微生物学报

Organism	Substrate	Types of metal(loid)s	Methanogenesis	Main transformation products	References
Methanosarcina barkeri	H₂/CO₂	Amorphous Fe(OH)₃/goethite/ nontronite NAu-2	Inhibition	Fe(Ⅱ)	[26-27,29,31]
Methanosarcina barkeri	Methanol	Amorphous Fe(OH)₃	Inhibition	Fe(Ⅱ)	[26-27]
Methanosarcina barkeri	Acetate	Amorphous Fe(OH)₃	Inhibition	Fe(Ⅲ)	[26-27]
Methanosarcina barkeri	Acetate	Nontronite NAu-2	-	Fe(Ⅲ)	[31]
Methanosarcina barkeri	Methanol	Nontronite NAu-2	Inhibit initially but enhance ultimately	Fe(Ⅱ)	[31]
Methanosarcina barkeri	Close to natural conditions	Amorphous Fe(OH)₃/ hematite/magnetite	Inhibition	Fe(Ⅱ)	[28,30]
Methanosarcina barkeri	Acetate	NanoFe₃O₄	Enhancement	Fe(Ⅱ)	[42]
Methanosarcina barkeri	H₂/CO₂	Ferrihydrite	-	Fe(Ⅱ) and ZVI	[43]
Methanosarcina mazei	Methanol	Clay minerals (nontronite NAu-2/mixed-layer illite-smectite RAr-1 and ISCz-1/illite IMt-1)	Inhibition	Fe(Ⅱ)	[25]
Methanosarcina mazei	Acetate	NanoFe₃O₄	Enhancement	Redox cycling of Fe(Ⅱ) and Fe(Ⅲ)	[36]
Methanosarcina mazei	Acetate	Ferric citrate/ferrihydrite	Enhancement	Fe(Ⅱ)	[38]
Methanosarcina mazei	Methanol	Ferrihydrite	Enhancement	Fe(Ⅱ)	[37]
Methanosarcina mazei	Methanol	Goethite/hematite	No impact	Fe(Ⅲ)	[37]
Methanococcus voltae	H₂/CO₂	Amorphous Fe(OH)₃	Inhibition	Fe(Ⅱ)	[26]
Methanospirillum hungatei	H₂/CO₂/acetate	Amorphous Fe(OH)₃	Inhibition	-	[27]
Methanothrix soehngenii	Acetate	Amorphous Fe(OH)₃	Inhibition	-	[27]
Methanothermobacter thermautotrophicus	H₂/CO₂	Clay minerals (nontronite NAu-2/wyoming montmorillonite SWy-2)/ferrihydrite	Inhibition	Fe(Ⅱ)	[32-33]
Methanothrix thermoacetophila	Acetate	Ferrihydrite	Inhibition	Fe(Ⅲ)	[33]
Methanothrix thermoacetophila (high-density cultures)	H₂/CO₂	Ferrihydrite	-	Fe(Ⅱ)	[33]
Methanothrix thermoacetophila (high-density cultures)	Acetate and H₂/CO₂	Ferrihydrite	Inhibition	Fe(Ⅱ)	[33]
Methanosarcina thermophila	Methanol and H₂/CO₂	Ferrihydrite	Little inhibition	Fe(Ⅱ)	[33]
Methanosarcina thermophila	H₂/CO₂	Ferrihydrite	-	Fe(Ⅱ)	[33]
Methanosarcina thermophila	Acetate/methanol	Ferrihydrite	Inhibition	Fe(Ⅲ)	[33]
Methanopyrus kandleri	H₂/CO₂	Ferric citrate	-	Fe(Ⅱ)	[20]
Methanothermococcus thermolithotrophicus	H₂/CO₂	Ferric citrate	-	Fe(Ⅱ)	[20]
Methanosarcina barkeri	Methanol	Pyrite	-	Fe(Ⅱ) (reductive dissolution of FeS₂)	[48]
Methanococcus voltae	Formate	Pyrite	-	Fe(Ⅱ) (reductive dissolution of FeS₂)	[48]
Methanosarcina acetivorans	Acetate	Ferrihydrite	Enhancement	Fe(Ⅱ)	[39]
Methanospirillum hungatei	Na-formate	HgCl₂	-	MeHg	[55]
Methanomethylovorans hollandica	Methanol	Inorganic Hg	-	MeHg	[57]
Methanolobus tindarius	Methanol	Inorganic Hg	-	MeHg	[57]
Methanomassiliicoccus luminyensis	-	Inorganic Hg	-	MeHg	[58]
Methanosarcina acetivorans	Methanol	CdCl₂	No impact	-	[63]
Methanosarcina acetivorans	Acetate	CdCl₂	Enhancement	-	[63]
Methanosarcina mazei	Methanol	NaVO₃	Inhibition	V(Ⅳ)	[72]
Methanosarcina mazei	Acetate	NaVO₃	Inhibition	V(Ⅳ)	[72]
Methanosarcina mazei	H₂/CO₂	NaVO₃	Inhibition	V(Ⅳ)	[72]
Methanothermobacter thermautotrophicus	H₂/CO₂	NaVO₃	Inhibition	V(Ⅳ)	[72]
Methanothermobacter thermautotrophicus	H₂/CO₂	K₂Cr₂O₇	Inhibition	Cr(Ⅲ)	[73]
Methanosarcina thermophila	-	Arsenite	-	Methylated thioarsenates	[82]
Methanosarcina acetivorans	Methanol	As(Ⅲ)	-	MMA	[80,83]
Methanomassiliicoccus luminyensis	Methanol	DMA(Ⅲ)	-	As(Ⅲ)	[85]
Methanosarcina acetivorans	Methanol	SeNPs	Concentration-dependent promotion and inhibition	Inorganic selenium and organic selenium species	[91]

Organism	Substrate	Types of metal(loid)s	Methanogenesis	Main transformation products	References
Methanosarcina barkeri	H₂/CO₂	Amorphous Fe(OH)₃/goethite/ nontronite NAu-2	Inhibition	Fe(Ⅱ)	[26-27,29,31]
Methanosarcina barkeri	Methanol	Amorphous Fe(OH)₃	Inhibition	Fe(Ⅱ)	[26-27]
Methanosarcina barkeri	Acetate	Amorphous Fe(OH)₃	Inhibition	Fe(Ⅲ)	[26-27]
Methanosarcina barkeri	Acetate	Nontronite NAu-2	-	Fe(Ⅲ)	[31]
Methanosarcina barkeri	Methanol	Nontronite NAu-2	Inhibit initially but enhance ultimately	Fe(Ⅱ)	[31]
Methanosarcina barkeri	Close to natural conditions	Amorphous Fe(OH)₃/ hematite/magnetite	Inhibition	Fe(Ⅱ)	[28,30]
Methanosarcina barkeri	Acetate	NanoFe₃O₄	Enhancement	Fe(Ⅱ)	[42]
Methanosarcina barkeri	H₂/CO₂	Ferrihydrite	-	Fe(Ⅱ) and ZVI	[43]
Methanosarcina mazei	Methanol	Clay minerals (nontronite NAu-2/mixed-layer illite-smectite RAr-1 and ISCz-1/illite IMt-1)	Inhibition	Fe(Ⅱ)	[25]
Methanosarcina mazei	Acetate	NanoFe₃O₄	Enhancement	Redox cycling of Fe(Ⅱ) and Fe(Ⅲ)	[36]
Methanosarcina mazei	Acetate	Ferric citrate/ferrihydrite	Enhancement	Fe(Ⅱ)	[38]
Methanosarcina mazei	Methanol	Ferrihydrite	Enhancement	Fe(Ⅱ)	[37]
Methanosarcina mazei	Methanol	Goethite/hematite	No impact	Fe(Ⅲ)	[37]
Methanococcus voltae	H₂/CO₂	Amorphous Fe(OH)₃	Inhibition	Fe(Ⅱ)	[26]
Methanospirillum hungatei	H₂/CO₂/acetate	Amorphous Fe(OH)₃	Inhibition	-	[27]
Methanothrix soehngenii	Acetate	Amorphous Fe(OH)₃	Inhibition	-	[27]
Methanothermobacter thermautotrophicus	H₂/CO₂	Clay minerals (nontronite NAu-2/wyoming montmorillonite SWy-2)/ferrihydrite	Inhibition	Fe(Ⅱ)	[32-33]
Methanothrix thermoacetophila	Acetate	Ferrihydrite	Inhibition	Fe(Ⅲ)	[33]
Methanothrix thermoacetophila (high-density cultures)	H₂/CO₂	Ferrihydrite	-	Fe(Ⅱ)	[33]
Methanothrix thermoacetophila (high-density cultures)	Acetate and H₂/CO₂	Ferrihydrite	Inhibition	Fe(Ⅱ)	[33]
Methanosarcina thermophila	Methanol and H₂/CO₂	Ferrihydrite	Little inhibition	Fe(Ⅱ)	[33]
Methanosarcina thermophila	H₂/CO₂	Ferrihydrite	-	Fe(Ⅱ)	[33]
Methanosarcina thermophila	Acetate/methanol	Ferrihydrite	Inhibition	Fe(Ⅲ)	[33]
Methanopyrus kandleri	H₂/CO₂	Ferric citrate	-	Fe(Ⅱ)	[20]
Methanothermococcus thermolithotrophicus	H₂/CO₂	Ferric citrate	-	Fe(Ⅱ)	[20]
Methanosarcina barkeri	Methanol	Pyrite	-	Fe(Ⅱ) (reductive dissolution of FeS₂)	[48]
Methanococcus voltae	Formate	Pyrite	-	Fe(Ⅱ) (reductive dissolution of FeS₂)	[48]
Methanosarcina acetivorans	Acetate	Ferrihydrite	Enhancement	Fe(Ⅱ)	[39]
Methanospirillum hungatei	Na-formate	HgCl₂	-	MeHg	[55]
Methanomethylovorans hollandica	Methanol	Inorganic Hg	-	MeHg	[57]
Methanolobus tindarius	Methanol	Inorganic Hg	-	MeHg	[57]
Methanomassiliicoccus luminyensis	-	Inorganic Hg	-	MeHg	[58]
Methanosarcina acetivorans	Methanol	CdCl₂	No impact	-	[63]
Methanosarcina acetivorans	Acetate	CdCl₂	Enhancement	-	[63]
Methanosarcina mazei	Methanol	NaVO₃	Inhibition	V(Ⅳ)	[72]
Methanosarcina mazei	Acetate	NaVO₃	Inhibition	V(Ⅳ)	[72]
Methanosarcina mazei	H₂/CO₂	NaVO₃	Inhibition	V(Ⅳ)	[72]
Methanothermobacter thermautotrophicus	H₂/CO₂	NaVO₃	Inhibition	V(Ⅳ)	[72]
Methanothermobacter thermautotrophicus	H₂/CO₂	K₂Cr₂O₇	Inhibition	Cr(Ⅲ)	[73]
Methanosarcina thermophila	-	Arsenite	-	Methylated thioarsenates	[82]
Methanosarcina acetivorans	Methanol	As(Ⅲ)	-	MMA	[80,83]
Methanomassiliicoccus luminyensis	Methanol	DMA(Ⅲ)	-	As(Ⅲ)	[85]
Methanosarcina acetivorans	Methanol	SeNPs	Concentration-dependent promotion and inhibition	Inorganic selenium and organic selenium species	[91]

