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Applications of factor analysis in study of chemistry of groundwater quality, Mojave River Valley, California

Factor analysis is applied to results of chemical analyses of 103 water samples from wells in the Upper and Middle Mojave River valley, San Bernardino County, California. Chemical analyses showed that there are three principal chemical types of water, calcium bicarbonate, sodium sulfate, and sodium chloride, as well as many mixtures of the three. Data were studied by factor analysis to learn the relative importance of each principal ion in determining the variations among the samples, and to examine the possibility of chemical equilibrium between aqueous and solid phases in the aquifers. Most of the covariance in the system may be accounted for by variances of Ca +2 , Mg +2 , Na +1 , SO 4 −2 , and Cl −1 . There is almost identical loading on the constituents Na +1 and Cl −1 . The variance in chemical composition of the hydrochemical system is governed largely by sources of sodium chloride. None of the components is controlled by equilibrium between ions in the water and minerals in the aquifers. Concentrations of NO 3 −1 and F −1 vary independently of other constituents. Geographic distribution of statistical loadings of the principal constituents at individual wells does not reveal sources of the constituents, which must be deduced from geologic and hydrologic evidence. Factor analysis, however, furnished the critical information on chemical relationships basic to the deduction.

California↗

Water-Quality Conditions of Chester Creek, Anchorage, Alaska, 1998-2001

Between October 1998 and September 2001, the U.S. Geological Survey's National Water-Quality Assessment Program evaluated the water-quality conditions of Chester Creek, a stream draining forest and urban settings in Anchorage, Alaska. Data collection included water, streambed sediments, lakebed sediments, and aquatic organisms samples from urban sites along the stream. Urban land use ranged from less than 1 percent of the basin above the furthest upstream site to 46 percent above the most downstream site. Findings suggest that water quality of Chester Creek declines in the downstream direction and as urbanization in the watershed increases. Water samples were collected monthly and during storms at a site near the stream's mouth (Chester Creek at Arctic Boulevard) and analyzed for major ions and nutrients. Water samples collected during water year 1999 were analyzed for selected pesticides and volatile organic compounds. Concentrations of fecal-indicator bacteria were determined monthly during calendar year 2000. During winter, spring, and summer, four water samples were collected at a site upstream of urban development (South Branch of South Fork Chester Creek at Tank Trail) and five from an intermediate site (South Branch of South Fork Chester Creek at Boniface Parkway). Concentrations of calcium, magnesium, sodium, chloride, and sulfate in water increased in the downstream direction. Nitrate concentrations were similar at the three sites and all were less than the drinking-water standard. About one-quarter of the samples from the Arctic Boulevard site had concentrations of phosphorus that exceeded the U.S. Environmental Protection Agency (USEPA) guideline for preventing nuisance plant growth. Water samples collected at the Arctic Boulevard site contained concentrations of the insecticide carbaryl that exceeded the guideline for protecting aquatic life. Every water sample revealed a low concentration of volatile organic compounds, including benzene, toluene, tetrachloroethylene, methyl tert-butyl ether, and chloroform. No water samples contained volatile organic compounds concentrations that exceeded any USEPA drinking-water standard or guideline. Fecal-indicator bacteria concentrations in water from the Arctic Boulevard site commonly exceeded Federal and State guidelines for water-contact recreation. Concentrations of cadmium, copper, lead, and zinc in streambed sediments increased in the downstream direction. Some concentrations of arsenic, chromium, lead, and zinc in sediments were at levels that can adversely affect aquatic organisms. Analysis of sediment chemistry in successive lakebed-sediment layers from Westchester Lagoon near the stream's mouth provided a record of water-quality trends since about 1970. Concentrations of lead have decreased from peak levels in the mid-1970s, most likely because of removing lead from gasoline and lower lead content in other products. However, concen-trations in recently-deposited lakebed sediments are still about 10 times greater than measured in streambed sediments at the upstream Tank Trail site. Zinc concentrations in lakebed sediments also increased in the early 1970s to levels that exceeded guidelines to protect aquatic life and have remained at elevated but variable levels. Pyrene, benz[a]anthracene, and phenanthrene in lakebed sediments also have varied in concentrations and have exceeded protection guidelines for aquatic life since the 1970s. Concentrations of dichloro-diphenyl-trichloroethane, polychlorinated biphenyls (PCBs), or their by-products generally were highest in lakebed sediments deposited in the 1970s. More recent sediments have concentrations that vary widely and do not show distinct temporal trends. Tissue samples of whole slimy sculpin (Cottus cognatus), a non-migratory species of fish, showed con-centrations of trace elements and organic contaminants. Of the constituents analyzed, only selenium concentra-tions showed levels of potential concern for

Scientific Investigations Report↗

Machine learning approaches to identify lithium concentration in petroleum produced waters

Prices for battery-grade lithium have increased substantially since 2020, which is propelling the search for additional sources of this important element. Battery-grade lithium is predominately recovered from continental brines. Most crude oil and natural gas wells recover briny formation water, which may represent an additional source. Chemical analysis of these waters has been shown to indicate the presence of varying concentrations of lithium and related elements. This paper briefly reviews developments and literature supporting the presence of lithium in petroleum reservoir brines. It also describes the coverage and distribution of lithium data analyses in the United States Geological Survey National Produced Waters Geochemical Database (PWGD). It then addresses the question as to whether a lithium concentration can be accurately predicted using constituents of ion chemistry in produced brines from specific geologic formations. Four machine learning algorithms are employed to classify the commercial potential of lithium in oil field brines using data from oil wells recovering formation water from the Smackover Formation. The calibrated classification models are further applied to new (out-of-sample) data from the Marcellus Formation in the Appalachian Basin. Among the approaches considered, the predictive performance and wider applicability of the gradient boosted tree and the deep neural network models are determined to be the most promising. Finally, we discuss how the calibrated models could be applied to assure the quality of the data reported from chemical laboratory analysis and for imputation when lithium values are missing.

