超高分辨率显微镜成像技术与同位素示踪技术相结合的纳米二次离子质谱技术(NanoSIMS)具有较高的灵敏度和离子传输效率、极高的质量分辨率和空间分辨率(<50 nm),代表着当今离子探针成像技术的最高水平。利用稳定性或者放射性同位素在...超高分辨率显微镜成像技术与同位素示踪技术相结合的纳米二次离子质谱技术(NanoSIMS)具有较高的灵敏度和离子传输效率、极高的质量分辨率和空间分辨率(<50 nm),代表着当今离子探针成像技术的最高水平。利用稳定性或者放射性同位素在原位或者微宇宙条件下示踪目标微生物,然后将样品进行固定、脱水、树脂包埋或者导电镀膜处理,制备成可供二次离子质谱分析的薄片,进一步通过NanoSIMS成像分析,不仅能够在单细胞水平上提供微生物的生理生态特征信息,而且能够准确识别复杂环境样品中的代谢活跃的微生物细胞及其系统分类信息,对于认识微生物介导的元素生物地球化学循环机制具有重要意义。介绍了纳米二次离子质谱技术的工作原理和技术路线,及其与同位素示踪技术、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、荧光原位杂交技术(FISH)、催化报告沉积荧光原位杂交技术(CARD-FISH)、卤素原位杂交技术(Halogen In SituHybridization,HISH)等联合使用在微生物生态学研究方面的应用。展开更多
微生物分子生态学技术的不断发展,使得同时分析复杂生态系统中微生物的分布和功能特征成为可能.为了研究荧光原位杂交-纳米二次离子质谱技术(fluorescence in situ hybridization-Nano secondary ion mass spectroscopy,FISH-Nano SIMS...微生物分子生态学技术的不断发展,使得同时分析复杂生态系统中微生物的分布和功能特征成为可能.为了研究荧光原位杂交-纳米二次离子质谱技术(fluorescence in situ hybridization-Nano secondary ion mass spectroscopy,FISH-Nano SIMS)在环境微生物生态学上的应用,本研究采用稳定同位素标记的化合物13C-C6H12O6、15N-NH4Cl作为C源和N源,分别对纯培养锰氧化细菌假单胞菌Pseudomonas sp.QJX-1(培养基加锰及不加锰两种条件下),以及浅层土壤及厌氧污泥两种环境样品进行培养.利用FISH-NanoSIMS技术检测培养后样品中微生物体内12C-、13C-、12C14N-、12C15N-的分布特征及其丰度值,进而探讨纯菌及环境样品中微生物利用同位素碳氮源的情况.结果显示所有样品细菌分布区域对应的同位素碳氮(13C、15N)的含量均显著大于其自然丰度值,这表明Pseudomonas sp.QJX-1及环境样品中的微生物均能代谢13C-C6H12O6和15N-NH4Cl.研究进一步发现,Pseudomonas sp.QJX-1在碳氮源消耗至较低浓度时才进行锰氧化;浅层土壤和厌氧污泥中可能都存在同步硝化反硝化细菌群落.FISH和Nano SIMS技术联用能同时分析环境样品中特定微生物的分布特征及代谢功能,进而能更好地掌握环境样品中微生物群落的生理生态学特征.展开更多
We report an imaging method of zircon U-Pb dating with NanoSIMS 50 L, which overcomes the significant U-Pb fractionation as the pit was sputtered deeper during conventional spot mode analysis and can be applied to irr...We report an imaging method of zircon U-Pb dating with NanoSIMS 50 L, which overcomes the significant U-Pb fractionation as the pit was sputtered deeper during conventional spot mode analysis and can be applied to irregular small grains or heterogeneous areas of zircon. The U-Pb and Pb-Pb ages can be acquired simultaneously for 2 μm×2 μm(for small grains) or 1 μm×9 μm(for zoned grains), together with Zr, Y and other trace elements distributions. Using zircon M257 as standard, the U-Pb ages of other zircon standards, including Qinghu, Plesovice, Temora and 91500, were measured to(2σ) as158.8±0.8, 335.9±3.4, 412.0±12 and 1067±12 Ma, respectively, consistent with the recommended values within the analytical uncertainties. Tiny zircon grains in the impact melt breccia of the lunar meteorite SaU 169 were also measured in this study,with a Pb-Pb age of 3912±14 Ma and a U-Pb age of 3917±17 Ma, similar to previous results reported for the same meteorite.The imaging method was also applied to determine U-Pb age of the thin overgrowth rims of Longtan metamorphic zircon, with a Pb-Pb age of 1933±27 Ma and a U-Pb age of 1935±25 Ma, clearly distinct from the Pb-Pb age of 2098±61 Ma and the U-Pb age of 2054±40 Ma for detrital cores.展开更多
Despite the significant improvement on spatial resolution,Nano SIMS still preserves relatively high mass resolution,sensitivity,and analytical precision.It has become an important analytical platform to determine chem...Despite the significant improvement on spatial resolution,Nano SIMS still preserves relatively high mass resolution,sensitivity,and analytical precision.It has become an important analytical platform to determine chemical compositions of solid materials,and has been widely used in space,earth,life,and