Effects of Flow Regime on Metal Concentrations and the Attainment of Water Quality Standards in a Remediated Stream Reach, Butte, Montana.

Low-flow synoptic sampling campaigns are often used as the primary tool to characterize watersheds affected by mining. Although such campaigns are an invaluable part of site characterization, investigations which focus solely on low-flow conditions may yield misleading results. The objective of this paper is to demonstrate this point and elucidate the mechanisms responsible for the release of metals during rainfall runoff. This objective is addressed using data from diel and synoptic sampling campaigns conducted over a two-day period. Low-flow synoptic sampling results indicate that concentrations of most constituents meet aquatic standards. This finding is in contrast to findings from a diel sampling campaign that captured dramatic increases in concentrations during rainfall runoff. Concentrations during the rising limb of the hydrograph were 2-23 times concentrations observed during synoptic sampling (most increases were >10-fold), remaining elevated during the receding limb of the hydrograph to produce a clockwise hysteresis loop. Hydrologic mechanisms responsible for the release of metals include increased transport due to resuspension of streambed solids, erosion of alluvial tailings, and overland flow. Rainfall also elevated the alluvial groundwater table and increased infiltration through the vadose zone, likely resulting in dissolution from alluvial tailings that were dry prior to the event.

Diel changes in water chemistry in an arsenic-rich stream and treatment-pond system.

Arsenic concentrations are elevated in surface waters of the Warm Springs Ponds Operable Unit (WSPOU), located at the head of the upper Clark Fork River Superfund site, Montana, USA. Arsenic is derived from historical deposition of smelter emissions (Mill and Willow Creeks) and historical mining and milling wastes (Silver Bow Creek). Although long-term monitoring has characterized the general seasonal and flow-related trends in As concentrations in these streams and the pond system used to treat Silver Bow Creek water, little is known about solubility controls and sorption processes that influence diel cycles in As concentrations. Diel (24-h) sampling was conducted in July 2004 and August 2005 at the outlet of the treatment ponds, at two locations along a nearby reconstructed stream channel that diverts tributary water around the ponds, and at Silver Bow Creek 2 km below the ponds. Dissolved As concentration increased up to 51% during the day at most of the stream sites, whereas little or no diel change was displayed at the treatment-pond outlet. The strong cycle in streams is explained by pH- and temperature-dependent sorption of As onto hydrous metal oxides or biofilms on the streambed. Concentrations of dissolved Ca(2+) and HCO(3)(-) at the stream sites showed a diel temporal pattern opposite to that of As, and geochemical modeling supports the hypothesis that the concentrations of Ca(2+) and HCO(3)(-) were controlled by precipitation of calcite during the warm afternoon hours when pH rose above 9.0. Nightly increases in dissolved Mn and Fe(II) concentrations were out of phase with concentrations of other divalent cations and are more likely explained by redox phenomena.

Diel mercury-concentration variations in streams affected by mining and geothermal discharge.

Diel variations of concentrations of unfiltered and filtered total Hg and filtered methyl Hg were documented during 24-h sampling episodes in water from Silver Creek, which drains a historical gold-mining district near Helena, Montana, and the Madison River, which drains the geothermal system of Yellowstone National Park. The concentrations of filtered methyl Hg had relatively large diel variations (increases of 68 and 93% from morning minima) in both streams. Unfiltered and filtered (0.1-microm filtration) total Hg in Silver Creek had diel concentration increases of 24% and 7%, respectively. In the Madison River, concentrations of unfiltered and filtered total Hg did not change during the sampling period. The concentration variation of unfiltered total Hg in Silver Creek followed the diel variation in suspended-particle concentration. The concentration variation of filtered total and methyl Hg followed the solar photocycle, with highest concentrations during the early afternoon and evening and lowest concentrations during the morning. None of the diel Hg variations correlated with diel variation in streamflow or major ion concentrations. The diel variation in filtered total Hg could have been produced by adsorption-desorption of Hg2+ or by reduction of Hg(II) to Hg0 and subsequent evasion of Hg0. The diel variation in filtered methyl Hg could have been produced by sunlight- and temperature-dependent methylation. This study is the first to examine diel Hg cycling in streams, and its results reinforce previous conclusions that diel trace-element cycling in streams is widespread but often not recognized and that parts of the biogeochemical Hg cycle respond quickly to the daily photocycle.

