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At least 1,783 records · Page 99Linked to original sources

Direct-push geochemical profiling for assessment of inorganic chemical heterogeneity in aquifers

Discrete-depth sampling of inorganic groundwater chemistry is essential for a variety of site characterization activities. Although the mobility and rapid sampling capabilities of direct-push techniques have led to their widespread use for evaluating the distribution of organic contaminants, complementary methods for the characterization of spatial variations in geochemical conditions have not been developed. In this study, a direct-push-based approach for high-resolution inorganic chemical profiling was developed at a site where sharp chemical contrasts and iron-reducing conditions had previously been observed. Existing multilevel samplers (MLSs) that span a fining-upward alluvial sequence were used for comparison with the direct-push profiling. Chemical profiles obtained with a conventional direct-push exposed-screen sampler differed from those obtained with an adjacent MLS because of sampler reactivity and mixing with water from previous sampling levels. The sampler was modified by replacing steel sampling components with stainless-steel and heat-treated parts, and adding an adapter that prevents mixing. Profiles obtained with the modified approach were in excellent agreement with those obtained from an adjacent MLS for all constituents and parameters monitored (Cl, NO3, Fe, Mn, DO, ORP, specific conductance and pH). Interpretations of site redox conditions based on field-measured parameters were supported by laboratory analysis of dissolved Fe. The discrete-depth capability of this approach allows inorganic chemical variations to be described at a level of detail that has rarely been possible. When combined with the mobility afforded by direct-push rigs and on-site methods of chemical analysis, the new approach is well suited for a variety of interactive site-characterization endeavors. ?? 2003 Elsevier B.V. All rights reserved.

Journal of Contaminant Hydrology↗

Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling

In many natural and contaminated aquifers, geochemical processes result in the production or consumption of dissolved gases. In cases where methanogenesis or denitrification occurs, the production of gases may result in the formation and growth of gas bubbles below the water table. Near the water table, entrapment of atmospheric gases during water table rise may provide a significant source of O 2 to waters otherwise depleted in O 2 . Furthermore, the presence of bubbles will affect the hydraulic conductivity of an aquifer, resulting in changes to the groundwater flow regime. The interactions between physical transport, biogeochemical processes, and gas bubble formation, entrapment and release is complex and requires suitable analysis tools. The objective of the present work is the development of a numerical model capable of quantitatively assessing these processes. The multicomponent reactive transport code MIN3P has been enhanced to simulate bubble growth and contraction due to in-situ gas production or consumption, bubble entrapment due to water table rise and subsequent re-equilibration of the bubble with ambient groundwater, and permeability changes due to trapped gas phase saturation. The resulting formulation allows for the investigation of complex geochemical systems where microbially mediated redox reactions both produce and consume gases as well as affect solution chemistry, alkalinity, and pH. The enhanced model has been used to simulate processes in a petroleum hydrocarbon contaminated aquifer where methanogenesis is an important redox process. The simulations are constrained by data from a crude oil spill site near Bemidji, MN. Our results suggest that permeability reduction in the methanogenic zone due to in-situ formation of gas bubbles, and dissolution of entrapped atmospheric bubbles near the water table, both work to attenuate the dissolved gas plume emanating from the source zone. Furthermore, the simulations demonstrate that under the given conditions more than 50% of all produced CH 4 partitions to the gas phase or is aerobically oxidised near the water table, suggesting that these processes should be accounted for when assessing the rate and extent of methanogenic degradation of hydrocarbons.