materials sciences,etc.By using a Cs+ion beam with a size as small as 50nm scanning over sample surfaces,we are able to obtain high spatial resolution images of up to 7 species simultaneously.When utilizing Faraday cup,high analytical precision of 0.3‰–0.5‰(1SD)for C,O and S isotopic analysis can be achieved.Although this precision level is still lower than that of conventional SIMS,it already meets the major requirements of Earth Sciences.In 2011,the first Nano SIMS of China(Cameca Nano SIMS 50L)was installed at Institute of Geology and Geophysics,Chinese Academy of Sciences.Based on the working mechanism and analytical modes of the instrument,this paper will systematically introduce the analytical methods established with the Nano SIMS and their potential applications in earth sciences.These methods include trace element distribution images in mineral zoning,high spatial resolution(2–5?m)Pb-Pb and U-Pb dating,water content and H isotopic analysis for silicate glass and apatite,C isotopic analysis for diamond and graphite,O isotopic analysis for carbonate,S isotopic analysis for sulfides.In addition,the specific requirements for sample preparation will also be introduced in order to facilitate domestic earth scientists’use.展开更多
The fault-controlled Nibao Carlin-type gold deposit,together with the strata-bound Shuiyindong deposit,comprise a significant amount of the disseminated gold deposits in southwestern Guizhou Province,China.Five main t...The fault-controlled Nibao Carlin-type gold deposit,together with the strata-bound Shuiyindong deposit,comprise a significant amount of the disseminated gold deposits in southwestern Guizhou Province,China.Five main types and two sub-types of pyrite at the Nibao deposit(Py1a/Py1b,Py2,Py3,Py4,Py5)were distinguished based on detailed mineralogical work.Py1,Py2and Py3 are Au-poor,whereas Py4 and Py5 are Au-rich,corresponding to a sedimentary and hydrothermal origin,respectively.Through systematic in situ analyses of NanoSIMS sulfur isotopes,the framboid pyrite Py1a with negative δ^34S values(-53.3 to-14.9%)from the Nibao deposit were found to originate from bacterial sulfate reduction(BSR)processes in an open and sulfate-sufficient condition while the superheavy pyrite Py1b(73.7–114.8%)is probably due to the potential influence of closed-system Rayleigh fractionation or the lack of preservation of deepsea sediments.Data of Py2 and Py3 plot within the area of S isotope compositions from biogenic and abiogenic sulfate reduction.In view of few coeval magmatic rocks in the mining district,the near zero δ^34S values of the Au-rich pyrites(Py4 and Py5)may discount the potential involvement of magmatic but metamorphic or sedimentary origin.LA-ICP-MS and TEM work show that Au in ore-related pyrite is present as both nanoparticles and structurally bound.LA-ICP-MS analyses show that the Au-rich pyrite also contains higher As,Cu,Sb,Tl and S than other types of pyrite,which inferred a distal manifestation of deep hydrothermal mineralization systems.展开更多