Influence of in-stream diel concentration cycles of dissolved trace metals on acute toxicity to one-year-old cutthroat trout (Oncorhynchus clarki lewisi).

Extrapolating results of laboratory bioassays to streams is difficult, because conditions such as temperature and dissolved metal concentrations can change substantially on diel time scales. Field bioassays conducted for 96 h in two mining-affected streams compared the survival of hatchery-raised, metal-naïve westslope cutthroat trout (Oncorhynchus clarki lewisi) exposed to dissolved (0.1-microm filtration) metal concentrations that either exhibited the diel variation observed in streams or were controlled at a constant value. Cadmium and Zn concentrations in these streams increased each night by as much as 61 and 125%, respectively, and decreased a corresponding amount the next day, whereas Cu did not display a diel concentration cycle. In High Ore Creek (40 km south of Helena, MT, USA), survival (33%) after exposure to natural diel-fluctuating Zn concentrations (range, 214-634 microg/L; mean, 428 microg/L) was significantly (p = 0.008) higher than survival (14%) after exposure to a controlled, constant Zn concentration (422 microg/L). Similarly, in Dry Fork Belt Creek (70 km southeast of Great Falls, MT, USA), survival (75%) after exposure to diel-fluctuating Zn concentrations (range, 266-522 microg/L; mean, 399 microg/L) was significantly (p = 0.022) higher than survival (50%) in the constant-concentration treatment (392 microg/L). Survival likely was greater in these diel treatments, both because the periods of lower metal concentrations provided some relief for the fish and because toxicity during periods of higher metal concentrations was lessened by the simultaneous occurrence each night of lower water temperatures, which reduce the rate of metal uptake. Based on the present study, current water-quality criteria appear to be protective for streams with diel concentration cycles of Zn (and, perhaps, Cd) for the hydrologic conditions tested.

Fate of geothermal mercury from Yellowstone National Park in the Madison and Missouri Rivers, USA.

Mercury is a worldwide contaminant derived from natural and anthropogenic sources. River systems play a key role in the transport and fate of Hg because they drain widespread areas affected by aerial Hg deposition, transport Hg away from point sources, and are sites of Hg biogeochemical cycling and bioaccumulation. The Madison and Missouri Rivers provide a natural laboratory for studying the fate and transport of Hg contributed by geothermal discharge in Yellowstone National Park and from the atmosphere for a large drainage basin in Montana and Wyoming, United States of America (USA). Assessing Hg in these rivers also is important because they support fishery-based recreation and irrigated agriculture. During 2002 to 2006, Hg concentrations were measured in water, sediment, and fish from the main stem, 7 tributaries, and 6 lakes. Using these data, the geothermal Hg load to the Madison River and overall fate of Hg along 378 km of the Missouri River system were assessed. Geothermal Hg was the primary source of elevated total Hg concentrations in unfiltered water (6.2-31.2 ng/L), sediment (148-1100 ng/g), and brown and rainbow trout (0.12-1.23 µg total Hg/g wet weight skinless filet) upstream from Hebgen Lake (the uppermost impoundment). Approximately 7.0 kg/y of geothermal Hg was discharged from the park via the Madison River, and an estimated 87% of that load was lost to sedimentation in and volatilization from Hebgen Lake. Consequently, Hg concentrations in water, sediment, and fish from main-stem sites downstream from Hebgen Lake were not elevated and were comparable to concentrations reported for other areas affected solely by atmospheric Hg deposition. Some Hg was sequestered in sediment in the downstream lakes. Bioaccumulation of Hg in fish along the river system was strongly correlated (r(2)=0.76-0.86) with unfiltered total and methyl Hg concentrations in water and total Hg in sediment.

Assessing time-integrated dissolved concentrations and predicting toxicity of metals during diel cycling in streams.