Mineral Economics↗

Changes in stream chemistry in the east-central Adirondack region of New York State, 2010–2018

Decreased acidic deposition occurred through the 2010s, extending the long-term decrease begun in the early 1980s. The overall decline has resulted in rates of acidic deposition in the Adirondack region that are similar to those estimated for the early 1900s. This achievement increased attention on the issue of acidic deposition recovery and raised the question of how the low deposition levels of the 2010s were affecting the Adirondack region of New York State, where past acidic deposition effects were among the highest in the United States. This report presents stream resampling results of the East-Central Adirondack Stream Survey (ECASS), the Adirondack high-elevation stream sampling program, and the first five years of stream chemistry measurements in the Boreas River Long-Term Monitoring Watersheds. In addition, a regional comparison of stream chemistry between ECASS and the Western Adirondack Stream Survey (WASS) is presented. The primary objective of these stream resampling programs was to evaluate changes in stream chemistry during the 2010s to evaluate ongoing recovery of acidic deposition within the Adirondack region. Streams in the ECASS region (19,658 km 2 ) were sampled during spring snowmelt in 2011, 2017, and 2018; summer baseflow in 2010 and 2017; and late autumn in 2011 and 2017. ECASS stream sampling results for snowmelt in 2018 are also compared with WASS stream sampling results during snowmelt of the same year to provide a spatial assessment of stream chemistry for the entire Adirondack region. In addition, high-elevation streams were sampled in 2010-2011 and 2017 during spring snowmelt and summer baseflow, and three streams in the Boreas River watershed were sampled biweekly from 2014 through 2019. Streams were selected for sampling from the approximately 200 streams sampled originally in both the ECASS and WASS. The original ECASS and WASS streams were randomly selected from the populations of accessible streams within their respective regions. For the study reported here, subsets of streams were selected from the two original groups using a random stratified design based on the stream chemistry of the original ECASS and WASS. ECASS data are presented only for streams that were sampled in each of the seasonal surveys, which was 59, 48, and 61 streams for spring snowmelt, summer baseflow, and autumn surveys, respectively. WASS data are presented for 60 streams and high-elevation data are presented for 11 streams sampled during summer baseflow and 12 streams sampled during spring snowmelt. Overall, mean values of chemical measurements did not indicate large changes between 2010-2011 and 2017-2018 in the ECASS snowmelt, summer baseflow, or autumn surveys. Minimal acidification was observed in mean values measured in any of the surveys. Mean values of acid-neutralizing capacity (ANC) remained above 80 microequivalents per liter (µeq L -1 ), mean pH remained above 6.37, and inorganic monomeric aluminum (Al i ) remained below 1.0 micromoles per liter (µmol L -1 ), with the exception of the mean value of 1.2 µmol L -1 in the 2017 autumn survey. However, in the 2017 and 2018 snowmelt samplings 15% and 10% of the streams, respectively, had Al i concentrations above 1.0 µmol L 1 , the concentration above which is toxic to fish. Based on the estimated total length of headwater streams in the ECASS region of 11,494 km, the 10% of ECASS streams that experienced harmful Al i concentrations (Al i >1.0 µmol L -1 ) during the 2018 snowmelt survey equated to a total length of 1,091 km of headwater stream length in the region. During both summer baseflow and snowmelt sampling, high-elevation streams were less acidic in 2017 than in 2010-2011. However, in 2017 the mean Al i concentration during snowmelt was 2.6 µmol L -1 , a value that reflected low to moderate toxicity to brook trout. Concentrations of Al i in 9 out of the 12 streams were above 1.5 µmol L -1 , which exceeds the value which impairs fish communities. Greater dilution of calcium (Ca 2+ ) concentrations than sulfate (SO 4 2- ) concentrations during snowmelt was a contributing factor to the more acidic stream water measured during snowmelt than summer baseflow. Comparison of 2018 ECASS and WASS snowmelt chemistry under the current low levels of acidic deposition indicated that the spatial pattern of acidification effects on stream chemistry is largely driven by inherent Ca 2+ availability tied to spatial variations in geologic factors that control acid buffering more effectively in the ECASS region than the WASS region. The higher degree of acidification in the WASS region than the ECASS region is likely to extend into the future as a result of the relatively high dissolved organic carbon (DOC) concentrations in the WASS. Pronounced increasing trends in DOC and similarly pronounced decreasing trends in Ca 2+ and nitrate (NO 3 - ) were observed in the streams of all three Boreas River watersheds. These strong increasing DOC trends occurred in streams during a period with little or no indication of further chemical recovery from acidic deposition. The strong DOC trends in Durgin Brook and Balsam Brook, which are streams that are unlikely to have ever experienced more than minimal acidification, suggest the need for further investigation to expand our understanding of the mechanisms behind the increasing DOC trends.

