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Increasing aeolian dust deposition to snowpacks in the Rocky Mountains inferred from snowpack, wet deposition, and aerosol chemistry

Mountain snowpacks are a vital natural resource for ∼1.5 billion people in the northern Hemisphere, helping to meet human and ecological demand for water in excess of that provided by summer rain. Springtime warming and aeolian dust deposition accelerate snowmelt, increasing the risk of water shortages during late summer, when demand is greatest. While climate networks provide data that can be used to evaluate the effect of warming on snowpack resources, there are no established regional networks for monitoring aeolian dust deposition to snow. In this study, we test the hypothesis that chemistry of snow, wet deposition, and aerosols can be used as a surrogate for dust deposition to snow. We then analyze spatial patterns and temporal trends in inferred springtime dust deposition to snow across the Rocky Mountains, USA, for 1993–2014. Geochemical evidence, including strong correlations (r 2 ≥ 0.94) between Ca 2+ , alkalinity, and dust concentrations in snow deposited during dust events, indicate that carbonate minerals in dust impart a strong chemical signature that can be used to track dust deposition to snow. Spatial patterns in chemistry of snow, wet deposition, and aerosols indicate that dust deposition increases from north to south in the Rocky Mountains, and temporal trends indicate that winter/spring dust deposition increased by 81% in the southern Rockies during 1993–2014. Using a multivariate modeling approach, we determined that increases in dust deposition and decreases in springtime snowfall combined to accelerate snowmelt timing in the southern Rockies by approximately 7–18 days between 1993 and 2014. Previous studies have shown that aeolian dust emissions may have doubled globally during the 20th century, possibly due to drought and land-use change. Climate projections for increased aridity in the southwestern U.S., northern Africa, and other mid-latitude regions of the northern Hemisphere suggest that aeolian dust emissions may continue to increase, compounding the risk that climate warming poses to snowpack water resources in arid/semi-arid regions of the world.

Atmospheric Environment↗

Water quality and hydrology of the Yellow Dog and Salmon Trout Watersheds, Marquette County, Michigan 2013–16

In 2013, the U.S. Geological Survey, in cooperation with the Keweenaw Bay Indian Community, began monitoring the water quality of springs and seeps within the Yellow Dog and Salmon Trout watersheds in Marquette County, Michigan. The objectives of this study were to (1) monitor streamflow and analyze the hydrology of the watersheds and (2) characterize the water quality in the watersheds prior to development of mineral resources within the watershed. Three continuous-record streamgages (U.S. Geological Survey stations 04043238, 04043244, and 04043275) were examined to identify runoff and baseflow components of streamflow and the relative magnitudes of those components. Streamflow at each station was dominated by groundwater discharge with about 70 to 80 percent of the annual streamflow being groundwater-derived baseflow. From May 2013 to October 2016, 239 water-quality samples were collected at 15 stations within the Yellow Dog and Salmon Trout watersheds. Of the 15 stations sampled, 8 of the stations were springs and 7 of the stations were streams. Samples were analyzed for nutrient, trace metal, and major-ion species at all stations with additional suspended-sediment samples collected at the 7 stream stations. Where applicable, water-quality results were compared to aquatic health guidelines used by the Michigan Department of Environmental Quality. Copper concentrations exceeded the final chronic value five times and the aquatic maximum value once, whereas silver concentrations exceeded the final chronic value twice and the aquatic maximum value once. Results indicate that chloride concentrations may be increasing at some stations, but values are generally low with a median concentration of 0.25 milligram per liter. Bed-sediment chemistry was evaluated twice for each stream sampling station. Samples were collected in the first and last year of the study and analyzed for trace metals. Sediment chemistry results were compared to consensus-based sediment quality guidelines. None of the metal constituents analyzed exceeded the threshold effect concentration or probable effect concentration thresholds, indicating a healthy aquatic environment in relation to bed-sediment quality.

Michigan↗

Long-term tillage and crop rotation effects on residual nitrate in the crop root zone and nitrate accumulation in the intermediate vadose zone

Tillage influences the physical and biological environment of soil. Rotation of crops with a legume affects the soil N status. A furrow irrigated site was investigated for long-term tillage and crop rotation effects on leaching of nitrate from the root zone and accumulation in the intermediate vadose zone (IVZ). The investigated tillage systems were disk-plant (DP), ridge-till (RT) and slot-plant (SP). These tillage treatments have been maintained on the Hastings silt loam (Udic Argiustoll) and Crete silt loam (Pachic Argiustoll) soils since 1976. Continuous corn (CC) and corn soybean (CS) rotations were the subtreatments. Since 1984, soybeans have been grown in CS plots in even calendar years. All tillage treatments received the same N rate. The N rate varied annually depending on the root zone residual N. Soybeans were not fertilized with N-fertilizer. Samples for residual nitrate in the root zone were taken in 8 of the 15 year study while the IVZ was only sampled at the end of the study. In seven of eight years, root zone residual soil nitrate-N levels were greater with DP than RT and SP. Residual nitrate-N amounts were similar in RT and SP in all years. Despite high residual nitrate-N with DP and the same N application rate, crop yields were higher in RT and SP except when DP had an extremely high root zone nitrate level. By applying the same N rates on all tillage treatments, DP may have been fertilized in excess of crop need. Higher residual nitrate-N in DP was most likely due to a combination of increased mineralization with tillage and lower yield compared to RT and SP. Because of higher nitrate availability with DP, the potential for nitrate leaching from the root zone was greater with DP as compared to the RT and SP tillage systems. Spring residual nitrate-N contents of DP were larger than RT and SP in both crop rotations. Ridge till and SP systems had greater nitrate-N with CS than CC rotations. Nitrate accumulation in IVZ at the upstream end of the field was twice as high with DP compared to RT and SP. At the downstream end, it was 2.4 and 1.6 times greater with DP than RT and SP, respectively. Nitrate concentration was greater in the IVZ of DP compared to RT and SP tillage systems. Nitrate accumulations in IVZ of RT and SP were not different. Continuous corn had slightly higher nitrate levels in IVZ than CS. The depth of nitrate penetration at the upstream end was greater than that of the downstream end. Estimated rates of nitrate movement ranged from 0.87 to 0.92 m yr-1 at the upstream end and 0.73 to 0.78 m yr-1 at the downstream end.

