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Changes in streamflow and the flux of nutrients in the Mississippi-Atchafalaya River Basin, USA, 1980-2007

Nutrients and freshwater delivered by the Mississippi and Atchafalaya Rivers drive algal production in the northern Gulf of Mexico, which eventually results in the widespread occurrence of hypoxic bottom waters along the Louisiana and Texas coast. Researchers have demonstrated a relation between the extent of the hypoxic zone and the magnitude of streamflow, nutrient fluxes, and nutrient concentrations in the Mississippi River, with springtime streamflows and fluxes being the most predictive. In 1999 the U.S. Geological Survey (USGS) estimated the flux of nitrogen, phosphorus, and silica at selected sites in the Mississippi Basin and to the Gulf of Mexico for 1980-1996. These flux estimates provided the baseline information used by the Mississippi River/Gulf of Mexico Watershed Nutrient Task Force to develop an Action Plan for reducing hypoxia in the northern Gulf of Mexico. The primary goal of the Action Plan was to achieve a reduction in the size (areal extent) of the hypoxic zone from an average of approximately 14,000 square kilometers in 1996-2000 to a 5-year moving average of less than 5,000 square kilometers by 2015. Improved statistical models and adjusted maximum likelihood estimation using USGS Load Estimator (LOADEST) software were used to estimate annual and seasonal nutrient fluxes for 1980-2007 at selected sites on the Mississippi River and its tributaries. These data provide a means to evaluate the influence of natural and anthropogenic effects on delivery of water and nutrients to the Gulf of Mexico; to define subbasins that are the most important contributors of nutrients to the gulf; and to investigate the relations among streamflow, nutrient fluxes, and the size and duration of the Gulf of Mexico hypoxic zone. A comparative analysis between the baseline period of 1980-1996 and 5-year moving averages thereafter indicate that the average annual streamflow and fluxes of total nitrogen, nitrate, orthophosphate, and silica to the Gulf of Mexico have decreased. However, the flux of total phosphorus between the baseline period and subsequent 5-year periods has increased. The average spring (April, May, and June) streamflow and fluxes of silica, total nitrogen, nitrate, and orthophosphate to the Gulf of Mexico also decreased, whereas the spring flux of total phosphorus has increased. Similar changes in streamflow and nutrient flux were observed at many sites Buxtonwithin the basin. The inputs of water, total nitrogen, and total phosphorus from the major subbasins of the Mississippi-Atchafalaya River Basin as a percentage of the to-the-gulf totals have increased from the Ohio River Basin, decreased from the Missouri River Basin, and remained relatively unchanged from the Upper Mississippi, Red, and Arkansas River Basins. Changes in streamflow and nutrient fluxes are related, but short-term variations in sources of streamflow and nutrients complicate the interpretation of factors that affect nutrient delivery to the Gulf of Mexico. Parametric time-series models are used to try and separate natural variability in nutrient flux from changes due to other causes. Results indicate that the decrease in annual nutrient fluxes that has occurred between the 1980-1996 baseline period and more recent years can be largely attributed to natural causes (climate and streamflow) and not management actions or other human controlled activities in the Mississippi-Atchafalaya River Basin. The downward trends in total nitrogen, nitrate, ammonium, and orthophosphate that were detected at either the Mississippi River near St. Francisville, La., or the Atchafalaya River at Melville, La., occurred prior to 1995. In spite of the general decrease in nutrient flux, the average size of the Gulf of Mexico hypoxic zone has increased between 1997 and 2007. The reasons for this are not clear but could be due to the type or nature of nutrient delivery. Whereas the annual flux of total nitrogen to the Gulf of Mexico has decreased, the proporti

Scientific Investigations Report↗

Ground-survey and water-quality data for selected wetlands on or near the Lower Brule Indian Reservation in South Dakota, 2012-13

