Geology topics

Carleton R. Bern

Publications and source records attributed to Carleton R. Bern.

At least 19 recordsLinked to original sources

USGS2025

Characterization of suspended sediment flux and streamflow trends in the Fountain Creek watershed, Colorado, 1998 through 2022

The U.S. Geological Survey evaluated long-term suspended sediment flux and streamflow datasets for temporal trends (monotonic and step trends) at 10 streamgage sites within the Fountain Creek watershed in central Colorado using the Mann-Kendall test (monotonic trend) and the Wilcoxon signed-rank test (step trend). Data were collected in cooperation with Colorado Springs Stormwater Enterprise. In this study, 10 sites with long-term suspended sediment records were evaluated during their operational periods, which ranged from 1998 through 2022. To assess how stream behavior might relate to shifts in suspended sediment transport, the Richards-Baker flashiness index, a measure of flashiness, was evaluated for each site. The Richards-Baker flashiness index was calculated for the same months as streamflow and suspended sediment (April through September) using all available streamflow data for a given site. Additionally, cumulative double-mass curves were developed to define temporal variation in the relation between streamflow and suspended sediment loads. This was completed by assessing differences in slopes before and after an observed break in the double-mass curve plots. Five streamgage sites showed statistically significant ( p <0.05) negative trends for suspended sediment flux, and nonsignificant decreases were indicated at the other five sites. The statistically significant negative trends are distributed across the watershed and include smaller tributaries and the main stem of Fountain Creek closer to its confluence with the Arkansas River. Such a broad distribution of negative trends is most likely an indication of improved water quality in the watershed with regards to suspended sediment. Assessing causes for the decreases in suspended sediment loads is beyond the scope of this report; however, spatially distributed bank erosion control projects, stormflow retention projects in the watershed, and changes in climate and storm patterns could be some of the potential drivers of the suspended sediment load trends in this watershed. The flashiness of the streamflow was assessed and can be dismissed on the basis of this study as a potential driver of trends in suspended sediment flux because the magnitude of changes was found to be negligible at all sites.

Colorado↗

USGS2025

Groundwater dominates snowmelt runoff and controls streamflow efficiency in the western United States

Climate change in seasonally snow-covered mountain catchments is reducing water supply and decreasing streamflow predictability. Here, we use tritium age dating to show that contrary to the common assumption that snowmelt quickly contributes to runoff, streamflow during snowmelt in western US catchments is dominated by older groundwater. The average age of streamwater during snowmelt runoff (5.7 ± 4.3 years) was intermediate to the average age of groundwater (10.4 ± 4.5 years) and recent precipitation, indicating that 58% (±34%) of snowmelt runoff was derived from groundwater. Water ages, streamflow, and groundwater storage were mediated by bedrock geology: low-permeability hard rock/shale catchments exhibited younger ages, less storage, and more efficient streamflow generation than high-permeability sandstone/clastic catchments. Our results demonstrate that snowmelt runoff is the result of multiple prior years of climate mediated by groundwater storage. Including these interactions will be crucial for predicting water resources as climate and landscape changes accelerate.

western united States↗

USGS2024

Agricultural return flow dynamics on a reach of the East River, Colorado, as assessed by mass balance

The U.S. Geological Survey, in cooperation with the Upper Gunnison River Water Conservancy District, studied historical streamflow in a reach of the East River, Colorado, to gain a preliminary understanding of return flow dynamics. Return flow is agricultural irrigation water that is not consumed by evapotranspiration and instead reaches streams by surface and subsurface flow paths. The study reach had a contributing area of 50 square miles and contained 5.23 square miles of pastures irrigated with water diverted from the East River and its tributaries. By comparing upstream inflows to downstream outflows, the net water balance of the study reach from 1994 to 2023 was assessed. Two general hydrologic conditions for the study reach were identified. One hydrologic condition was characterized by a net loss or consumption of water, termed here as general deficit. This general deficit condition extended about 16 years, from 1997 to 2012. During general deficit years, there was usually a notable net loss of streamflow from April through July, and a small net gain, possibly related to return flows, occurred in August about 75 days after the minimums for losses. The second hydrologic condition was characterized by a net gain of water, termed here as general surplus. This second condition extended about 10 years, from 2014 to 2023. During general surplus years, two separate transitions from net loss to net gain commonly occurred during June through August. Losses during general surplus years were smaller than losses during general deficit years, the respective gains were larger, and times between losses and gains were about 18 and 22 days. Differences between the two hydrologic conditions could reflect interactions among irrigation water, available capacity to store additional shallow groundwater, and streamflow. However, deciphering the causes for the shifts between the two general hydrologic conditions was beyond the scope of this report.