Transactions of the American Society of Agricultur↗

Isotopic ratios of Saturn's rings and satellites: Implications for the origin of water and Phoebe

Isotopic ratios have long been used to learn about physical processes acting over a wide range of geological environments, and in constraining the origin and/or evolution of planetary bodies. We report the spectroscopic detection of deuterium in Saturn's rings and satellites, and use these measurements to determine the (D/H) ratios in their near-surface regions. Saturn's moons, Phoebe and Iapetus, show a strong signature of CO2 and the 13C component of this molecule is detected and quantified. Large averages of spectra obtained by the Cassini Visual and Infrared Mapping Spectrometer, VIMS, were computed for the rings and icy satellites. The observed intensities of the infrared absorptions in H2O and CO2 and their isotopes were calibrated using laboratory data and radiative transfer models to derive the D/H and 13C/12C ratios. We find that the D/H in Saturn's rings and satellites is close to the Vienna Standard Mean Ocean Water (VSMOW) and bulk Earth (4% lower than VSMOW) value except for Phoebe, which is 8.3 times the VSMOW value. This is the highest value for any Solar-System surface yet measured, and suggests that Phoebe formed from material with a different D/H ratio than the other satellites in the Saturn system. Phoebe’s 13C/12C ratio is also unusual: 4.7 times greater than terrestrial, and greater than values measured for the interstellar medium and the galactic center. The high 13C abundance in the CO2 suggests that Phoebe was never warm enough for the large D/H ratio in its surface to have originated by evaporative fractionation of its waterice (e.g., from heating in the inner Solar System before its eventual capture by Saturn). We also report the detection of a probable O-D stretch absorption due to OD in minerals on Phoebe at 3.62 μm. This absorption is not detected on other Saturnian satellites. Stronger signatures of bound water absorptions are found in the dark material of Iapetus and we report a new detection of bound water at 1.9 μm. The position of this absorption matches that seen in spectra of hydrated iron oxides but does not match absorptions seen in spectra of tholins. Despite the strong bound water signature in the Iapetus dark material, no 3.62-μm OD absorption is seen in the spectra, further indicating the high deuterium level on Phoebe is unusual. As such, it is likely that Phoebe originated in a colder part of the outer Solar System, relative to the prevailing temperatures at Saturn’s distance from the Sun.

Icarus↗

Organic petrographic evaluation of carbonaceous material in sediments of the Kinnickinnic River, Milwaukee, WI, U.S.A.

This study examines the use of organic petrology techniques to quantify the amount of coal and carbonaceous combustion by-products (i.e., coke, coal tar/pitch, cenospheres) in sediments taken from the Kinnickinnic River adjacent to the former site of the Milwaukee Solvay Coke and Gas Company. These materials are of concern as contaminants like polycyclic aromatic hydrocarbons (PAHs) are known to readily adsorb to coal and combustion byproducts. Kinnickinnic River sediment samples (n = 36) ranging in depth (1–11 ft.) were collected from eight core locations to quantify and characterize carbonaceous material in the sediments. To determine the amount (vol%) of organic particulates, U.S. Geological Survey (USGS) modified the existing ASTM D2799 using the following categories: coal, coke, coal tar/pitch, inertinite organics, plant material, cenospheres, and mineral matter. Coal fragments were subdivided by rank using vitrinite reflectance (R o , %) and organic components were further subdivided into the size fractions of coarse (250–1000 μm), fine (63–250 μm), and very fine (<63 μm). Of the 36 samples analyzed, concentrations of coal, coke, and coal tar/pitch ranged from 0 to 18.2 vol%, 0 to 32.0 vol%, and 0 to 2.6 vol%, respectively, with the highest concentrations occurring near point sources (e.g. discharge pipe and coal unloading operations). Samples that were furthest upstream and downstream from the Solvay site exhibited a marked decrease in particulate organics, with exception of one upstream location which had 19.8 vol% coke. Overall, the modified ASTM method provided a means to quantify the abundance of carbonaceous material present in the sediments. Petrography and total PAH concentrations did not provide a clear correlation to organic matter type or size fraction but the samples with the highest vol% organic matter in each core generally corresponded to the sample with the highest bulk PAH content.

Wisconsin↗

Degradation of RDX (Hexahydro-1,3,5-trinitro-1,3,5-triazine) in contrasting coastal marine habitats: Subtidal non-vegetated (sand), subtidal vegetated (silt/eel grass), and intertidal marsh

Hundreds of explosive-contaminated marine sites exist globally, many of which contain the common munitions constituent hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Quantitative information about RDX transformation in coastal ecosystems is essential for management of many of these sites. Isotopically labelled RDX containing 15 N in all 3 nitro groups was used to track the fate of RDX in three coastal ecosystem types. Flow-through mesocosms representing subtidal vegetated (silt/eel grass), subtidal non-vegetated (sand) and intertidal marsh ecosystems were continuously loaded with isotopically labelled RDX for 16–17 days. Sediment, pore-water and overlying surface water were analyzed to determine the distribution of RDX, nitroso-triazine transformation products (NXs) and nitrogen containing complete mineralization products, including ammonium, nitrate+nitrite, nitrous oxide and nitrogen gas. The marsh, silt, and sand ecotypes transformed 94%, 90% and 76% of supplied RDX, respectively. Total dissolved NXs accounted for 2%–4% of the transformed 15 N-RDX. The majority of RDX transformation in the water column was by mineralization to inorganic N (dissolved and evaded; 64%–78% of transformed 15 N-RDX). RDX was mineralized primarily to N 2 O (62–74% of transformed 15 N-RDX) and secondarily to N 2 (1–2% of transformed 15 N-RDX) which exchanged with the atmosphere. Transformation of RDX was favored in carbon-rich lower redox potential sediments of the silt and marsh mesocosms where anaerobic processes of iron and sulfate reduction were most prevalent. RDX was most persistent in the carbon-poor sand mesocosm. Partitioning of 15 N derived from RDX onto sediment and suspended particulates was negligible in the overall mass balance of RDX transformation (2%–3% of transformed 15 N-RDX). The fraction of 15 N derived from RDX that was sorbed or assimilated in sediment was largest in the marsh mesocosm (most organic carbon), and smallest in the sand mesocosm (largest grain size and least organic carbon). Sediment redox conditions and available organic carbon stores affect the fate of RDX in different coastal marine habitats.

