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Evaluating the efficiency of environmental monitoring programs

Statistical uncertainty analyses can be used to improve the efficiency of environmental monitoring, allowing sampling designs to maximize information gained relative to resources required for data collection and analysis. In this paper, we illustrate four methods of data analysis appropriate to four types of environmental monitoring designs. To analyze a long-term record from a single site, we applied a general linear model to weekly stream chemistry data at Biscuit Brook, NY, to simulate the effects of reducing sampling effort and to evaluate statistical confidence in the detection of change over time. To illustrate a detectable difference analysis, we analyzed a one-time survey of mercury concentrations in loon tissues in lakes in the Adirondack Park, NY, demonstrating the effects of sampling intensity on statistical power and the selection of a resampling interval. To illustrate a bootstrapping method, we analyzed the plot-level sampling intensity of forest inventory at the Hubbard Brook Experimental Forest, NH, to quantify the sampling regime needed to achieve a desired confidence interval. Finally, to analyze time-series data from multiple sites, we assessed the number of lakes and the number of samples per year needed to monitor change over time in Adirondack lake chemistry using a repeated-measures mixed-effects model. Evaluations of time series and synoptic long-term monitoring data can help determine whether sampling should be re-allocated in space or time to optimize the use of financial and human resources.

Ecological Indicators↗

Quaternary vegetation and climate change in the western United States: Developments, perspectives, and prospects

This chapter explores the strengths and shortcomings of the major sources of data on Quaternary vegetation and climate change and discusses the use of models as a means to explore past and potential future environmental changes. The flora and major vegetation types of the western United States are present for several million years. Ongoing changes in atmospheric chemistry , climate, and human activities may lead to major vegetation changes over the coming decades to centuries. The combination of observations from the paleoenvironmental record, modern ecological studies, and modeling now permit assessments of the magnitude of potential future changes in the context of natural variability. They also provide opportunities for hypothesis testing and identification of the processes driving past changes in vegetation and climate. Understanding the dynamics of paleoenvironmental change can contribute to current conservation and natural resource management efforts and will help conservation and natural resource managers anticipate the potential rate, magnitude, and complexity of future vegetation change.

western United States↗

Geochemical investigation of the Arbuckle-Simpson Aquifer, South-Central Oklahoma, 2004-06

A geochemical reconnaissance investigation of the Arbuckle-Simpson aquifer in south-central Oklahoma was initiated in 2004 to characterize the ground-water quality at an aquifer scale, to describe the chemical evolution of ground water as it flows from recharge areas to discharge in wells and springs, and to determine the residence time of ground water in the aquifer. Thirty-six water samples were collected from 32 wells and springs distributed across the aquifer for chemical analysis of major ions, trace elements, isotopes of oxygen and hydrogen, dissolved gases, and age-dating tracers. In general, the waters from wells and springs in the Arbuckle-Simpson aquifer are chemically suitable for all regulated uses, such as public supplies. Dissolved solids concentrations are low, with a median of 347 milligrams per liter (mg/L). Two domestic wells produced water with nitrate concentrations that exceeded the U.S. Environmental Protection Agency's nitrate maximum contaminant level (MCL) of 10 mg/L. Samples from two wells in the confined part of the aquifer exceeded the secondary maximum contaminant level (SMCL) for chloride of 250 mg/L and the SMCL of 500 mg/L for dissolved solids. Water samples from these two wells are not representative of water samples from the other wells and springs completed in the unconfined part of the aquifer. No other water samples from the Arbuckle-Simpson geochemical reconnaissance exceeded MCLs or SMCLs, although not every chemical constituent for which the U.S. Environmental Protection Agency has established a MCL or SMCL was analyzed as part of the Arbuckle-Simpson geochemical investigation. The major ion chemistry of 34 of the 36 samples indicates the water is a calcium bicarbonate or calcium magnesium bicarbonate water type. Calcium bicarbonate water type is found in the western part of the aquifer, which is predominantly limestone. Calcium magnesium bicarbonate water is found in the eastern part of the aquifer, which is predominantly a dolomite. The major ion chemistry for these 34 samples is consistent with a set of water-rock interactions. Rainfall infiltrates the soil zone, where the host rock, limestone or dolomite, dissolves as a result of uptake of carbon dioxide gas. Some continued dissolution of dolomite and precipitation of calcite occur as the water flows through the saturated zone. The major ion chemistry of the two samples from wells completed in the confined part of the aquifer indicates the water is a sodium chloride type. Geochemical inverse modeling determined that mixing of calcite-saturated recharge water with brine and dissolving calcite, dolomite, and gypsum accounts for the water composition of these two samples. One of the two samples, collected at Vendome Well in Chickasaw National Recreation Area, had a mixing fraction of brine of about 1 percent. The brine component of the sample at Vendome Well is likely to account for the relatively large concentrations of many of the trace elements (potassium, fluoride, bromide, iodide, ammonia, arsenic, boron, lithium, selenium, and strontium) measured in the water sample. Carbon-14, helium-3/tritium, and chlorofluorocarbons were used to calculate ground-water ages, recharge temperatures, and mixtures of ground water in the Arbuckle-Simpson aquifer. Thirty four of 36 water samples recharged the aquifer after 1950, indicating that water is moving quickly from recharge areas to discharge at streams and springs. Two exceptions to this classification were noted in samples 6 and 15 (Vendome Well). Ground-water ages determined for these two samples by using carbon-14 are 34,000 years (site 6) and 10,500 years (site 15). Concentrations of dissolved argon, neon, and xenon in water samples were used to determine the temperature of the water when it recharged the aquifer. The mean annual air temperature at Ada, Oklahoma, is 16 degrees Celsius (C) and the median temperature of the 30 reconnaissance water samples was 18.1 C. The av

