Distributions of humic substances in an estuarine region (Otsuchi Bay, Japan) determined using electrochemical and optical methods

Humic substances are major components of the dissolved organic carbon pool in aquatic environments that can bind to trace metals like copper and iron as organic ligands. The unique chromophoric and fluorescence properties of humic substances enabled measurements using conventional optical methods but recently a new electrochemical method using cathodic stripping voltammetry has emerged. In this study, we employed both methods to measure humic substances and elucidate their distribution patterns in Otsuchi Bay in Japan. The electroactive humic substances (eHS) detected using the electrochemical method were higher in the rivers (range 0.24 to 4.3 mg L⁻¹) than in the coastal bay (range 0.08 to 0.69 mg L⁻¹). Both methods revealed significantly higher humic concentrations in the surrounding rivers than in Otsuchi Bay, indicating that riverine sources are an important source of humic substances to Otsuchi Bay, consistent with previous observations in riverine systems globally. eHS correlated well with optical indices of dissolved organic matter (DOM) including humic and marine humic-like fluorescent DOM and chromophoric DOM. Furthermore, comparison with data from the literature suggests that about 20% of the weaker Cu-binding organic ligand pool in Otsuchi Bay may consist of eHS. As Cu-binding organic ligands, eHS may be important in buffering temporal or seasonal increases in Cu fluxes in estuarine regions, with possible implications for nutrient bioavailability and toxicity for primary producers.