Connecticut, New York↗

Geologic sources and concentrations of selenium in the West-Central Denver Basin, including the Toll Gate Creek watershed, Aurora, Colorado, 2003-2007

Toll Gate Creek, in the west-central part of the Denver Basin, is a perennial stream in which concentrations of dissolved selenium have consistently exceeded the Colorado aquatic-life standard of 4.6 micrograms per liter. Recent studies of selenium in Toll Gate Creek identified the Denver lignite zone of the non-marine Cretaceous to Tertiary-aged (Paleocene) Denver Formation underlying the watershed as the geologic source of dissolved selenium to shallow ground-water and surface water. Previous work led to this study by the U.S. Geological Survey, in cooperation with the City of Aurora Utilities Department, which investigated geologic sources of selenium and selenium concentrations in the watershed. This report documents the occurrence of selenium-bearing rocks and groundwater within the Cretaceous- to Tertiary-aged Denver Formation in the west-central part of the Denver Basin, including the Toll Gate Creek watershed. The report presents background information on geochemical processes controlling selenium concentrations in the aquatic environment and possible geologic sources of selenium; the hydrogeologic setting of the watershed; selenium results from groundwater-sampling programs; and chemical analyses of solids samples as evidence that weathering of the Denver Formation is a geologic source of selenium to groundwater and surface water in the west-central part of the Denver Basin, including Toll Gate Creek. Analyses of water samples collected from 61 water-table wells in 2003 and from 19 water-table wells in 2007 indicate dissolved selenium concentrations in groundwater in the west-central Denver Basin frequently exceeded the Colorado aquatic-life standard and in some locations exceeded the primary drinking-water standard of 50 micrograms per liter. The greatest selenium concentrations were associated with oxidized groundwater samples from wells completed in bedrock materials. Selenium analysis of geologic core samples indicates that total selenium concentrations were greatest in samples containing indications of reducing conditions and organic matter (dark gray to black claystones and lignite horizons). The Toll Gate Creek watershed is situated in a unique hydrogeologic setting in the west-central part of the Denver Basin such that weathering of Cretaceous- to Tertiary-aged, non-marine, selenium-bearing rocks releases selenium to groundwater and surface water under present-day semi-arid environmental conditions. The Denver Formation contains several known and suspected geologic sources of selenium including: (1) lignite deposits; (2) tonstein partings; (3) organic-rich bentonite claystones; (4) salts formed as secondary weathering products; and possibly (5) the Cretaceous-Tertiary boundary. Organically complexed selenium and/or selenium-bearing pyrite in the enclosing claystones are likely the primary mineral sources of selenium in the Denver Formation, and correlations between concentration of dissolved selenium and dissolved organic carbon in groundwater indicate weathering and dissolution of organically complexed selenium from organic-rich claystone is a primary process mobilizing selenium. Secondary salts accumulated along fractures and bedding planes in the weathered zone are another potential geologic source of selenium, although their composition was not specifically addressed by the solids analyses. Results from this and previous work indicate that shallow groundwater and streams similarly positioned over Denver Formation claystone units at other locations in the Denver Basin also may contain concentrations of dissolved selenium greater than the Colorado aquatic-life standard or the drinking- water standard.

Colorado↗

Quantity and quality of groundwater discharge in a hypersaline lake environment

Geophysical and geochemical surveys were conducted to understand groundwater discharge to Great Salt Lake (GSL) and assess the potential significance of groundwater discharge as a source of selenium (Se). Continuous resistivity profiling (CRP) focusing below the sediment/water interface and fiber-optic distributed temperature sensing (FO-DTS) surveys were conducted along the south shore of GSL. FO-DTS surveys identified persistent cold-water temperature anomalies at 10 separate locations. Seepage measurements were conducted at 17 sites (mean seepage rate = 0.8 cm/day). High resistivity anomalies identified by the CRP survey were likely a mirabilite (Na 2 SO 4 ·10H 2 O) salt layer acting as a semi-confining layer for the shallow groundwater below the south shore of the lake. Positive seepage rates measured along the near-shore areas of GSL indicate that a ∼1-m thick oolitic sand overlying the mirabilite layer is likely acting as a shallow, unconfined aquifer. Using the average seepage rate of 0.8 cm/day over an area of 1.6 km 2 , an annual Se mass loading to GSL of 23.5 kg was estimated. Determination of R/Ra values (calculated 3 He/ 4 He ratio over the present-day atmospheric 3 He/ 4 He ratio) <1 and tritium activities of 1.2–2.0 tritium units in groundwater within and below the mirabilite layer indicates a convergence of regional and local groundwater flow paths discharging into GSL. Groundwater within and below the mirabilite layer obtains its high sulfate salinity from the dissolution of mirabilite. The δ 34 S and δ 18 O isotopic values in samples of dissolved sulfate from the shallow groundwater below the mirabilite are almost identical to the isotopic signature of the mirabilite core material. The saturation index calculated for groundwater samples using PHREEQC indicates the water is at equilibrium with mirabilite. Water samples collected from GSL immediately off shore contained Se concentrations that were 3–4 times higher than other sampling sites >25 km offshore from the study site and may be originating from less saline groundwater seeps mixing with the more saline water from GSL. Additional evidence for mixing with near shore seeps is found in the δD and δ 18 O isotopic values and Br:Cl ratios. Geochemical modeling for a water sample collected in the vicinity of the study area indicates that under chemically reducing conditions, arsenic- (As) bearing minerals could dissolve while Se-bearing minerals will likely precipitate out of solution, possibly explaining why the shallow groundwater below and within the mirabilite salt layer contains low concentrations of Se (0.9–2.3 μg/L).