Oklahoma↗

Shallow groundwater and soil chemistry response to 3 years of subsurface drip irrigation using coalbed-methane-produced water

Disposal of produced waters, pumped to the surface as part of coalbed methane (CBM) development, is a significant environmental issue in the Wyoming portion of the Powder River Basin, USA. High sodium adsorption ratios (SAR) of the waters could degrade agricultural land, especially if directly applied to the soil surface. One method of disposing of CBM water, while deriving beneficial use, is subsurface drip irrigation (SDI), where acidified CBM waters are applied to alfalfa fields year-round via tubing buried 0.92 m deep. Effects of the method were studied on an alluvial terrace with a relatively shallow depth to water table (∼3 m). Excess irrigation water caused the water table to rise, even temporarily reaching the depth of drip tubing. The rise corresponded to increased salinity in some monitoring wells. Three factors appeared to drive increased groundwater salinity: (1) CBM solutes, concentrated by evapotranspiration; (2) gypsum dissolution, apparently enhanced by cation exchange; and (3) dissolution of native Na–Mg–SO 4 salts more soluble than gypsum. Irrigation with high SAR (∼24) water has increased soil saturated paste SAR up to 15 near the drip tubing. Importantly though, little change in SAR has occurred at the surface.

Wyoming↗

Distribution of algae in the San Joaquin River, California, in relation to nutrient supply, salinity and other environmental factors

1. The taxonomic composition and biomass of the phytoplankton and the taxonomic composition of the phytobenthos of the San Joaquin River and its major tributaries were examined in relation to water chemistry, habitat and flow regime. Agricultural drainage and subsurface flow contribute to a complex gradient of salinity and nutrients in this eutrophic, 'lowland type' river. 2. Because of light-limiting conditions for growth, maintenance demands of the algae exceed production during summer and autumn in the San Joaquin River where there is no inflow from tributaries. In contrast to substantial gains in concentration of inorganic nitrogen and soluble reactive phosphorus during the summer of normal-flow years, net losses of algal biomass (2-4 ??g L -1 day -1 chlorophyll a) occurred in a mid-river segment with no significant tributary inflow. However, downstream of a large tributary draining the Sierra Nevada, a substantial net gain in algal biomass (6-11 μg L -1 day -1 ) occurred in the summer, but not in the spring (loss of 1-6 μg L -1 day -1 ) or autumn (loss of 2-5 ??g L -1 day -1 ). 3. The phytoplankton was dominated in summer by 'r-selected' centric diatoms (Thalassiosirales), species both tolerant of variable salinity and widely distributed in the San Joaquin River. Pennate diatoms were proportionally more abundant (in biomass) in the winter, spring and autumn. Abundant taxa included the diatoms Cyclotella meneghiniana, Skeletonema cf. potamos, Cyclostephanos invisitatus, Thalassiosira weissflogii, Nitzschia acicularis, N. palea and N. reversa, and the chlorophytes Chlamydomonas sp. and Scenesdesmus quadricauda. Patterns in the abundance of species indicated that assembly of the phytoplankton is limited more by light and flow regime than by nutrient supply. 4. The phytobenthos was dominated by larger, more slowly reproducing pennate diatoms. Few of the abundant species are euryhaline. The diatoms Navicula recens and Nitzschia inconspicua and cyanophytes, Oscillatoria spp., were the principal late-summer benthic species upstream in the mainstem and in drainages of the San Joaquin Valley. Many of the other abundant diatoms (Amphora veneta, Bacillaria paxillifer, Navicula symmetrica, Nitzschia amphibia, N. fonticola, N. palea, Pleurosigma salinarum) of late-summer assemblages in these segments also are motile species. While many of these species also were abundant in segments downstream of confluences with rivers draining the Sierra Nevada, the relative abundance of prostrate (Cocconeis placentula var. euglypta, Navicula minima) and erect or stalked (Achnanthidium deflexum, Achnanthes lanceolata, Gomphonema kobayasii, G. parvulum var. lagenula) diatoms and Stigeoclonium sp. was greater in these lower San Joaquin River segments. 5. A weighted-averaging regression model, based on salinity and benthic-algal abundance in the San Joaquin River and segments of its major tributaries within the San Joaquin Valley, yielded a highly significant coefficient-of-determination (r 2 = 0.84) and low prediction error between salinity inferred from the species and that observed, indicating that salinity tolerance is a primary constraint on growth and assembly of the phytobenthos. The same measures of predictability indicated poor performance of a model based on inorganic nitrogen. However, with a greater representation of tributaries (including segments within the Sierra Nevada foothills) in the sample set, an inorganic nitrogen model also yielded a highly significant coefficient-of-determination (r 2 = 0.87) and low prediction error between the species-inferred and the observed concentration. As with the salinity model (r 2 = 0.94) for the enlarged data set, a systematic difference (increased deviation of residuals) existed at high inorganic nitrogen concentrations. These results indicate substantial interaction between salinity and inorganic nitrogen as constraints on the structure of benthic-algal communities of the San Joaquin River basin.

