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P. L. Verplanck

Publications and source records attributed to P. L. Verplanck.

14 recordsLinked to original sources

Lagrangian mass-flow investigations of inorganic contaminants in wastewater-impacted streams

Understanding the potential effects of increased reliance on wastewater treatment plant (WWTP) effluents to meet municipal, agricultural, and environmental flow requires an understanding of the complex chemical loading characteristics of the WWTPs and the assimilative capacity of receiving waters. Stream ecosystem effects are linked to proportions of WWTP effluent under low-flow conditions as well as the nature of the effluent chemical mixtures. This study quantifies the loading of 58 inorganic constituents (nutrients to rare earth elements) from WWTP discharges relative to upstream landscape-based sources. Stream assimilation capacity was evaluated by Lagrangian sampling, using flow velocities determined from tracer experiments to track the same parcel of water as it moved downstream. Boulder Creek, Colorado and Fourmile Creek, Iowa, representing two different geologic and hydrologic landscapes, were sampled under low-flow conditions in the summer and spring. One-half of the constituents had greater loads from the WWTP effluents than the upstream drainages, and once introduced into the streams, dilution was the predominant assimilation mechanism. Only ammonium and bismuth had significant decreases in mass load downstream from the WWTPs during all samplings. The link between hydrology and water chemistry inherent in Lagrangian sampling allows quantitative assessment of chemical fate across different landscapes.

Environmental Science & Technology

A comparison of pre- and post-remediation water quality, Mineral Creek, Colorado

Pre- and post-remediation data sets are used herein to assess the effectiveness of remedial measures implemented in the headwaters of the Mineral Creek watershed, where contamination from hard rock mining has led to elevated metal concentrations and acidic pH. Collection of pre- and post-remediation data sets generally followed the synoptic mass balance approach, in which numerous stream and inflow locations are sampled for the constituents of interest and estimates of streamflow are determined by tracer dilution. The comparison of pre- and post-remediation data sets is confounded by hydrologic effects and the effects of temporal variation. Hydrologic effects arise due to the relatively wet conditions that preceded the collection of pre-remediation data, and the relatively dry conditions associated with the post-remediation data set. This difference leads to a dilution effect in the upper part of the study reach, where pre-remediation concentrations were diluted by rainfall, and a source area effect in the lower part of the study reach, where a smaller portion of the watershed may have been contributing constituent mass during the drier post-remediation period. A second confounding factor, temporal variability, violates the steady-state assumption that underlies the synoptic mass balance approach, leading to false identification of constituent sources and sinks. Despite these complications, remedial actions completed in the Mineral Creek headwaters appear to have led to improvements in stream water quality, as post-remediation profiles of instream load are consistently lower than the pre-remediation profiles over the entire study reach for six of the eight constituents considered (aluminium, arsenic, cadmium, copper, iron, and zinc). Concentrations of aluminium, cadmium, copper, lead, and zinc remain above chronic aquatic-life standards, however, and additional remedial actions may be needed. Future implementations of the synoptic mass balance approach should be preceded by an assessment of temporal variability, and modifications to the synoptic sampling protocol should be made if necessary.

Colorado

Application of iron and zinc isotopes to track the sources and mechanisms of metal loading in a mountain watershed

Here the hydrogeochemical constraints of a tracer dilution study are combined with Fe and Zn isotopic measurements to pinpoint metal loading sources and attenuation mechanisms in an alpine watershed impacted by acid mine drainage. In the tested mountain catchment, δ 56 Fe and δ 66 Zn isotopic signatures of filtered stream water samples varied by ∼3.5‰ and 0.4‰, respectively. The inherent differences in the aqueous geochemistry of Fe and Zn provided complimentary isotopic information. For example, variations in δ 56 Fe were linked to redox and precipitation reactions occurring in the stream, while changes in δ 66 Zn were indicative of conservative mixing of different Zn sources. Fen environments contributed distinctively light dissolved Fe (<−2.0‰) and isotopically heavy suspended Fe precipitates to the watershed, while Zn from the fen was isotopically heavy (>+0.4‰). Acidic drainage from mine wastes contributed heavier dissolved Fe (∼+0.5‰) and lighter Zn (∼+0.2‰) isotopes relative to the fen. Upwelling of Fe-rich groundwater near the mouth of the catchment was the major source of Fe ( δ 56 Fe ∼ 0‰) leaving the watershed in surface flow, while runoff from mining wastes was the major source of Zn. The results suggest that given a strong framework for interpretation, Fe and Zn isotopes are useful tools for identifying and tracking metal sources and attenuation mechanisms in mountain watersheds.

