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D. A. Nimick

Publications and source records attributed to D. A. Nimick.

At least 19 recordsLinked to original sources
USGS2009

An empirical method for estimating instream pre-mining pH and dissolved Cu concentration in catchments with acidic drainage and ferricrete

Methods for assessing natural background water quality of streams affected by historical mining are vigorously debated. An empirical method is proposed in which stream-specific estimation equations are generated from relationships between either pH or dissolved Cu concentration in stream water and the Fe/Cu concentration ratio in Fe-precipitates presently forming in the stream. The equations and Fe/Cu ratios for pre-mining deposits of alluvial ferricrete then were used to reconstruct estimated pre-mining longitudinal profiles for pH and dissolved Cu in three acidic streams in Montana, USA. Primary assumptions underlying the proposed method are that alluvial ferricretes and modern Fe-precipitates share a common origin, that the Cu content of Fe-precipitates remains constant during and after conversion to ferricrete, and that geochemical factors other than pH and dissolved Cu concentration play a lesser role in determining Fe/Cu ratios in Fe-precipitates. The method was evaluated by applying it in a fourth, naturally acidic stream unaffected by mining, where estimated pre-mining pH and Cu concentrations were similar to present-day values, and by demonstrating that inflows, particularly from unmined areas, had consistent effects on both the pre-mining and measured profiles of pH and Cu concentration. Using this method, it was estimated that mining has affected about 480 m of Daisy Creek, 1.8 km of Fisher Creek, and at least 1 km of Swift Gulch. Mean values of pH decreased by about 0.6 pH units to about 3.2 in Daisy Creek and by 1-1.5 pH units to about 3.5 in Fisher Creek. In Swift Gulch, mining appears to have decreased pH from about 5.5 to as low as 3.6. Dissolved Cu concentrations increased due to mining almost 40% in Daisy Creek to a mean of 11.7 mg/L and as much as 230% in Fisher Creek to 0.690 mg/L. Uncertainty in the fate of Cu during the conversion of Fe-precipitates to ferricrete translates to potential errors in pre-mining estimates of as much as 0.25 units for pH and 22% for dissolved Cu concentration. The method warrants further testing in other mined and unmined watersheds. Comparison of pre-mining water-quality estimates derived from the ferricrete and other methods in single watersheds would be particularly valuable. The method has potential for use in monitoring remedial efforts at mine sites with ferricrete deposits. A reasonable remediation objective might be realized when the downstream pattern of Fe/Cu ratios in modern streambed Fe-precipitates corresponds to the pattern in pre-mining alluvial ferricrete deposits along a stream valley.

Applied Geochemistry↗
USGS2008

Photoreduction fuels biogeochemical cycling of iron in Spain's acid rivers

A number of investigations have shown that photoreduction of Fe(III) causes midday accumulations of dissolved Fe(II) in rivers and lakes, leading to large diel (24-h) fluctuations in the concentration and speciation of total dissolved iron. Less well appreciated is the importance of photoreduction in providing chemical energy for bacteria to thrive in low pH waters. Diel variations in water chemistry from the highly acidic (pH 2.3 to 3.1) Río Tinto, Río Odiel, and Río Agrio of southwestern Spain (Iberian Pyrite Belt) resulted in daytime increases in Fe(II) concentration of 15 to 66 µM at four diel sampling locations. Dissolved Fe(II) concentrations increased with solar radiation, and one of the stream sites showed an antithetic relationship between dissolved Fe(II) and Fe(III) concentrations; both results are consistent with photoreduction. The diel data were used to estimate rates of microbially catalyzed Fe(II) oxidation (1 to 3 nmol L − 1 s − 1 ) and maximum rates of Fe(III) photoreduction (1.7 to 4.3 nmol L − 1 s − 1 ). Bioenergetic calculations indicate that the latter rates are sufficient to build up a population of Fe-oxidizing bacteria to the levels observed in the Río Tinto in about 30 days. We conclude that photoreduction plays an important role in the bioenergetics of the bacterial communities of these acidic rivers, which have previously been shown to be dominated by autotrophic Fe(II)-oxidizers such as Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans . Given the possibility of the previous existence of acidic, Fe(III)-rich water on Mars, photoreduction may be an important process on other planets, a fact that could have implications to astrobiological research.