Utah↗

Gravity investigations of the Chickasaw National Recreation Area, south-central Oklahoma

The geological configuration of the Arbuckle Uplift in the vicinity of Chickasaw National Recreation Area in south-central Oklahoma plays a governing role in the distribution of fresh and mineral springs within the park and in the existence of artesian wells in and around the park. A confining layer of well-cemented conglomerate lies immediately below the surface of the recreation area, and groundwater migrates from an area of meteoric recharge where rocks of the Arbuckle-Simpson Aquifer crop out as close as two kilometers to the east of the park. Prominent, Pennsylvanian-aged faults are exposed in the aquifer outcrop, and two of the fault traces project beneath the conglomerate cover toward two groups of springs within the northern section of the park. We conducted gravity fieldwork and analysis to investigate the subsurface extensions of these major faults beneath Chickasaw National Recreation Area. By defining gravity signatures of the faults where they are exposed, we infer that the Sulphur and Mill Creek Faults bend to the south-west where they are buried. The South Sulphur Fault may project westward linearly if it juxtaposes rocks that have a density contrast opposite that of that fault's density configuration in the Sulphur Syncline area. The Sulphur Syncline, whose eastern extent is exposed in the outcrop area of the Arbuckle-Simpson Aquifer, does not appear to extend beneath Chickasaw National Recreation Area nor the adjacent City of Sulphur. The South Sulphur Fault dips steeply northward, and its normal sense of offset suggests that the Sulphur Syncline is part of a graben. The Mill Creek Fault dips vertically, and the Reagan Fault dips southward, consistent with its being mapped as a thrust fault. The Sulphur and Mill Creek Synclines may have formed as pull-apart basins in a left-lateral, left-stepping strike-slip environment. The character of the gravity field of Chickasaw National Recreation Area is different from the lineated gravity field in the area of Arbuckle-Simpson Aquifer outcrop. This change in character is not due to the presence of the overlying conglomerate layer, which is quite thin (<100 m) in the area of the park with the springs. The presence of relatively high-density Precambrian basement rocks in a broader region suggests that significant gravity anomalies may arise from variations in basement topography. Understanding of the geological configuration of Chickasaw National Recreation Area can be improved by expanding the study area and by investigating complementary geophysical and borehole constraints of the subsurface.

Open-File Report↗

Flow and sorption controls of groundwater arsenic in individual boreholes from bedrock aquifers in central Maine, USA

To understand the hydrogeochemical processes regulating well water arsenic (As) evolution in fractured bedrock aquifers, three domestic wells with [As] up to 478 &mu;g/L are investigated in central Maine. Geophysical logging reveals that fractures near the borehole bottom contribute 70-100% of flow. Borehole and fracture water samples from various depths show significant proportions of As (up to 69%) and Fe (93-99%) in particulates (>0.45 &mu;m). These particulates and those settled after a 16-day batch experiment contain 560-13,000 g/kg of As and 14-35% weight/weight of Fe. As/Fe ratios (2.5-20 mmol/mol) and As partitioning ratios (adsorbed/dissolved [As], 20,000-100,000 L/kg) suggest that As is sorbed onto amorphous hydrous ferric oxides. Newly drilled cores also show enrichment of As (up to 1300 mg/kg) sorbed onto secondary iron minerals on the fracture surfaces. Pumping at high flow rates induces large decreases in particulate As and Fe, a moderate increase in dissolved [As] and As(III)/As ratio, while little change in major ion chemistry. The &delta;D and &delta; 18 O are similar for the borehole and fracture waters, suggesting a same source of recharge from atmospheric precipitation. Results support a conceptual model invoking flow and sorption controls on groundwater [As] in fractured bedrock aquifers whereby oxygen infiltration promotes the oxidation of As-bearing sulfides at shallower depths in the oxic portion of the flow path releasing As and Fe; followed by Fe oxidation to form Fe oxyhydroxide particulates, which are transported in fractures and sorb As along the flow path until intercepted by boreholes. In the anoxic portions of the flow path, reductive dissolution of As-sorbed iron particulates could re-mobilize As. For exposure assessment, we recommend sampling of groundwater without filtration to obtain total As concentration in groundwater.

Maine↗

Data resources for the Wyoming Landscape Conservation Initiative (WLCI) Integrated Assessment (IA)

The data contained in this report were compiled, modified, and analyzed for the Wyoming Landscape Conservation Initiative (WLCI) Integrated Assessment (IA). The WLCI is a long-term science based effort to assess and enhance aquatic and terrestrial habitats at a landscape scale in southwest Wyoming while facilitating responsible energy development through local collaboration and partnerships. The IA is an integrated synthesis and analysis of WLCI resource values based on best available data and information collected from multiple agencies and organizations. It is a support tool for landscape-scale conservation planning and evaluation, and a data and analysis resource that can be used for addressing specific management questions. The IA analysis was conducted using a Geographic Information System in a raster (that is, a grid) environment using a cell size of 30 meters. To facilitate the interpretation of the data in a regional context, mean values were summarized and displayed at the subwatershed unit (WLCI subwatersheds were subset from the National Hydrography Dataset, Hydrologic Unit Code 12/Level 6). A dynamic mapping platform, accessed via the WLCI webpage at http://www.wlci.gov is used to display the mapped information, and to access underlying resource values that were combined to produce the final mapped results. The raster data used in the IA are provided here for use by interested parties to conduct additional analyses and can be accessed via the WLCI webpage. This series contains 74 spatial data sets: WLCI subwatersheds (vector) and 73 geotiffs (raster) that are segregated into the major categories of Multicriteria Index (including Resource Index and Condition), Change Agents, and Future Change. The Total Multicriteria Index is composed of the Aquatic Multicriteria Index and the Terrestrial Multicriteria Index. The Aquatic Multicriteria Index is composed of the Aquatic Resource Index and the Aquatic Condition. The Aquatic Resource Index is composed of the following components: Groundwater, Special Management Areas, and Priority Areas. The Aquatic Condition is composed of the following components: Focal Species, Species of Concern, Focal Ecosystems, and Proper Functioning Condition. The Terrestrial Multicriteria Index is composed of the Terrestrial Resource Index and the Terrestrial Condition. The Terrestrial Resource Index is composed of the following components: Special Management Areas, Agriculture, and Priority Areas. The Terrestrial Condition is composed of the following components: Focal Species, Big Game, Species of Concern, Rare Plants, and Focal Ecosystems. The Change Agents are composed the following components: Roads, Energy, Mines, and Urban. The Future Change is composed of the following components: Oil-Gas-Coal, Wind, Minerals, Climate-Temperature, Invasive Species, and Urban.