产甲烷古菌介导(类)金属转化的研究进展

PDF下载

黄馨 , 李冠慧 , 梁艳萍 , 闫震 ^*

微生物学报 | 综述 2025,65(6): 2433-2448

收起

微生物学报 | 综述 2025, 65(6): 2433-2448

产甲烷古菌介导(类)金属转化的研究进展

全屏

黄馨, 李冠慧, 梁艳萍, 闫震^*

作者信息

山东大学环境科学与工程学院，山东省水环境污染控制与资源化重点实验室，山东青岛

Advances and prospects in metal(loid) transformation driven by methanogenic archaea

Xin HUANG, Guanhui LI, Yanping LIANG, Zhen YAN^*

Affiliations

Shandong Key Laboratory of Water Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Shandong University, Qingdao, Shandong, China

出版时间: 2025-06-04 doi: 10.13343/j.cnki.wsxb.20250296

文章导航

摘要

收起

产甲烷古菌是缺氧环境中碳循环的核心驱动者。近年的研究表明，产甲烷古菌还参与了(类)金属的生物地球化学循环，但其介导的金属转化机制尚未得到系统的总结。本文综合了最新的研究成果，重点解析了产甲烷古菌对铁(Fe)、汞(Hg)、钒(V)、铬(Cr)、镉(Cd)、砷(As)、硒(Se)等典型(类)金属的氧化、还原、甲基化及去甲基化过程。(1) Fe(Ⅲ)还原对甲烷生成具有双向调控作用，当胞外Fe(Ⅲ)还原不能耦合能量代谢时，会显著抑制产甲烷古菌的生长及产甲烷过程，例如巴氏甲烷八叠球菌(Methanosarcina barkeri)；而当胞外Fe(Ⅲ)还原耦合能量代谢时，则会促进产甲烷古菌的生理代谢活性，例如噬乙酸甲烷八叠球菌(Methanosarcina acetivorans)；(2) 在汞甲基化机制方面，产甲烷古菌通过hgcAB基因簇编码的甲基转移酶实现Hg(Ⅱ)向甲基汞(methylmercury, MeHg)的转化，且部分菌株，如卢米尼甲烷马赛球菌(Methanomassiliicoccus luminyensis)的甲基化活性与死细胞释放的酶活性相关；(3) 砷转化机制呈现多样性，M. acetivorans通过As(Ⅲ)S-腺苷甲硫氨酸甲基转移酶(arsenic methyltransferase, ArsM)催化As(Ⅲ)甲基化，同时可利用砷酸盐还原酶(arsenate reductase, ArsC)还原As(V)为As(Ⅲ)，而稻田古菌群落还表现出有机胂的去甲基化能力；(4) 硒的生物转化具有双重性，低浓度硒纳米颗粒(selenium nanoparticles, SeNPs)能够促进产甲烷活性并诱导有机硒合成，而高浓度则会引发氧化应激。在环境效应方面，(类)金属通过改变氧化还原电位、竞争电子受体或诱导毒性胁迫，显著影响产甲烷古菌的代谢活性与群落结构。本文系统地揭示了产甲烷古菌在(类)金属循环中的多功能性，并提出未来需要结合宏组学与代谢组学技术解析关键酶的分子机制，同时探索基于产甲烷古菌的(类)金属污染生物修复新策略。

关键词

产甲烷古菌 / (类)金属转化 / 还原 / 甲基化 / 去甲基化

Abstract

收起

Methanogenic archaea are pivotal drivers of carbon cycling in anoxic environments. Growing evidence shows that they also participate in the biogeochemical cycling of metal(loid)s, yet the underlying transformation mechanisms have not been systematically summarized. This review integrates the latest findings to dissect how methanogenic archaea oxidize, reduce, methylate, and demethylate representative metal(loid)s, including iron (Fe), mercury (Hg), vanadium (V), chromium (Cr), cadmium (Cd), arsenic (As), and selenium (Se). The research findings are summarized as follows: (1) Fe(Ⅲ) reduction exerts bidirectional control over methanogenesis. When extracellular Fe(Ⅲ) reduction is not coupled to energy metabolism, it markedly suppresses the growth and methane production of methanogenic archaea (e.g., Methanosarcina barkeri). Conversely, when extracellular Fe(Ⅲ) reduction is coupled to energy metabolism, it stimulates the physiological and metabolic activities of methanogenic archaea (e.g., Methanosarcina acetivorans). (2) For mercury methylation, methanogenic archaea convert Hg(Ⅱ) to methylmercury (MeHg) via a methyltransferase encoded by the hgcAB gene cluster. In some species (e.g., Methanomassiliicoccus luminyensis), the observed methylation activity is associated with enzymes released from lysed cells. (3) Arsenic transformation runs with diverse mechanisms. Methanosarcina acetivorans methylates As(Ⅲ) via the arsenic methyltransferase (ArsM) and concurrently reduces As(V) to As(Ⅲ) through arsenate reductase (ArsC), whereas archaeal communities in paddy soils are capable of demethylating organic arsine. (4) Selenium biotransformation exhibits dual effects: low concentrations of selenium nanoparticles (SeNPs) enhance methanogenic activity and induce organoselenium synthesis, whereas high concentrations trigger oxidative stress. Environmentally, metal (loid)s markedly affect the metabolic activity and community structure of methanogenic archaea by altering redox potential, competing for electron acceptors, or imposing toxic stress. This review highlights the multifunctionality of methanogenic archaea in metal (loid) cycling and proposes that future work should combine meta-omics and metabolomics approaches to elucidate enzyme-level mechanisms, while exploring methanogenic archaea-based strategies for the bioremediation of metal (loid) contamination.

Key words

methanogenic archaea / metal(loid) transformation / reduction / methylation / demethylation

引用本文

黄馨, 李冠慧, 梁艳萍, 闫震. 产甲烷古菌介导(类)金属转化的研究进展. 微生物学报, 2025 , 65 (6) : 2433 -2448 . DOI: 10.13343/j.cnki.wsxb.20250296

Xin HUANG, Guanhui LI, Yanping LIANG, Zhen YAN. Advances and prospects in metal(loid) transformation driven by methanogenic archaea[J]. Acta Microbiologica Sinica, 2025 , 65 (6) : 2433 -2448 . DOI: 10.13343/j.cnki.wsxb.20250296

正文

收起

作为地球上最古老的生命形式之一，产甲烷古菌在碳的生物地球化学循环中发挥着重要作用^[1]。越来越多的研究证实，产甲烷古菌能够参与多种(类)金属的生物转化过程。这一发现表明，产甲烷古菌不仅在碳的生物地球化学循环中，同时在某些(类)金属的生物地球化学循环中也扮演着关键角色^[2]。尤为重要的是，其介导的(类)金属转化过程展现出独特的代谢特征和生态功能。其中最显著的特征在于(类)金属转化过程与产甲烷代谢形成直接的能量偶联。具体而言，在环境暴露或生物转化过程中，产甲烷古菌的生理功能可能通过多种途径受到调控，进而影响缺氧环境中的甲烷排放通量。这一作用不仅会改变局部生态系统的碳循环，还可能干扰全球甲烷收支平衡，进而对温室气体排放产生多尺度的深远环境影响。此外，与假单胞菌(Pseudomonas)、希瓦氏菌(Shewanella)等常见好氧或兼性厌氧微生物不同，产甲烷古菌在深层沉积物、湿地等严格厌氧环境，以及陆地热泉、深海热液等极端环境中仍能维持较高的(类)金属转化活性^[3]，这一特性为开发针对极端环境(类)金属污染的生物修复技术提供了新思路。本研究通过系统整合最新研究进展，重点综述了产甲烷古菌对多种(类)金属的转化机制(图1)，同时探讨了(类)金属暴露及其生物转化过程对产甲烷古菌自身的影响，以期为该领域的深入研究提供理论基础，并对未来研究方向提出展望。

1 产甲烷古菌类群

收起

甲烷(CH₄)在全球碳和能量循环中起着重要作用^[4]。直接参与CH₄生产的微生物属于古菌域(archaea)，称为产甲烷古菌^[3]。系统发育学上，常规的产甲烷古菌均属于古菌域广古菌门(Euryarchaeota)中的7个目^[5-6]：甲烷杆菌目(Methanobacteriales)、甲烷球菌目(Methanococcales)、甲烷微菌目(Methanomicrobiales)、甲烷八叠球菌目(Methanosarcinales)、甲烷火球菌目(Methanopyrales)、甲烷胞菌目(Methanocellales)和Methanoplasmatales。随着对产甲烷古菌研究的不断深入，2012年，Dridi等^[7]发现了属于Euryarchaeota的第8目——Methanomassiliicoccales；随后2018年，Sorokin等^[8]报道了属于该门的第9目——Methanonatronarchaeales；2019年，Borrel等^[9]又发现了第10目——Methanoliparales。2021年，Rinke等^[10]提出了基因组分类法的标准化古菌分类法，将产甲烷古菌的10个目重新划分至3个门(Methanobacteriota、Halobacteriota、Thermoplasmatota)中，而根据2023年NCBI数据库的分类标准，产甲烷古菌则存在于Euryarchaeota、Ca.Thermoplasmatota以及TACK超门中^[11]。

产甲烷古菌是目前已知的唯一大量产甲烷的微生物，广泛存在于地球上各种缺氧环境中，如稻田土壤、海洋沉积物、湿地甚至热泉等极端环境^[3,12]，在地球主要元素的生物化学循环过程中扮演关键角色^[13]。根据代谢底物差异，其产甲烷途径大致可分为3类(图2)^[14]：(1) H₂/CO₂途径^[15]，又称还原CO₂途径，以H₂或甲酸为电子供体还原CO₂产CH₄，是大多数产甲烷古菌的主要代谢方式。(2) 甲基营养途径^[12]，通过甲基化合物本身的歧化作用或H₂还原甲基化合物中的甲基来产生CH₄。(3) 乙酸途径^[16]，裂解乙酸通过其中的甲基还原和羧基氧化生成CH₄和CO₂。直到2016年，日本研究团队报道了一种新的产甲烷途径——甲氧基型产甲烷途径^[17]，打破了对产甲烷古菌仅能利用简单碳氢氧化合物的固有认知。2021年，Zhou等^[18]提出了第5种产甲烷途径——烷基型产甲烷途径。证实了产甲烷古菌也具备利用复杂有机化合物进行产甲烷代谢的能力^[19]。

2 产甲烷古菌对金属的转化

收起

2.1 铁

铁是地球上最丰富的过渡金属元素，其 Fe(Ⅲ)/Fe(Ⅱ)氧化还原循环产生电子跃迁为地球表层系统提供了丰富的能量通量^[20]。多种原生和次生铁矿物(如水铁矿、针铁矿和赤铁矿等)普遍存在于缺氧土壤、自然湿地和沉积物中^[21]，同时这种缺氧环境也为产甲烷古菌的生长提供了良好的基质和环境条件，使得产甲烷古菌与Fe(Ⅲ)矿物存在着密切的共存关系。此外，含铁黏土矿物在土壤、沉积物和沉积岩中也无处不在^[22-23]，黏土矿物中结构铁价态的变化会影响其物理和化学性质^[24]，从而对营养循环、植物生长、污染物迁移和石油生产等许多环境过程产生影响^[22-23,25]。