In the northwestern margin of the Youjiang basin(NWYB)in SW China,many Carlin-like gold deposits are highly antimony(Sb)-rich,and many vein-type Sb deposits contain much Au.These deposits have similar ages,host rocks,...In the northwestern margin of the Youjiang basin(NWYB)in SW China,many Carlin-like gold deposits are highly antimony(Sb)-rich,and many vein-type Sb deposits contain much Au.These deposits have similar ages,host rocks,ore-forming temperatures,ore-related alterations and ore mineral assemblages,but the Au and Sb metallogenic relations and their ore-forming process remain enigmatic.Here we investigate the large Qinglong Sb deposit in the NWYB,which has extensive sub-economic Au mineralization,and present a new metallogenic model based on in-situ trace elements(EPMA and LA-ICP-MS)and sulfur isotopes(NanoSIMS and fs-LA-MC-ICPMS)of the ore sulfides.At Qinglong,economic Sb ores contain coarse-grained stibnite,jasperoid quartz and fluorite,whilst the sub-economic Au–Sb ores comprise dominantly veined quartz,arsenian pyrite and fine-grained stibnite.Three generations of ore-related pyrite(Py1,Py2 and Py3)and two generations of stibnite(Stb1 and Stb2)are identified based on their texture,chemistry,and sulfur isotopes.The pre-ore Py1 is characterized by the lower ore element(Au,As,Sb,Cu and Ag)contents(mostly below the LA-ICP-MS detection limit)and Co/Ni ratios(average 0.31)than the ore-stage pyrites(Py2 and Py3),implying a sedimentary/diagenetic origin.The Py2 and Py3 have elevated ore element abundance(maximum As=6500 ppm,Au=22 ppm,Sb=6300 ppm,Cu=951 ppm,Ag=77 ppm)and Co/Ni ratios(average 1.84),and have positive As vs.Au–Sb–Cu–Ag correlations.Early-ore Stb1 has lower As(0.12–0.30 wt.%)than late-ore Stb2(0.91–1.20 wt.%).These features show that the progressive As enrichment in ore sulfides is accompanied by increasing Au,Sb,Cu and Ag with the hydrothermal evolution,thereby making As a good proxy for Au.As-rich,As-poor and As-free zones are identified via NanoSIMS mapping of the Au-bearing pyrite.The As-rich zones in the Qinglong Au-bearing pyrites(Py2 and Py3)and ore stibnites(Stb1 and Stb2)have narrowδ^(34)SH_(2)S ranges(-8.9‰to +4.1‰,average-3.1‰)and-2.9‰to +6.9‰,average + 1.3‰),respectively,indicating that the Au-rich and Sb-rich fluids may have had the same sulfur source.Published in-situ sulfur isotopic data of pyrite As-rich zones from other Carlin-like Au deposits(Shuiyindong,Taipingdong,Nayang,Getang and Lianhuashan)in the NWYB have similar ore-fluidδSH_(2)S values(-4.5‰to +6.7‰,average-0.6‰)to those of Qinglong.Therefore,we infer that the sulfur of both Au and Sb mineralization was derived from the same magmatic-related source(0±5‰)in the NWYB.Moreover,the core of pyrites(Py1)has variable S isotope fractionation(-18.9‰to +18.1‰,mostly +3‰to +12‰),suggesting that the higher-^(34)S H_(2)S was produced by bacterial sulfate reduction(BSR).The hydrothermal pyrite(Py2 and Py3)δ^(34)S values gradually decrease with increasing As concentrations,and ultimately,within the restricted range(-5‰to +5‰)in As-rich zones.This variation implies that the As-rich pyrite was formed through ongoing interactions of the magmatic-hydrothermal fluid with pre-existing sedimentary pyrites,causing the progressive decreasing δ^(34)S values with As content increase,Hence,the fluid/mineral interaction may have generated the observed variation in δ^(34)S and As contents.Overall,comparing the Au and Sb deposits in the NWYB,we favor a magmatic-related source for the Au–Sb–As-rich fluids,but the Au-and Sb-ore fluids were likely evolved at separate stages in the ore-forming system.展开更多
