Advancements in studying the biogeochemistry of methane in marine depositional systems through trace element geochemistry
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摘要:
由地质过程与微生物作用共同塑造的地球环境,当前正受到全球变暖的威胁,其中甲烷作为一种极为重要的温室气体,对全球变暖的贡献率已经达到了20%。海洋沉积物是地球最大的甲烷储库,在海洋富甲烷环境,微生物参与的产甲烷、甲烷厌氧氧化和甲烷有氧氧化过程广泛存在,是研究错综复杂的甲烷生物地球化学循环过程的理想实验室。本文从地质微生物学角度解析了含微量元素的酶或辅酶介导的甲烷循环过程,梳理了微生物潜在的微量元素需求,并重点综述了近年来主要涉及海洋甲烷循环过程研究的微量元素和同位素地球化学证据。由于参与甲烷循环过程的微生物纯培养相对困难,而地球化学研究又难以实现对生物地球化学过程的精细刻画,微生物学与地球化学的学科交叉研究优势明显、前景广阔。阐明海洋富甲烷环境微生物活动与微量元素的耦合关系,对于探索当前全球变暖背景下海洋甲烷循环过程和全球甲烷排放的调控至关重要,也有望为解析地质历史时期的甲烷排放事件及其全球生态环境效应提供独特的视角。
Abstract:The habitable planet, shaped by geological processes and microbial activity, is currently threatened by global warming. Methane, as an important greenhouse gas, is responsible for 20% of global warming. The largest amount of methane on the Earth is found in marine sediment. In these methane-rich marine environments, microbial process such as methanogenesis, anaerobic methane oxidation, and aerobic methane oxidation play a crucial role. In this review, the methane cycle mediated by enzymes or coenzymes containing trace elements was analyzed from the perspective of geological microbiology, the potential trace element demand of microorganisms was examined, and the geochemical evidence of trace elements and isotopes that primarily related to the study of the marine methane cycle in recent years were emphasized. At present, the pure culture of microorganisms involved in the methane cycle presents challenges, and to accurately describe biogeochemical processes in geochemical research is difficult. Therefore, interdisciplinary research that combines microbiology and geochemistry offers clear advantages and promising prospects. Understanding the interplay between microbial activities and trace elements in marine methane-rich environments is crucial for investigating the marine methane cycle and regulating global methane emissions in the context of current global warming. Additionally, this knowledge is anticipated to offer a distinctive vantage point for analyzing historical methane emission events and their global ecological/environmental impacts.
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Keywords:
- marine depositional systems /
- methane cycle /
- microbial activity /
- trace elements
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图 1 酶或辅酶介导的产甲烷途径 [24]
浅蓝色椭圆和长方形框内为促进产甲烷作用的各种酶,目前并不确定Ftr/Mch、Mtd/Mer和Pta/Ack是否会形成复合体,其他已知酶分别为:Fwd:甲酰甲烷呋喃脱氢酶;Mtr:四氢甲蝶呤S-甲基转移酶复合物;Mcr:甲基辅酶M还原酶; Acs:乙酰辅酶A合成酶; Codh:一氧化碳脱氢酶;Mt:甲基转移酶;Mto:辅酶M甲基转移酶系统;Acr:烷基辅酶M还原酶复合物。
Figure 1. Different pathways of methanogenesis mediated by enzyme or coenzyme [24]
The blue ovals and boxes contain various enzymes that promote methanogenesis. It is uncertain whether Ftr/Mch, Mtd/Mer, and Pta/Ack will form a complex at present, and other known enzymes are: Fwd: formyl-methanofuran dehydrogenase complex; Mtr: tetrahydromethanopterin S-methyl-transferase complex; Mcr: methyl-coenzyme M reductase complex; Acs: acetyl-CoA synthase; Codh: carbon monoxide dehydrogenase; Mt: methyltransferase; Mto: methoxyltransferase; Acr: alkyl-coenzyme M reductase complex.
图 3 目前已知的甲烷有氧氧化过程
据文献[70]修改。浅蓝色长方形框内为促进反应的各种酶和中间产物。MMO:甲烷单加氧酶; MDH:甲醇脱氢酶; FADH:甲醛脱氢酶; FDH:甲酸脱氢酶。
Figure 3. Currently known process of aerobic oxidation of methane
Modified from reference [70]. Various enzymes and intermediates that promote this process are shown in the blue rectangular. MMO: methane monooxygenase; MDH: methanol dehydrogenase; FADH: formaldehyde dehydrogenase; FDH: formate dehydrogenase.