Chemical Geology↗
USGS2006

Light-mediated Zn uptake in photosynthetic biofilm

Our experiments conducted under controlled laboratory conditions demonstrate diel uptake and release of zinc (Zn) in lab-cultured biofilm exposed to Zn concentrations that are present in some mining-impacted streams (1–2 mg Zn/l). Specifically, at constant pH, temperature, and aqueous Zn concentrations in the exposure water, biofilm accumulated Zn during the light periods of the photocycle and released Zn during the dark periods of the photocycle. The range of Zn uptake measured in biofilm during one light period in these laboratory experiments (0.6–8.3 mg Zn/g dw biofilm) encompassed the estimated Zn uptake (1.5–3.7 mg Zn/g dw biofilm) necessary to attribute aqueous diel Zn cycling in a mining-impacted stream in Montana (High Ore Creek) to uptake in biofilm. This is relevant to in situ studies of diel Zn cycling because we controlled three important parameters that naturally fluctuate daily in the field, thus demonstrating the potential for biofilm to remove large percentages of Zn from some mining-impacted streams. Researchers, modelers, regulators, and reclamation teams working in metals-contaminated streams should be aware of diel metal cycling, because the highest Zn concentrations (and therefore, perhaps the most toxic conditions) in the water column might occur at night, and the greatest exposure of grazers of phototrophs to dietborne Zn might occur during daylight hours.

Hydrobiologia↗
USGS2005

Arsenic hydrogeochemistry in an irrigated river valley - A reevaluation

Arsenic concentrations in ground water of the lower Madison River valley, Montana, are high (16 to 176 μg/L). Previous studies hypothesized that arsenic-rich river water, applied as irrigation, was evapoconcentrated during recharge and contaminated the thin alluvial aquifer. Based on additional data collection and a reevaluation of the hydrology and geochemistry of the valley, the high arsenic concentrations in ground water are caused by a unique combination of natural hydrologic and geochemical factors, and irrigation appears to play a secondary role. The high arsenic concentrations in ground water have several causes: direct aquifer recharge by Madison River water having arsenic concentrations as high as 100 μg/L, leaching of arsenic from Tertiary volcano-clastic sediment, and release of sorbed arsenic where redox conditions in ground water are reduced. The findings are consistent with related studies that demonstrate that arsenic is sorbed by irrigated soils in the valley. Although evaporation of applied irrigation water does not significantly increase arsenic concentrations in ground water, irrigation with arsenic-rich water raises other environmental concerns.

Groundwater↗
USGS2005

Seasonality of diel cycles of dissolved trace-metal concentrations in a Rocky Mountain stream

Substantial diel (24-h) cycles in dissolved (0.1-μm filtration) metal concentrations were observed during summer low flow, winter low flow, and snowmelt runoff in Prickly Pear Creek, Montana. During seven diel sampling episodes lasting 34–61.5 h, dissolved Mn and Zn concentrations increased from afternoon minimum values to maximum values shortly after sunrise. Dissolved As concentrations exhibited the inverse timing. The magnitude of diel concentration increases varied in the range 17–152% for Mn and 70–500% for Zn. Diel increases of As concentrations (17–55%) were less variable. The timing of minimum and maximum values of diel streamflow cycles was inconsistent among sampling episodes and had little relation to the timing of metal concentration cycles, suggesting that geochemical rather than hydrological processes are the primary control of diel metal cycles. Diel cycles of dissolved metal concentrations should be assumed to occur at any time of year in any stream with dissolved metals and neutral to alkaline pH.

Environmental Geology↗
USGS2005

Does biofilm contribute to diel cycling of Zn in High Ore Creek, Montana?

Concentrations of metals cycle daily in the water column of some mining-impacted streams in the Rocky Mountains of the western USA. We hypothesized that biofilm in High Ore Creek, Montana, USA, sorbs and releases Zn on a diel cycle, and this uptake-and-release cycle controls the total and dissolved (0.45-μm filtered) Zn concentrations. We collected water samples from three sites (upstream, middle and downstream at 0, 350 and 650 m, respectively) along a 650-m reach of High Ore Creek during a 47-h period in August 2002 and from the upstream and downstream sites during a 24-h period in August 2003; we also collected biofilm samples at these sites. In 2002 and 2003, total and dissolved Zn concentrations did not exhibit a diel cycle at the upstream sampling site, which was ~30 m downstream from a settling pond through which the creek flows. However, total and dissolved Zn concentrations exhibited a diel cycle at the middle and downstream sampling sites, with the highest Zn concentrations occurring at dawn and the lowest Zn concentrations occurring during late afternoon (>2-fold range of concentrations at the downstream site). Based on (1) concentrations of Zn in biofilm at the three sites and (2) results of streamside experiments that demonstrated Zn uptake and release by naïve biofilm during the light and dark hours of a photocycle, respectively, we conclude that Zn uptake in photosynthetic biofilms could contribute a large percentage to the cycling of Zn concentrations in the water column in High Ore Creek.