California↗

Soil and sediment chemistry in the Mississippi River Delta following Hurricane Katrina

In October 2005, the U.S. Geological Survey's (USGS) Mid-Continent Geographic Science Center and the University of Missouri-Rolla's (UMR) Environmental Research Center for Emerging Contaminants partnered to collect perishable environmental data along the Mississippi River Delta to catalog the effects of Hurricane Katrina, a category 3 storm that caused nearly complete destruction to the delta's population support structure and industry. The data presented here begin the process of characterizing the chemical composition of sediments and soil along the delta following this significant natural disaster.

Louisiana↗

Hydrodynamics of coalbed methane reservoirs in the Black Warrior Basin: Key to understanding reservoir performance and environmental issues

The Black Warrior Basin of the southeastern United States hosts one of the world's most prolific and long-lived coalbed methane plays, and the wealth of experience in this basin provides insight into the relationships among basin hydrology, production performance, and environmental issues. Along the southeast margin of the basin, meteoric recharge of reservoir coal beds exposed in an upturned fold limb exerts a strong control on water chemistry, reservoir pressure, and production performance. Fresh-water plumes containing Na-HCO3 waters with low TDS content extend from the structurally upturned basin margin into the interior of the basin. Northwest of the plumes, coal beds contain Na-Cl waters with moderate to high-TDS content. Carbon isotope data from produced gas and mineral cements suggest that the fresh-water plumes have been the site of significant bacterial activity and that the coalbed methane reservoirs contain a mixture of thermogenic and late-stage biogenic gases. Water produced from the fresh-water plumes may be disposed safely at the surface, whereas underground injection has been used locally to dispose of highly saline water. Wells in areas that had normal hydrostatic reservoir pressure prior to development tend to produce large volumes of water and may take up to 4 a to reach peak gas production. In contrast, wells drilled in naturally underpressured areas distal to the fresh-water plumes typically produce little water and achieve peak gas rates during the first year of production. Environmental debate has focused largely on issues associated with hydrologic communication between deep reservoir coal beds and shallow aquifers. In the coalbed methane fields of the Black Warrior Basin, a broad range of geologic evidence suggests that flow is effectively confined within coal and that the thick intervals of marine shale separating coal zones limit cross-formational flow. ?? 2007 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

Relationships between indicators of acid-base chemistry and fish assemblages in streams of the Great Smoky Mountains National Park

