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Tapwater exposures, residential risk, and mitigation in a PFAS-impacted-groundwater community

Tapwater (TW) safety and sustainability are priorities in the United States. Per/polyfluoroalkyl substance(s) (PFAS) contamination is a growing public-health concern due to prolific use, widespread TW exposures, and mounting human-health concerns. Historically-rural, actively-urbanizing communities that rely on surficial-aquifer private wells incur elevated risks of unrecognized TW exposures, including PFAS, due to limited private-well monitoring and contaminant-source proliferation in urbanizing landscapes. Here, a broad-analytical-scope TW-assessment was conducted in a hydrologically-vulnerable, Mississippi River alluvial-island community, where PFAS contamination of the shallow-alluvial drinking-water aquifer has been documented, but more comprehensive contaminant characterization to inform decision-making is currently lacking. In 2021, we analyzed 510 organics, 34 inorganics, and 3 microbial groups in 11 residential and community locations to assess (1) TW risks beyond recognized PFAS issues, (2) day-to-day and year-to-year risk variability, and (3) suitability of the underlying sandstone aquifer as an alternative source to mitigate TW-PFAS exposures. Seventy-six organics and 25 inorganics were detected. Potential human-health risks of detected TW exposures were explored based on cumulative benchmark-based toxicity quotients ( ∑ TQ ). Elevated risks ( ∑ TQ ≥ 1) from organic and inorganic contaminants were observed in all alluvial-aquifer-sourced synoptic samples but not in sandstone-aquifer-sourced samples. Repeated sampling at 3 sites over 52–55 h indicated limited variability in risk over the short-term. Comparable PFAS-specific ∑ TQ for spatial-synoptic, short-term (3 days) temporal, and long-term (3 years quarterly) temporal samples indicated that synoptic results provided useful insight into the risks of TW-PFAS exposures at French Island over the long-term. No PFAS detections in sandstone-aquifer-sourced samples over a 3 year period indicated no PFAS-associated risk and supported the sandstone aquifer as an alternative drinking-water source to mitigate community TW-PFAS exposures. This study illustrated the importance of expanded contaminant monitoring of private-well TW, beyond known concerns (in this case, PFAS), to reduce the risks of a range of unrecognized contaminant exposures.

Wisconsin

Geologic map of MTM −15032 and −20032 quadrangles, western Ladon basin, Mars

Our mapping efforts focused on the geomorphic terrains and geologic units contained within Mars Transverse Mercator (MTM) −15032 and −20032 quadrangles. These two quadrangles are located along the west side of Ladon basin and span lat −12.5° N. to −22.5° N. and long 325° E. to 330° E. The western part of Ladon basin and its bounding basin ring structures to the west preserved features that help to understand the long history of drainage across the Margaritifer Terra region of Mars. Our geologic map provides new insight into the extent of aqueous activity across western Ladon basin and the adjoining highlands, which includes the northern part of Ladon Valles, Arda Valles, numerous small valleys in the western highlands, and light-toned layered deposits associated with these fluvial features. The Mars Odyssey Thermal Emission Imaging System (THEMIS) infrared (IR) daytime mosaic (100 meters per pixel) was used as the primary base map. We constructed the geologic map of western Ladon basin at 1:1,000,000 scale. We identified 20 geologic units in the map area, which we divided into the following groups: crater units; volcanic units; chaotic units; basin fill units; crater, valley, and channel units; and plateau and highlands units. We observed the following sequence of events: (1) formation of Ladon and Holden impact basins in the middle Noachian, producing a mountainous unit; (2) landscape degradation and infilling during the Late Noachian to Late Hesperian forming terra units; (3) formation of Ladon Valles in the Late Noachian to Early Hesperian by catastrophic flooding, producing channel units; (4) accumulation of sediments in the Late Noachian to Early Amazonian, forming basin fill units; (5) formation of a smooth crater fill unit during the Early to Late Hesperian; (6) deposition during the Late Hesperian to Early Amazonian, creating light-toned layered units within Ladon Valles, Ladon basin, and other smaller valley networks along the western uplands, as well as formation of a light-toned unit along some crater floors; (7) formation a of chaotic unit in the Early to Middle Amazonian, formation of alluvial fans in the Early Amazonian, and eruption of a volcanic unit in the Middle Amazonian; and (8) formation of craters throughout the geologic history of the map region.

Scientific Investigations Map

Geological context and significance of the clay-sulfate transition region in Mount Sharp, Gale crater, Mars: An integrated assessment based on orbiter and rover data

On Mars, phyllosilicate (“clay”) minerals are often associated with older terrains, and sulfate minerals are associated with younger terrains, and this dichotomy is taken as evidence that Mars’ surface dried up over time. Therefore, in situ investigation of the Mount Sharp strata in Gale crater, which record a shift from dominantly clay-bearing to sulfate-bearing minerals, as seen in visible−near-infrared orbital reflectance spectra, is a key science objective for the Mars Science Laboratory (MSL) Curiosity rover mission. Here, we present regional (orbiter-based) and in situ (rover-based) evidence for a low-angle erosional unconformity that separates the lacustrine and marginal lacustrine deposits of the Carolyn Shoemaker formation from the dominantly eolian deposits of the lower Mirador formation within the orbitally defined clay-sulfate transition region. The up-section record of wetter (Carolyn Shoemaker formation) to drier (lower Mirador formation) depositional conditions is accompanied by distinct changes in diagenesis. Clay minerals occur preferentially within the Carolyn Shoemaker formation and are absent within the lower members of the Mirador formation. At and above the proposed unconformity, strata are characterized by an increase in diagenetic nodules enriched in X-ray amorphous Mg-sulfate. Early clay formation in the Carolyn Shoemaker formation may have created a hydraulic barrier such that later migrating magnesium- and sulfur-rich fluids accumulated preferentially within the lower members of the Mirador formation. The proposed unconformity may have also acted as a fluid conduit to further promote Mg-sulfate nodule formation at the Carolyn Shoemaker−Mirador formation boundary. These results confirm an association of the clay-sulfate transition with the drying of depositional environments, but they also suggest that at least some orbital sulfate signatures within the region are not time-congruent with the environmental signals extracted from primary sedimentology. Our findings highlight that complex interactions among primary depositional environment, erosion, and diagenesis contribute to the transition in clay-sulfate orbital signatures observed in the stratigraphy of Mount Sharp.