Numerous lakes, ponds, and wetlands are located within the Lower Brule Indian Reservation. Wetlands are an important resource providing aquatic habitat for plants and animals, and acting as a natural water filtration system. Several of the wetlands on or near the reservation are of particular interest, but information on the physical and biological integrity of these wetlands was needed to provide a base-line reference when planning for future water management needs. A reconnaissance-level study of selected wetlands on and near the Lower Brule Indian Reservation was completed in 2012–13 by the U.S. Geological Survey in cooperation with the Lower Brule Sioux Tribe using ground surveys and water-quality analyses. Ground surveys of six wetland areas (Dorman Slough, Little Bend Wetlands, Miller Pond, Potter Slough, an unnamed slough, and West Brule Community wetlands) were completed to map land, water, vegetation, and man-made features of the selected wetland areas using real-time kinematic global navigation satellite systems equipment. Water samples were collected from four of the selected wetlands. Two separate waterbodies were sampled at one of the wetlands for a total of five sampling locations. Water samples were analyzed for physical properties, selected inorganics, metals, nutrients, and suspended sediment. Concentrations of calcium, sodium, and sulfate were greater at the two wetland sites fed by ground water, compared to the wetland sites fed by surface runoff.

South Dakota↗

Models of metal binding structures in fulvic acid from the Suwannee River, Georgia

Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca2+, Cd2+, Cu2+, Ni2+, and Zn2+ ions at pH 6 before and after extensive fractionation that was designed to reveal the nature of metal binding functional groups. The binding constant for Ca2+ ion had the greatest increase of all the ions in a metal binding fraction that was selected for intensive characterization for the purpose of building quantitative average model structures. The 'metal binding' fraction was characterized by quantitative 13C NMR, 1H NMR, and FT-1R spectrometry and elemental, titrimetric, and molecular weight determinations. The characterization data revealed that carboxyl groups were clustered in short- chain aliphatic dibasic acid structures. The Ca2+ binding data suggested that ether-substituted oxysuccinic acid structures are good models for the metal binding sites at pH 6. Structural models were derived based upon oxidation and photolytic rearrangements of cutin, lignin, and tannin precursors. These structural models rich in substituted dibasic acid structures revealed polydentate binding sites with the potential for both inner-sphere and outer-sphere type binding. The majority of the fulvic acid molecule was involved with metal binding rather than a small substructural unit.Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca2+, Cd2+, Cu2+, Ni2+, and Zn2+ ions at pH 6 before and after extensive fractionation that was designed to reveal the nature of metal binding functional groups. The binding constant for Ca2+ ion had the greatest increase of all the ions in a metal binding fraction that was selected for intensive characterization for the purpose of building quantitative average model structures. The `metal binding' fraction was characterized by quantitative 13C NMR, 1H NMR, and FT-IR spectrometry and elemental, titrimetric, and molecular weight determinations. The characterization data revealed that carboxyl groups were clustered in short-chain aliphatic dibasic acid structures. The Ca2+ binding data suggested that ether-substituted oxysuccinic acid structures are good models for the metal binding sites at pH 6. Structural models were derived based upon oxidation and photolytic rearrangements of cutin, lignin, and tannin precursors. These structural models rich in substituted dibasic acid structures revealed polydentate binding sites with the potential for both inner-sphere and outer-sphere type binding. The majority of the fulvic acid molecule was involved with metal binding rather than a small substructural unit.

Georiga↗

Estimation of unaltered daily mean streamflow at ungaged streams of New York, excluding Long Island, water years 1961-2010

The lakes, rivers, and streams of New York State provide an essential water resource for the State. The information provided by time series hydrologic data is essential to understanding ways to promote healthy instream ecology and to strengthen the scientific basis for sound water management decision making in New York. The U.S. Geological Survey, in cooperation with The Nature Conservancy and the New York State Energy Research and Development Authority, has developed the New York Streamflow Estimation Tool to estimate a daily mean hydrograph for the period from October 1, 1960, to September 30, 2010, at ungaged locations across the State. The New York Streamflow Estimation Tool produces a complete estimated daily mean time series from which daily flow statistics can be estimated. In addition, the New York Streamflow Estimation Tool provides a means for quantitative flow assessments at ungaged locations that can be used to address the objectives of the Clean Water Act—to restore and maintain the chemical, physical, and biological integrity of the Nation’s waters. The New York Streamflow Estimation Tool uses data from the U.S. Geological Survey streamflow network for selected streamgages in New York (excluding Long Island) and surrounding States with shared hydrologic boundaries, and physical and climate basin characteristics to estimate the natural unaltered streamflow at ungaged stream locations. The unaltered streamflow is representative of flows that are minimally altered by regulation, diversion, or mining, and other anthropogenic activities. With the streamflow network data, flow-duration exceedance probability equations were developed to estimate unaltered streamflow exceedance probabilities at an ungaged location using a methodology that equates streamflow as a percentile from a flow-duration curve for a particular day at a hydrologically similar reference streamgage with streamflow as a percentile from the flow-duration curve for the same day at an ungaged location. The reference streamgage is selected using map correlation, a geostatistical method in which variogram models are developed that correlate streamflow at one streamgage with streamflows at all other locations in the study area. Regression equations used to predict 17 flow-duration exceedance probabilities were developed to estimate the flow-duration curves at ungaged locations for New York using geographic information system-derived basin characteristics. A graphical user interface, with an integrated spreadsheet summary report, has been developed to estimate and display the daily mean streamflows and statistics and to evaluate different water management or water withdrawal scenarios with the estimated monthly data. This package of regression equations, U.S. Geological Survey streamgage data, and spreadsheet application produces an interactive tool to estimate an unaltered daily streamflow hydrograph and streamflow statistics at ungaged sites in New York. Among other uses, the New York Streamflow Estimation Tool can assist water managers with permitting water withdrawals, implementing habitat protection, estimating contaminant loads, or determining the potential affect from chemical spills.