The acidity of many streams in the Great Smoky Mountains National Park (GRSM) has increased significantly since pre-industrial (∼1850) times due to the effects of highly acidic atmospheric deposition in poorly buffered watersheds. Extensive stream-monitoring programs since 1993 have shown that fish and macroinvertebrate assemblages have been adversely affected in many streams across the GRSM. Matching chemistry and fishery information collected from 389 surveys performed at 52 stream sites over a 22-year period were assessed using logistic regression analysis to help inform the U.S. Environmental Protection Agency’s assessment of the environmental impacts of emissions of oxides of nitrogen (NO x ) and sulfur (SO x ). Numerous logistic equations and associated curves were derived that defined the relations between acid neutralizing capacity (ANC) or pH and different levels of community richness, density, and biomass; and density and biomass of brook trout, rainbow trout, and small prey (minnow) populations in streams of the GRSM. The equations and curves describe the status of fish assemblages in the GRSM under contemporary emission levels and deposition loads of nitrogen (N) and sulfur (S) and provide a means to estimate how newly proposed (and various alternative) target deposition loads, which strongly influence stream ANC, might affect key ecological indicators. Several examples using ANC, community richness, and brook trout density are presented to illustrate the steps needed to predict how future changes in stream chemistry (resulting from different target deposition loads of N and S) will affect the probabilities of observing specific levels of selected biological indicators in GRSM streams. The implications of this study to the regulation of NO x and SO x emissions, water quality, and fisheries management in streams of the GRSM are discussed, but also qualified by the fact that specific examples provided need to be further explored before recommendations concerning their use as ecological indicators could be proposed.

North Carolina, Tennessee↗

A novel high-frequency groundwater quality monitoring system

High-frequency, long-term monitoring of water quality has revolutionized the study of surface waters in recent years. However, application of these techniques to groundwater has been limited by the ability to remotely pump and analyze groundwater. This paper describes a novel autonomous groundwater quality monitoring system which samples multiple wells to evaluate temporal changes and identify trends in groundwater chemistry. The system, deployed near Fresno, California, USA, collects and transmits high-frequency data, including water temperature, specific conductance, pH, dissolved oxygen, and nitrate, from supply and monitoring wells, in real-time. The system consists of a water quality sonde and optical nitrate sensor, manifold, submersible three-phase pump, variable frequency drive, data collection platform, solar panels, and rechargeable battery bank. The manifold directs water from three wells to a single set of sensors, thereby reducing setup and operation costs associated with multi-sensor networks. Sampling multiple wells at high frequency for several years provided a means of monitoring the vertical distribution and transport of solutes in the aquifer. Initial results show short period variability of nitrate, specific conductivity, and dissolved oxygen in the shallow aquifer, while the deeper portion of the aquifer remains unchanged—observations that may be missed with traditional discrete sampling approaches. In this aquifer system, nitrate and specific conductance are increasing in the shallow aquifer, while invariant changes in deep groundwater chemistry likely reflect relatively slow groundwater flow. In contrast, systems with high groundwater velocity, such as karst aquifers, have been shown to exhibit higher-frequency groundwater chemistry changes. The stability of the deeper aquifer over the monitoring period was leveraged to develop estimates of measurement system uncertainty, which were typically lower than the manufacturer’s stated specifications, enabling the identification of subtle variability in water chemistry that may have otherwise been missed.

California↗

Beyond sticks and stones: Integrating physical and ecological conditions into watershed restoration assessments using a food web modeling approach

Watershed assessments have become common for prioritizing restoration in river networks. These assessments primarily focus on geomorphic conditions of rivers but less frequently incorporate non-geomorphic abiotic factors such as water chemistry and temperature, and biotic factors such as the structure of food webs. Using a dynamic food web model that integrates physical and ecological environmental conditions of rivers, we simulated how juvenile salmon ( Oncorhynchus spp.) biomass responded to restoration at twelve sites distributed across the Methow River (Washington, USA), ranging from headwater tributaries to mainstem reaches. We explored responses to three common river restoration strategies: (1) physical habitat modification, (2) nutrient supplementation, and (3) increased riparian vegetation cover. We also simulated how different food web configurations that exist in salmon-bearing streams, such as the presence of ‘non-target’ fishes and ‘armored’ predation resistant invertebrates, could mediate restoration outcomes. Some locations in the river network experienced relatively large increases in modeled fish biomass with restoration, whereas other locations were almost entirely unresponsive. Spatial variation in restoration outcomes was primarily controlled by non-geomorphic environmental conditions, such as nutrient availability, water temperature, and stream canopy cover. Restoration responses also varied significantly with different food web configurations, suggesting that as the structure of food webs varies across river networks, so too could the outcome of restoration. These findings illustrate that ecological responses to restoration may exhibit substantial spatial variation within river networks, resulting from heterogeneity in environmental conditions that are commonly overlooked—but which can and should be considered—in restoration planning and prioritization.