Wyoming↗

Water-quality characteristics for selected streams in Lawrence County, South Dakota, 1988-92

During the 1980’s, significant economic development and population growth began to occur in Lawrence County in the northern part of the Black Hills of western South Dakota. Rising gold prices and heap-leach extraction methods allowed the economic recovery of marginal gold ore deposits, resulting in development of several large-scale, open-pit gold mines in Lawrence County. There was increasing local concern regarding potential impacts on the hydrologic system, especially relating to the quantity and quality of water in the numerous streams and springs of Lawrence County. In order to characterize the water quality of selected streams within Lawrence County, samples were collected from 1988 through 1992 at different times of the year and under variable hydrologic conditions. During the time of this study, the Black Hills area was experiencing a drought; thus, most samples were collected during low-flow conditions. Streamflow and water-quality characteristics in Lawrence County are affected by both geologic conditions and precipitation patterns. Most streams that cross outcrops of the Madison Limestone and Minnelusa Formation lose all or large part of their streamflow to aquifer recharge. Streams that are predominantly spring fed have relatively stable streamflow, varying slightly with dry and wet precipitation cycles. Most streams in Lawrence County generally have calcium magnesium bicarbonate type waters. The sites from the mineralized area of central Lawrence County vary slightly from other streams in Lawrence County by having higher concentrations of sodium, less bicarbonate, and more sulfate. False Bottom Creek near Central City has more sulfate than bicarbonate. Nitrogen, phosphorous, and cyanide concentrations were at or near the laboratory reporting limits for most sites and did not exceed any of the water-quality standards. Nitrite plus nitrate concentrations at Annie Creek near Lead, Whitetail Creek at Lead, Squaw Creek near Spearfish, and Spearfish Creek below Robison Gulch were somewhat higher than at other sites. Mining activity, agricultural activity, and domestic development are possible sources of nitrogen to the streams. Increased mining activities were identified as the probable cause of increased nitrogen concentrations in Annie Creek. In the mineralized area of the northern Black Hills, detectable concentrations of trace elements are common in stream water, occasionally exceeding beneficial-use and aquatic-life criteria. In addition, many basins have been disturbed by both historical and recent mining operations and cleanup activities. The maximum dissolved arsenic concentration at Annie Creek near Lead (48 micrograms per liter) approached the current arsenic drinking-water standard. Concentrations at or greater than 5 micrograms per liter were found in samples from Annie Creek near Lead, Spearfish Creek above Spearfish, Whitetail Creek at Lead, and False Bottom Creek near Spearfish. Bear Butte Creek near Deadwood had one sample with a dissolved copper concentration that exceeded acute and chronic aquatic-life criteria. Bear Butte Creek near Deadwood had several manganese concentrations that exceeded the secondary maximum contaminant level of 50 micrograms per liter. Bed-sediment and water-quality data from selected sites in small drainage basins were used to determine if factors such as pH, arsenic concentrations in bed sediments, and calcite saturation control dissolved arsenic concentrations. Arsenic solubility is controlled by adsorption, mainly on ferrihydrite. In addition, adsorption/desorption of arsenic is controlled by the pH of the stream, with high arsenic concentrations appearing only at higher pH conditions (above 8). There are significant arsenic sources available to almost all the small streams of the northern Black Hills mining area, but arsenic is less mobile in streams that are not influenced to the higher pH values by calcite. Streams where arsenic is more mobile have lower iron concentrations in their bed sediments, and they have relatively high concentrations of calcite Additional water-quality data have been collected as part of other studies or monitoring programs by the South Dakota Department of Environment and Natural Resources, U.S. Environmental Protection Agency, U.S. Forest Service, and the U.S. Geological Survey. Summaries of selected data from these other sources are included as additional information.

South Dakota↗

Iron dissolution and speciation in atmospheric mineral dust: Metal-metal synergistic and antagonistic effects

Under acidic atmospheric conditions, iron leached from atmospheric mineral dust may influence the distribution of bioavailable iron at a global scale. However, the effects of non-Fe-containing minerals on iron dissolution remain unknown. This work describes metal-metal synergistic and antagonistic effects on iron dissolution that go beyond aggregation and ionic strength effects in mineral dust mixtures. In this study, we investigated iron mobilization by proton-promoted dissolution in natural mineral dust samples from the Kalahari Desert (SZ1) and Australian Red Dawn event (RO), along with one iron oxide proxy, hematite. The total iron dissolution in natural dust samples highly corresponds with the respective amount of Ti, rather than their particle sizes or Fe contents. The dust sample with high Ti content, SZ1, also showed a higher fraction of dissolved Fe(II), under dark conditions. These observations are in good agreement with the dissolution data for hematite artificially mixed with metal oxides. Total iron dissolution in hematite, mixed with TiO 2 , is 1.5- and 2-fold higher compared to that of just hematite under dark and light conditions, respectively. However, dissolution of hematite is suppressed when mixed with Al 2 O 3 and CaO. Under dark conditions, furthermore, dissolved Fe(II) fraction is enhanced for hematite when mixed with TiO 2 compared to that of other mixtures or hematite alone. Yet, dissolved Fe(II) is lower in hematite mixed with TiO 2 under light conditions compared to that of hematite alone, suggesting photo-oxidation of Fe(II) by reactive oxygen species, such as OH radicals.

Atmospheric Environment↗

Wildland fire ash: Production, composition and eco-hydro-geomorphic effects

Fire transforms fuels (i.e. biomass, necromass, soil organic matter) into materials with different chemical and physical properties. One of these materials is ash, which is the particulate residue remaining or deposited on the ground that consists of mineral materials and charred organic components. The quantity and characteristics of ash produced during a wildland fire depend mainly on (1) the total burned fuel (i.e. fuel load), (2) fuel type and (3) its combustion completeness. For a given fuel load and type, a higher combustion completeness will reduce the ash organic carbon content, increasing the relative mineral content, and hence reducing total mass of ash produced. The homogeneity and thickness of the ash layer can vary substantially in space and time and reported average thicknesses range from close to 0 to 50 mm. Ash is a highly mobile material that, after its deposition, may be incorporated into the soil profile, redistributed or removed from a burned site within days or weeks by wind and water erosion to surface depressions, footslopes, streams, lakes, reservoirs and, potentially, into marine deposits. Research on the composition, properties and effects of ash on the burned ecosystem has been conducted on material collected in the field after wildland and prescribed fires as well as on material produced in the laboratory. At low combustion completeness (typically T < 450 °C), ash is organic-rich, with organic carbon as the main component. At high combustion completeness (T > 450 °C), most organic carbon is volatized and the remaining mineral ash has elevated pH when in solution. It is composed mainly of calcium, magnesium, sodium, potassium, silicon and phosphorous in the form of inorganic carbonates, whereas at T > 580 °C the most common forms are oxides. Ash produced under lower combustion completeness is usually darker, coarser, and less dense and has a higher saturated hydraulic conductivity than ash with higher combustion completeness, although physical reactions with CO 2 and when moistened produce further changes in ash characteristics. As a new material present after a wildland fire, ash can have profound effects on ecosystems. It affects biogeochemical cycles, including the C cycle, not only within the burned area, but also globally. Ash incorporated into the soil increases temporarily soil pH and nutrient pools and changes physical properties such as albedo, soil texture and hydraulic properties including water repellency. Ash modifies soil hydrologic behavior by creating a two-layer system: the soil and the ash layer, which can function in different ways depending on (1) ash depth and type, (2) soil type and (3) rainfall characteristics. Key parameters are the ash's water holding capacity, hydraulic conductivity and its potential to clog soil pores. Runoff from burned areas carries soluble nutrients contained in ash, which can lead to problems for potable water supplies. Ash deposition also stimulates soil microbial activity and vegetation growth. Further work is needed to (1) standardize methods for investigating ash and its effects on the ecosystem, (2) characterize ash properties for specific ecosystems and wildland fire types, (3) determine the effects of ash on human and ecosystem health, especially when transported by wind or water, (4) investigate ash's controls on water and soil losses at slope and catchment scales, (5) examine its role in the C cycle, and (6) study its redistribution and fate in the environment.