Journal of Contaminant Hydrology↗

Cyclic biogeochemical processes and nitrogen fate beneath a subtropical stormwater infiltration basin

A stormwater infiltration basin in north–central Florida, USA, was monitored from 2007 through 2008 to identify subsurface biogeochemical processes, with emphasis on N cycling, under the highly variable hydrologic conditions common in humid, subtropical climates. Cyclic variations in biogeochemical processes generally coincided with wet and dry hydrologic conditions. Oxidizing conditions in the subsurface persisted for about one month or less at the beginning of wet periods with dissolved O 2 and NO 3 - showing similar temporal patterns. Reducing conditions in the subsurface evolved during prolonged flooding of the basin. At about the same time O 2 and NO 3 - reduction concluded, Mn, Fe and SO 4 2 - reduction began, with the onset of methanogenesis one month later. Reducing conditions persisted up to six months, continuing into subsequent dry periods until the next major oxidizing infiltration event. Evidence of denitrification in shallow groundwater at the site is supported by median NO 3 -–N less than 0.016 mg L -1 , excess N 2 up to 3 mg L -1 progressively enriched in δ 15 N during prolonged basin flooding, and isotopically heavy δ 15 N and δ 18 O of NO 3 - (up to 25‰ and 15‰, respectively). Isotopic enrichment of newly infiltrated stormwater suggests denitrification was partially completed within two days. Soil and water chemistry data suggest that a biogeochemically active zone exists in the upper 1.4 m of soil, where organic carbon was the likely electron donor supplied by organic matter in soil solids or dissolved in infiltrating stormwater. The cyclic nature of reducing conditions effectively controlled the N cycle, switching N fate beneath the basin from NO 3 - leaching to reduction in the shallow saturated zone. Results can inform design of functionalized soil amendments that could replace the native soil in a stormwater infiltration basin and mitigate potential NO 3 - leaching to groundwater by replicating the biogeochemical conditions under the observed basin.

Florida↗

Per- and polyfluoroalkyl substances (PFAS) mass flux and mass balance at an aqueous film-forming foam release site in semiarid eastern New Mexico, USA

Passive flux meters (PFMs) directly measure groundwater chemistry mass flux and Darcy flux, providing insight into contaminant source-zone architecture and transport properties. This study uses PFMs to characterize PFAS flux in groundwater at a semiarid site with a thick (greater than 90-m) unsaturated zone where groundwater has been contaminated with per - and polyfluoroalkyl substances (PFAS) related to the use of aqueous film-forming foam (AFFF) for fire training and fire suppression. PFAS mass discharge (PFAS mass flux integrated over a control plane) in groundwater downgradient from several PFAS release areas is calculated using PFM results. In groundwater downgradient from fire-training areas, total PFAS mass discharge (summed across 14 compounds) was estimated to be between 6.0 and 31 g per day in 2020 and between 5.9 and 23 g per day in 2021. Site-specific documentation, generic information on AFFF properties, and literature values of PFAS concentration in AFFF are used to estimate site-specific PFAS-application rates at fire-training areas. These PFAS-application rates are compared to groundwater PFAS-discharge rates. Results suggest that transformation processes (exact pathways unknown) have led to increased discharge of measured PFAS in groundwater relative to initial AFFF formulations. The mass balance approach has broad applicability as a high-level approach that can provide insight into PFAS transport at AFFF sites.

New Mexico↗

Seasonal patterns in hydrochemical mixing in three Great Lakes rivermouth ecosystems

Rivermouth ecosystems in the Laurentian Great Lakes represent complex hydrologic mixing zones where lake and river water combine to form biologically productive areas that are functionally similar to marine estuaries. As urban, industrial, shipping, and recreational centers, rivermouths are the focus of human interactions with the Great Lakes and, likewise, may represent critical habitat for larval fish and other biota. The hydrology and related geomorphology in these deltaic systems form the basis for ecosystem processes and wetland habitat structure but are poorly understood. To this end, a multidisciplinary team of scientists examined hydrogeomorphic structure and lake-tributary mixing in rivermouths using water chemistry, stable isotopes, and current profiling over a five-month period. Results showed that the maximum depth of the rivermouth ecosystem influenced mixing, with temperature-related, density-dependent wedging and layering that isolated lake water below river water occurring in deeper systems. The inherent size of the rivermouth ecosystem, local geomorphology, and human modifications such as shoreline armoring and dredging influenced mixing by altering the propensity for density differences to occur. The improved scientific understanding and framework for characterizing hydrogeomorphic processes in Great Lakes rivermouths across a disturbance gradient is useful for conservation, management, restoration, and protection of critical habitats needed by native species.

