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USGS2000

Hydrogeologic setting and potential for denitrification in ground water, Coastal Plain of southern Maryland

The types and distribution of Coastal Plain sediments in the Patuxent River Basin may contribute to relatively low concentrations of nitrate (typically less than 1 milligram per liter) in stream base flow because of the chemical reduction of dissolved nitrate (denitrification) in ground water. Water chemistry data from synoptic stream base-flow surveys in the Patuxent River Basin show higher dissolved nitrate concentrations in the Piedmont than in the Coastal Plain section of the watershed. Stream base flow reflects closely the chemistry of ground water discharging from the surficial (unconfined) aquifer to the stream. Because land use in the sampled subbasins is virtually the same in each section, differences in the physical and geochemical characteristics of the surficial aquifer may explain the observed differences in water chemistry. One possible cause of lower nitrate concentrations in the Coastal Plain is denitrification within marine sediments that contain chemically reduced compounds. During denitrification, the oxygen atoms on the nitrate (N0 3 -) molecule are transferred to a reduced compound and N gas is produced. Organic carbon and ferrous iron (Fe 2+ ), derived from the dissolution of minerals such as pyrite (FeS 2 ) and glauconite (an iron aluminosilicate clay), can act as reducing substrates; these reduced chemical species are common in the marine and estuarine deposits in Southern Maryland. The spatial distribution of geologic units and their lithology (sediment type) has been used to create a map of the potential for denitrification of ground water in the surficial aquifer of the Coastal Plain in Southern Maryland.

Maryland↗

USGS1979

Geology, petrology, and chemistry of the Leadville Dolomite: host for uranium at the Pitch Mine, Saguache County, Colorado

Newly documented uranium ore in the Pitch Mine occurs chiefly in brecciated Mississippian Leadville Dolomite along the Chester reverse fault zone, and to a lesser extent in sandstone, siltstone, and carbonaceous shale of the Pennsylvanian Belden Formation and in Precambrian granitic rocks and schist. Uranium-mineralized zones are generally thicker, more consistent, and of higher grade in dolomite than in other hosts, and roughly 50 percent of the new reserves are in dolomite. Strong physical control by dolomite is evident, as this is the only lithology that is pervasively brecciated within the fault slices that make up the footwall of the reverse fault zone. Other lithologies tend to either remain unbroken or undergo ductile deformation. Chemical controls are subtle and appear to involve chiefly formation of FeS2 as pyrite and marcasite, which accompany uranium. Leadville Dolomite in the area is about 130 m thick and is predominantly nonfossiliferous dolomicrite. In the Pitch Mine, Leadville Dolomite is bound by faults and maximum known thickness is about 17 m. Mud texture, paucity of fossils and other allochems, thin laminations, and probable algal mat structures suggest sedimentation in a tidal-flat (possibly supratidal) environment. Preservation of mud texture and lack of replacement features indicate that dolomitization was an early, prelithification process, as in modern tidal flats, and produced a chemically and texturally uniform rock over tens of meters with relatively few limestone beds surviving. The sedimentary and diagenetic environment of the tidal-flat dolomite, apparently most favorable for uranium deposits, probably obtained over a large area and should consistute an exploration target over a broad area of central Colorado. Carbonate rocks of the Belden Formation, in contrast to those of the Leadville, contain calcite in great excess of dolomite, more than 5 percent silt-size quartz and clay, and abundant fossils and oolites. Belden limestones (sandy micrite and sandy wackestone) probably were deposited in an intertidal or subtidal environment. Very little uranium ore occurs in these rocks. Chemical aspects, such as the iron, sulfur, and organic carbon contents, are very similar to those of Leadville dolomites, and hence seem favorable, but Belden limestones generally are only mildly fractured. The minor-element content of ore-bearing dolomites is generally normal judging from the relatively scarce data yet published for comparable rocks. Elements enriched in ore include iron, sulfur, molybdenum, and lead. One surface expression of ore in dolomite is ocher-colored, leached, porous gossan that is characterized by residual silica and limonite and by high radioactivity but low chemical uranium content.

