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Stable isotope geochemistry of sphalerite and other mineral matter in coal beds of the Illinois and Forest City basins

Cleat and clastic dikes of Middle Pennsylvanian-age coal beds of the Illinois and Forest City basins of Illinois, Iowa, Missouri, and Kansas locally contain appreciable amounts of sphalerite within a kaolinite-pyrite-sphalerite (+ or - pyrite)-calcite paragenetic sequence. The sphalerite and associated minerals are of interest as a partial record of the history of fluids in the sedimentary basin and as possible indicators of Mississippi Valley-type mineralization. Moreover, zinc from the sphalerite may represent an exploitable by-product of coal mining and combustion.Pyrite is abundant in these coals both as fine-grained disseminated framboids that formed during early diagenesis and as coarser grained cleat fillings, etc., that formed much later. The delta 34 S values of this later pyrite, the sphalerite, and the coal organic matter range from -12 to 19 per mil. Within individual samples, however, pyrite, sphalerite, and organic matter sulfur delta 34 S values are nearly identical. This similarity strongly suggests related origins. The delta 34 S values of pyrite, sphalerite, and organic matter from coals of the Illinois basin and the central and southern Forest City basin range from -12 to 0 per mil. This range is not unique to the sphalerite-bearing coals; pyrite and organic matter from sphalerite-free high sulfur coals have similar delta 34 S values (Price and Shieh, 1979). We believe that sulfur produced by the breakdown of organosulfur compounds in the coal is incorporated into the epigenetic sulfides. In the northern Forest City basin, however, many samples have delta 34 S values between 8 and 19 per mil. These are similar to the delta 34 S values of sphalerite and pyrite from the Upper Mississippi Valley Zn-Pb district which lies northeast of the Forest City basin and north of the Illinois basin. This similarity suggests input from a Mississippi Valley-type hydrothermal system.Cleat kaolinite has delta D values of -36 to -24 per mil and delta 18 O values of 19.2 to 20.2 per mil. Assuming that clearing postdated the lignite rank of coalification implies that kaolinite was deposited between 40 degrees and 100 degrees C. At the lower temperatures, the kaolinite fluid would have had an isotopic composition similar to seawater; at the higher temperatures, it would have had a composition similar to the sphalerite-depositing fluid. Sphalerite was deposited from a fluid that was chemically and isotopically similar to the fluids responsible for the main-stage ores of the Upper Mississippi Valley Zn-Pb district (75 degrees -113 degrees C, approximately 21 equiv wt % NaCl, delta D = -65 to -3ppm, and delta 18 O = -0.9-9.9ppm). The isotopic compositions (delta 13 C = -12.4 to -2.7ppm and delta 18 O = 21.1-25.8ppm) and paragenetic positions of the cleat calcite samples are similar to those of the late-stage calcite of the Upper Mississippi Valley Zn-Pb and Illinois-Kentucky fluorspar districts. Calcite inclusion fluids had delta D (sub H 2 O) values of -80 and -58 per mil, implying a meteoric water source. At probable temperatures of 15 degrees to 75 degrees C, this calcite formed from fluids having calculated delta 18 O (sub H 2 O) values of -9 to 1 per mil, implying slight to moderate exchange with sedimentary rocks. The diagenetic-epigenetic history of fluids recorded by the cleat minerals probably began with a slightly evolved seawater, followed by a metal-bearing deep basin brine, and concluded with a cooler, slightly evolved, meteoric-water fluid.

Economic Geology↗

Geology, Water, and Wind in the Lower Helmand Basin, Southern Afghanistan

This report presents an overview of the geology, hydrology, and climate of the lower Helmand Basin, a large, closed, arid basin in southern Afghanistan. The basin is drained by the Helmand River, the only perennial desert stream between the Indus and Tigris-Euphrates Rivers. The Helmand River is the lifeblood of southern Afghanistan and has supported desert civilizations in the Sistan depression for over 6,000 years. The Helmand Basin is a structurally closed basin that began to form during the middle Tertiary as a consequence of the collision of several Gondwanaland fragments. Aeromagnetic studies indicate the basin is 3-5 kilometers deep over basement rocks. Continued subsidence along basin-bounding faults in Iran and Pakistan throughout the Neogene has formed the Sistan depression in the southwest corner of the basin. Lacustrine, eolian, and fluvial deposits are commonly exposed in the basin and were intruded by latest Miocene-middle Quaternary volcanoes, which indicates that depositional environments in the lower Helmand Basin have not substantially changed for nearly 10 million years. Lakes expanded in the Sistan depression during the Quaternary; however, the size and extent of these pluvial lakes are unknown. Climate conditions in the lower Helmand Basin likely mirrored climate changes in the Rajasthan Desert to the east and in Middle Eastern deserts to the west: greater aridity during global episodes of colder temperatures and increased available moisture during episodes of warmer temperatures. Eolian processes are unusually dominant in shaping the landscape in the basin. A strong wind blows for 120 days each summer, scouring dry lakebeds and creating dune fields from annual flood deposits. Nearly one-third of the basin is mantled with active or stabilized dunes. Blowing winds combined with summer temperatures over 50? Celsius and voluminous insect populations hatched from the deltaic wetlands create an environment referred to as the 'most odious place on earth' by 19th century visitors. During dry years, large plumes of dust originating from Sistan are recorded by weather satellites. The Helmand River drains about 40 percent of Afghanistan and receives most of its moisture from melting snow and spring storms. Similar to many desert streams, the Helmand and its main tributary, the Arghandab River, are characterized by large fluctuations in monthly and annual discharges. Water from the Helmand accumulates in several hamuns (shallow lakes) in the Sistan depression. The wetlands surrounding these hamuns are the largest in western Asia and are directly affected by droughts and floods on the Helmand. Average annual discharge on the Helmand is about 6.12 million megaliters (million cubic meters), and the annual discharge varies by a factor of five. In 2005, the region was just beginning to recover from the longest drought (1998-2005) of record back to 1830. Annual peak discharges range from less than 80 cubic meters per second in 1971 to nearly 19,000 cubic meters per second in 1885. Large floods fill each hamun to overflowing to create one large lake that overflows into the normally dry Gaud-i Zirreh basin. The interaction of flooding, active subsidence, and wind erosion causes frequent channel changes on the Helmand delta. A major development effort on the Helmand River was initiated after World War II with substantial aid from the United States. Two dams and several major canals were completed in the 1950s; however, poor drainage conditions on the newly prepared agricultural fields caused extensive waterlogging and salinization. New drains were installed and improved agricultural methods were implemented in the 1970s, and some lands became more productive. Since 1980, Afghanistan has endured almost constant war and civil and political strife. In 2005, the country was on a path to rebuild much of its technical infrastructure. Revitalization of agricultural lands in the lower Helmand Basin and improved managem

Scientific Investigations Report↗

Groundwater quality and the relation between pH values and occurrence of trace elements and radionuclides in water samples collected from private wells in part of the Kickapoo Tribe of Oklahoma Jurisdictional Area, central Oklahoma, 2011

From 1999 to 2007, the Indian Health Service reported that gross alpha-particle activities and concentrations of uranium exceeded the Maximum Contaminant Levels for public drinking-water supplies in water samples from six private wells and two test wells in a rural residential neighborhood in the Kickapoo Tribe of Oklahoma Jurisdictional Area, in central Oklahoma. Residents in this rural area use groundwater from Quaternary-aged terrace deposits and the Permian-aged Garber-Wellington aquifer for domestic purposes. Uranium and other trace elements, specifically arsenic, chromium, and selenium, occur naturally in rocks composing the Garber-Wellington aquifer and in low concentrations in groundwater throughout its extent. Previous studies have shown that pH values above 8.0 from cation-exchange processes in the aquifer cause selected metals such as arsenic, chromium, selenium, and uranium to desorb (if present) from mineral surfaces and become mobile in water. On the basis of this information, the U.S. Geological Survey, in cooperation with the Kickapoo Tribe of Oklahoma, conducted a study in 2011 to describe the occurrence of selected trace elements and radionuclides in groundwater and to determine if pH could be used as a surrogate for laboratory analysis to quickly and inexpensively identify wells that might contain high concentrations of uranium and other trace elements. The pH and specific conductance of groundwater from 59 private wells were measured in the field in an area of about 18 square miles in Lincoln and Pottawatomie Counties. Twenty of the 59 wells also were sampled for dissolved concentrations of major ions, trace elements, gross alpha-particle and gross beta-particle activities, uranium, radium-226, radium-228, and radon-222 gas. Arsenic concentrations exceeded the Maximum Contaminant Level of 10 micrograms per liter in one sample having a concentration of 24.7 micrograms per liter. Selenium concentrations exceeded the Maximum Contaminant Level of 50 micrograms per liter in one sample having a concentration of 147 micrograms per liter. Both samples had alkaline pH values, 8.0 and 8.4, respectively. Uranium concentrations ranged from 0.02 to 383 micrograms per liter with 5 of 20 samples exceeding the Maximum Contaminant Level of 30 micrograms per liter; the five wells with uranium concentrations exceeding 30 micrograms per liter had pH values ranging from 8.0 to 8.5. Concentrations of uranium and radon-222 and gross alpha-particle activity showed a positive relation to pH, with the highest concentrations and activity in samples having pH values of 8.0 or above. The groundwater samples contained dissolved oxygen and high concentrations of bicarbonate; these characteristics are also factors in increasing uranium solubility. Concentrations of radium-226 and radium-228 (combined) ranged from 0.03 to 1.7 picocuries per liter, with a median concentration of 0.45 picocuries per liter for all samples. Radon-222 concentrations ranged from 95 to 3,600 picocuries per liter with a median concentration of 261 picocuries per liter. Eight samples having pH values ranging from 8.0 to 8.7 exceeded the proposed Maximum Contaminant Level of 300 picocuries per liter for radon-222. Eight samples exceeded the 15 picocuries per liter Maximum Contaminant Level for gross alpha-particle activity at 72 hours (after sample collection) and at 30 days (after the initial count); those samples had pH values ranging from 8.0 to 8.5. Gross beta-particle activity increased in 15 of 21 samples during the interval from 72 hours to 30 days. The increase in gross beta-particle activity over time probably was caused by the ingrowth and decay of uranium daughter products that emit beta particles. Water-quality data collected for this study indicate that pH values above 8.0 are associated with potentially high concentrations of uranium and radon-222 and high gross alpha-particle activity in the study area. High pH values also are associated with potentially high concentrations of arsenic, chromium, and selenium in groundwater when these elements occur in the aquifer matrix along groundwater-flow paths.

Oklahoma↗

Sediment distribution and hydrologic conditions of the Potomac aquifer in Virginia and parts of Maryland and North Carolina

Sediments of the heavily used Potomac aquifer broadly contrast across major structural features of the Atlantic Coastal Plain Physiographic Province in eastern Virginia and adjacent parts of Maryland and North Carolina. Thicknesses and relative dominance of the highly interbedded fluvial sediments vary regionally. Vertical intervals in boreholes of coarse-grained sediment commonly targeted for completion of water-supply wells are thickest and most widespread across the central and southern parts of the Virginia Coastal Plain. Designated as the Norfolk arch depositional subarea, the entire sediment thickness here functions hydraulically as a single interconnected aquifer. By contrast, coarse-grained sediment intervals are thinner and less widespread across the northern part of the Virginia Coastal Plain and into southern Maryland, designated as the Salisbury embayment depositional subarea. Fine-grained intervals that are generally avoided for completion of water-supply wells are increasingly thick and widespread northward. Fine-grained intervals collectively as thick as several hundred feet comprise two continuous confining units that hydraulically separate three vertically spaced subaquifers. The subaquifers are continuous northward but merge southward into the single undivided Potomac aquifer. Lastly, far southeastern Virginia and northeastern North Carolina are designated as the Albemarle embayment depositional subarea, where both coarse- and fine-grained intervals are of only moderate thickness. The entire sediment thickness functions hydraulically as a single interconnected aquifer. A substantial hydrologic separation from overlying aquifers is imposed by the upper Cenomanian confining unit. Potomac aquifer sediments were deposited by a fluvial depositional complex spanning the Virginia Coastal Plain approximately 100 to 145 million years ago. Westward, persistently uplifted granite and gneiss source rocks sustained a supply of coarse-grained sand and gravel. Immature, high-gradient braided streams deposited longitudinal bars and channel fills across the Norfolk arch subarea. By contrast, across the Salisbury and Albemarle embayment subareas, mature, medium- to low-gradient meandering streams deposited medium- to coarse-grained channel fills and point bars segregated from fine-grained overbank deposits. The Virginia depositional complex merged northward across the Salisbury embayment subarea with another complex in Maryland. Here, additional sediments were received from schist source rocks that underwent three cycles of initial uplift and rapid erosion followed by crustal stability and erosional leveling. Because of the predominance of coarse-grained sediments, transmissivity, hydraulic conductivity, and regional velocities of lateral flow through the Potomac aquifer are greatest across the Norfolk arch depositional subarea, but decrease progressively northward with increasingly fine-grained sediments. Confining units hydraulically separate the Potomac aquifer from overlying aquifers, as indicated by large vertical hydraulic gradients. By contrast, most of the Potomac aquifer internally functions hydraulically as a single interconnected aquifer, as indicated by uniformly small vertical gradients. Most fine-grained sediments within the aquifer do not hydraulically separate overlying and underlying coarse-grained sediments. Across the Salisbury embayment depositional subarea, however, hydraulic separation among the vertically spaced subaquifers is imposed by the intervening confining units. The Potomac aquifer is the largest and most heavily used source of groundwater in the Virginia Coastal Plain. Water-level declines as great as 200 feet create the potential for saltwater intrusion. Conventional stratigraphic correlation has been generally ineffective at accurately characterizing complexly distributed fluvial sediments that compose the Potomac aquifer. Consequently, the aquifer’s internal hydraulic connectivity and overall hydrologic function have not been well understood. Water-supply planning and development efforts have been hampered, and interpretations of regulatory criteria for allowable water-level declines have been ambiguous. An investigation undertaken during 2010–11 by the U.S. Geological Survey, in cooperation with the Virginia Department of Environmental Quality, provides a comprehensive regional description of the spatial distribution of Potomac aquifer sediments and their relation to hydrologic conditions. Altitudes and thicknesses of 2,725 vertical sediment intervals represent the spatial distribution of Potomac aquifer sediments in the Virginia Coastal Plain and adjacent parts of Maryland and North Carolina. Sediment intervals are designated as either dominantly coarse or fine grained and were determined by interpretation of geophysical logs and ancillary information from 456 boreholes. Sediment-interval and borehole summary statistical data indicate regional trends in sediment lithology and stratigraphic continuity, upon which three structurally based and hydrologically distinct sediment depositional subareas are designated. Broad patterns of sediment deposition over time are inferred from published sediment pollen-age data. Discrepancies in previously drawn hydrostratigraphic relations between southeastern Virginia and northeastern North Carolina are partly resolved based on borehole geophysical logs and a recently documented geologic map and corehole. A conceptual model theorizes the depositional history of the sediments and geologically accounts for their distribution. Documented pumping tests of the Potomac aquifer at 197 locations produced 336 values of transmissivity and 127 values of storativity. Based on effective aquifer thicknesses, 296 values of sediment hydraulic conductivity and 113 values of sediment specific storage are calculated. Vertical hydraulic gradients are calculated from 9,479 pairs of water levels measured between November 17, 1953, and October 4, 2011, in 129 closely spaced pairs of wells. Borehole sediment-interval and related data provide a means to achieve high yielding production wells in the Potomac aquifer by site-specific targeting of drilling operations toward water-bearing coarse-grained sand and gravel. Advance knowledge of the potential of different parts of the aquifer also aids in planning optimal groundwater-development areas. Depositional subareas further provide a possible context for resource management. Current (2013) regulatory limits on water-level declines are relative to top surfaces of subdivided upper, middle, and lower Potomac aquifers across the entire Virginia Coastal Plain, but have the potential to exceed the same limit relative to a single undivided Potomac aquifer. By contrast, designation of the sediments as a single aquifer in the Norfolk arch and Albemarle embayment subareas—and as a series of vertically spaced subaquifers and intervening confining units in the Salisbury embayment subarea—best reflects understanding of the Potomac aquifer and can avoid the potential for excessive water-level declines. Simulation modeling to evaluate effects of groundwater withdrawals could be designed similarly, including vertical discretization and (or) zonation of the Potomac aquifer based on depositional subareas and a geostatistical distribution of aquifer properties derived from borehole sediment-interval data. Further resource-management information needs extend beyond the developed part of the Potomac aquifer, particularly across the Northern Neck and Middle Peninsula where only the shallowest part of the aquifer is known, and include structural aspects such as faults, basement bedrock, and the Chesapeake Bay impact crater.