New York↗

Molybdenum blue reaction and determination of phosphorus in waters containing arsenic, silicon, and germanium

Microgram amounts of phosphate are usually determined by the molybdenum blue reaction, but this reaction is not specific for phosphorus. The research established the range of conditions under which phosphate, arsenate, silicate, and germanate give the molybdenum blue reaction for differentiating these elements, and developed a method for the determination of phosphate in waters containing up to 10 p.p.m. of the oxides of germanium, arsenic(V), and silicon. With stannous chloride or 1-amino-2-naphthol-4-sulfonic acid as the reducing agent no conditions were found for distinguishing silicate from germanate and phosphate from arsenate. In the recommended procedure the phosphate is concentrated by coprecipitation on aluminum hydroxide, and coprecipitated arsenic, germanium, and silicon are volatilized by a mixture of hydrofluoric, hydrochloric, and hydrobromic acids prior to the determination of phosphate. The authors are able to report that the total phosphorus content of several samples of sea water from the Gulf of Mexico ranged from 0.018 to 0.059 mg. of phosphorus pentoxide per liter of water.

Analytical Chemistry↗

Water-quality characteristics of quaternary unconsolidated-deposit aquifers and lower tertiary aquifers of the Bighorn Basin, Wyoming and Montana, 1999-2001

As part of the Yellowstone River Basin National Water Quality Assessment study, ground-water samples were collected from Quaternary unconsolidated-deposit and lower Tertiary aquifers in the Bighorn Basin of Wyoming and Montana from 1999 to 2001. Samples from 54 wells were analyzed for physical characteristics, major ions, trace elements, nutrients, dissolved organic carbon, radionuclides, pesticide compounds, and volatile organic compounds (VOCs) to evaluate current water-quality conditions in both aquifers. Water-quality samples indicated that waters generally were suitable for most uses, and that natural conditions, rather than the effects of human activities, were more likely to limit uses of the waters. Waters in both types of aquifers generally were highly mineralized, and total dissolved-solids concentrations frequently exceeded the U.S. Environmental Protection Agency (USEPA) Secondary Maximum Contaminant Level (SMCL) of 500 milligrams per liter (mg/L). Because of generally high mineralization, waters from nearly one-half of the samples from Quaternary aquifers and more than one-half of the samples from lower Tertiary aquifers were not classified as fresh (dissolved-solids concentration were not less than 1,000 mg/L). The anions sulfate, fluoride, and chloride were measured in some ground-water samples at concentrations greater than SMCLs. Most waters from the Quaternary aquifers were classified as very hard (hardness greater than 180 mg/L), but hardness varied much more in waters from the lower Tertiary aquifers and ranged from soft (less than 60 mg/L) to very hard (greater than 180 mg/L). Major-ion chemistry varied with dissolved-solids concentrations. In both types of aquifers, the predominant anion changes from bicarbonate to sulfate with increasing dissolved-solids concentrations. Samples from Quaternary aquifers with fresh waters generally were calcium-bicarbonate, calcium-sodium-bicarbonate, and calcium-sodium-sulfate-bicarbonate type waters, whereas samples with larger concentrations generally were calcium-sodium-sulfate, calcium-sulfate, or sodium-sulfate-type waters. In the lower Tertiary aquifers, samples with fresh waters generally were sodium-bicarbonate or sodium-bicarbonate-sulfate type waters, whereas samples with larger concentrations were sodium-sulfate or calcium-sodium-sulfate types. Concentrations of most trace elements in both types of aquifers generally were small and most were less than applicable USEPA standards. The trace elements that most often did not meet USEPA secondary drinking-water standards were iron and manganese. In fact, the SMCL for manganese was the most frequently exceeded standard; 68 percent of the samples from the Quaternary aquifers and 31 percent of the samples from the lower Tertiary aquifers exceeded the manganese standard. Geochemical conditions may control manganese in both aquifers as concentrations in Quaternary aquifers were negatively correlated with dissolved oxygen concentrations and concentrations in lower Tertiary aquifers decreased with increasing pH. Elevated nitrate concentrations, in addition to detection of pesticides and VOCs in both aquifers, indicated some effects of human activities on ground-water quality. Nitrate concentrations in 36 percent of the wells in Quaternary aquifers and 28 percent of the wells in lower Tertiary aquifers were greater than 1 mg/L, which may indicate ground-water contamination from human sources. The USEPA drinking-water Maximum Contaminant Level (MCL) for nitrate, 10 mg/L, was exceeded in 8 percent of samples collected from Quaternary aquifers and 3 percent from lower Tertiary aquifers. Nitrate concentrations in Quaternary aquifers were positively correlated with the percentage of cropland and other agricultural land (non-cropland), and negatively correlated with rangeland and riparian land. In the lower Tertiary aquifers, nitrate concentrations only were correlated with the percentage of cropland. Concentratio

Scientific Investigations Report↗

Effects of wastewater effluent discharge and treatment facility upgrades on environmental and biological conditions of Indian Creek, Johnson County, Kansas, June 2004 through June 2013