Washington↗

Use of behavioral and physiological indicators to evaluate Scaphirhynchus sturgeon spawning success

Thirty gravid, female shovelnose sturgeon ( Scaphirhynchus platorynchus ) were captured in the Lower Missouri River in March 2004 to evaluate the effectiveness of physiology, telemetry and remote sensor technology coupled with change point analysis in identifying when and where Scaphirhynchus sturgeon spawn. Captured sturgeons were instrumented with ultrasonic transmitters and with archival data storage tags (DST) that recorded temperature and pressure. Female sturgeon were tracked through the suspected spawning period. Thereafter, attempts were made to recapture fish to evaluate spawning success. At the time of transmitter implantation, blood and an ovarian biopsy were taken. Reproductive hormones and cortisol were measured in blood. Polarization indices and germinal vesicle breakdown were assessed on the biopsied oocytes to determine readiness to spawn. Behavioral data collected using telemetry and DST sensors were used to determine the direction and magnitude of possible spawning-related movements and to identify the timing of potential spawning events. Upon recapture observations of the ovaries and blood chemistry provided measures of spawning success and comparative indicators to explain differences in observed behavior. Behavioral and physiological indicators of spawning interpreted along with environmental measures may assist in the determination of variables that may cue sturgeon reproduction and the conditions under which sturgeon successfully spawn.

Journal of Applied Ichthyology↗

A selected bibliography of water-related research in the upper Klamath Basin, Oregon

A bibliography containing 165 selected references was compiled to assist local, State, and Federal agencies that have ongoing water-related research interests in the Upper Klamath Basin. The report has two parts. Part 1 is a list of bibliographic citations alphabetized by author, and Part 2 is a subject index that references bibliographic entries. Categories of the subject index include chemistry, ecology, geology, hydrology, land use, and water management related reports. Maps, reports, proposals, theses, dissertations, and journal articles are referenced. Some of the environmental issues addressed by references in the bibliography are hypereutrophication, nuisance algal blooms, endangered fish species, water allocation questions, wetland and riparian habitat restoration, and pesticide and fertilizer utilization.

Open-File Report↗

Surface-water quality in agricultural watersheds of the North Carolina Coastal Plain associated with concentrated animal feeding operations

The effects of concentrated animal feeding operations (CAFOs) on water quality were investigated at 54 agricultural stream sites throughout the North Carolina Coastal Plain during 2012 and 2013. Three general watershed land-use types were examined during the study, including 18 background watersheds with no active CAFOs (BK sites), 18 watersheds with one or more active swine CAFOs but no poultry CAFOs (SW sites), and 18 watersheds with at least one active swine CAFO and one active dry-litter poultry CAFO (SP sites). The watershed drainage areas for these 54 stream sites ranged from 1.2 to 17.5 square miles. Conventional fertilizers used for crop production are the primary source of nutrients at the BK sites. Animal-waste manures represent an additional source of nutrients at the SW and SP study sites. Land cover, soil drainage, and CAFO attributes were compiled for each watershed. Water-quality field measurements were made and samples were collected at the 54 primary sites during 6 bimonthly sampling periods from June 2012 to April 2013. An additional 23 secondary sites were sampled once during April 2013 to provide supplemental data at stream locations directly adjacent or in close proximity to swine CAFOs and (or) background agricultural areas within 9 of the primary watersheds. The watershed drainage areas for the 23 secondary sites ranged from 0.2 to 8.9 square miles. Water temperature, specific conductance, dissolved-oxygen concentration, and pH were measured directly in the streams. Water samples were analyzed for major ions, nutrients, and stable isotopes, including delta hydrogen-2 (δ 2 H) and delta oxygen-18 (δ 18 O) of water and delta nitrogen-15 (δ 15 N) and δ 18 O of dissolved nitrate plus nitrite. Most of the water-quality properties and constituents varied significantly among the six sampling periods, changing both seasonally and in response to hydrologic conditions. The differences noted among the sampling periods indicate that the interactions between seasonal climatic differences, streamflow conditions, and instream biotic and abiotic processes are complex and their integrated effects can have varying degrees of influence on individual nutrients. Water-quality differences were noted for the SW and SP land-use groups relative to the BK group. Median values of specific conductance, several major ions (magnesium, sodium, potassium, and chloride), and nitrogen fractions (ammonia plus organic nitrogen, ammonia, nitrate plus nitrite, total nitrogen, and δ 15 N of nitrate plus nitrite) were higher for the SW and SP groups compared to the BK group. No significant differences in water temperature, dissolved oxygen, calcium, total organic nitrogen, orthophosphate, total phosphorus, or δ 18 O of nitrate plus nitrite were noted among the land-use groups. When compared on the basis of land-use type, there was an overall measurable effect of CAFO waste manures on stream water quality for the SW and SP watershed groups. Some individual sites within the SW and SP groups showed no measurable CAFO effects on water quality despite having CAFOs present upstream. An evaluation of sodium plus potassium concentrations coupled with δ 15 N values of nitrate plus nitrite proved valuable for distinguishing which SW and SP sites had a water-quality signature indicative of CAFO waste manures. Sites with CAFO manure effects were characterized by higher sodium plus potassium concentrations (commonly between 11 and 33 milligrams per liter) and δ 15 N values of nitrate plus nitrite (commonly between 11 and 26 parts per thousand) relative to sites reflecting background agricultural conditions, which commonly had sodium plus potassium concentrations between 6 and 14 milligrams per liter and δ 15 N values of nitrate plus nitrite between 6 and 15 parts per thousand. On the basis of the results of this study, land applications of waste manure at swine CAFOs influenced ion and nutrient chemistry in many of the North Carolina Coastal Plain streams that were studied. A classification tree model was developed to examine relations of watershed environmental attributes among the study sites with and without CAFO manure effects. Model results indicated that variations in swine barn density, percentage of wetlands, and total acres available for applying swine-waste manures had an important influence on those watersheds where CAFO effects on water quality were either evident or mitigated. Measurable effects of CAFO waste manures on stream water quality were most evident in those SW and SP watersheds having lower percentages of wetlands combined with higher swine barn densities and (or) higher total acres available for applying waste manure at the swine CAFOs. Stream water quality was similar to background agricultural conditions in SW and SP watersheds with lower swine barn densities coupled with higher percentages of wetlands or lower acres available for swine manure applications. The model provides a useful tool for exploring and identifying similar, unmonitored watersheds in the North Carolina Coastal Plain with potential CAFO manure influences on water quality that might warrant further examination.

