USGS2021
Diel cycles are known to occur in all types of waters, and increasing studies indicate routine water samples may not provide an accurate snapshot in concentrations of trace elements and nutrients. Diel behavior in neutral to alkaline pH ranges is independent of streamflow variability and concentration. Extensive historical U.S. Geological Survey (USGS) water-quality data have been collected in the Eagle River Basin during daylight hours, which is defined as the period of time between one-half hour prior to sunrise and one-half hour after sunset. However, no USGS data have been collected throughout the nighttime, defined as the time between one-half hour after sunset and one-half hour prior to sunrise, making the evaluation of diel cycles impossible. To assess the importance of diel cycling within the Eagle River Basin, the USGS, in cooperation with Eagle River Watershed Council, developed a study to assess the mechanisms, patterns, and magnitude of change during the diel cycle for selected constituents. Water-quality monitors at five USGS streamgage sites (09065500, Gore Creek at Upper Station, near Minturn, Colorado, 09063000, Eagle River at Red Cliff, Colorado, 09064600, Eagle River near Minturn, Colorado, 09066325, Gore Creek above Red Sandstone Creek at Vail, Colorado, and 394220106431500, Eagle River below Milk Creek near Wolcott, Colorado) were deployed in 2017 to evaluate the water-quality field parameters and to determine if water conditions were favorable for the diel cycling of nutrients and trace elements. Based on the evaluation of water-quality parameters, three of the five sites were sampled for nutrient and trace-element concentrations in 2018 to confirm the presence and magnitude of diel cycling. Historical data were also analyzed to assess the effect of time of day on measured nutrient and trace-element concentrations. An assessment of the effect of land use on diel cycling was also investigated. Measurable nutrients displayed a diel cycle at all three sites with the largest percentage change at the most downstream site (394220106431500), located on the Eagle River. More notable diel cycles at this site include filtered nitrate plus nitrite, which varied 179 percent, with concentrations from 0.24 to 0.67 milligrams per liter (mg/L) and filtered orthophosphate, which varied 71 percent, with concentrations from 0.07 to 0.12 mg/L. Filtered nitrate plus nitrite at site 09066325 varied 57 percent, ranging from 0.14 to 0.22 mg/L. Maximum concentrations occurred prior to noon, decreased through the afternoon (between noon and sunset), and increased during the night (between sunset and sunrise). That pattern is consistent with nutrient uptake in response to daytime (between sunrise and sunset) photosynthesis along with biologically driven denitrification and nitrification cycles. Nutrient concentrations at sites 09064600 and 09066325 were generally low and below laboratory reporting limits, which is the smallest measured concentration that nutrients could be measured by a given analytical method. Trace-element concentrations were detectable at all sites with the largest percentage change at the most downstream site (394220106431500) and exhibited diel concentration variation from 11.6 to 284 percent. Appreciable diel cycles included filtered copper (0.98–1.40 micrograms per liter [µg/L], 42.9 percent), filtered zinc (less than [<] 4.00–5.50 µg/L, greater than [>] 37.5 percent), total manganese (9.70–19.5 µg/L, 101 percent), and total arsenic (0.30–0.40 µg/L, 33.3 percent). The largest percentage change in concentration was filtered manganese (2.84–10.9 µg/L, 284 percent). Diel cycles at site 09064600 ranged from 9.1 to 64.5 percent across the trace elements measured. Dissolved trace elements with appreciable diel cycles during the sampling period include filtered cadmium (0.09–0.12 µg/L, 33.3 percent), filtered copper (0.99–1.40 µg/L, 41.4 percent), and total arsenic (0.20–0.30 µg/L, 50 percent). The largest percentage change was filtered zinc (38.3–63.0 µg/L, 65 percent). Trace-element concentrations at site 09066325 were below laboratory reporting limits for many parameters, and no diel cycle could be assessed for these parameters. However, total recoverable iron, filtered barium, filtered manganese, and filtered selenium exhibited changes in concentrations of <10.0–19.4 µg/L (>94 percent), 115–121 µg/L (5 percent), 1.44–1.72 µg/L (19.4 percent), and 0.25–0.28 µg/L (12 percent), respectively. At sites 09064600 and 394220106431500, maximum trace-element concentrations occurred during nighttime with some variation regarding the timing of the peak. The exceptions to this were filtered copper, total arsenic, and filtered selenium, which had maximum concentrations around noon or as the sun disappeared below the horizon. The timing of minimum concentrations occurred in the afternoon for many trace elements, with filtered copper, total arsenic, and filtered selenium having minimum concentrations in the morning or just prior to the appearance of the sun. Analysis of historical data also showed evidence of diel cycling. Historical samples collected from July through October were used to identify diel cycling in base-flow conditions. The resulting diel pattern in the median concentration for filtered manganese, filtered zinc at water-quality site 09064600, and filtered manganese and filtered nitrate plus nitrite at water-quality site 39422016431500 were consistent with the diel pattern in the September 2018 samples, and indicate time of day can bias sampling results even during daylight hours. Diel cycling in the Eagle River Basin appears to be driven primarily by instream, biological processes. However, land use, particularly human effects downstream from urban areas, mining, and agriculture, may affect these processes. At some locations, diel variations in nutrient and trace-element concentrations are small enough to be of low concern. At other locations, however, variations in concentrations up to 284 percent in the data collected for this study and 214 percent in base-flow historical data, indicate daytime-only sampling, particularly in late afternoon, can underestimate daily average nutrient and trace-element concentrations. When feasible, the potential of diel cycling warrants consideration in sample design to account for the potential of diel cycles, or at a minimum, be recognized as a component of the river dynamic and the potential consequences that diel cycles may have in data interpretation and river management decisions.