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The Colorado River is an important water source in the southwestern United States and northern Mexico. High concentrations of dissolved solids in the river, sourced mainly from the Upper Colorado River Basin (UCOL), cause hundreds of millions of dollars in damages annually to crops and infrastructure. Determinations of total dissolved solids (TDS) in river and tributary samples often rely on summed concentrations of constituents in solution reported as the sum of constituents (SOC), which includes the bicarbonate concentration converted to the equivalent carbonate mass that would be present as a residue after drying. Alternatively, salinity, similar to SOC but including the entire concentration of bicarbonate in solution, may be used as a measure of dissolved solids. Use of SOC results may under-represent actual dissolved-solids concentrations and loads in streams where bicarbonate is a substantial component of the dissolved solids in solution. The objective of this manuscript is to evaluate the differences between the SOC and salinity determinations of dissolved solids in UCOL streams and rivers. Water-quality data from the U.S. Geological Survey were used to compute salinity concentrations at UCOL stream sites for comparison with SOC determinations. Results from 8,001 samples at 418 UCOL sites indicate a median increase in dissolved solids of 20% (13% and 30%, 25th and 75th percentiles, respectively) using the salinity method compared with SOC results. Differences in dissolved solids attributable to the computational approach for handling bicarbonate at UCOL sites were significantly greater than laboratory variability based on results from 890 replicate analyses. Salinity may be a more useful indicator of water quality than SOC in systems with substantial proportions of bicarbonate in the composition of dissolved solids, including the Colorado River and UCOL sites. [ABSTRACT FROM AUTHOR]

Breccia pipe deposits of the Grand Canyon region contain ore grade copper and uranium. Horn Creek is located near the Orphan Mine mineralized breccia pipe deposit, and groundwater emerging from the bedrock in the headwaters of Horn Creek has the highest uranium concentrations in the region. Uranium decreases an order of magnitude between the groundwater at the top of the watershed and the groundwater emerging from the alluvial material lower in the watershed. Horn Creek water has low sulfur and uranium isotopic ratios which may suggest interaction with sulfide and uranium minerals found in mineralized breccia pipe deposits. Per- and polyfluoroalkyl substances were found in low concentrations in groundwater from the bedrock and may be related to mining process materials or other anthropogenic activities. PHREEQC modelling suggests that water that is elevated in uranium emerging from the bedrock in the upper watershed may mix with other groundwater and atmospheric precipitation infiltrated into the alluvial material in the lower watershed. Tritium is elevated in Horn Creek groundwaters, suggesting a component of modern water, some of which may have interacted with Orphan Mine workings. Additional studies could build on this understanding of chemistry changes in the waters of Horn Creek to provide more direct evidence of the contribution of water moving through the Orphan Mine. Supplementary material: Chemical data for this paper are available at https://doi.org/10.5066/F7P55KJN, PHREEQC geochemical simulations are available at https://doi.org/10.5066/P9X17FKG and groundwater chemistry from south of Grand Canyon, AZ is available at https://doi.org/10.6084/m9.figshare.c.6747638 Thematic collection: This article is part of the Geochemical processes related to mined, milled, or natural metal deposits collection available at: https://www.lyellcollection.org/topic/collections/geochemical-processes-related-to-mined-milled-or-natural-metal-deposits [ABSTRACT FROM AUTHOR]

The Colorado River is a critical water resource in the southwestern United States, supplying drinking water for 40 million people in the region and water for irrigation of 2.2 million hectares of land. Extended drought in the Upper Colorado River Basin (UCOL) and the prospect of a warmer climate in the future pose water availability challenges for those charged with managing the river. Limited water availability in the future also may negatively affect aquatic ecosystems and wildlife that depend upon them. Water availability components of special importance in the UCOL include streamflow, salinity in groundwater and surface water, groundwater levels and storage, and the role of snow in the UCOL water cycle. This manuscript provides a review of current "state of the science" for these UCOL water availability components with a focus on identifying gaps in data, modeling, and trends in the basin. Trends provide context for evaluations of current conditions and motivation for further investigation and modeling, models allow for investigation of processes and projections of future water availability, and data support both efforts. Information summarized in this manuscript will be valuable in planning integrated assessments of water availability in the UCOL. [ABSTRACT FROM AUTHOR]

