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Title: A comparative ToF-SIMS and GC–MS analysis of phototrophic communities collected from an alkaline silica-depositing hot spring

Abstract

One of few techniques that is able to spatially resolve chemical data, including organic molecules, to morphological features in modern and ancient geological samples, is time-of-flight secondary ion mass spectrometry (ToF-SIMS). The ability to connect chemical data to morphology is key for interpreting the biogenicity of preserved remains in ancient samples. However, due to the lack of reference data for geologically relevant samples and the ease with which samples can be contaminated, ToF-SIMS data may be difficult to interpret. In this project, we aimed to build a ToF-SIMS spectral database by performing parallel ToF-SIMS and gas chromatography–mass spectrometry (GC–MS) analyses of extant photosynthetic microbial communities collected from an alkaline silica-depositing hot spring in Yellowstone National Park, USA. We built the library by analyzing samples of increasing complexity: pure lipid standards commonly found in thermophilic phototrophs, solvent extracts of specific lipid fractions, total lipid extracts, pure cultures of dominant phototrophic community members, and unsilicified phototrophic streamer communities. The results showed that important lipids and pigments originating from phototrophs were detected by ToF-SIMS (e.g., wax esters, monogalactosyldiacylglycerol, digalactosyldiacylglycerol, sufloquinovosyldiaglycerol, alkanes, etc.) in the streamer lipid extracts. Many of the lipids were also detected in situ in the unsilicified streamer, and could evenmore » be spatially resolved to individual cells within the streamer community. Together with the ToF-SIMS database, this mapping ability will be used to further explore other microbial mats and their fossilized counterparts in the geological record. This is likely to expand the geochemical understanding of these types of samples.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1371997
Report Number(s):
PNNL-SA-127253
Journal ID: ISSN 0146-6380; 49675; 453040196
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Organic Geochemistry; Journal Volume: 109; Journal Issue: C
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 58 GEOSCIENCES; Environmental Molecular Sciences Laboratory