GSA Bulletin

Metal fingerprints of Eocene rhyolite magmas coincident with Carlin-type gold deposition in Nevada USA

Eocene magmatic systems contemporaneous with world-class Carlin-type Au deposits in Nevada (USA) have been proposed by some researchers as a key ingredient for Au mineralization, though evidence conclusively demonstrating their genetic relationship remains tenuous. This study provides the first direct evidence of the pre-eruptive metal budget of volatile- and metal-charged silicic magmas coincident in time (~41 to 34 Ma) and space (within 5 km) with Carlin-type Au deposits. We characterize the pre-eruptive metal fingerprints of these diverse magmatic systems to assess their potential as sources of metals for Carlin-type Au mineralization. Metal abundances from quartz-hosted melt inclusions (Au, Te, Ag, Sb, Tl, Mo, W, Sn, As, Pb, Co, Cu, Ni, and Zn) characterized in situ by SHRIMP-RG and LA-ICP-MS represent our best (and only) estimates for the pre-eruptive metal budget in these systems. Median metal concentrations are generally within one order of magnitude of average upper crust and average continental rhyolite values. But there are two notable exceptions, with median Au contents extending >1 order of magnitude higher than average upper crust and median Cu contents ranging >1 order of magnitude lower than upper crust. Despite this, melts contain lower Au/Cu (<0.1), Au/Ag (<5), and Au/Tl (<0.3) than most ore-grade Carlin-type rock samples and quartz-hosted fluid inclusions, regardless of their age and timing relative to nearby Carlin-type Au mineralization. The metal fingerprints of these magmatic systems, de-fined both by traditional and multivariate compositional data analysis techniques, are distinct from one another. Yet none are particularly specialized, e.g., high Au/Cu, in terms of being ideal ingredients as postulated by magmatic models for Carlin-type Au mineralization. Magmatic Au contents do not appear to be correlated with rhyolite “flavors” in the way that Cu, Sn, and Nb contents are. Fluid/melt partitioning modeling and magma volume estimates support the idea that a diverse array of non-specialized silicic magmas could feasibly contribute some or potentially all of the Au, Ag, and Cu in Carlin-type systems. The compositional diversity among contemporaneous magmatic systems could possibly contribute to some of the diversity observed across Carlin-type Au districts in Nevada.

Nevada

Potential for leakage among principal aquifers in the Memphis area, Tennessee

The principal aquifers in the Memphis area consist primarily of sand or sand and gravel, and the confining beds consist of clay, silt, sand, and lignite. The Jackson Formation and upper part of the Claiborne Group serve as the confining bed separating the water table aquifers from the Memphis Sand; the Flour Island Formation separates the Memphis Sand from the Fort Pillow Sand. Differences in total hydraulic head among the principal aquifers in the Memphis urban area result in vertical hydraulic gradients which create a potential for inter-aquifer exchange of water. Throughout this area, the gradient is downward from the water table aquifers to the Memphis Sand. In the central part of the Memphis urban area, the vertical hydraulic gradient is upward from the Fort Pillow Sand to the Memphis Sand, and in the eastern and western parts, it is downward from the Memphis Sand to the Fort Pillow Sand. The vertical distribution of carbon-14 data for water from the fluvial deposits, Memphis Sand, and Fort Pillow Sand shows an increase in the relative age of the water with depth. The areal distribution of carbon-14 data for water from the upper part of the Memphis Sand indicates that relatively recent water has been brought into the major cone of depression in the potentiometric surface of the Memphis Sand, either by horizontal movement or from downward vertical leakage. The normal, near-surface geothermal gradient in the Memphis area was determined to be 0.6 C/100 ft. Deviations from the normal geothermal gradient, in areas affected by intense pumping from the Memphis Sand, indicate that downward vertical leakage occurs from the water table aquifers through the Jackson-upper Claiborne confining bed to the Memphis Sand. The velocity of downward vertical leakage of water from the Memphis Sand through the Flour Island confining bed to the Fort Pillow Sand was determined to be 0.0066 ft/day by analysis of borehole temperature data from an observation well in the northeastern part of the Memphis area. From this velocity and the head difference between the Memphis Sand and the Fort Pillow Sand at this locality, the hydraulic conductivity of the Flour Island confining bed was determined to be 0.00114 ft/day. (Lantz-PTT)

Tennessee

Unprecedented burning in tropical peatlands during the 20th century compared to the previous two millennia