Demonstrating the biogenicity of presumptive microfossils in the geological record often requires supporting chemical signatures, including isotopic signatures. Understanding the mechanisms that promote the preservati...Demonstrating the biogenicity of presumptive microfossils in the geological record often requires supporting chemical signatures, including isotopic signatures. Understanding the mechanisms that promote the preservation of microbial biosignatures associated with microfossils is fundamental to unravelling the palaeomicrobiological history of the material. Organomineralization of microorganisms is likely to represent the first stages of microbial fossilisation and has been hypothesised to prevent the autolytic degradation of microbial cell envelope structures. In the present study, two distinct fossilisation textures(permineralised microfossils and iron oxide encrusted cell envelopes)identified throughout iron-rich rock samples were analysed using nanoscale secondary ion mass spectrometry(NanoSIMS). In this system, aluminium is enriched around the permineralised microfossils, while iron is enriched within the intracellularly, within distinct cell envelopes. Remarkably,while cell wall structures are indicated, carbon and nitrogen biosignatures are not preserved with permineralised microfossils. Therefore, the enrichment of aluminium, delineating these microfossils appears to have been critical to their structural preservation in this iron-rich environment. In contrast,NanoSIMS analysis of mineral encrusted cell envelopes reveals that preserved carbon and nitrogen biosignatures are associated with the cell envelope structures of these microfossils. Interestingly, iron is depleted in regions where carbon and nitrogen are preserved. In contrast aluminium appears to be slightly enriched in regions associated with remnant cell envelope structures. The correlation of aluminium with carbon and nitrogen biosignatures suggests the complexation of aluminium with preserved cell envelope structures before or immediately after cell death may have inactivated autolytic activity preventing the rapid breakdown of these organic, macromolecular structures.Combined, these results highlight that aluminium may play an important role in the preservation of microorganisms within the rock record.展开更多
文摘超高分辨率显微镜成像技术与同位素示踪技术相结合的纳米二次离子质谱技术(NanoSIMS)具有较高的灵敏度和离子传输效率、极高的质量分辨率和空间分辨率(<50 nm),代表着当今离子探针成像技术的最高水平。利用稳定性或者放射性同位素在原位或者微宇宙条件下示踪目标微生物,然后将样品进行固定、脱水、树脂包埋或者导电镀膜处理,制备成可供二次离子质谱分析的薄片,进一步通过NanoSIMS成像分析,不仅能够在单细胞水平上提供微生物的生理生态特征信息,而且能够准确识别复杂环境样品中的代谢活跃的微生物细胞及其系统分类信息,对于认识微生物介导的元素生物地球化学循环机制具有重要意义。介绍了纳米二次离子质谱技术的工作原理和技术路线,及其与同位素示踪技术、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、荧光原位杂交技术(FISH)、催化报告沉积荧光原位杂交技术(CARD-FISH)、卤素原位杂交技术(Halogen In SituHybridization,HISH)等联合使用在微生物生态学研究方面的应用。
文摘微生物分子生态学技术的不断发展,使得同时分析复杂生态系统中微生物的分布和功能特征成为可能.为了研究荧光原位杂交-纳米二次离子质谱技术(fluorescence in situ hybridization-Nano secondary ion mass spectroscopy,FISH-Nano SIMS)在环境微生物生态学上的应用,本研究采用稳定同位素标记的化合物13C-C6H12O6、15N-NH4Cl作为C源和N源,分别对纯培养锰氧化细菌假单胞菌Pseudomonas sp.QJX-1(培养基加锰及不加锰两种条件下),以及浅层土壤及厌氧污泥两种环境样品进行培养.利用FISH-NanoSIMS技术检测培养后样品中微生物体内12C-、13C-、12C14N-、12C15N-的分布特征及其丰度值,进而探讨纯菌及环境样品中微生物利用同位素碳氮源的情况.结果显示所有样品细菌分布区域对应的同位素碳氮(13C、15N)的含量均显著大于其自然丰度值,这表明Pseudomonas sp.QJX-1及环境样品中的微生物均能代谢13C-C6H12O6和15N-NH4Cl.研究进一步发现,Pseudomonas sp.QJX-1在碳氮源消耗至较低浓度时才进行锰氧化;浅层土壤和厌氧污泥中可能都存在同步硝化反硝化细菌群落.FISH和Nano SIMS技术联用能同时分析环境样品中特定微生物的分布特征及代谢功能,进而能更好地掌握环境样品中微生物群落的生理生态学特征.