Maryland, North Carolina, Virginia↗

An application of thermometry to the study of ground water

Except for studies of temperature data related to ground-water developments that induce infiltration from streams, little attention has been given to the possibility of using temperature fluctuations as a tool for studying the elements of the hydrologic cycle involving ground water. The temperature of the water discharged from large installations that induce river infiltration through alluvial deposits depends primarily on the following factors: (a) the porosity of the aquifer, (b) the specific heat of the rocks or mineral grains making it up, (c) the temperature of the ground water in storage, (d) the temperature of the river water, and (e) the amount of mixing that occurs as a result of pumping. In six installations of this type, where the annual rivertemperature fluctuations ranged from 44° to 52°F, the average range in groundwater temperature was 22 °F. The cycles of ground-water temperature lagged behind the river-temperature cycles by 1 to 5 1 / 2 months. Under the conditions that existed, the lag of the minima of the cycles was much greater than that of the maxima, largely because of variations in pumpage and of the effect of viscosity differences on the rate of flow. An experimental study was made at Worthington in southwestern Minnesota to determine whether temperature fluctuations could be used to study rates and directions of ground-water movement or to evaluate recharge conditions. Three shallow glacial-outwash aquifers were studied by measuring temperatures at approximately monthly intervals in three municipal-supply wells whose average yields were about 60 to 150 gpm (gallons per minute). Temperatures were read with an accuracy of 0.01° to 0.02°C, and the data were analyzed graphically and correlated in detail with lake levels, lake temperatures, precipitation, and groundwater levels. Thermographs for 2 wells, 1 completed in a semiconfined aquifer about 200 feet from Okabena Lake and the other in a water-table aquifer about 850 feet from the lake, indicate that pumping induces water to move from the lake into the aquifers. A larger percentage of cold lake water was mixed with ground water from January to March 1958 than from January to March 1959. On the assumption that the cold or warm lake water was a distinct mass, the average time required for water to move from the lake to the well 200 feet away, under the prevailing hydraulic gradient, was 2 to 4 months; and to the well 850 feet away, 5 to 7 months. The thermograph for a well 1,800 feet from the lake, completed in an artesian aquifer that is confined by relatively impervious glacial till, indicates that the till acts as an insulating medium. However, despite the apparently low permeability of the till, the thermograph suggests that the lowering of artesian pressure, which results from pumping, induces warmer water to move downward through the till. The infiltration of relatively warm spring and summer rainfall can be detected on the thermographs of all the wells. The precise measurement of fluctuations in ground-water temperature, based on monthly readings in shallow glacial-outwash aquifers (up to about 70 feet deep), is useful in the study of ground-water movement and recharge. In addition to the study of natural phenomena in the hydrologic cycle, thermometry may be used as a tool in making detailed studies of (1) the effects of inducing the infiltration of surface water, (2) artificial recharge, (3) the effects of injecting petroleum products or radioactive or other wastes into the ground, and (4) ground-water movement in mines.

Water Supply Paper↗

Stratigraphy and sedimentology of a dry to wet eolian depositional system, Burns formation, Meridiani Planum, Mars

Outcrop exposures of sedimentary rocks at the Opportunity landing site (Meridiani Planum) form a set of genetically related strata defined here informally as the Burns formation. This formation can be subdivided into lower, middle, and upper units which, respectively, represent eolian dune, eolian sand sheet, and mixed eolian sand sheet and interdune facies associations. Collectively, these three units are at least 7 m thick and define a “wetting-upward” succession which records a progressive increase in the influence of groundwater and, ultimately, surface water in controlling primary depositional processes. The Burns lower unit is interpreted as a dry dune field (though grain composition indicates an evaporitic source), whose preserved record of large-scale cross-bedded sandstones indicates either superimposed bedforms of variable size or reactivation of lee-side slip faces by episodic (possibly seasonal) changes in wind direction. The boundary between the lower and middle units is a significant eolian deflation surface. This surface is interpreted to record eolian erosion down to the capillary fringe of the water table, where increased resistance to wind-induced erosion was promoted by increased sediment cohesiveness in the capillary fringe. The overlying Burns middle unit is characterized by fine-scale planar-laminated to low-angle-stratified sandstones. These sandstones accumulated during lateral migration of eolian impact ripples over the flat to gently undulating sand sheet surface. In terrestrial settings, sand sheets may form an intermediate environment between dune fields and interdune or playa surfaces. The contact between the middle and upper units of the Burns formation is interpreted as a diagenetic front, where recrystallization in the phreatic or capillary zones may have occurred. The upper unit of the Burns formation contains a mixture of sand sheet facies and interdune facies. Interdune facies include wavy bedding, irregular lamination with convolute bedding and possible small tepee or salt-ridge structures, and cm-scale festoon cross-lamination indicative of shallow subaqueous flows marked by current velocities of a few tens of cm/s. Most likely, these currents were gravity-driven, possibly unchannelized flows resulting from the flooding of interdune/playa surfaces. However, evidence for lacustrine sedimentation, including mudstones or in situ bottom-growth evaporites, has not been observed so far at Eagle and Endurance craters. Mineralogical and elemental data indicate that the eolian sandstones of the lower and middle units, as well as the subaqueous and eolian deposits of the Burns upper unit, were derived from an evaporitic source. This indirectly points to a temporally equivalent playa where lacustrine evaporites or ground-water-generated efflorescent crusts were deflated to provide a source of sand-sized particles that were entrained to form eolian dunes and sand sheets. This process is responsible for the development of sulfate eolianites at White Sands, New Mexico, and could have provided a prolific flux of sulfate sediment at Meridiani. Though evidence for surface water in the Burns formation is mostly limited to the upper unit, the associated sulfate eolianites provide strong evidence for the critical role of groundwater in controlling sediment production and stratigraphic architecture throughout the formation.

Earth and Planetary Science Letters↗

Transgressive-regressive cycles in the metalliferous, oil-shale-bearing Heath Formation (Upper Mississippian), central Montana

The Upper Mississippian Heath Formation, which accumulated in the Big Snowy Trough of central Montana, has been known for three decades to contain mudrocks highly enriched in Zn, V, Mo, Ni and other metals, and source rocks for oil. The unit has more recently been recognized as a prospective tight oil play. Here we present petrographic, paleontologic, geochemical, and carbon and sulfur isotope data on seven continuous drill cores spanning ≤146 m of immature to marginally mature strata in order to improve understanding of the depositional setting of the Heath. The unit consists of five third-order transgressive-regressive cycles (C1–C5 from bottom to top) that were deposited during a fluctuating climatic regime. Cycles comprise thinly interbedded gray to black mudrock and carbonate strata capped by either coal, implying a humid climate (C1, C3 and C4), or gypsum, implying more arid conditions (C2); the upper part of C5 is not preserved in our study area. Mfs (maximum flooding surfaces) in C1, C2, C4, and C5 lie within black mudrock beds ~0.5–3-m thick with >10% TOC (total organic carbon), type I and type II kerogen (determined by programmed pyrolysis), high contents of Zn, V, Mo, and other metals, relatively low values of δ13CTOC and δ34Spyrite, and a limited-diversity fauna of locally abundant, thin-shelled pelecypods (Dunbarella? sp.). The mfs in C2 is within the Cox Ranch oil shale bed, which is known from previous studies to be metalliferous; new analyses reported here show ≤28 wt % TOC, 5140 ppm Zn, 1910 ppm V, 1590 ppm Mo, and 509 ppm Ni. Strata that contain the mfs of C1, C4, and C5 are shown here for the first time to also have high metal contents, with maximum values of 1030–7340 ppm Zn, 446–1980 ppm V, 72–859 ppm Mo, and 221–452 ppm Ni. Cycle C3, which contains more gray mudrock and carbonate beds than the other cycles, has lower TOC (≤4.2 wt %), lower metals, and mainly type III kerogen. Carbonate beds include normal-marine crinoidal mudstone to packstone and lesser (dolo)mudstone with fenestral fabric, peloids, intraclasts, and a euryhaline fauna. Mid-Chesterian (early Serpukhovian) foraminifers in C3, combined with previously published fossil data, suggest that third-order cycles in the Heath Formation were ~1–2 myr in duration. They formed during a time of active block faulting in the Big Snowy Trough and global cooling linked to Gondwanan glaciation. Tectonic, climatic, and paleogeographic factors shaped the cycles of the Heath Formation. Faunal and geochemical evidence indicate that conditions were most favorable for marine life during C3. Molybdenum concentrations >100 ppm and organic geochemical data suggest euxinic conditions during deposition of the black mudrock in C2, C4, and C5, but the presence of shell beds (1 mm–6-cm thick) within this mudrock requires bottom water with sufficient oxygen to support life, at least periodically. The apparent conflict between the geochemical and paleontologic observations likely reflects the different time scales of these two environmental proxies: 1000s of yrs vs <1–10s of yrs, respectively. Metal- and organic-rich strata in the Heath Formation formed by slow, condensed sedimentation from periodically anoxic or euxinic bottom waters in a marine basin. Fossil data indicate that anoxia was episodic, perhaps seasonal and/or linked to longer-duration climate shifts. On a millennial time scale, metal enrichments in the Heath reflect a balance between primary productivity that was high enough for oxygen to be consumed by sinking organic matter and oxic seawater inflow that was strong enough to maintain a supply of metals without compromising anoxia. Organic-rich mudrock in the Heath shares intriguing lithologic and geochemical similarities with mudrock in other Middle to Upper Paleozoic units such as the Devonian-Mississippian Bakken Formation and Pennsylvanian cyclothems (e.g., Excello Shale).