Indian Creek is one of the most urban drainage basins in Johnson County, Kansas, and environmental and biological conditions of the creek are affected by contaminants from point and other urban sources. The Johnson County Douglas L. Smith Middle Basin (hereafter referred to as the “Middle Basin”) and Tomahawk Creek Wastewater Treatment Facilities (WWTFs) discharge to Indian Creek. In summer 2010, upgrades were completed to increase capacity and include biological nutrient removal at the Middle Basin facility. There have been no recent infrastructure changes at the Tomahawk Creek facility; however, during 2009, chemically enhanced primary treatment was added to the treatment process for better process settling before disinfection and discharge with the added effect of enhanced phosphorus removal. The U.S. Geological Survey, in cooperation with Johnson County Wastewater, assessed the effects of wastewater effluent on environmental and biological conditions of Indian Creek by comparing two upstream sites to four sites located downstream from the WWTFs using data collected during June 2004 through June 2013. Environmental conditions were evaluated using previously and newly collected discrete and continuous data and were compared with an assessment of biological community composition and ecosystem function along the upstream-downstream gradient. This study improves the understanding of the effects of wastewater effluent on stream-water and streambed sediment quality, biological community composition, and ecosystem function in urban areas. After the addition of biological nutrient removal to the Middle Basin WWTF in 2010, annual mean total nitrogen concentrations in effluent decreased by 46 percent, but still exceeded the National Pollutant Discharge Elimination System (NPDES) wastewater effluent permit concentration goal of 8.0 milligrams per liter (mg/L); however, the NPDES wastewater effluent permit total phosphorus concentration goal of 1.5 mg/L or less was achieved at the Middle Basin WWTF. At the Tomahawk Creek WWTF, after the addition of chemically enhanced primary treatment in 2009, effluent discharges also had total phosphorus concentrations below 1.5 mg/L. After the addition of biological nutrient removal, annual total nitrogen and phosphorus loads from the Middle Basin WWTF decreased by 42 and 54 percent, respectively, even though effluent volume increased by 11 percent. Annual total phosphorus loads from the Tomahawk Creek WWTF after the addition of chemically enhanced primary treatment decreased by 54 percent despite a 33-percent increase in effluent volume. Total nitrogen and phosphorus from the WWTFs contributed between 30 and nearly 100 percent to annual nutrient loads in Indian Creek depending on streamflow conditions. In-stream total nitrogen primarily came from wastewater effluent except during years with the highest streamflows. Most of the in-stream total phosphorus typically came from effluent during dry years and from other urban sources during wet years. During 2010 through 2013, annual mean discharge from the Middle Basin WWTF was about 75 percent of permitted design capacity. Annual nutrient loads likely will increase when the facility is operated at permitted design capacity; however, estimated maximum annual nutrient loads from the Middle Basin WWTF were 27 to 38 percent lower than before capacity upgrades and the addition of biological nutrient removal to treatment processes. Thus, the addition of biological nutrient removal to the Middle Basin wastewater treatment process should reduce overall nutrient loads from the facility even when the facility is operated at permitted design capacity. The effects of wastewater effluent on the water quality of Indian Creek were most evident during below-normal and normal streamflows (about 75 percent of the time) when wastewater effluent represented about 24 percent or more of total streamflow. Wastewater effluent had the most substantial effect on nutrient concentrations in Indian Creek. Total and inorganic nutrient concentrations at the downstream sites during below-normal and normal streamflows were 10 to 100 times higher than at the upstream sites, even after changes in treatment practices at the WWTFs. Median total phosphorus concentrations during below-normal and normal streamflows at a downstream site were 43 percent lower following improvements in wastewater treatment processes. Similar decreases in total nitrogen were not observed, likely because total nitrogen concentrations only decreased in Middle Basin effluent and wastewater contributed a higher percentage to streamflows when nutrient samples were collected during the after-upgrade period. The wastewater effluent discharges to Indian Creek caused changes in stream-water quality that may affect biological community structure and ecosystem processes, including higher concentrations of bioavailable nutrients (nitrate and orthophosphorus) and warmer water temperatures during winter months. Other urban sources of contaminants also caused changes in stream-water quality that may affect biological community structure and ecosystem processes, including higher turbidities downstream from construction areas and higher specific conductance and chloride concentrations during winter months. Chloride concentrations exceeded acute and chronic exposure criteria at all Indian Creek study sites, regardless of wastewater influence, for weeks or months during winter. Streambed sediment chemistry was affected by wastewater (elevated nutrient and organic wastewater-indicator compound concentrations) and other contaminants from urban sources (elevated polyaromatic hydrocarbon concentrations). Overall habitat conditions were suboptimal or marginal at all sites; general decline in habitat conditions along the upstream-downstream gradient likely was caused by the cumulative effects of urbanization with increasing drainage basin size. Wastewater effluent likely affected algal periphyton biomass and community composition, primary production, and community respiration in Indian Creek. Functional stream health, evaluated using a preliminary framework based on primary production and community respiration, was mildly or severely impaired at most downstream sites relative to an urban upstream Indian Creek site. The mechanistic cause of the changes in these biological variables are unclear, though elevated nutrient concentrations were positively correlated with algal biomass, primary production, and community respiration. Macroinvertebrate communities indicated impairment at all sites, and Kansas Department of Health and Environment aquatic life support scores indicated conditions nonsupporting of aquatic life, regardless of wastewater influences. Urban influences, other than wastewater effluent discharge, likely control macroinvertebrate community structure in Indian Creek. Changes in treatment processes at the Middle Basin and Tomahawk Creek WWTFs improved wastewater effluent quality and decreased nutrient loads, but wastewater effluent discharges still had negative effects on the environmental and biological conditions at downstream Indian Creek sites. Wastewater effluent discharge into Indian Creek likely contributed to changes in measures of ecosystem structure (streamflow, water and streambed-sediment chemistry, algal biomass, and algal periphyton community composition) and function (primary production and community respiration) along the upstream-downstream gradient. Wastewater effluent discharges maintained streamflows and increased nutrient concentrations, algal biomass, primary production, and community respiration at the downstream sites. Functional stream health was severely impaired downstream from the Middle Basin WWTF and mildly impaired downstream from the Tomahawk WWTF relative to the urban upstream site. As distance from the Middle Basin WWTF increased, nutrient concentrations, algal biomass, primary production, and community respiration decreased, and functional stream health was no longer impaired 9.5 kilometers downstream from the discharge relative to the urban upstream site. Therefore, although wastewater effluent caused persistent changes in environmental and biological conditions and functional stream health at sites located immediately downstream from WWTF effluent discharges, some recovery to conditions more similar to the urban upstream site occurred within a relatively short distance.