Earth-Science Reviews↗

The Shallow Magmatic Plumbing System of the Deccan Traps, Evidence from Plagioclase Megacrysts and Their Host Lavas

We investigate the shallow plumbing system of the Deccan Traps Large Igneous Province using rock and mineral data from Giant Plagioclase Basalt (GPB) lava flows from around the entire province, but with a focus on the Saurashtra Peninsula, the Malwa Plateau, and the base and top of the Western Ghats (WG) lava pile. GPB lavas in the WG typically occur at the transition between chemically distinct basalt formations. Most GPB samples are evolved basalts, with high Fe and Ti contents, and show major and trace elements and Sr-Nd-Pb isotopic compositions generally similar to those of previously studied Deccan basalts. Major element modeling suggests that high-Fe, evolved melts typical of GPB basalts may derive from less evolved Deccan basalts by low-pressure fractional crystallization in a generally dry magmatic plumbing system. The basalts are strongly porphyritic, with 6–25% of mm- to cm-sized plagioclase megacrysts, frequently occurring as crystal clots, plus relatively rare olivine and clinopyroxene. The plagioclase crystals are mostly labradoritic, but some show bytownitic cores (general range of anorthite mol%: 78–55). A common feature is a strong Fe enrichment at the plagioclase rims, indicating interaction with an Fe-rich melt similar to that represented by the matrix compositions (FeOt up to 16–17 wt%). Plagioclase minor and trace elements and Sr isotopic compositions analyzed by laser ablation inductively coupled plasma mass spectrometry show evidence of a hybrid and magma mixing origin. In particular, several plagioclase crystals show variable 87 Sr/ 86 Sr i , which only partially overlaps with the 87 Sr/ 86 Sr i of the surrounding matrix. Diffusion modeling suggests residence times of decades to centuries for most plagioclase megacrysts. Notably, some plagioclase crystal clots show textural evidence of deformation as recorded by electron back-scatter diffraction analyses and chemical maps, which suggest that the plagioclase megacrysts were deformed in a crystal-rich environment in the presence of melt. We interpret the plagioclase megacrysts as remnants of a crystal mush originally formed in the shallow plumbing system of the Deccan basalts. In this environment, plagioclase acquired a zoned composition due to the arrival of chemically distinct basaltic magmas. Prior to eruption, a rapidly rising but dense Fe-rich magma was capable of disrupting the shallow level crystal mush, remobilizing part of it and carrying a cargo of buoyant plagioclase megacrysts. Our findings suggest that basaltic magmas from the Deccan Traps, and possibly from LIPs in general, are produced within complex transcrustal magmatic plumbing systems with widespread crystal mushes developed in the shallow crust.

Journal of Petrology↗

Stratiform chromite deposit model

A new descriptive stratiform chromite deposit model was prepared which will provide a framework for understanding the characteristics of stratiform chromite deposits worldwide. Previous stratiform chromite deposit models developed by the U.S. Geological Survey (USGS) have been referred to as Bushveld chromium, because the Bushveld Complex in South Africa is the only stratified, mafic-ultramafic intrusion presently mined for chromite and is the most intensely researched. As part of the on-going effort by the USGS Mineral Resources Program to update existing deposit models for the upcoming national mineral resource assessment, this revised stratiform chromite deposit model includes new data on the geological, mineralogical, geophysical, and geochemical attributes of stratiform chromite deposits worldwide. This model will be a valuable tool in future chromite resource and environmental assessments and supplement previously published models used for mineral resource evaluation. Stratiform chromite deposits are found throughout the world, but the chromitite seams of the Bushveld Complex, South Africa, are the largest and most intensely researched. The chromite ore is located primarily in massive chromitite seams and, less abundantly, in disseminated chromite-bearing layers, both of which occur in the ultramafic section of large, layered mafic-ultramafic stratiform complexes. These mafic-ultramafic intrusions mainly formed in stable cratonic settings or during rift-related events during the Archean or early Proterozoic, although exceptions exist. The chromitite seams are cyclic in nature as well as laterally contiguous throughout the entire intrusion. Gangue minerals include olivine, pyroxenes (orthopyroxene and clinopyroxene), plagioclase, sulfides (pyrite, chalcopyrite, pyrrhotite, pentlandite, bornite), platinum group metals (mainly laurite, cooperite, braggite), and alteration minerals. A few deposits also contain rutile and ilmenite. The alteration phases include serpentine, chlorite, talc, magnetite, kaemmererite, uvarovite, hornblende, and carbonate minerals, such as calcite and dolomite. Stratiform chromite deposits are primarily hosted by peridotites, harzburgites, dunites, pyroxenites, troctolites, and anorthosites. Although metamorphism may have altered the ultramafic regions of layered intrusions postdeposition, only igneous processes are responsible for formation. From a diagnostic standpoint and for assessment purposes, they have no temporal or spatial relation to sedimentary rocks. The exact mechanisms responsible for the development of stratiform chromite deposits and the large, layered mafic-ultramafic intrusions where they are found are highly debated. The leading argument postulates that a parent magma mixed with a more primitive magma during magma chamber recharge. The partially differentiated magma could then be forced into the chromite stability field, resulting in the massive chromitite layers found in stratiform complexes. Contamination of the parent magma by localized assimilation of felsic country rock at the roof of the magma chamber has also been proposed as a mechanism of formation. Others suggest that changes in pressure or oxygen fugacity may be responsible for the occurrence of massive chromitite seams in layered mafic, ultramafic intrusions. The massive chromitite layers contain high levels of chromium and strong associations with platinum group elements. Anomalously high magnesium concentrations as well as low sodium, potassium, and phosphorus concentrations are also important geochemical features of stratiform chromite deposits. The presence of orthopyroxenite in many of the deposits suggests high silica and high magnesium concentrations in the parent magma. Most environmental concerns associated with the mining and processing of chromite ore focus on the solubility of chromium and its oxidation state. Although trivalent chromium (Cr 3+ ) is an essential micronutrient for humans, hexavalent chromium (Cr 6+ ) is highly toxic. Chromium-bearing solid phases that occur in the chromite ore-processing residue, for example, can effect the geochemical behavior and oxidation state of chromium in the environment.

