Sources, transport, and trends for selected trace metals and nutrients in the Coeur d'Alene and Spokane River Basins, Idaho, 1990-2013

Abstract

Data collected at 18 streamflow-gaging and water-quality sampling sites in the Coeur d’Alene and Spokane River Basins of northern Idaho were used to estimate mean streamflow‑weighted concentrations and annual loads of total and dissolved cadmium, lead, and zinc, and total phosphorus (TP) and nitrogen (TN) for water years (WYs) 2009–13. Chronic Ambient Water Quality Criteria (AWQC) and AWQC ratios also were calculated to evaluate Idaho aquatic life criteria for chronic exposure to cadmium and zinc in streams. At four sites with a longer period of record, a Seasonal Kendall trend test was used to assess historical trends in the concentrations of total cadmium, lead, and zinc, and chronic AWQC ratios for cadmium and zinc during WYs 1990–2013. Concentrations of dissolved and total cadmium, lead, and zinc varied widely both at and among sites. At most sites, dissolved cadmium and zinc constituted most of the total concentrations; dissolved lead generally constituted less than 10 percent of the total lead concentration. Trace metal concentrations increased by 2 to 4 orders of magnitude along the South Fork Coeur d’Alene River (SFCDR) from near Mullan (site 2) downstream to near Pinehurst (site 13). The mean streamflow-weighted concentrations of total cadmium, lead, and zinc in the SFCDR near Pinehurst for WYs 2009–13 were 3.71, 61.4, and 514 micrograms per liter (μg/L), respectively. In the Coeur d’Alene River (CDR) near Harrison (site 15), downstream of the confluence of the metal-enriched SFCDR and the relatively dilute North Fork Coeur d’Alene River (NFCDR), the mean streamflow-weighted concentrations of total cadmium, lead, and zinc were 1.58, 125, and 236 μg/L, respectively. Trace‑metal concentrations were smaller in the Spokane River than in the CDR because of dilution and retention of trace metals in Coeur d’Alene Lake. The mean streamflow-weighted concentrations of total cadmium, lead, and zinc in the Spokane River near Post Falls (site 18) were 0.231, 2.91, and 48.9 μg/L, respectively. AWQC ratios indicate that cadmium and zinc concentrations met the chronic criteria (ratio of less than 1.0) for the protection of aquatic life at only three sites: the NFCDR at Enaville (site 1), the upper SFCDR near Mullan (site 2), and the St. Joe River near St. Maries (site 16). Cadmium and zinc concentrations at sites on the Spokane River (sites 17 and 18) generally were close to the chronic AWQC values. The sites with the largest chronic AWQC ratios in the Coeur d’Alene and Spokane River Basins for both cadmium and zinc were in the Canyon and Ninemile Creek basins (sites 3–6). Concentrations of TP and TN generally were low along the SFCDR downstream to Kellogg. From the SFCDR near Kellogg (site 9) downstream to the SFCDR above Pine Creek (site 11), the mean streamflow-weighted concentration of the nutrients TP and TN increased by 0.036 milligram per liter (mg/L) (200 percent) and 0.124 mg/L (78 percent), respectively. The increases in nutrient concentrations along the SFCDR likely are in response to discharge from wastewater‑treatment facilities. Mean streamflow-weighted concentrations for TP and TN (0.054 and 0.284 mg/L, respectively) were the highest in the sampling network in the SFCDR above Pine Creek (site 11). LOADEST modeling was used to relate mass transport, or load, of trace metals and nutrients to variations in streamflow and time. Results indicate that most of the cadmium and zinc load in the Coeur d’Alene and Spokane Rivers is derived from the SFCDR, and that most of the lead load is derived from the Coeur d’Alene River downstream of the confluence of the NFCDR and SFCDR. Major tributary sources of trace metals to the SFCDR are Canyon Creek and Ninemile Creek. Combined, these two tributaries contributed estimated mean loads of about 0.575 ton per year (ton/yr) of total cadmium, 5.29 ton/yr of total lead, and 90.9 ton/yr of total zinc to the SFCDR during WYs 2009–13. Groundwater discharge and tributaries near the Central Impoundment Area between SFCDR near Kellogg (site 9) and SFCDR near Smelterville (site 10) were other primary sources of cadmium and zinc. Combined, these sources contributed an estimated 1.39 ton/yr of total cadmium and 143 ton/yr of total zinc to the SFCDR during WYs 2009–13. Erosion and transport of sediment-bound lead contained in the CDR flood plain and on the river bottom between Cataldo (site 14) and Harrison (site 15) were the primary source of lead. During WYs 2009–13, the mean load of trace metals delivered to Coeur d’Alene Lake included about 4.66 ton/yr of total cadmium, 398 ton/yr of total lead, and 698 ton/yr of total zinc. About 99 percent of the trace-metal load to the lake was from the CDR as measured near site 15 at Harrison. During WYs 2009–13, about 1.48 ton/yr of cadmium, 18 ton/yr of lead, and 350 ton/yr of zinc were transported from Coeur d’Alene Lake into the Spokane River as measured at the lake outlet (site 17). During WYs 2009–13, the loads of TP and TN delivered from the Coeur d’Alene and St. Joe Rivers to Coeur d’Alene Lake were about equivalent. On average, the CDR transported about 93.6 tons of TP and 369 tons of TN, and the St. Joe River transported about 92.9 tons of TP and 360 tons of TN to the lake during 2009–13. About 52.9 ton/yr of TP and 628 ton/yr of TN were transported from Coeur d’Alene Lake to the Spokane River during WYs 2009–13. Results from Seasonal Kendall trend tests indicate statistically significant downward temporal trends during WYs 1990–2013 for total cadmium, lead, zinc, and chronic AWQC ratios of cadmium and zinc in the SFCDR at Elizabeth Park (site 8) and near Pinehurst (site 13), and in the CDR near Harrison (site 15). Statistically significant downward temporal trends for total lead, zinc, and the chronic AWQC ratio of zinc also occurred in the Spokane River near Post Falls (site 18) during WYs 1991–2013. Seasonal Kendall trend tests for WYs 2003–13 indicated statistically significant downward trends for total cadmium, zinc, and chronic AWQC ratios of cadmium and zinc in the SFCDR at Elizabeth Park (site 8). The Spokane River near Post Falls (site 18) had a statistically significant downward trend for total zinc during WYs 2003–13, and a significant upward trend for the chronic AWQC ratio of cadmium. No significant trends were found in trace-metal concentrations or chronic AWQC ratios in the SFCDR near Pinehurst (site 13) and the CDR near Harrison (site 15) during WYs 2003–13. Results from this study indicate that remedial activities conducted since the 1990s have been successful in reducing the concentrations and loads of trace metals in streams and rivers in the Coeur d’Alene and Spokane River Basins. Soils, sediment, surface water, and groundwater in areas of the Coeur d’Alene and Spokane River Basins are contaminated, and the hydrological relations between these media are complex and difficult to characterize. Trace metals have variable source areas, are transported differently depending on hydrologic conditions, and behave differently in response to remedial activities in upstream basins. Based on these findings, no single remedial action would be completely effective in reducing all trace metals to nontoxic concentrations throughout the Coeur d’Alene and Spokane River Basins. Instead, unique cleanup activities targeted at specific media and specific source areas may be necessary to achieve long-term water-quality goals.