Montana↗

Applied Geochemistry Special Issue on Environmental geochemistry of modern mining

Environmental geochemistry is an integral part of the mine-life cycle, particularly for modern mining. The critical importance of environmental geochemistry begins with pre-mining baseline characterization and the assessment of environmental risks related to mining, continues through active mining especially in water and waste management practices, and culminates in mine closure. The enhanced significance of environmental geochemistry to modern mining has arisen from an increased knowledge of the impacts that historical and active mining can have on the environment, and from new regulations meant to guard against these impacts. New regulations are commonly motivated by advances in the scientific understanding of the environmental impacts of past mining. The impacts can be physical, chemical, and biological in nature. The physical challenges typically fall within the purview of engineers, whereas the chemical and biological challenges typically require a multidisciplinary array of expertise including geologists, geochemists, hydrologists, microbiologists, and biologists. The modern mine-permitting process throughout most of the world now requires that potential risks be assessed prior to the start of mining. The strategies for this risk assessment include a thorough characterization of pre-mining baseline conditions and the identification of risks specifically related to the manner in which the ore will be mined and processed, how water and waste products will be managed, and what the final configuration of the post-mining landscape will be. In the Fall 2010, the Society of Economic Geologists held a short course in conjunction with the annual meeting of the Geological Society of America in Denver, Colorado (USA) to examine the environmental geochemistry of modern mining. The intent was to focus on issues that are pertinent to current and future mines, as opposed to abandoned mines, which have been the focus of numerous previous short courses. The geochemical challenges of current and future mines share similarities with abandoned mines, but differences also exist. Mining and ore processing techniques have changed; the environmental footprint of waste materials has changed; environmental protection has become a more integral part of the mine planning process; and most historical mining was done with limited regard for the environment. The 17 papers in this special issue evolved from the Society of Economic Geologists’ short course. The relevant geochemical processes encompass the source, transport, and fate of contaminants related to the life cycle of a mine. Contaminants include metals and other inorganic species derived from geologic sources such as ore and solid mine waste, and substances brought to the site for ore processing, such as cyanide to leach gold. Factors, such as mine-waste mineralogy, hydrologic setting, mine-drainage chemistry, and microbial activity, that affect the hydrochemical risks from mining are reviewed by Nordstrom et al. In another paper, Nordstrom discusses baseline characterization at mine sites in a regulatory framework, and emphasizes the influence of mineral deposits in producing naturally elevated concentrations of many trace elements in surface water and groundwater. Surface water quality in mineralized watersheds is influenced by a number of processes that act on daily (diel) cycles and can produce dramatic variations in trace element concentrations as described by Gammons et al. Pre-mining baseline characterization studies should strive to capture the magnitude of these diel variations. Desbarats et al., using a case study of mine drainage from a gold mine, illustrate how elements that commonly occur as negatively charged species (anions) in solution, such as arsenic as arsenate, behave in an opposite fashion than most metals, which occur as positively charged species (cations). Significant improvement in the understanding of factors that influence the toxicity of metals to aquatic organisms in surface water has highlighted the importance of aqueous chemistry, particularly dissolved organic carbon, as described by Smith et al. Stream sediment contamination is another important pathway for affecting aquatic organisms, as reviewed by Besser et al. Understanding and predicting environmental consequences from mining begins with knowing the mineralogy and mineral reactivity of the ore, the wastes, and of secondary minerals formed later. Jamieson et al. review the importance of mineralogical studies in mine planning and remediation. A number of types of site-specific studies are needed to identify environmental risks related to individual mines. Lapakko reviews the general framework of mine waste characterization studies that are integral to the mine planning process. Hageman et al. present a comparative study of several static tests commonly used to characterize mine waste. The mining and ore processing practices employed at a specific mine site will vary on the basis of the commodities being targeted, the geology of the deposit, the geometry of the deposit, and the mining and ore processing methods used. Thus, these factors, in addition to the waste management practices used, can result in a variety of end-member mine waste features, each of which has its own set of challenges. Open pit mines and underground mines require waste rock to be removed to access ore. Waste rock presents unique problems because the rock is commonly mineralized at sub-economic grades and has not been processed to remove potentially problematic minerals, such as pyrite. Amos et al. examine the salient aspects of the geochemistry of waste rock. Mill tailings – the waste material after ore minerals have been removed – are a volumetrically important solid waste at many mine sites. Their fine grain size and the options for their management make their behavior in the environment distinct from that of waste rock. Lindsay et al. describe some of these differences through three case-study examples. Subaqueous disposal of tailings is another option described by Moncur et al. Cyanide leaching for gold extraction is a common method throughout the world. Johnson describes environmental aspects of cyanidation. Uranium mining presents unique environmental challenges, particularly since in-situ recovery has seen widespread use. Campbell et al. review the environmental geochemistry of uranium mining and current research on bioremediation. Ore concentrates from many types of metal mining undergo a pyrometallurgical technique known as smelting to extract the metal. Slag is the result of smelting, and it may be an environmental liability or a valuable byproduct, as described by Piatak et al. Finally, the open pits that result from surface mining commonly reach below the water table. At the end of mining, these pits may fill to form lakes that become part of the legacy of the mine. Castendyk et al., in two papers, review theoretical aspects of the environmental limnology of pit lakes. They also describe approaches that have been used to model pit lake water balance, wall-rock contributions to pit lake chemistry, pit lake water quality, and limnological processes, such as vertical mixing, through the use of three case studies.

Applied Geochemistry↗

Major and trace elements in Mahogany zone oil shale in two cores from the Green River Formation, piceance basin, Colorado

The Parachute Creek Member of the lacustrine Green River Formation contains thick sequences of rich oil-shale. The richest sequence and the richest oil-shale bed occurring in the member are called the Mahogany zone and the Mahogany bed, respectively, and were deposited in ancient Lake Uinta. The name "Mahogany" is derived from the red-brown color imparted to the rock by its rich-kerogen content. Geochemical abundance and distribution of eight major and 18 trace elements were determined in the Mahogany zone sampled from two cores, U. S. Geological Survey core hole CR-2 and U. S. Bureau of Mines core hole O1-A (Figure 1). The oil shale from core hole CR-2 was deposited nearer the margin of Lake Uinta than oil shale from core hole O1-A. The major- and trace-element chemistry of the Mahogany zone from each of these two cores is compared using elemental abundances and Q-mode factor modeling. The results of chemical analyses of 44 CR-2 Mahogany samples and 76 O1-A Mahogany samples are summarized in Figure 2. The average geochemical abundances for shale (1) and black shale (2) are also plotted on Figure 2 for comparison. The elemental abundances in the samples from the two cores are similar for the majority of elements. Differences at the 95% probability level are higher concentrations of Ca, Cu, La, Ni, Sc and Zr in the samples from core hole CR-2 compared to samples from core hole O1-A and higher concentrations of As and Sr in samples from core hole O1-A compared to samples from core hole CR-2. These differences presumably reflect slight differences in depositional conditions or source material at the two sites. The Mahogany oil shale from the two cores has lower concentrations of most trace metals and higher concentrations of carbonate-related elements (Ca, Mg, Sr and Na) compared to the average shale and black shale. During deposition of the Mahogany oil shale, large quantities of carbonates were precipitated resulting in the enrichment of carbonate-related elements and dilution of most trace elements as pointed out in several previous studies. Q-mode factor modeling is a statistical method used to group samples on the basis of compositional similarities. Factor end-member samples are chosen by the model. All other sample compositions are represented by varying proportions of the factor end-members and grouped as to their highest proportion. The compositional similarities defined by the Q-mode model are helpful in understanding processes controlling multi-element distributions. The models for each core are essentially identical. A four-factor model explains 70% of the variance in the CR-2 data and 64% of the O1-A data (the average correlation coefficients are 0. 84 and 0. 80, respectively). Increasing the number of factors above 4 results in the addition of unique instead of common factors. Table I groups the elements based on high factor-loading scores (the amount of influence each element has in defining the model factors). Similar elemental associations are found in both cores. Elemental abundances are plotted as a function of core depth using a five-point weighted moving average of the original data to smooth the curve (Figure 3 and 4). The plots are grouped according to the four factors defined by the Q-mode models and show similar distributions for elements within the same factor. Factor 1 samples are rich in most trace metals. High oil yield and the presence of illite characterize the end-member samples for this factor (3, 4) suggesting that adsorption of metals onto clay particles or organic matter is controlling the distribution of the metals. Precipitation of some metals as sulfides is possible (5). Factor 2 samples are high in elements commonly associated with minerals of detrital or volcanogenic origin. Altered tuff beds and lenses are prevalent within the Mahogany zone. The CR-2 end-member samples for this factor contain analcime (3) which is an alteration product within the tuff beds of the Green River Formation. Th

Conference Paper↗

Water resources of Red River Parish, Louisiana

Red River Parish is on the eastern flank of the Sabine uplift in northwestern Louisiana. The 'area is underlain by lignitic clay and sand of Paleocene and Eocene age which dip to the east at the rate of about 30 feet per mile. The Red River is entrenched in these rocks in the western part of the parish. Alternating valley filling and erosion during the Quaternary period have resulted in the present lowland with flanking terraces. In the flood-plain area moderate to large quantities of very hard, iron-bearing water, suitable for irrigation, are available to wells in the alluvial sand and gravel of Quaternary age. The aquifer ranges in thickness from 20 to slightly more than 100 feet. It is recharged by downward seepage of rainfall through overlying clay and silt, by inflow from older sands adjacent to and beneath the entrenched valley, and by infiltration from the streams where the water table is below stream level during flood stages or as a result of pumping. Water levels are highest in the middle of the valley. Ground water moves mainly toward the Red River on the east and Bayou Pierre on the west, but small amounts move down the valley. Computations based on water-level and aquifer-test data indicate that the Quaternary alluvium contains more than 330 billion gallons of ground water in storage and that the maximum discharge of ground water to the streams is slightly more than 30 mgd (million gallons per day). At times of high river stage, surface water flows into the aquifer at a rate that depends in part upon the height and duration of the river stage. Moderate supplies of soft, iron-bearing water may be obtained from dissected Pleistocene terrace deposits that flank the flood plains of the Red River and Black Lake Bayou. However, the quantity of water that can be pumped from these deposits varies widely from place to place because of differences in the areal extent and saturated thickness of the segments of the deposits; this extent and thickness are governed in turn by the amount of erosion the deposits have undergone. Beds of fine-grained lignitic sands of Tertiary age contain water of generally good quality to depths of 150 to 450 feet. The thinness and low permeability of the sands restrict their development to low-yield wells. Water from these sands in the western part of the parish, where they lie beneath the alluvial valley, is more mineralized than that from the younger Tertiary sands exposed in the east-central area. Streamflow records have been collected on the principal streams in Red River Parish since 1939. Additional spot low-flow data were obtained on several small streams originating within the parish for a study made in connection with the preparation of this report. Quality-of-water data for streams in the parish were collected on an occasional spot-sampling basis prior to and during this investigation. The largest source of surface water in the parish is the Red River, which drains approximately 63,400 square miles upstream from the parish. The Red River has an average flow of about 13,100 cfs (cubic feet per second), or about 8,500 mgd. Many of the streams that drain the upland area are not dependable sources of supply because their flows are not well sustained during dry seasons. The average annual precipitation over the parish is about 52 inches, of which about 17 inches becomes runoff; this runoff is equivalent to a continuous flow of about 1.25 cfs per square mile. Seasonal and annual runoff varies, but no significant trends have been noticed. The principal surface-water problems in the parish pertain to flood control, drainage, irrigation, and navigation. Flood problems have been alleviated considerably by the operation of Denison Dam (Lake Texoma), the completion of levees on the Red River, channel improvements on Bayou Pierre, and the completion of Wallace Lake reservoir on Cypress Bayou. There are wet lands along the Red River that would be very productive if properly drained

Water Supply Paper↗

Science mission requirements for a globally ranging, riserless drilling vessel for U.S. Scientific Ocean Drilling

Through the collection and analysis of shallow and deep subseafloor sediments, rocks, fluids, and life, scientific ocean drilling has enriched our understanding of the complex Earth system. Among other achievements, scientific ocean drilling has documented the history of Earth’s climate, the waxing and waning of polar ice sheets, the past changes in ocean and atmospheric circulation, the existence and function of microbial life in the subseafloor, the compositional variations in Earth’s crust and underlying mantle, and the physical and chemical processes acting at subduction zones, including those associated with tsunamigenic earthquakes. Over the decades, more than 12,000 articles that depend on analyses of scientific ocean drilling samples and geophysical data have been published, many detailing breakthrough contributions to global knowledge about the Earth system. Approximately 45% of these publications were led by U.S.-affiliated authors (International Ocean Discovery Program Publication Services, 2021). Since the mid-1980s, the workhorse of this multidisciplinary, international research effort has been the riserless D/V JOIDES Resolution, operated by Texas A&M University with funding from the U.S. National Science Foundation (NSF). D/V JOIDES Resolution has conducted the vast majority of scientific ocean drilling expeditions and collected most of the scientific cores over that period, including 82% of the expeditions and 93% of the cores in the last decade alone, despite being one of three platforms that is operated within the International Ocean Discovery Program. However, D/V JOIDES Resolution is approaching the end of its useful life. With a strong commitment to continue scientific ocean drilling beyond the end of the current phase, the community developed a document outlining the research frontiers that should be pursued. Exploring Earth by Scientific Ocean Drilling: 2050 Science Framework (Koppers and Coggon, 2020) describes seven scientific strategic objectives that focus on understanding interconnections within the Earth system and five flagship initiatives that integrate these objectives into long-term research efforts that address issues facing society. Additional elements in the 2050 Science Framework, including STEM education, workforce development, technology development, and innovative applications of data analytics, will advance the goals of scientific ocean drilling. Addressing the 2050 Science Framework also requires building partnerships with allied U.S. and international science programs and strengthening existing ones. To implement a significant portion of the 2050 Science Framework, the U.S. scientific community seeks to lease or acquire a newly built, globally ranging, state-of-the art, riserless drilling vessel. The many and varied technical and human resources requirements for successful accomplishment of scientific and educational goals summarized in this document and described in detail in the 2050 Science Framework require broad community input and careful consideration. Following receipt of NSF’s formal Request for Assistance to the United States Science Support Program (USSSP), the U.S. scientific ocean drilling community conducted a one-year exercise to identify its national scientific needs and priorities in order to determine the Science Mission Requirements (SMRs) presented here. This community effort included: (1) a U.S. community-wide survey to identify the specific operational and technical capabilities critical to addressing science in the 2050 Science Framework; (2) a series of online workshops focusing on critical capabilities identified by the survey; and (3) a large in-person workshop to synthesize the results of the survey and the virtual workshops (Appendix 1). The approach was designed to reach as many participants as possible. Overall, 278 survey responses were received from U.S. community members, representing 104 unique institutions from 39 states and the District of Columbia, and 137 unique individuals participated in the workshops (Appendix 2). The results of this effort comprise two classes of SMRs: Foundational Science Mission Requirements and Primary Science Mission Requirements. Foundational SMRs define minimum criteria for a new riserless drilling vessel that can address significant portions of the 2050 Science Framework. Primary SMRs build upon the Foundational SMRs and will create more robust science opportunities and data collection capabilities, will increase progress in addressing the 2050 Science Framework objectives, and will provide more real-time ship-to-shore interaction to improve science productivity, engagement, and outreach. Modern safety and environmental standards, including meeting standards to access protected waters such as exclusive economic zones, extended continental shelves, or high latitudes, while being cognizant of the vessel’s environmental footprint. Safe and efficient operations in global locations and in water depths from 70 m to 6000+ m, with total drill string length of at least 7000 m. High-quality core and data collection from a range of key subseafloor environments. Advanced heave compensation, dynamic positioning, and drill pipe stability. Modern mud and cement/casing systems. Critical onboard measurements for safety, operational decision-making, documentation of ephemeral properties, mission-specific science, and long-term science goals that extend beyond a single expedition. Designated and appropriate space for sample and data preservation. Highly skilled onboard personnel, including technical staff for curation and core handling; support for safety, time-sensitive, and critical shipboard measurements; computer support; equipment and instrument repair; application support; and data assurance. Primary Science Mission Requirements include: Flexible shipboard space for laboratories and on deck to ensure safe, successful implementation of diverse science objectives and operations. Minimizing contamination of recovered samples. Over-the-side capabilities for science-supporting technology (e.g., remotely operated vehicles, water- column sampling, sediment-water interface sampling). Downhole logging and measurements. Expanded borehole observatory capabilities. Reliable and consistent ship-to-shore communications. NSF’s investment in a new globally ranging, riserless drilling vessel will have a powerful economic multiplier effect, including the infusion of additional science support funds in the United States for training and research, the development of new technologies and tools, and the associated scientific and technical workforce development. The skills and knowledge gained through scientific ocean drilling are translatable to careers in fields such as sustainable energy development (e.g., geothermal and offshore wind), carbon sequestration, data management and cyberinfrastructure, biotechnology, communications, science education, policy, hazard mitigation, and environmental management. The United States is a leader in a well-established and internationally collaborative scientific ocean drilling community. A modern, globally ranging, riserless drilling vessel will allow the United States to expand its leadership position, address broad scientific questions that current capabilities preclude, and cultivate equitable international, multidisciplinary collaborations that will ensure scientific ocean drilling’s future success.

