Daily Freeze–Thaw Cycles Affect the Transport of Metals in Streams Affected by Acid Drainage

Paula Guerra,Kyle Simonson,Christian González,Gonzalo Pizarro,Pablo Pasten,Jorge Gironás,Carlos Bonilla,Cristian Escauriaza

doi:10.3390/w8030074

Abstract

Stream flow rates with seasonal, daily, or hourly cycles due to freezing and thawing can control downstream chemical processes by changing the mixing ratio of reactive flows. The extent of these hydrologic-chemical interactions has not been fully realized yet. This work explored the link between daily freeze-thaw cycles and the fate and transport of metals at a model stream impacted by acid drainage. We characterized hydrological and physicochemical parameters at the confluence between the Caracarani River (pH ~8.6) and the Azufre River (pH < 2), in northern Chile. Hourly water depth, temperature, and electrical conductivity monitoring coupled with pH and turbidity measurements revealed that maximum flow rates from thawing of the Azufre River induced characteristic daily drops in pH and turbidity. Shifts in pH controlled the precipitation and dissolution of arsenic-rich iron and aluminum reactive phases. Thus freeze-thaw processes are critical at streams receiving acid drainage where iron and aluminum phases form and are likely to impact the fate and transport of toxic metals in the system. This work highlights the importance of assessing the hydrological controls on flows and mixing ratios when studying the chemical reactivity and fate of contaminants at systems affected by acid drainage.

Highlights

Water quality may be strongly affected by annual, seasonal, and daily periodicity in stream flow rate [1,2,3,4,5]
The flow rates of the Azufre River (QAzufre ) and Caracarani River (QCaracarani ) showed daily cycles, as illustrated in Figure 4, where flow rates measured in August 2011 are shown
We developed a preliminary geochemical model that considered the formation of amorphous iron hydroxide (Fe(OH)3(a)) and amorphous aluminum hydroxide (Al(OH)3(a)) at different mixing ratios between the Azufre River and Caracarani River

Summary

Introduction

Water quality may be strongly affected by annual, seasonal, and daily periodicity in stream flow rate [1,2,3,4,5]. Changes in water quality can be caused by incoming waters that can dilute or concentrate chemical species [1,2,3,6,7,8] or incorporate sediments or nutrients into the rivers [1,9,10,11]. These processes can exert an important control in chemical speciation. In terms of chemical processes, dissolved salts are displaced during the freezing process to the liquid phase This is especially critical in systems affected by streams of acid drainage (pH < 3). The melting of acid drainage produces trace metals, abrupt peaks in the concentration of anions (SO4 ́2 and Cl ), and

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