Tropical peatland wildfire incidence has risen in recent decades, driven by drainage for land use and intensified by severe droughts with global climate change. These disturbances have altered vegetation structure, disrupted ecosystem functioning, and increased carbon emissions, particularly in Southeast Asia. However, the long-term history and characteristics of wildfires in tropical peatlands remain largely unknown. Here, we compiled fifty-eight macro-charcoal records from peatlands across the tropics, ranging from lowland forested to montane peatlands, to assess millennia-scale changes and controlling factors of tropical peatland burning. We divided the datasets into four main sub-regions: Neotropical, Afrotropical, Indomalayan and Australasian ecoregions to explore regional variability. Tropical peatlands had high burning levels between 0 and 850 ce , followed by a relatively low and stable period until a marked increase during the 20th century. The general trend in tropical peatland burning follows changes in global temperature, and climate variables that control the length and severity of drought events have a notable influence on peat burning before 1900 ce . During the 20th century, regional differences were observed, with declining fire trends in the Neotropical and Afrotropical regions and increasing fire trends in the Indomalayan and Australasian regions. This difference is likely attributable to human activities, and such intervention is also evident in palm swamps and hardwood swamps under similar wet, weakly seasonal climates. With the increase in anthropogenic pressures on peatlands and greater climate variability, future wildfires in peatlands are likely to become more frequent and widespread across all tropical ecoregions. Conservation and sustainable land-use practices could be used to mitigate and control peatland burning and protect these carbon-rich sinks.

Global Change Biology

Geochemistry of quartz and fluid inclusions associated with gold, tungsten, and antimony in the Stibnite-Yellow Pine district, Idaho

Deposits in the historic Stibnite-Yellow Pine district in east-central Idaho were mined for Ag, Au, Hg, Sb, and W. Ore is hosted in breccia and fault zones along NE-striking faults that transect the Atlanta lobe of the Late Cretaceous Idaho batholith and metamorphosed Neoproterozoic to lower Paleozoic rocks. Geochronological studies have delineated five superimposed and zoned hydrothermal events in the mining district which range in age from Late Cretaceous to the Eocene. They formed the following consecutive assemblages: (1) vein and disseminated pre-ore milky quartz (± calcite), muscovite, and brassy pyrite with minor molybdenite and base metal sulfides; (2) vein and disseminated quartz, calcite, sericite, auriferous-pyrite, and arsenopyrite; (3) potassium feldspar, quartz, dolomite, and calcite with vein and disseminated scheelite ± pyrite and arsenopyrite; (4) Au-Ag veins that contain adularia; and (5) breccia, vein, and disseminated quartz, calcite, and stibnite with minor Ag sulfosalts and distal zones of cinnabar and realgar at Fern and Hermes mines. In this study, the pressure, temperature, and composition of ore-forming fluids were measured in Au-, W-, and Sb-bearing samples collected from drill core and surface exposures. Using optical petrography, scanning electron microscopy cathodoluminescence (SEM-CL) and electron microprobe cathodoluminescence (EMPA-CL) imaging, as well as electron microprobe (EMP) and laser ablation-inductively coupled plasma-mass spectrometry trace element analyses, four major overprinting generations of hydrothermal quartz are defined. Fluid inclusion assemblages (FIAs) in each generation of quartz were characterized by microthermometry and laser Raman spectroscopy. Quartz and fluid inclusion paragenesis are as follows: (Qi) altered and overprinted Qi with no coeval FIAs that formed before or during event 1; (Q1) early veins as well as disseminated quartz with dull gray SEM-CL and H 2 O-NaCl-CO 2 FIAs that formed at minimum temperatures and pressures of 281° to 358°C and 1346 to 1789 bar during event 2 (Au); (Q2) vein and disseminated quartz, often euhedral, with H 2 O-NaCl ± CO 2 ± CH 4 FIAs that formed at minimum temperatures and pressures of 183° to 213°C and 72 to 602 bar during event 3 (W); and (Q3) euhedral and disseminated quartz with H 2 O-NaCl FIAs that formed at minimum temperature and pressures of 156° to 161°C and 5 to 6 bar during event 5 (Sb). Stibnite hosts H 2 O-NaCl FIAs trapped at minimum temperatures and pressures of 150° to 189°C and 5 to 12 bar that are similar to those of Q3-hosted FIAs. The quartz paragenetic history in the district follows a progressive temporal path from Tienriched quartz deposited by a relatively deep and higher temperature aqueous-carbonic fluid to a Li, Al, and Sb enriched quartz precipitated from a lower temperature aqueous fluid. Gases in fluid inclusion extracts from ore and gangue minerals were analyzed by mass spectrometry. Noble gas isotope analysis of fluid inclusion extracts revealed three signatures. Pre-ore Qi has R/R A (the isotopic ratio of the sample 3 He/ 4 He to atmospheric 3 He/ 4 He (1.384 × 10 −6 )) values that reflect the composition of the crustal melt-derived Atlanta lobe of the Idaho batholith. Quartz (Q1) and auriferous arsenian pyrite of hydrothermal event 2 have 20 Ne/ 4 He and R/R A values that plot along the air-crust mixing line, and these gases were likely introduced by metamorphic fluids derived from metasedimentary rocks. Stibnite with associated quartz (Q3 ± Q2) have 20 Ne/ 4 He and R/R A values that extend from the air-crust mixing line to the air-mantle mixing line, showing a shift from a crustal signature to an overprinting mantle signature. Late calcite has 20 Ne/ 4 He and R/R A values that extend from air toward the mantle end member, which suggests that magmatic volatiles condensed into meteoric groundwater late in the paragenesis. A mantle volatile source is also supported by high 20 Ne/ 22 Ne ratios. The Stibnite-Yellow Pine district is similar to other Au-W-Sb districts around the world in ore fluid chemistries, with late-stage stibnite being a product of cooling. The fluid pressure-temperature-composition (P-T-X) estimates and the crustal source of He during hydrothermal event 2 gold mineralization are characteristic of orogenic Au deposits, and the observed inclusion reequilibration textures indicate that trapped fluid inclusions were deformed during transitions between the brittle-ductile environment. Scheelite was deposited during event 3 with Q2 quartz and is overgrown by Q3 quartz and stibnite. Our interpretation of the quartz texture, chemistry, and fluid inclusion P-T-X data suggest that Au, W, and Sb mineralization occurred as hydrothermal fluids evolved from H 2 O-NaCl-CO 2 at >300°C and depths of ~4 to 6 km near the ductile to brittle transition to H 2 O-NaCl at ~150°C and epithermal depths as the Idaho batholith was exhumed. Geochronology indicates that from the Late Cretaceous to early Eocene, overprinting hydrothermal events formed deep orogenic Au, intermediate W, and shallow epithermal Au-Ag and Sb. Without comprehensive geochronologic constraints, our fluid inclusion data and textural observations could be interpreted as a single evolving hydrothermal system, as has been done in many other mining districts with similar mineralization.