Open-File Report↗

USGS2016

Assessing open-system behavior of 14C in terrestrial gastropod shells

In order to assess open-system behavior of radiocarbon in fossil gastropod shells, we measured the 14 C activity on 10 aliquots of shell material recovered from Illinoian (~190–130 ka) and pre-Illinoian (~800 ka) loess and lacustrine deposits in the Midwestern USA. Eight of the 10 aliquots yielded measurable 14 C activities that ranged from 0.25 to 0.53 percent modern carbon (pMC), corresponding to apparent 14 C ages between 48.2 and 42.1 ka. This small level of open-system behavior is common in many materials that are used for 14 C dating (e.g. charcoal), and typically sets the upper practical limit of the technique. Two aliquots of gastropod shells from the Illinoian-aged Petersburg Silt (Petersburg Section) in central Illinois, USA, however, yielded elevated 14 C activities of 1.26 and 1.71 pMC, which correspond to apparent 14 C ages of 35.1 and 32.7 ka. Together, these results suggest that while many fossil gastropods shells may not suffer from major (>1%) open-system problems, this is not always the case. We then examined the mineralogy, trace element chemistry, and physical characteristics of a suite of fossil and modern gastropod shells to identify the source of contamination in the Petersburg shells and assess the effectiveness of these screening techniques at identifying samples suitable for 14 C dating. Mineralogical (XRD) and trace element analyses were inconclusive, which suggests that these techniques are not suitable for assessing open-system behavior in terrestrial gastropod shells. Analysis with scanning electron microscopy (SEM), however, identified secondary mineralization (calcium carbonate) primarily within the inner whorls of the Petersburg shells. This indicates that SEM examination, or possibly standard microscope examination, of the interior of gastropod shells should be used when selecting fossil gastropod shells for 14 C dating.

Radiocarbon↗

USGS1997

Chain of custody; recommendations for acceptance and analysis of evidentiary geochemical samples

Personnel from the Analytical Chemistry Services Group (ACSG), Mineral Resource Survey Program, formed a team to determine the policies for acceptance and analysis of geochemical samples. This team contacted law enforcement agencies that handle litigious samples, laboratories that work with samples of special nature, and the Solicitor General, Department of the Interior. Using the knowledge from these agencies as well as the expertise of ACSG personnel, sample control routine procedures, sample control evidentiary procedures, personnel policy governing chain-of-custody samples, and the general polices governing physical security of chain-of custody samples have been enacted.

Circular↗

USGS2010

Regional and grain size influences on the geochemistry of soil at Gusev Crater

Congruous with earlier work, Martian soil along the Spirit Rover's traverse at Gusev crater can be divided into three broad groups by size: fines (<150 μ m), sand, and a mix of various grain sizes. The key chemical observation is greater homogeneity in fines relative to the other two, consistent with regional‐ and global‐scale sampling of chemical compositions by finer particle sizes. The mix class is generally more heterogeneous as are samples from the Columbia Hills within each class. Variation in the trace element Ni is consistent with a CI contribution not exceeding 3%, while that of Ti is compatible with Fe‐Ti oxide enrichment not exceeding 3%. Physical mixing models are poorly supported. Among many potential binary and three‐component mixing models, only two show some consistency with the soil data: typical fines with the opaline Si end‐member identified at Home Plate and typical fines with sulfates (bearing a variable mix of Ca, Fe, and Mg cations). We also infer that binary mixing transcends classes, contrasting strongly with terrestrial sediments, and that mixing trends are consistent with significant nonmixing contributions, perhaps including localized chemical alteration. The decoupling between chemistry and grain size classes also suggests that processes linking composition with grain size, such as heavy mineral sorting, may have been minimal or absent entirely. The primary exception to this is the correlation between Cl and Si, Cl‐S, and Al‐Si, which is strongest in the fines class.

Journal of Geophysical Research E: Planets↗

USGS2013

Effects of depletion sampling by standard three-pass pulsed DC electrofishing on blood chemistry parameters of fishes from Appalachian streams

Adverse effects on fishes captured by electrofishing techniques have long been recognized, although the extent of associated physical injury and behavioral alterations are highly variable and dependent on a number of factors. We examined the effects of three-pass pulsed DC (PDC) electrofishing on two salmonid species (Rainbow Trout Oncorhynchus mykiss and Brook Trout Salvelinus fontinalis) and five other genera (Green Sunfish Lepomis cyanellus, Potomac Sculpin Cottus girardi, Fathead Minnow Pimephales promelas, Largemouth Bass Micropterus salmoides, and Channel Catfish Ictalurus punctatus) common to Appalachian streams. We examined the corresponding effects of PDC electroshock on the following physiological indicators of stress and trauma: blood glucose and serum lactate, as well as on other blood chemistry, namely, enzymes, electrolytes, minerals, and proteins. All species demonstrated physiological responses to PDC electroshock, indicated by the biochemical differences in blood parameters in unshocked and shocked groups of fish with or without gross evidence of hemorrhagic trauma. Serum lactate was the most consistent indicator of these effects. Significant differences in whole blood glucose levels were also noted in treatment groups in all species except Green Sunfish, although the patterns observed were not as consistent as for serum lactate. Elevations in the serum enzymes, aspartate aminotransferase and creatine kinase, in the electroshocked fish occurred only in the two salmonid species. In many instances, although blood parameters were elevated in electroshocked fish compared with the unshocked controls for a given species, there were no differences in those levels in electroshocked fish based on the presence of gross hemorrhagic trauma to axial musculature. While some of the blood parameters examined correlated with both the occurrence of electroshock and the resultant tissue injury, there was no apparent link between the altered blood chemistry and increased mortality 30 d after electrofishing.