Report↗

Geophysics- and geochemistry-based assessment of the geochemical characteristics and groundwater-flow system of the U.S. part of the Mesilla Basin/Conejos-Médanos aquifer system in Doña Ana County, New Mexico, and El Paso County, Texas, 2010–12

One of the largest rechargeable groundwater systems by total available volume in the Rio Grande/Río Bravo Basin (hereinafter referred to as the “Rio Grande”) region of the United States and Mexico, the Mesilla Basin/Conejos-Médanos aquifer system, supplies water for irrigation as well as for cities of El Paso, Texas; Las Cruces, New Mexico; and Ciudad Juárez, Chihuahua, Mexico. The U.S. Geological Survey in cooperation with the Bureau of Reclamation assessed the groundwater resources in the Mesilla Basin and surrounding areas in Doña Ana County, N. Mex., and El Paso County, Tex., by using a combination of geophysical and geochemical methods. The study area consists of approximately 1,400 square miles in Doña Ana County, N. Mex., and 100 square miles in El Paso County, Tex. The Mesilla Basin composes most of the study area and can be divided into three parts: the Mesilla Valley, the West Mesa, and the East Bench. The Mesilla Valley is the part of the Mesilla Basin that was incised by the Rio Grande between Selden Canyon to the north and by a narrow valley (about 4 miles wide) to the southeast near El Paso, Tex., named the Paso del Norte, which is sometimes referred to in the literature as the “El Paso Narrows.” Previously published geophysical data for the study area were compiled and these data were augmented by collecting additional geophysical and geochemical data. Geophysical resistivity measurements from previously published helicopter frequency domain electromagnetic data, previously published direct-current resistivity soundings, and newly collected (2012) time-domain electromagnetic soundings were used in the study to detect spatial changes in the electrical properties of the subsurface, which reflect changes that occur within the hydrogeology. The geochemistry of the groundwater system was evaluated by analyzing groundwater samples collected in November 2010 for physicochemical properties, major ions, trace elements, nutrients, pesticides (reported but not used in the assessment), and environmental tracers. The data obtained from these samples (with the exception of the pesticide data) were used to gain insights into processes controlling the groundwater movement through the groundwater system in the study area. Results from the geophysical and geochemical assessments facilitated the interpretation of the geochemical characteristics of the groundwater sources and geochemical groups within the groundwater system. The groundwater-flow system in the study area consists primarily of the Mesilla Basin aquifer system, which can be divided into four hydrogeologic units by using an informal classification scheme based on basin-fill stratigraphy and sedimentology with an emphasis on aquifer characteristics. The four hydrogeologic units are (1) the Rio Grande alluvium, which is the shallow aquifer of the Mesilla Basin within the confines of the Mesilla Valley, and the three hydrogeologic units that compose the Santa Fe Group: (2) the lower part of the Santa Fe Group, which is the least productive zone, (3) the middle part of the Santa Fe Group, which is the primary water-bearing hydrogeologic unit in the basin and is generally saturated, and (4) the upper part of the Santa Fe Group, which is the most productive water-bearing unit within the Santa Fe Group but is only partially saturated in the north and largely unsaturated in the south and western parts of the Mesilla Basin. The helicopter frequency domain electromagnetic survey results indicated that approximately half of the resistivity values were less than 10 ohm-meters at depths of 50 and 100 feet with a transition where the resistivity values changed from relatively high values (greater than 20 ohm-meters) to relatively low resistivity values (less than 10 ohm-meters) near Vado, New Mexico. Slightly more than 25 percent of the gridded resistivity values from the three-dimensional grid of the combined inverse modeling results of the direct-current resistivity and time-domain electromagnetic soundings were equal to or less than 10 ohm-meters with large regions of low resistivity becoming apparent in the southernmost part of the study area near the Paso Del Norte where these low resistivity features are spatially the widest at or below the top of the bedrock. These low resistivity values might represent clayey deposits, sediments composed largely of sand and gravel saturated with saline water, or both. Historical dissolved-solids-concentration data within the surface geophysical subset area of the study area were compiled and compared to the inverse modeling results of the combined direct-current resistivity and time-domain soundings; this comparison was done to strengthen the interpretation made from the combined inverse modeling results that the low resistivity features were representative of sand and gravel deposits saturated with saline water and not clayey deposits. Water-level altitudes within the Rio Grande alluvium generally decreased from north to south, with a west to east decrease in water-level altitudes near Las Cruces, New Mexico, as a result of groundwater pumping. Groundwater flow within the Santa Fe Group is more complex than the groundwater flow within the Rio Grande alluvium because of the larger lateral and vertical extent of the Santa Fe Group compared to the Rio Grande alluvium. Groundwater from the Organ Mountains flows directly south towards the Paso del Norte. Groundwater from the Robledo Mountains, the Rough and Ready Hills, and the Sleeping Lady Hills generally flows to the southeast. Groundwater flowing near the north end of the midbasin uplift generally continues east towards the Rio Grande and then flows south on the east side of the midbasin uplift. Groundwater flowing near the west side of the midbasin uplift generally continues south parallel to the faults that make up the midbasin uplift and then flows east towards the Paso del Norte when it reaches the south end of the midbasin uplift. Groundwater from the Aden Hills and the East and West Potrillo Mountains flows to the south end of the midbasin uplift and then continues east towards the Paso del Norte. Throughout most of the Mesilla Valley, the vertical hydraulic gradient was downward because the water-level altitude in the Rio Grande alluvium was higher than it was in the Santa Fe Group, but in some areas (typically in the middle and southern parts of the Mesilla Valley), the vertical hydraulic gradient was substantially reduced or even reversed to an upward hydraulic gradient. The geochemistry data indicate that there was a complex system of multiple geochemical endmembers and mixing between these endmembers with recharge to the Rio Grande alluvium and Santa Fe Group composed mostly of seepage from the Rio Grande, inflows from deeper or neighboring water systems, and mountain-front recharge. Five distinct geochemical groups were identified in the Mesilla Basin study area: (1) ancestral Rio Grande (pre-Pleistocene) geochemical group, (2) modern Rio Grande (Pleistocene to present) geochemical group, (3) mountain-front geochemical group, (4) deep groundwater upwelling geochemical group, and (5) unknown freshwater geochemical group. The ancestral Rio Grande groundwater was water that recharged into the system as seepage losses from the ancestral Rio Grande; this groundwater generally flows from north to south-southeast towards the Paso del Norte. Groundwater on the west side of the midbasin uplift generally flows south until it reaches the southern part of the study area; from the southern part of the study area, the groundwater flows east towards the Paso del Norte. Groundwater on the east side of the midbasin uplift flows south-southeast towards the Paso del Norte where it mixes with groundwater from the modern Rio Grande, uplifted areas in the west, and the deep saline source. The water type of the modern Rio Grande geochemical group ranged from calcium-sulfate water type in the northern part of the study area to sodium-chloride-sulfate water type in the southern part of the study area; from north to south there was a substantial increase in specific conductance, strontium-87/strontium-86 ratio, potassium, and the trace metals of iron and lithium, changing the water chemistry such that it became similar to the water chemistry of the deep groundwater upwelling geochemical group. From age-dating results, water in the modern Rio Grande geochemical group was recharged to the Rio Grande alluvium within the past 10 years. The mountain-front geochemical group was generally old water (apparent age was greater than 10,000 carbon-14 years before present) that was somewhat mineralized and has relatively high concentrations of fluoride and silica, which might indicate longer exposure to volcanic and siliciclastic rocks or aluminosilicate minerals. There were five different locations of recharge determined from the groundwater geochemistry within the mountain-front geochemical group, all having a slightly different geochemical signature: (1) the Rough and Ready Hills, Robledo Mountains, and the Sleeping Lady Hills, (2) the Doña Ana Mountains, (3) the Aden Hills and West Potrillo Mountains, (4) the East Potrillo Mountains, and (5) the Sierra Juárez in Mexico. The groundwater from the Rough and Ready Hills, Robledo Mountains, the Sleeping Lady Hills, and the Doña Ana Mountains generally flows toward the Rio Grande and eventually mixes together and with the modern Rio Grande groundwater. The groundwater originating from the Aden Hills and East and West Potrillo Mountains generally flows east to southeast at a slow rate and eventually mixes and continues east, where it mixes with groundwater from the ancestral Rio Grande geochemical group and with the groundwater from the Sierra Juárez. The groundwater from the Sierra Juárez flows north and then east towards the Paso del Norte where it mixes with groundwater from the uplifted areas in the west, ancestral and modern Rio Grande groundwater, and the upwelling groundwater from a deep saline source. The deep groundwater upwelling geochemical group had the highest concentrations of bicarbonate, potassium, silica, aluminum, iron, and lithium within the study area, indicating that it had been in contact with carbonate and siliciclastic rocks for a much longer period of time and at higher temperatures compared to the other geochemical groups, and was most likely ancient marine groundwater originating from the Paleozoic and Cretaceous carbonate rocks which was upwelling into the Mesilla Basin aquifer system in the southeastern part of the study area through the extensive fault systems. Direct-current resistivity and time-domain electromagnetic soundings support the interpretation of ancient marine groundwater upwelling into the Mesilla Basin aquifer system, as do the analytical results from wells, and the helicopter frequency domain electromagnetic data collected along the Rio Grande. The hydrogen-2/hydrogen-1 ratio and oxygen-18/oxygen-16 ratio isotopic results for samples in the unknown freshwater geochemical group did not plot on the Rio Grande evaporation line, indicating this group did not have a Rio Grande signature (that is, there was no isotopic evidence of a component of Rio Grande water) and it also had the lowest mineralized content of any geochemical group in the study area.

New Mexico, Texas↗

U.S. Geological Survey Karst Interest Group Proceedings, Carlsbad, New Mexico, April 29-May 2, 2014