基金financially supported by the National Natural Science Foundation of China (Grant Nos. 41430105, 41490631, 41573057 & 41521062)
文摘We report an imaging method of zircon U-Pb dating with NanoSIMS 50 L, which overcomes the significant U-Pb fractionation as the pit was sputtered deeper during conventional spot mode analysis and can be applied to irregular small grains or heterogeneous areas of zircon. The U-Pb and Pb-Pb ages can be acquired simultaneously for 2 μm×2 μm(for small grains) or 1 μm×9 μm(for zoned grains), together with Zr, Y and other trace elements distributions. Using zircon M257 as standard, the U-Pb ages of other zircon standards, including Qinghu, Plesovice, Temora and 91500, were measured to(2σ) as158.8±0.8, 335.9±3.4, 412.0±12 and 1067±12 Ma, respectively, consistent with the recommended values within the analytical uncertainties. Tiny zircon grains in the impact melt breccia of the lunar meteorite SaU 169 were also measured in this study,with a Pb-Pb age of 3912±14 Ma and a U-Pb age of 3917±17 Ma, similar to previous results reported for the same meteorite.The imaging method was also applied to determine U-Pb age of the thin overgrowth rims of Longtan metamorphic zircon, with a Pb-Pb age of 1933±27 Ma and a U-Pb age of 1935±25 Ma, clearly distinct from the Pb-Pb age of 2098±61 Ma and the U-Pb age of 2054±40 Ma for detrital cores.
基金supported by the National Natural Science Foundation of China(Grants Nos.41173012,41103031,41230209,41322022,41221002)
文摘Despite the significant improvement on spatial resolution,Nano SIMS still preserves relatively high mass resolution,sensitivity,and analytical precision.It has become an important analytical platform to determine chemical compositions of solid materials,and has been widely used in space,earth,life,and materials sciences,etc.By using a Cs+ion beam with a size as small as 50nm scanning over sample surfaces,we are able to obtain high spatial resolution images of up to 7 species simultaneously.When utilizing Faraday cup,high analytical precision of 0.3‰–0.5‰(1SD)for C,O and S isotopic analysis can be achieved.Although this precision level is still lower than that of conventional SIMS,it already meets the major requirements of Earth Sciences.In 2011,the first Nano SIMS of China(Cameca Nano SIMS 50L)was installed at Institute of Geology and Geophysics,Chinese Academy of Sciences.Based on the working mechanism and analytical modes of the instrument,this paper will systematically introduce the analytical methods established with the Nano SIMS and their potential applications in earth sciences.These methods include trace element distribution images in mineral zoning,high spatial resolution(2–5?m)Pb-Pb and U-Pb dating,water content and H isotopic analysis for silicate glass and apatite,C isotopic analysis for diamond and graphite,O isotopic analysis for carbonate,S isotopic analysis for sulfides.In addition,the specific requirements for sample preparation will also be introduced in order to facilitate domestic earth scientists’use.