Colorado↗

USGS2024

Potential climate and human water-use effects on water-quality trends in a semiarid, western U.S. watershed: Fountain Creek, Colorado, USA

Nutrients, total dissolved solids (TDS), and trace elements affect the suitability of water for human and natural needs. Here, trends in such water-quality constituents are analyzed for 1999–2022 for eight nested monitoring sites in the 24,000 km 2 Fountain Creek watershed in Colorado, USA, by using the weighted regressions on time, discharge, and season (WRTDS) methodology. Fountain Creek shares characteristics with other western U.S. watersheds: (1) an expanding but more water-efficient population, (2) a heavy reliance on imported water, (3) a semiarid climate trending towards warmer and drier conditions, and (4) shifts of water from agricultural to municipal uses. The WRTDS analysis found both upward and downward trends in the concentrations of nutrients that reflected possible shifts in effluent management, instream uptake, and water conservation by a watershed population that grew by about 40%. Selenium, other trace elements, and TDS can pose water-quality challenges downstream and their concentrations were found to have a downwards trend. Those trends could be driven by either a warming and drying of the local climate or decreased agricultural irrigation, as both would reduce recharge and subsequent mobilization from natural geologic sources via groundwater discharge. The patterns illustrate how changes in climate and water use may have affected water quality in Fountain Creek and demonstrate the patterns to look for in other western watersheds.

Colorado↗

USGS2024

Stream water sourcing from high-elevation snowpack inferred from stable isotopes of water: A novel application of d-excess values

About 80 % of the precipitation at the Colorado River's headwaters is snow, and the resulting snowmelt-driven hydrograph is a crucial water source for about 40 million people. Snowmelt from alpine and subalpine snowpack contributes substantially to groundwater recharge and river flow. However, the dynamics of snowmelt progression are not well understood because observations of the high-elevation snowpack are difficult due to challenging access in complex mountainous terrain as well as the cost and labor intensity of currently available methods. We present a novel approach to infer the processes and dynamics of high-elevation snowmelt contributions predicated upon stable hydrogen and oxygen isotope ratios observed in streamflow. We show that deuterium-excess (d-excess) values of stream water could serve as a comparatively cost-effective proxy for a catchment-integrated signal of high-elevation snowmelt contributions to catchment runoff. We sampled stable hydrogen and oxygen isotope ratios of the precipitation, snowpack, and stream water in the East River, a headwater catchment of the Colorado River, and the stream water of larger catchments at sites on the Gunnison River and Colorado River. The d-excess of snowpack increased with elevation; the upper subalpine and alpine snowpack ( > 3200 m) had substantially higher d-excess compared to lower elevations ( < 3200 m) in the study area. The d-excess values of stream water reflected this because d-excess values increased as the higher-elevation snowpack contributed more to stream water generation later in the snowmelt/runoff season. End-member mixing analyses based on the d-excess data showed that the share of high-elevation snowmelt contributions within the snowmelt hydrograph was on average 44 % and generally increased during melt period progression, up to 70 %. The observed pattern was consistent during 6 years for the East River, and a similar relation was found for the larger catchments on the Gunnison and Colorado rivers. High-elevation snowpack contributions were found to be higher for years with lower snowpack and warmer spring temperatures. Thus, we conclude that the d-excess of stream water is a viable proxy to observe changes in high-elevation snowmelt contributions in catchments at various scales. Inter-catchment comparisons and temporal trends of the d-excess of stream water could therefore serve as a catchment-integrated measure to monitor if mountain systems rely on high-elevation water inputs more during snow drought compared to years of average snowpack depths.