研究表明，多种产甲烷古菌介导无定形铁还原从而抑制甲烷生成^[26-28]。Bond等^[26]研究了5种产甲烷古菌在不同底物条件下还原Fe(Ⅲ)氧化物的能力，巴氏甲烷八叠球菌(Methanosarcina barkeri)MS和沃氏甲烷球菌(Methanococcus voltae) A3利用H₂作为电子供体显著还原Fe(Ⅲ)，其生长和甲烷生成受到抑制；当以甲醇为底物时，Methanosarcina barkeri MS还原Fe(Ⅲ)的能力大大降低；由于CH₄产生和Fe(Ⅲ)还原同时进行，部分电子被分流用于 Fe(Ⅲ)还原，因此，含Fe(Ⅲ)培养物产生的甲烷比对照组产生的甲烷少；当以乙酸盐为电子供体时，Methanosarcina barkeri MS的CH₄产生、细胞生长和Fe(Ⅲ)还原均受到完全抑制；兔甲烷球形菌(Methanosphaera cuniculi) 1R7只能通过以H₂为电子供体的甲醇还原来产甲烷，其在还原Fe(Ⅲ)时未检测到甲烷的产生，细胞无活性，生长受到抑制；利用H₂和二级醇作为电子供体的沼泽甲烷杆菌(Methanobacterium palustre) F未表现出任何显著的Fe(Ⅲ)还原，该菌株也不能产生CH₄；同样地，瓦尔肯甲烷叶菌(Methanolobus vulcani)PL-12/M也未观察到显著的Fe(Ⅲ)还原，其在Fe(Ⅲ)存在下生长不良^[26]。随后，van Bodegom等^[27]发现添加无定形Fe(OH)₃能够直接抑制产甲烷古菌产生CH₄，且以H₂/CO₂为底物生长的亨氏甲烷螺菌(Methanospirillum hungatei)和Methanosarcina barkeri对Fe(Ⅲ)的敏感性高于以乙酸盐为底物生长的索氏产甲烷丝菌(Methanothrix soehngenii)和Methanosarcina barkeri。当以H₂/CO₂或甲醇为底物时，Methanosarcina barkeri还显示出还原Fe(Ⅲ)的能力^[27]。也有研究表明，Methanosarcina barkeri在接近自然条件(无H₂且底物受限)情况下，也会迅速从产甲烷过程转变为Fe(OH)₃还原^[28]。

此外，产甲烷古菌还可还原铁矿物中的结构Fe(Ⅲ)。Liu等^[29]发现，以H₂为唯一底物，Methanosarcina barkeri能够还原针铁矿中的结构Fe(Ⅲ)，但极大地抑制了其生长和甲烷生成。Eliani-Russak等^[30]研究了Methanosarcina barkeri在接近自然条件下对3种天然氧化铁的还原能力，证实了其不仅可以还原高反应性的无定形铁，还可以还原低反应性的磁铁矿和赤铁矿；其中，无定形铁还原程度最高，磁铁矿次之，赤铁矿最低，而甲烷产量则呈现相反趋势，Fe(Ⅲ)的还原抑制了甲烷的产生。此外，Liu等^[31]研究表明，Methanosarcina barkeri还可以还原黏土矿物绿脱石(nontronite NAu-2)中的结构Fe(Ⅲ)。他们利用3种底物进行实验，发现Methanosarcina barkeri在H₂/CO₂或甲醇为底物时可以还原NAu-2中的Fe(Ⅲ)，但乙酸盐为底物时不具备还原能力；此外，在H₂/CO₂培养条件下Fe(Ⅲ)还原抑制了甲烷生成，而以甲醇为底物培养时，虽然前期甲烷生成受到了抑制，但最终产量较无NAu-2对照组甚至有所提升，由于结构Fe(Ⅲ)的生物还原，NAu-2部分溶解，形成了高电荷蒙脱石和生物二氧化硅^[31]。随后，Zhang等^[25]发现索氏产甲烷丝菌(Methanosarcina mazei)能够还原多种黏土矿物中的结构Fe(Ⅲ)，将Methanosarcina mazei暴露于4种不同的黏土矿物(富铁蒙脱石NAu-2、伊利石-蒙脱石混合层矿物RAr-1和ISCz-1、伊利石IMt-1)中，均发现Fe(Ⅲ)被还原，其还原程度与每种黏土矿物中的蒙脱石比例呈正相关，蒙脱石中的Fe(Ⅲ)最易还原，伊利石最难；所有矿物中Fe(Ⅲ)的生物还原均抑制了甲烷生成，但程度不同；该过程同时诱导了生物源伊利石-蒙脱石混合层矿物、二氧化硅和蓝铁矿的形成。随后，该团队发现嗜热产甲烷古菌热自养甲烷热杆菌(Methanothermobacter thermautotrophicus)以H₂/CO₂为底物，能够还原富铁蒙脱石(绿脱石NAu-2)和贫铁蒙脱石(怀俄明蒙脱石SWy-2)中的Fe(Ⅲ)，其中NAu-2的生物还原程度更高；当通过添加产甲烷抑制剂2-溴乙烷磺酸盐(2-bromoethane sulfonate, BES)抑制甲烷生成时，NAu-2和SWy-2的生物还原程度都有所降低，表明Fe(Ⅲ)生物还原和甲烷生成是互惠互利的；这可能是由于Fe(Ⅲ)生物还原降低了系统的还原电位，从而有利于甲烷生成，而甲烷生成又反向刺激了产甲烷古菌的生长，从而增强了Fe(Ⅲ)的生物还原^[32]。与以前使用相同粒径NAu-2的报道^[25,31]相比，Methanothermobacter thermautotrophicus的NAu-2初始生物还原速率比Methanosarcina barkeri高出近1个数量级，几乎是Methanosarcina mazei还原速率的2倍。除Methanothermobacter thermautotrophicus外，嗜热产甲烷古菌坎氏甲烷火菌(Methanopyrus kandleri)和热自养产甲烷热球菌(Methanothermococcus thermolithotrophicus)也被报道可以利用H₂作为电子供体对柠檬酸铁进行生物还原^[20]。然而，当时尚未研究其还原不溶性Fe(Ⅲ)矿物的能力及Fe(Ⅲ)对甲烷生成的影响。2014年，Yamada等^[33]进一步研究了3种嗜热产甲烷古菌[Methanothermococcus thermolithotrophicus、热嗜醋产甲烷丝菌(Methanothrix thermoacetophila)、嗜热甲烷八叠球菌(Methanosarcina thermophila)]还原水铁矿的能力，研究表明只有在底物中存在H₂时，水铁矿才能被这3种嗜热产甲烷古菌还原，虽然添加水铁矿导致3种产甲烷古菌完全抑制或抑制甲烷生成，但其对水铁矿的还原部分减轻了该抑制作用。

从这些研究来看，学者们提出了2种Fe(Ⅲ)矿物抑制产甲烷作用的潜在机制：(1) 在胞外Fe(Ⅲ)存在条件下，电子流从CO₂还原(CH₄生成)转向Fe(Ⅲ)还原^[26-27,31]。(2) 水铁酸盐的存在会导致其周围环境的氧化还原电位增加^[25,27,33]。由于产甲烷古菌作为专性厌氧菌需要生长在较低的氧化还原电位中，环境氧化还原电位的升高会严重抑制其生长和甲烷生成^[34-35]。

与上述铁氧化物还原抑制甲烷生成的报道不同，陆雅海团队发现从青藏高原天然湿地分离的产甲烷古菌Methanosarcina mazei zm-15能够还原Fe(Ⅲ)，并显著促进甲烷生成^[36-38]。在乙酸型产甲烷过程中，磁铁矿(nanoFe₃O₄)的添加显著促进了CH₄生成，这与矿物中结构Fe(Ⅱ)/Fe(Ⅲ)的氧化还原循环相关。培养初期Methanosarcina mazei zm-15和对照组的Fe(Ⅱ)/Fe(Ⅲ)比率均增加，随后对照组趋于稳定，而实验组呈现先降后升趋势，其中Fe(Ⅱ)氧化期与CH₄产量的快速增加相对应，表明磁铁矿的这种氧化还原循环与产甲烷的促进作用相一致^[36]。同样利用乙酸盐作为底物时，柠檬酸铁和水铁矿的还原也显著促进了Methanosarcina mazei zm-15生长，且无定形的柠檬酸铁比水铁矿更容易还原，磁铁矿是水铁矿的主要还原产物^[38]。在甲基营养型产甲烷过程中，Methanosarcina mazei zm-15还原水铁矿能力较强，并显著促进其生长和甲烷生成，但该菌株不能还原高结晶度的针铁矿和赤铁矿，蓝铁矿是水铁矿的主要还原产物^[37]。

此外，部分产甲烷古菌还能通过耦合呼吸代谢过程进行Fe(Ⅲ)的还原。在乙酸型产甲烷过程中，如噬乙酸甲烷八叠球菌(Methanosarcina acetivorans)能够通过细胞色素c进行依赖Fe(Ⅲ)还原的呼吸代谢，显著促进了其生长和甲烷产量，而细胞膜结合的多血红素细胞色素c (multiheme c-type cytochrome, MHC)可能在这一途径中发挥了重要作用^[39]。MHC广泛分布于具有Fe(Ⅲ)还原能力的细菌(如Shewanella)中，由于血红素或铁卟啉的存在，MHC可能参与电子向可溶性或不溶性Fe(Ⅲ)转移的过程中。Song等^[40]发现从Methanosarcina acetivorans膜组分分离的吡咯喹啉醌(pyrroloquinoline quinone, PQQ)可以显著提高产甲烷古菌胞外电子传递效率，揭示了MHC或许并不是唯一的膜电子传递载体，为(类)金属与产甲烷古菌的呼吸性还原提供了新的可能性。Yan等^[41]通过Methanosarcina acetivorans的膜体外实验证实，还原性铁氧还蛋白对可溶性柠檬酸铁的还原与跨膜形成的Na⁺梯度相结合，促进了ATP的合成，可能通过能量代谢和胞内氧化还原物质的转化来逆转甲烷生成和甲烷氧化生长。随后，该团队进一步通过体内实验证实，Methanosarcina acetivorans C2A能够通过Fe(Ⅲ)还原进行呼吸驱动的CH₄营养生长，主要表现为蛋白质产量增加和CH₄消耗，水铁矿的还原表现为Fe(Ⅱ)增加和磁铁矿特有的磁性颗粒的积累，并通过另一株海洋产甲烷古菌Methanococcoides orientis验证了上述研究的普适性^[4]。

Wang等^[36]和Fu等^[42]还发现，纳米磁铁矿(nanoFe₃O₄)添加均促进了Methanosarcina mazei和Methanosarcina barkeri的乙酸型产甲烷过程。此外，Shang等^[43]在Methanosarcina barkeri的培养体系中添加水铁矿后，除已被报道的还原产物Fe(Ⅱ)外，还发现了零价铁矿物(zero-valent iron, ZVI)的存在。这一发现为铁金属保护及ZVI的绿色合成方法提供了新思路。也有一些研究表明，氧化铁矿物作为天然电极可能发挥作用，以产生独特的共养相互作用，促进甲烷的产生^[44-45]。黄铁矿(FeS₂)是地壳中最丰富的硫化物矿物^[46]，但FeS₂在低温下是稳定的，并且在无氧气的条件下具备生物不可利用性^[47-48]。研究报道，从海洋和淡水环境中分离的产甲烷古菌Methanococcus voltae A3和Methanosarcina barkeri MS都可以在低温(≤38 °C)下催化FeS₂的还原溶解，并利用溶解产物来满足细胞代谢对Fe和S的需求^[48]。