Karst aquifer systems are present throughout parts of the United States and some of its territories, and have developed in carbonate rocks (primarily limestone and dolomite) that span an interval of time encompassing more than 550 million years. The depositional environments, diagenetic processes, post-depositional tectonic events, and geochemical weathering processes that form karst aquifers are varied and complex, and involve biological, chemical, and physical changes. These factors, combined with the diverse climatic regimes under which karst development in these rocks has taken place, result in the unique dual- or triple-porosity nature of karst aquifers. These complex hydrogeologic systems typically represent challenging and unique conditions to scientists attempting to study groundwater flow and contaminant transport in these terrains. The dissolution of carbonate rocks and the subsequent development of distinct and beautiful landscapes, caverns, and springs has resulted in the most exceptional karst areas of the United States being designated as national or state parks; commercial caverns and known privately owned caves number in the tens of thousands. Both public and private properties provide access for scientists to study the flow of groundwater in situ. Likewise, the range and complexity of landforms and groundwater flow systems associated with karst terrains are enormous, perhaps more than for any other aquifer type. Karst aquifers and landscapes that form in tropical areas, such as the cockpit karst along the north coast of Puerto Rico, differ greatly from karst landforms in more arid climates, such as the Edwards Plateau in west-central Texas or the Guadalupe Mountains near Carlsbad, New Mexico, where hypogenic processes have played a major role in speleogenesis. Many of these public and private lands also contain unique flora and fauna associated with these karst hydrogeologic systems. As a result, numerous federal, state, and local agencies have a strong interest in the study of karst terrains. Many of the major springs and aquifers in the United States have developed in carbonate rocks, such as the Floridan aquifer system in Florida and parts of Alabama, Georgia, and South Carolina; the Ozark Plateaus aquifer system in parts of Arkansas, Kansas, Missouri, and Oklahoma; and the Edwards-Trinity aquifer system in west-central Texas. These aquifers, and the springs that discharge from them, serve as major water-supply sources and as unique ecological habitats. Competition for the water resources of karst aquifers is common, and urban development and the lack of attenuation of contaminants in karst areas can impact the ecosystem and water quality of these aquifers. The concept for developing a platform for interaction among scientists within the U.S. Geological Survey (USGS) working on karst-related studies evolved from the November 1999 National Ground-Water Meeting of the USGS. As a result, the Karst Interest Group (KIG) was formed in 2000. The KIG is a loose-knit, grass-roots organization of USGS and non-USGS scientists and researchers devoted to fostering better communication among scientists working on, or interested in, karst science. The primary mission of the KIG is to encourage and support interdisciplinary collaboration and technology transfer among scientists working in karst areas. Additionally, the KIG encourages collaborative studies between the different mission areas of the USGS as well as other federal and state agencies, and with researchers from academia and institutes. The KIG also encourages younger scientists by participation of students in the poster and oral sessions. To accomplish its mission, the KIG has organized a series of workshops that are held near nationally important karst areas. To date (2014) six KIG workshops, including the workshop documented in this report, have been held. The workshops typically include oral and poster sessions on selected karst-related topics and research, as well as field trips to local karst features. Proceedings of the workshops are published by the USGS and are available online at http://water.usgs.gov/ogw/karst/kig . The first KIG workshop was held in St. Petersburg, Florida, February 13–16, 2001, in the vicinity of the large springs and other karst features of the Floridan aquifer system. The second KIG workshop was held August 20–22, 2002, in Shepherdstown, West Virginia, in proximity to the carbonate aquifers of the northern Shenandoah Valley and highlighted an invited presentation on karst literature by the late Barry F. Beck of P.E. LaMoreaux and Associates. The third KIG workshop was held September 12–15, 2005, in Rapid City, South Dakota, nearby to karst features in evaporites and limestones of the Madison Group in the Black Hills of South Dakota, including Wind Cave National Park and Jewel Cave National Monument. The workshop also included a featured presentation by Thomas Casadevall, Central Region Director, USGS, on the status of earth science at the USGS and evening trips to Jewel Cave led by Mike Wiles, National Park Service (NPS) and Wind Cave led by Rod Horrocks, NPS. The fourth KIG workshop was held May 27–29, 2008, and hosted by the Hoffman Environmental Research Institute and Center for Cave and Karst Studies at Western Kentucky University in Bowling Green, Kentucky, near Mammoth Cave National Park and karst features of the Chester Upland and Pennyroyal Plateau. The workshop featured a late-night field trip into Mammoth Cave with Rickard Toomey and Rick Olsen, NPS. The fifth workshop was held April 26–29, 2011, and was a joint meeting of the USGS KIG and University of Arkansas HydroDays, hosted by the Department of Geosciences at the University of Arkansas in Fayetteville. The workshop featured an outstanding field trip to the unique karst terrain along the Buffalo National River of the southern Ozarks and a keynote presentation on paleokarst in the United States by Art and Peggy Palmer. This sixth and current 2014 KIG workshop is hosted by the National Cave and Karst Research Institute (NCKRI) in Carlsbad, New Mexico, with Director of NCKRI, George Veni, serving as co-chair of the workshop with Eve Kuniansky, USGS. The session planning committee for this sixth workshop includes Van Brahana, USGS retired and University of Arkansas Professor Emeritus; Tom Byl, USGS and Tennessee State University; Zelda Bailey, former Director of NCKRI and retired Director, National Institute of Standards and Technology, Boulder Laboratory, Colorado; Patrick Tucci, USGS retired; and Mike Bradley, Allan Clark, Geoff Delin, Daniel Doctor, James Kaufmann, Eve Kuniansky, Randy Orndorff, Larry Spangler, and Dave Weary of the USGS. The karst hydrology field trip on Thursday will be led by Lewis Land (NCKRI karst hydrologist) and the optional Friday field trip on the geology of Carlsbad Caverns National Park will be led by George Veni. The keynote speaker is Dr. Penelope Boston, Director of Cave and Karst Studies at New Mexico Tech, Socorro, and Academic Director at NCKRI, who will address the future of karst research. Additionally, there is a featured presentation “Irish karst and its management,” by Caoimhe Hickey, The Geological Survey of Ireland, preceding a panel discussion on “Collaboration During Times of Limited Resources.” The extended abstracts of USGS authors were peer reviewed and approved for publication by the U.S. Geological Survey. Articles submitted by university researchers and other federal and state agencies did not go through the formal USGS peer review and approval process, and therefore may not adhere to our editorial standards or stratigraphic nomenclature and is not research conducted or data collected by the USGS. However, all articles had at a minimum of two peer reviews, and all articles were edited for consistency of appearance in the published Proceedings. The use of trade, firm or product names in any article is for descriptive purposes only and does not imply endorsement by the U.S. Government. The USGS, Office of Groundwater, provides technical support for the Karst Interest Group website and public availability of the Proceedings from these workshops, and the USGS Groundwater Resources Program funds the publication costs. Finally, the cover illustration is the work of Ann Tihansky, USGS, used since the first KIG workshop in 2000.

Scientific Investigations Report↗

Hydrogeologic characterization of the San Antonio Creek Valley watershed, Santa Barbara County, California

The San Antonio Creek Valley watershed (SACVW) is located in western Santa Barbara County, about 15 miles south of Santa Maria and 55 miles north of Santa Barbara, California. The SACVW is about 135 square miles and encompasses the San Antonio Creek Valley groundwater basin; the SACVW is separated from adjacent groundwater basins by the Casmalia and Solomon Hills to the north, and the Purisima Hills to the south. At the western, downstream part of the valley, uplifted, consolidated rocks cause groundwater to discharge at land surface at Barka Slough. Since the late 1800s, groundwater has been the primary source of water for agricultural, military, municipal, and domestic uses. Groundwater withdrawal by pumping exceeded the amount of water replenishing the aquifer system during water years 1948–2018, causing groundwater-level declines of more than 150 feet in parts of the valley and reducing base flow at Barka Slough. Reliance on groundwater for agricultural water use (primarily for the irrigation and frost protection of vineyards, and fruit and berry crops) continues to strain the sustainability of the groundwater system. Through a cooperative agreement, the Santa Barbara County Water Agency and Vandenberg Space Force Base invited the U.S. Geological Survey to address declines in groundwater levels, develop a better understanding of the hydrogeologic system, and provide tools to help evaluate and manage the effects of future development of the San Antonio Creek Valley groundwater basin within the encompassing San Antonio Creek Valley watershed (SACVW). The objectives of this study were to (1) refine the hydrogeologic framework of the San Antonio Creek Valley watershed, (2) quantify the hydrologic budget of the valley, and (3) develop hydrologic modeling tools to evaluate and aid in managing the groundwater resource. This report focuses on the first and second objectives to construct a hydrogeologic framework and characterize the historical and present-day hydrologic conditions of the SACVW during water years 1948–2018. As part of the second objective, work included quantifying the hydrologic budget and evaluating the hydrogeologic system using a combination of existing data and geologic and hydrologic data collected for this study. The groundwater-flow system in the SACVW consists of five hydrogeologic units. These separate water-bearing units were identified based on hydrogeologic properties, such as sediment grain size, vertical-head differences in multiple-depth, monitoring-well sites, long-term groundwater level responses to pumping and climate, and the chemical character of groundwater and groundwater age in the mostly semi-consolidated to unconsolidated basin-fill sediments. The hydrogeologic units that comprise the different aquifers vary in their lithologic composition. The upper and lower aquifers (upper Paso Robles Formation, and lower Paso Robles Formation and Careaga Sandstone, respectively) are relatively coarse grained and are comprised of sand, gravel, and clay; the middle confining unit (the middle Paso Robles Formation) is relatively fine grained and is comprised of primarily clay, silt, and sand. The Pezzoni-Casmalia and Los Alamos faults, which are inferred to transect the SACVW between the western and eastern areas of the valley floor, do not appear to substantially affect the groundwater system. Present-day recharge to the study area occurs primarily as infiltration from precipitation and streams in the upland areas of the Casmalia Hills and Solomon Hills, and along the main channel of San Antonio Creek. Reported estimates of annual natural recharge during water years 1948–2018 generally ranged from about 5,000 acre-feet to more than about 30,000 acre-feet. Stable and radioactive isotopes show that groundwater from the lower aquifer is old and probably was recharged as infiltration from precipitation and streams in the eastern upland areas of the Solomon Hills; however, the infiltration and recharge from these sources probably does not occur under present-day climatic conditions. Anthropogenic recharge, from sources such as return flow from agricultural irrigation, municipal water systems, and wastewater effluent, was estimated to range from about 600 acre-feet in 1948 to about 6,600 acre-feet in 2018. The average annual amount of groundwater removed from the SACVW by pumping during 1948–2018 was estimated to be about 17,200 acre-feet per year, increasing from about 3,000 acre-feet in 1948 to about 32,600 acre-feet in 2018. Estimates of annual pumpage generally exceeded estimates of annual recharge beginning in the mid-1970s and continuing through 2018. The predominant direction of groundwater flow under historical and present-day conditions was from the eastern uplands in the Solomon Hills to the west along San Antonio Creek to the discharge area in Barka Slough, and from the northern uplands in the Casmalia Hills south to San Antonio Creek. Pumpage since the early 1900s and the subsequent groundwater-level declines have substantially reduced the amount of natural groundwater discharge at Barka Slough. Estimates of base flow to San Antonio Creek at the western, downstream extent of the SACVW have varied over time in response to changes in groundwater pumpage and climate; however, there was an overall decline in base flow during water years 1956–2018, decreasing from an average of about 1,700 acre-feet per year during 1956–69, to about 300 acre-feet per year during 2016–18. The long-term extraction of groundwater correlates with a decrease in groundwater levels by more than about 150 feet since the early 1940s in the eastern part of the basin near Los Alamos, and as much as about 50 feet in the upland areas and in the western part of the basin. At Barka Slough, groundwater levels have declined below land surface in some places, altering native riparian vegetation in and around the slough. Surface-water quality in the SACVW varied depending on location and the time of year the samples were collected and on the amount of annual precipitation Most groundwater in the SACVW was calcium-bicarbonate-type water with total dissolved-solids concentrations of about 500–800 milligrams per liter generally representing water naturally recharged as infiltration from precipitation and streams. Total dissolved-solids concentrations in some wells ranged from 800 to 8,000 milligrams per liter, suggesting mixing of naturally recharged infiltrated water with water associated with oil-bearing geologic formations, agricultural products, or the evaporation of shallow groundwater. Concentrations of total dissolved solids and the chemical constituents chloride, nitrate plus nitrite (as nitrogen), calcium, and magnesium at selected wells generally increased during water years 1980–2018; increasing concentrations of these constituents may be associated with the expansion of agriculture in the watershed over time and the corresponding increase in the use of nitrates and calcium- and magnesium-based fertilizers and soil additives in modern agricultural practices. The predominant direction of groundwater flow during historical and present-day conditions was from the eastern uplands in the Solomon Hills to the west along San Antonio Creek toward Barka Slough, and from the western uplands in the Casmalia Hills south to San Antonio Creek. The age of groundwater in the SACVW was evaluated using radioactive isotopes, and the flow of groundwater within the SACVW was evaluated using radioactive and stable isotopes. Modern groundwater (recharged after 1952) was generally found adjacent to San Antonio Creek and its tributaries in wells with perforated depths that averaged about 270 feet below land surface. Pre-modern groundwater (recharged before 1952) was found in wells that had average perforation depths of about 540 ft below land surface. Pre-modern groundwater identified in wells in the eastern upland area is interpreted to have had long, slow travel times to the western part of the SACVW where it was eventually discharged as base flow at Barka Slough or extracted as groundwater pumpage.

California↗

Simulated effects of hydrologic, water quality, and land-use changes of the Lake Maumelle watershed, Arkansas, 2004–10