Idaho

Water-quality appraisal of NASQAN stations below impoundments, eastern Tennessee

The National Stream Quality Accounting Network (NASQAN) is a network of stations at which systematic and continuing water-quality data are collected. Major objectives of this U.S. Geological Survey program are (1) to depict areal variability of streamflow and water-quality conditions nationwide on a year-by-year basis and (2) to detect long-term changes in streamflow and stream quality. Several NASQAN stations in East Tennessee are downstream from impoundments which have a significant effect on water quality. NASQAN data obtained from the Tennessee River below Watts Bar Dam and the Clinch River below Melton Hill Dam were compared to water-quality data from the basins upstream. The comparison indicates that NASQAN data obtained below impoundment may not be adequate to describe a composite picture of water quality in the accounting unit. Detention time of storage in the impoundments is believed to moderate the range of constituent values observed at the NASQAN stations. Data obtained upstream and downstream from Watts Bar Dam indicate that the water sampled at the NASQAN station comes from stratified layers of the impoundment and is not representative of an integrated sample of water from the impoundment. Values of total recoverable iron suggest that, because of adsorption to sediments in impoundments, some constituents are not accurately described by sampling below impoundments. Relations between water-quality constituents and flow at stations on the Clinch River and Tennessee River are not well defined due to regulation. Direct load computations for many constituents were therefore not possible, which diminished the utility of data from these NASQAN stations to account for quantity versus quality of the water. Load computations were only possible for ionic constituents through use of a continuous specific-conductance record as an intermediary. Compensation for the effects of discharge prior to application of the Seasonal Kendall test for trends could not be done and identification of trends in water-quality constituents caused by some process (source) change was not possible. Some water-quality trends indicated by data from the Clinch and Tennessee Rivers might reflect the decreasing trend in discharge during the 1972-82 water years. Thus the stations below Watts Bar Dam and below Melton Hill Dam do not adequately meet the NASQAN objective to detect and assess long-term changes in stream quality.

Tennessee

Application of acoustical methods for estimating water flow and constituent loads in Perdido Bay, Florida

Water flow and quality data were collected from December 1994 to September 1995 to evaluate variations in discharge, water quality, and chemical fluxes (loads) through Perdido Bay, Florida. Data were collected at a cross section parallel to the U.S. Highway 98 bridge. Discharges measured with an acoustic Doppler current profiler (ADCP) and computed from stage-area and velocity ratings varied roughly between + or - 10,000 cubic feet per second during a typical tidal cycle. Large reversals in flow direction occurred rapidly (less than 1 hour), and complete reversals (resulting in near peak net-upstream or downstream discharges) occurred within a few hours of slack water. Observations of simultaneous upstream and downstream flow (bidirectional flow) were quite common in the ADCP measurements, with opposing directions of flow occurring predominantly in vertical layers. Continuous (every 15 minutes) discharge data were computed for the period from August 18, 1995, to September 28, 1995, and filtered daily mean discharge values were computed for the period from August 19 to September 26, 1995. Data were not computed prior to August 18, 1995, either because of missing data or because the velocity rating was poorly defined (because of insufficient data) for the period prior to landfall of hurricane Erin (August 3, 1995). The results of the study indicate that acoustical techniques can yield useful estimates of continuous (instantaneous) discharge in Perdido Bay. Useful estimates of average daily net flow rates can also be obtained, but the accuracy of these estimates will be limited by small rating shifts that introduce bias into the instantaneous values that are used to compute the net flows. Instantaneous loads of total nitrogen ranged from -180 to 220 grams per second for the samples collected during the study, and instantaneous loads of total phosphorous ranged from -10 to 11 grams per second (negative loads indicate net upstream transport). The chloride concentrations from the water samples collected from Perdido Bay indicated a significant amount of mixing of saltwater and freshwater. Mixing effects could greatly reduce the accuracy of estimates of net loads of nutrients or other substances. The study results indicate that acoustical techniques can yield acceptable estimates of instantaneous loads in Perdido Bay. However, estimates of net loads should be interpreted with great caution and may have unacceptably large errors, especially when saltwater and freshwater concentrations differ greatly.