Kansas↗

Stable-isotope and solute-chemistry approaches to flow characterization in a forested tropical watershed, Luquillo Mountains, Puerto Rico

The prospect of changing climate has led to uncertainty about the resilience of forested mountain watersheds in the tropics. In watersheds where frequent, high rainfall provides ample runoff, we often lack understanding of how the system will respond under conditions of decreased rainfall or drought. Factors that govern water supply, such as recharge rates and groundwater storage capacity, may be poorly quantified. This paper describes 8-year data sets of water stable isotope composition ( δ 2 H and δ 18 O) of precipitation (4 sites) and a stream (1 site), and four contemporaneous stream sample sets of solute chemistry and isotopes, used to investigate watershed response to precipitation inputs in the 1780-ha Río Mameyes basin in the Luquillo Mountains of northeastern Puerto Rico. Extreme δ 2 H and δ 18 O values from low-pressure storm systems and the deuterium excess ( d -excess) were useful tracers of watershed response in this tropical system. A hydrograph separation experiment performed in June 2011 yielded different but complementary information from stable isotope and solute chemistry data. The hydrograph separation results indicated that 36% of the storm rain that reached the soil surface left the watershed in a very short time as runoff. Weathering-derived solutes indicated near-stream groundwater was displaced into the stream at the beginning of the event, followed by significant dilution. The more biologically active solutes exhibited a net flushing behavior. The d- excess analysis suggested that streamflow typically has a recent rainfall component (∼25%) with transit time less than the sampling resolution of 7 days, and a more well-mixed groundwater component (∼75%). The contemporaneous stream sample sets showed an overall increase in dissolved solute concentrations with decreasing elevation that may be related to groundwater inputs, different geology, and slope position. A considerable amount of water from rain events runs off as quickflow and bypasses subsurface watershed flowpaths, and better understanding of shallow hillslope and deeper groundwater processes in the watershed will require sub-weekly data and detailed transit time modeling. A combined isotopic and solute chemistry approach can guide further studies to a more comprehensive model of the hydrology, and inform decisions for managing water supply with future changes in climate and land use.

Applied Geochemistry↗

Groundwater quality at Alabama Plating and Vincent Spring, Vincent, Alabama, 2007–2008

The former Alabama Plating site in Vincent, Alabama, includes the location where the Alabama Plating Company operated an electroplating facility from 1956 until 1986. The operation of the facility generated waste containing cyanide, arsenic, cadmium, chromium, copper, lead, zinc, and other heavy metals. Contamination resulting from the site operations was identified in groundwater, soil, and sediment. Vincent Spring, used as a public water supply by the city of Vincent, Alabama, is located about ½ mile southwest of the site. The U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency, conducted an investigation at Vincent Spring and the Alabama Plating site, Vincent, Alabama, during 2007–2008 to evaluate the groundwater quality and evaluate the potential effect of contaminated groundwater on the water quality of Vincent Spring. The results of the investigation will provide scientific data and information on the occurrence, fate, and transport of contaminants in the water resources of the area and aid in the evaluation of the vulnerability of the public water supply to contamination. Samples were analyzed to evaluate the water quality at the former plating site, investigate the presence of possible contaminant indicators at Vincent Spring, and determine the usefulness of stable isotopes and geochemical properties in understanding groundwater flow and contaminant transport in the area. Samples collected from 16 monitor wells near the plating site and Vincent Spring were analyzed for major constituents, trace metals, nutrients, and the stable isotopes for hydrogen ( 2 H/H) and oxygen ( 18 O/ 16 O). Groundwater collected from Vincent Spring was characterized as a calcium-magnesium-bicarbonate water type with total dissolved solids concentrations ranging from 110 to 120 milligrams per liter and pH ranging from about 7.5 to 7.9 units. Groundwater chemistry at the monitor wells at the Alabama Plating site was highly variable by location and depth. Dissolved solids concentrations ranged from 28 to 2,880 milligrams per liter, and the water types varied from calcium-magnesium-bicarbonate-chloride, to calcium-sulfate or calcium-magnesium-sulfate, to sodium-chloride water types. The stable isotope ratios for hydrogen ( 2 H/H) and oxygen ( 18 O/ 16 O) for water from the monitor wells and from Vincent Spring, based on a single sampling event, can be separated into three groups: (1) Vincent Spring, (2) monitor wells MW03 and MW28, and (3) the remaining Alabama Plating monitor wells. The geochemical and stable isotope analyses indicate that water from Vincent Spring is distinct from water from the Alabama Plating monitor wells; however, this evaluation is based on a single sampling event. Although the water from Vincent Spring, for this sampling event, is different and does not seem to be affected by contaminated groundwater from the Alabama Plating site, additional hydrologic and water-quality data are needed to fully identify flow paths, the potential for contaminant transport, and water-quality changes through time.