New York↗

Capacitively Coupled Resistivity Survey of Selected Irrigation Canals Within the North Platte River Valley, Western Nebraska and Eastern Wyoming, 2004 and 2007-2009

Due to water resources of portions of the North Platte River basin being designated as over-appropriated by the State of Nebraska Department of Natural Resources (DNR), the North Platte Natural Resources District (NPNRD), in cooperation with the DNR, is developing an Integrated Management Plan (IMP) for groundwater and surface water in the NPNRD. As part of the IMP, a three-dimensional numerical finite difference groundwater-flow model is being developed to evaluate the effectiveness of using leakage of water from selected irrigation canal systems to manage groundwater recharge. To determine the relative leakage potential of the upper 8 m of the selected irrigation canals within the North Platte River valley in western Nebraska and eastern Wyoming, the U.S. Geological Survey performed a land-based capacitively coupled (CC) resistivity survey along nearly 630 km of 13 canals and 2 laterals in 2004 and from 2007 to 2009. These 13 canals were selected from the 27 irrigation canals in the North Platte valley due to their location, size, irrigated area, and relation to the active North Platte valley flood plain and related paleochannels and terrace deposits where most of the saturated thickness in the alluvium exists. The resistivity data were then compared to continuous cores at 62 test holes down to a maximum depth of 8 m. Borehole electrical conductivity (EC) measurements at 36 of those test holes were done to correlate resistivity values with grain sizes in order to determine potential vertical leakage along the canals as recharge to the underlying alluvial aquifer. The data acquired in 2004, as well as the 25 test hole cores from 2004, are presented elsewhere. These data were reprocessed using the same updated processing and inversion algorithms used on the 2007 through 2009 datasets, providing a consistent and complete dataset for all collection periods. Thirty-seven test hole cores and borehole electrical conductivity measurements were acquired based on the 2008 data. This report presents comparisons between the CC resistivity data and results from the 37 test holes and includes all binned and inverted CC resistivity datasets from all four years as well as the EC log data for the 37 test holes acquired in 2008 and 2009. The information gained from these data can help State and local water managers and scientists better understand the characteristics of the shallow subsurface underlying the irrigation canals so that the water resources can be managed more effectively.

Scientific Investigations Report↗

Techniques for estimating peak-flow frequency relations for North Dakota streams

This report presents techniques for estimating peak-flow frequency relations for North Dakota streams. In addition, a generalized skew coefficient analysis was completed for North Dakota to test the validity of using the generalized skew coefficient map in Bulletin 17B of the Hydrology Subcommittee of the Interagency Advisory Committee on Water Data, 1982, "Guidelines for Determining Flood Flow Frequency." The analysis indicates that the generalized skew coefficient map in Bulletin 17B provides accurate estimates of generalized skew coefficient values for natural-flow streams in North Dakota. Peak-flow records through 1988 for 192 continuous- and partial-record streamflow gaging stations that had 10 or more years of record were used in a generalized least-squares regression analysis that relates peak flows for selected recurrence intervals to selected basin characteristics. Peak-flow equations were developed for recurrence intervals of 2, 10, 15, 25, 50, 100, and 500 years for three hydrologic regions in North Dakota. The peak-flow equations are applicable to natural-flow streams that have drainage areas of less than or equal to 1,000 square miles. The standard error of estimate for the three hydrologic regions ranges from 60 to 70 percent for the 100-year peak-flow equations. Methods are presented for transferring peak-flow data from gaging stations to ungaged sites on the same stream and for determining peak flows for ungaged sites on ungaged streams. Peak-flow relations, weighted estimates of peak flow, and selected basin characteristics are tabulated for the 192 gaging stations used in the generalized skew coefficient and regression analyses. Peak-flow relations also are provided for 63 additional gaging stations that were not used in the generalized skew coefficient and regression analyses. These 63 gaging stations generally represent streams that are significantly controlled by regulation and those that have drainage areas greater than 1,000 square miles.

