Briant A. Kimball

Iron Photoreduction and Oxidation in an Acidic Mountain Stream

In a small mountain stream in Colorado that receives acidic mine drainage, photoreduction of ferric iron results in a well-defined increase in dissolved ferrous iron during the day. To quantify this process, an instream injection of a conservative tracer was used to measure discharge at the time that each sample was collected. Daytime production of ferrous iron by photoreduction was almost four times as great as nighttime oxidation of ferrous iron. The photoreduction process probably involves dissolved or colloidal ferric iron species and limited interaction with organic species because concentrations of organic carbon are low in this stream.

Effects of colloids on metal transport in a river receiving acid mine drainage, upper Arkansas River, Colorado, U.S.A.

Abstract Inflows of metal-rich, acidic water that drain from mine dumps and tailings piles in the Leadville, Colorado, area enter the non-acidic water in the upper Arkansas River. Hydrous iron oxides precipitate as colloids and move downstream in suspension, particularly downstream from California Gulch, which has been the major source of metal loads. The colloids influence the concentrations of metals dissolved in the water and the concentrations in bed sediments. To determine the role of colloids, samples of water, colloids, and fine-grained bed sediment were obtained at stream-gaging sites on the upper Arkansas River and at the mouths of major tributaries over a 250-km reach. Dissolved and colloidal metal concentrations in the water column were operationally defined using tangential-flow filtration through 0.001-pm membranes to separate the water and the colloids. Surface-extractable and total bed sediment metal concentrations were obtained on the

Assessment of metal loads in watersheds affected by acid mine drainage by using tracer injection and synoptic sampling: Cement Creek, colorado, USA

Watersheds in mineralized zones may contain many mines, each of which can contribute to acidity and the metal load of a stream. In this study the authors delineate hydrogeologic characteristics determining the transport of metals from the watershed to the stream in the watershed of Cement Creek, Colorado. Combining the injection of a chemical tracer, to determine a discharge, with synoptic sampling, to obtain chemistry of major ions and metals, spatially detailed load profiles are quantified. Using the discharge and load profiles, the authors (1) identified sampled inflow sources which emanate from undisturbed as well as previously mined areas; (2) demonstrate, based on simple hydrologic balance, that unsampled, likely dispersed subsurface, inflows are significant; and (3) estimate attenuation. For example, along the 12-km study reach, 108 kg per day of Zn were added to Cement Creek. Almost half of this load came from 10 well-defined areas that included both mined and non-mined parts of the watershed. However, the combined effect of many smaller inflows also contributed a substantial load that could limit the effectiveness of remediation. Of the total Zn load, 58.3 kg/day came from stream segments with no visible inflow, indicating the importance of contributions from dispersed subsurface inflow. The subsurface inflow mostly occurred in areas with substantial fracturing of the bedrock or in areas downstream from tributaries with large alluvial fans. Despite a pH generally less than 4.5, there was 58.4 kg/day of Zn attenuation that occurred in mixing zones downstream from inflows with high pH. Mixing zones can have local areas of pH that are high enough for sorption and precipitation reactions to have an effect. Principal component analysis classified inflows into 7 groups with distinct chemical signatures that represent water-rock interaction with different mineral-alteration suites in the watershed. The present approach provides a detailed snapshot of metal load for the watershed to support remediation decisions, and quantifies processes affecting metal transport.

Colloid formation and metal transport through two mixing zones affected by acid mine drainage near Silverton, Colorado

Stream discharges and concentrations of dissolved and colloidal metals (Al, Ca, Cu, Fe, Mg, Mn, Pb, and Zn), SO4, and dissolved silica were measured to identify chemical transformations and determine mass transports through two mixing zones in the Animas River that receive the inflows from Cement and Mineral Creeks. The creeks were the dominant sources of Al, Cu, Fe, and Pb, whereas the upstream Animas River supplied about half of the Zn. With the exception of Fe, which was present in dissolved and colloidal forms, the metals were dissolved in the acidic, high-SO4 waters of Cement Creek (pH 3.8). Mixing of Cement Creek with the Animas River increased pH to near-neutral values and transformed Al and some additional Fe into colloids which also contained Cu and Pb. Aluminium and Fe colloids had already formed in the mildly acidic conditions in Mineral Creek (pH 6.6) upstream of the confluence with the Animas River. Colloidal Fe continued to form downstream of both mixing zones. The Fe- and Al-rich colloids were important for transport of Cu, Pb, and Zn, which appeared to have sorbed to them. Partitioning of Zn between dissolved and colloidal phases was dependent on pH and colloid concentration. Mass balances showed conservative transports for Ca, Mg, Mn, SO4, and dissolved silica through the two mixing zones and small losses (<10%) of colloidal Al, Fe and Zn from the water column. Published by Elsevier Science Ltd.