Scientific Investigations Report↗

Effects of aquifer storage and recovery activities on water quality in the Little Arkansas River and Equus Beds Aquifer, south-central Kansas, 2011–14

The Equus Beds aquifer in south-central Kansas is aprimary water source for the city of Wichita. The Equus Beds aquifer storage and recovery (ASR) project was developed to help the city of Wichita meet increasing current (2016) and future water demands. The Equus Beds ASR project pumps water out of the Little Arkansas River during above-base flow conditions, treats it using drinking-water quality standards as a guideline, and recharges it into the Equus Beds aquifer for later use. Phase II of the Equus Beds ASR project currently (2016) includes a river intake facility and a surface-water treatment facility with a 30 million gallon per day capacity. Water diverted from the Little Arkansas River is delivered to an adjacent presedimentation basin for solids removal. Subsequently, waste from the surface-water treatment facility and the presedimentation basin is returned to the Little Arkansas River through a residuals return line. The U.S. Geological Survey, in cooperation with the city of Wichita, developed and implemented a hydrobiological monitoring program as part of the ASR project to characterize and quantify the effects of aquifer storage and recovery activities on the Little Arkansas River and Equus Beds aquifer water quality. Data were collected from 2 surface-water sites (one upstream and one downstream from the residuals return line), 1 residuals return line site, and 2 groundwater well sites (each having a shallow and deep part): the Little Arkansas River upstream from the ASR facility near Sedgwick, Kansas (upstream surface-water site 375350097262800), about 0.03 mile (mi) upstream from the residuals return line site; the Little Arkansas River near Sedgwick, Kans. (downstream surface-water site 07144100), about 1.68 mi downstream from the residuals return line site; discharge from the Little Arkansas River ASR facility near Sedgwick, Kansas (residuals return line site 375348097262800); 25S 01 W 07BCCC01 SMW–S11 near CW36 (MW–7 shallow groundwater well site 375327097285401); 25S01 W 07BCCC02 DMW–S10 near CW36 (MW–7 deep groundwater well site 375327097285402); 25S 01W 07BCCA01 SMW–S13 near CW36 (MW–8 shallow groundwater well site 375332097284801); and 25S 01W 07BCCA02 DMW–S14 near CW36 (MW–8 deep groundwater well site 375332097284802). The U.S. Geological Survey, in cooperation with the city of Wichita, assessed the effects of the ASR Phase II facility residuals return line discharges on stream quality of the Little Arkansas River by measuring continuous physicochemical properties and collecting discrete water-quality and sediment samples for about 2 years pre- (January 2011 through April 2013) and post-ASR (May 2013 through December 2014) Phase II facility operation upstream and downstream from the ASR Phase II facility. Additionally, habitat variables were quantified and macroinvertebrate and fish communities were sampled upstream and downstream from the ASR Phase II facility during the study period. To assess the effects of aquifer recharge on Equus Beds groundwater quality, continuous physicochemical properties were measured and discrete water-quality samples were collected before and during the onset of Phase II aquifer recharge in two (shallow and deep) groundwater wells. Little Arkansas River streamflow was about 10 times larger after the facility began operating because of greater rainfall. Residuals return line release volumes were a very minimal proportion (0.06 percent) of downstream streamflow volume during the months the ASR facility was operating. Upstream and downstream continuously measured water temperature and dissolved oxygen median differences were smaller post-ASR than pre-ASR. Turbidity generally was smaller at the downstream site throughout the study period and decreased at both sites after the ASR Phase II facility began discharging despite a median residuals return line turbidity that was about an order of magnitude larger than the median turbidity at the downstream site. Upstream and downstream continuously measured turbidity median differences were larger post-ASR than pre-ASR. Median post-ASR continuously measured nitrite plus nitrate and continuously computed total suspended solids and suspended-sediment concentrations were smaller than pre-ASR likely because of higher streamflows and dilution; whereas, median continuously computed dissolved and total organic carbon concentrations were larger likely because of higher streamflows and runoff conditions. None of the discretely measured water-quality constituents (dissolved and suspended solids, primary ions, suspended sediment, nutrients, carbon, trace elements, viral and bacterial indicators, and pesticides) in surface water were significantly different between the upstream and downstream sites after the ASR Phase II facility began discharging; however, pre-ASR calcium, sodium, hardness, manganese, and arsenate concentrations were significantly larger at the upstream site, which indicates that some water-quality conditions at the upstream and downstream sites were more similar post-ASR. Most of the primary constituents that make up dissolved solids decreased at both sites after the ASR Phase II facility began operation. Discretely collected total suspended solids concentrations were similar between the upstream and downstream sites before the facility began operating but were about 27 percent smaller at the downstream site after the facility began operating, despite the total suspended solids concentrations in the residuals return line being 15 times larger than the downstream site. Overall habitat scores were indicative of suboptimal conditions upstream and downstream from the ASR Phase II facility throughout the study period. Substrate fouling and sediment deposition mean scores indicated marginal conditions at the upstream and downstream sites during the study period, demonstrating that sediment deposition was evident pre- and post-ASR and no substantial changes in these habitat characteristics were noted after the ASR Phase II facility began discharging. Macroinvertebrate community composition (evaluated using functional feeding, behavioral, and tolerance metrics) generally was similar between sites during the study period. Fewer macroinvertebrate metrics were significant between the upstream and downstream sites post-ASR (6) than pre-ASR (14), which suggests that macroinvertebate communities were more similar after the ASR facility began discharging. Upstream-downstream comparisons in macroinvertebrate aquatic-life-support metrics had no significant differences for the post-ASR time period and neither site was fully supporting for any of the Kansas Department of Health and Environment aquatic-life-support metrics (Macroinvertebrate Biotic Index; Kansas Biotic Index with tolerances for nutrients and oxygen-demanding substances; Ephemeroptera, Plecoptera, and Trichoptera [EPT] richness; and percentage of EPT species). Overall, using macroinvertebrate aquatic life-support criteria from the Kansas Department of Health and Environment, upstream and downstream sites were classified as partially supporting before and after the onset of ASR facility operations. Fish community trophic status and tolerance groups generally were similar among sites during the study period. Fish community Little Arkansas River Basin Index of Biotic Integrity scores at the upstream and downstream sites were indicative of fair-to-good conditions before the facility began operating and decreased to fair conditions after the facility began operating. Groundwater physicochemical changes concurrent with the beginning of recharge operations at the Sedgwick basin were more pronounced in shallow groundwater. No constituent concentrations in the pre-recharge period in comparison to the post-recharge period increased to concentrations exceeding drinking water regulations; however, nitrate decreased significantly from a pre-recharge exceedance of the U.S. Environmental Protection Agency maximum contaminant level to a post recharge nonexceedance. Shallow groundwater chemical concentrations or rates of detection increased after artificial recharge began for the ions potassium, chloride, and fluoride; phosphorus and organic carbon species; trace elements barium, manganese, nickel, arsenate, arsenic, and boron; agricultural pesticides atrazine, metolachlor, metribuzin, and simazine; organic disinfection byproducts bromodichloromethane and trichloromethane; and gross beta levels. Additionally, water temperature, and pH were larger after recharge began; and total solids and slime-forming bacteria concentrations and densities were smaller. Total solids, nitrate, and selenium significantly decreased; and potassium, chloride, nickel, arsenic, fluoride, phosphorus and carbon species, and gross beta levels significantly increased in shallow groundwater after artificial recharge. Results of biological activity reaction tests indicated that water quality microbiology was different before and after artificial recharge began; at times, these differences may lead to changes in dominant bacterial populations that, in turn, may lead to formation and expansion in populations that may cause bioplugging and other unwanted effects. Calcite, iron (II) hydroxide, hydroxyapatite, and similar minerals, had shifts in saturation indices that generally were from undersaturation toward equilibrium and, in some cases, toward oversaturation. These shifts toward neutral saturation indices might suggest reduced weathering of the minerals present in the Equus Beds aquifer. Chemical weathering in the shallow parts of the aquifer may be accelerated because of the increased water temperatures and the system is more vulnerable to clogged pores and mineral dissolution as the equilibrium state is affected by recharge and withdrawal. When oversaturation is indicated for iron minerals, plugging of aquifer materials may happen.