Applied Geochemistry

Aquatic ecosystems in Central Colorado are influenced by mineral forming processes and historical mining

Stream water and sediment toxicity to aquatic insects were quantified from central Colorado catchments to distinguish the effect of geologic processes which result in high background metals concentrations from historical mining. Our sampling design targeted small catchments underlain by rocks of a single lithology, which allowed the development of biological and geochemical baselines without the complication of multiple rock types exposed in the catchment. By accounting for geologic sources of metals to the environment, we were able to distinguish between the environmental effects caused by mining and the weathering of different mineralized areas. Elevated metal concentrations in water and sediment were not restricted to mined catchments. Impairment of aquatic communities also occurred in unmined catchments influenced by hydrothermal alteration. Hydrothermal alteration style, deposit type, and mining were important determinants of water and sediment quality and aquatic community structure. Weathering of unmined porphyry Cu-Mo occurrences resulted in water (median toxic unit (TU) = 108) and sediment quality (TU = 1.9) that exceeded concentrations thought to be safe for aquatic ecosystems (TU = 1). Metalsensitive aquatic insects were virtually absent from streams draining catchments with porphyry Cu-Mo occurrences (1.1 individuals/0.1 m2 ). However, water and sediment quality (TU = 0.1, 0.5 water and sediment, respectively) and presence of metalsensitive aquatic insects (204 individuals/0.1 m2 ) for unmined polymetallic vein occurrences were indistinguishable from that for unmined and unaltered streams (TU = 0.1, 0.5 water and sediment, respectively; 201 individuals/0.1 m2 ). In catchments with mined quartz-sericite-pyrite altered polymetallic vein deposits, water (TU = 8.4) and sediment quality (TU = 3.1) were degraded and more toxic to aquatic insects (36 individuals/0.1 m2 ) than water (TU = 0.4) and sediment quality (TU = 1.7) from mined propylitically altered polymetallic vein deposits. The sampling approach taken in this study distinguishes the effects of different mineral deposits on ecosystems and can be used to more accurately quantify the effect of mining on the environment.

Conference Paper

Geochemical controls of elevated arsenic concentrations in groundwater, Ester Dome, Fairbanks district, Alaska

Ester Dome, an upland area near Fairbanks, Alaska, was chosen for a detailed hydrogeochemical study because of the previously reported elevated arsenic in groundwater, and the presence of a large set of wells amenable to detailed sampling. Ester Dome lies within the Fairbanks mining district, where gold-bearing quartz veins, typically containing 2–3 vol.% sulfide minerals (arsenopyrite, stibnite, and pyrite), have been mined both underground and in open cuts. Gold-bearing veins on Ester Dome occur in shear zones and the sulfide minerals in these veins have been crushed to fine-grained material by syn- or post-mineralization movement. Groundwater at Ester Dome is circumneutral, Ca–HCO 3 to Ca–SO 4 type, and ranges from dilute (specific conductance of 48 µS/cm) to more concentrated (specific conductance as high as 2070 µS/cm). In general, solute concentrations increase down hydrologic gradient. Redox species indicate that the groundwaters range from oxic to sub-oxic (low dissolved oxygen, Fe(III) reduction, no SO 4 reduction). Waters with the highest Fe concentrations, as high as 10.7 mg/L, are the most anoxic. Dissolved As concentrations range from < 1 to 1160 µg/L, with a median value of 146 µg/L. Arsenic concentrations are not correlated with specific conductance or Fe concentrations, suggesting that neither groundwater residence time, nor reductive dissolution of iron oxyhydroxides, control the arsenic chemistry. Furthermore, As concentrations do not covary with other constituents that form anions and oxyanions in solution (e.g., HCO 3 , Mo, F, or U) such that desorption of arsenic from clays or oxides also does not control arsenic mobility. Oxidation of arsenopyrite and dissolution of scorodite, in the near-surface environment appears to be the primary control of dissolved As in this upland area. More specifically, the elevated As concentrations are spatially associated with sulfidized shear zones and localities of gold-bearing quartz veins. Consistent with this interpretation, elevated dissolved Sb concentrations (as high as 59 µg/L), also correlated with occurrences of hypogene sulfide minerals, were measured in samples with high dissolved As concentrations.