EUGsphere↗

USGS2023

Assessment of salinity retention or mobilization by sediment-retention ponds near Delta, Colorado, 2019

Salinity control efforts in the Colorado River Basin have focused on mobilization of salts from irrigated land, but nonirrigated rangelands are also a source of salinity. In particular, lands where soils have formed from the Late Cretaceous Mancos Shale under arid and semiarid climates contain considerable quantities of salt, mainly in the subsurface. Hundreds of thousands of contour furrows and check dams (gully plugs) were constructed by the Bureau of Land Management (BLM) and Bureau of Reclamation in the late 1950s and 1960s to reduce runoff, sedimentation, and salt mobilization from ephemeral stream channels on rangelands. Sediment-retention ponds associated with check dams are dry most of the year, except immediately following substantial rain events. Generally, no maintenance has been performed on these structures, some have degraded over time, and their current and past influence on salinity is poorly understood. To assess the influence of check dams and their associated ponds on salt retention and mobilization, the U.S. Geological Survey, in cooperation with the BLM, conducted a study of such ponds within the Gunnison Gorge National Conservation Area (GGNCA) near Delta, Colorado. This report includes conceptual models of how sediment-retention ponds function relative to salinity, and a collection of environmental data to evaluate the conceptual models. An inventory of 69 ponds indicated that 38 percent no longer had water holding capacity, and another 20 percent could hold 1 foot or less of water. Check-dam degradation was the main cause, but sediment infill of ponds contributed as well. Water content of soil profiles collected beneath ponds and immediately downstream from check dams indicated little penetration of water below 60 centimeters for most ponds and little evidence for lateral movement of water beneath check dams. Patterns of salt content in the soil profiles indicated no accumulation of salts at the pond surface from evaporating waters and little evidence for salt redistribution in the form of salt bulges or salt depletion curves at intermediate depths. Based on the conceptual models presented and interpretations of data collected by this study, it appears that the sediment-retention ponds in the GGNCA have neither mobilized nor retained substantial quantities of salt during their lifetimes.

Colorado↗

USGS2023

Source contributions to suspended sediment and particulate selenium export from the Loutsenhizer Arroyo and Sunflower Drain watersheds in Colorado