North Carolina↗

A reactive transport approach to modeling cave seepage water chemistry II: Elemental signatures

Karst systems are useful for examining spatial and temporal variability in Critical Zone processes because they provide a window into the subsurface where waters have interacted with vegetation, soils, regolith, and bedrock across a range of length and timescales. These hydrologic pathways frequently include the precipitation of speleothems, which provide long-term archives of climate and environmental change. Trace element ratios in speleothems (Mg/Ca, Sr/Ca, Ba/Ca) have the potential to provide information about past changes in rainfall and infiltration, but controls on them can be complex and their interpretation must be based on an understanding of the modern cave system. Here we integrate observations of surface conditions, bedrock, soil, and drip water chemistry of Blue Spring Cave in Tennessee, USA with the reactive transport model CrunchTope, which we have calibrated for karst systems to investigate the primary controls on trace element variations in cave seepage waters. We find that measured drip water Mg/Ca and Sr/Ca are captured within the model through variable amounts of limestone dissolution followed by precipitation of secondary calcite that happens within the cave rather than the host limestone. However, strong spatial controls on drip water Mg/Ca and Sr/Ca likely reflect seepage water interactions with variable amounts of diagenetic phases in the host rock. In contrast, Ba/Ca values are consistent across the cave and vary with effective rainfall, suggesting that this parameter may be the most consistent metric for limestone dissolution and prior calcite precipitation and can act as a proxy for rainfall and infiltration in this cave system. Our findings emphasize the importance of evaluating spatial heterogeneity in cave drip waters and outline a novel modeling approach for determining the dominant controls on drip water chemistry in support of the interpretations of paleoclimate records.

Geochimica et Cosmochimica Acta↗

How could a freshwater swamp produce a chemical signature characteristic of a saltmarsh?

Reduction–oxidation (redox) reaction conditions, which are of great importance for the soil chemistry of coastal marshes, can be temporally dynamic. We present a transect of cores from northwest Florida wherein radical postdepositional changes in the redox regime has created atypical geochemical profiles at the bottom of the sedimentary column. The stratigraphy is consistent along the transect, consisting of, from the bottom upward, carbonate bedrock, a gray clay, an organic mud section, a dense clay layer, and an upper organic mud unit representing the current saltwater marsh. However, the geochemical signature of the lower organic mud unit suggests pervasive redox reactions, although the interval has been identified as representing a freshwater marsh, an unlikely environment for such conditions. Analyses indicate that this discrepancy results from postdepositional diagenesis driven by millennial-scale environmental parameters. Rising sea level that led to the deposition of the capping clay layer, created anaerobic conditions in the freshwater swamp interval, and isolated it hydrologically from the rest of the sediment column. The subsequent infiltration of marine water into this organic material led to sulfate reduction, the buildup of H 2 S and FeS, and anoxic conditions. Continued sulfidation eventually resulted in euxinic conditions, as evidenced by elevated levels of Fe, S, and especially Mo, the diagnostic marker of euxinia. Because this chemical transformation occurred long after the original deposition the geochemical signature does not reflect soil chemistry at the time of deposition and cannot be used to infer syn-depositional environmental conditions, emphasizing the importance of recognizing diagenetic processes in paleoenvironmental studies.