Appalachian Mountains↗

USGS2013

Hydrologic controls on the transport and cycling of carbon and nitrogen in a boreal catchment underlain by continuous permafrost

Boreal ecosystems represent a large carbon (C) reservoir and a substantial source of greenhouse gases. Hydrologic conditions dictate whether C leached from boreal soils is processed in catchments or flushed to less productive environments via the stream. This study quantified hydrologic and biogeochemical C loss from a boreal catchment underlain by frozen silt, where flowpaths may deepen as the active layer thaws over the summer. We hypothesized a decrease in the magnitude of C mineralization over the summer associated with changing flowpaths and decreasing hydrologic connectivity, organic matter lability, and nitrogen (N) availability. Conservative tracers were used to partition C and N loss between catchment export and biogeochemical processing. Coupling tracers with tributary and porewater chemistry indicated C and N cycling in soil flowpaths, with an exponential decrease over the summer. Nitrate was primarily reduced in hillslope flowpaths and the lack of N reaching the stream appeared to limit C mineralization. Stream export accounted for the greatest loss of C, removing 247 and 113 mol hr −1 in the early and late summer, respectively. Reactivity was related to hydrologic connectivity between the soils and stream, which was greatest early in the summer and following a large flood. While a warming climate may increase storage potential in thawed soils, the early‐season flush of labile material and late‐season runoff through mineral flowpaths may maintain high C export rates. Therefore, we highlight physical export as a dominant cause of aqueous C loss from silty catchments as the Arctic continues to thaw.

Journal of Geophysical Research G: Biogeosciences↗

USGS1984

Regional investigations of soil and overburden analysis and plant uptake of metals

Regional studies on the bioavailability of metals at native and disturbed sites were conducted over the past seven years by the USGS. The work was concentrated in the Fort Union, Powder River, and Green River coal resource regions where measures of extractable metals in soils were found to have limited use in predicting metal levels in plants. Correlations between Cu, Fe, and Zn in plants and extractable (DTPA, EDTA, and oxalate) or total levels in native A- and C-horizons of soil were occasionally significant. A simple linear model is generally not adequate, however, in estimating element uptake by plants. Prediction capabilities were improved when a number of soil chemical and physical parameters were included as independent variables in a stepwise linear multiple regression analysis; however, never more than 54% of the total variability in the data was explained by the equations for these metals. Soil pH was the most important variable relating soil chemistry to plant chemistry. This relation was always positive and apparently a response to soil levels of metal carbonates and not Fe and Mn oxides. Studies that compared the metal uptake by rehabilitation species to extractable (DTPA) metal levels in mice soils produced similar results. ?? 1984 Science and Technology Letters.

Minerals and the Environment↗

USGS2003

Reactive-transport simulation of phosphorus in the sewage plume at the Massachusetts Military Reservation, Cape Cod, Massachusetts

The subsurface transport of phosphorus introduced by the disposal of treated sewage effluent to ground-infiltration disposal beds at the Massachusetts Military Reservation on western Cape Cod was simulated with a three-dimensional reactive-transport model. The simulations were used to estimate the load of phosphorus transported to Ashumet Pond during operation of the sewage-treatment plant from 1936 to 1995 and for 60 years following cessation of sewage disposal. The model accounted for spatial and temporal changes in water discharge from the sewage-treatment plant, ground-water flow, transport of associated chemical constituents, and a set of chemical reactions, including phosphorus sorption on aquifer materials, dissolution and precipitation of iron- and manganese-oxyhydroxide and iron phosphate minerals, organic carbon sorption and decomposition, cation sorption, and irreversible denitrification. The flow and transport in the aquifer were simulated by using parameters consistent with those used in previous flow models of this area of Cape Cod, except that numerical dispersion was much larger than the physical dispersion estimated in previous studies. Sorption parameters were fit to data derived from phosphorus sorption and desorption laboratory column experiments. Rates of organic carbon decomposition were adjusted to match the location of iron concentrations in an anoxic iron zone within the sewage plume. The sensitivity of the simulated load of phosphorus transported to Ashumet Pond was calculated for a variety of processes and input parameters. Model limitations included large uncertainties associated with the loading of the sewage beds, the flow system, and the chemistry and sorption characteristics in the aquifer. The results of current model simulations indicate a small load of phosphorus transported to Ashumet Pond during 1965-85, but this small load was particularly sensitive to model parameters that specify flow conditions and the chemical process by which non-desorbable phosphorus is incorporated in the sediments. The uncertainties were large enough to make it difficult to determine whether loads of phosphorus transported to Ashumet Pond in the 1990s were greater or less than loads during the previous two decades. The model simulations indicate substantial discharge of phosphorus to Ashumet Pond after about 1965. After the period 2000-10 the simulations indicate that the load of phosphorus transported to Ashumet Pond decreases continuously, but the load of phosphorus remains substantial for many decades. The current simulations indicate a peak in phosphorus discharge to Ashumet Pond of about 1,000 kilograms per year during the 1990s; however, comparisons of simulated phosphorus concentrations with measured concentrations in 1993 indicate that the peak in phosphorus load transported to Ashumet Pond may be larger and moving more quickly in the model simulations than in the aquifer. The results of the three-dimensional reactive-transport simulations are consistent with the loading history, experimental laboratory data, and field measurements. The results of the simulations adequately reproduce the spatial distribution of phosphorus concentrations measured in 1993, the magnitude of changes in phosphorus concentration with time in a profile near the disposal beds following cessation of sewage disposal, the observed iron zone in the sewage plume, the approximate flow of treated sewage effluent into Ashumet Valley, and laboratory-column data for phosphorus sorption and desorption.