Michigan, Wisconsin↗

Seasonal differences in larval sea lamprey (Petromyzon marinus) sensitivity to the pesticide TFM

Invasive sea lamprey ( Petromyzon marinus ) are controlled in the Great Lakes with 4-nitro-3-(trifluoromethyl)phenol (commonly 3-trifluoromethyl-4-nitrophenol or TFM). The proper amount of TFM must be applied during treatments to effectively kill larval sea lamprey while minimizing impacts to non-target species. In this study, bioassay tests were conducted in May, July, and September in a portable test trailer at six larval sea lamprey infested rivers in Michigan to determine potential seasonal changes in sensitivity of larval sea lamprey to TFM. Larvae greater than 60 mm were collected from each stream and exposed for 12 h in TFM-treated stream water using two independent continuous-flow diluter systems. A suite of water chemistries and larval physiological parameters were collected during the tests and modeled as potential predictors of seasonal changes in the sensitivity of larval sea lamprey to TFM. The observed minimum lethal concentrations to larval sea lamprey were 0–40% lower (May), 8% lower–59% higher (July), and 49–117% higher (September) than sea lamprey control personnel treatment prediction charts. Water temperature, liver glycogen content, and time of year were strongly associated with seasonal differences in TFM sensitivity, offering sea lamprey control personnel more exact predictions to limit potential residual lamprey surviving future treatments.

Michigan↗

Tile drainage as karst: Conduit flow and diffuse flow in a tile-drained watershed

The similarity of tiled-drained watersheds to karst drainage basins can be used to improve understanding of watershed-scale nutrient losses from subsurface tile drainage networks. In this study, short-term variations in discharge and chemistry were examined from a tile outlet collecting subsurface tile flow from a 963 ha agricultural watershed. Study objectives were to apply analytical techniques from karst springs to tile discharge to evaluate water sources and estimate the loads of agricultural pollutants discharged from the tile with conduit, intermediate and diffuse flow regimes. A two-member mixing model using nitrate, chloride and specific conductance was used to distinguish rainwater versus groundwater inputs. Results indicated that groundwater comprised 75% of the discharge for a three-day storm period and rainwater was primarily concentrated during the hydrograph peak. A contrasting pattern of solute concentrations and export loads was observed in tile flow. During base flow periods, tile flow consisted of diffuse flow from groundwater sources and contained elevated levels of nitrate, chloride and specific conductance. During storm events, suspended solids and pollutants adhered to soil surfaces (phosphorus, ammonium and organic nitrogen) were concentrated and discharged during the rapid, conduit flow portion of the hydrograph. During a three-day period, conduit flow occurred for 5.6% of the time but accounted for 16.5% of the total flow. Nitrate and chloride were delivered primarily with diffuse flow (more than 70%), whereas 80-94% of total suspended sediment, phosphorus and ammonium were exported with conduit and intermediate flow regimes. Understanding the water sources contributing to tile drainage and the manner by which pollutant discharge occurs from these systems (conduit, intermediate or diffuse flow) may be useful for designing, implementing and evaluating non-point source reduction strategies in tile-drained landscapes. ?? 2007 Elsevier B.V. All rights reserved.

