Terrigenous humic substances regulate the concentrations of dissolved Fe and Cu (but not Al, Mn, Ni or Zn) in the Gaoping River plume

Abstract

The small mountainous rivers of Oceania discharge a large fraction of their dissolved and particulate load of materials within a very small percentage of the time. As a result, the yearly inputs and physicochemical forms of dissolved metals exported to the ocean by these rivers are poorly quantified. We investigated the wet-season distribution patterns of metals and fluorescent organic substances in the surface waters of the Gaoping River plume, SW Taiwan, under both moderate (Sep 2020) and strong flow conditions (Aug 2021). The mixing behaviour of both soluble (<5 kDa) and colloidal (>5 kDa) metals and fluorescent components was examined over the salinity range 3.0–32.2 in 2020 and 5.8–31.1 in 2021. We detected two humic-like and one protein-like fluorescent components, the same on both surveys. The humic-like components, C1 and C3, originated from the Gaoping River and correlated strongly with Cu and Fe, respectively. Component C3 showed a greater enrichment relative to C1 in the colloidal (C3/C1 > 0.8) than in the soluble phase (C3/C1 = 0.4). The protein-like component, C2, came from both terrestrial and marine sources and displayed a more complex mixing behaviour than the other two. One striking result was that the effective zero-salinity concentrations of Fe (∼300 nM) and Cu (∼23 nM) did not change significantly in response to a 10-fold increase in river discharge between Sep 2020 and Aug 2021. Similarly to Fe and Cu, the distribution patterns of Components C1 and C3 did not change significantly between the moderate and the strong plume, and C3 and C1 correlated strongly with Fe and Cu, respectively. We conclude that subtropical mountainous rivers can provide soil-derived humic substances which facilitate and regulate the delivery of Fe and Cu to the ocean, provided mountain forests are preserved.