Coupling of hydrologic transport and chemical reactions in a stream affected by Acid mine drainage.

Experiments in St. Kevin Gulch, an acid mine drainage stream, examined the coupling of hydrologic transport to chemical reactions affecting metal concentrations. Injection of LiCl as a conservative tracer was used to determine discharge and residence time along a 1497-m reach. Transport of metals downstream from inflows of acidic, metal-rich water was evaluated based on synoptic samples of metal concentrations and the hydrologic characteristics of the stream. Transport of SO4 and Mn was generally conservative, but in the subreaches most affected by acidic inflows, transport was reactive. Both 0.1-pm filtered and particulate Fe were reactive over most of the stream reach. Filtered A1 partitioned to the particulate phase in response to high instream concentrations. Simulations that accounted for the removal of Sod, Mn, Fe, and A1 with firstorder reactions reproduced the steady-state profiles. The calculated rate constants for net removal used in the simulations embody several processes that occur on a stream-reach scale. The comparison between rates of hydrologic transport and chemical reactions indicates that reactions are only important over short distances in the stream near the acidic inflows, where reactions occur on a comparable time scale with hydrologic transport and thus affect metal concentrations.

Reactive solute transport in streams: A surface complexation approach for trace metal sorption

A model for trace metals that considers in-stream transport, metal oxide precipitation-dissolution, and pH-dependent sorption is presented. Linkage between a surface complexation submodel and the stream transport equations provides a framework for modeling sorption onto static and/or dynamic surfaces. A static surface (e.g., an iron- oxide-coated streambed) is defined as a surface with a temporally constant solid concentration. Limited contact between solutes in the water column and the static surface is considered using a pseudokinetic approach. A dynamic surface (e.g., freshly precipitated metal oxides) has a temporally variable solid concentration and is in equilibrium with the water column. Transport and deposition of solute mass sorbed to the dynamic surface is represented in the stream transport equations that include precipitate settling. The model is applied to a pH-modification experiment in an acid mine drainage stream. Dissolved copper concentrations were depressed for a 3 hour period in response to the experimentally elevated pH. After passage of the pH front, copper was desorbed, and dissolved concentrations returned to ambient levels. Copper sorption is modeled by considering sorption to aged hydrous ferric oxide (HFO) on the streambed (static surface) and freshly precipitated HFO in the water column (dynamic surface). Comparison of parameter estimates with reported values suggests that naturally formed iron oxides may be more effective in removing trace metals than synthetic oxides used in laboratory studies. The models ability to simulate pH, metal oxide precipitation-dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between trace metal chemistry and hydrologic transport at the field scale.

Mechanisms of iron photoreduction in a metal-rich, acidic stream (St. Kevin Gulch, Colorado, U.S.A.)

Abstract Iron photoreduction in metal-rich, acidic streams affected by mine drainage accounts for some of the variability in metal chemistry of such streams, producing diel variations in Fe(II). Differentiation of the mechanisms of the Fe photoreduction reaction by a series of in-stream experiments at St. Kevin Gulch, Colorado, indicates that a homogeneous, solution-phase reaction can occur in the absence of suspended particulate Fe and bacteria, and the rate of reaction is increased by the presence of Fe colloids in the stream water. In-stream Fe photoreduction is limited during the diel cycle by the available Fe(III) in the water column and streambed. The quantum yield of Fe(II) was reproducible in diel measurements: the quantum yield, in mol E −1 (from 300 to 400 nm) was 1.4 · 10 −3 in 1986, 0.8 · 10 −3 in 1988 and 1.2 · 10 −3 in 1989, at the same location and under similar streamflow and stream-chemistry conditions. In a photolysis control experiment, there was no detectable production of Fe(II) above background concentrations in stream-water samples that were experimentally excluded from sunlight.