氧化铁矿物和产甲烷古菌无处不在，并在缺氧环境中共存。Fe(Ⅲ)还原对甲烷生成具有双向调控作用。当胞外Fe(Ⅲ)还原不能耦合能量代谢时，产甲烷古菌的生长及产甲烷过程受到显著抑制；而当胞外Fe(Ⅲ)还原耦合能量代谢时，则会促进产甲烷古菌的生理代谢活性。此外，产甲烷古菌介导的铁转化过程多样，在铁的生物地球化学循环中发挥重要作用，并可能对全球甲烷通量产生重要影响。

2.2 汞

汞(Hg)是一种剧毒重金属，对人类和环境健康具有严重危害^[49]。自然环境中的汞可分为无机汞和有机汞两类，其中无机汞主要以0、+1、+2价存在，而有机汞主要包括甲基汞、乙基汞和苯基汞等^[50]。一般认为，汞甲基化是一种天然的微生物过程，可以将无机的Hg(Ⅱ)转化为毒性最强的甲基汞(methylmercury, MeHg)^[51-52]，这一过程是汞生物地球化学循环中的重要环节。

早在1968年，产甲烷古菌就被提出可以进行汞甲基化^[53]，因为产甲烷古菌Methanobacterium bryantii的细胞提取物被发现可以将Hg(Ⅱ)转化为MeHg。然而，后来报道了硫酸盐还原菌(sulfate-reducing bacteria, SRB)能够主导汞甲基化后，产甲烷古菌的汞甲基化似乎被忽视了。直到2011年，Hamelin等^[54]报道淡水湖周丛植物生物膜的汞甲基化是由产甲烷古菌主导的，因为当他们添加产甲烷抑制剂2-溴乙烷磺酸(2-bromoethane sulfonic acid, BESA)后，发现汞甲基化过程被显著抑制了。随后，Yu等^[55]发现，产甲烷古菌Methanospirillum hungatei JF-1在无硫化物培养基中汞甲基化速率与某些SRB和铁还原菌(iron-reducing bacteria, IRB)相当，且产率更高，这是产甲烷古菌纯培养物对汞甲基化的首次报道。HgcAB (编码汞甲基化的基因)可以调控微生物的汞甲基化过程，是汞甲基化微生物的标志性基因^[56]。2013年，Gilmour等^[57]发现，2种具有hgcAB近缘同源基因的产甲烷古菌荷兰食甲基甲烷菌(Methanomethylovorans hollandica)和廷达尔角甲烷叶菌(Methanolobus tindarius)可以进行汞甲基化。紧接着，Podar等^[58]报道，从人类粪便分离出的产甲烷古菌卢米尼甲烷马赛球菌(Methanomassiliicoccus luminyensis)也具有hgcAB，能够进行汞甲基化，且其甲基化速率与Methanomethylovorans hollandica相似，远高于Methanolobus tindarius^[57]。Gilmour等^[59]还从已知的19种携带hgcAB基因的产甲烷古菌中选取了9种，进行了甲基汞生成能力的定量测定与比较，发现其中有8种产甲烷古菌能够产生比对照组更多的MeHg，证实了大多数携带hgcAB基因的产甲烷古菌能够进行汞甲基化。此外，除了大量研究报道的产甲烷古菌具有汞甲基化能力外，产甲烷古菌可能也参与了MeHg去甲基化过程^[52,60]。

微生物介导的甲基化过程是无机汞生物转化的主要途径。然而，在过去很长一段时间，SRB和IRB被认为是主要的汞甲基化微生物。上述研究表明，产甲烷古菌在汞甲基化过程中同样发挥重要作用，其参与沉积物、水体和土壤等多种环境中的汞甲基化过程，同时还参与了有机汞的去甲基化过程，极大地拓展了对汞生物地球化学循环的认知。

2.3 镉

镉(Cd)是一种剧毒的非必需重金属，在自然环境中仅以+2价形式稳定存在。广泛存在于土壤、海洋、湖泊、河流等自然环境中^[61]，由于人类活动和不恰当的处置方法，已经成为土壤和水体的严重污染物^[61-62]。

据报道^[63-64]，在甲基型产甲烷过程中，低浓度(100 μmol/L)镉的添加不会改变Methanosarcina acetivorans的生长和甲烷生成，而利用乙酸盐为底物时，此过程被略微促进；更高浓度(500 μmol/L)镉对细胞具有毒性，完全抑制了其生长和甲烷产生。然而进一步研究发现，经过长期低浓度(50 μmol/L) Cd(Ⅱ)预适应的Methanosarcina acetivorans能够耐受更高浓度(0.8 mmol/L)镉^[65]。值得一提的是，Methanosarcina acetivorans能够通过与含硫分子偶联在胞内积累Cd(Ⅱ)，从而在一定程度上去除培养基中的镉^[63]。

2.4 钒和铬

钒是一种过渡金属元素，自然环境中一般以+3、+4、+5价存在^[66]。铬是一种重要的金属元素，一般以+3、+6价2种稳定的形式存在^[67]。钒和铬在环境中的毒性和迁移性随其价态的升高而增加。钒酸盐形式的V(V)毒性和迁移性最强，而V(Ⅵ)毒性较小，且在中性pH条件下不溶于水^[68]；类似地，Cr(Ⅵ)被认为是一种剧毒物质，而Cr(Ⅲ)在水中溶解度低、流动性差、毒性小^[69]。

自20世纪70年代以来，多种细菌或真菌[如奥奈达湖希瓦氏菌(Shewanella oneidensis)]对钒的生物还原能力被陆续报道^[70]，然而古菌是否有该能力尚未见报道^[71]。直到2015年，Zhang等^[72]发现嗜温产甲烷古菌Methanosarcina mazei和嗜热产甲烷古菌Methanothermobacter thermautotrophicus在生长和非生长条件下均具有还原V(V)的能力，还原速率和程度取决于不同的底物和V(V)浓度，V(V)的生物还原发生在胞外，并伴随着无定形V(Ⅳ)沉淀的形成；同时，V(V)的还原抑制了甲烷的生成，这可能是由于部分电子从甲烷生成转移到了钒酸盐还原。此外，以甲烷为电子供体，在添加了钒酸盐的厌氧污泥生物反应器中也观察到了产甲烷古菌丰度的增加^[68]。

以H₂/CO₂作为底物，Methanothermobacter thermautotrophicus还被报道能够还原Cr(Ⅵ)，在0.2 mmol/L和0.4 mmol/L低浓度下能达到完全还原，在较高浓度下则能实现3.7%-43.6%的还原，这可能是由于高浓度铬对产甲烷古菌产生了毒性；还原态铬主要以氢氧化物或氧化物样的无定形固体形式存在，并含有一定比例的可溶性Cr(Ⅲ)，其甲烷生成也受到了不同程度抑制，可能是由于Cr(Ⅵ)具有细胞毒性，也可能由于部分电子从甲烷生成转移到了铬还原^[73]。

将高毒性、迁移性的V(V)和Cr(Ⅵ)还原为较低的氧化态，被认为是一种从受污染地下水等环境去除钒和铬的修复方法，而产甲烷古菌介导的V(V)和Cr(Ⅵ)的生物还原在缺氧环境污染修复上展现出重要应用潜力。截至目前，关于其具体还原机制与调控网络仍不清楚，还需进一步深入探究。

3 产甲烷古菌对类金属的转化

收起

3.1 砷

砷(As)是一种广泛存在于自然界的剧毒元素^[74]，其环境中的化学形态多样，且不同形态对生物体的毒性差异显著^[75]。一般而言，As(Ⅲ)的毒性和迁移性均高于As(V)，而+3价有机胂的毒性甚至超过无机砷，+5价有机胂则相反^[76]。微生物能够介导多种砷形态的转化，包括As(V)和As(Ⅲ)之间的氧化还原反应，以及砷化合物的甲基化和去甲基化过程等^[75]，直接或间接影响其在环境中的迁移转化。其中，产甲烷古菌在砷的生物地球化学循环中扮演着关键角色^[77]。

研究表明^[78-79]，产甲烷古菌Methanosarcina mazei具有砷甲基化能力，但这主要通过与产甲烷过程的核心辅因子反应相耦合，并不依赖于(类)金属特异性甲基转移酶，产甲烷古菌是否存在砷甲基化的酶促途径尚不清楚。直到2014年，朱永官团队首次从产甲烷古菌Methanosarcina acetivorans C2A中鉴定并表征了As(Ⅲ)S-腺苷甲硫氨酸甲基转移酶(arsenic methyltransferase, ArsM)，证实了该菌株具有将无机砷转化为有机胂的能力^[80]。Viacava等^[81]评估了编码活性ArsM的7种微生物的砷甲基化能力，发现产甲烷古菌(Methanosarcina mazei Gö1和Methanosarcina acetivorans C2A)相较于其他厌氧微生物具有更好的甲基化效率，并进一步证实了这些产甲烷古菌的甲基化可能不是由于活细胞进行的主动代谢，而是由于在稳定期从死细胞释放的与甲烷生成相关的甲基转移酶、辅因子或ArsM (如果表达)所介导的被动事件，为产甲烷古菌的砷甲基化提供了另一种解释。Wang等^[82]在富含硫化物的温泉沉积物富集培养物中，检测到了唯一产甲烷古菌属甲烷八叠球菌属(Methanosarcina)，并利用该属中的纯菌株Methanosarcina thermophila TM-1进一步验证，发现其确实可以使砷甲基化，并且甲基化后的产物在富含硫的环境中发生非生物硫醇化反应，生成了毒性更高的甲基化硫代砷酸盐。近期，Liang等^[83]也证实，产甲烷古菌Methanosarcina acetivorans C2A可以利用ArsM催化As(Ⅲ)转化为一甲基胂(monomethylarsine, MMA)，若底物条件和电子供体充足，还可以进一步催化生成二甲基胂(dimethylarsine, DMA)和三甲基胂(trimethylarsine, TMA)。值得一提的是，该团队还首次报道了Methanosarcina acetivorans C2A可以利用砷酸盐还原酶(arsenate reductase, ArsC)催化As(V)还原为As(Ⅲ)，并且低浓度As(V)的添加促进了其生长和产气，高浓度As(V)的添加则显著抑制了该过程^[83]。

与上述研究不同的是，产甲烷古菌还被报道能够使稻田土壤中的有机胂去甲基化^[84-85]。Chen等^[84]发现，水稻土富集培养物中的产甲烷古菌能催化DMA(Ⅲ)去甲基化，研究利用¹³C标记等手段，首次揭示了甲基化砷能被甲基营养型产甲烷古菌去甲基化。随后，该团队在富集培养物中分离出了能够去甲基化DMA(Ⅲ)的H₂依赖性甲基营养型产甲烷古菌Methanomassiliicoccus luminyensis CZDD1^[85]。

这些研究表明产甲烷古菌在砷的甲基化、还原、去甲基化过程中均发挥了关键作用，产甲烷古菌介导砷的转化呈现多样性，同时最新的报道也阐明了产甲烷古菌不同于细菌的砷转化机制，为理解砷的生物地球化学循环提供了新的理论依据。