Journal of Hydrology↗

Subsurface transport of orthophosphate in five agricultural watersheds, USA

Concentrations of dissolved orthophosphate (ortho P) in the unsaturated zone, groundwater, tile drains, and groundwater/stream water interfaces were assessed in five agricultural watersheds to determine the potential for subsurface transport. Concentrations of iron oxides were measured in the aquifer material and adsorption of ortho P on oxide surfaces was assessed by geochemical modeling. Attenuation of ortho P in these aquifers was attributed primarily to sorption onto iron oxides, and in one location onto clay minerals. Only one location showed a clear indication of phosphorus transport to a stream from groundwater discharge, although groundwater did contribute to the stream load elsewhere. Subsurface ortho P movement at a site in California resulted in a plume down gradient from orchards, which was attenuated by a 200 m thick riparian zone with natural vegetation. Iron oxides had an effect on phosphorus movement and concentrations at all locations, and groundwater chemistry, especially pH, exerted a major control on the amount of phosphorus adsorbed. Groundwater pH at a site in Maryland was below 5 and that resulted in complete sequestration of phosphorus and no movement toward the stream. Geochemical modeling indicated that as the surfaces approached saturation, groundwater concentrations of ortho P rise rapidly.

Journal of Hydrology↗

Soil disturbance as a driver of increased stream salinity in a semiarid watershed undergoing energy development

Salinization is a global threat to the quality of streams and rivers, but it can have many causes. Oil and gas development were investigated as one of several potential causes of changes in the salinity of Muddy Creek, which drains 2470 km2 of mostly public land in Wyoming, U.S.A. Stream discharge and salinity vary with seasonal snowmelt and define a primary salinity-discharge relationship. Salinity, measured by specific conductance, increased substantially in 2009 and was 53-71% higher at low discharge and 33-34% higher at high discharge for the years 2009-2012 compared to 2005-2008. Short-term processes (e.g., flushing of efflorescent salts) cause within-year deviations from the primary relation but do not obscure the overall increase in salinity. Dissolved elements associated with increased salinity include calcium, magnesium, and sulfate, a composition that points to native soil salts derived from marine shales as a likely source. Potential causes of the salinity increase were evaluated for consistency by using measured patterns in stream chemistry, slope of the salinity-discharge relationship, and inter-annual timing of the salinity increase. Potential causes that were inconsistent with one or more of those criteria included effects from precipitation, evapotranspiration, reservoirs, grazing, irrigation return flow, groundwater discharge, discharge of energy co-produced waters, and stream habitat restoration. In contrast, surface disturbance of naturally salt-rich soil by oil and gas development activities, such as pipeline, road, and well pad construction, is a reasonable candidate for explaining the salinity increase. As development continues to expand in semiarid lands worldwide, the potential for soil disturbance to increase stream salinity should be considered, particularly where soils host substantial quantities of native salts.

Journal of Hydrology: Regional Studies↗

Prediction and visualization of redox conditions in the groundwater of Central Valley, California

Regional-scale, three-dimensional continuous probability models, were constructed for aspects of redox conditions in the groundwater system of the Central Valley, California. These models yield grids depicting the probability that groundwater in a particular location will have dissolved oxygen (DO) concentrations less than selected threshold values representing anoxic groundwater conditions, or will have dissolved manganese (Mn) concentrations greater than selected threshold values representing secondary drinking water-quality contaminant levels (SMCL) and health-based screening levels (HBSL). The probability models were constrained by the alluvial boundary of the Central Valley to a depth of approximately 300 m. Probability distribution grids can be extracted from the 3-D models at any desired depth, and are of interest to water-resource managers, water-quality researchers, and groundwater modelers concerned with the occurrence of natural and anthropogenic contaminants related to anoxic conditions. Models were constructed using a Boosted Regression Trees (BRT) machine learning technique that produces many trees as part of an additive model and has the ability to handle many variables, automatically incorporate interactions, and is resistant to collinearity. Machine learning methods for statistical prediction are becoming increasing popular in that they do not require assumptions associated with traditional hypothesis testing. Models were constructed using measured dissolved oxygen and manganese concentrations sampled from 2767 wells within the alluvial boundary of the Central Valley, and over 60 explanatory variables representing regional-scale soil properties, soil chemistry, land use, aquifer textures, and aquifer hydrologic properties. Models were trained on a USGS dataset of 932 wells, and evaluated on an independent hold-out dataset of 1835 wells from the California Division of Drinking Water. We used cross-validation to assess the predictive performance of models of varying complexity, as a basis for selecting final models. Trained models were applied to cross-validation testing data and a separate hold-out dataset to evaluate model predictive performance by emphasizing three model metrics of fit: Kappa; accuracy; and the area under the receiver operator characteristic curve (ROC). The final trained models were used for mapping predictions at discrete depths to a depth of 304.8 m. Trained DO and Mn models had accuracies of 86–100%, Kappa values of 0.69–0.99, and ROC values of 0.92–1.0. Model accuracies for cross-validation testing datasets were 82–95% and ROC values were 0.87–0.91, indicating good predictive performance. Kappas for the cross-validation testing dataset were 0.30–0.69, indicating fair to substantial agreement between testing observations and model predictions. Hold-out data were available for the manganese model only and indicated accuracies of 89–97%, ROC values of 0.73–0.75, and Kappa values of 0.06–0.30. The predictive performance of both the DO and Mn models was reasonable, considering all three of these fit metrics and the low percentages of low-DO and high-Mn events in the data.