Montana↗
USGS2005

Diel behavior of iron and other heavy metals in a mountain stream with acidic to neutral pH: Fisher Creek, Montana, USA

Three simultaneous 24-h samplings at three sites over a downstream pH gradient were conducted to examine diel fluctuations in heavy metal concentrations in Fisher Creek, a small mountain stream draining abandoned mine lands in Montana. Average pH values at the upstream (F1), middle (F2), and downstream (F3) monitoring stations were 3.31, 5.46, and 6.80, respectively. The downstream increase in pH resulted in precipitation of hydrous ferric oxide (HFO) and hydrous aluminum oxide (HAO) on the streambed. At F1 and F2, Fe showed strong diel cycles in dissolved concentration and Fe(II)/Fe(III) ratio; these cycles were attributed to daytime photoreduction of Fe(III) to Fe(II), reoxidation of Fe(II) to Fe(III), and temperature-dependent hydrolysis and precipitation of HFO. At the near-neutral downstream station, no evidence of Fe(III) photoreduction was observed, and suspended particles of HFO dominated the total Fe load. HFO precipitation rates between F2 and F3 were highest in the afternoon, due in part to reoxidation of a midday pulse of Fe 2+ formed by photoreduction in the upper, acidic portions of the stream. Dissolved concentrations of Fe(II) and Cu decreased tenfold and 2.4-fold, respectively, during the day at F3. These changes were attributed to sorption onto fresh HFO surfaces. Results of surface complexation modeling showed good agreement between observed and predicted Cu concentrations at F3, but only when adsorption enthalpies were added to the thermodynamic database to take into account diel temperature variations. The field and modeling results illustrate that the degree to which trace metals adsorb onto actively forming HFO is strongly temperature dependent. This study is an example of how diel Fe cycles caused by redox and hydrolysis reactions can induce a diel cycle in a trace metal of toxicological importance in downstream waters.

Montana↗
USGS2005

Diel behavior of rare earth elements in a mountain stream with acidic to neutral pH

Diel (24-h) changes in concentrations of rare earth elements (REE) were investigated in Fisher Creek, a mountain stream in Montana that receives acid mine drainage in its headwaters. Three simultaneous 24-h samplings were conducted at an upstream station (pH = 3.3), an intermediate station (pH = 5.5), and a downstream station (pH = 6.8). The REE were found to behave conservatively at the two upstream stations. At the downstream station, REE partitioned into suspended particles to a degree that varied with the time of day, and concentrations of dissolved REE were 2.9- to 9.4-fold (190% to 830%) higher in the early morning vs. the late afternoon. The decrease in dissolved REE concentrations during the day coincided with a corresponding increase in the concentration of REE in suspended particles, such that diel changes in the total REE concentrations were relatively minor (27% to 55% increase at night). Across the lanthanide series, the heavy REE partitioned into the suspended solid phase to a greater extent than the light REE. Filtered samples from the downstream station showed a decrease in shale-normalized REE concentration across the lanthanide series, with positive anomalies at La and Gd, and a negative Eu anomaly. As the temperature of the creek increased in the afternoon, the slope of the REE profile steepened and the magnitude of the anomalies increased. The above observations are explained by cyclic adsorption of REE onto suspended particles of hydrous ferric and aluminum oxides (HFO, HAO). Conditional partition coefficients for each REE between the suspended solids and the aqueous phase reached a maximum at 1700 hours and a minimum at 0700 hours. This pattern is attributed to diel variations in stream temperature, possibly reinforced by kinetic factors (i.e., slower rates of reaction at night than during the day). Estimates of the enthalpy of adsorption of each REE onto suspended particles based on the field results averaged +82 kJ/mol and are similar in magnitude to estimates in the literature for adsorption of divalent metal cations onto clays and hydrous metal oxides. The results of this study have important implications to the use of REE as hydrogeochemical tracers in streams.

