The biogeochemical cycling of soil organic matter (SOM) plays a central role in regulating soil health, water quality, carbon storage, and greenhouse gas emissions. Thus, many studies have been conducted to reveal how anthropogenic and climate variables affect carbon sequestration and nutrient cycling. Among the analytical techniques used to better understand the speciation and transformation of SOM, Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) is the only technique that has sufficient mass resolving power to separate and accurately assign elemental compositions to individual SOM molecules. The global increase in the application of FTICR MS to address SOM complexity has highlighted the many challenges and opportunities associated with SOM sample preparation, FTICR MS analysis, and mass spectral interpretation. Here, we provide a critical review of recent strategies for SOM characterization by FTICR MS with emphasis on SOM sample collection, preparation, analysis, and data interpretation. Data processing and visualization methods are presented with suggested workflows that detail the considerations needed for the application of molecular information derived from FTICR MS. Finally, we highlight current research gaps, biases, and future directions needed to improve our understanding of organic matter chemistry and cycling within terrestrial ecosystems.

Reductive dissolution during permafrost thaw releases iron-bound organic carbon to porewaters, rendering previously stable carbon vulnerable to microbial decomposition and subsequent release to the atmosphere. How mineral iron stability and the microbial processes influencing mineral dissolution vary during transitional permafrost thaw are poorly understood, yet have important implications for carbon cycling and emissions. Here we determine the reactive mineral iron and associated organic carbon content of core extracts and porewaters along thaw gradients in a permafrost peatland in Abisko, Sweden. We find that iron mineral dissolution by fermentative and dissimilatory iron(III) reduction releases aqueous Fe2+ and aliphatic organic compounds along collapsing palsa hillslopes. Microbial community analysis and carbon emission measurements indicate that this release is accompanied by an increase in hydrogenotrophic methanogen abundance and methane emissions at the collapsing front. Our findings suggest that dissolution of reactive iron minerals contributes to carbon dioxide and methane production and emission, even before complete permafrost thaw.

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Reactive iron (Fe) minerals can preserve organic carbon (OC) in soils overlying intact permafrost. With permafrost thaw, reductive dissolution of iron minerals releases Fe and OC into the porewater, potentially increasing the bioavailability of OC for microbial decomposition. However, the stability of this so-called rusty carbon sink, the microbial community driving mineral dissolution, the identity of the iron-associated carbon and the resulting impact on greenhouse gas emissions are unknown. We examined palsa hillslopes, gradients from intact permafrost-supported palsa to semi-wet partially-thawed bog in a permafrost peatland in Abisko (Sweden). Using high-resolution mass spectrometry, we found that Fe-bound OC in intact palsa is comprised of loosely bound more aliphatic and strongly-bound more aromatic species. Iron mineral dissolution by both fermentative and dissimilatory Fe(III) reduction releases Fe-bound OC along the palsa hillslopes, before complete permafrost thaw. The increasing bioavailability of dissolved OC (DOC) leads to its further decomposition, demonstrated by an increasing nominal oxidation state of carbon (NOSC) and a peak in bioavailable acetate (61.7±42.6 mg C/L) at the collapsing palsa front. The aqueous Fe2+ released is partially re-oxidized by Fe(II)-oxidizing bacteria but cannot prevent the overall loss of the rusty carbon sink with palsa collapse. The increasing relative abundance and activity of Fe(III)-reducers is accompanied by an increasing abundance of methanogens and a peak in methane (CH4) emissions at the collapsing front. Our data suggest that the loss of the rusty carbon sink directly contributes to carbon dioxide (CO2) production by Fe(III) reduction coupled to OC oxidation and indirectly to CH4 emission by promoting methanogenesis even before complete permafrost thaw.

Over the past several decades, agricultural sulfur (S) use has dramatically increased. Excess S in the environment can cause several biogeochemical and ecologic consequences, including methylmercury production. This study investigated agriculturally associated changes to organic Sthe most dominant form of S within soilsfrom field-to-watershed scales. Using a novel complementary suite of analytical methods, we combined Fourier transform ion cyclotron resonance mass spectrometry, δ34S-DOS, and S X-ray absorption spectroscopy to characterize dissolved organic S (DOS) in soil porewater and surface water samples from vineyard agriculture (S addition) and forest/grassland areas (no S addition) within the Napa River watershed (California, U.S.). Vineyard soil porewater dissolved organic matter samples had two-fold higher S content compared to forest/grasslands and had unique CHOS2 chemical formulasthe latter also found in tributary and Napa River surface water. The isotopic difference between δ34S-DOS and δ34S–SO4 2– values provided insights into the likely dominant microbial S processes by land use/land cover (LULC), whereas the S oxidation state did not strongly differ by LULC. The results add to our understanding of the modern S cycle and point to upland agricultural areas as S sources with the potential for rapid S transformations in downgradient environments.