Massachusetts↗

USGS2011

Groundwater chemistry near an impoundment for produced water, Powder River Basin, Wyoming, USA

The Powder River Basin is one of the largest producers of coal-bed natural gas (CBNG) in the United States. An important environmental concern in the Basin is the fate of the large amounts of groundwater extracted during CBNG production. Most of this produced water is disposed of in unlined surface impoundments. A 6-year study of groundwater flow and water chemistry at one impoundment, Skewed Reservoir, has produced the most detailed data set for any impoundment in the Basin. Data were collected from a network of 21 observation wells and three suction lysimeters. A groundwater mound formed atop bedrock within initially unsaturated, unconsolidated deposits underlying the reservoir. Heterogeneity in physical and chemical properties of sediments resulted in complex groundwater flow paths and highly variable groundwater chemistry. Sulfate, bicarbonate, sodium, and magnesium were the dominant ions in all areas, but substantial variability existed in relative concentrations; pH varied from less than 3 to more than 9, and total dissolved solids concentrations ranged from less than 5000 to greater than 100,000 mg/L. Selenium was a useful tracer of reservoir water; selenium concentrations exceeded 300 μg/L in samples obtained from 18 of the 24 sampling points. Groundwater travel time from the reservoir to a nearby alluvial aquifer (a linear distance of 177 m) was calculated at 474 days on the basis of selenium concentrations. The produced water is not the primary source of solutes in the groundwater. Naturally occurring salts and minerals within the unsaturated zone, dissolved and mobilized by infiltrating impoundment water, account for most of the solute mass in groundwater. Gypsum dissolution, cation-exchange, and pyrite oxidation appear to be important reactions. The complex geochemistry and groundwater flow paths at the study site underscore the difficulty in assessing effects of surface impoundments on water resources within the Powder River Basin.

Wyoming↗

USGS1948

Mineralogy and petrology of the currant creek magnesite deposits and associated rocks of Nevada

Cryptocrystalline magnesite occurs as relatively small dense, white masses in a Tertiary volcanic tuff, here named the Currant tuff, in White Pine and Nye counties, 29 miles southwest of Ely, Nevada. The deposits are small, but some of the magnesite is of very high quality with almost no iron or aluminum. However, much of the magnesite is mixed with dolomite and calcite, and a serpentinelike mineral occurs in one of the deposits in sufficient abundance to be of possible use in ceramics. In scattered areas the tuff has been altered by solutions rich in magnesium and bicarbonic acid to dolomite, magnesite, magnesium silicate, and calcite. Mineral and chemical characteristics are the same throughout the entire rock assemblage of flows and tuffs, suggesting that all the rocks have been derived from the same parent magma. The tuff formation, which ranges in thickness from a few feet to over 400 feet, occurs between two groups of volcanic flows here referred to as the lower volcanics and the upper volcanics. The lower volcanics is composed mainly of flows of hypersthene dacite, but in the southwestern part of the area flows of a hypersthene andesite of balsaltic habit occur between the dacite and the overlying Currant tuff. The upper volcanics which overlie the Currant tuff consist of porphyritic quartz latite and an overlying massive latite crystal tuff. The Currant tuff containing the magnesite has both unmodified and reworked tuff members. The formation of hydrothermal dolomite, magnesite, and deweylite is discussed in detail, and the physical chemistry of solutions containing calcium, magnesium, and carbon dioxide is applied in an explanation of the origin of magnesium-rich solutions.

Nevada↗

USGS2011

An approach to modeling coupled thermal-hydraulic-chemical processes in geothermal systems

Interactions between hydrothermal fluids and rock alter mineralogy, leading to the formation of secondary minerals and potentially significant physical and chemical property changes. Reactive transport simulations are essential for evaluating the coupled processes controlling the geochemical, thermal and hydrological evolution of geothermal systems. The objective of this preliminary investigation is to successfully replicate observations from a series of hydrothermal laboratory experiments [Morrow et al., 2001] using the code TOUGHREACT. The laboratory experiments carried out by Morrow et al. [2001] measure permeability reduction in fractured and intact Westerly granite due to high-temperature fluid flow through core samples. Initial permeability and temperature values used in our simulations reflect these experimental conditions and range from 6.13 × 10−20 to 1.5 × 10−17 m2 and 150 to 300 °C, respectively. The primary mineralogy of the model rock is plagioclase (40 vol.%), K-feldspar (20 vol.%), quartz (30 vol.%), and biotite (10 vol.%). The simulations are constrained by the requirement that permeability, relative mineral abundances, and fluid chemistry agree with experimental observations. In the models, the granite core samples are represented as one-dimensional reaction domains. We find that the mineral abundances, solute concentrations, and permeability evolutions predicted by the models are consistent with those observed in the experiments carried out by Morrow et al. [2001] only if the mineral reactive surface areas decrease with increasing clay mineral abundance. This modeling approach suggests the importance of explicitly incorporating changing mineral surface areas into reactive transport models.