基金funded by the National 973 Program of China (2014CB440906)
文摘The fault-controlled Nibao Carlin-type gold deposit,together with the strata-bound Shuiyindong deposit,comprise a significant amount of the disseminated gold deposits in southwestern Guizhou Province,China.Five main types and two sub-types of pyrite at the Nibao deposit(Py1a/Py1b,Py2,Py3,Py4,Py5)were distinguished based on detailed mineralogical work.Py1,Py2and Py3 are Au-poor,whereas Py4 and Py5 are Au-rich,corresponding to a sedimentary and hydrothermal origin,respectively.Through systematic in situ analyses of NanoSIMS sulfur isotopes,the framboid pyrite Py1a with negative δ^34S values(-53.3 to-14.9%)from the Nibao deposit were found to originate from bacterial sulfate reduction(BSR)processes in an open and sulfate-sufficient condition while the superheavy pyrite Py1b(73.7–114.8%)is probably due to the potential influence of closed-system Rayleigh fractionation or the lack of preservation of deepsea sediments.Data of Py2 and Py3 plot within the area of S isotope compositions from biogenic and abiogenic sulfate reduction.In view of few coeval magmatic rocks in the mining district,the near zero δ^34S values of the Au-rich pyrites(Py4 and Py5)may discount the potential involvement of magmatic but metamorphic or sedimentary origin.LA-ICP-MS and TEM work show that Au in ore-related pyrite is present as both nanoparticles and structurally bound.LA-ICP-MS analyses show that the Au-rich pyrite also contains higher As,Cu,Sb,Tl and S than other types of pyrite,which inferred a distal manifestation of deep hydrothermal mineralization systems.
基金the National Natural Science Foundation of China(Grant No.41802107)Guizhou Scientific and Technology Fund(Grant No.QKHJC[2019]1315+2 种基金QKHJC[2019]1149H)China Postdoctoral Science Foundation(Grant No.2019M653495)the Talent Introduction Project of Guizhou University(Grant No.201772).
文摘In the northwestern margin of the Youjiang basin(NWYB)in SW China,many Carlin-like gold deposits are highly antimony(Sb)-rich,and many vein-type Sb deposits contain much Au.These deposits have similar ages,host rocks,ore-forming temperatures,ore-related alterations and ore mineral assemblages,but the Au and Sb metallogenic relations and their ore-forming process remain enigmatic.Here we investigate the large Qinglong Sb deposit in the NWYB,which has extensive sub-economic Au mineralization,and present a new metallogenic model based on in-situ trace elements(EPMA and LA-ICP-MS)and sulfur isotopes(NanoSIMS and fs-LA-MC-ICPMS)of the ore sulfides.At Qinglong,economic Sb ores contain coarse-grained stibnite,jasperoid quartz and fluorite,whilst the sub-economic Au–Sb ores comprise dominantly veined quartz,arsenian pyrite and fine-grained stibnite.Three generations of ore-related pyrite(Py1,Py2 and Py3)and two generations of stibnite(Stb1 and Stb2)are identified based on their texture,chemistry,and sulfur isotopes.The pre-ore Py1 is characterized by the lower ore element(Au,As,Sb,Cu and Ag)contents(mostly below the LA-ICP-MS detection limit)and Co/Ni ratios(average 0.31)than the ore-stage pyrites(Py2 and Py3),implying a sedimentary/diagenetic origin.The Py2 and Py3 have elevated ore element abundance(maximum As=6500 ppm,Au=22 ppm,Sb=6300 ppm,Cu=951 ppm,Ag=77 ppm)and Co/Ni ratios(average 1.84),and have positive As vs.Au–Sb–Cu–Ag correlations.Early-ore Stb1 has lower As(0.12–0.30 wt.%)than late-ore Stb2(0.91–1.20 wt.