California↗

Geochemical characterization and modeling of regional groundwater contributing to the Verde River, Arizona between Mormon Pocket and the USGS Clarkdale gage

We use synoptic surveys of stream discharge, stable isotopes, and dissolved noble gases to identify the source of groundwater discharge to the Verde River in central Arizona. The Verde River more than doubles in discharge in Mormon Pocket over a 1.4 km distance that includes three discrete locations of visible spring input to the river and other diffuse groundwater inputs. A detailed study of the Verde River between Mormon Pocket and the USGS Clarkdale Gage was conducted to better constrain the location of groundwater inputs, the geochemical signature and constrain the source of groundwater input. Discharge, water quality parameters (temperature, pH, specific conductance, and dissolved oxygen), stable isotopes (δ18O and δ2H), noble gases (He, Ne, Ar, Kr and Xe), and radon (222Rn) from river water were collected. Groundwater samples from springs and wells in the area were collected and analyzed for tracers measured in the stream along with some additional analytes (major ions, strontium isotopes (87Sr/86Sr), carbon-14, δ13C, and tritium). Groundwater isotopic signature is consistent with a regional groundwater source. Groundwater springs discharging to the river have a depleted stable isotopic signature indicating recharge source up to 1000 m higher than the discharge location in the Verde River and are significantly fresher than stream water. Spring water has a radiocarbon age of several thousand years and some areas have tritium less than the laboratory reporting level or low concentrations of tritium (1.5 TU). The strontium isotopes indicate groundwater interaction with tertiary volcanic rock and Paleozoic sedimentary rocks. Along the study reach with distance downstream, Verde stream water chemistry shows increased 222Rn, freshening, increased 4He, and isotopic depletion with distance downstream. We estimated total groundwater discharge by inverting a stream transport model against 222Rn and discharge measured in the stream. The salinity, 4He, and stable isotope composition of discharging groundwater was then estimated by fitting modeled values to observed in-stream values. Estimated groundwater inflow to the stream was well within the ranges observed in springs, indicating that the main source of streamflow is deep, regional groundwater. These results show that synoptic surveys of environmental tracers in streams can be used to estimate the isotopic composition and constrain the source of groundwater discharging to streams. Our data provide direct field evidence that deep, regional groundwater discharge can be a significant source of streamflow generation in arid, topographically complex watersheds.