3.2 硒

硒是一种微量元素，既是生物体必需的营养元素，也是一种环境毒物^[86-87]。硒的毒性和生物利用度与其价态密切相关^[88]。自然环境中，硒以4种不同的价态(-2、0、+4、+6)存在，包括多种无机(硒酸盐、亚硒酸盐、元素硒、硒化物)和有机(氨基酸、甲基化化合物)形式^[89]。其中，硒酸盐和亚硒酸盐在高浓度下具有生物毒性，解毒可以通过甲基化挥发来实现^[90]。硒纳米颗粒(selenium nanoparticles, SeNPs)是硒的一种单质形式^[91]，其细胞毒性低于硒酸盐和亚硒酸盐。

在古菌中，只有甲烷球菌属(Methanococcus)、甲烷热球菌属(Methanocaldococcus)和甲烷火菌属(Methanopyrus)可以合成硒蛋白，它们仅通过甲烷生成的氢营养途径保存能量以供生长^[92-93]。绝大多数古菌硒蛋白都参与了产甲烷代谢过程，以模式产甲烷古菌海沼甲烷球菌(Methanococcus maripaludis) JJ为例，其9种硒蛋白中有7种都直接参与这一代谢途径^[94]，但在培养过程中，如果硒被剥夺或硒蛋白合成途径被破坏，它们可以被含半胱氨酸的亚型取代，从而进行不依赖于硒的生长^[95]。据报道，甲烷球菌属(Methanococcus)能够利用2种形态的硒：亚硒酸钠和二甲基硒(dimethylselenide, DMSe)^[90]。然而最新研究发现，该属的Methanococcus maripaludis除了能利用这2种形态的硒外，部分硒源(如硒氰酸盐)的利用效率与亚硒酸盐相当甚至更高，而硒酸盐和硒代氨基酸需在非生理性高浓度下才能被利用，二苯基二硒和硒脲则完全无法被利用^[96]。值得注意的是，对于一些依赖含硒酶进行核心代谢的生物，硒必不可少。如当培养基中硒缺乏时，会导致超嗜热产甲烷古菌詹氏甲烷热球菌(Methanocaldococcus jannaschii)无法生长^[97]，Methanococcus voltae生长速率降低^[98-99]。然而，Niess等^[90]报道Methanococcus voltae可能含有一个参与DMSe去甲基化过程的基因簇sdmAC，在硒缺乏条件下能够诱导该蛋白簇的高效表达，SdmA和SdmC两种不同的甲基转移酶可能参与了DMSe的逐步去甲基化，二甲基硒化物的去甲基化也为Methanococcus voltae的正常生长开辟了另一种硒源。

近期，Liu等^[91]发现，当产甲烷古菌Methanosarcina acetivorans C2A暴露于低浓度的SeNPs时，显著促进了其生长和CH₄产生，这可能由于低浓度的SeNPs促进了离子转运和氨基酸合成，而在较高浓度下，SeNPs会诱导氧化应激，破坏代谢过程并抑制生长和CH₄产生；此外，该研究还证实了SeNPs能够被Methanosarcina acetivorans C2A转化为多种有机硒和无机硒化物，体现了SeNPs的生物可用性；令人惊喜的是，还检测到了挥发性硒物种——DMSe、二甲基二硒化物(dimethyldiselenide, DMDSe)和二甲基硒酮(dimethylselenone, DMSeO₂)，表明该菌株具有催化SeNPs转化为挥发性硒的特殊代谢途径，这种策略可能用于硒解毒。

上述研究表明，产甲烷古菌在硒的利用、去甲基化等过程中均发挥了关键作用，同时其对SeNPs的生物转化具有双重性：低浓度SeNPs会促进产甲烷活性并诱导有机硒合成，而高浓度则引发氧化应激。这些发现对进一步解析硒的生物地球化学循环及其环境影响具有重要的研究价值。

本文汇总整理了上述多种产甲烷古菌对(类)金属的转化情况及其生长代谢受到的影响，详见表１。

4 总结与展望

收起

产甲烷古菌是生物产甲烷过程的关键微生物，在全球碳循环和生物能源生产中发挥着重要作用。近年来，产甲烷古菌在(类)金属生物地球化学循环中的重要作用已被广泛报道。本文系统梳理了产甲烷古菌对部分(类)金属——Fe、Hg、V、Cr、Cd、As、Se的转化机制，并阐述了该转化过程对产甲烷古菌自身生长和产气的影响。

然而，目前关于产甲烷古菌对(类)金属的转化机制其实还缺乏更为深入的研究。例如，产甲烷古菌是通过何种机制进行钒和铬的还原？产甲烷古菌对于有机胂的去甲基化又是如何实现的？因此未来研究应重点关注以下方向：首先，需要结合新型实验技术和方法，深入探究产甲烷古菌对(类)金属的转化机理。考虑到不同产甲烷古菌的代谢底物和电子传递途径可能存在显著差异，可整合比较基因组学、转录组分析等高通量技术，并结合基因敲除等分子生物学手段，以阐明这些转化行为背后的分子机制。其次，应进一步探究复杂环境基质中多种(类)金属的协同转化规律，开发基于产甲烷古菌的(类)金属污染生物修复技术。此外，还需综合运用元素通量模型、同位素示踪与指纹分析、长期监测与大数据整合等手段，系统评估此类转化过程对全球元素循环的贡献，研究重点包括：量化局部环境中的(类)金属形态转化速率、结合地球化学模型(如Geochemist’s Workbench)解析(类)金属转化对碳-硫耦合循环的影响、预测未来气候变化下的生物转化趋势，从而为环境治理和可持续发展提供创新的生物技术策略支持。

作者利益冲突公开声明

收起

作者声明绝无任何可能会影响本文所报告工作的已知经济利益或个人关系。

基金

收起

国家自然科学基金(42477232)
国家自然科学基金(22008142)
山东省自然科学基金(ZR2022YQ31)
泰山学者青年专家基金(tsqn202310123)

参考文献

收起

文献

收起

参考文献引证文献

排序方式：

[1]

ROTHMAN

, FOURNIER

, FRENCH

, ALM EJ, BOYLE

, CAO

, SUMMONS

. Methanogenic burst in the end-Permian carbon cycle[J]. Proceedings of the National Academy of Sciences of the United States of America, 2014, 111(15): 5462-5467.

[2]

MEYER

, MICHALKE

, KOURIL

, HENSEL

. Volatilisation of metals and metalloids: an inherent feature of methanoarchaea[J]. Systematic and Applied Microbiology, 2008, 31(2): 81-87.

[3]

STARR

, STOLP

, TRÜPER

, BALOWS

, SCHLEGEL

. The Prokaryotes: a Handbook on Habitats, Isolation and Identification of Bacteria[M]. Berlin: Springer Science & Business Media, 2013: 6-662.

[4]

YAN

, DU

, YAN

, HUANG

, ZHU

, YUAN

, WANG

, FERRY

. Respiration-driven methanotrophic growth of diverse marine methanogens[J]. Proceedings of the National Academy of Sciences of the United States of America, 2023, 120(39): e2303179120.

[5]

WOESE

, KANDLER

, WHEELIS

. Towards a natural system of organisms: proposal for the domains archaea, bacteria, and eucarya[J]. Proceedings of the National Academy of Sciences of the United States of America, 1990, 87(12): 4576-4579.

[6]

方晓瑜, 李家宝, 芮俊鹏, 李香真. 产甲烷生化代谢途径研究进展[J]. 应用与环境生物学报, 2015, 21(1): 1-9.

FANG

, LI

, RUI

, LI

. Research progress in biochemical pathways of methanogenesis[J]. Chinese Journal of Applied and Environmental Biology, 2015, 21(1): 1-9 (in Chinese).

[7]

DRIDI

, FARDEAU

, OLLIVIER

, RAOULT

, DRANCOURT

. Methanomassiliicoccus luminyensis gen. nov., sp. nov., a methanogenic archaeon isolated from human faeces[J]. International Journal of Systematic and Evolutionary Microbiology, 2012, 62(Pt 8): 1902-1907.

[8]

SOROKIN

, MERKEL

, ABBAS

, MAKAROVA

, RIJPSTRA

WIC

, KOENEN

, SINNINGHE DAMSTÉ

, GALINSKI

, KOONIN

, van LOOSDRECHT

MCM

. Methanonatronarchaeum Thermophilum gen. nov., sp. nov. and “Candidatus Methanohalarchaeum thermophilum”, extremely halo(natrono)philic methyl-reducing methanogens from hypersaline lakes comprising a new euryarchaeal class Methanonatronarchaeia classis nov.[J]. International Journal of Systematic and Evolutionary Microbiology, 2018, 68(7): 2199-2208.

[9]

BORREL

, ADAM

, McKAY

, CHEN

, SIERRA-GARCÍA

, SIEBER

CMK

, LETOURNEUR

, GHOZLANE

, ANDERSEN

, LI

, HALLAM

, MUYZER

, de OLIVEIRA

, INSKEEP

, BANFIELD

, GRIBALDO

. Wide diversity of methane and short-chain alkane metabolisms in uncultured archaea[J]. Nature Microbiology, 2019, 4(4): 603-613.

[10]

RINKE

, CHUVOCHINA

, MUSSIG

, CHAUMEIL

, DAVÍN

, WAITE

, WHITMAN

, PARKS

, HUGENHOLTZ

. A standardized archaeal taxonomy for the genome taxonomy database[J]. Nature Microbiology, 2021, 6(7): 946-959.

[11]

任师杰, 孔令豆, 刘骏, 李乐, 张勍, 陈集双, 周俊. 产甲烷古菌的分类及代谢途径研究进展[J]. 中国生物工程杂志, 2024, 44(9): 100-112.

REN

, KONG

, LIU

, LI

, ZHANG

, CHEN

, ZHOU

. Advances in classification and metabolic pathways of methanogenic archaea[J]. China Biotechnology, 2024, 44(9): 100-112 (in Chinese).

[12]

LIU

, WHITMAN

. Metabolic, phylogenetic, and ecological diversity of the methanogenic archaea[J]. Annals of the New York Academy of Sciences, 2008, 1125(1): 171-189.

[13]

OFFRE

, SPANG

, SCHLEPER

. Archaea in biogeochemical cycles[J]. Annual Review of Microbiology, 2013, 67: 437-457.

[14]

承磊, 郑珍珍, 王聪, 张辉. 产甲烷古菌研究进展[J]. 微生物学通报, 2016, 43(5): 1143-1164.

CHENG

, ZHENG

, WANG

, ZHANG

. Recent advances in methanogens[J]. Microbiology China, 2016, 43(5): 1143-1164 (in Chinese).

[15]

LEADBETTER

, BREZNAK

. Physiological ecology of Methanobrevibacter cuticularis sp. nov. and Methanobrevibacter curvatus sp. nov., isolated from the hindgut of the termite Reticulitermes flavipes [J]. Applied and Environmental Microbiology, 1996, 62(10): 3620-3631.

[16]

FERRY

. Enzymology of one-carbon metabolism in methanogenic pathways[J]. FEMS Microbiology Reviews, 1999, 23(1): 13-38.