Florida

Ground-water quality atlas of Oakland County, Michigan

The U.S. Geological Survey (USGS), in cooperation with Oakland County Health Division (OCHD), collected 140 water samples from 38 wells in Oakland County during 1998 to better understand ground-water quality. OCHD had observed temporal variations in concentrations of various constituents, so two additional sets of samples were collected to evaluate potential short-term variability related to sample collection procedures and long-term seasonal variability. Replicate samples from 28 wells were analyzed in the Michigan Department of Environmental Quality (MDEQ) Drinking Water Laboratory to compare MDEQ&rsquo;s analytical results to those obtained from the USGS National Water Quality Laboratory. Several additional databases describing population, land use, water supply, soils, geology, and flows of ground water and surface water are presented in the first part of the report to assist in interpreting the water-quality data. Maps created from these databases are provided in the first portion of the report as an extension of the study-area description. The U.S. Environmental Protection Agency (USEPA) has established Maximum Contaminant Levels (MCL) and Secondary Maximum Contaminant Levels (SMCL) for which samples were analyzed in this study. Water from the 38 wells sampled by the USGS did not exceed the SMCL or MCL for sulfate, fluoride, or nitrite. However, water from 26 wells exceeded the SMCL for iron, water from 12 wells exceeded the SMCL for manganese, and water from 12 wells exceeded the SMCL for dissolved solids. Water from two wells exceeded the MCL for nitrate, although nitrate concentrations in water from most wells was below the detection limit. Water from seven wells exceeded the SMCL for chloride, and water from all wells contained detectable concentrations of chloride. Water from five wells exceeded the MCL for arsenic, and most of the wells sampled contained detectable concentrations of arsenic. These five wells were identified from previous MDEQ analyses to have elevated arsenic concentrations, and were sampled to obtain additional chemistry information. Replicate samples were collected from 26 of the 38 wells for analysis at the MDEQ Drinking-Water Laboratory to compare the results with the USGS National Water Quality Laboratory. The results of the replicate analyses indicate close agreement between the laboratories, with mean differences for nitrate, chloride, and arsenic of 0.10 milligrams per liter (mg/L) as nitrogen, 6.8 mg/L, and 0.0008 mg/L, respectively between the USGS and MDEQ analyses. Potential health effects associated with ingesting nitrate, chloride, and arsenic are provided with the water-quality data, along with references for further information.

Michigan

Assimilation of reduced carbon triggers platinum alloy saturation in mafic and ultramafic magmas

It is generally observed that magmatic sulfide ores have higher ratios of Pd/Pt than the mantle-like values of their parental magmas. This discrepancy has defied simple explanation because the partitioning behavior of both elements between sulfide and silicate liquids is very similar. Assimilation of sulfur- and carbon-rich country rocks by mafic and ultramafic magmas is considered a critical, if not essential, step in the formation of magmatic base metal sulfide deposits. Although there is general consensus that the assimilation of external sulfur and carbon promotes sulfide saturation, the effect of carbon assimilation on the solubilities of platinum-group elements in natural S-bearing silicate melt has been overlooked. In this study, we investigate the variations of platinum and palladium solubilities during assimilation of graphite and methane through thermodynamic modeling, in comparison with data from an array of highly distinctive magmatic sulfide ore systems representing ages from Archean to Paleozoic, melt compositions from komatiite to basalt, and magmatic settings including lavas, hypabyssal intrusions, plutonic continental arc roots, and plutonic layered intrusions, namely: Raglan, Norilsk-Talnakh, Lac des Iles, and the J-M Reef of the Stillwater Complex. We model assimilation-fractional crystallization processes to estimate the reduction of oxygen fugacity ( ⁠fO2⁠ ) of the melt due to incorporation of graphite and methane. The simulations show that although Pd remains highly soluble during the progressive assimilation of reduced carbon, Pt solubility decreases significantly as the silicate melt becomes increasingly reduced. With less than 8 % of sediment assimilation, Pt alloy may saturate and then deviate from sulfide-undersaturated silicate melts, concomitantly increasing the Pd/Pt value of the remaining melts of the Raglan and Norilsk-Talnakh systems. For the Lac des Iles and Stillwater systems, a higher extent of assimilation is needed to reach Pt saturation because of the relatively carbon-poor nature of the lower crustal rocks. The assimilation of methane volatiles is shown to be more effective than graphite assimilation, and it provides a pathway to Pt alloy fractionation in the absence of detectable amounts of bulk host-rock assimilation. High Pd/Pt values have been documented in many world-class magmatic sulfide deposits whose parental magmas have demonstrably experienced crustal contamination. Our model suggests that although anomalous Pd/Pt values may be explained by other mechanisms such as incongruent melting of preexisting sulfide or differences in the diffusivities of the metals within achieving equilibration, the assimilation of graphite or methane may play an important role in the global occurrence of magmatic sulfide ores with elevated Pd/Pt values.

Economic Geology

Generalized potentiometric maps of the Fort Union, Hell Creek, and Fox Hills aquifers within the Standing Rock Reservation

Generalized potentiometric surfaces of the Fort Union, Hell Creek, and Fox Hills aquifers were constructed to assess the groundwater resources of the Standing Rock Reservation. Additionally, this information can provide water managers with tools and data to effectively manage water resources in the future. Previous studies that mapped the geology and hydrogeology of the area at differing scales were used to confirm in which aquifer the study wells were completed. Water-level data from wells are provided by the U.S. Geological Survey Groundwater System Inventory database, the South Dakota Department of Agriculture and Natural Resources, and the North Dakota Department of Water Resources. Hydrographs were constructed for five selected observation wells to evaluate historical water-level fluctuations and trends. Hydrographs for the Hell Creek aquifer showed a flat trend with a rise in 2020. Hydrographs for the deeper Fox Hills aquifer showed that water levels fluctuated in response to climatic conditions and demonstrated an increasing trend in water-level elevations starting in 2010. Hydrographs were not constructed for any wells completed in the Fort Union Formation because none of the wells had continuous long-term measurements. Generalized potentiometric surfaces, constructed from interpolating water-level elevations, gave insight into groundwater flow directions. Groundwater in the Fort Union aquifer likely flows radially outward from the northwest part of the study area to the northeast and south-southeast parts. Groundwater in the Hell Creek aquifer generally flows from higher elevations in the northwest towards lower areas, where surface-water tributaries have incised into the aquifer. Groundwater in the Fox Hills aquifer likely flows from higher elevations in the west, southwest, and central parts of the study area towards the valleys of the Grand River and Missouri River. Most wells used for constructing potentiometric maps had only one recorded water-level measurement from drillers at the time of well construction. These measurements are often subject to error because the well is still recovering and because of spatial limitations of data availability. Also, because single water-level measurements were recorded at different points in time, additional uncertainty is introduced by fluctuating climatic conditions effect on water levels. Potentiometric map interpretation limitations are a result of areas with sparse data. Limitations also arise from potentiometric surfaces generalizing a complex and dynamic hydrogeologic system; however, the generalized potentiometric surface maps can be used to assist water managers and can help prioritize locations for future monitoring in areas with high uncertainty from sparse existing data.