Selenium in aquatic ecosystems of the lower Gunnison River Basin in Colorado is affecting the recovery of populations of endangered, native fish species. Dietary exposure is the primary pathway for bioaccumulation of selenium in fish, and particulate selenium can be consumed directly by fish or by the invertebrates on which fish feed. Although selenium can be incorporated into particulate matter via biogeochemical processes, particulate selenium can also enter aquatic ecosystems of the lower Gunnison River Basin from sediments derived from the selenium-rich Mancos Shale. The U.S. Geological Survey, in cooperation with the Colorado Water Conservation Board, conducted this study during 2018–19 to identify sources of selenium-rich suspended sediments from two watersheds underlain by Mancos Shale: Loutsenhizer Arroyo and Sunflower Drain, which is a locally known agricultural drainage near the municipality of Delta, Colorado. A multipronged approach (fieldwork, laboratory work, and computer modeling) referred to as “sediment fingerprinting” was used to evaluate sources of suspended sediments in the streams flowing out of the two studied watersheds. Four potential source types for suspended sediments were identified and sampled (using soil plugs) within the watersheds: rangelands, agricultural fields, arroyo walls, and streambanks. The sediment fingerprinting approach used elemental concentrations and naturally occurring fallout radionuclides as tracers to apportion percent contributions from the four source types of suspended sediments found in streamflow from both watersheds. To determine the dominant sources of suspended sediment in streamflow from both watersheds, a mathematical “unmixing” model was used. Unmixing models apportion source percentages to samples of material in which those sources are mixed. These models used elemental and isotopic data in the suspended sediments to unmix them into proportional contributions from source types. The results indicated that arroyo walls and streambanks generally dominated as sources of the suspended sediment. Arroyo walls and streambanks were channel-adjacent sources, with sediments mobilized by water flowing within the stream channel. These sources accounted for greater than 50 percent of suspended sediment in all but one sample and accounted for 100 percent of suspended sediment in 5 of the 11 samples collected. Rangeland and agricultural field sources were located in uplands outside of stream channels and were detected more often during the non-irrigation season. Rangeland and agricultural field sources each were found in 5 of the 11 samples collected. Concentrations of selenium in sediment-source samples were comparatively greater in streambanks and lower in rangelands, with agricultural fields and arroyo walls being intermediate. As a result, source apportionments for particulate selenium skewed towards sources adjacent to stream channels more than for suspended sediments. Water imports for irrigation have changed the hydrology of the watersheds, and a notable fraction of imported water passes through the watersheds rapidly. The rapid flowthrough water during the irrigation season likely contributes heavily to sediment erosion and transport in Loutsenhizer Arroyo and Sunflower Drain, particularly from channel-adjacent sources of sediment. Decreases in irrigation season streamflow, at least in Loutsenhizer Arroyo, may have decreased sediment erosion and transport during the 2018–20 irrigation seasons compared to the 2015–17 seasons.

Colorado↗

USGS2022

Examination of dissolved uranium concentrations in regional shallow groundwater relative to Operable Unit 8 of the Denver Radium Superfund Site

A radium industry existed between about 1914 and 1920 in Denver, Colorado, with operations located along the South Platte River. Sites associated with that industry were contaminated with radium and uranium processing residues and were incorporated into clean-up efforts as Operating Units (OUs) of the Denver Radium Superfund Site. Concentrations of uranium exceeding the U.S. Environmental Protection Agency maximum contaminant level of 0.03 milligrams per liter for drinking water are present in shallow groundwater at OU8. However, previous studies have shown concentrations of dissolved uranium can be naturally high in shallow groundwater of the South Platte River valley compared to other rivers of the world. This report compares dissolved uranium concentrations measured by the U.S. Geological Survey across the South Platte River valley to data collected at the OU8 of the Denver Radium Superfund Site. The U.S. Geological Survey data represent 5 distinct urban or agricultural geographic areas and included 230 sampling events at 114 wells during 1993 to 2013. The OU8 data represent 13 wells and groundwater discharge locations sampled during the years 2017 and 2018. Dissolved uranium concentrations were statistically significantly greater for both years of the OU8 data compared to three datasets from shallow groundwater beneath urban areas in the Denver metropolitan area. However, compared to OU8, concentrations were significantly greater in shallow groundwater from an agricultural area of the South Platte River valley distant from Denver. Additionally, each of the urban area datasets contained some individual dissolved uranium concentrations greater than the greatest concentrations from the two OU8 datasets. Thus, naturally occurring concentrations of dissolved uranium in shallow groundwater that are greater than those observed at OU8 are not uncommon in the South Platte River valley.

Colorado↗

USGS2022

Characterization of and temporal changes in groundwater quality of the Upper Black Squirrel Creek Basin, El Paso County, Colorado, 2018–20