Arizona↗

Summer runoff generation in foothill catchments of the Colorado Front Range

Climatic shifts, disturbances, and land-use change can alter hydrologic flowpaths, water quality, and water supply to downstream communities. Prior research investigating streamflow generation processes in mountainous areas has largely focused on high-elevation alpine and subalpine catchments; less is known about these processes in lower-elevation foothills and montane catchments. In these lower-elevation ecoregions, precipitation shifts seasonally from snow to rain, which can result in differing seasonal flowpaths. We analyzed stream water for electrical conductivity, SiO 2 , Ca, Mg, Na, Cl, SO 4 , K, and dissolved organic carbon on both a weekly and storm event basis from April to August 2018 in three small (<10 km 2 ) foothill catchments, and one larger (63.2 km 2 ) catchment extending from the foothills to the subalpine ecoregions, in the Colorado Front Range. Using two end-member hydrograph separations and concentration-runoff relationships, we inferred the dominant catchment-scale flowpaths of precipitation to the streams. We selected catchments with varying land use to investigate the relationship between these characteristics and hydrologic flowpaths. We observed that concentrations of lithogenic constituents generally increased and dissolved organic carbon decreased as seasonal runoff decreased in the three foothill catchments, reflecting a transition from shallow subsurface flowpaths to deeper subsurface flowpaths. Elevated SO 4 and Cl concentrations during low-flow periods in two of our catchments suggest that historical or current anthropogenic activities, such as mining, application of road salt, and/or near-stream septic systems, affect local stream and groundwater chemistry. In a foothill catchment with anthropogenic and geologic impervious surfaces, streamflow during storm responses was sourced from faster, surficial flowpaths compared to a less disturbed neighboring catchment, highlighting the influence of anthropogenic land-use on runoff generation. This study provides insight into the fundamental hydrology of foothill catchments and how they may function in the future with human development, precipitation shifts and disturbances.

Colorado↗

The impact of ventilation patterns on calcite dissolution rates within karst conduits

Erosion rates in streams vary dramatically over time, as differences in streamflow and sediment load enhance or inhibit erosion processes. Within cave streams, and other bedrock channels incising soluble rocks, changes in water chemistry are an important factor in determining how erosion rates will vary in both time and space. Prior studies in surface streams, springs, and caves suggest that variation in dissolved CO 2 is the strongest control on variation in calcite dissolution rates. However, the controls on CO 2 variation remain poorly quantified. Limited data suggest that ventilation of karst systems can substantially influence dissolved CO 2 within karst conduits. However, the interactions among cave ventilation, air-water CO 2 exchange, and dissolution dynamics have not been studied in detail. In this study, three years of time series measurements of dissolved and gaseous CO 2 , cave airflow velocity, and specific conductance from Blowing Springs Cave, Arkansas, were analyzed and used to estimate continuous calcite dissolution rates and quantify the correlations between those rates and potential physical and chemical drivers. We find that chimney effect airflow creates temperature-driven switches in airflow direction, and that the resulting seasonal changes in airflow regulate both gaseous and dissolved CO 2 within the cave. As in previous studies, partial pressure of CO 2 ( p CO 2 ) is the strongest chemical control of dissolution rate variability. However, we also show that cave airflow direction, rather than streamflow, is the strongest physical driver of changes in dissolution rate, contrary to the typical situation in surface channel erosion where floods largely determine the timing and extent of geomorphic work. At the study site, chemical erosion is typically active in the summer, during periods of cave downdraft (airflow from upper to lower entrances), and inactive in the winter, during updraft (airflow from lower to upper entrances). Storms provide only minor perturbations to this overall pattern. We also find that airflow direction modulates dissolution rate variation during storms, with higher storm variability during updraft than during downdraft. Finally, we compare our results with the limited set of other studies that have examined dissolution rate variation within cave streams and draw an initial hypothesis that evolution of cave ventilation patterns strongly impacts how dissolution rate dynamics evolve over the lifetime of karst conduits.

Arkansas, Missouri↗

The influence of land cover and storm magnitude on hydrologic flowpath activation and runoff generation in steep tropical catchments of central Panama

