Unraveling the Linkages between Molecular Abundance and Stable Carbon Isotope Ratio in Dissolved Organic Matter Using Machine Learning

Dissolved organic matter (DOM) is a complex mixture of molecules that constitutes one of the largest reservoirs of organic matter on Earth. While stable carbon isotope values (δ¹³C) provide valuable insights into DOM transformations from land to ocean, it remains unclear how individual molecules respond to changes in DOM properties such as δ¹³C. To address this, we employed Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to characterize the molecular composition of DOM in 510 samples from the China Coastal Environments, with 320 samples having δ¹³C measurements. Utilizing a machine learning model based on 5199 molecular formulas, we predicted δ¹³C values with a mean absolute error (MAE) of 0.30‰ on the training data set, surpassing traditional linear regression methods (MAE 0.85‰). Our findings suggest that degradation processes, microbial activities, and primary production regulate DOM from rivers to the ocean continuum. Additionally, the machine learning model accurately predicted δ¹³C values in samples without known δ¹³C values and in other published data sets, reflecting the δ¹³C trend along the land to ocean continuum. This study demonstrates the potential of machine learning to capture the complex relationships between DOM composition and bulk parameters, particularly with larger learning data sets and increasing molecular research in the future. © 2023 American Chemical Society.