In 2018–20, the U.S. Geological Survey, in cooperation with Upper Black Squirrel Creek Ground Water Management District, sampled 48 wells for Phase III of a multiphase plan investigating groundwater quality in the alluvial aquifer of the Upper Black Squirrel Creek Basin (UBSB), El Paso County, Colorado. Results for samples collected from October to December each year were used to assess spatial and temporal changes in groundwater quality and to differentiate sources of nitrate. Groundwater was predominantly classified as mixed-cation and mixed-anion water type in the aquifer, with variable chemistry along the periphery. Concentrations of constituents in groundwater were generally less than regulatory standards, except for nitrate in four wells. Isotopes of nitrogen and oxygen in nitrate identified four different potential sources or processes affecting nitrate in the alluvial aquifer: naturally occurring nitrate from soils, nitrate from animal and (or) human waste, and an unknown source, along with evidence of denitrification. Pharmaceutical compounds and personal-care products were detected in seven wells, with three wells having multiple detections. Stable isotopes of water indicated variability in seasonality of recharge throughout the UBSB alluvial aquifer. Nitrate concentrations from the 1984 study and the 1996 study were compared to the more recent concentrations in the 2013 study and the 2018–20 study. The northern one-third of the UBSB alluvial aquifer had a statistically significant increase in nitrate concentration from the 2013 study to the 2018–20 study, but no change was shown from the 1984 study to the 1996 study. The opposite was found true for the southern two-thirds of the UBSB alluvial aquifer with no statistically significant difference in nitrate concentration from the 2013 study to the 2018–20 study. Analysis of temporal changes indicated an increase in median and maximum nitrate concentrations from the 2013 study to the 2018–20 study throughout the UBSB alluvial aquifer. Continued sampling of wells in the UBSB would be beneficial to better determine temporal changes in groundwater quality, characterize human effects on water quality, and understand characteristics of the alluvial aquifer pertaining to sustainability of the resource.

Colorado↗

USGS2022

Laboratory simulation of groundwater along uranium-mining-affected flow paths near the Grand Canyon, Arizona, USA

Mining of volumetrically small, but relatively enriched (average 0.6% U 3 O 8 ) breccia pipe uranium (BPU) deposits near the Grand Canyon, Arizona, USA has the potential to affect groundwater and springs in the area. Such deposits also contain base metal sulfides that can oxidize to generate acid mine drainage and release trace metals. In this study, sequential batch experiments were conducted to simulate the geochemistry of local shallow groundwater that contacts BPU ore and then moves downgradient through sedimentary strata. The experiments simulated shallow groundwater in a carbonate aquifer followed by contact with BPU ore. The experiments subsequently simulated contact with sedimentary rocks and changing oxygen availability. Concentrations of several contaminants of potential concern became substantially elevated in the waters exposed to BPU ore, including As, Co, Ni, U, and Zn, and to a lesser extent, Mo. Of these, Co, Mo, Ni, and U were minimally attenuated by downgradient processes, whereas Zn was partially attenuated. Sb and Tl concentrations were more moderately elevated but also generally minimally attenuated. Although the mixture of elements is particular to these BPU ore deposits, sulfide oxidation in the ore and carbonate buffering of pH by sedimentary rocks generates patterns of water chemistry common in acid mine drainage settings. Ultimately, downgradient concentrations of elements sourced from BPU ore will also be strongly influenced by non-geochemical factors such as the quantities of water contacting BPU materials, heterogeneity of materials along flow paths, and mixing with waters that have not contacted BPU materials.

Arizona↗

USGS2021

Water–rock interaction and the concentrations of major, trace, and rare earth elements in hydrocarbon-associated produced waters of the United States

Studies of co-produced waters from hydrocarbon extraction across multiple energy-producing basins have generally focused on major ions or a few select tracers, and studies that examine trace elements and involve laboratory experiments have generally been basin specific. Here, new perspective is sought through a broad analysis of concentration data for 26 elements from three hydrocarbon well types using the U.S. Geological Survey National Produced Waters Geochemical Database (v2.3). Those data are compared to leachates (water, hydrochloric acid, and artificial brine) from 12 energy-resource related shales from across the United States. Both lower pH and higher ionic strength were associated with greater concentrations of many trace elements in produced waters. However, individual effects were difficult to distinguish because higher ionic strengths drive decreases in pH. Water–rock interactions in the leaching experiments generally replicated produced water concentrations for trace elements including Al, As, Cd, Co, Cu, Mo, Ni, Pb, Sb, Si, and Zn. Enhanced middle rare earth element (REE) mobilization relative to shale REE content occurred with low pH leachates. Produced water concentrations of Li, Sr, and Ba were not replicated by the leaching experiments. Patterns of high Li, Sr, and Ba concentrations and ratios relative to other elements across produced waters types indicate controls on these elements in many settings related to pore space pools of salts, brines, and ion-exchange sites affected by diagenetic processes. The size of those pools is diluted and masked by other water–rock interaction processes at the water–rock ratios necessitated by laboratory experiments. The results broadly link water–rock interaction processes and environmental patterns across a wide variety of produced waters and host formations and thus provide context for trace element data from other environmental and laboratory studies of such waters.