Chemical Geology

Questa baseline and pre-mining ground-water quality investigation. 20. Water chemistry of the Red River and selected seeps, tributaries, and precipitation, Taos County, New Mexico, 2000-2004

As part of a multi-year project to infer the pre-mining ground-water quality at Molycorp's Questa mine site, surface-water samples of the Red River, some of its tributaries, seeps, and snow samples were collected for analysis of inorganic solutes and of water and sulfate stable isotopes in selected samples. The primary aim of this study was to document diel, storm event, and seasonal variations in water chemistry for the Red River and similar variations in water chemistry for Straight Creek, a natural analog site similar in topography, hydrology, and geology to the mine site for inferring pre-mining water-quality conditions. Red River water samples collected between 2000 and 2004 show that the largest variations in water chemistry occur during late summer rainstorms, often monsoonal in nature. Within hours, discharge of the Red River increased from 8 to 102 cubic feet per second and pH decreased from 7.80 to 4.83. The highest concentrations of metals (iron, aluminum, zinc, manganese) and sulfate also occur during such events. Low-pH and high-solute concentrations during rainstorm runoff are derived primarily from alteration 'scar' areas of naturally high mineralization combined with steep topography that exposes continually altered rock because erosion is too rapid for vegetative growth. The year 2002 was one of the driest on record, and Red River discharge reflected the low seasonal snow pack. No snowmelt peak appeared in the hydrograph record, and a late summer storm produced the highest flow for the year. Snowmelt was closer to normal during 2003 and demonstrated the dilution effect of snowmelt on water chemistry. Two diel sampling events were conducted for the Red River, one during low flow and the other during high flow, at two locations, at the Red River gaging station and just upstream from Molycorp's mill site. No discernible diel trends were observed except for dissolved zinc and manganese at the upstream site during low flow. Straight Creek drainage water was sampled periodically from 2001 to 2004 at the down stream end of surface drainage near the point at which it disappeared into the debris fan. This water has a minimal range in pH (2.7 to 3.2) but a substantial concentration range in many solutes; for example, sulfate concentrations varied from 525 to 2,660 mg/L. Many elements covary with sulfate suggesting that dilution is the primary control of the range in solute concentrations. A transect of water samples higher in the scar area were collected in October of 2003. They had a lower range in pH (2.44 to 3.05) and higher solute concentrations than those collected periodically from lower in the catchment. Water isotopes for the upper transect samples indicated slight evaporation, and in part, may account for the higher solute concentrations. Drainage waters also were collected from Hottentot, Junebug, Hansen, Little Hansen, and Goat Hill Gulch drainages. Most constituents from other scar drainage waters showed ranges of concentration similar to those of the Straight Creek waters. An exception was water collected from Goat Hill Gulch, which has some of the highest concentrations of any surface-water sample collected but also contained waste-rock leachates.

New Mexico

Geochemistry and source waters of rock glacier outflow, Colorado Front Range

We characterize the seasonal variation in the geochemical and isotopic content of the outflow of the Green Lake 5 rock glacier (RG5), located in the Green Lakes Valley of the Colorado Front Range, USA. Between June and August, the geochemical content of rock glacier outflow does not appear to differ substantially from that of other surface waters in the Green Lakes Valley. Thus, for this alpine ecosystem at this time of year there does not appear to be large differences in water quality among rock glacier outflow, glacier and blockslope discharge, and discharge from small alpine catchments. However, in September concentrations of Mg2+ in the outflow of the rock glacier increased to more than 900 ??eq L-1 compared to values of less than 40 ??eq L-1 at all the other sites, concentrations of Ca2+ were greater than 4,000 ??eq L-1 compared to maximum values of less than 200 ??eq L-1 at all other sites, and concentrations of SO42- reached 7,000 ??eq L-1, compared to maximum concentrations below 120 ??eq L-1 at the other sites. Inverse geochemical modelling suggests that dissolution of pyrite, epidote, chlorite and minor calcite as well as the precipitation of silica and goethite best explain these elevated concentrations of solutes in the outflow of the rock glacier. Three component hydrograph separation using end-member mixing analysis shows that melted snow comprised an average of 30% of RG5 outflow, soil water 32%, and base flow 38%. Snow was the dominant source water in June, soil water was the dominant water source in July, and base flow was the dominant source in September. Enrichment of ?? 18O from - 10??? in the outflow of the rock glacier compared to -20??? in snow and enrichment of deuterium excess from +17.5??? in rock glacier outflow compared to +11??? in snow, suggests that melt of internal ice that had undergone multiple melt/freeze episodes was the dominant source of base flow. Copyright ?? 2005 John Wiley & Sons, Ltd.