North Dakota, South Dakota

Benthic habitat map of Olowalu Reef, Maui, Hawaii—Geomorphological structure, biological cover, and geologic zonation determined with spectral, lidar, and acoustic data

The fringing coral reef off Olowalu, Maui, Hawaii, has been identified as a local conservation priority site. In 2007, the National Oceanic and Atmospheric Administration (NOAA) produced a benthic habitat map of the Hawaiian Islands that was used as a foundation for this study. To support place-based management of the reef in the future, the U.S. Geological Survey (USGS) mapped the geologic zone, major and dominant geomorphological structure, biological cover type, and percent of biological cover for 11 square kilometers (km 2 ) of Olowalu Reef at a minimum mapping unit (MMU) of 100 square meters (m 2 ) to create a benthic habitat map. Heads-up digitization was employed on 0.50-meter (m) natural color satellite orthoimagery with ancillary 1-m acoustic backscatter imagery from single-scan sonar (sound navigation and ranging). A 1-m, 4-m, and 8-m digital bathymetric model (DBM) was interpolated from bathymetric lidar (light detection and ranging), and various geomorphometric layers derived from the DBMs were used for habitat interpretation. Still-frame imagery of the seafloor extracted from vessel-towed underwater video transects on Olowalu Reef served as ground validation points ( n =870) during active mapping and accuracy assessment points ( n =216) for thematic accuracy assessment. Thematic accuracy was cross-validated by the Hawai‘i Department of Land and Natural Resources Division of Aquatic Resources. Final thematic accuracy was 88.8 percent for major structure, 85.6 percent for dominant structure, 86.0 percent for major biological cover, and 78.6 percent for type and percent of major biological cover. Reef and hardbottom constituted 52 percent of the total mapped habitat, comprising mostly aggregate reef (31 percent) and pavement (11 percent), with large swaths of spur-and-groove (9 percent). Of this hardbottom, 17 percent was covered with moderate (10 to <50 percent) coral and 27 percent with high coral cover (50 to <90 percent). High (50 to <90 percent) macroalgae cover dominated the continuous sand sheets in offshore bank/shelf zones. The map created in this study supplements the NOAA 2007 map and expands on the observations made by USGS sampling of the reef. The NOAA 2007 map and our map differed in total areal extent by a negligible 6 m 2 and were in general thematic agreement. Our map is intended to serve as a baseline for public access, general research, local-level management, and reef change for future studies.

Hawaii

Spatiotemporal variability of algal biomass and nitrate in Owasco and Seneca Lakes in the Finger Lakes Region, New York, in 2019

Cyanobacterial harmful algal blooms (CyanoHABs) have become increasingly common, threatening the security of water resources globally. The U.S. Geological Survey conducted high-resolution nearshore mapping surveys using boat-mounted multiparameter sondes and nitrate sensors during the summer and fall of 2019 on Owasco Lake and Seneca Lake, two lakes with documented CyanoHABs in the Finger Lakes region of New York State. Discrete sensor measurements and water-quality samples were collected at fixed points along survey routes and continuous data were generated at open-water monitoring platforms. This investigation examined whether water-quality information from nearshore surveys was representative of open-water conditions and if nearshore surveys could be used to identify areas with localized nearshore CyanoHABs and potential sources of nutrients not captured by tributary sampling. In addition to comparisons across methods, nearshore concentrations of nitrate and chlorophyll were evaluated relative to tributary outlets, cyanobacterial abundance and biovolume at discrete locations, and the locations of near-surface CyanoHABs that were designated as “confirmed with high toxins” by the New York State Department of Environmental Conservation. Nitrate and chlorophyll concentrations were comparable across methods for each lake, although concentration ranges were typically higher for nearshore mapping datasets than for nearshore discrete datasets. Nearshore surveys indicated areas of nitrate enrichment that varied temporally in both lakes. Orthophosphate was not routinely detected. Across methods, median chlorophyll concentrations were higher for the summer survey than for the fall survey in Owasco Lake. Nearshore chlorophyll concentrations varied more temporally in Owasco Lake than in Seneca Lake. Phytoplankton and cyanobacterial abundance and biovolume were about five times higher in Owasco Lake than in Seneca Lake. Cyanobacteria dominated the phytoplankton community in most samples, and Microcystis comprised the bulk of the cyanobacterial biovolume. The most abundant potential cyanotoxin-producing (specifically microcystins) genera were Microcystis , Synechococcus , Aphanocapsa , and Pseudanabaena . The cyanobacterial community composition was comparable between open-water monitoring platforms and nearshore samples. Microcystins were detected in seven survey samples from Owasco Lake, in one survey sample from Seneca Lake, and in one sample each from the open-water monitoring platforms on Owasco and Seneca Lakes that were collected about 7 days before the fall surveys. Microcystin detections were not consistently associated with high cyanobacterial cell counts or cyanotoxin-producing genera. Results from nearshore surveys were comparable to open-water monitoring platforms and discrete nearshore observations in the absence of nearshore or open-water CyanoHABs in these systems during the study. Patterns of nearshore concentrations of nitrate and chlorophyll from nearshore surveys may aid in the identification of areas with localized nitrate loading and shifts in phytoplankton abundance and community composition.