Lake Maumelle, located in central Arkansas northwest of the cities of Little Rock and North Little Rock, is one of two principal drinking-water supplies for the Little Rock, and North Little Rock, Arkansas, metropolitan areas. Lake Maumelle and the Maumelle River (its primary tributary) are more pristine than most other reservoirs and streams in the region with 80 percent of the land area in the entire watershed being forested. However, as the Lake Maumelle watershed becomes increasingly more urbanized and timber harvesting becomes more extensive, concerns about the sustainability of the quality of the water supply also have increased. Two hydrodynamic and water-quality models were developed to examine the hydrology and water quality in the Lake Maumelle watershed and changes that might occur as the watershed becomes more urbanized and timber harvesting becomes more extensive. A Hydrologic Simulation Program–FORTRAN watershed model was developed using continuous streamflow and discreet suspended-sediment and water-quality data collected from January 2004 through 2010. A CE–QUAL–W2 model was developed to simulate reservoir hydrodynamics and selected water-quality characteristics using the simulated output from the Hydrologic Simulation Program–FORTRAN model from January 2004 through 2010. The calibrated Hydrologic Simulation Program–FORTRAN model and the calibrated CE–QUAL–W2 model were developed to simulate three land-use scenarios and to examine the potential effects of these land-use changes, as defined in the model, on the water quality of Lake Maumelle during the 2004 through 2010 simulation period. These scenarios included a scenario that simulated conversion of most land in the watershed to forest (scenario 1), a scenario that simulated conversion of potentially developable land to low-intensity urban land use in part of the watershed (scenario 2), and a scenario that simulated timber harvest in part of the watershed (scenario 3). Simulated land-use changes for scenarios 1 and 3 resulted in little (generally less than 10 percent) overall effect on the simulated water quality in the Hydrologic Simulation Program–FORTRAN model. The land-use change of scenario 2 affected subwatersheds that include Bringle, Reece, and Yount Creek tributaries and most other subwatersheds that drain into the northern side of Lake Maumelle; large percent increases in loading rates (generally between 10 and 25 percent) included dissolved nitrite plus nitrate nitrogen, dissolved orthophosphate, total phosphorus, suspended sediment, dissolved ammonia nitrogen, total organic carbon, and fecal coliform bacteria. For scenario 1, the simulated changes in nutrient, suspended sediment, and total organic carbon loads from the Hydrologic Simulation Program–FORTRAN model resulted in very slight (generally less than 10 percent) changes in simulated water quality for Lake Maumelle, relative to the baseline condition. Following lake mixing in the falls of 2006 and 2007, phosphorus and nitrogen concentrations were higher than the baseline condition and chlorophyll a responded accordingly. The increased nutrient and chlorophyll a concentrations in late October and into 2007 were enough to increase concentrations, on average, for the entire simulation period (2004–10). For scenario 2, the simulated changes in nutrient, suspended sediment, total organic carbon, and fecal coliform bacteria loads from the Lake Maumelle watershed resulted in slight changes in simulated water quality for Lake Maumelle, relative to the baseline condition (total nitrogen decreased by 0.01 milligram per liter; dissolved orthophosphate increased by 0.001 milligram per liter; chlorophyll a decreased by 0.1 microgram per liter). The differences in these concentrations are approximately an order of magnitude less than the error between measured and simulated concentrations in the baseline model. During the driest summer in the simulation period (2006), phosphorus and nitrogen concentrations were lower than the baseline condition and chlorophyll a concentrations decreased during the same summer season. The decrease in nitrogen and chlorophyll a concentrations during the dry summer in 2006 was enough to decrease concentrations of these constituents very slightly, on average, for the entire simulation period (2004–10). For scenario 3, the changes in simulated nutrient, suspended sediment, total organic carbon, and fecal coliform bacteria loads from Lake Maumelle watershed resulted in very slight changes in simulated water quality within Lake Maumelle, relative to the baseline condition, for most of the reservoir. Among the implications of the results of the modeling described in this report are those related to scale in both space and time. Spatial scales include limited size and location of land-use changes, their effects on loading rates, and resultant effects on water quality of Lake Maumelle. Temporally, the magnitude of the water-quality changes simulated by the land-use change scenarios over the 7-year period (2004–10) are not necessarily indicative of the changes that could be expected to occur with similar land-use changes persisting over a 20-, 30-, or 40- year period, for example. These implications should be tempered by realization of the described model limitations. The Hydrologic Simulation Program–FORTRAN watershed model was calibrated to streamflow and water-quality data from five streamflow-gaging stations, and in general, these stations characterize a range of subwatershed areas with varying land-use types. The CE–QUAL–W2 reservoir model was calibrated to water-quality data collected during January 2004 through December 2010 at three reservoir stations, representing the upper, middle, and lower sections of the reservoir. In general, the baseline simulation for the Hydrologic Simulation Program–FORTRAN and the CE–QUAL–W2 models matched reasonably well to the measured data. Simulated and measured suspended-sediment concentrations during periods of base flow (streamflows not substantially influenced by runoff) agree reasonably well for Maumelle River at Williams Junction, the station representing the upper end of the watershed (with differences—simulated minus measured value—generally ranging from -15 to 41 milligrams per liter, and percent difference—relative to the measured value—ranging from -99 to 182 percent) and Maumelle River near Wye, the station just above the reservoir at the lower end (differences generally ranging from -20 to 22 milligrams per liter, and percent difference ranging from -100 to 194 percent). In general, water temperature and dissolved-oxygen concentration simulations followed measured seasonal trends for all stations with the largest differences occurring during periods of lowest temperatures or during the periods of lowest measured dissolved-oxygen concentrations. For the CE–QUAL–W2 model, simulated vertical distributions of water temperatures and dissolved-oxygen concentrations agreed with measured vertical distributions over time, even for the most complex water-temperature profiles. Considering the oligotrophic-mesotrophic (low to intermediate primary productivity and associated low nutrient concentrations) condition of Lake Maumelle, simulated algae, phosphorus, and nitrogen concentrations compared well with generally low measured concentrations.

Arkansas↗

U.S. Geological Survey Karst Interest Group Proceedings, San Antonio, Texas, May 16–18, 2017

Introduction and Acknowledgments Karst aquifer systems are present throughout parts of the United States and some of its territories, and have developed in carbonate rocks (primarily limestone and dolomite) and evaporites (gypsum, anhydrite, and halite) that span an interval of time encompassing more than 550 million years. The depositional environments, diagenetic processes, post-depositional tectonic events, and geochemical weathering processes that form karst aquifers are varied and complex. These factors involve biological, chemical, and physical changes that when combined with the diverse climatic regimes in which karst development has taken place, result in the unique dual- or triple-porosity nature of karst aquifers. These complex hydrogeologic systems typically represent challenging and unique conditions to scientists attempting to study groundwater flow and contaminant transport in these terrains. The dissolution of carbonate rocks and the subsequent development of distinct and beautiful landscapes, caverns, and springs have resulted in the most exceptional karst areas being designated as national or state parks. Tens of thousands of similar areas in the United States have been developed into commercial caverns and known privately owned caves. Both public and private properties provide access for scientists to study the flow of groundwater in situ . Likewise, the range and complexity of landforms and groundwater flow systems associated with karst terrains are enormous, perhaps more than for any other aquifer type. Karst aquifers and landscapes that form in tropical areas, such as the cockpit karst along the north coast of Puerto Rico, differ greatly from karst landforms in more arid climates, such as the Edwards Plateau in west-central Texas or the Guadalupe Mountains near Carlsbad, New Mexico, where hypogenic processes have played a major role in speleogenesis. Many of these public and private lands also contain unique flora and fauna associated with these karst hydrogeologic systems. As a result, numerous federal, state, and local agencies have a strong interest in the study of karst terrains. Many of the major springs and aquifers in the United States have developed in carbonate rocks, such as the Floridan aquifer system in Florida and parts of Alabama, Georgia, and South Carolina; the Ozark Plateaus aquifer system in parts of Arkansas, Kansas, Missouri, and Oklahoma; and the Edwards-Trinity aquifer system in west-central Texas. These aquifers, and the springs that discharge from them, serve as major water-supply sources and form unique ecological habitats. Competition for the water resources of karst aquifers is common, and urban development and the lack of attenuation of contaminants in karst areas due to dissolution features that form direct pathways into karst aquifers can impact the ecosystem and water quality associated with these aquifers. The concept for developing a platform for interaction among scientists within the U.S. Geological Survey (USGS) working on karst-related studies evolved from the November 1999 National Groundwater Meeting of the USGS. As a result, the Karst Interest Group (KIG) was formed in 2000. The KIG is a loose-knit, grass-roots organization of USGS and non-USGS scientists and researchers devoted to fostering better communication among scientists working on, or interested in, karst science. The primary mission of the KIG is to encourage and support interdisciplinary collaboration and technology transfer among scientists working in karst areas. Additionally, the KIG encourages collaborative studies between the different mission areas of the USGS as well as with other federal and state agencies, and with researchers from academia and institutes. To accomplish its mission, the KIG has organized a series of workshops that have been held near nationally important karst areas. To date (2017) seven KIG workshops, including the workshop documented in this report, have been held. The workshops typically include oral and poster sessions on selected karst-related topics and research, as well as field trips to local karst areas. To increase non-USGS participation an effort was made for the workshops to be held at a university or institute beginning with the fourth workshop. Proceedings of the workshops are published by the USGS and are available online at the USGS publications warehouse https://pubs.er.usgs.gov/ by using the search term “karst interest group.” The first KIG workshop was held in St. Petersburg, Florida, in 2001, in the vicinity of the large springs and other karst features of the Floridan aquifer system. The second KIG workshop was held in 2002, in Shepherdstown, West Virginia, in proximity to the carbonate aquifers of the northern Shenandoah Valley, and highlighted an invited presentation on karst literature by the late Barry F. Beck of P.E. LaMoreaux and Associates. The third KIG workshop was held in 2005, in Rapid City, South Dakota, near evaporite karst features in limestones of the Madison Group in the Black Hills of South Dakota. The Rapid City KIG workshop included field trips to Wind Cave National Park and Jewel Cave National Monument, and featured a presentation by Thomas Casadevall, then USGS Central Region Director, on the status of Earth science at the USGS. The fourth KIG workshop in 2008 was hosted by the Hoffman Environmental Research Institute and Center for Cave and Karst Studies at Western Kentucky University in Bowling Green, Kentucky, near Mammoth Cave National Park and karst features of the Chester Upland and Pennyroyal Plateau. The workshop featured a late-night field trip into Mammoth Cave led by Rickard Toomey and Rick Olsen, National Park Service. The fifth KIG workshop in 2011 was a joint meeting of the USGS KIG and University of Arkansas HydroDays, hosted by the Department of Geosciences at the University of Arkansas in Fayetteville. The workshop featured an outstanding field trip to the unique karst terrain along the Buffalo National River in the southern Ozarks, and a keynote presentation on paleokarst in the United States was delivered by Art and Peggy Palmer. The sixth KIG workshop was hosted by the National Cave and Karst Research Institute (NCKRI) in 2014, in Carlsbad, New Mexico. George Veni, Director of the NCKRI, served as a co-chair of the workshop with Eve Kuniansky of the USGS. The workshop featured speaker Dr. Penelope Boston, Director of Cave and Karst Studies at New Mexico Tech, Socorro, and Academic Director at the NCKRI, who addressed the future of karst research. The field trip on evaporite karst of the lower Pecos Valley was led by Lewis Land (NCKRI karst hydrologist), and the field trip on the geology of Carlsbad Caverns National Park was led by George Veni. This current seventh KIG workshop is being held in San Antonio at the University of Texas at San Antonio (UTSA). This 2017 workshop is being hosted by the Department of Geological Sciences’ Student Geological Society (SGS), and student chapters of the American Association of Petroleum Geologists (AAPG) and Association of Engineering Geologists (AEG), with support by the UTSA Department of Geological Sciences and Center for Water Research. The UTSA student chapter presidents, Jose Silvestre (SGS), John Cooper (AAPG), and Tyler Mead (AEG) serve as co-chairs of the 2017 workshop with Eve Kuniansky of the USGS. The technical session committee is chaired by Eve Kuniansky, USGS, and includes Michael Bradley, Tom Byl, Rebecca Lambert, John Lane, and James Kaufmann, all USGS, and Patrick Tucci, retired USGS. The logistics committee includes Amy Clark, Yongli Gao, and Lance Lambert (Department Chair), UTSA Department of Geological Sciences; and Ryan Banta and Allan Clark, USGS, San Antonio, Texas. The field trip committee is chaired by Allan Clark and includes Amy Clark, Yongli Gao, and Keith Muehlestein, UTSA; Marcus Gary, Edwards Aquifer Authority and University of Texas at Austin; Ron Green, Southwest Research Institute; Geary Schindel, Edwards Aquifer Authority; and George Veni, NCKRI. Additionally, two organizations have assisted the UTSA student chapters in hosting the meeting by donating funds to the chapters: the Edwards Aquifer Authority, San Antonio, Texas, and the Barton Springs Edwards Aquifer Authority, Austin, Texas. Additionally, Yongli Gao, Center for Water Research and Department of Geological Sciences, UTSA, helped develop sessions on cave and karst research in China for this workshop. These proceedings could not have been accomplished without the assistance of Lawrence E. Spangler as co-editor who not only has subject matter expertise, but also serves as an editor with the USGS Science Publishing Network. We sincerely hope that this workshop continues to promote future collaboration among scientists of varied and diverse backgrounds, and improves our understanding of karst aquifer systems in the United States and its territories. The extended abstracts of USGS authors were peer reviewed and approved for publication by the USGS. Articles submitted by university researchers and other federal and state agencies did not go through the formal USGS peer review and approval process, and therefore may not adhere to USGS editorial standards or stratigraphic nomenclature. However, all articles had a minimum of two peer reviews and were edited for consistency of appearance in the proceedings. The use of trade, firm or product names is for descriptive purposes only and does not imply endorsement by the U.S. Government. The USGS Water Availability and Use Science Program funded the publication costs of the proceedings.