Conference Paper↗

USGS2012

Characterization of major-ion chemistry and nutrients in headwater streams along the Appalachian National Scenic Trail and within adjacent watersheds, Maine to Georgia

An inventory of water-quality data on field parameters, major ions, and nutrients provided a summary of water quality in headwater (first- and second-order) streams within watersheds along the Appalachian National Scenic Trail (Appalachian Trail). Data from 1,817 sampling sites in 831 catchments were used for the water-quality summary. Catchment delineations from NHDPlus were used as the fundamental geographic units for this project. Criteria used to evaluate sampling sites for inclusion were based on selected physical attributes of the catchments adjacent to the Appalachian Trail, including stream elevation, percentage of developed land cover, and percentage of agricultural land cover. The headwater streams of the Appalachian Trail are generally dilute waters, with low pH, low acid neutralizing capacity (ANC), and low concentrations of nutrients. The median pH value was slightly acidic at 6.7; the median specific conductance value was 23.6 microsiemens per centimeter, and the median ANC value was 98.7 milliequivalents per liter (μeq/L). Median concentrations of cations (calcium, magnesium, sodium, and potassium) were each less than 1.5 milligrams per liter (mg/L), and median concentrations of anions (bicarbonate, chloride, fluoride, sulfate, and nitrate) were less than 10 mg/L. Differences in water-quality constituent levels along the Appalachian Trail may be related to elevation, atmospheric deposition, geology, and land cover. Spatial variations were summarized by ecological sections (ecosections) developed by the U.S. Forest Service. Specific conductance, pH, ANC, and concentrations of major ions (calcium, chloride, magnesium, sodium, and sulfate) were all negatively correlated with elevation. The highest elevation ecosections (White Mountains, Blue Ridge Mountains, and Allegheny Mountains) had the lowest pH, ANC, and concentrations of major ions. The lowest elevation ecosections (Lower New England and Hudson Valley) generally had the highest pH, ANC, and concentrations of major ions. The geology in discrete portions of these two ecosections was classified as containing carbonate minerals which has likely influenced the chemical character of the streamwater. Specific conductance, pH, ANC, and concentrations of major ions (calcium, chloride, magnesium, sodium, and sulfate) were all positively correlated with percentages of developed and agricultural land uses at the lower elevations of the central region of the Appalachian Trail (including the Green-Taconic-Berkshire Mountains, Lower New England, Hudson Valley, and Northern Ridge and Valley ecosections). The distinctly different chemical character of the streams in the central sections of the Appalachian Trail is likely related to the lower elevations, the presence of carbonate minerals in the geology, higher percentages of developed and agricultural land uses, and possibly the higher inputs of sulfate and nitrate from atmospheric deposition. Acid deposition of sulfate and nitrate are important influences on the acid-base chemistry of the surface waters of the Appalachian Trail. Atmospheric deposition estimates are consistently high (more than 18 kilograms per hectare (kg/ha) for sulfate, and more than 16 kg/ha for nitrate) at both the highest and lowest elevations. However, the lowest elevation (Green-Taconic-Berkshire Mountains, Lower New England, Hudson Valley, Northern Glaciated Allegheny Plateau, and Northern Ridge and Valley ecosections) included the largest spatial area of sustained high estimates of atmospheric deposition. Calcium-bicarbonate was the most frequently calculated water type in the Lower New England and Hudson Valley ecosections. In the northern and southern sections of the Appalachian Trail mix-cation water types were most prevalent and sulfate was the predominate anion. The predominance of the sulfate anion in the surface waters of the northern and southern ecosections likely reflects the influence of sulfate deposition. Although the central portion of the Appalachian Trail has the largest spatial area of high atmospheric acid deposition, the lower ionic strength waters in the northern and southern ecosections of the Appalachian Trail may have been more adversely affected by acid deposition. The low ionic strength of the streams in the White Mountains, Blue Ridge Mountains, and Allegheny Mountains ecosections makes parts of these regions susceptible to seasonal or event-driven episodic acidification, which can be detrimental to health of aquatic and terrestrial ecosystems. Median catchment ANC values were classified into three groups - acidic, sensitive, and insensitive. The White Mountains, Blue Ridge Mountains, and Allegheny Mountains ecosections included the highest frequency of catchments classified as acidic or sensitive. More than 56 percent of the catchments from the White Mountains ecosection were classified as sensitive to acidic inputs. In the Blue Ridge ecosection, 1.6 percent of the catchments were classified as acidic, and 38.2 percent of the catchments were classified as sensitive to acidic inputs. In the Allegheny Mountains ecosection, 17.6 percent of the catchments were classified as acidic, and 29.4 percent of the catchments were classified as sensitive to acidic inputs. Median concentrations of nitrogen species were less than 0.4 mg/L, and median concentrations of total phosphorus were less than 0.02 mg/L along the Appalachian Trail. A comparison of median catchment concentrations of nutrients to estimated national background concentrations demonstrated that concentrations along the Appalachian Trail are generally lower. A comparison of median concentrations of total nitrogen and total phosphorus to the U.S. Environmental Protection Agency's (USEPA) nutrient criteria for the Eastern U.S. ecoregions showed that the concentrations of total nitrogen in the northern section of the Appalachian Trail were generally higher than the USEPA criterion. Similarly, median concentrations of total phosphorus in the southern regions of the Appalachian Trail were approximately twice as high as USEPA criteria. Sections of the Appalachian Trail are adjacent to modest amounts of agricultural and developed land areas. These nonforested land areas may be contributing to the percentage of catchments in which concentrations of total nitrogen and total phosphorus are higher than USEPA nutrient ecoregion criteria.

