Research papersNon-free ionic transport of sodium, magnesium, and calcium in streams of two adjacent headwater catchments with different vegetation types in Japan

- We examined the difference in transport of Na, Mg, and Ca in headwater streams.
- Non-free ionic fractions relative to total element ranged from 0% to 70%.
- Non-free ionic fractions during a heavy rainstorm could be in bonding to humic substances.
- The metal bonding with humic substances was predominantly enhanced in the deciduous catchment.
- Differing vegetation and resultant hillslope hydrology was key to provide the different transport of major metals.

Sodium (Na), magnesium (Mg), calcium (Ca) are usually believed to occur mostly as free ions in the fresh water and consequently little is known about their chemical species. To understand the importance of non-free ionic fractions (NIF) of major metals in freshwater streams, Na, Mg, Ca, silicon (Si), and fulvic acid-like materials (FAM) were measured in streams of mountainous adjacent headwater catchments dominated by different vegetation types (planted evergreen coniferous forest and natural deciduous broadleaf forest). During both no rainfall periods and rainstorms, the proportion of NIF relative to total elements was lower in the coniferous catchment than in the deciduous catchment, although it sometimes accounted for half or more of the total concentrations of Na, Mg, and Ca in both catchments. The solubility of metal compounds was higher than the measured maximum concentrations of Na+, Mg2+, and Ca2+ to the extent that inorganic bonding was hardly possible. During no rainfall periods when FAM was slightly produced into the streams, the fluxes of NIF and Si were highly correlated (r > 0.92, p < 0.0001, n = 30) in both catchments. During a small rainstorm, the flux of NIF correlated weakly with that of Si but did not correlate with that of FAM in both catchments. In contrast, during a heavy rainstorm, the flux of NIF correlated strongly (r ⩾ 0.83, p < 0.0001, n = 26) with that of FAM in the deciduous catchment where relatively deep soil water compared to near-surface water was the predominant component of stream water. However, during the heavy rainstorm in the coniferous catchment, only the flux of NIF originated in the quick-flow component (i.e., surface or near-surface water) in stream water (ΔNIF) correlated strongly (r ⩾ 0.81, p < 0.0001, n = 22) with that of FAM. These findings imply that heavy rainstorms may enhance the bonding of the major metals with humic substances mainly in the deciduous catchment; and also exhibit that, in the headwater catchments, both water flow pathways resulted from the different vegetation types play a very important role to promote the bonding of major metals with humic substances in stream water.

122