Scientific Investigations Report↗

Geology and paleontology of the Santa Maria district, California

Stratigraphy, paleontology, and geologic history.-A basement' consisting of igneous rocks of the Jurassic(?) Franciscan formation and sediments of the Upper Jurassic Knoxville formation, and formations of Tertiary and Quaternary age are exposed in the Santa Maria district. The outcrop section, exclusive of the Franciscan, has a maximum thickness of about 10,000 feet, the subsurface section about 27,000 feet. At no locality, however, is either outcrop or subsurface section as thick as the total maxima for the formations. The outcrop Franciscan is made up of altered basalt, gabbro (generally- greatly altered), and minor areas of peridotite and serpentine. The marine Knoxville formation, consisting of shale, thin-bedded calcareous sandstone, and conglomerate, was deposited on the igneous rocks of the Franciscan. It has an outcrop thickness of about 500 feet and a known subsurface thickness of at least 1,250 feet. Aucella cf. A. piochii, which occurs in both outcrop and subsurface sections, suggests late Jurassic age. The Franciscan and Knoxville were probably uplifted during Taliaferro's Diablan orogeny at the close of the Jurassic and formed a land area that presumably endured during early Cretaceous and perhaps during much of late Cretaceous time. If sediments were laid down while 10,000 feet of Upper Cretaceous were deposited in the adjoining San Rafael Mountains, they were eroded following uplift at the close of the Cretaceous, when Reed and Hollister's San Rafael uplift was formed. The district is inferred to have been part of a Franciscan and Knoxville land area at the south border of the San Rafael uplift during all of early Tertiary time. The known history of the district as part of a Tertiary basin began in the early Miocene(?), possibly a little earlier or possibly 3: little later, when the nonmarine sediments of the early Miocene(?) Lospe formation were deposited. The Lospe formation has a maximum thickness of 2, 700 feet, and is made up of coarse-grained reddish sandstone and conglomerate, and greenish sandstone, gypsiferous siltstone, and mudstone. White tuff is a minor but conspicuous constituent. The Lospe formation overlies the Knoxville, or&middot; overlaps it and rests on the Franciscan. The first known Tertiary invasion of the sea took place immediately thereafter in early middle Miocene time, and from then on until approximately the end of the Pliocene the sea occupied continuously at least most of the region. The extent of the Miocene basin is not certainly known, but it was part of an extensive&middot; basin that has been designated the Santa Barbara embayment. The early middle Miocene Point Sal formation is the earliest marine Tertiary formation. It has an outcrop thickness of as much as 1,500 feet and a maximum subsurface thickness of 3,600 feet, and consists of siltstone, mudstone, and thin beds of sandstone. The Point Sal formation overlies the Lospe formation without marked discontinuity, or overlaps it and rests on Knoxville or Franciscan. It contains a large foraminiferal fauna representing the Siphogenerina hughesi zone, or the lower part of Kleinpell's Relizian stage. The Monterey shale overlies the Point Sal formation without noticeable discontinuity, or overlaps all the older sedimentary formations and rests on the Franciscan. It has a maximum outcrop thickness of 2,100 feet, but is as much as 5,000 feet thick in some subsurface sections. The Monterey is divided into three mapped members. The lower member is characterized by phosphatic shale and somewhat porcelaneous shale; the middle member by chert and cherty shale; and the upper member by porcelaneous shale, or by both porcelaneous shale and diatomaceous strata. The lower member contains Foraminifera representing the upper part of Kleinpell's Relizian stage and all of his Luisian stage, the middle member a few species indicating the lower part of his Mohnian stage, and the upper member a fauna representing the upper part of the Bolivina hughesi zone, at the top of the Mohnian, and in part a younger unnamed faunal division; that is, the Monterey is of late middle and late Miocene age. The diverse stratigraphic relations of the Lospe and Point Sal formations and Monterey shale along the borders of the Franciscan rocks forming Point Sal Ridge are inferred to be the result of repeated movements during Miocene time in the area of basement rocks west of the district, presumably extending westward beyond the present coast. Toward the close of the Miocene, low ridges appeared on the floor of the sea, ridges that grew during Pliocene time and were destined to become anticlines. At the same time deformation took place in the northeastern part of the district, and elsewhere on some anticlines, or on other structural highs bounded by faults. In those areas the Sisquoc formation overlies the Monterey shale with marked discordance; elsewhere there is no discordance. Two facies of the Sisquoc formation are mapped: a marginal sandstone facies, designated the Tinaquaic sandstone member, and a basin facies. The Tinaquaic sandstone member is 1,400 feet thick and contains megafossils of middle Pliocene age (also early Pliocene just east of the mapped area). It is unconformable on the Monterey. The basin facies, at least 3,000 feet thick in outcrop sections and 5,000 in some subsurface sections, consists of diatomaceous mudstone, other types of diatomaceous &middot;strata, somewhat porcelaneous mudstone, and porcelaneous shale-deposits that are ordinarily characteristic of the Monterey shale. Even in areas where the two formations are lithologically indistinguishable and conformable, a field basis for differentiating them has been established. The basin facies of the Sisquoc conformably overlies the Monter.ey in outcrop sections, but in some subsurface sections the formations are unconformable, and on the north limb of the Santa Maria Valley syncline the basin facies of the Sisquoc overlaps the Monterey onto the basement, thus forming the overlap trap for the oil in the Monterey in the Santa Maria Valley field. The lower and middle parts of the basin facies contain Foraminifera of the Bolivina obliqua zone. Kleinpell assigned that zone to the lower part of his late upper Miocene Delmontian stage. Assignment to the upper Delmontian, however, appears to be preferable. The upper few hundred feet of the basin facies contain Foraminifera similar to those in the overlying Foxen mudstone and megafossils of middle Pliocene affinities. The basin facies is therefore considered late upper Miocene to middle Pliocene. The submarine ridges were growing during Pilocene time. The Foxen mudstone is missing on them and in the northeastern part of the district. On the north limb of the Santa Maria Valley syncline, the Foxen overlaps the Sisquoc formation and rests on the basement. In the basins between the submarine ridges, the mudstone, siltstone, and fine-grained sandstone of the Foxen (800 feet thick in outcrop sections and as much as 2, 750 in subsurface sections) overlie conformably the Sisquoc formation. In some of the areas where the Foxen is missing as a lithologic unit, it appears to be represented by condensed deposits of phosphatic pellets, mapped with the underlying or overlying Formation, depending on the matrix, or by a condensed section of fine-grained sand, mapped with lithologically indistinguishable sand in the basal part of the overlying formation. Though foraminifera are abundant in the Foxen mudstone, relatively few species are represented. Those from the lower part of the formation may be of middle Pliocene age. Megafossils from the upper part of the Foxen are considered late Pliocene. The formation is therefore assigned to the middle(?) and upper Pliocene. Movements during Pliocene time in the basement area west of Point Sal Ridge are indicated by the occurrence in the western Casmalia Hills of coarse detritus from the Monterey in the upper part of the Sisquoc formation and in the Foxen mudstone. During late Pliocene time, when the Careaga sandstone was deposited, the Pliocene sea had its greatest extent. The region then flooded may be referred to as the Santa Maria basin. Throughout most of the district two mapped members of the Careaga sandstone are differentiated: the Cebada fine-grained member, which has a maximum outcrop thickness of 1,000 feet, and the Graciosa coarse-grained member, 50 to 425 feet thick. Mild deformation continued during the late Pliocene. The Cebada fine-grained member is missing on the embryonic anticlines, where it is overlapped by the Graciosa coarse-grained member. Both members of the Careaga sandstone contain a large megafauna. The nonmarine Paso Robles formation conformably overlies the Careaga sandstone. The Paso Robles consists chiefly of sand and gravel, but clay, marl, and limestone are the most characteristic constituents. The maximum outcrop thickness is 2,000 feet, the estimated maximum subsurface thickness 4,500 feet. The Paso Robles fresh-water fauna is meager, consisting of a few species similar to living forms. The formation is currently assigned to the interval including late Pliocene and early Pleistocene(?). The age assignment late Pliocene(?) and early Pleistocene, however, may be preferable for the Santa Maria district. Then followed the only period of strong general deformation in the known Tertiary and Pleistocene history of the district. The present structural features of the district were formed at that time, and the submarine ridges appeared as fully formed anticlines. Dating of the deformation is uncertain, because of uncertainty concerning the age of the Paso Robles formation. It is, however, without much doubt of the same age as the welldated strong middle Pleistocene deformation in the Ventura basin. Terrace deposits, laid down on both wave-cut and stream-cut platforms, are rather arbitrarily assigned to the late Pleistocene. The oldest and most extensive terrace deposits, not more than 100 feet thick, are designated the Orcutt sand. The Orcutt sand itself is tilted as much as 12&deg; on the limbs of anticlines and is faulted on the north limb of the Graciosa anticline, indicating renewed growth of the anticlines, presumably in late Pleistocene time. Terrace deposits apparently younger than the Orcutt sand are arched in a low anticline west of lower Foxen Canyon. Structure.-Santa Maria Valley is the boundary between two structural provinces. To the north, valleys and hills are either synclines or anticlines. To the south, on the contrary, major valleys coincide generally with major synclines, and the hills are anticlinal. Santa Maria Valley itself is a syncline. Unlike valleys farther south in the district, however, it lies athwart an older uplift. Also unlike most of the valleys farther south, the axis of the syncline is not in the middle of the valley, but is far to the south near the bordering hills. Indeed, in the western Casmalia Hills, the anticline in the bordering hills is overturned and overrides the axis of the syncline. The major structural features of the district have a general west-northwestward trend parallel to the trend of the basin. Minor westward-trending and northward-trending folds and faults, however, extend across the trend of the major features. The district includes areas of wide, open folds and also areas of narrow, closely spaced, and steeply tilted folds, as well as some major overturned anticlines, most of the latter overturned northward. The closely spaced folds coincide almost invariably with outcrops of the Monterey shale and Point Sal formation. Physiography.-The surface on which the terrace deposits, designated the Orcutt sand, were deposited is extensive but is locally deformed, and only remnants are preserved. Toward the coast it changes from a stream-cut surface to a wave-cut surface. In the coastal area three main marine terraces are recognized: the high terrace (altitude about 800 feet), the intermediate terrace (altitude about 600 feet), and the low terrace (altitude 50 to 125 feet). An indurated layer is present at or near the surface at many localities scattered throughout the district. It is suggested that the indurated layer is an ancient hardpan, the incomplete skeleton of a former soil profile developed on a former surface of less relief than the present surface. Sand dunes extend inland from the coast at the north and south borders of the mapped area. They are classified under three age groups: old, intermediate, and modern. The old dunes, which have a protective cover of natural vegetation and are now inactive, are far more extensive than those of the other two groups. They cover many square miles on a terrace bordering Santa Maria Valley, and extend 20 miles inland. It has not been determined whether their inactivity is due to a cutting off of the supply of sand, or to a climatic change. Occurrence of oil.--Oil has been produced in the Santa Maria district since 1901, the total production to the end of 1947 being 269,657,000 barrels. Throughout the district most of the oil is heavy. Seven producing fields are located in the mapped area. In order of discovery from oldest to youngest the fields are as follows: Orcutt, Lompoc, West Cat Canyon, East Cat Canyon, Casmalia, Gato Ridge, and Santa Maria Valley. The Santa Maria Valley field is the largest in both area and productive capacity. It is the largest overlap field in coastal California, and one of the last major fields found in the State up to 1947. The Las Flores (Monterey) pool is transforming the West Cat Canyon field into one of the major fields of the district. The Monterey shale is the chief oil-bearing formation, and the principal reservoir in the Monterey consists of fractured chert and cherty shale. Sand in the Sisquoc formation is the sole reservoir in the minor East Cat Canyon field and in the Pliocene pool of the West Cat Canyon field. The Point Sal formation yields some oil in the southeastern part of the Santa Maria Valley field (the only part of that field where the formation is present) and a recent well in the Casmalia field is producing a small amount of relatively light oil from the Point Sal. The Lospe formation is also productive in a recent well in the Casmalia field. The Knoxville formation is productive in three areas in the northern part of the Santa Maria Valley field. The Point Sal formation offers the greatest promise for deeper-zone production. The Lospe and Knoxville formations can no longer be ignored in areas where younger marine formations overlap against them. Oil possibilities in undeveloped areas.--Two matters weigh heavily in prospecting in the Santa Maria district: the degree of fracturing of chert and cherty shale in the Monterey shale, and the gravity of the oil. Other things being equal, the productivity of the Monterey varies directly with the amount of fracturing. Very heavy oil, too heavy to produce commercially under present conditions, has befln found ii the Monterey in the northeastern part of the district, where five discoveries (one east of the mapped area) have been made in recent years. Among areas of possible interest, three appear to be favorable for prospecting on the basis of surface geology: an area east of Foxen Canyon, where oil may be trapped in the basal part of the Tinaquaic sandstone member of the Sisquoc formation by westward overlap of successively higher Tinaquaic strata onto the Monterey shale; an area so1tth of the I ... ions Head fault, where oil may be trapped by the fault; and the offshore extension of the north border of Point Sal Ridge, where oil may possibly be trapped in the Monterey by overlap of the Sisquoc formation.

California↗

Spatial and temporal variation of stream chemistry associated with contrasting geology and land-use patterns in the Chesapeake Bay watershed—Summary of results from Smith Creek, Virginia; Upper Chester River, Maryland; Conewago Creek, Pennsylvania; and Difficult Run, Virginia, 2010–2013