Evaluating water quality and the health of aquatic organisms is challenging in systems with systematic diel (24 h) or less predictable runoff-induced changes in water composition. To advance our understanding of how to evaluate environmental health in these dynamic systems, field studies of diel cycling were conducted in two streams (Silver Bow Creek and High Ore Creek) affected by historical mining activities in southwestern Montana. A combination of sampling and modeling tools was used to assess the toxicity of metals in these systems. Diffusive Gradients in Thin Films (DGT) samplers were deployed at multiple time intervals during diel sampling to confirm that DGT integrates time-varying concentrations of dissolved metals. Site specific water compositions, including time-integrated dissolved metal concentrations determined from DGT, a competitive, multiple-toxicant biotic ligand model, and the Windemere Humic Aqueous Model Version 6.0 (WHAM VI) were used to determine the equilibrium speciation of dissolved metals and biotic ligands. The model results were combined with previously collected toxicity data on cutthroat trout to derive a relationship that predicts the relative survivability of these fish at a given site. This integrative approach may prove useful for assessing water quality and toxicity of metals to aquatic organisms in dynamic systems and evaluating whether potential changes in environmental health of aquatic systems are due to anthropogenic activities or natural variability.

Diel cycling of zinc in a stream impacted by acid rock drainage: initial results from a new in situ Zn analyzer.

Recent work has demonstrated that many trace metals undergo dramatic diel (24-h) cycles in near neutral pH streams with metal concentrations reproducibly changing up to 500% during the diel period (Nimick et al., 2003). To examine diel zinc cycles in streams affected by acid rock drainage, we have developed a novel instrument, the Zn-DigiScan, to continuously monitor in situ zinc concentrations in near real-time. Initial results from a 3-day deployment at Fisher Creek, Montana have demonstrated the ability of the Zn-DigiScan to record diel Zn cycling at levels below 100 microg/l. Longer deployments of this instrument could be used to examine the effects of episodic events such as rainstorms and snowmelt pulses on zinc loading in streams affected by acid rock drainage.

Concentrations of metals in water, sediment, biofilm, benthic macroinvertebrates, and fish in the Boulder River watershed, Montana, and the role of colloids in metal uptake.

To characterize the partitioning of metals in a stream ecosystem, concentrations of trace metals including As, Cd, Cu, Pb, and Zn were measured in water, colloids, sediment, biofilm (also referred to as aufwuchs), macroinvertebrates, and fish collected from the Boulder River watershed, Montana. Median concentrations of Cd, Cu, and Zn in water throughout the watershed exceeded the U.S. EPA acute and chronic criteria for protection of aquatic life. Concentrations of As, Cd, Cu, Pb, and Zn in sediment were sufficient in the tributaries to cause invertebrate toxicity. The concentrations of As, Cu, Cd, Pb, and Zn in invertebrates from lower Cataract Creek (63, 339, 59, 34, and 2,410 microg/g dry wt, respectively) were greater than the concentrations in invertebrates from the Clark Fork River watershed, Montana (19, 174, 2.3, 15, and 648 microg/g, respectively), that were associated with reduced survival, growth, and health of cutthroat trout fed diets composed of those invertebrates. Colloids and biofilm seem to play a critical role in the pathway of metals into the food chain and concentrations of As, Cu, Pb, and Zn in these two components are significantly correlated. We suggest that transfer of metals associated with Fe colloids to biological components of biofilm is an important pathway where metals associated with abiotic components are first available to biotic components. The significant correlations suggest that Cd, Cu, and Zn may move independently to biota (biofilm, invertebrates, or fish tissues) from water and sediment. The possibility exists that Cd, Cu, and Zn concentrations increase in fish tissues as a result of direct contact with water and sediment and indirect exposure through the food chain. However, uptake through the food chain to fish may be more important for As. Although As concentrations in colloids and biofilm were significantly correlated with As water concentrations, As concentrations in fish tissues were not correlated with water. The pathway for Pb into biological components seems to begin with sediment because concentrations of Pb in water were not significantly correlated with any other component and because concentrations of Pb in the water were often below detection limits.