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[1] Substantial diel (24-hour) cycles in dissolved (0.1-mm filtration) metal concentrations were observed during low flow for 18 sampling episodes at 14 sites on 12 neutral and alkaline streams draining historical mining areas in Montana and Idaho. At some sites, concentrations of Cd, Mn, Ni, and Zn increased as much as 119, 306, 167, and 500%, respectively, from afternoon minimum values to maximum values shortly after sunrise. Arsenic concentrations exhibited the inverse temporal pattern with increases of up to 54%. Variations in Cu concentrations were small and inconsistent. Diel metal cycles are widespread and persistent, occur over a wide range of metal concentrations, and likely are caused primarily by instream geochemical processes. Adsorption is the only process that can explain the inverse temporal patterns of As and the divalent metals. Diel metal cycles have important implications for many types of water-quality studies and for understanding trace-metal mobility.

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Rivers with high biological productivity typically show substantial increases in pH and dissolved oxygen (DO) concentration during the day and decreases at night, in response to changes in the relative rates of aquatic photosynthesis and respiration. These changes, coupled with temperature variations, may impart diel (24-h) fluctuations in the concentration of trace metals, nutrients, and other chemical species. A better understanding of diel processes in rivers is needed and will lead to improved methods of data collection for both monitoring and research purposes. Previous studies have used stable isotopes of dissolved oxygen (DO) and dissolved inorganic carbon (DIC) as tracers of geochemical and biological processes in streams, lakes, and marine systems. Although seasonal variation in 6180 of DO in rivers and lakes has been documented, no study has investigated diel changes in this parameter. Here, we demonstrate large (up to 13%o) cycles in delta18O-DO for two late summer sampling periods in the Big Hole River of southwest Montana and illustrate that these changes are correlated to variations in the DO concentration, the C-isotopic composition of DIC, and the primary productivity of the system. The magnitude of the diel cycle in delta18O-DO was greater in August versus September because of the longer photoperiod and warmer water temperatures. This study provides another biogeochemical tool for investigating the O2 and C budgets in rivers and may also be applicable to lake and groundwater systems.