Evaluating remedial alternatives for an acid mine drainage stream: a model post audit.

A post audit for a reactive transport model used to evaluate acid mine drainage treatment systems is presented herein. The post audit is based on a paired synoptic approach in which hydrogeochemical data are collected at low (existing conditions) and elevated (following treatment) pH. Data obtained under existing, low-pH conditions are used for calibration, and the resultant model is used to predict metal concentrations observed following treatment. Predictions for Al, As, Fe, H(+), and Pb accurately reproduce the observed reduction in dissolved concentrations afforded by the treatment system, and the information provided in regard to standard attainment is also accurate (predictions correctly indicate attainment or nonattainment of water quality standards for 19 of 25 cases). Errors associated with Cd, Cu, and Zn are attributed to misspecification of sorbent mass (precipitated Fe). In addition to these specific results, the post audit provides insight in regard to calibration and sensitivity analysis that is contrary to conventional wisdom. Steps taken during the calibration process to improve simulations of As sorption were ultimately detrimental to the predictive results, for example, and the sensitivity analysis failed to bracket observed metal concentrations.

Evaluating an unconfined aquifer by analysis of age-dating tracers in stream water

The mean transit time (MTT) is a fundamental property of a groundwater flow system that is strongly related to the ratio of recharge rate to storage volume. However, obtaining samples for estimating the MTT using environmental tracers is problematic as flow-weighted samples over the full spectrum of transit times are needed. Samples collected from the base flow of a gaining stream in the North Carolina Coastal Plain (West Bear Creek) that were corrected for exchange with the atmosphere yielded environmental tracer concentrations (SF6 and CFC-11) very similar to flow-weighted values from nine or ten streambed piezometers that directly sampled groundwater during low streamflow. At higher streamflow on the falling limb of the hydrograph, stream tracer concentrations (after correction for gas exchange) were significantly higher than the flow-weighted mean from piezometers, consistent with dominance of the stream tracer signal by transient influx of surface water and/or younger subsurface water. The apparent MTT derived from SF6 in low flow stream water samples was 26 years, suggesting a groundwater recharge rate of about 210 mm/yr, that is consistent with vertical profiles obtained by sampling nested piezometers in the aquifer. When sampled under low flow conditions when streamflow consists of a high component of groundwater discharge, West Bear Creek appears to act as a flow-weighted integrator of transit times and, streamflow samples can provide fundamental information regarding groundwater recharge rate and MTT. Our study suggests that watershed-scale evaluation of some groundwater flow systems is possible without utilizing monitoring wells.

A stream-based methane monitoring approach for evaluating groundwater impacts associated with unconventional gas development.

Gaining streams can provide an integrated signal of relatively large groundwater capture areas. In contrast to the point-specific nature of monitoring wells, gaining streams coalesce multiple flow paths. Impacts on groundwater quality from unconventional gas development may be evaluated at the watershed scale by the sampling of dissolved methane (CH4 ) along such streams. This paper describes a method for using stream CH4 concentrations, along with measurements of groundwater inflow and gas transfer velocity interpreted by 1-D stream transport modeling, to determine groundwater methane fluxes. While dissolved ionic tracers remain in the stream for long distances, the persistence of methane is not well documented. To test this method and evaluate CH4 persistence in a stream, a combined bromide (Br) and CH4 tracer injection was conducted on Nine-Mile Creek, a gaining stream in a gas development area in central Utah. A 35% gain in streamflow was determined from dilution of the Br tracer. The injected CH4 resulted in a fivefold increase in stream CH4 immediately below the injection site. CH4 and δ(13) CCH4 sampling showed it was not immediately lost to the atmosphere, but remained in the stream for more than 2000 m. A 1-D stream transport model simulating the decline in CH4 yielded an apparent gas transfer velocity of 4.5 m/d, describing the rate of loss to the atmosphere (possibly including some microbial consumption). The transport model was then calibrated to background stream CH4 in Nine-Mile Creek (prior to CH4 injection) in order to evaluate groundwater CH4 contributions. The total estimated CH4 load discharging to the stream along the study reach was 190 g/d, although using geochemical fingerprinting to determine its source was beyond the scope of the current study. This demonstrates the utility of stream-gas sampling as a reconnaissance tool for evaluating both natural and anthropogenic CH4 leakage from gas reservoirs into groundwater and surface water.