Kansas↗

Factors Affecting Spatial and Temporal Variability in Nutrient and Pesticide Concentrations in the Surficial Aquifer on the Delmarva Peninsula

Water quality in the unconfined, unconsolidated surficial aquifer on the Delmarva Peninsula is influenced by the availability of soluble ions from natural and human sources, and by geochemical factors that affect the mobility and fate of these ions within the aquifer. Ground-water samples were collected from 60 wells completed in the surficial aquifer of the peninsula in 2001 and analyzed for major ions, nutrients, and selected pesticides and degradation products. Analytical results were compared to similar data from a subset of sampled wells in 1988, as well as to land use, soils, geology, depth, and other potential explanatory variables to demonstrate the effects of natural and human factors on water quality in the unconfined surficial aquifer. This study was conducted as part of the National Water-Quality Assessment Program of the U.S. Geological Survey, which is designed (in part) to describe the status and trends in ground-water quality and to provide an understanding of natural and human factors that affect ground-water chemistry in different parts of the United States. Results of this study may be useful for water-resources managers tasked with addressing water-quality issues of local and regional importance because the surficial aquifer on the Delmarva Peninsula is a major source of water for domestic and public supply and provides the majority of flow in local streams. Human impacts are apparent in ground-water quality throughout the surficial aquifer. The surficial aquifer on the Delmarva Peninsula is generally sandy and very permeable with well-oxygenated ground water. Dissolved constituents found throughout various depths of the unconfined aquifer are likely derived from the predominantly agricultural practices on the peninsula, although effects of road salt, mineral dissolution, and other natural and human influences are also apparent in some areas. Nitrate occurred at concentrations exceeding natural levels in many areas, and commonly exceeded 10 milligrams per liter (as nitrogen). In addition to land use in the aquifer recharge area, concentrations of nitrate in ground water are related to regional patterns in soil drainage that affect underlying aquifer redox conditions. Over the peninsula, nitrate concentrations are not related to recharge date of the water, but are positively correlated with depth in shallow wells screened beneath agricultural areas. Nitrate concentrations increased in oxic areas (dissolved oxygen greater than 1 milligram per liter) of the deeper part of the surficial aquifer used for domestic supply by an average of about 2 milligrams per liter between 1988 and 2001, although no changes were apparent in shallower parts of the aquifer over that same period. Water in the surficial aquifer generally flows from land-surface recharge to surface-water discharge areas in less than 30 years. As a result, the entire flow system in the surficial aquifer has likely been affected by human activities on and near the land surface over the past several decades. Pesticide compounds occurred widely at low levels throughout the surficial aquifer. The most commonly used herbicides (metolachlor, alachlor, and atrazine) were the most commonly detected. These pesticides primarily occurred in ground water in the form of degradation products. The widespread occurrence of these and other pesticide compounds reflects their abundant use as well as chemical properties and aquifer characteristics that allow their movement into ground water. Mixtures of pesticides are common. Most samples contained at least 3 different compounds; several samples contained as many as 11. Pesticide concentrations in the surficial aquifer are relatively high beneath recharge areas with well-drained soils in the shallow part of the aquifer and in oxic environments throughout the surficial aquifer. Concentrations are generally below existing drinking-water standards, although standards are not available for all of the pesticide compound

Scientific Investigations Report↗