[17]

MAYUMI

, MOCHIMARU

, TAMAKI

, YAMAMOTO

, YOSHIOKA

, SUZUKI

, KAMAGATA

, SAKATA

. Methane production from coal by a single methanogen[J]. Science, 2016, 354(6309): 222-225.

[18]

ZHOU

, ZHANG

, LIU

, FU

, LASO-PÉREZ

, YANG

, BAI

, LI

, YANG

, LIN

, WANG

, WEGENER

, LI

, CHENG

. Non-syntrophic methanogenic hydrocarbon degradation by an archaeal species[J]. Nature, 2021, 601(7892): 257-262.

[19]

易悦, 周卓, 黄艳, 承磊. 我国产甲烷古菌研究进展与展望[J]. 微生物学报, 2023, 63(5): 1796-1814.

, ZHOU

, HUANG

, CHENG

. Methanogen research in China: current status and prospective[J]. Acta Microbiologica Sinica, 2023, 63(5): 1796-1814 (in Chinese).

[20]

VARGAS

, KASHEFI

, BLUNT-HARRIS

, LOVLEY

. Microbiological evidence for Fe(Ⅲ) reduction on early earth[J]. Nature, 1998, 395(6697): 65-67.

[21]

KAPPLER

, BRYCE

, MANSOR

, LUEDER

, BYRNE

, SWANNER

. An evolving view on biogeochemical cycling of iron[J]. Nature Reviews Microbiology, 2021, 19(6): 360-374.

[22]

STUCKI

, KOSTKA

. Microbial reduction of iron in smectite[J]. Comptes Rendus Geoscience, 2006, 338(6/7): 468-475.

[23]

DONG

, JAISI

, KIM

, ZHANG

. Microbe-clay mineral interactions[J]. American Mineralogist, 2009, 94(11/12): 1505-1519.

[24]

STUCKI

, LEE

, ZHANG

, LARSON

. Effects of iron oxidation states on the surface and structural properties of smectites[J]. Pure and Applied Chemistry, 2002, 74(11): 2145-2158.

[25]

ZHANG

, DONG

, LIU

, FISCHER

, WANG

, HUANG

. Microbial reduction of Fe(Ⅲ) in illite-smectite minerals by methanogen Methanosarcina mazei [J]. Chemical Geology, 2012, 292: 35-44.

[26]

BOND

, LOVLEY

. Reduction of Fe(Ⅲ) oxide by methanogens in the presence and absence of extracellular quinones[J]. Environmental Microbiology, 2002, 4(2): 115-124.

[27]

van BODEGOM

, SCHOLTEN

JCM

, STAMS

AJM

. Direct inhibition of methanogenesis by ferric iron[J]. FEMS Microbiology Ecology, 2004, 49(2): 261-268.

[28]

SIVAN

, SHUSTA

, VALENTINE

. Methanogens rapidly transition from methane production to iron reduction[J]. Geobiology, 2016, 14(2): 190-203.

[29]

LIU

, WANG

, DONG

, QIU

, DONG

, CRAVOTTA

. Mineral transformations associated with goethite reduction by Methanosarcina barkeri [J]. Chemical Geology, 2011, 288(1/2): 53-60.

[30]

ELIANI-RUSSAK

, TIK Z, UZI-GAVRILOV

, MEIJLER

, SIVAN

. The reduction of environmentally abundant iron oxides by the methanogen Methanosarcina barkeri [J]. Frontiers in Microbiology, 2023, 14: 1197299.

[31]

LIU

, DONG

, BISHOP

, WANG

, AGRAWAL

, TRITSCHLER

, EBERL

, XIE

. Reduction of structural Fe(Ⅲ) in nontronite by methanogen Methanosarcina barkeri [J]. Geochimica et Cosmochimica Acta, 2011, 75(4): 1057-1071.

[32]

ZHANG

, DONG

, LIU

, AGRAWAL

. Microbial reduction of Fe(Ⅲ) in smectite minerals by thermophilic methanogen Methanothermobacter thermautotrophicus [J]. Geochimica et Cosmochimica Acta, 2013, 106: 203-215.

[33]

YAMADA

, KATO

, KIMURA

, ISHII

, IGARASHI

. Reduction of Fe(Ⅲ) oxides by phylogenetically and physiologically diverse thermophilic methanogens[J]. FEMS Microbiology Ecology, 2014, 89(3): 637-645.

[34]

HIRANO

, MATSUMOTO

, MORITA

, SASAKI

, OHMURA

. Electrochemical control of redox potential affects methanogenesis of the hydrogenotrophic methanogen Ethanothermobacter thermautotrophicus [J]. Letters in Applied Microbiology, 2013, 56(5): 315-321.

[35]

FETZER

, CONRAD

. Effect of redox potential on methanogenesis by Methanosarcina barkeri [J]. Archives of Microbiology, 1993, 160(2): 108-113.

[36]

WANG

, BYRNE

, LIU

, DONG

, LU

. Redox cycling of Fe(Ⅱ) and Fe(Ⅲ) in magnetite accelerates aceticlastic methanogenesis by Methanosarcina mazei [J]. Environmental Microbiology Reports, 2020, 12(1): 97-109.

[37]

GUO

, LU

. Cometabolism of ferrihydrite reduction and methyl-dismutating methanogenesis by Methanosarcina mazei [J]. Applied and Environmental Microbiology, 2025, 91(3): e0223824.

[38]

YANG

, LU

. Coupling methanogenesis with iron reduction by acetotrophic Methanosarcina mazei zm-15[J]. Environmental Microbiology Reports, 2022, 14(5): 804-811.

[39]

PRAKASH

, CHAUHAN

, FERRY

. Life on the thermodynamic edge: respiratory growth of an acetotrophic methanogen[J]. Science Advances, 2019, 5(8): eaaw9059.

[40]

SONG

, HUANG

, LI

, DU

, ZHU

, SONG

, YUAN

, WANG

, FERRY

, ZHOU

, YAN

. Humic acid-dependent respiratory growth of Methanosarcina acetivorans involves pyrroloquinoline quinone[J]. The ISME Journal, 2023, 17(11): 2103-2111.

[41]

YAN

, JOSHI

, GORSKI

, FERRY

. A biochemical framework for anaerobic oxidation of methane driven by Fe(Ⅲ)-dependent respiration[J]. Nature Communications, 2018, 9(1): 1642.

[42]

, ZHOU

, WANG

, YOU

, LU

, YU

, ZHOU

. NanoFe₃O₄ as solid electron shuttles to accelerate acetotrophic methanogenesis by Methanosarcina barkeri [J]. Frontiers in Microbiology, 2019, 10: 388.

[43]

SHANG

, DAYE

, SIVAN

, BORLINA

, TAMURA

, WEISS

, BOSAK

. Formation of zerovalent iron in iron-reducing cultures of Methanosarcina barkeri [J]. Environmental Science & Technology, 2020, 54(12): 7354-7365.

[44]

KATO

, HASHIMOTO

, WATANABE

. Methanogenesis facilitated by electric syntrophy via (semi)conductive iron-oxide minerals[J]. Environmental Microbiology, 2012, 14(7): 1646-1654.

[45]

JIANG

, PARK

, YOON

, LEE

, WU

, DAN

, SADOWSKY

, HUR HG. Methanogenesis facilitated by geobiochemical iron cycle in a novel syntrophic methanogenic microbial community[J]. Environmental Science & Technology, 2013, 47(17): 10078-10084.

[46]

BERNER

. Sedimentary pyrite formation: an update[J]. Geochimica et Cosmochimica Acta, 1984, 48(4): 605-615.

[47]

CANFIELD

, HABICHT

, THAMDRUP

. The Archean sulfur cycle and the early history of atmospheric oxygen[J]. Science, 2000, 288(5466): 658-661.

[48]

PAYNE

, SPIETZ

, BOYD

. Reductive dissolution of pyrite by methanogenic archaea[J]. The ISME Journal, 2021, 15(12): 3498-3507.

[49]

, BARKAY

. Advances in Applied Microbiology[M]. Amsterdam: Elsevier Academic Press, 2022: 31-90.

[50]

陶少洋, 杨婧铱, 高峻, 董洪哲, 刘丽红, 何滨, 毛宇翔, 胡立刚, 江桂斌. 产甲烷菌中汞甲基化研究进展与展望[J]. 环境化学, 2024, 43(7): 2153-2165.

TAO

, YANG

, GAO

, DONG

, LIU

, HE

, MAO

, HU

, JIANG

. Research progress and prospect of mercury methylation in methanogens[J]. Environmental Chemistry, 2024, 43(7): 2153-2165 (in Chinese).

[51]

GILMOUR

, ELIAS

, KUCKEN

, BROWN

, PALUMBO

, SCHADT

, WALL

. Sulfate-reducing bacterium Desulfovibrio desulfuricans ND132 as a model for understanding bacterial mercury methylation[J]. Applied and Environmental Microbiology, 2011, 77(12): 3938-3951.

[52]

, DU

, WANG

. Mercury methylation by anaerobic microorganisms: a review[J]. Critical Reviews in Environmental Science and Technology, 2019, 49(20): 1893-1936.

[53]

WOOD

, KENNEDY

, ROSEN

. Synthesis of methyl-mercury compounds by extracts of a methanogenic bacterium[J]. Nature, 1968, 220(5163): 173-174.

[54]

HAMELIN

, AMYOT

, BARKAY

, WANG

, PLANAS

. Methanogens: principal methylators of mercury in lake periphyton[J]. Environmental Science & Technology, 2011, 45(18): 7693-7700.

[55]

, REINFELDER

, HINES

, BARKAY

. Mercury methylation by the methanogen Methanospirillum hungatei [J]. Applied and Environmental Microbiology, 2013, 79(20): 6325-6330.

[56]

PARKS

, JOHS

, PODAR

, BRIDOU

, HURT RA Jr, SMITH

, TOMANICEK

, QIAN

, BROWN

, BRANDT

, PALUMBO

, SMITH

, WALL

, ELIAS

, LIANG

. The genetic basis for bacterial mercury methylation[J]. Science, 2013, 339(6125): 1332-1335.

[57]

GILMOUR

, PODAR

, BULLOCK

, GRAHAM

, BROWN

, SOMENAHALLY

, JOHS

, HURT RA Jr, BAILEY

, ELIAS

. Mercury methylation by novel microorganisms from new environments[J]. Environmental Science & Technology, 2013, 47(20): 11810-11820.

[58]

PODAR

, GILMOUR

, BRANDT

, SOREN

, BROWN

, CRABLE

, PALUMBO

, SOMENAHALLY

, ELIAS

. Global prevalence and distribution of genes and microorganisms involved in mercury methylation[J]. Science Advances, 2015, 1(9): e1500675.

[59]

GILMOUR

, BULLOCK

, McBURNEY

, PODAR

, ELIAS

. Robust mercury methylation across diverse methanogenic archaea[J]. mBio, 2018, 9(2): e02403-17.

[60]

OREMLAND

, CULBERTSON

, WINFREY

. Methylmercury decomposition in sediments and bacterial cultures: involvement of methanogens and sulfate reducers in oxidative demethylation[J]. Applied and Environmental Microbiology, 1991, 57(1): 130-137.

[61]

CHENG

. Heavy metal pollution in China: origin, pattern and control[J]. Environmental Science and Pollution Research, 2003, 10(3): 192-198.

