Optimizing Cryo-Focused Pyrolysis GC/MS for Tracing Soil Organic Matter Across Diverse Ecosystems

Shahriar, Abrar; Zavarin, Mavrik; Nuccio, Erin E.; Grant, Katherine E.; McFarlane, Karis J.; Pett-Ridge, Jennifer; Toews, Daniel; Sexton, Jason P.; Ryals, Rebecca; Baccei, Joy; Berndt, Aiden J.; Boiteau, Rene; Jawad, Ishtiaq Ahmed; Yang, Yu; Bansal, Sheel; O’Loughlin, Edward J.; Kemner, Kenneth M.; Matamala, Roser; Morrison, Keith D.

doi:10.1021/acs.est.5c16415

Optimizing Cryo-Focused Pyrolysis GC/MS for Tracing Soil Organic Matter Across Diverse Ecosystems

Journal Article · Mon Mar 16 00:00:00 EDT 2026 · Environmental Science and Technology

DOI:https://doi.org/10.1021/acs.est.5c16415· OSTI ID:3027523

^[1]; ^[1]; ^[1]; Grant, Katherine E. ^[1]; McFarlane, Karis J. ^[1]; ^[2]; Toews, Daniel ^[3]; Sexton, Jason P. ^[3]; ^[3]; Baccei, Joy ^[4]; ^[5]; ^[5]; Jawad, Ishtiaq Ahmed ^[6]; ^[6]; Bansal, Sheel ^[7]; ^[8]; Kemner, Kenneth M. ^[8]; Matamala, Roser ^[8]; ^[1]

Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Univ. of California, Merced, CA (United States); Univ. of California, Berkeley, CA (United States). Applied Science and Technology
Univ. of California, Merced, CA (United States)
University of California Natural Reserve System, Merced, CA (United States)
Univ. of Minnesota, Minneapolis, MN (United States)
Univ. of Nevada, Reno, NV (United States)
US Geological Survey, Jamestown, ND (United States). Northern Prairie Wildlife Research Center
Argonne National Laboratory (ANL), Argonne, IL (United States)

The cycling of organic matter in terrestrial soils and sediments is central to a range of biogeochemical processes that regulate nutrient cycling, crop productivity, trace gas emissions, and contaminant transport. Pyrolysis-gas chromatography/mass spectrometry (py-GC/MS) is a powerful tool for characterizing bulk soil organic matter (SOM) at the molecular level. In this study, we used a cryo-focused py-GC/MS system to analyze soil samples from seven diverse ecosystems: vernal pool, prairie pothole, temperate forest, tropical forest, tundra, wildfire-affected boreal forest, and grassland. We addressed a key bottleneck in molecular-level SOM characterization by developing an automated data analysis pipeline to optimize py-GC/MS and complementary evolved gas analysis/mass spectrometry (EGA/MS) methods, incorporating advanced tools for peak deconvolution, developing a custom compound class library, and implementing fragmentation spectrum-based molecular networking for the first time. This improved workflow was applied to soil samples from all seven ecosystems, including multiple depths and density fractions. Our findings demonstrate that ecosystem type plays a dominant role in shaping compositional differences in SOM. We also identified trends in the source of SOM compounds (e.g., microbial vs plantderived) across soil depth and density fractions, which are critical for understanding persistence and turnover of SOM. Our molecular networking analysis indicated that although many compounds are widespread across ecosystems, others are restricted to specific environments, such as wetlands. This underscores the utility of molecular-level data in elucidating the complexity of SOM composition and the environmental drivers that shape it. Such molecular-level insights can deepen our knowledge of biogeochemical SOM cycles.

View Accepted Manuscript (DOE)

Research Organization:: Colorado State Univ., Fort Collins, CO (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC52-07NA27344; SC0023084

Other Award/Contract Number:: 24-SI-002
DE-AC02-06CH113
SCW1632
2108270
2148056

OSTI ID:: 3027523

Alternate ID(s):: OSTI ID: 3029329

Report Number(s):: LLNL-JRNL-2013596-REV-1

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 12 Vol. 60; ISSN 1520-5851; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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54 ENVIRONMENTAL SCIENCES
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