Agricultural Sulfur Applications Alter the Quantity and Composition of Dissolved Organic Matter from Field-to-Watershed Scales.

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-SO42- 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.

Soil Organic Matter Characterization by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR MS): A Critical Review of Sample Preparation, Analysis, and Data Interpretation.

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.