Despite abundant research documenting that land use/land cover (LULC) have substantial impacts on the hydrology of humid tropical systems, field-based evidence for the physical mechanisms behind these impacts are still lacking. In particular, our understanding of the hydrologic flowpaths that generate runoff in these systems, and how they vary with respect to LULC is insufficient to inform both physically-based hydrologic modeling and land-use decision-making. In this study, we use end-member mixing analysis (EMMA) of stream chemistry, and hydrometric characterizations of hillslope soil moisture to identify hydrologic flowpaths in humid tropical steep-land catchments of varying LULC: mature tropical forest, young secondary tropical forest, cattle pasture. EMMA was applied to data from 14 storm events (six at the mature forest, five at the young secondary forest, and three at the cattle pasture) that were intensively sampled during the 2017 wet season representing a wide range of rainfall magnitudes and intensities. Additionally, volumetric-soil-moisture responses at multiple depths were characterized during and after 74 storm events occurring from 2015 to 2017. EMMA results indicated that lateral preferential flow within the top 30 cm of the soil profile was a dominant source of runoff generation at the two forested catchments, with the contribution of this flow path increasing with rainfall magnitude and intensity. This was corroborated by volumetric-soil-moisture data, that showed that a perched zone of saturation developed at 30 cm at the time of peak storm runoff during the largest events and lasted for the remaining duration of the event. EMMA indicated that runoff was a combination of infiltration-excess overland flow and lateral subsurface flow in the actively grazed pastoral catchment. There, overland flow contributed 62 % of runoff during the highest runoff rate sampled (35.3 mm/hr) and this contribution increased substantially with storm magnitude. This flowpath identification was also supported by volumetric-soil-moisture data at the pasture, with peak saturation at all depths during the largest storm events occurring up to 30 min after peak runoff. These results provide a mechanistic explanation for previously observed hydrologic differences among tropical LULCs. Additionally, the wide range of hydrologic conditions during these storm events provide a basis for understanding how future changes to this, and similar humid tropical regions will impact hydrological processes and water availability.

Journal of Hydrology↗

Hydrologic variability and groundwater age of springs in eastern Oregon and northern Nevada, USA

The ecological importance of springs in semiarid regions is far greater than their small size and sparse distribution, yet little is known about the hydrologic functioning of these systems. During 2016–22, 261 springs were visited in the volcanic terrane of eastern Oregon and northern Nevada. When conditions were suitable, measurements of discharge, water temperature, and specific conductance were made, and samples for the analysis of carbon-14, tritium, and water stable isotopes (WSI) were collected. A subset of 60 springs was revisited during different seasons in the same year and during the dry season in multiple years to evaluate variability in discharge, chemistry, and groundwater age. Specific conductance and WSI varied considerably among springs across the study area but were unexpectedly stable across seasons and years at individual springs. Seasonal and interannual variability in spring discharge was related to the residence time of the discharging groundwater. Springs discharging older groundwater (10 3 –10 4 years) had significantly less variability in their discharge compared to springs discharging younger groundwater (10 0 –10 1 years). Variability among springs discharging younger groundwater included cessation of late-summer discharge at 18 % of the repeat-visit springs. A logistic regression model predicted the age of discharging spring water with 89 % accuracy using only the spring latitude, longitude, elevation, and δ 2 H value. This study framework provides a simple, inexpensive, and robust method to provisionally assess the hydrologic behavior of springs having little or no prior information in understudied, semiarid regions across the globe.

Nevada, Oregon↗

Ongoing hydrothermal heat loss from the 1912 ash-flow sheet, Valley of Ten Thousand Smokes, Alaska

The June 1912 eruption of Novarupta filled nearby glacial valleys on the Alaska Peninsula with ash-flow tuff (ignimbrite), and post-eruption observations of thousands of steaming fumaroles led to the name ‘Valley of Ten Thousand Smokes’ (VTTS). By the late 1980s most fumarolic activity had ceased, but the discovery of thermal springs in mid-valley in 1987 suggested continued cooling of the ash-flow sheet. Data collected at the mid-valley springs between 1987 and 2001 show a statistically significant correlation between maximum observed chloride (Cl) concentration and temperature. These data also show a statistically significant decline in the maximum Cl concentration. The observed variation in stream chemistry across the sheet strongly implies that most solutes, including Cl, originate within the area of the VTTS occupied by the 1912 deposits. Numerous measurements of Cl flux in the Ukak River just below the ash-flow sheet suggest an ongoing heat loss of ∼250 MW. This represents one of the largest hydrothermal heat discharges in North America. Other hydrothermal discharges of comparable magnitude are related to heat obtained from silicic magma bodies at depth, and are quasi-steady on a multidecadal time scale. However, the VTTS hydrothermal flux is not obviously related to a magma body and is clearly declining. Available data provide reasonable boundary and initial conditions for simple transient modeling. Both an analytical, conduction-only model and a numerical model predict large rates of heat loss from the sheet 90 years after deposition.