Connecticut, Georgia, Maine, Massachusetts, Maryla↗

USGS2018

Geochemistry and microbiology of groundwater and solids from extraction and monitoring wells and their relation to well efficiency at a Federally operated confined disposal facility, East Chicago, Indiana

In cooperation with the U.S. Army Corps of Engineers, Chicago District, the U.S. Geological Survey investigated the processes affecting water quality, geochemistry, and microbiology in representative extraction and monitoring wells at a confined disposal facility (CDF) in East Chicago, Indiana. The CDF is a 140-acre Federally-managed facility that was the former location of an oil refinery and is now used for the long-term disposal and storage of dredge material from the Indiana Harbor and Indiana Harbor Canal. Residual petroleum hydrocarbons and leachate from the CDF are contained within the facility by use of a groundwater cutoff wall. The wall consists of a soil-bentonite slurry and a gradient control system made up of an automated network of 96 extraction wells, 42 monitoring wells, and 2 ultrasonic sensors that maintain an inward hydraulic gradient at the site. The pumps in the extraction wells require vigilant maintenance and must be replaced when unable to withdraw water at a rate sufficient to maintain the required inward gradient. The wells are screened in the Calumet aquifer, a coarse-grained sand and gravel unit that extends approximately 35 feet below the land surface and is not utilized for drinking-water supply at the CDF or in the surrounding area. This study was initiated to identify the cause of decreased pump discharges and to identify potential mitigation strategies. For this study, the U.S. Geological Survey collected groundwater and solids from monitoring and extraction wells. Groundwater samples were collected during June 2014 for precautionary health screening and on four occasions during September 2014 through November 2014. Groundwater samples collected from two extraction wells during June 2014 were analyzed for concentrations of anthropogenic organic constituents. During September through November 2014, groundwater samples were collected from one additional extraction well, and samples from three monitoring wells were analyzed for concentrations of inorganic and organic constituents, dissolved gases, and bacterial abundance and diversity. Solid samples were collected during April 2014, during September 2014 through November 2014, and during November 2016. Solid samples were collected from the exterior of extraction-well pumps and as flocculent from water samples. Solid samples were collected from 10 wells, including 1 extraction well and 3 monitoring wells sampled for water quality. Solid samples were analyzed for mineralogy, solid-phase habit, geochemistry, and organic composition. The following is a list of observations that were made during this study: (1) the water quality is substantially variable among the six well locations sampled as part of this study—lower (more negative) redox values and higher concentrations of many constituents (including calcium, magnesium, sodium, and sulfate) and properties (including dissolved solids, hardness, and turbidity) were detected in sampled wells located near the extraction wells with the highest frequency of failure; (2) water-level drawdown is variable between extraction wells—wells with the greatest drawdown may pull deeper groundwater into the borehole; (3) dissolved gas results indicate reducing oxidation-reduction processes in the aquifer material that can feasibly contribute iron, carbon dioxide, and other byproducts from hydrocarbon degradation to precipitates and solids that accumulate on and impair pump operation; (4) crystalline and amorphous solid-phase minerals are precipitating in the borehole; (5) several types of bacteria are present in water pumped from extraction wells and are likely responsible for bonding mineral and microbiologic matter to the pump (and other well components); and (6) bacteria may create microenvironments that facilitate precipitation of solids or inhibit dissolution of unstable minerals once the bacteria adhere to biofilm attached to the pump. Results of the study indicate that bacteria may be accumulating and entrapping solid material on the exterior of pumps. This accumulation reduces heat transfer and water discharge from the pump and may lead to decreased efficiency or mechanical failure. Observations could not be made on the well screen, gravel pack, or surrounding geologic formation; therefore, mitigating measures in the borehole may not solve well-productivity issues. Remedies for the pump fouling problems were derived from the review and interpretation of data collected during this study and from information documented in other sources about groundwater well fouling. Potential remedies to problems associated with pump fouling at the CDF may include the following: (1) reducing attractiveness of the extraction wells for microbiological growth by modifying the chemical or physical environment of the well, (2) modifying the pump exterior to decrease microbiological adherence, (3) changing the pumping regime to control the chemistry of water entering the well from the surrounding aquifer material, (4) modifying the pumps to be less physically and thermally attractive, and (5) removing hydrocarbons from groundwater and the aquifer material surrounding the wells or adding surfactants to make them more mobile. Pilot scale testing may be necessary to identify the most effective treatment or combination of treatments.