Alabama↗

Storm clouds on Saturn: Lightning-induced chemistry and associated materials consistent with Cassini/VIMS spectra

Thunderstorm activity on Saturn is associated with optically detectable clouds that are atypically dark throughout the near-infrared. As observed by Cassini/VIMS, these clouds are ~20% less reflective than typical neighboring clouds throughout the spectral range from 0.8 ??m to at least 4.1 ??m. We propose that active thunderstorms originating in the 10-20 bar water-condensation region vertically transport dark materials at depth to the ~1 bar level where they can be observed. These materials in part may be produced by chemical processes associated with lightning, likely within the water clouds near the ~10 bar freezing level of water, as detected by the electrostatic discharge of lightning flashes observed by Cassini/RPWS (e.g., Fischer et al. 2008, Space Sci. Rev., 137, 271-285). We review lightning-induced pyrolytic chemistry involving a variety of Saturnian constituents, including hydrogen, methane, ammonia, hydrogen sulfide, phosphine, and water. We find that the lack of absorption in the 1-2 ??m spectral region by lightning-generated sulfuric and phosphorous condensates renders these constituents as minor players in determining the color of the dark storm clouds. Relatively small particulates of elemental carbon, formed by lightning-induced dissociation of methane and subsequently upwelled from depth - perhaps embedded within and on the surface of spectrally bright condensates such as ammonium hydrosulfide or ammonia - may be a dominant optical material within the dark thunderstorm-related clouds of Saturn. ?? 2009 Elsevier Ltd. All rights reserved.

Planetary and Space Science↗

Factors Controlling Pre-Columbian and Early Historic Maize Productivity in the American Southwest, Part 1: The Southern Colorado Plateau and Rio Grande Regions

Maize is the New World's preeminent grain crop and it provided the economic basis for human culture in many regions within the Americas. To flourish, maize needs water, sunlight (heat), and nutrients (e. g., nitrogen). In this paper, climate and soil chemistry data are used to evaluate the potential for dryland (rainon-field) agriculture in the semiarid southeastern Colorado Plateau and Rio Grande regions. Processes that impact maize agriculture such as nitrogen mineralization, infiltration of precipitation, bare soil evaporation, and transpiration are discussed and evaluated. Most of the study area, excepting high-elevation regions, receives sufficient solar radiation to grow maize. The salinities of subsurface soils in the central San Juan Basin are very high and their nitrogen concentrations are very low. In addition, soils of the central San Juan Basin are characterized by pH values that exceed 8.0, which limit the availability of both nitrogen and phosphorous. In general, the San Juan Basin, including Chaco Canyon, is the least promising part of the study area in terms of dryland farming. Calculations of field life, using values of organic nitrogen for the upper 50 cm of soil in the study area, indicate that most of the study area could not support a 10-bushel/acre crop of maize. The concepts, methods, and calculations used to quantify maize productivity in this study are applicable to maize cultivation in other environmental settings across the Americas. ?? 2010 US Government.

Journal of Archaeological Method and Theory↗

Fate, bioavailability and toxicity of silver in estuarine environments

The chemistry and bioavailability of Ag contribute to its high toxicity in marine and estuarine waters. Silver is unusual, in that both the dominant speciation reaction in seawater and the processes important in sorbing Ag in sediments favour enhanced bioavailability. Formation of a stable chloro complex favours dispersal of dissolved Ag, and the abundant chloro complex is available to biota. Sequestration by sediments also occurs, but with relatively slow kinetics. Amorphous aggregated coatings enhance Ag accumulation in sediments, as well as Ag uptake from sediments by deposit feeders. In estuaries, the bioaccumulation of Ag increases 56-fold with each unit of increased Ag concentration in sediments. Toxicity for sensitive marine species occurs at absolute concentrations as low as those observed for any nonalkylated metal, partly because bioaccumulation increases so steeply with contamination. The environmental window of tolerance to Ag in estuaries could be narrower than for many elements.

Marine Pollution Bulletin↗

Major-ion and selected trace-metal chemistry of the Biscayne Aquifer, Southeast Florida

The major-ion and selected trace-metal chemistry of the Biscayne aquifer was characterized as part of the Florida Ground-Water Quality Monitoring Network Program, a multiagency cooperative effort concerned with delineating baseline water quality for major aquifer systems in the State. The Biscayne aquifer is unconfined and serves as the sole source of drinking water for more than 3 million people in southeast Florida. The Biscayne aquifer consists of highly permeable interbedded limestone and sandstone of Pleistocene and Pliocene age underlying most of Dade and Broward Counties and parts of Palm Beach and Monroe Counties. The high permeability is largely caused by extensive carbonate dissolution. Water sampled from 189 wells tapping the Biscayne aquifer was predominantly a calcium bicarbonate type with some mixed types occurring in coastal areas and near major canals. Major - ion is areally uniform throughout the aquifer. According to nonparametric statistical tests of major ions and dissolved solids, the concentrations of calcium, sodium, bicarbonate, and dissolved solids increased significantly with well depth ( 0.05 significance level ), probably a result of less circulation at depth. Potassium and nitrate concentrations decreased significantly with depth. Although the source of recharge to the aquifer varies seasonally, there was no statistical difference in the concentration of major ions in pared water samples from 27 shallow wells collected during wet and dry seasons. Median concentrations for barium, chromium, copper, lead, and manganese were below maximum or secondary maximum contaminant levels set by the US Environmental Protection Agency. The median iron concentration only slightly exceeded the secondary maximum contaminant level. The concentration of barium was significantly related (0.05 significance level) to calcium and bicarbonate concentration. No distinct areal pattern or vertical distribution of the selected trace metals was evident in water from the Biscayne aquifer. Sources for trace metals found in water from the Biscayne aquifer may include local contamination, well-construction techniques, canal - aquifer interactions, and natural occurrence in area soils and rock.