Environmental Science: Processes & Impacts↗

USGS2020

Nontuberculous mycobacterial disease and molybdenum in Colorado watersheds

Nontuberculous mycobacteria (NTM) are environmental bacteria that may cause chronic lung disease. Environmental factors that favor NTM growth likely increase the risk of NTM exposure within specific environments. We aimed to identify water-quality constituents (Al, As, Cd, Ca, Cu, Fe, Pb, Mg, Mn, Mo, Ni, K, Se, Na, Zn, and pH) associated with NTM disease across Colorado watersheds. We conducted a geospatial, ecological study, associating data from patients with NTM disease treated at National Jewish Health and water-quality data from the Water Quality Portal. Water-quality constituents associated with disease risk were identified using generalized linear models with Poisson-distributed discrete responses. We observed a highly robust association between molybdenum (Mo) in the source water and disease risk. For every 1- unit increase in the log concentration of molybdenum in the source water, disease risk increased by 17.0%. We also observed a statistically significant association between calcium (Ca) in the source water and disease risk. The risk of NTM varied by watershed and was associated with watershed-specific water-quality constituents. These findings may inform mitigation strategies to decrease the overall risk of exposure.

Colorado↗

USGS2020

Salt flushing, salt storage, and controls on selenium: A 31-year mass-balance analysis of an irrigated, semiarid valley

Salinity, selenium, and uranium pose water‐quality challenges for the Arkansas River in southeastern Colorado and other rivers that support irrigation in semiarid regions. This study used 31 years of continuous discharge and specific conductance (SC) monitoring data to assess interannual patterns in water quality using mass balance on a 120‐km reach of river. Discrete sampling data were used to link the SC records to salinity, selenium, and uranium. Several important patterns emerged. Consumptive use reduced discharge by a median value of 33% and drove corresponding increases in salinity and uranium concentrations. Increased water availability for irrigation from rainfall and upstream snowpack in 1995–1999 flushed additional salinity and uranium into the river in 1996–2000; average annual total dissolved solids (salinity) concentrations increased 25%, and loads increased 131%. Smaller flushing events have occurred, sometimes lagging an increase in water availability by about one year. The pattern indicates flushing of salts temporarily stored, evaporatively concentrated, or of geologic origin. Mobilization of selenium from the reach was minor compared to salinity and uranium, and net selenium removal from the river was suggested in some years. Several processes related to irrigation could be removing selenium. The results provide context for efforts to improve water quality in the Arkansas River and rivers in other semiarid regions.

Colorado↗

USGS2020

Effects of John Martin Reservoir on water quality and quantity: Assessment by chemical, isotopic, and mass-balance methods