Assessing chemical loading from streams in remote, difficult-to-access watersheds is challenging. The Grand Canyon area in northern Arizona, an international tourist destination and sacred place for many Native Americans, is characterized by broad plateaus divided by canyons as much as two-thousand meters deep and hosts some of the highest-grade uranium deposits in the U.S. From 2015–2018 major surface waters in Grand Canyon were monitored for select elements associated with breccia-pipe uranium deposits in the area, including uranium, arsenic, cadmium, and lead. Dissolved constituents in the Colorado River were monitored upstream (Lees Ferry), in the middle (Phantom Ranch), and downstream (Diamond Creek) of uranium mining areas. Concentrations of uranium, arsenic, cadmium, and lead at these main-stem sites varied little during the study period and were all well below human health and aquatic life benchmark criteria (30, 10, 5, and 15 μg/L maximum contaminant levels and 15, 150, 0.8, and 3.1 μg/L aquatic life criteria, respectively). Additionally, dissolved and sediment-bound constituents were monitored during a wide range of streamflow conditions at Little Colorado River, Kanab Creek, and Havasu Creek tributaries, whose watersheds have experienced different levels of uranium mining activities over time. Samples from the tributary sites contained ≤3.8 μg/L of dissolved cadmium and lead, and ≤17 μg/L of dissolved uranium. Dissolved arsenic also was mostly below human and aquatic life criteria at Little Colorado River and Kanab Creek; however, 63% of water samples from Havasu Creek were above the maximum contaminant level for arsenic. Arsenic in suspended sediment was greater than sediment quality guidelines in 9%, 35%, and 35% of samples from Little Colorado River, Kanab Creek, and Havasu Creek, respectively. At the concentrations observed during this study, tributaries contributed on average only about 0.12 μg/L of arsenic and 0.03 μg/L of uranium to the main-stem river. This study demonstrates how chemical loading from mined watersheds may be reliably assessed across a wide range of flow conditions in challenging locations. [ABSTRACT FROM AUTHOR]

Hydrologic model input datasets such as climate, land use, elevation, soil, and geology information are available in a range of scales for use in water resources investigations. Smaller spatial and temporal scale input data allow groundwater recharge models to simulate more physically realistic processes and presumably result in more accurate estimates of groundwater recharge. Projected climate data are, therefore, often downscaled to smaller spatial and temporal scales for use in these models. It is unknown, however, if increasingly smaller-scale climate data produce substantially different simulated recharge results, either in magnitude or trend. Also, even if simulated recharge results are different at a higher space and time resolution, simulation at coarser resolution might be adequate to provide recharge information at decision scales (e.g., meeting Colorado River compact requirements on a ten-year moving average basis). Historical climate datasets at three spatial (∼800 m, ∼4 km, and ∼12 km) and two temporal (daily and monthly) scales were used in a Soil Water Balance (SWB) model of the upper Colorado River basin (UCRB) to simulate groundwater recharge over the water-year 1982–2014 time period. The magnitude of annual and moving ten-year annual average recharge results for daily climate data were within 5% and 7% of ∼4 km results for ∼800 m and ∼12 km climate data, respectively, with deviations from 1982 to 2014 means within 1% and 3% (median), respectively. Comparison of simulated recharge results using the coarsest spatial and temporal climate data with results from the finest scale data indicated similar small differences over ten-year moving annual averages, over water years, and during high recharge months. While differences in simulated groundwater recharge magnitude, which may be important for groundwater-flow simulations, were substantial during some seasonal comparisons, trends in recharge were almost identical across scales, leading to similar conclusions about change from “normal”. Considering the uncertainty inherent in projected climate data, coarser spatial and longer temporal scale input data may be sufficient for water resources managers who need to understand changes in trends in groundwater recharge over water-year or longer time periods. [ABSTRACT FROM AUTHOR]

The Colorado River is an important source of water in the western United States, supplying the needs of more than 38 million people in the United States and Mexico. Groundwater discharge to streams has been shown to be a critical component of streamflow in the Upper Colorado River Basin ( UCRB), particularly during low-flow periods. Understanding impacts on groundwater in the basin from projected climate change will assist water managers in the region in planning for potential changes in the river and groundwater system. A previous study on changes in basin-wide groundwater recharge in the UCRB under projected climate change found substantial increases in temperature, moderate increases in precipitation, and mostly periods of stable or slight increases in simulated groundwater recharge through 2099. This study quantifies projected spatial and seasonal changes in groundwater recharge within the UCRB from recent historical (1950 to 2015) through future (2016 to 2099) time periods, using a distributed-parameter groundwater recharge model with downscaled climate data from 97 Coupled Model Intercomparison Project Phase 5 ( CMIP5) climate projections. Simulation results indicate that projected increases in basin-wide recharge of up to 15% are not distributed uniformly within the basin or throughout the year. Northernmost subregions within the UCRB are projected an increase in groundwater recharge, while recharge in other mainly southern subregions will decline. Seasonal changes in recharge also are projected within the UCRB, with decreases of 50% or more in summer months and increases of 50% or more in winter months for all subregions, and increases of 10% or more in spring months for many subregions. [ABSTRACT FROM AUTHOR]