Florida↗

Sources and cycling of major ions and nutrients in Devils Lake, North Dakota

Devils Lake is a saline lake in a large, closed drainage basin in northeastern North Dakota. Previous studies determined that major-ion and nutrient concentrations in Devils Lake are strongly affected by microbially mediated sulfate reduction and dissolution of sulfate and carbonate minerals in the bottom sediments. These studies documented substantial spatial variability in the magnitude of calculated benthic fluxes coincident with the horizontal salinity gradient in Devils Lake. The purpose of the present study is to evaluate seasonal variability in benthic-flux rates, and to understand the effect of these fluxes on the major-ion and nutrient chemistries in Devils Lake between May and October 1991. During the study period, the water column was well mixed, and specific conductance, pH, and temperature did not vary with depth. Dissolved oxygen was enriched near the lake surface due to photosynthesis. Major-ion concentrations and nutrient concentrations did not vary with depth. Because the water-quality data were obtained during open-water periods, the vertical profiles reflect well-mixed conditions. However, the first and last profiles for the study period did document near-bottom maxima of major cations. Secchi-disk depth varied from 0.82 meter on May 7,1991, to 2.13 meters on June 5, 1991. The mean Secchi-disk depth during the study period was 1.24 meters. Seasonal variations in Secchi-disk depths were attributed to variations in primary productivity and phytoplankton communities. Nutrient cycles in Devils Lake were evaluated using gross primary productivity rate data, sediment trap data, and major-ion and nutrient benthic-flux rate data. Gross primary productivity rate was smallest in May (0.076 gram of carbon per square meter per day) and largest in September (1.8 grams of carbon per square meter per day). Average gross primary productivity for the study period was 0.87 gram of carbon per square meter per day. Average gross primary productivity is consistent with historic data from Devils Lake and with data from other eutrophic lakes. The average flux of organic carbon for the study period was 12 grams per square meter per day. The calculated carbon to nitrogen to phosphorus ratio (317:25:1) is similar to the Redfield ratio (106:16:1); therefore, most organic matter probably is derived from lacustrine phytoplankton. Calculated benthic-flux rates indicated that bottom sediments are important sources of majorions and nutrients to Devils Lake. Only one of the cores collected during this study indicated a net sulfate flux from the lake into the sediments. Seasonal variations in major-ion and nutrient benthic fluxes generally were small. However, there were important differences between the calculated benthic fluxes for this study and the calculated benthic fluxes for 1990. Calculated benthic fluxes of bicarbonate, ammonia, and phosphorus for this study were smaller than calculated benthic fluxes for 1990. The large differences between fluxes for 1990 and 1991 were attributed to calm, stratified water-column conditions in 1990 and well-mixed water-column conditions in 1991. The role of benthic fluxes in the chemical mass balances in Devils Lake was evaluated by calculating response times for major ions and nutrients in Devils Lake. The calculated response times for major ions in Devils Lake ranged from 6.7 years for bicarbonate to 34 years for sulfur (as 804). The response times for major ions are significantly shorter than previous estimates that did not include benthic fluxes. In addition, the relatively short response times for nitrogen (4.2 years) and phosphorus (0.95 year) indicate that nutrients are recycled rapidly between bottom sediments and the lake. During the study period, benthic fluxes were the dominant source of major ions and nutrients to Devils Lake and greatly reduced the response times of all major ions and nutrients for Devils Lake. As a result, bottom-sediment processes appear to buffer major-ion and nutrient concentrations in the lake. Any future attempt to evaluate water quality in Devils Lake should include the effects of bottom-sediment processes.

Water-Resources Investigations Report↗

Geophysical identification of potential groundwater – surface water interactions in the Bonita Peak Mining District, San Juan County, Colorado

This report includes the results and interpretation of geophysical investigations to aid in the location, identification, and conceptual site model (CSM) development of the near surface groundwater and surface water hydrology of the Upper Cement Creek and California Gulch of the Animas Rivers within the Bonita Peak Mining Districts (BPMD). Mine influenced water (MIW) from numerous mine adits within the BPMD has altered the geochemistry and ecology of these ground and surface waters. Many studies of varying scales have investigated the geology, hydrogeology, geochemistry, and aqueous chemistry of these adits and impacted areas. Field investigations using non-invasive geophysical methods were conducted in the summer of 2019 to aid in identifying potential groundwater inputs to these streams and further the CSM of the near surface within and along these streams. Two field deployments were completed in August and September of 2019. In August 2019, Phase 1 was completed using multifrequency electromagnetic induction (EMI) and thermal infrared imaging (TIR) to measure the bulk electrical conductivity, magnetic susceptibility, and the temperature response at known and suspected groundwater seeps into the Upper Cement Creek and California Gulch stretches of these alpine streams. Results and interpretation from Phase 1 were used to co-locate stretches of these streams for further detailed fiber optic distributed temperature system (FODTS) monitoring of the temperature dynamics for submeter identification of potential groundwater seeps during Phase 2. Phase 2 included additional EMI measurements, FODTS measurements, and repeated some Phase 1 measurements for improved data quality. All these data were used for the combined qualitative interpretation identifying seep locations. The data from both Phase 1 and Phase 2 are available in the USGS data release at: https://www.sciencebase.gov/catalog/item/5f18a30082cef313ed84879b. These data include detailed near-surface electrical conductivity and magnetic susceptibility mapping, discrete TIR imaging, and several kilometers of FODTS data. These data were georeferenced and used to identify potential groundwater seeps into these streams. The results indicate a complex near surface geophysical and hydrogeologic regime. Seeps are classified and spatially correlated to the EMI, TIR, and geochemical sampling results. This report is a thorough compilation of the geophysical field efforts in the summer of 2019, the data processing, and interpretations of these data. These data alone should not be used for final interpretations of the complex hydrogeology within these alpine systems. Rather, these data should be combined with other known data from various investigations to further refine the CSM and guide decisions for future investigations, watershed protective measures, and other site decisions. Geographical information system (GIS) layers of these results are available to project managers for such integration and combined interpretations.