Permafrost and Periglacial Processes

Chemical loading into surface water along a hydrological, biogeochemical, and land use gradient: A holistic watershed approach

Identifying the sources and impacts of organic and inorganic contaminants at the watershed scale is a complex challenge because of the multitude of processes occurring in time and space. Investigation of geochemical transformations requires a systematic evaluation of hydrologic, landscape, and anthropogenic factors. The 1160 km 2 Boulder Creek Watershed in the Colorado Front Range encompasses a gradient of geology, ecotypes, climate, and urbanization. Streamflow originates primarily as snowmelt and shows substantial annual variation. Water samples were collected along a 70-km transect during spring-runoff and base-flow conditions, and analyzed for major elements, trace elements, bulk organics, organic wastewater contaminants (OWCs), and pesticides. Major-element and trace-element concentrations were low in the headwaters, increased through the urban corridor, and had a step increase downstream from the first major wastewater treatment plant (WWTP). Boron, gadolinium, and lithium were useful inorganic tracers of anthropogenic inputs. Effluent from the WWTP accounted for as much as 75% of the flow in Boulder Creek and was the largest chemical input. Under both hydrological conditions, OWCs and pesticides were detected in Boulder Creek downstream from the WWTP outfall as well as in the headwater region, and loads of anthropogenic-derived contaminants increased as basin population density increased. This report documents a suite of potential endocrine-disrupting chemicals in a reach of stream with native fish populations showing indication of endocrine disruption.

Environmental Science & Technology

Rare earth element partitioning between hydrous ferric oxides and acid mine water during iron oxidation

Ferrous iron rapidly oxidizes to Fe (III) and precipitates as hydrous Fe (III) oxides in acid mine waters. This study examines the effect of Fe precipitation on the rare earth element(REE) geochemistry of acid mine waters to determine the pH range over which REEs behave conservatively and the range over which attenuation and fractionation occur. Two field studies were designed to investigate REE attenuation during Fe oxidation in acidic, alpine surface waters. To complement these field studies, a suite of six acid mine waters with a pH range from 1.6 to 6.1 were collected and allowed to oxidize in the laboratory at ambient conditions to determine the partitioning of REEs during Fe oxidation and precipitation. Results from field experiments document that even with substantial Fe oxidation, the REEs remain dissolved in acid, sulfate waters with pH below 5.1. Between pH 5.1 and 6.6 the REEs partitioned to the solid phases in the water column, and heavy REEs were preferentially removed compared to light REEs. Laboratory experiments corroborated field data with the most solid-phase partitioning occurring in the waters with the highest pH.

Applied Geochemistry

Chemical analyses of ground and surface waters, Ester Dome, central Alaska, 2000-2001

Water analyses are reported for ground and surface waters collected at 33 sites on and near Ester Dome, Fairbanks area, central Alaska during 2000-2001. This interdisciplinary study focused on documenting the temporal and spatial chemical variations in arsenic concentrations to elucidate the processes that lead to elevated arsenic concentrations in ground water. Field parameters and water analyses are reported for 17 domestic wells, 13 monitoring well sites, and 3 surface water sites. Sampling occurred during November 2000, February 2001, May 2001, July 2001, and September 2001. Waters in the study area are primarily Ca-HCO 3 type, with pH values ranging from 5.97 to 7.87. Dissolved arsenic concentrations ranged from less than 3 to 1160 micrograms per liter.

Alaska

Standard reference water samples for rare earth element determinations

Standard reference water samples (SRWS) were collected from two mine sites, one near Ophir, CO, USA and the other near Redding, CA, USA. The samples were filtered, preserved, and analyzed for rare earth element (REE) concentrations (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) by inductively coupled plasma-mass spectrometry (ICP-MS). These two samples were acid mine waters with elevated concentrations of REEs (0.45–161 μg/l). Seventeen international laboratories participated in a ‘round-robin’ chemical analysis program, which made it possible to evaluate the data by robust statistical procedures that are insensitive to outliers. The resulting most probable values are reported. Ten to 15 of the participants also reported values for Ba, Y, and Sc. Field parameters, major ion, and other trace element concentrations, not subject to statistical evaluation, are provided.

Applied Geochemistry