Accurate quantification of natural attenuation of volatile organic compounds (VOCs) in groundwater requires an accounting of all VOC mass-loss processes, including volatilization into soil gas with ultimate transport to land surface and the atmosphere. This paper compares two methods of estimating VOC flux to the atmosphere. The first method measures VOC flux at land surface using a vertical flux chamber (VFC). The VFC has been shown in a previous laboratory study to reliably measure organic vapor fluxes from soil to the atmosphere that are caused by either gas phase diffusion or a combination of advection plus diffusion [ Tillman, 2003]. The second method simulates VOC flux using a transient, one-dimensional gas flow and transport model incorporating the effects of gas phase diffusion, equilibrium air-water partitioning of organic vapors, and unsaturated zone airflow caused by atmospheric pressure changes (i.e., barometric pumping). Flux chamber measurements were made concurrently with field data measurements required for the flow and transport model at a trichloroethene (TCE)-contaminated field site. The two methods of VOC flux estimation provided comparable results in nine sets of field comparisons with the flux chamber estimating a lower flux during most of the time periods. Sensitivity analyses of model input parameters produce upper and lower bounds on best estimate flux simulations. Average VFC measurements fall within these upper and lower bounds of combined parameter values for all nine comparison events. The ease of use, lack of a priori site knowledge and accuracy of the VFC compared with the data-intensive flow and transport model suggests that direct measurement of VOC flux from the subsurface to the atmosphere at contaminated sites could become routine practice, providing important information to decision makers about the progress of monitored natural attenuation. [ABSTRACT FROM AUTHOR]

Elevated concentrations of dissolved-solids (salinity) including calcium, sodium, sulfate, and chloride, among others, in the Colorado River cause substantial problems for its water users. Previous efforts to reduce dissolved solids in upper Colorado River basin (UCRB) streams often focused on reducing suspended-sediment transport to streams, but few studies have investigated the relationship between suspended sediment and salinity, or evaluated which watershed characteristics might be associated with this relationship. Are there catchment properties that may help in identifying areas where control of suspended sediment will also reduce salinity transport to streams? A random forests classification analysis was performed on topographic, climate, land cover, geology, rock chemistry, soil, and hydrologic information in 163 UCRB catchments. Two random forests models were developed in this study: one for exploring stream and catchment characteristics associated with stream sites where dissolved solids increase with increasing suspended-sediment concentration, and the other for predicting where these sites are located in unmonitored reaches. Results of variable importance from the exploratory random forests models indicate that no simple source, geochemical process, or transport mechanism can easily explain the relationship between dissolved solids and suspended sediment concentrations at UCRB monitoring sites. Among the most important watershed characteristics in both models were measures of soil hydraulic conductivity, soil erodibility, minimum catchment elevation, catchment area, and the silt component of soil in the catchment. Predictions at key locations in the basin were combined with observations from selected monitoring sites, and presented in map-form to give a complete understanding of where catchment sediment control practices would also benefit control of dissolved solids in streams. [ABSTRACT FROM AUTHOR]

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It was hypothesized that atmospheric pressure changes can induce gas flow in the unsaturated zone to such an extent that the advective flux of organic vapors in unsaturated-zone soil gas can be significant relative to the gas-phase diffusion flux of these organic vapors. To test this hypothesis, a series of field measurements and computer simulations were conducted to simulate and compare diffusion and advection fluxes at a trichloroethene-contaminated field site at Picatinny Arsenal in north-central New Jersey. Moisture content temperature, and soil-gas pressure were measured at multiple depths (including at land surface) and times for three distinct sampling events in August 1996, October 1996, and August 1998. Gas pressures in the unsaturated zone changed significantly over time and followed changes measured in the atmosphere. Gas permeability of the unsaturated zone was estimated using data from a variety of sources, including laboratory gas permeability measurements made on intact soil cores from the site, a field air pump test, and calibration of a gas-flow model to the transient, one-dimensional gas pressure data. The final gas-flow model reproduced small pressure gradients as observed in the field during the three distinct sampling events. The velocities calculated from the gas-flow model were used in transient, one-dimensional transport simulations to quantify advective and diffusive fluxes of TCE vapor from the subsurface to the atmosphere as a function of time for each sampling event. Effective diffusion coefficients used for these simulations were determined from independent laboratory measurements made on intact soil cores collected from the field site. For two of the three sampling events (August 1996 and August 1998), the TCE gas-phase diffusion flux at land surface was significantly greater than the advection flux over the entire sampling period. For the second sampling event (October 1996), the advection flux was frequently larger than the diffusion flux. When averaged over the second sampling event, the advection and diffusion fluxes were comparable in magnitude. Sensitivity analyses indicate that diffusion fluxes increase significantly with increases in air-filled porosity near land surface, whereas advection fluxes do not. For October 1996, the comparable advection and diffusion fluxes were caused by high moisture content near land surface and a subsequent reduction in the diffusion flux relative to the advection flux. These results indicate that under certain environmental conditions, the organic vapor advection flux from the unsaturated zone to the atmosphere may be equal to or greater than the diffusion flux.