Citation Formats

Siljeström, S., Parenteau, M. N., Jahnke, L. L., and Cady, S. L. A comparative ToF-SIMS and GC–MS analysis of phototrophic communities collected from an alkaline silica-depositing hot spring. United States: N. p., 2017. Web. doi:10.1016/j.orggeochem.2017.03.009.
Siljeström, S., Parenteau, M. N., Jahnke, L. L., & Cady, S. L. A comparative ToF-SIMS and GC–MS analysis of phototrophic communities collected from an alkaline silica-depositing hot spring. United States. doi:10.1016/j.orggeochem.2017.03.009.
Siljeström, S., Parenteau, M. N., Jahnke, L. L., and Cady, S. L. 2017. "A comparative ToF-SIMS and GC–MS analysis of phototrophic communities collected from an alkaline silica-depositing hot spring". United States. doi:10.1016/j.orggeochem.2017.03.009.
@article{osti_1371997,
title = {A comparative ToF-SIMS and GC–MS analysis of phototrophic communities collected from an alkaline silica-depositing hot spring},
author = {Siljeström, S. and Parenteau, M. N. and Jahnke, L. L. and Cady, S. L.},
abstractNote = {One of few techniques that is able to spatially resolve chemical data, including organic molecules, to morphological features in modern and ancient geological samples, is time-of-flight secondary ion mass spectrometry (ToF-SIMS). The ability to connect chemical data to morphology is key for interpreting the biogenicity of preserved remains in ancient samples. However, due to the lack of reference data for geologically relevant samples and the ease with which samples can be contaminated, ToF-SIMS data may be difficult to interpret. In this project, we aimed to build a ToF-SIMS spectral database by performing parallel ToF-SIMS and gas chromatography–mass spectrometry (GC–MS) analyses of extant photosynthetic microbial communities collected from an alkaline silica-depositing hot spring in Yellowstone National Park, USA. We built the library by analyzing samples of increasing complexity: pure lipid standards commonly found in thermophilic phototrophs, solvent extracts of specific lipid fractions, total lipid extracts, pure cultures of dominant phototrophic community members, and unsilicified phototrophic streamer communities. The results showed that important lipids and pigments originating from phototrophs were detected by ToF-SIMS (e.g., wax esters, monogalactosyldiacylglycerol, digalactosyldiacylglycerol, sufloquinovosyldiaglycerol, alkanes, etc.) in the streamer lipid extracts. Many of the lipids were also detected in situ in the unsilicified streamer, and could even be spatially resolved to individual cells within the streamer community. Together with the ToF-SIMS database, this mapping ability will be used to further explore other microbial mats and their fossilized counterparts in the geological record. This is likely to expand the geochemical understanding of these types of samples.},
doi = {10.1016/j.orggeochem.2017.03.009},
journal = {Organic Geochemistry},
number = C,
volume = 109,
place = {United States},
year = 2017,
month = 7
}
  • One of few techniques that is able to spatially resolve chemical data, including organic molecules, to morphological features in modern and ancient geological samples, is time-of-flight secondary ion mass spectrometry (ToF-SIMS). The ability to connect chemical data to morphology is key for interpreting the biogenicity of preserved remains in ancient samples. However, due to the lack of reference data for geologically relevant samples and the ease with which samples can be contaminated, ToF-SIMS data may be difficult to interpret. In this project, we aimed to build a ToF-SIMS spectral database by performing parallel ToF-SIMS and gas chromatography–mass spectrometry (GC–MS) analysesmore » of extant photosynthetic microbial communities collected from an alkaline silica-depositing hot spring in Yellowstone National Park, USA. We built the library by analyzing samples of increasing complexity: pure lipid standards commonly found in thermophilic phototrophs, solvent extracts of specific lipid fractions, total lipid extracts, pure cultures of dominant phototrophic community members, and unsilicified phototrophic streamer communities. The results showed that important lipids and pigments originating from phototrophs were detected by ToF-SIMS (e.g., wax esters, monogalactosyldiacylglycerol, digalactosyldiacylglycerol, sufloquinovosyldiaglycerol, alkanes, etc.) in the streamer lipid extracts. Many of the lipids were also detected in situ in the unsilicified streamer, and could even be spatially resolved to individual cells within the streamer community. Together with the ToF-SIMS database, this mapping ability will be used to further explore other microbial mats and their fossilized counterparts in the geological record. This is likely to expand the geochemical understanding of these types of samples.« less
  • One of few techniques that is able to spatially resolve chemical data, including organic molecules, to morphological features in modern and ancient geological samples, is time-of-flight secondary ion mass spectrometry (ToF-SIMS). The ability to connect chemical data to morphology is key for interpreting the biogenicity of preserved remains in ancient samples. However, due to the lack of reference data for geologically relevant samples and the ease with which samples can be contaminated, ToF-SIMS data may be difficult to interpret. In this project, we aimed to build a ToF-SIMS spectral database by performing parallel ToF-SIMS and gas chromatography–mass spectrometry (GC–MS) analysesmore » of extant photosynthetic microbial communities collected from an alkaline silica-depositing hot spring in Yellowstone National Park, USA. We built the library by analyzing samples of increasing complexity: pure lipid standards commonly found in thermophilic phototrophs, solvent extracts of specific lipid fractions, total lipid extracts, pure cultures of dominant phototrophic community members, and unsilicified phototrophic streamer communities. The results showed that important lipids and pigments originating from phototrophs were detected by ToF-SIMS (e.g., wax esters, monogalactosyldiacylglycerol, digalactosyldiacylglycerol, sufloquinovosyldiaglycerol, alkanes, etc.) in the streamer lipid extracts. Many of the lipids were also detected in situ in the unsilicified streamer, and could even be spatially resolved to individual cells within the streamer community. Together with the ToF-SIMS database, this mapping ability will be used to further explore other microbial mats and their fossilized counterparts in the geological record. This is likely to expand the geochemical understanding of these types of samples.« less
  • A diode array detector system for microscale light measurements with fiber-optic microprobes was developed; it measures intensities of 400-900-nm light over >6 orders of magnitude with a spectral resolution of 2-5 nm. Fiber-optic microprobes to measure field radiance or scalar irradiance were coupled to the detector system and used for spectral light measurements in hypersaline microbial mats and in laminated phototrophic communities of coastal sediments. The vertical distribution of major photopigments of microalgae, cyanobacteria, and anoxygenic phototrophic bacteria could be identified from extinction maxima in measured radiance spectra at 430-550 nm (Chl a and carotenoids), 620-625 nm (phycocyanin), 675 nmmore » (Chl a), 745-750 nm (BChl c), 800-810 nm, and 860-880 nm (BChl a). Scalar irradiance spectra exhibited a different spectral composition and a higher light intensity at the sediment surface as compared to incident light. IR light thus reached 200% of incident at the sediment surface. Maximal light penetration was found for IR light, whereas visible light was strongly attenuated in the upper 0-2 mm of the sediment. Measurements of photon scalar irradiance (400-700 nm) were combined with microelectrode measurements of oxygenic photosynthesis in the coastal sediment. With an incident light intensity of 200 [mu]Einst m[sup [minus]2]s[sup [minus]1], photon scalar irradiance reached a maximum of 283 [mu]Einst m[sup [minus]2]s[sup [minus]1] at the sediment surface. The lower boundary of the euphotic zone was 2.2 mm below the surface at a light intensity of 12 [mu]Einst m[sup [minus]2]s[sup [minus]1]. 20 refs., 6 figs.« less
  • Phototrophic microbial mats frequently exhibit sharp, light-dependent redox gradients that regulate microbial respiration on specific electron acceptors as a function of depth. In this work, a benthic phototrophic microbial mat from Hot Lake, a hypersaline, epsomitic lake located near Oroville in north-central Washington, was used to develop a microscale electrochemical method to study local electron transfer processes within the mat. To characterize the physicochemical variables influencing electron transfer, we initially quantified redox potential, pH, and dissolved oxygen gradients by depth in the mat under photic and aphotic conditions. We further demonstrated that power output of a mat fuel cell wasmore » light-dependent. To study local electron transfer processes, we deployed a microscale electrode (microelectrode) with tip size ~20 μm. To enrich a subset of microorganisms capable of interacting with the microelectrode, we anodically polarized the microelectrode at depth in the mat. Subsequently, to characterize the microelectrode- associated community and compare it to the neighboring mat community, we performed amplicon sequencing of the V1-V3 region of the 16S gene. Differences in Bray-Curtis beta diversity, illustrated by large changes in relative abundance at the phylum level, suggested successful enrichment of specific mat community members on the microelectrode surface. The microelectrode-associated community exhibited substantially reduced alpha diversity and elevated relative abundances of Prosthecochloris, Loktanella, Catellibacterium, other unclassified members of Rhodobacteraceae, Thiomicrospira, and Limnobacter, compared with the community at an equivalent depth in the mat. Our results suggest that local electron transfer to an anodically polarized microelectrode selected for a specific microbial population, with substantially more abundance and diversity of sulfur-oxidizing phylotypes compared with the neighboring mat community.« less