[62]

SIMPSON

. A critical review of cadmium in the marine environment[J]. Progress in Oceanography, 1981, 10(1): 1-70.

[63]

LIRA-SILVA

, SANTIAGO-MARTÍNEZ

, HERNÁNDEZ-JUÁREZ

, GARCÍA-CONTRERAS

, MORENO-SÁNCHEZ

, JASSO-CHÁVEZ

. Activation of methanogenesis by cadmium in the marine archaeon Methanosarcina acetivorans [J]. PLoS One, 2012, 7(11): e48779.

[64]

JASSO-CHÁVEZ

, LIRA-SILVA

, GONZÁLEZ-SÁNCHEZ

, LARIOS-SERRATO

, MENDOZA-MONZOY

, PÉREZ-VILLATORO

, MORETT

, VEGA-SEGURA

, TORRES-MÁRQUEZ

, ZEPEDA-RODRÍGUEZ

, MORENO-SÁNCHEZ

. Marine archaeon Methanosarcina acetivorans enhances polyphosphate metabolism under persistent cadmium stress[J]. Frontiers in Microbiology, 2019, 10: 2432.

[65]

LIRA-SILVA

, SANTIAGO-MARTÍNEZ

, GARCÍA-CONTRERAS

, ZEPEDA-RODRÍGUEZ

, MARÍN-HERNÁNDEZ

, MORENO-SÁNCHEZ

, JASSO-CHÁVEZ

. Cd²⁺ resistance mechanisms in Methanosarcina acetivorans involve the increase in the coenzyme M content and induction of biofilm synthesis[J]. Environmental Microbiology Reports, 2013, 5(6): 799-808.

[66]

HUANG

, HUANG

, EVANS

, GLASAUER

. Vanadium: global (bio)geochemistry[J]. Chemical Geology, 2015, 417: 68-89.

[67]

ZHONG

, YIN

, LI

, WU

, JIANG

, GU

, LIANG

. Column study of enhanced Cr(Ⅵ) removal and longevity by coupled abiotic and biotic processes using Fe⁰ and mixed anaerobic culture[J]. Water Research, 2017, 122: 536-544.

[68]

ZHANG

, JIANG

, ZUO

, HE

, DAI

, REN

. Microbial vanadate and nitrate reductions coupled with anaerobic methane oxidation in groundwater[J]. Journal of Hazardous Materials, 2020, 382: 121228.

[69]

, LI

, YIN

, ZHANG

, ZHONG

, LI

, DENG

, WU

. Effects of electron donors and acceptors on Cr(Ⅵ) removal in biotic Fe0 columns preloaded with microorganisms[J]. Water, Air, & Soil Pollution, 2022, 233(12): 483.

[70]

CARPENTIER

, SANDRA

, de SMET

, BRIGÉ

, de SMET

, BEEUMEN

. Microbial reduction and precipitation of vanadium by Shewanella oneidensis [J]. Applied and Environmental Microbiology, 2003, 69(6): 3636-3639.

[71]

REHDER

. Is vanadium a more versatile target in the activity of primordial life forms than hitherto anticipated[J]. Organic & Biomolecular Chemistry, 2008, 6(6): 957-964.

[72]

ZHANG

, DONG

, ZHAO

, McCARRICK

, AGRAWAL

. Microbial reduction and precipitation of vanadium by mesophilic and thermophilic methanogens[J]. Chemical Geology, 2014, 370: 29-39.

[73]

SINGH

, DONG

, LIU

, ZHAO

, MARTS

, FARQUHAR

, TIERNEY

, ALMQUIST

, BRIGGS

. Reduction of hexavalent chromium by the thermophilic methanogen Methanothermobacter thermautotrophicus [J]. Geochimica et Cosmochimica Acta, 2015, 148: 442-456.

[74]

ABERNATHY

, THOMAS

, CALDERON

. Health effects and risk assessment of arsenic[J]. The Journal of Nutrition, 2003, 133(5): 1536S-1538S.

[75]

ZHU

, YOSHINAGA

, ZHAO

, ROSEN

. Earth abides arsenic biotransformations[J]. Annual Review of Earth and Planetary Sciences, 2014, 42: 443-467.

[76]

AKTER

, OWENS

, DAVEY

, NAIDU

. Arsenic speciation and toxicity in biological systems[J]. Reviews of Environmental Contamination and Toxicology, 2005, 184: 97-149.

[77]

ZHAO

, MA

, ZHU

, TANG

, McGRATH

. Soil contamination in China: current status and mitigation strategies[J]. Environmental Science & Technology, 2015, 49(2): 750-759.

[78]

THOMAS

, DIAZ-BONE

, WUERFEL

, HUBER

, WEIDENBACH

, SCHMITZ

, HENSEL

. Connection between multimetal(loid) methylation in methanoarchaea and central intermediates of methanogenesis[J]. Applied and Environmental Microbiology, 2011, 77(24): 8669-8675.

[79]

WUERFEL

, THOMAS

, SCHULTE

, HENSEL

, DIAZ-BONE

. Mechanism of multi-metal(loid) methylation and hydride generation by methylcobalamin and cob(I)alamin: a side reaction of methanogenesis[J]. Applied Organometallic Chemistry, 2012, 26(2): 94-101.

[80]

WANG

, SUN

, ZHU

. Identification and characterization of arsenite methyltransferase from an archaeon, Methanosarcina acetivorans C2A[J]. Environmental Science & Technology, 2014, 48(21): 12706-12713.

[81]

VIACAVA

, MEIBOM

, ORTEGA

, DYER

, GELB

, FALQUET

, MINTON

, MESTROT

, BERNIER-LATMANI

. Variability in arsenic methylation efficiency across aerobic and anaerobic microorganisms[J]. Environmental Science & Technology, 2020, 54(22): 14343-14351.

[82]

WANG

, GUO

, WU

, YU

, NININ

JML

, PLANER-FRIEDRICH

. Methanogens-driven arsenic methylation preceding formation of methylated thioarsenates in sulfide-rich hot springs[J]. Environmental Science & Technology, 2023, 57(19): 7410-7420.

[83]

LIANG

, YAN

, SHI

, WANG

, YUAN

, WANG

, YE

, YAN

. Molecular basis of thioredoxin-dependent arsenic transformation in methanogenic archaea[J]. Environmental Science & Technology, 2025, 59(1): 443-453.

[84]

CHEN

, LI

, HUANG

, ZHANG

, XIE

, LU

, DONG

, ZHAO

. Sulfate-reducing bacteria and methanogens are involved in arsenic methylation and demethylation in paddy soils[J]. The ISME Journal, 2019, 13(10): 2523-2535.

[85]

CHEN

, LI

, WANG

, DONG

, ZHAO

. Methylotrophic methanogens and bacteria synergistically demethylate dimethylarsenate in paddy soil and alleviate rice straighthead disease[J]. The ISME Journal, 2023, 17(11): 1851-1861.

[86]

RAYMAN

. Selenium and human health[J]. The Lancet, 2012, 379(9822): 1256-1268.

[87]

FAN

TWM

, TEH SJ, HINTON

, HIGASHI

. Selenium biotransformations into proteinaceous forms by foodweb organisms of selenium-laden drainage waters in California[J]. Aquatic Toxicology, 2002, 57(1/2): 65-84.

[88]

AMWEG

, STUART

, WESTON

. Comparative bioavailability of selenium to aquatic organisms after biological treatment of agricultural drainage water[J]. Aquatic Toxicology, 2003, 63(1): 13-25.

[89]

ASTRATINEI

, van HULLEBUSCH

, LENS

. Bioconversion of selenate in methanogenic anaerobic granular sludge[J]. Journal of Environmental Quality, 2006, 35(5): 1873-1883.

[90]

NIESS

, KLEIN

. Dimethylselenide demethylation is an adaptive response to selenium deprivation in the archaeon Methanococcus voltae [J]. Journal of Bacteriology, 2004, 186(11): 3640-3648.

[91]

LIU

, MA

, WANG

, DUAN

, FENG

, ZHU

, SUN

, YAN

, YUAN

. Chemical dynamics of selenium nanoparticles in archaeal systems[J]. ACS Nano, 2024, 18(24): 15661-15670.

[92]

STOCK

, SELZER

, ROTHER

. In vivo requirement of selenophosphate for selenoprotein synthesis in archaea[J]. Molecular Microbiology, 2010, 75(1): 149-160.

[93]

ROTHER

, RESCH

, WILTING

, BÖCK

. Selenoprotein synthesis in archaea[J]. BioFactors, 2001, 14(1/2/3/4): 75-83.

[94]

POEHLEIN

, HEYM

, QUITZKE

, FERSCH

, DANIEL

, ROTHER

. Complete genome sequence of the Methanococcus maripaludis type strain JJ (DSM 2067), a model for selenoprotein synthesis in archaea[J]. Genome Announcements, 2018, 6(14): e00237-18.

[95]

QUITZKE

, FERSCH

, SEYHAN

, ROTHER

. Selenium-dependent gene expression in Methanococcus maripaludis: involvement of the transcriptional regulator HrsM[J]. Biochimica et Biophysica Acta (BBA) - General Subjects, 2018, 1862(11): 2441-2450.

[96]

FUNKNER

, POEHLEIN

, JEHMLICH

, EGELKAMP

, DANIEL

, von BERGEN

, ROTHER

. Proteomic and transcriptomic analysis of selenium utilization in Methanococcus maripaludis [J]. mSystems, 2024, 9(5): e0133823.

[97]

MUKHOPADHYAY

, JOHNSON

, WOLFE

. Reactor-scale cultivation of the hyperthermophilic methanarchaeon Methanococcus jannaschii to high cell densities[J]. Applied and Environmental Microbiology, 1999, 65(11): 5059-5065.

[98]

BURGGRAF

, FRICKE

, NEUNER

, KRISTJANSSON

, ROUVIER

, MANDELCO

, WOESE

, STETTER

. Methanococcus igneus sp. nov., a novel hyperthermophilic methanogen from a shallow submarine hydrothermal system[J]. Systematic and Applied Microbiology, 1990, 13: 263-269.

[99]

WHITMAN

, ANKWANDA

, WOLFE

. Nutrition and carbon metabolism of Methanococcus voltae [J]. Journal of Bacteriology, 1982, 149(3): 852-863.