North Dakota↗

Map showing selected surface-water data for the Nephi 30 x 60-minute quadrangle, Utah

This is one of a series of maps that describe the geology and related natural resources of the Nephi 30 x 60 minute quadrangle, Utah. Streamflow records used to compile this map were collected by the U.S. Geological Survey in cooperation with the Utah Department of Natural Resources, Division of Water Rights, and the Utah Department of Transportation. The principal runoff-producing areas shown on the map were delineated from a work map (scale 1:250,000) compiled to estimate water yields in Utah (Bagley and others, 1964). Sources of information about recorded floods resulting from cloudbursts included Woolley (1946) and Butler and Marsell (1972); sources of information about the chemical quality of streamflow included Hahl and Cabell (1965) Mundorff (1972 and 1974), and Waddell and others (1982).

Utah↗

An experimental investigation of interaction between andesite and hyperacidic volcanic lake water

Alteration in magmatic-hydrothermal systems leads to distinct changes in rock texture and mineralogy, and a strong redistribution of elements between fluid and rock. Here, we experimentally interacted andesite scoria with hyperacidic, high-sulfidation style fluids from Kawah Ijen volcano (Indonesia) at 25 and 100˚C, seeking to reproduce the textures observed in natural samples from this volcano, and to understand the element fluxes that accompany alteration. The susceptibility to alteration in the experiments is Cu-Fe-sulphide > calcic plagioclase > pyroxene > titano-magnetite > sodic plagioclase, with complete preservation of glass. Silicate minerals alter to opaline silica, and gypsum, barite and a Zr-phase precipitate. The selective alteration of the phenocryst minerals results in a preferential release of compatible elements, as the glass is the main incompatible element host. The experiments reproduce the alteration textures of the natural samples, including the preservation of glass, but the predicted compatible over incompatible element enrichment in the alteration element flux is not observed in the natural setting. This suggests that alteration at Kawah Ijen is dominated by lithologies that lack abundant glass, in particular lava flows where the glass has devitrified, despite these lava flows having a lower surface area compared to scoria.

Kawah Ijen↗

Quantifying canal leakage rates using a mass-balance approach and heat-based hydraulic conductivity estimates in selected irrigation canals, western Nebraska, 2007 through 2009