Florida↗

Groundwater hydrology, groundwater and surface-water interactions, water quality, and groundwater-flow simulations for the Wet Mountain Valley alluvial aquifer, Custer and Fremont Counties, Colorado, 2017–19

In 2017, the U.S. Geological Survey, in cooperation with the Upper Arkansas Water Conservancy District, began a study to provide a comprehensive analysis of the Wet Mountain Valley alluvial aquifer, Custer and Fremont Counties, Colorado. The study included collection of data pertaining to groundwater hydrology, groundwater and surface-water interactions, and water quality in the alluvial aquifer. In addition to providing foundational information on the hydrology of the alluvial aquifer, a numerical groundwater-flow model was developed to estimate the potential effects of additional storage of groundwater in the alluvial aquifer. Groundwater-level elevation data from 30 wells were used to estimate groundwater-flow directions in the alluvial aquifer, which were generally from the southwest to northeast, away from the Sangre de Cristo Mountains and towards perennial streams in the center of the valley. Although some seasonal variation was apparent in groundwater-level elevation records, no statistically significant seasonal trends were indicated. Statistically significant long-term trends were indicated in groundwater-level elevation records for 8 of the 30 wells, and of these wells with statistically significant trends, all but 1 indicated a negative trend of groundwater-level elevations. Spatial evaluation of wells with statistically significant negative groundwater-level elevation trends showed many are in areas of denser well drilling for domestic or other uses, indicating increasing groundwater use could potentially be causing groundwater-level elevation declines. There were instances of wells with no statistically significant groundwater-level elevation trends also located in areas of greater density of well completions. Additional investigations may be necessary to more fully characterize the processes responsible for negative groundwater-level elevation trends. Streamflow gain or loss calculations were completed for low flow in 2017–19 and for high flow in 2018 in nine reaches of streams within the study area. Stream reaches of the upper Texas Creek, upper Grape Creek, upper-middle Grape Creek, and Taylor Creek displayed consistent streamflow loss in each period from 2017 to 2019. These stream reaches represent long-term sources of recharge to the alluvial aquifer. Streamflow gain or loss varies through time in other stream reaches (lower Texas Creek, lower-middle Grape Creek, lower Grape Creek below Westcliffe, and lower Grape Creek above DeWeese Reservoir). The temporally variable behavior indicates these stream reaches may be sources of groundwater recharge or areas of groundwater discharge, likely depending on temporal dynamics between the elevation of the water table and the stream. Water-quality samples were collected from 10 groundwater wells and 10 stream sites during September through November 2019. All groundwater and stream samples were analyzed for major and trace elements and stable isotopes of water. A subset of groundwater samples was also analyzed for the environmental tracers sulfur hexafluoride, tritium, and noble gases. Comparison of water-quality results to U.S. Environmental Protection Agency drinking water-quality standards indicated no constituents exceeded primary standards for human health. Spatial evaluation of water quality indicated the concentrations of various constituents are likely controlled by groundwater and surface-water interactions and by spatial variability in bedrock geology underlying the alluvial aquifer. Specifically, streams shown to gain from groundwater had water chemistry constituent compositions similar to groundwater, whereas streams exiting the Sangre de Cristo Mountains tended to have compositions consistent with snowmelt. Groundwater geochemistry appeared to be partially controlled by oxidation-reduction processes and by proximity to igneous rocks in the Wet Mountains. Environmental tracers used to estimate groundwater age indicated all sampled groundwater contained tracers representing modern recharge (approximately less than 65 years old) but mixing of premodern recharge (approximately more than 65 years old) also occurs. Spatial evaluation of environmental tracers indicated large faults may be conduits for upwelling of older groundwater. No trends were observed in groundwater age with well depth, indicating all sampled wells are located within the zone of active groundwater flow. The presence of modern groundwater in wells with statistically significant negative groundwater-level elevation trends indicates groundwater storage depletions may be partially offset by capture of modern recharge. Repeated sampling of groundwater age would be necessary, however, to determine if any trends in groundwater age exist, which may indicate changing groundwater recharge, storage, or discharge. Additional investigations could also consider quantifying groundwater age in deeper wells to more fully define the depth of active groundwater flow. A numerical groundwater-flow model was developed to estimate components of the water budget, simulate groundwater and surface-water interactions, and evaluate the potential effects of aquifer storage and recovery. Simulated groundwater-level elevations from the calibrated groundwater-flow model are similar to the observed pattern of groundwater-level elevations with higher elevations in the western part of the study area along the Sangre de Cristo Mountains. Simulated water-budget components indicate most of the recharge to the alluvial aquifer is derived from streamflow losses, which is consistent with observations of losing streams along the mountain front. The largest groundwater discharge component of the alluvial aquifer was to streams in the center of the valley, where observations of stream gain or loss indicated the predominance of gaining conditions. Comparison of groundwater and surface-water interactions between the calibrated groundwater-flow model for 2000-19 (the base-case model) and a simulation including additional recharge, representing potential aquifer storage and recovery operations, indicated the additional recharge distributed throughout the area had minimal effects on streamflow in the nearby Grape Creek. An analysis of subregional groundwater budgets showed approximately 54 percent of the additional recharge flowed back to nearby Grape Creek, and the other 46 percent was distributed laterally into adjacent cells in the alluvial aquifer. The comparison of simulations and subregional water budget show the additional recharge did not substantially alter groundwater-level elevations or basin wide groundwater storage. Although the analysis of additional recharge provided in the numerical groundwater-flow model considers only one of many possible recharge scenarios, the model provides a useful tool that could be modified for various scenarios to understand potential effects of managed aquifer recharge.