Alaska↗

Volatile emissions and gas geochemistry of Hot Spring Basin, Yellowstone National Park, USA

We characterize and quantify volatile emissions at Hot Spring Basin (HSB), a large acid-sulfate region that lies just outside the northeastern edge of the 640 ka Yellowstone Caldera. Relative to other thermal areas in Yellowstone, HSB gases are rich in He and H2, and mildly enriched in CH4 and H2S. Gas compositions are consistent with boiling directly off a deep geothermal liquid at depth as it migrates toward the surface. This fluid, and the gases evolved from it, carries geochemical signatures of magmatic volatiles and water-rock reactions with multiple crustal sources, including limestones or quartz-rich sediments with low K/U (or 40*Ar/4*He). Variations in gas chemistry across the region reflect reservoir heterogeneity and variable degrees of boiling. Gas-geothermometer temperatures approach 300 C and suggest that the reservoir feeding HSB is one of the hottest at Yellowstone. Diffuse CO2 flux in the western basin of HSB, as measured by accumulation-chamber methods, is similar in magnitude to other acid-sulfate areas of Yellowstone and is well correlated to shallow soil temperatures. The extrapolation of diffuse CO2 fluxes across all the thermal/altered area suggests that 410 ?? 140??t d- 1 CO2 are emitted at HSB (vent emissions not included). Diffuse fluxes of H2S were measured in Yellowstone for the first time and likely exceed 2.4 t d- 1 at HSB. Comparing estimates of the total estimated diffuse H2S emission to the amount of sulfur as SO42- in streams indicates ~ 50% of the original H2S in the gas emission is lost into shallow groundwater, precipitated as native sulfur, or vented through fumaroles. We estimate the heat output of HSB as ~ 140-370 MW using CO2 as a tracer for steam condensate, but not including the contribution from fumaroles and hydrothermal vents. Overall, the diffuse heat and volatile fluxes of HSB are as great as some active volcanoes, but they are a small fraction (1-3% for CO2, 2-8% for heat) of that estimated for the entire Yellowstone system.

Journal of Volcanology and Geothermal Research↗

Long-term changes in quiescent degassing at Mount Baker Volcano, Washington, USA; Evidence for a stalled intrusion in 1975 and connection to a deep magma source

Long-term changes have occurred in the chemistry, isotopic ratios, and emission rates of gas at Mount Baker volcano following a major thermal perturbation in 1975. In mid-1975 a large pulse in sulfur and carbon dioxide output was observed both in emission rates and in fumarole samples. Emission rates of CO2 and H2S were ∼ 950 and 112 t/d, respectively, in 1975; these decreased to ∼ 150 and < 1 t/d by 2007. During the peak of the activity the C/S ratio was the lowest ever observed in the Cascade Range and similar to magmatic signatures observed at other basaltic–andesite volcanoes worldwide. Increases in the C/S ratio and decreases in the CO2/CH4 ratio since 1975 suggest a long steady trend back toward a more hydrothermal gas signature. The helium isotope ratio is very high (> 7 Rc/RA), but has declined slightly since the mid-1970s, and δ13C–CO2 has decreased by ≥ 1‰ over time. Both trends are expected from a gradually crystallizing magma. While other scenarios are investigated, we conclude that magma intruded the mid- to shallow-crust beneath Mount Baker during the thermal awakening of 1975. Since that time, evidence for fresh magma has waned, but the continued emission of CO2 and the presence of a long-term hydrothermal system leads us to suspect some continuing connection between the surface and deep convecting magma.

Washington↗