The water supply in areas of the North Platte River Basin in the Nebraska Panhandle has been designated as fully appropriated or overappropriated by the Nebraska Department of Natural Resources (NDNR). Enacted legislation (Legislative Bill 962) requires the North Platte Natural Resources District (NPNRD) and the NDNR to develop an Integrated Management Plan (IMP) to balance groundwater and surface-water supply and demand in the NPNRD. A clear understanding of the groundwater and surface-water systems is critical for the development of a successful IMP. The primary source of groundwater recharge in parts of the NPNRD is from irrigation canal leakage. Because canal leakage constitutes a large part of the hydrologic budget, spatially distributing canal leakage to the groundwater system is important to any management strategy. Surface geophysical data collected along selected reaches of irrigation canals has allowed for the spatial distribution of leakage on a relative basis; however, the actual magnitude of leakage remains poorly defined. To address this need, the U.S. Geological Survey, in cooperation with the NPNRD, established streamflow-gaging stations at upstream and downstream ends from two selected canal reaches to allow a mass-balance approach to be used to calculate daily leakage rates. Water-level and sediment temperature data were collected and simulated at three temperature monitoring sites to allow the use of heat as a tracer to estimate the hydraulic conductivity of canal bed sediment. Canal-leakage rates were estimated by applying Darcy's Law to modeled vertical hydraulic conductivity and either the estimated or measured hydraulic gradient. This approach will improve the understanding of the spatial and temporal variability of canal leakage in varying geologic settings identified in capacitively coupled resistivity surveys. The high-leakage potential study reach of the Tri-State Canal had two streamflow-gaging stations and two temperature monitoring sites along its length. Calculated leakage rates from the mass-balance approach varied from year to year and were generally dependent on local climatic conditions, and the timing and magnitude of the initial seasonal diversion into the Tri-State Canal. Leakage rates ranged from 0.98 meter per day (m/d) on June 22, 2007, to about to 0 m/d during July 2009. Drier conditions generally resulted in higher leakage rates because of reduced flow from Spottedtail Creek, lower groundwater levels near Spottedtail Creek, and no unmeasured flow entering the reach. Of the three years studied (2007-09), 2007 was the driest, and therefore had the highest canal leakage rates. The moderately low leakage potential study reach of Interstate Canal had two streamflow-gaging stations and one temperature monitoring site along its length. Excluding the leakage calculations from early May 2007, leakage rates ranged from 0.08 to 0.7 m/d. Less variability in leakage from year to year indicates that climatic conditions may have less of an effect for Interstate Canal compared to Tri-State Canal. This may be because Interstate Canal was cut into the northern edge of the North Platte alluvial valley and consequently the canal bed is well above the local groundwater table resulting in a constant (1 meter per meter [m/m]) hydraulic gradient. Interstate Canal also does not receive any captured flow that can vary substantially year to year. Two temperature monitoring sites were installed within the high-leakage potential reach of Tri-State Canal. Site TCTEMP1 was established in 2007 where the water table was well below the canal bed surface. The vertical hydraulic conductivity of the poorly sorted sand and gravel beneath site TCTEMP1 was estimated using a calibrated one-dimensional VS2DH model. Using a trial-and-error approach, the best-fit vertical hydraulic conductivity for the site TCTEMP1 model domain was 1.1 m/d. Site TCTEMP2 was established at the mouth of Spottedtail Creek where a shallow

Scientific Investigations Report↗

The Chief Joseph Hatchery Program 2013 Annual Report

The Chief Joseph Hatchery is the fourth hatchery obligated under the Grand Coulee Dam/Dry Falls project, originating in the 1940s. Leavenworth, Entiat, and Winthrop National Fish Hatcheries were built and operated as mitigation for salmon blockage at Grand Coulee Dam, but the fourth hatchery was not built, and the obligation was nearly forgotten. After the Colville Tribes successfully collaborated with the United States to resurrect the project, planning of the hatchery began in 2001 and construction was completed in 2013. The monitoring program began in 2012 and adult Chinook Salmon were brought on station for the first time in June 2013. BPA is the primary funding source for CJH, and the Mid-Columbia PUDs (Douglas, Grant and Chelan County) have entered into cost-share agreements with the tribes and BPA in order to meet some of their mitigation obligations. The CJH production level was set at 60% in 2013 in order to train staff and test hatchery facility systems during the first year of operation. Leavenworth National Fish Hatchery (LNFH) provided 422 Spring Chinook broodstock in June, 2013; representing the official beginning of CJH operations. In July and August the CCT used a purse seine vessel to collect 814 summer/fall Chinook as broodstock that were a continuation and expansion of the previous Similkameen Pond program. In-hatchery survival for most life stages exceeded survival targets and, as of April 2014, the program was on track to exceed the 60% production target for its start-up year. The CJH monitoring project collected field data to determine Chinook population status, trend, and hatchery effectiveness centered on five major activities; 1) rotary screw traps (juvenile outmigration, natural-origin smolt PIT tagging) 2) beach seine (naturalorigin smolt PIT tagging) 3) lower Okanogan adult fish pilot weir (adult escapement, proportion of hatchery-origin spawners [pHOS], broodstock) 4) spawning ground surveys (redd and carcass surveys)(viable salmonid population [VSP] parameters) 5) eDNA collection (VSP parameter—distribution/spatial structure). Adult summer/fall Chinook spawning escapement in 2013 was estimated to be 8,193, with more than 6,227 natural-origin spawners, which exceeded the recent five year and long term averages. The values for pHOS (0.24) and proportion of natural influence (PNI) (0.79) in 2013 exceeded the objectives (0.67), but the five year averages fell short of the goals (0.39 and 0.62, respectively). An Annual Program Review (APR) was held in March, 2014 to share hatchery production and monitoring data, review the salmon forecast for the upcoming year, and develop action plans for the hatchery, selective harvest, and monitoring projects. Based on a strong pre-season forecast of 67,500 Upper Columbia summer/fall Chinook, the plan for 2014 is to operate the hatchery at full program levels of 2 million summer/fall Chinook and 900,000 spring Chinook. To maximize PNI, broodstock for the integrated program should Chief Joseph Hatchery Program 2013 Annual Report 3 be 100% natural-origin broodstock (NOB) and CCT should plan to harvest their full allocation with the selective harvest program removing as many adult hatchery Chinook as possible with the purse seine, the weir, and at the hatchery ladder.

