3 Beggiatoa EET H 2S H 2S Fe (III) H 2S Beggiatoa EET H 2S Fe (III) H 2S 4. おわりに EET 1 EET biomineralization FeS FeS 2 EET EET O 2 H 2S Dead Zone EET H 2S 文 1) Jørgensen, B.B. and S. Kasten Sulfur cycling and methane oxidation, pp In H.D. Schulz and M. Zabel (eds.), Marine Geochemistry, 2nd ed. Springer, Berlin. 2) Jørgensen, B.B. and D.C. Nelson Sulfide oxidation in marine sediments: Geochemistry meets microbiology, pp In J.P. Amend, K.J. Edwards, and T.W. Lyons (eds.), Sulfur Biogeochemistry Past and Present. Geological Society of America. 3) Jørgensen, B.B Bacteria and marine biogeochemistry, pp In H.D. Schulz and M. Zabel (eds.), Marine Geochemistry, 2nd ed. Springer, Berlin. 4) Haese, R.R The biogeochemistry of Iron, pp 献

8 32 In H.D. Schulz and M. Zabel (eds.), Marine Geochemistry, 2nd ed. Springer, Berlin. 5) Preisler, A., D. de Beer, A. Lichtschlag, G. Lavik, A. Boetius and B.B. Jørgensen Biological and chemical sulfide oxidation in a Beggiatoa inhabited marine sediment. ISME J. 1: ) Sayama, M Presence of nitrate-accumulating sulfur bacteria and their influence on nitrogen cycling in a shallow coastal marine sediment. Appl. Environ. Microbiol. 67: ) Sayama, M., N. Risgaard-Petersen, L.P. Nielsen, H. Fossing and P.B. Christensen Impact of bacterial NO 3 transport on sediment biogeochemistry. Appl. Environ. Microbiol. 71: ) Lovley, D.R Reach out and touch someone: potential impact of DIET (direct interspecies energy transfer) on anaerobic biogeochemistry, bioremediation, and bioenergy. Rev. Environ. Sci. Bio-Technol. 10: ) Lovley, D.R. and K.P. Nevin A shift in the current: New applications and concepts for microbe-electrode electron exchange. Curr. Opin. Biotechnol. 22: ) Rabaey, K., J. Rodriguez, L.L. Blackall, J. Keller, P. Gross, D. Batstone, W. Verstraete and K.H. Nealson Microbial ecology meets electrochemistry: electricity-driven and driving communities. ISME J. 1: ) Nielsen, L.P., N. Risgaard-Petersen, H. Fossing, P.B. Christensen and M. Sayama Electric currents couple spatially separated biogeochemical processes in marine sediment. Nature. 463:

Analysis of Hypoxia Dynamics Using Pelagic and Benthic Biogeochemical Model: Focus on the Formation and Release of Hydrogen Sulfide Masayasu IRIE, Shu

Analysis of Hypoxia Dynamics Using Pelagic and Benthic Biogeochemical Model: Focus on the Formation and Release of Hydrogen Sulfide Masayasu IRIE, Shuzo NISHIDA, Kyosuke TERANAKA, Yohei TSUJI Mitsunari