Water quality and quantity can be influenced by transit through and storage in reservoirs. Assessing such effects can be challenging, however, because of mixing and residence times, and inter-annual net storage and release from both the reservoir itself and surrounding porosity. Here, different methodologies were used to assess the effect of John Martin Reservoir (JMR), located on the Arkansas River, on water volumes and the problematic constituents salinity (total dissolved solids, TDS), selenium (Se), and uranium (U). Methodologies addressed short-term (16 months) and long-term (31 years) effects depending upon data availability. Evaporation was assessed by using isotopes of water to determine 12% short-term evaporation, and by pan evaporation and changes in storage to determine 11% long-term evaporation. Salinity, Se, and U mass balance were assessed by using chloride (Cl−) as an index by which to measure short-term gains or losses between inflows and outflows in the short term. Chloride gain from ungaged inflows skewed those results to overestimate retention. Continuous monitoring of discharge and specific conductance for inflows and outflows, along with discrete sampling for dissolved constituents were used to compute long-term, load-based mass balance. Mild gains of TDS (34,000 ± 15,000 Mg/yr) and U (0.1 ± 0.5 Mg/yr) in JMR were detected. Although the additions are small relative to uncertainty, they indicate little to no retention of TDS and U and likely additions from ungaged inflows. In contrast, an average of 0.6 ± 0.2 Mg/yr or 23% of gaged inflow Se was removed in JMR. The study illustrates the benefit of long-term records for assessing the influence of reservoirs for which net storage and release keep them from approaching steady-state conditions.

Colorado↗

USGS2019

Improved enrichment factor calculations through principal component analysis: Examples from soils near breccia pipe uranium mines, Arizona, USA

The enrichment factor (EF) is a widely used metric for determining how much the presence of an element in a sampling media has increased relative to average natural abundance because of human activity. Calculation of an EF requires the selection of both a background composition and a reference element, choices that can strongly influence the result of the calculation. Here, it is shown how carefully applied, classical principal component analysis (PCA) examined via biplots can guide the selections of background compositions and reference elements. Elemental data were treated using the centered log ratio (CLR) transformation, and multiple subsets of major and trace elements were examined to gain different perspectives. The methodology was applied to a dataset of elemental soil concentrations from around breccia pipe uranium mines in Arizona, U.S.A., with most samples collected via incremental sampling methodology. Storage of ore at the surface creates the potential for wind dispersal of ore-derived material. Uranium was found to be the best individual tracer of dispersal of ore-derived material to nearby soils, with EF values up to 75. Sulfur, As, Mo, and Cu were also enriched but to lesser degrees. The results demonstrate several practical benefits of a PCA in these situations: (1) the ability to identify one or more elements best suited to distinguish a specific source of enrichment from background composition; (2) understanding how background compositions vary within and between sites; (3) identification of samples containing enriched or anthropogenic materials based upon their integrated, multi-element composition. Calculating the most representative EF values is useful for numerical assessment of enrichment, whether anthropogenic or natural. As shown here, however, the PCA and biplot method provide a visual approach that integrates information from all elements for a given subset of data in a manner that yields geochemical insights beyond the power of the EF.

Arizona↗

USGS2019

Comment on “Particle fluxes in groundwater change subsurface rock chemistry over geologic time”

Over the last decade, studies at the Shale Hills Critical Zone Observatory (Shale Hills) have greatly expanded knowledge of weathering in previously understudied, shale-mantled terrains, as well as Earth's Critical Zone as a whole. Among the many discoveries made was the importance of redistribution and losses of micron-sized particles during development of shale-derived soils. A geochemical fingerprint of this process for Al and Fe was illustrated quantitatively by Jin et al. (2010). Subsequent papers, too numerous to list in a Comment, built upon this new recognition by evaluating the spatial and temporal aspects element mobilization. Recently, Kim et al. (2018) examined the composition of suspended, generally micron-sized particles in the Shale Hills stream, along with the dissolved load, across seasons and ranges of discharge. One prominent conclusion from Kim et al. (2018) is that Zr is essentially immobile at Shale Hills. Such a broad conclusion is in direct contradiction with one from Bern and Yesavage (2018) that Zr has been mobilized from soils at Shale Hills, and the losses relative to soil parent material are significant (median 41%). The point is important, because assuming Zr immobility is necessary to index gains and losses of other elements using the open-chemical-system transport function ( τ ). Both papers draw upon patterns and calculations using elemental concentration data from Shale Hills and attempt to construct conceptual frameworks to explain the results. Here, the argument is made that the understanding of substantial Zr mobility from soils at Shale Hills described by Bern and Yesavage (2018) is more accurate. Additionally, issues with adaptations of the standard τ equations used in Kim et al. (2018) and some previous papers are also addressed.