New York

Water-quality assessment of the Ozark Plateaus study unit, Arkansas, Kansas, Missouri, and Oklahoma — Nutrients, bacteria, organic carbon, and suspended sediment in surface water, 1993-95

Nutrient, bacteria, organic carbon, and suspended- sediment samples were collected from 1993-95 at 43 surface-water-quality sampling sites within the Ozark Plateaus National Water- Quality Assessment Program study unit. Most surface-water-quality sites have small or medium drainage basins, near-homogenous land uses (primarily agricultural or forest), and are located predominantly in the Springfield and Salem Plateaus. The water-quality data were analyzed using selected descriptive and statistical methods to determine factors affecting occurrence in streams in the study unit. Nitrogen and phosphorus fertilizer use increased in the Ozark Plateaus study unit for the period 1965-85, but the application rates are well below the national median. Fertilizer use differed substantially among the major river basins and physiographic areas in the study unit. Livestock and poultry waste is a major source of nutrient loading in parts of the study unit. The quantity of nitrogen and phosphorus from livestock and poultry wastes differed substantially among the river basins of the study unit's sampling network. Eighty six municipal sewage-treatment plants in the study unit have effluents of 0.5 million gallons per day or more (for the years 1985-91). Statistically significant differences existed in surface-water quality that can be attributed to land use, physiography, and drainage basin size. Dissolved nitrite plus nitrate, total phosphorus, fecal coliform bacteria, and dissolved organic carbon concentrations generally were larger at sites associated with agricultural basins than at sites associated with forested basins. A large difference in dissolved nitrite plus nitrate concentrations occurred between streams draining basins with agricultural land use in the Springfield and Salem Plateaus. Streams draining both small and medium agricultural basins in the Springfield Plateau had much larger concentrations than their counterparts in the Salem Plateau. Drainage basin size was not a significant factor in affecting total phosphorus, fecal coliform bacteria, or dissolved organic carbon concentrations. Suspended-sediment concentrations generally were small and indicative of the clear water in streams in the Ozark Plateaus. A comparison of the dissolved nitrite plus nitrate, total phosphorus, and fecal coliform data collected at the fixed and synoptic sites indicates that generally the data for streams draining basins of similar physiography, land-use setting, and drainage basin size group together. Many of the variations are most likely the result of differences in percent agricultural land use between the sites being compared or are discharge related. The relation of dissolved nitrite plus nitrate, total phosphorus, and fecal coliform concentration to percent agricultural land use has a strong positive 2 Water-Quality Assessment-Nutrients, Bacteria, Organic Carbon, and Suspended Sediment in Surface Water, 1993-95 correlation, with percent agricultural land use accounting for between 42 and 60 percent of the variation in the observed concentrations.

Arkansas, Kansas, Missouri, Oklahoma

Pre-eruptive characteristics of “suspect” silicic magmas in Carlin-type Au-forming systems

World-class Carlin-type Au deposits hosted in sedimentary rock were formed when profuse Eocene silicic magmatism swept across northern Nevada in response to arc migration. Carlin-type Au deposits formed along with porphyry/skarn Cu-Mo-W-Au deposits, epithermal Ag-Au deposits, and distal disseminated Ag-Au deposits. But unlike these other Au-bearing deposits that have clear associations with igneous intrusions, Carlin-type ore deposits appear to have formed distant from concealed plutons, and their origin remains controversial. Despite decades of abundant geophysical, geochronological, and geochemical studies suggesting the involvement of magmas, concrete evidence for magmatic involvement is still lacking. Consequently, the involvement of contemporaneous igneous systems remains inferred based on age, proximity, and variable isotopic, geochemical, and geophysical clues. A recent synthesis of deposit models postulates that Carlin-type Au deposits are intrusion-related, but that the causative magmas reside deeper (∼6–12 km) than in typical porphyry and peripheral systems (∼3–5 km), meaning that Carlin-type deposits are perhaps more distal expressions of igneous intrusions. We investigate a collection of “suspect” magmatic systems over a ∼7 m.y. timespan (∼41–34 Ma) that are contemporaneous with and near known Carlin-type ore deposits. We report results of a multifaceted array of in situ geochemical analyses (FTIR, EMP, SHRIMP-RG, LA-ICP-MS) of quartz-hosted melt inclusions, biotite, and quartz to better characterize the pre-eruptive characteristics of these magmas. We also report results of thermobarometry and thermodynamic phase equilibria modeling to help place constraints on magmatic reservoir depths and processes. Rather than a single “flavor” of silicic magma, we observe a surprisingly broad compositional spectrum of rhyolites, with one end of the spectrum exhibiting more arc-like (I-type) characteristics and the other end displaying more post-subduction, thick-crust extensional (A-type) characteristics. This broad compositional spectrum suggests a more complex picture of silicic crustal magmatism operating over a narrow span of time during slab rollback. Despite this spectrum, magmatic systems in this study are consistently ferroan and generally peraluminous, which we interpret as an expression of the relatively elevated geotherm at the time and incorporation of variable amounts of highly peraluminous metasedimentary crustal components. The silicic magma spectrum encompasses a range of mineralization associations, including subduction-related Cu-Mo-W-Au-Ag and post-subduction, thick-crust extensional rare-metal Mo-Sn-W-F-Be-Ag-Au, consistent with the prolific and diverse array of ore deposits that formed during this time. Carlin-type Au deposition appears to be associated with nearly the entire magmatic spectrum. This apparent indifference to silicic magma “flavor” would seem to imply that if magmas are involved in Carlin-type Au deposit genesis, they perhaps do not need to be compositionally specialized and/or possibly are only relevant as heat sources driving circulation to remobilize and redistribute metals.