Indiana↗

USGS2023

Summary of the history and research of the U.S. Geological Survey gas hydrate properties laboratory in Menlo Park, California, active from 1993 to 2022

The U.S. Geological Survey (USGS) Clathrate Hydrate Properties Project, active from 1993 to 2022 in Menlo Park, California, stemmed from an earlier project on the properties of planetary ices supported by the National Aeronautics and Space Administration’s (NASA’s) Planetary Geology and Geophysics Program. We took a material science approach in both projects, emphasizing chemical purity of samples, having controlled grain size and grain texture, and having verified crystal structures and phase relations. A foundational contribution from our USGS Gas Hydrate Properties Laboratory (GHPL) was in demonstrating the ability to reproducibly create such pure clathrate hydrate samples for study. Clathrate sample synthesis was achieved by heating sieved and weighed pure granular water ice in the presence of cold clathrate-forming gas or liquid. During heating, the ice melts at the grain scale and reacts with the gas to form clathrate. The resulting material has the desired uniformity and purity, with known intergranular porosity; our subsequent measurements showed that these clathrates exhibited the established clathrate structures and phase relations. This novel synthesis method was successful in creating clathrates of pure methane, ethane, propane, carbon dioxide, and multi-component gases. By mixing sand or silt with granular ice, we were also able to make clathrate-sediment aggregates with controlled grain textures. This simple method, adopted by many others in the community, permitted us to measure the physical and chemical properties of well-characterized and well-crystallized clathrates and clathrate/sediment aggregates. At about the same time, we adapted conventional scanning electron microscopy to cryogenic conditions for analysis of grain-scale characteristics of clathrates made in the GHPL as well as those collected from nature by drill core. The uniformity and reproducibility of our samples also allowed us to investigate how clathrates respond to environmental changes in chemistry, temperature, and pressure: we measured chemical exchange rates with dissolved gas species—such as noble gases and chlorofluorocarbons—as well as rates of clathrate dissolution and decomposition. These advances include the first accurate mapping of the conditions that promote the remarkable process of “anomalous preservation” at room pressure, a metastability that offers potential application for low-cost and safe transportation of natural gas from gas fields far from pipelines. Another advancement stemming from the GHPL was the compaction of as-synthesized porous clathrates to nearly full density by applying external pressure using three different techniques. Compaction allows for high-accuracy measurements of many fundamental physical and chemical properties of these materials, such as elastic wavespeeds and moduli, complete thermal properties, decomposition rates, thermal expansion, and clathrate equations of state. These properties and others, in turn, have helped USGS scientists to interpret geophysical well logs and active geophysical surveys, as well as model the rates of gas production from hydrate deposits in nature. Studying this class of icy minerals that occur in abundance on Earth and in the outer solar system has been a fascinating laboratory journey. Here, we summarize the history and major findings of the USGS GHPL in Menlo Park, including both in-house research as well as findings from the synergistic collaborations with other agencies and institutes that were key to the success of our laboratory. The Menlo Park GHPL was more formally incorporated within the USGS Gas Hydrates Project, a collaboration among multiple USGS Science Centers, in the early 2000s under the leadership of Deborah Hutchinson, and now under the leadership of Carolyn Ruppel and Timothy Collett.

Open-File Report↗

USGS1983

Clay mineral formation and transformation in rocks and soils

Three mechanisms for clay mineral formation (inheritance, neoformation, and transformation) operating in three geological environments (weathering, sedimentary, and diagenetic-hydrothermal) yield nine possibilities for the origin of clay minerals in nature. Several of these possibilities are discussed in terms of the rock cycle. The mineralogy of clays neoformed in the weathering environment is a function of solution chemistry, with the most dilute solutions favoring formation of the least soluble clays. After erosion and transportation, these clays may be deposited on the ocean floor in a lateral sequence that depends on floccule size. Clays undergo little reaction in the ocean, except for ion exchange and the neoformation of smectite; therefore, most clays found on the ocean floor are inherited from adjacent continents. Upon burial and heating, however, dioctahedral smectite reacts in the diagenetic environment to yield mixed-layer illite-smectite, and finally illite. With uplift and weathering, the cycle begins again. Refs.