%).These features show that the progressive As enrichment in ore sulfides is accompanied by increasing Au,Sb,Cu and Ag with the hydrothermal evolution,thereby making As a good proxy for Au.As-rich,As-poor and As-free zones are identified via NanoSIMS mapping of the Au-bearing pyrite.The As-rich zones in the Qinglong Au-bearing pyrites(Py2 and Py3)and ore stibnites(Stb1 and Stb2)have narrowδ^(34)SH_(2)S ranges(-8.9‰to +4.1‰,average-3.1‰)and-2.9‰to +6.9‰,average + 1.3‰),respectively,indicating that the Au-rich and Sb-rich fluids may have had the same sulfur source.Published in-situ sulfur isotopic data of pyrite As-rich zones from other Carlin-like Au deposits(Shuiyindong,Taipingdong,Nayang,Getang and Lianhuashan)in the NWYB have similar ore-fluidδSH_(2)S values(-4.5‰to +6.7‰,average-0.6‰)to those of Qinglong.Therefore,we infer that the sulfur of both Au and Sb mineralization was derived from the same magmatic-related source(0±5‰)in the NWYB.Moreover,the core of pyrites(Py1)has variable S isotope fractionation(-18.9‰to +18.1‰,mostly +3‰to +12‰),suggesting that the higher-^(34)S H_(2)S was produced by bacterial sulfate reduction(BSR).The hydrothermal pyrite(Py2 and Py3)δ^(34)S values gradually decrease with increasing As concentrations,and ultimately,within the restricted range(-5‰to +5‰)in As-rich zones.This variation implies that the As-rich pyrite was formed through ongoing interactions of the magmatic-hydrothermal fluid with pre-existing sedimentary pyrites,causing the progressive decreasing δ^(34)S values with As content increase,Hence,the fluid/mineral interaction may have generated the observed variation in δ^(34)S and As contents.Overall,comparing the Au and Sb deposits in the NWYB,we favor a magmatic-related source for the Au–Sb–As-rich fluids,but the Au-and Sb-ore fluids were likely evolved at separate stages in the ore-forming system.
基金support from the Vale S.A.-UQ Geomicrobiology initiative and the Australian Research Council Linkage Program(LP140100805) to G. Southam and P. Vasconcelos
文摘Demonstrating the biogenicity of presumptive microfossils in the geological record often requires supporting chemical signatures, including isotopic signatures. Understanding the mechanisms that promote the preservation of microbial biosignatures associated with microfossils is fundamental to unravelling the palaeomicrobiological history of the material. Organomineralization of microorganisms is likely to represent the first stages of microbial fossilisation and has been hypothesised to prevent the autolytic degradation of microbial cell envelope structures. In the present study, two distinct fossilisation textures(permineralised microfossils and iron oxide encrusted cell envelopes)identified throughout iron-rich rock samples were analysed using nanoscale secondary ion mass spectrometry(NanoSIMS). In this system, aluminium is enriched around the permineralised microfossils, while iron is enriched within the intracellularly, within distinct cell envelopes. Remarkably,while cell wall structures are indicated, carbon and nitrogen biosignatures are not preserved with permineralised microfossils. Therefore, the enrichment of aluminium, delineating these microfossils appears to have been critical to their structural preservation in this iron-rich environment. In contrast,NanoSIMS analysis of mineral encrusted cell envelopes reveals that preserved carbon and nitrogen biosignatures are associated with the cell envelope structures of these microfossils. Interestingly, iron is depleted in regions where carbon and nitrogen are preserved. In contrast aluminium appears to be slightly enriched in regions associated with remnant cell envelope structures. The correlation of aluminium with carbon and nitrogen biosignatures suggests the complexation of aluminium with preserved cell envelope structures before or immediately after cell death may have inactivated autolytic activity preventing the rapid breakdown of these organic, macromolecular structures.Combined, these results highlight that aluminium may play an important role in the preservation of microorganisms within the rock record.