Report↗

Genetic structure in a previously extirpated population of gray wolves following reintroduction and natural recolonization

Genetic structuring in wildlife populations is driven by barriers that restrict gene flow as well as the history of population demography. Mechanisms driving genetic structuring can be nuanced in group-living species, such as gray wolves ( Canis lupus ). Behavioral factors, such as social affiliation and resistance, natal habitat imprinting, and trade-offs between dispersal from natal packs and territorial biding, affect habitat selection of wolves despite landscape barriers providing little resistance to their extensive dispersal capabilities. Wolves were previously extirpated from Idaho, USA, and current populations are the result of both reintroductions in 1995 and 1996 and natural dispersal from Canada. In this context we examined genetic structure of wolves in Idaho using 101 individuals genotyped at 18 nuclear DNA microsatellite loci and a subset of 38 individuals genotyped at 1019 single nucleotide polymorphism markers. We hypothesized panmictic (i.e., random mating) genetic structure in Idaho due to the long-distance dispersal abilities of gray wolves. Contrary to our hypothesis, we found three genetic clusters of gray wolves in Idaho, primarily supported by SNP markers. Microsatellite data suggested similar patterns, but permutation tests indicated these differences were not statistically significant. The extent of differentiation and evidence of gene flow, however, suggests that the three genetic clusters are not wholly isolated from one another. The distinctions between clusters spatially align with areas of reintroduction into central Idaho and Yellowstone National Park, as well ongoing natural recolonization from adjacent populations in Canada and Montana. Wolves at the periphery of analysis areas showed more admixture than those in the core, consistent with territoriality and mating behaviors contributing to genetic structuring. We demonstrate how management history, including reintroduction efforts, and animal behavior may interact and contribute to patterns of genetic structure in wild populations.

Idaho, Montana, Wyoming↗

Determining climate change management priorities: A case study from Wisconsin

A burgeoning dialogue exists regarding how to allocate resources to maximize the likelihood of long-term biodiversity conservation within the context of climate change. To make effective decisions in natural resource management, an iterative, collaborative, and learning-based decision process may be more successful than a strictly consultative approach. One important, early step in a decision process is to identify priority species or systems. Although this promotes the conservation of select species or systems, it may inadvertently alter the future of non-target species and systems. We describe a process to screen terrestrial wildlife for potential sensitivity to climate change and then use the results to engage natural resource professionals in a process of identifying priorities for monitoring, research, and adaptation strategy implementation. We demonstrate this approach using a case study from Wisconsin. In Wisconsin, experts identified 23 out of 353 species with sufficient empirical research and management understanding to inform targeted action. Habitat management and management of hydrological conditions were the common strategies for targeted action. Although there may be an interest in adaptation strategy implementation for many species and systems, experts considered existing information inadequate to inform targeted action. According to experts, 40% of the vertebrate species in Wisconsin will require near-term intervention for climate adaptation. These results will inform state-wide conservation planning as well as regional efforts.

Wisconsin↗

Prediction of resource volumes at untested locations using simple local prediction models

This paper shows how local spatial nonparametric prediction models can be applied to estimate volumes of recoverable gas resources at individual undrilled sites, at multiple sites on a regional scale, and to compute confidence bounds for regional volumes based on the distribution of those estimates. An approach that combines cross-validation, the jackknife, and bootstrap procedures is used to accomplish this task. Simulation experiments show that cross-validation can be applied beneficially to select an appropriate prediction model. The cross-validation procedure worked well for a wide range of different states of nature and levels of information. Jackknife procedures are used to compute individual prediction estimation errors at undrilled locations. The jackknife replicates also are used with a bootstrap resampling procedure to compute confidence bounds for the total volume. The method was applied to data (partitioned into a training set and target set) from the Devonian Antrim Shale continuous-type gas play in the Michigan Basin in Otsego County, Michigan. The analysis showed that the model estimate of total recoverable volumes at prediction sites is within 4 percent of the total observed volume. The model predictions also provide frequency distributions of the cell volumes at the production unit scale. Such distributions are the basis for subsequent economic analyses. ?? Springer Science+Business Media, LLC 2007.