图 4 产甲烷和甲烷厌氧氧化作用的野外证据
a: 黑海冷泉细菌席两种含Ni蛋白质[19];b:法国南部晚阿普弟阶Marnes Bleues组地层出露的冷泉碳酸盐岩,富有机质区Ni含量剧增[86];c:甲烷循环过程的微生物成矿作用被认为一定程度上造就了哥伦比亚高Ni品味红土矿床,其中Ni含量最高达8 wt.%[85];d:产甲烷菌造成了大范围的Ni同位素分馏[88];e:Ni同位素指示产甲烷作用增强一定程度上驱动了6.35亿年前雪球地球的终止[92]。
Figure 4. Field evidence of methanogenesis and anaerobic oxidation of methane
a: two types of Ni-containing proteins were identified in the bacterial mats within the Black Sea cold seep area[19]; b: the cold seep carbonates exposed from the Marnes Bleues formation in southern France during the late Apudian Period exhibit a significant increase in Ni content within the organic-rich zone[86]; c: microbial mineralization during the methane cycle is believed to have contributed, to some extents, to the formation of a high Ni-grade laterite deposit in Colombia, where the maximum Ni content reaches 8 wt.%[85]; d: methanogenic bacteria have been shown to cause significant Ni isotope fractionation[88]; e: Ni isotopes suggest that the intensification of methanogenesis played a role in partially ending the Snowball Earth (635 million years ago)[92].
图 5 甲烷有氧氧化作用的野外证据
a: 极端嗜酸性甲烷氧化菌在加入轻REE后生长速率明显加快[20];b: 墨西哥湾漏油事故发生后,在水深900-1200m处形成了碳氢化合物羽流区。该深度范围内海水甲烷浓度明显升高,但轻REE含量明显降低[21];c: 甲烷有氧氧化作用造成了马尾藻海200-500m水深处海水中轻REE含量明显减少[23];d: 甲烷营养型双壳的软组织和钙质壳体都有明显的轻REE富集,但硫营养型双壳则没有此类特征[22];e: 管状蠕虫Escarpia southwardae几丁质外壳的Cu和La含量含量在顶端明显升高[95];f: 在大氧化事件开始之前,AeOM过程就已经不断增强并持续了一段时间,造成晚太古代沉积体系的δ65Cu值明显降低[97]。
Figure 5. Field evidence of aerobic oxidation of methane
a: the growth rate of highly acidophilic methane-oxidizing bacteria is significantly enhanced upon the introduction of light rare earth elements[20]; b: following the oil spill in the Gulf of Mexico, a hydrocarbon plume region developed at a water depth ranging from 900 to 1200 m. In this depth range, there was a noticeable increase in the concentration of methane in seawater, while the abundance of light rare earth elements decreased significantly[21]; c: the aerobic oxidation of methane led to a significant decrease in light rare earth elements in seawater at depths of 200-500m in the Sargasso Sea[23]; d: methanotrophic bivalves exhibit enrichment of light REE in their soft tissues and calcareous shells, whereas thiotrophic bivalves lack this characteristic[22]; e: the chitinous tube of the tubeworm Escarpia southwardae showed a noticeable increase in Cu and La contents at the top[95]; f: prior to the Great Oxidation Event, the aerobic oxidation of methane intensified continuously over a period, resulting in a significant decrease in the δ65Cu value of the late Archean sediments[97].
表 1 涉及甲烷循环过程的反应方程式
Table 1 Reaction equations of methane cycle processes
反应 甲烷循环过程 具体类型 反应方程式 1 产甲烷作用 氢营养型 4H2 + CO2 → CH4 + 2H2O 2 4HCOOH → CH4 + 3CO2 + 2H2O 3 4CO + 2H2O → CH4 + 3CO2 4 乙酸营养型 CH3COOH → CH4 + CO2 5 甲基营养型 CH3OH + H2 → CH4 + H2O 6 4CH3OH→3CH4 + CO2 + 2H2O 7 2(CH3)2-S + 2H2O → 3CH4 + CO2 + 2H2S 8 4CH3-NH2 + 2H2O → 3CH4 + CO2 + 4NH3 9 2(CH3)2-NH + 2H2O → 3CH4 + CO2 + 2NH3 10 4(CH3)-N + 6H2O → 9CH4 + 3CO2 + 4NH3 11 4CH3NH3Cl + 2H2O → 3CH4 + CO2 + 4NH4Cl 12 甲氧基营养型 4CH3-O-R + 2H2O → 3CH4 + CO2 + 4R-OH 13 烷基营养型 4C16H34 + 30H2O → 49CH4 + 15CO2 14 甲烷厌氧氧化 反向产甲烷 CH4 + 2H2O → CO2 + 4H2 15 SO42– + 4H2 + H+ → HS– + 4H2O 16 乙酸生成 2CH4 + 2H2O → CH3COOH + 4H2 17 (同15) SO42– + 4H2 + H+ → HS– + 4H2O 18 CH3COOH + SO42– → 2HCO3– + HS– + H+ 19 CH4 + SO42– → HCO3– + HS– + H2O 20 CH4 + HCO3– → CH3COO– + H2O 21 CH3COO– + SO42– → 2HCO3– + 2HS– 22 (同19) CH4 + SO42– → HCO3– + HS– + H2O 23 甲基生成 3CH4 + HCO3– + 5H+ + 4HS– → CH3-SH + 3H2O 24 4CH3-SH + 3SO42– → 4HCO3– +7HS– + 5H+ 25 甲烷有氧氧化 总反应 CH4 + 2O2 → CO2 + 2H2O 26 甲烷转化为甲醇 CH4 + O2 + 2e– + 2H+ → CH3OH + H2O 27 甲醇转化为甲醛 CH3OH → HCHO + H2 28 甲醛转化为甲酸 HCHO + H2O → HCOOH + H2 29 甲酸转化为CO2和H2 HCOOH → CO2 + H2 -
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