Geochimica et Cosmochimica Acta↗
USGS2004

Relative effect of temperature and pH on diel cycling of dissolved trace elements in Prickly Pear Creek, Montana

Diel (24 hr) cycles in dissolved metal and As concentrations have been documented in many northern Rocky Mountain streams in the U.S.A. The cause(s) of the cycles are unknown, although temperature- and pH-dependent sorption reactions have been cited as likely causes. A light/dark experiment was conducted to isolate temperature and pH as variables affecting diel metal cycles in Prickly Pear Creek, Montana. Light and dark chambers containing sediment and a strand of macrophyte were placed in the stream to simulate instream temperature oscillations. Photosynthesis-induced pH changes were allowed to proceed in the light chambers while photosynthesis was prevented in the dark chambers. Water samples were collected periodically for 22 hr in late July 2001 from all chambers and the stream. In the stream, dissolved Zn concentrations increased by 300% from late afternoon to early morning, while dissolved As concentrations exhibited the opposite pattern, increasing 33% between early morning and late afternoon. Zn and As concentrations in the light chambers showed similar, though less pronounced, diel variations. Conversely, Zn and As concentrations in the dark chambers had no obvious diel variation, indicating that light, or light-induced reactions, caused the variation. Temperature oscillations were nearly identical between light and dark chambers, strongly suggesting that temperature was not controlling the diel variations. As expected, pH was negatively correlated ( P < 0.01) with dissolved Zn concentrations and positively correlated with dissolved As concentrations in both the light and dark chambers. From these experiments, photosynthesis-induced pH changes were determined to be the major cause of the diel dissolved Zn and As cycles in Prickly Pear Creek. Further research is necessary in other streams to verify that this finding is consistent among streams having large differences in trace-element concentrations and mineralogy of channel substrate.

Montana↗
USGS1997

Hydrologic and water-quality data related to the occurrence of arsenic for areas along the Madison and Upper Missouri Rivers, southwestern and west-central Montana

Geothermal waters in Yellowstone National Park contribute large quantities of arsenic to the headwaters of the Madison River. Water in some Quaternary and Tertiary valley-fill deposits along the Madison and upper Missouri Rivers also is locally enriched in arsenic. Arsenic in surface and ground water in these valleys is an important public- health concern because arsenic concentrations frequently exceed the State of Montana water- quality human health standard of 18 micrograms per liter as well as the U.S. Environmental Protection Agency Maximum Contaminant Level of 50 micrograms per liter. This report presents hydrologic and water-quality data for the Madison and upper Missouri Rivers and selected tributaries, irrigation supply canals or ditches, drains, springs and seeps, for Lake Helena, and for ground water in adjacent areas. Hydrologic and water-quality data were collected and compiled to provide information to more fully understand the extent, magnitude, and source of arsenic in surface and ground water along the Madison and upper Missouri Rivers; to assess, to the extent possible, the mechanisms that control arsenic concentrations; and to assess the effect of irrigation on arsenic concentrations. Hydrologic and arsenic- concentration data were collected by the U.S. Geological Survey and other agencies for 104 surface-water sites and 273 ground-water sites during this and previous studies. The quality of analytical results for arsenic concentrations was evaluated by quality-control samples that were submitted from the field and analyzed in the laboratory with routing samples. Quality-control samples consisted of replicates, standard reference samples, interlaboratory comparison samples, and field blanks.

Open-File Report↗
USGS1996

Detailed study of selenium in soil, water, bottom sediment, and biota in the Sun River Irrigation Project, Freezout Lake Wildlife Management Area, and Benton Lake National Wildlife Refuge, west-central Montana, 1990-92

Selenium and other constituents are adversely affecting water quality and creating a potential hazard to wildlife in several areas of the Sun River Irrigation Project, Freezout Lake Wildlife Management Area, and Benton Lake National Wildlife Refuge in west-central Montana. Selenium derived from Cretaceous shale and Tertiary and Quaternary deposits containing shale detritus is transported in the oxic shallow ground-water systems. At Freezout Lake Wildlife Management Area, drainage from irrigated glacial deposits is the primary source of selenium; drainage from non-irrigated farmland is a significant source locally. Benton Lake generally receives more selenium from natural runoff from its non-irrigated basin than from the trans-basin diversion of irrigation return flow. Selenium has accumulated in aquatic plants and invertebrates, fish, and water birds, particularly in wetlands that receive the largest selenium loads. Although selenium residues in biological tissue from some wetland units exceeded biological risk levels, water-bird reproduction generally has not been impaired. The highest selenium residues in biota commonly occurred in samples from Priest Butte Lakes, which also had the highest selenium concentration in wetland water. Selenium concentrations in all invertebrate samples from Priest Butte Lakes and the south end of Freezeout Lake exceeded the critical dietary threshold for water birds. Selenium delivered to wetlands accumulates in bottom sediment, predominantly in near-shore areas. Potential impacts to water quality, and presumably biota, may be greatest near the mouths of inflows. Most selenium delivered to wetlands will continue to accumulate in bottom sediment and biota.

Water-Resources Investigations Report↗