Despite widespread and ongoing implementation of conservation practices throughout the Chesapeake Bay watershed, water quality continues to be degraded by excess sediment and nutrient inputs. While the Chesapeake Bay Program has developed and maintains a large-scale and long-term monitoring network to detect improvements in water quality throughout the watershed, fewer resources have been allocated for monitoring smaller watersheds, even though water-quality improvements that may result from the implementation of conservation practices are likely to be first detected at smaller watershed scales. In 2010, the U.S. Geological Survey partnered with the U.S. Environmental Protection Agency and the U.S. Department of Agriculture to initiate water-quality monitoring in four selected small watersheds that were targeted for increased implementation of conservation practices. Smith Creek watershed is an agricultural watershed in the Shenandoah Valley of Virginia that is dominated by cattle and poultry production, and the Upper Chester River watershed is an agricultural watershed on the Eastern Shore of Maryland that is dominated by row-cropping activities. The Conewago Creek watershed is an agricultural watershed in southeastern Pennsylvania that is characterized by mixed agricultural activities. The fourth watershed, Difficult Run, is a suburban watershed in northern Virginia that is dominated by medium density residential development. The objective of this study was to investigate spatial and temporal variations in water chemistry and suspended sediment in these four relatively small watersheds that represent a range of land-use patterns and underlying geology to (1) characterize current water-quality conditions in these watersheds, and (2) identify the dominant sources, sinks, and transport processes in each watershed. The general study design involved two components. The first included intensive routine water-quality monitoring at an existing streamgage within each study area (including continuous water-quality monitoring as well as discrete water-quality sampling) to develop a detailed understanding of the temporal and hydrologic variability in stream chemistry and sediment transport in each watershed. The second component involved extensive water-quality monitoring at various sites throughout each watershed to develop a detailed understanding of spatial patterns. Both components were used to improve understanding of sources and transport processes affecting stream chemistry, including nutrients and suspended sediments, and their implications for detecting long-term trends related to best management practices. This report summarizes the results of monitoring that was performed from April 2010 through September 2013. Individual Small Watershed Summaries Summaries for each of the four small watersheds are presented below. Each watershed has a more descriptive and detailed section in the report, but these summaries may be particularly useful for some watershed managers and stakeholders desiring slightly less technical detail. Smith Creek Smith Creek is a 105.39-mi 2 watershed within the Shenandoah Valley that drains to the North Fork Shenandoah River. The long-term Smith Creek base-flow index is 72.3 percent, indicating that on average, approximately 72 percent of Smith Creek flow was base flow, which suggests that Smith Creek streamflow is dominated by groundwater discharge rather than stormwater runoff. A series of cluster and principal components analyses demonstrated that the majority of the variability in Smith Creek water quality could be attributed to hydrologic and seasonal variability. Statistically significant positive correlations with flow were observed for turbidity, suspended sediments, total nitrogen, ammonium, orthophosphate, iron, total phosphorus, and the ratio of calcium to magnesium. Statistically significant inverse correlations with flow were observed for specific conductance, magnesium, δ 15 N of nitrate, pH, bicarbonate, calcium, and δ 18 O of nitrate. Of particular note, flow and nitrate were not statistically significantly correlated, likely because of the relatively complex concentration-discharge relationship observed in continuous and discrete datasets. Statistically significant seasonal patterns were observed for numerous water-quality constituents: water temperature, turbidity, orthophosphate, total phosphorus, suspended-sediment concentration, and silica were higher during the warm season, but pH, dissolved oxygen, and sulfate were higher during the cool season. Surrogate regression models were developed to compute sediment and nutrient loads in Smith Creek using the continuous water-quality monitors. The mean Smith Creek in-stream sediment load was approximately 6,900 tons per year, with nearly 90 percent of the sediment load over the 3-year study period contributed during the eight largest storm events during that period. The Smith Creek total phosphorus load was approximately 21,000 pounds of phosphorus per year, with the majority of the load contributed during stormflow periods, although a substantial phosphorus load still occurs during base-flow conditions. The Smith Creek total nitrogen load was approximately 400,000 pounds per year, with total nitrogen accumulation less dominated by stormflow contributions (as was the case for sediment and total phosphorus) and strongly affected by base-flow export of nitrogen from the basin. Extensive water-quality monitoring throughout the Smith Creek watershed revealed how the complex geology and hydrology interacted to result in variable water chemistry. During relatively dry and low base-flow periods, much of the discharge in Smith Creek was contributed by a single dominant spring—Lacey Spring. During wetter base-flow periods, the flows in Smith Creek were largely generated by a mixture of headwater springs and forested mountain tributaries with very different geochemical composition. The headwater springs generally issued from limestone bedrock and were characterized as having relatively high nitrate, specific conductance, calcium, and magnesium, as well as relatively low concentrations of phosphorus, ammonium, iron, and manganese. The undeveloped, high-gradient, forested mountain sites were generally characterized by low ionic strength waters with low nutrient concentrations. Nitrate isotope data from the limestone springs generally were consistent with manure-derived nitrogen sources (such as cattle and poultry), although the possibility of other mixed sources cannot be excluded. Nitrate isotope data from the undeveloped, high-gradient forested mountain sites were more consistent with nitrogen from undisturbed soils, atmospheric deposition, or nitrogen fixation. Regardless of the nitrogen source, oxygen isotope data indicate that the nitrate was largely a result of nitrification. Land-use data indicate that manure sources of nitrogen dominated watershed nitrogen inputs. Phosphorus sources were less well studied. The presence of a single point-source discharge near the town of New Market contributed the majority of the phosphorus to Smith Creek under base-flow conditions, but nonpoint sources of phosphorus dominated the loading to Smith Creek during stormflow periods. Implementation of conservation practices increased in the Smith Creek watershed during the study period, and even though a broad range of practice types was implemented, the most common practices included stream fencing (for cattle exclusion), the development of nutrient management plans, conservation crop rotation, and the planting of cover crops. While the implementation of these conservation practices is encouraging, results indicate small increases in nitrate concentrations at the streamgage over the last 29 years, concurrent with small decreases in nitrate fluxes. It will likely be years before the cumulative effect of these practices can be detected in the Smith Creek water quality, and the magnitude of the effect of these conservation practices detected in Smith Creek will depend largely on whether nutrient loading (of manure and commercial fertilizer) is reduced over time. Upper Chester River The Upper Chester River watershed includes the 36-square-mile (mi 2 ) watershed area around several nontidal tributaries that drain into the tidal Chester River. The streamgage is on Chesterville Branch, the largest nontidal tributary (approximately 6.12 mi 2 ) and is the site for continuous water-quality monitoring for this project. The base-flow index at Chesterville Branch is about 72 percent and indicates that, as in most of the Coastal Plain, groundwater is the greatest contributor to streamflow. As such, more than 90 percent of the nitrogen in the stream is in the form of nitrate from groundwater. Continuous and discrete data collected at Chesterville Branch show the effects of streamflow and season on water quality. Significantly positive correlations with flow were observed for ammonium, dissolved and total phosphorus, sediment, and turbidity as runoff carried these constituents from the land surface into Chesterville Branch. Other constituents that increased significantly with flow include potassium, sulfate, iron, and manganese, which are likely contributed from near-stream areas and ponds with high organic-matter content. Total nitrogen, pH, and specific conductance, along with chemical constituents associated with groundwater inputs including nitrate, calcium, ratio of calcium to magnesium, silica, bicarbonate, and sodium, were negatively correlated with flow because concentrations of these constituents were diluted by runoff. Seasonal differences in water chemistry, which are most likely related to increased biologic effects on the uptake and release of chemicals in the stream and near-stream areas, also were observed. Water temperature, orthophosphate, δ 15 N of nitrate, bicarbonate, sodium, and the ratio of sodium to chloride were higher during the warm season, and dissolved oxygen, total nitrogen, nitrate, magnesium, sulfate, and manganese were higher during the cool season. Surrogate-regression models developed by using continuous water-quality data showed that the annual sediment load for the 2013 water year was about 2,600 tons, with more than 90 percent of this sediment contributed during two storms. The total phosphorus load in 2013 was about 13,000 pounds with more than 90 percent contributed during the same two storms as sediment. The load of total nitrogen, 140,000 pounds, accumulated steadily throughout the 2013 water year as nitrate in groundwater continuously discharged into the stream. The same two large storms that contributed 90 percent of the suspended-sediment and total phosphorus load only contributed about 20 percent of the annual total nitrogen load. Extensive water-quality monitoring of stream base flow throughout the Upper Chester River watershed identified how differences in land use and hydrogeology affected water chemistry. In parts of the watershed with well-drained soil and thick sandy aquifer sediments, concentrations of nitrate and other chemicals associated with fertilizer and lime application increased in streams as agricultural land use increased. More than 90 percent of the nitrogen in streams from these areas was in the form of nitrate, and concentrations ranged from about 5 milligrams per liter (mg/L) to 8 mg/L as nitrogen in the two largest tributaries. Stream nitrate concentrations were about 1 mg/L as nitrogen where soils were more poorly drained, the surficial aquifer sediments were thinner, and forests and wetlands were more widespread than agriculture. Nitrate isotope data were consistent with inorganic fertilizers ± atmospheric deposition and N 2 fixation as sources of nitrogen, and with nitrification as the dominant nitrate-forming process. Nitrate reduction was indicated by elevated δ 15 N and δ 18 O values in some samples from streams draining watersheds with poorly drained soils. An analysis of land-use data and SPARROW modeling input data attributed almost 90 percent of the nitrogen sources in the Upper Chester River watershed to inorganic fertilizer and fixation of atmospheric nitrogen by legumes, which is in agreement with the isotopic characteristics of nitrate in this watershed. Local sources of manure are limited in this area. Total phosphorus concentrations during base flow ranged from below detection to about 0.2 mg/L. Stream phosphorus concentrations during base flow were generally lower than those measured during storms because most phosphorus transport likely occurs as phosphorus attached to sediment particles during runoff. Because manure is not widely used in this area, the major source of phosphorus is likely fertilizer. The implementation of conservation practices in the Upper Chester River watershed increased substantially during the study period, with a total implementation of 1,194 U.S. Department of Agriculture-compliant practices. The most frequently used practices were oriented towards nutrient and sediment control, including cover crops, nutrient management planning, conservation crop rotation, conservation tillage, and irrigation management. The current Chesapeake Bay model for this area predicts that implementation of best management practices should result in a 13-percent decrease in overall delivery of nitrogen to the Upper Chester River. Because most nitrogen travels through the groundwater system for years to decades before being discharged to streams, the time period of monitoring was not sufficient to see the effects of these practices on water quality. The magnitude of the effect that may eventually be detected will depend on the degree to which nitrate leaching into the groundwater system is reduced over time. Loadings of phosphorus and sediment are primarily transported during large runoff events and are difficult to control and analyze for trends because of their timing and episodic nature. Conewago Creek Conewago Creek has two primary monitoring locations—one near the middle of the 47-mi 2 watershed and the other near the outlet just upstream of the Susquehanna River. The base-flow index was 47.3 percent for 2012–2013, indicating that on average, approximately 53 percent of the streamflow in Conewago Creek exited the watershed as surface flow, which suggests that the stormwater runoff was somewhat greater than groundwater discharge (base flow). A series of cluster and principal components analyses demonstrated that the majority of the variability in the Conewago Creek water quality could be attributed to hydrologic and seasonal variability. Statistically significant positive correlations with flow were observed at both monitoring sites for ammonium, total phosphorus, orthophosphate, iron, and manganese; additionally, at the upstream monitoring station, total nitrogen demonstrated a statistically significant positive correlation with flow. Statistically significant inverse correlations with flow were observed at both sites for water temperature, specific conductance (at the downstream site only), sulfate, chloride, calcium, and magnesium. Statistically significant seasonal patterns were observed for several water-quality constituents. Water temperature, phosphorus (upstream site only), and orthophosphate were higher during the warm season, and nitrate and total nitrogen (upstream site only) were higher during the cool season. Surrogate regression models were developed to compute sediment and nutrient load in Conewago Creek by using the continuous water-quality monitors and water-quality samples. Conewago Creek sediment load was approximately 9,900 tons in 2012 and approximately 18,900 tons in 2013, with nearly 80 percent of the sediment load in 2013 contributed by the three largest storm events. Annual total nitrogen loads could not be estimated due to poor model performance. The addition of continued monitoring or a continuously recording nitrate sensor could improve estimates of total nitrogen loads. During 2012 and 2013, phosphorus loads in Conewago Creek were approximately 50,000 pounds in each year. Combining data from one high-flow synoptic sampling with the data from routine sampling revealed how the geology and hydrology interact to result in variable water chemistry throughout the Conewago Creek watershed. The areas above the upstream gage in the headwaters are generally underlain by forested non-carbonate bedrock and are characterized by relatively low nitrate, specific conductance, calcium, and magnesium, as well as relatively low concentrations of phosphorus, ammonium, iron, and manganese. The more developed, agricultural areas below the upstream site were generally characterized by higher ionic strength waters with higher nutrient and metal concentrations. An analysis of land-use data and SPAtially Referenced Regressions On Watershed (SPARROW) modeling data indicates that manure sources of nitrogen dominate the input of nitrogen to the watershed. Implementation of conservation practices increased in the Conewago Creek watershed during the study period, and while a broad range of practice types were implemented, the most common practices included residue and tillage management, cover crops, nutrient management, terracing, and stream fencing (for animal exclusion or bank restoration). While the implementation of these conservation practices is encouraging, the cumulative effects of these practices probably will not be detected in Conewago Creek water quality for several years. The magnitude of the effects of these conservation practices on water quality in Conewago Creek will depend largely on the extent to which nutrient loading (septic, manure, and commercial fertilizer) and sediment-producing activities are reduced over time. Difficult Run The Difficult Run watershed is a 57.82-mi 2 watershed that drains to the Potomac River. The long-term Difficult Run base-flow index (from 1936 to 2010) was 57.9, indicating that approximately 58 percent of streamflow exited the watershed as base flow and 42 percent as stormflow; however, with continued development and urbanization of the watershed, the base-flow index has decreased to 50 percent during the last 20 years. This base-flow index was less than those of the other watersheds evaluated in this study, likely because the Difficult Run watershed largely is underlain by crystalline piedmont metamorphic rocks and has a greater proportion of impervious urban land cover. A series of cluster and principal components analyses indicated that most of the variability in Difficult Run water quality could be attributed to hydrologic variability and seasonality. Statistically significant positive correlations with flow were observed for turbidity, dissolved oxygen, suspended sediments, ammonium, orthophosphate, iron, and total phosphorus. Statistically significant inverse correlations with flow were observed for water temperature, pH, specific conductance, bicarbonate, calcium, magnesium, nitrate, δ 15 N of nitrate, and silica. Statistically significant seasonal patterns were observed for numerous water-quality constituents: water temperature, ammonium, orthophosphate, and δ 15 N of nitrate were higher during the warm season, and dissolved oxygen, nitrate, and manganese were higher during the cool season. Surrogate regression models were developed to compute sediment and nutrient loading rates. The Difficult Run sediment load was approximately 8,000 tons per year, with greater than 95 percent of the sediment load in the 2013 water year contributed by the seven largest storm events. The total phosphorus load in Difficult Run was approximately 14,000 pounds of phosphorus per year, with the majority of the load contributed during stormflow periods. The total nitrogen load in Difficult Run is estimated to have been approximately 140,000 pounds per year, with total nitrogen accumulation less dominated by stormflow contributions than that of phosphorus and strongly affected by base-flow export of nitrogen from the basin. Extensive water-quality monitoring throughout the Difficult Run watershed revealed relatively uniform generation of flow per unit of watershed area, as well as spatial variation in water quality that is strongly related to land-use activities. Elevated nitrate concentrations were observed in a subset of monitoring sites that are inversely correlated with population density and positively correlated to the septic system density within each subwatershed. The majority of the elevated nitrate concentrations for these sites are hypothesized to be caused by nitrate leaching from septic systems, more so than homeowner fertilizer usage among these subwatersheds that have lower population densities than other parts of the watershed. Nitrate isotope data, temporal patterns in the water-quality data, mass-balance computations, and a separate land-use analysis all generally indicate that leachate from septic systems was the likely source of the elevated nitrate. Another group of water-quality sites have relatively low nitrogen concentrations, are located in areas that are served by city sewer lines, and have experienced stream restoration activities. A final group of sites drained the areas with the highest imperviousness and had strongly elevated specific conductance, chloride, and sodium, which were likely caused by a combination of road salting and other anthropogenic sources draining these urbanized areas in the watershed. A fourth group of sites represents a mixture of water sources and had water quality similar to that at the Difficult Run streamgage. Analysis of the nitrate isotope data generally indicates a broad range of composition indicative of mixed natural and anthropogenic nitrogen sources. Implementation of conservation practices increased in the Difficult Run watershed during the study period, and while a broad range of practice types was implemented, the most common practices included stream restoration. While the implementation of these conservation practices is encouraging, the cumulative effect of these practices probably will not be detected in Difficult Run water quality for several years.

Maryland, Pennsylvania, Virginia↗