Natural Resources Research↗

Exploratory and spatial data analysis (EDA-SDA) for determining regional background levels and anomalies of potentially toxic elements in soils from Catorce-Matehuala, Mexico

The threshold between geochemical background and anomalies can be influenced by the methodology selected for its estimation. Environmental evaluations, particularly those conducted in mineralized areas, must consider this when trying to determinate the natural geochemical status of a study area, quantifying human impacts, or establishing soil restoration values for contaminated sites. Some methods in environmental geochemistry incorporate the premise that anomalies (natural or anthropogenic) and background data are characterized by their own probabilistic distributions. One of these methods uses exploratory data analysis (EDA) on regional geochemical data sets coupled with a geographic information system (GIS) to spatially understand the processes that influence the geochemical landscape in a technique that can be called a spatial data analysis (SDA). This EDA-SDA methodology was used to establish the regional background range from the area of Catorce-Matehuala in north-central Mexico. Probability plots of the data, particularly for those areas affected by human activities, show that the regional geochemical background population is composed of smaller subpopulations associated with factors such as soil type and parent material. This paper demonstrates that the EDA-SDA method offers more certainty in defining thresholds between geochemical background and anomaly than a numeric technique, making it a useful tool for regional geochemical landscape analysis and environmental geochemistry studies.

Applied Geochemistry↗

Determination and prediction of micro scale rare earth element geochemical associations in mine drainage treatment wastes

Acid mine drainage (AMD) has been proposed as a novel source of rare earth elements (REE), a group of elements that includes critical metals for clean energy and modern technologies. REE are sequestered in the Fe–Al–Mn-rich precipitates produced during the treatment of AMD. These AMD solids are typically managed as waste but could be a REE source. Here, results from AMD solids characterization and geochemical modeling are presented to determine the minerals/solid phases that are enriched in REE and identify the mechanism(s) of REE attenuation. AMD solids collected from limestone-based AMD treatment systems were subjected to sequential extraction and synchrotron microprobe analyses to characterize the binding nature of the REE. The results of these analyses indicated REEs were mainly associated with Al or Mn phases. Only selected REE (Gd, Dy) were associated with Fe phases, which were less abundant than Al and Mn phases in analyzed samples. The sequential extractions demonstrated that acidic and/or reducing extractions effectively mobilize REE from the AMD solids evaluated. The observed element associations in solids are consistent with geochemical model results that indicate dissolved REE can be effectively attenuated by adsorption on freshly precipitated Fe, Al, and Mn oxides/hydroxides. The model, which simulates dissolution of CaCO 3 and the precipitation of Fe, Al, and Mn oxides with increased pH, accurately predicts the pH dependent accumulation of dissolved REE with Al, Mn, and Fe oxides/hydroxides in the studied AMD treatment systems. The methods and results presented here can be used to identify conditions favorable for accumulation of REE-enriched AMD solids and possible passive or active treatment(s) to extract REE from AMD. This information can be used to design AMD treatment systems for the recovery of REE and is an opportunity to transform the challenges of addressing polluted mine drainage into an environmental and economic asset.

Pennsylvania↗

Coastal groundwater dynamics off Santa Barbara, California: combining geochemical tracers, electromagnetic seepmeters, and electrical resistivity