Pennsylvania↗

USGS2018

Dual-phase mass balance modeling of small mineral particle losses from sedimentary rock-derived soils

Losses of small mineral particles can be a significant physical process that affects the elemental composition of soils derived from sedimentary rocks. Shales, in particular, contain abundant clay-sized minerals that can be mobilized by simple disaggregation, and solutional weathering is limited because the parent rock is composed primarily of recalcitrant minerals previously subjected to continental weathering. Here, the dual-phase mass balance model is employed to quantify losses of small mineral particles as water dispersible colloids (WDCs) from three previously studied soil profiles along a hill slope at the Susquehanna Shale Hills Critical Zone Observatory (SSHO). WDCs were isolated from soil in the laboratory to determine their mineralogical and elemental compositions. Clay minerals dominated WDCs, including illite, vermiculite, and chlorite inherited from the parent shale, along with neoformed kaolinite. Quartz present in bulk soil was generally excluded from WDCs. Elements of low solubility and/or bound in recalcitrant forms, like Rb in illite, were employed in tracer ratios in the dual-phase model. Aluminum, Ga, and Rb were enriched in WDCs, and Zr and Hf were partially excluded. Six different combinations of elements into tracer ratios (Al/Zr, Ga/Zr, Rb/Zr, Al/Hf, Ga/Hf, Rb/Hf) each yielded similar model results. Mass losses of WDCs were large, ranging from − 68 ± 7% to − 15 ± 5% relative to soil parent material in different parts of the profiles. Mass losses via solution were smaller, ranging from − 7 ± 2% to a gain of 6 ± 1% in part of one profile. Losses of WDCs account for > 90% of total mass loss, surpassing chemical dissolution, and therefore dominate the weathering portion of denudation at SSHO. Zirconium concentrations were 97–158 ppm in the generally ≤ 1 μm WDCs, suggesting colloidal, Zr-bearing phases. Model-quantified losses of Zr via WDCs were large, with a median loss of 41% relative to parent material. Such losses indicate systematic underestimates of weathering by traditional mass balance that uses Zr as an index element. Losses of Ca, Mg, and K via WDCs exceeded losses via solution, countering assumptions of base cation losses primarily via mineral dissolution. The results illustrate a geochemical fingerprint of physical weathering and the ability of the dual-phase model to quantify that weathering process.

Chemical Geology↗

USGS2017

Modifications to EPA Method 3060A to Improve Extraction of Cr(VI) from Chromium Ore Processing Residue-Contaminated Soils

It has been shown that EPA Method 3060A does not adequately extract Cr(VI) from chromium ore processing residue (COPR). We modified various parameters of EPA 3060A toward understanding the transformation of COPR minerals in the alkaline extraction and improving extraction of Cr(VI) from NIST SRM 2701, a standard COPR-contaminated soil. Aluminum and Si were the major elements dissolved from NIST 2701, and their concentrations in solution were correlated with Cr(VI). The extraction fluid leached additional Al and Si from the method-prescribed borosilicate glass vessels which appeared to suppress the release of Cr(VI). Use of polytetrafluoroethylene vessels and intensive grinding of NIST 2701 increased the amount of Cr(VI) extracted. These modifications, combined with an increased extraction fluid to sample ratio of ≥900 mL g –1 and 48-h extraction time resulted in a maximum release of 1274 ± 7 mg kg –1 Cr(VI). This is greater than the NIST 2701 certified value of 551 ± 35 mg kg –1 but less than 3050 mg kg –1 Cr(VI) previously estimated by X-ray absorption near edge structure spectroscopy. Some of the increased Cr(VI) may have resulted from oxidation of Cr(III) released from brownmillerite which rapidly transformed during the extractions. Layered-double hydroxides remained stable during extractions and represent a potential residence for unextracted Cr(VI).

Environmental Science & Technology↗