Nevada

Magnitude and frequency of low flows in the Suwannee River Water Management District, Florida

Low-flow frequency statistics for 20 gaging stations having at least 10 years of continuous record and 31 other stations having less than 10 years of continu ous record or a series of at least two low- flow measurements are presented for unregulated streams in the Suwannee River Water Management District in north-central Florida. Statistics for the 20 continuous-record stations included are the annual and monthly minimum consecutive-day average low- flow magnitudes for 1, 3, 7, 14, and 30 consecutive days for recurrence intervals of 2, 5, 10, 20, and, for some long-term stations, 50 years, based on records available through the 1994 climatic year.Only theannual statistics are given for the 31 other stations; these are for the 7- and 30-consecutive day periods only and for recurrence intervals of 2 and 10 years only. Annual low-flow frequency statistics range from zero for many small streams to 5,500 cubic feet per second for the annual 30- consecutive-day average flow with a recurrenceinterval of 2 years for the Suwannee River near Wilcox (station 02323500). Monthly low-flow frequency statistics range from zero for many small streams to 13,800 cubic feet per second for the minimum 30-consecutive-day average flow with a 2-year recurrence interval for the month of March for the same station. Generally, low-flow characteristics of streams in the Suwannee River Water Management District are controlled by climatic, topographic, and geologic fac tors. The carbonate Floridan aquifer system underlies, or is at the surface of, the entire District. The terrane's karstic nature results in many sinkholes and springs. In some places, springs may contribute greatly to low streamflow and the contributing areas of such springs may include areas outside the presumed surface drainage area of the springs. In other places, water may enter sinkholes within a drainage basin, then reappear in springs downstream from a gage. Many of the smaller streams in the District go dry or have no flow for several months in many years. In addition to the low-flow statistics, four synoptic low-flow measurement surveys were conducted on 161 sites during 1990, 1995, and 1996. The measurements were made to provide "snapshots" of flow conditions of streams throughout the Suwannee River Water Management District. Magnitudes of low flows during the 1990 series of measurements were in the range associated with minimum 7-consecutive-day 50-year recurrence interval to the minimum 7-consecutive-day 20-year recurrence interval, except in Taylor and Dixie Counties, where the magnitudes ranged from the minimum 7-consecutive-day 5-year flow level to the7-consecutive-day 2-year flow level. The magnitudes were all greater than the minimum 7- consecutive-day 2-year flow level during 1995 and 1996. Observations of no flow were recorded at many of the sites for all four series of measurements.

Florida

Multiple-well monitoring site adjacent to the Midway- Sunset and Buena Vista Oil Fields, Kern County, California

Groundwater quality in and around oil fields in the Southern San Joaquin Valley is of interest to many California residents that rely heavily on groundwater for domestic, commercial, and agricultural use. To help assess the effects of historical oil-field activities and natural geologic sources on groundwater near the southwest margins of the Kern County Groundwater Subbasin, a multiple-well monitoring site was installed near the administrative boundary between the Midway-Sunset and Buena Vista Oil Fields in Kern County, California. The installation of the Midway-Sunset Buena Vista multiple-well monitoring site (MSBV) supports regional analysis of the relations of oil and gas sources to groundwater quality by providing information about the geology, hydrology, geophysical properties, and water quality of the alluvial and upper Tulare aquifers in areas where groundwater data were limited. Data collected from the site included drill cuttings, whole core samples, sidewall core samples, mud-gas analysis, borehole geophysical logs, depth to water measurements, and water quality samples. Whole cores were scanned using dual energy computed tomography. Subsamples of selected cores were analyzed for density, porosity, specific retention, and bulk minerology. Thin sections of the subsamples were prepared, photographed, and examined. Two samples were analyzed using scanning electron microscope technology to examine the microporosity of diatomite laden sediment. Instrumentation installed in the wells collect hourly depth to water measurements. Analysis of the data show there is 355 feet of alluvium overlying the Tulare Formation at the well site. The contact between the two formations is an aquitard resulting in a perched aquifer in the alluvium and unconfined aquifer in the Tulare Formation. The alluvium is more heterogenous and finer grained than the Tulare Formation resulting in markedly higher porosity in the alluvium compared to the Tulare Formation. Higher specific retention observed in the alluvium is attributed to the finer grained sediment and greater abundance of reworked diatomite (as represented by opal-CT [cristobalite-tridymite]) compared to the Tulare Formation. Total dissolved solids (TDS) approached or exceeded 10,000 milligrams per liter (mg/L) in the alluvium from approximately 176 to 242 feet below land surface and at the top of the Amnicola clay at approximately 670 feet below land surface within the Tulare Formation. Elevated TDS, chloride, and boron concentrations in the alluvium and on top of the Amnicola clay likely reflect groundwater that is mixed with oil-field water. Water chemistry and modern-aged groundwater in the alluvial monitoring well (MSBV #3) are consistent with the oil-field water in the alluvium being derived from documented historical surface disposal of oil-field water upslope (northwest) of the site. Water chemistry and pre-modern groundwater age in the deeper Tulare monitoring well (MSBV #1) on top of the Amnicola clay are consistent with oil-field fluids derived from upslope natural geologic sources or old oil wells that leak in the subsurface. Shallow groundwater in the Tulare (MSBV #2) is not affected by mixing with oil-field sources.

EarthArXiv