This paper presents repeat field measurements of 222 Rn and 223,224,226,228 Ra, electromagnetic seepage meter-derived advective fluxes, and multi-electrode, stationary and continuous marine resistivity surveys collected between November 2005 and April 2007 to study coastal groundwater dynamics within a marine beach in Santa Barbara, California. The study provides insight into magnitude and dynamics of submarine groundwater discharge (SGD) and associated nutrient loadings into near-shore coastal waters, where the predominant SGD drivers can be both spatially and temporally separated. Rn-222 and 223,224,226,228 Ra were utilized to quantify the total and saline contribution, respectively, of SGD. The two short-lived 224,223 Ra isotopes provided an estimate of apparent near-shore water mass age, as well as an estimate of the Ra-derived eddy diffusion coefficient, K h ( 224 Ra = 2.86 ± 0.7 m 2 s −1 ; 223 Ra = 1.32 ± 0.5 m 2 s −1 ). Because 222 Rn ( t ½ = 3.8 day) and 224 Ra ( t ½ = 3.66 day) have comparable half-lives and production terms, they were used in concert to examine respective water column removal rates. Electromagnetic seepage meters recorded the physical, bi-directional exchange across the sediment/water interface, which ranged from −6.7 to 14.5 cm day −1 , depending on the sampling period and position relative to the low tide line. Multi-day time-series 222 Rn measurements in the near-shore water column yielded total (saline + fresh) SGD rates that ranged from 3.1 ± 2.6 to 9.2 ± 0.8 cm day −1 , depending on the sampling season. Offshore 226 Ra ( t ½ = 1600 year) and 222 Rn gradients were used with the calculated K h values to determine seabed flux estimates (dpm m −2 day −1 ), which were then converted into SGD rates (7.1 and 7.9 cm day −1 , respectively). Lastly, SGD rates were used to calculate associated nutrient loads for the near-shore coastal waters off Santa Barbara. Depending on both the season and the SGD method utilized, the following SGD-derived nutrient inputs were computed (mol per day per meter of shoreline): NH 4 + = 0.06–0.29 mol day −1 m −1 ; SiO 4 = 0.22–0.29 mol day −1 m −1 ; PO 4 3− = 0.04–0.17 mol day −1 m −1 ; [NO 2 − + NO 3 − ] = 0–0.52 mol day −1 m −1 ; dissolved inorganic nitrogen (DIN) = 0.01–0.17 mol day −1 m −1 , and dissolved organic nitrogen (DON) = 0.08–0.09 mol day −1 m −1 . Compared to the ephemeral nature of fluvial and marine inputs into this region, such SGD-derived loadings can provide a sustained source of select nutrients to the coastal waters off Santa Barbara, California that should be accounted for in mass balance estimates.

California↗

Raman spectroscopy of efflorescent sulfate salts from Iron Mountain Mine Superfund Site, California

The Iron Mountain Mine Superfund Site near Redding, California, is a massive sulfide ore deposit that was mined for iron, silver, gold, copper, zinc, and pyrite intermittently for nearly 100 years. As a result, both water and air reached the sulfide deposits deep within the mountain, producing acid mine drainage consisting of sulfuric acid and heavy metals from the ore. Particularly, the drainage water from the Richmond Mine at Iron Mountain is among the most acidic waters naturally found on Earth. The mineralogy at Iron Mountain can serve as a proxy for understanding sulfate formation on Mars. Selected sulfate efflorescent salts from Iron Mountain, formed from extremely acidic waters via drainage from sulfide mining, have been characterized by means of Raman spectroscopy. Gypsum, ferricopiapite, copiapite, melanterite, coquimbite, and voltaite are found within the samples. This work has implications for Mars mineralogical and geochemical investigations as well as for terrestrial environmental investigations related to acid mine drainage contamination.

California↗

Post-independence fledgling ecology in a migratory songbird: Implications for breeding-grounds conservation

For migratory songbirds, breeding-grounds conservation and management plans are generally focused on habitat associated with locations of singing males and sometimes nesting females. However, habitat structure is often different in areas used for raising fledglings compared with areas used for song territories, and very little is known about habitat use by fledglings after independence from adult care. From 2010 to 2012, we used radiotelemetry to monitor 68 fledgling golden-winged warblers V ermivora chrysoptera after independence from adult care in mixed managed forests of Minnesota, US and Manitoba, Canada. This species is of high conservation concern in the US, is listed as threatened in Canada and is listed as near threatened on the International Union for Conservation of Nature Red List. We assessed distance and orientation of independent fledgling movements and we used compositional analysis to test for selection among cover types. Fledglings of this species, commonly described as a shrubland specialist, selected mature forest (78% of locations) over all other cover types, and foraged in forest canopy and understory in mixed-species flocks. Fledgling golden-winged warbler movements were apparently associated with habitat optimization (although prioritizing foraging over predator avoidance), and likely not with commencement of migration, or scouting future breeding territories. Ten days after independence, fledglings were an average of 1238 m north of their nest, which may be related to homing-target formation and the species' northward range expansion. We conclude that consideration for independent fledgling habitat associations is necessary for developing full-fledged forest management plans on the breeding grounds of migratory songbirds.

Manitoba, Minnesota↗