Colorado↗

Carboniferous climate teleconnections archived in coupled bioapatite δ18OPO4 and 87Sr/86Sr records from the epicontinental Donets Basin, Ukraine

Reconstructions of paleo-seawater chemistry are largely inferred from biogenic records of epicontinental seas. Recent studies provide considerable evidence for large-scale spatial and temporal variability in the environmental dynamics of these semi-restricted seas that leads to the decoupling of epicontinental isotopic records from those of the open ocean. We present conodont apatite δ 18 O PO4 and 87 Sr/ 86 Sr records spanning 24 Myr of the late Mississippian through Pennsylvanian derived from the U–Pb calibrated cyclothemic succession of the Donets Basin, eastern Ukraine. On a 2 to 6 Myr-scale, systematic fluctuations in bioapatite δ 18 O PO4 and 87 Sr/ 86 Sr broadly follow major shifts in the Donets onlap–offlap history and inferred regional climate, but are distinct from contemporaneous more open-water δ 18 O PO4 and global seawater Sr isotope trends. A −1 to −6‰ offset in Donets δ 18 O PO4 values from those of more open-water conodonts and greater temporal variability in δ 18 O PO4 and 87 Sr/ 86 Sr records are interpreted to primarily record climatically driven changes in local environmental processes in the Donets sea. Systematic isotopic shifts associated with Myr-scale sea-level fluctuations, however, indicate an extrabasinal driver. We propose a mechanistic link to glacioeustasy through a teleconnection between high-latitude ice changes and atmospheric p CO 2 and regional monsoonal circulation in the Donets region. Inferred large-magnitude changes in Donets seawater salinity and temperature, not archived in the more open-water or global contemporaneous records, indicate a modification of the global climate signal in the epicontinental sea through amplification or dampening of the climate signal by local and regional environmental processes. This finding of global climate change filtered through local processes has implications for the use of conodont δ 18 O PO4 and 87 Sr/ 86 Sr values as proxies of paleo-seawater composition, mean temperature, and glacioeustasy.

Donets Basin↗

Assessing environmental oil spill based on fluorescence images of water samples and deep learning

Measuring oil concentration in the aquatic environment is essential for determining the potential exposure, risk, or injury for oil spill response and natural resource damage assessment. Conventional analytical chemistry methods require samples to be collected in the field, shipped, and processed in the laboratory, which is also rather time-consuming, laborious, and costly. For rapid field response immediately after a spill, there is a need to estimate oil concentration in near real time. To make the oil analysis more portable, fast, and cost effective, we developed a plug-and-play device and a deep learning model to assess oil levels in water using fluorescent images of water samples. We constructed a 3D-printed device to collect fluorescent images of solvent-extracted water samples using an iPhone. We prepared approximately 1,300 samples of oil at different concentrations to train and test the deep learning model. The model comprises a convolutional neural network and a novel module of histogram bottleneck block with an attention mechanism to exploit the spectral features found in low-contrast images. This model predicts the oil concentration in weight per volume based on fluorescence image. We devised a confidence interval estimator by combining gradient boosting and polymodal regressor to provide a confidence assessment of our results. Our model achieved sufficient accuracy to predict oil levels for most environmental applications. We plan to improve the device and iPhone application as a near-real-time tool for oil spill responders to measure oil in water.

Journal of Environmental Informatics↗