The dynamics of arsenic and copper in solid and aqueous phases in reactive confluences receiving acid drainage: The role of turbidity and particle size

Abstract

The fate of suspended solids in aqueous systems enriched with copper (Cu) and arsenic (As) is still poorly understood, especially in mildly acidic streams with natural turbidity. This study integrated field, laboratory, and modeling to determine how turbidity, particle size distribution, and the partition of Cu and As interact in two model river confluences in an Andean watershed (upper Elqui, North-Central Chile). The mildly acidic Toro River (4<pH<5; As_TOTAL>0.4 mgL^-1; Cu_TOTAL>8 mgL^-1) was diluted and neutralized at two consecutive confluences, resulting in dissolved As and Cu lower than 0.04 and 0.1 mgL^-1, respectively. On-site laser scattering measurements showed that the size of suspended sediments was dominated by ultrafine (d<6 μm) and fine (6<d<63 μm) size modes, while larger modes (d>200 μm) were not observed, contrasting with other reactive Andean confluences that work as natural coagulation-flocculation reactors. Laboratory mixing experiments with filtered endmembers followed closely the trends observed in the field measurements. SEM observations and thermodynamic calculations, suggested that As-rich amorphous Fe minerals dominated the fine suspended solid inflow (d<15 μm) from the Toro River, while XRD did not reveal significant amounts of crystalline forms of Fe, As, or Cu minerals. Despite fresh precipitates that further associated dissolved As and Cu, the particles from the Toro River grew only slightly after the confluences, thus limiting particle settling potential and a significant metal-(loid)s removal. Consequently, the seasonal variation in the size and chemical nature of suspended solids in acid drainage inflows control the distinct physical and chemical fates of As and Cu after neutralization, as well as hydrodynamic or hydraulic conditions likely also constrain sediment deposition. The combined monitoring of chemical parameters and particle size distributions is a simple and cost-effective method to obtain information about the behavior of metal(loid)s and sediments.

Keywords: Acid drainage; Arsenic; Copper; Particle size; Reactive confluences; Turbidity.