2025年第65卷第6期

PDF下载

171

引用本文

BibTeX

文章信息

doi: 10.13343/j.cnki.wsxb.20250296

接收时间：2025-04-09
首发时间：2026-02-07
出版时间：2025-06-04

补充材料

相关文章

文章信息

作者

出版历史

收稿日期：2025-04-09
录用日期：2025-05-09

基金

National Natural Science Foundation of China(42477232)

国家自然科学基金(42477232)

National Natural Science Foundation of China(22008142)

国家自然科学基金(22008142)

Natural Science Foundation of Shandong Province(ZR2022YQ31)

山东省自然科学基金(ZR2022YQ31)

Taishan Scholars Project of Shandong Province(tsqn202310123)

泰山学者青年专家基金(tsqn202310123)

作者信息

山东大学环境科学与工程学院，山东省水环境污染控制与资源化重点实验室，山东青岛

通讯作者:

参考文献

分享链接

https://castjournals.cast.org.cn/joweb/wswxb/CN/10.13343/j.cnki.wsxb.20250296

分享至

全文二维码

扫描看全文

引用本文

BibTeX

本文的引用情况

2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

关闭全屏

BibTeX
EndNote
RefWorks
TxT

Organism	Substrate	Types of metal(loid)s	Methanogenesis	Main transformation products	References
Methanosarcina barkeri	H₂/CO₂	Amorphous Fe(OH)₃/goethite/ nontronite NAu-2	Inhibition	Fe(Ⅱ)	[26-27,29,31]
Methanosarcina barkeri	Methanol	Amorphous Fe(OH)₃	Inhibition	Fe(Ⅱ)	[26-27]
Methanosarcina barkeri	Acetate	Amorphous Fe(OH)₃	Inhibition	Fe(Ⅲ)	[26-27]
Methanosarcina barkeri	Acetate	Nontronite NAu-2	-	Fe(Ⅲ)	[31]
Methanosarcina barkeri	Methanol	Nontronite NAu-2	Inhibit initially but enhance ultimately	Fe(Ⅱ)	[31]
Methanosarcina barkeri	Close to natural conditions	Amorphous Fe(OH)₃/ hematite/magnetite	Inhibition	Fe(Ⅱ)	[28,30]
Methanosarcina barkeri	Acetate	NanoFe₃O₄	Enhancement	Fe(Ⅱ)	[42]
Methanosarcina barkeri	H₂/CO₂	Ferrihydrite	-	Fe(Ⅱ) and ZVI	[43]
Methanosarcina mazei	Methanol	Clay minerals (nontronite NAu-2/mixed-layer illite-smectite RAr-1 and ISCz-1/illite IMt-1)	Inhibition	Fe(Ⅱ)	[25]
Methanosarcina mazei	Acetate	NanoFe₃O₄	Enhancement	Redox cycling of Fe(Ⅱ) and Fe(Ⅲ)	[36]
Methanosarcina mazei	Acetate	Ferric citrate/ferrihydrite	Enhancement	Fe(Ⅱ)	[38]
Methanosarcina mazei	Methanol	Ferrihydrite	Enhancement	Fe(Ⅱ)	[37]
Methanosarcina mazei	Methanol	Goethite/hematite	No impact	Fe(Ⅲ)	[37]
Methanococcus voltae	H₂/CO₂	Amorphous Fe(OH)₃	Inhibition	Fe(Ⅱ)	[26]
Methanospirillum hungatei	H₂/CO₂/acetate	Amorphous Fe(OH)₃	Inhibition	-	[27]
Methanothrix soehngenii	Acetate	Amorphous Fe(OH)₃	Inhibition	-	[27]
Methanothermobacter thermautotrophicus	H₂/CO₂	Clay minerals (nontronite NAu-2/wyoming montmorillonite SWy-2)/ferrihydrite	Inhibition	Fe(Ⅱ)	[32-33]
Methanothrix thermoacetophila	Acetate	Ferrihydrite	Inhibition	Fe(Ⅲ)	[33]
Methanothrix thermoacetophila (high-density cultures)	H₂/CO₂	Ferrihydrite	-	Fe(Ⅱ)	[33]
Methanothrix thermoacetophila (high-density cultures)	Acetate and H₂/CO₂	Ferrihydrite	Inhibition	Fe(Ⅱ)	[33]
Methanosarcina thermophila	Methanol and H₂/CO₂	Ferrihydrite	Little inhibition	Fe(Ⅱ)	[33]
Methanosarcina thermophila	H₂/CO₂	Ferrihydrite	-	Fe(Ⅱ)	[33]
Methanosarcina thermophila	Acetate/methanol	Ferrihydrite	Inhibition	Fe(Ⅲ)	[33]
Methanopyrus kandleri	H₂/CO₂	Ferric citrate	-	Fe(Ⅱ)	[20]
Methanothermococcus thermolithotrophicus	H₂/CO₂	Ferric citrate	-	Fe(Ⅱ)	[20]
Methanosarcina barkeri	Methanol	Pyrite	-	Fe(Ⅱ) (reductive dissolution of FeS₂)	[48]
Methanococcus voltae	Formate	Pyrite	-	Fe(Ⅱ) (reductive dissolution of FeS₂)	[48]
Methanosarcina acetivorans	Acetate	Ferrihydrite	Enhancement	Fe(Ⅱ)	[39]
Methanospirillum hungatei	Na-formate	HgCl₂	-	MeHg	[55]
Methanomethylovorans hollandica	Methanol	Inorganic Hg	-	MeHg	[57]
Methanolobus tindarius	Methanol	Inorganic Hg	-	MeHg	[57]
Methanomassiliicoccus luminyensis	-	Inorganic Hg	-	MeHg	[58]
Methanosarcina acetivorans	Methanol	CdCl₂	No impact	-	[63]
Methanosarcina acetivorans	Acetate	CdCl₂	Enhancement	-	[63]
Methanosarcina mazei	Methanol	NaVO₃	Inhibition	V(Ⅳ)	[72]
Methanosarcina mazei	Acetate	NaVO₃	Inhibition	V(Ⅳ)	[72]
Methanosarcina mazei	H₂/CO₂	NaVO₃	Inhibition	V(Ⅳ)	[72]
Methanothermobacter thermautotrophicus	H₂/CO₂	NaVO₃	Inhibition	V(Ⅳ)	[72]
Methanothermobacter thermautotrophicus	H₂/CO₂	K₂Cr₂O₇	Inhibition	Cr(Ⅲ)	[73]
Methanosarcina thermophila	-	Arsenite	-	Methylated thioarsenates	[82]
Methanosarcina acetivorans	Methanol	As(Ⅲ)	-	MMA	[80,83]
Methanomassiliicoccus luminyensis	Methanol	DMA(Ⅲ)	-	As(Ⅲ)	[85]
Methanosarcina acetivorans	Methanol	SeNPs	Concentration-dependent promotion and inhibition	Inorganic selenium and organic selenium species	[91]

Organism

Substrate

Types of metal(loid)s

Methanogenesis

Main transformation products

References

Methanosarcina barkeri

H₂/CO₂

Amorphous Fe(OH)₃/goethite/

nontronite NAu-2

Inhibition

Fe(Ⅱ)

[26-27,29,31]

Methanosarcina barkeri

Methanol

Amorphous Fe(OH)₃

Inhibition

Fe(Ⅱ)

[26-27]

Methanosarcina barkeri

Acetate

Amorphous Fe(OH)₃

Inhibition

Fe(Ⅲ)

[26-27]

Methanosarcina barkeri

Acetate

Nontronite NAu-2

Fe(Ⅲ)

[31]

Methanosarcina barkeri

Methanol

Nontronite NAu-2

Inhibit initially but

enhance ultimately

Fe(Ⅱ)

[31]

Methanosarcina barkeri

Close to natural conditions

Amorphous Fe(OH)₃/

hematite/magnetite

Inhibition

Fe(Ⅱ)

[28,30]

Methanosarcina barkeri

Acetate

NanoFe₃O₄

Enhancement

Fe(Ⅱ)

[42]

Methanosarcina barkeri

H₂/CO₂

Ferrihydrite

Fe(Ⅱ) and ZVI

[43]

Methanosarcina mazei

Methanol

Clay minerals (nontronite NAu-2/mixed-layer illite-smectite RAr-1 and ISCz-1/illite IMt-1)

Inhibition

Fe(Ⅱ)

[25]

Methanosarcina mazei

Acetate

NanoFe₃O₄

Enhancement

Redox cycling of Fe(Ⅱ) and Fe(Ⅲ)

[36]

Methanosarcina mazei

Acetate

Ferric citrate/ferrihydrite

Enhancement

Fe(Ⅱ)

[38]

Methanosarcina mazei

Methanol

Ferrihydrite

Enhancement

Fe(Ⅱ)

[37]

Methanosarcina mazei

Methanol

Goethite/hematite

No impact

Fe(Ⅲ)

[37]

Methanococcus voltae

H₂/CO₂

Amorphous Fe(OH)₃

Inhibition

Fe(Ⅱ)

[26]

Methanospirillum hungatei

H₂/CO₂/acetate

Amorphous Fe(OH)₃

Inhibition

[27]

Methanothrix soehngenii

Acetate

Amorphous Fe(OH)₃

Inhibition

[27]

Methanothermobacter thermautotrophicus

H₂/CO₂

Clay minerals (nontronite

NAu-2/wyoming

montmorillonite SWy-2)/ferrihydrite

Inhibition

Fe(Ⅱ)

[32-33]

Methanothrix thermoacetophila

Acetate

Ferrihydrite

Inhibition

Fe(Ⅲ)

[33]

Methanothrix thermoacetophila (high-density cultures)

H₂/CO₂

Ferrihydrite

Fe(Ⅱ)

[33]

Methanothrix thermoacetophila (high-density cultures)

Acetate and H₂/CO₂

Ferrihydrite

Inhibition

Fe(Ⅱ)

[33]

Methanosarcina thermophila

Methanol and H₂/CO₂

Ferrihydrite

Little inhibition

Fe(Ⅱ)

[33]

Methanosarcina thermophila

H₂/CO₂

Ferrihydrite

Fe(Ⅱ)

[33]

Methanosarcina thermophila

Acetate/methanol

Ferrihydrite

Inhibition

Fe(Ⅲ)

[33]

Methanopyrus kandleri

H₂/CO₂

Ferric citrate

Fe(Ⅱ)

[20]

Methanothermococcus thermolithotrophicus

H₂/CO₂

Ferric citrate

Fe(Ⅱ)

[20]

Methanosarcina barkeri

Methanol

Pyrite

Fe(Ⅱ) (reductive dissolution of FeS₂)

[48]

Methanococcus voltae

Formate

Pyrite

Fe(Ⅱ) (reductive dissolution of FeS₂)

[48]

Methanosarcina acetivorans

Acetate

Ferrihydrite

Enhancement

Fe(Ⅱ)

[39]

Methanospirillum hungatei

Na-formate

HgCl₂

MeHg

[55]

Methanomethylovorans hollandica

Methanol

Inorganic Hg

MeHg

[57]

Methanolobus tindarius

Methanol

Inorganic Hg

MeHg

[57]

Methanomassiliicoccus luminyensis

Inorganic Hg

MeHg

[58]

Methanosarcina acetivorans

Methanol

CdCl₂

No impact

[63]

Methanosarcina acetivorans

Acetate

CdCl₂

Enhancement

[63]

Methanosarcina mazei

Methanol

NaVO₃

Inhibition

V(Ⅳ)

[72]

Methanosarcina mazei

Acetate

NaVO₃

Inhibition

V(Ⅳ)

[72]

Methanosarcina mazei

H₂/CO₂

NaVO₃

Inhibition

V(Ⅳ)

[72]

Methanothermobacter thermautotrophicus

H₂/CO₂

NaVO₃

Inhibition

V(Ⅳ)

[72]

Methanothermobacter thermautotrophicus

H₂/CO₂

K₂Cr₂O₇

Inhibition

Cr(Ⅲ)

[73]

Methanosarcina thermophila

Arsenite

Methylated thioarsenates

[82]

Methanosarcina acetivorans

Methanol

As(Ⅲ)

MMA

[80,83]

Methanomassiliicoccus luminyensis

Methanol

DMA(Ⅲ)

As(Ⅲ)

[85]

Methanosarcina acetivorans

Methanol

SeNPs

Concentration-dependent promotion and inhibition

Inorganic selenium and organic selenium species

[91]