Philosophical Transactions of the Royal Society A:↗

USGS2004

Age and source of water in springs associated with the Jacksonville Thrust Fault Complex, Calhoun County, Alabama

Water from wells and springs accounts for more than 90 percent of the public water supply in Calhoun County, Alabama. Springs associated with the Jacksonville Thrust Fault Complex are used for public water supply for the cities of Anniston and Jacksonville. The largest ground-water supply is Coldwater Spring, the primary source of water for Anniston, Alabama. The average discharge of Coldwater Spring is about 32 million gallons per day, and the variability of discharge is about 75 percent. Water-quality samples were collected from 6 springs and 15 wells in Calhoun County from November 2001 to January 2003. The pH of the ground water typically was greater than 6.0, and specific conductance was less than 300 microsiemens per centimeter. The water chemistry was dominated by calcium, carbonate, and bicarbonate ions. The hydrogen and oxygen isotopic composition of the water samples indicates the occurrence of a low-temperature, water-rock weathering reaction known as silicate hydrolysis. The residence time of the ground water, or ground-water age, was estimated by using analysis of chlorofluorocarbon, sulfur hexafluoride, and regression modeling. Estimated ground-water ages ranged from less than 10 to approximately 40 years, with a median age of about 18 years. The Spearman rho test was used to identify statistically significant covariance among selected physical properties and constituents in the ground water. The alkalinity, specific conductance, and dissolved solids increased as age increased; these correlations reflect common changes in ground-water quality that occur with increasing residence time and support the accuracy of the age estimates. The concentration of sodium and chloride increased as age increased; the correlation of these constituents is interpreted to indicate natural sources for chloride and sodium. The concentration of silica increased as the concentration of potassium increased; this correlation, in addition to the isotopic data, is evidence that silicate hydrolysis of clay minerals occurred. The geochemical modeling program NETPATH was used to investigate possible mixing scenarios that could yield the chemical composition of water collected from springs associated with the Jacksonville Thrust Fault Complex. The results of NETPATH modeling suggest that the primary source of water in Coldwater Spring is a deep aquifer, and only small amounts of rainwater from nearby sources are discharged from the spring. Starting with Piedmont Sports Spring and moving southwest along a conceptual ground-water flow path that parallels the Jacksonville Thrust Fault Complex, NETPATH simulated the observed water quality of each spring, in succession, by mixing rainwater and water from the spring just to the northeast of the spring being modeled. The percentage of rainwater and ground water needed to simulate the quality of water flowing from the springs ranged from 1 to 25 percent rainwater and 75 to 99 percent ground water.

Scientific Investigations Report↗

USGS1977

Mineralogical, chemical, and physical properties of the regolith overlying crystalline rocks, Fairfax County, Virginia: a preliminary report

Undisturbed cores of saprolite developed on crystalline rocks of the Piedmont Province in Fairfax County, Virginia have been obtained using a combination of Shelby tubes, Denison sampler, and modified diamond core-drilling. The principal purpose of the core study is to correlate variations in chemistry, mineralogy and texture with engineering properties throughout the weathering profile. Coring sites were chosen to obtain a maximum depth of weathering on diverse lithologies. The rocks investigated include pelitic schist, metagraywacke, granite, diabase and serpentinite. Four to twelve samples per core were selected, depending on thickness of 1) the weathering profile (from about 1 m in serpentinite to more than 30 m in pelitic schist) and on 2) megascopic changes in saprolite character for analysis of petrography, texture, clay mineralogy andd major element chemistry. Shear strength and compressibility were determined on corresponding segments of core. Standard penetration tests were performed adjacent to coring sites to evaluate engineering properties in situ. Geochemical changes of saprolite developed from each rock type follow predictable trends from fresh rock to soil profile, with relative Increases in Si, Ti, Al, Fe3+ and H20; variable K; and relative loss of Fe 2+, Mg, Ca, and Na. These variations are more pronounced in the weathering profiles over mafic and ultramafic rocks than metagraywacke. Clay minerals in granite, schist and metagraywacke saprolite are kaolinite, dioctahedral vermiculite, interlayered micavermiculite, and minor illite. Gibbsite is locally developed in near-surface samples of schist. Standard penetration test data for the upper 7 m of saprolite over schist and metagraywacke suggest alternations between stronger and weaker horizons than probably reflect variations in lithology including the presence of quartz lenses. Results for granite saprolite are most consistent but indicate lower strength. Shear strength increases fairly regularly downward in the weathering profile. The engineering behavior of diabase saprolite is controlled by a dense, plastic, near-surface clay layer (montmorillonite and kaolinite)overlying rock which is weathered to a granular state (grus), while engineering properties of serpentinite are determined by a very thin weathering profile.

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