Colorado↗

Integrated assessment of runoff from livestock farming operations: analytical chemistry, in vitro bioassays, and in vivo fish exposures

Animal waste from livestock farming operations can contain varying levels of natural and synthetic androgens and/or estrogens, which can contaminate surrounding waterways. In the present study, surface stream water was collected from 6 basins containing livestock farming operations. Aqueous concentrations of 12 hormones were determined via chemical analyses. Relative androgenic and estrogenic activity was measured using in vitro cell assays (MDA-kb2 and T47D-Kbluc assays, respectively). In parallel, 48-h static-renewal in vivo exposures were conducted to examine potential endocrine-disrupting effects in fathead minnows. Mature fish were exposed to surface water dilutions (0%, 25%, 50%, and 100%) and 10-ng/L of 17α-ethynylestradiol or 50-ng/L of 17β-trenbolone as positive controls. Hepatic expression of vitellogenin and estrogen receptor α mRNA, gonadal ex vivo testosterone and 17β-estradiol production, and plasma vitellogenin concentrations were examined. Potentially estrogenic and androgenic steroids were detected at low nanogram per liter concentrations. In vitro estrogenic activity was detected in all samples, whereas androgenic activity was detected in only 1 sample. In vivo exposures to the surface water had no significant dose-dependent effect on any of the biological endpoints, with the exception of increased male testosterone production in 1 exposure. The present study, which combines analytical chemistry measurements, in vitro bioassays, and in vivo fish exposures, highlights the integrated value and future use of a combination of techniques to obtain a comprehensive characterization of an environmental chemical mixture.

Arkansas, Iowa, Kentucky, New York, Wisconsin↗

Volcanic gas monitoring

Introduction As magma rises through the crust, decreasing pressure conditions allow volatiles to exsolve from the magma. These volatiles then migrate upward through the crust, where they can be stored at shallower levels or escape to the atmosphere. Rising magma also heats rock masses beneath volcanic centers, causing water in shallow aquifers and hydrothermal systems to boil and release additional gases and steam (see chapter F , this volume; Ingebritsen and Hurwitz, 2024). The chemistry and quantity of gases that reach the surface during periods of quiescence or volcanic unrest can reveal that gas-rich magma is ascending, crystallizing, or alternatively stalling, with important implications for volcanic hazard (for example, Sutton and others, 1992; Aiuppa and others, 2007, 2021; Werner and others, 2009, 2011, 2012; Moretti and others, 2013; de Moor and others, 2016; Lewicki and others, 2019; Edmonds and others, 2022; Kern and others, 2022; Kunrat and others, 2022). Most volcanoes in Alaska and the western United States are characterized by weak degassing, with one or more low-temperature fumaroles (typically near the local boiling temperature of water) and connect to a deeper and sometimes extensive hydrothermal system (for example, McGee and others, 2001; Symonds and others, 2003a, b). Hydrothermal systems will affect the chemistry of rising gases exsolved from deeper magma (Symonds and others, 2001), including sulfur dioxide (SO 2 ), hydrogen chloride (HCl), and water vapor (for example, Doukas and Gerlach, 1995; Gerlach and others, 1998, 2008; Symonds and others, 2001; Werner and others, 2013). As an example, depending on factors such as temperature, pressure, and oxidation state, rising SO 2 will react with groundwater to form hydrogen sulfide (H 2 S) gas, dissolved sulfate (SO 4 2− ), or elemental sulfur (Christenson, 2000; Symonds and others, 2001; Werner and others, 2008). The reaction and dissolution of SO 2 into shallow groundwater is commonly referred to as scrubbing, and can reduce the likelihood that ascending, degassing magma can be detected. Carbon dioxide, however, in addition to exsolving from magma early in the ascent process, is not easily removed by hydrothermal fluids (Lowenstern, 2001). As scrubbing and other processes take place, the SO 2 /H 2 S, CO 2 /SO 2 , and CO 2 /H 2 S ratios may change. High rates of SO 2 emission indicate that magma has moved to relatively shallow levels in the volcano and that the system has heated up enough to establish dry pathways from depth to the surface. Monitoring multiple gas species and the total output of those species is thereby useful for volcano monitoring during both periods of quiescence, to establish background degassing conditions, and during unrest, when gas geochemistry and emission rates can provide information on changing conditions, such as magma ascent. To provide context for multidisciplinary volcano forecasts, we focus on the following two key required capabilities: (1) characterizing baseline geochemistry and gas discharge from volcanoes and volcanic regions and (2) monitoring changes in gas geochemistry and discharge to inform forecasts of volcanic eruptions and their effects. Sufficient baseline data must be collected to identify and interpret anomalous degassing associated with volcanic unrest (for example, Sorey and others, 1998; Rouwet and others, 2014). Differences in volcano type, baseline degassing rates, local hydrology, and geography (for example, high versus low latitude) will result in a different baseline for each volcano. Volcanoes of any threat level that exhibit one or more degassing phenomena would ideally be monitored by techniques needed to establish baseline degassing data, with the sampling frequency of baseline data dictated by the threat level (table E1). Additional monitoring techniques become necessary during periods of unrest. In general, three of the most important techniques for gas monitoring are (1) direct sampling of fumarole, spring, and soil gases for laboratory geochemical measurements, (2) measurements of the chemical composition of the volcanic plume and emission rates of major gas species (for example, H 2 O, CO 2 , SO 2 , and H 2 S) by satellite, airborne, or ground-based techniques, and (3) measurements of diffuse emissions of CO 2 and other gases through soils. Various methods and instruments may be useful both for baseline studies and during unrest.

Scientific Investigations Report↗