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Carbonate apron models: Alternatives to the submarine fan model for paleoenvironmental analysis and hydrocarbon exploration

Sediment gravity flow deposition along the deep-water flanks of carbonate platforms typically does not produce submarine fans. Rather, wedge-shaped carbonate aprons develop parallel to the adjacent shelf/slope break. The major difference between submarine fans and carbonate aprons is a point source with channelized sedimentation on fans, versus a line source with sheet-flow sedimentation on aprons. Two types of carbonate aprons may develop. Along relatively gentle (< 4°) platform-margin slopes, aprons form immediately adjacent to the shallow-water platform and are referred to as carbonate slope aprons . Along relatively steep (4–15°) platform margin slopes, redeposited limestones accumulate in a base-of-slope setting, by-passing an upper slope via a multitude of small submarine canyons, and are referred to as carbonate base-of-slope aprons . Both apron types are further subdivided into inner and outer facies belts. Inner apron sediments consist of thick, mud-supported conglomerates and megabreccias (Facies F) as well as thick, coarse-grained turbidites (Facies A) interbedded with subordinate amounts of fine-grained, peri-platform ooze (Facies G). Outer apron sediments consist of thinner, grain-supported conglomerates and turbidites (Facies A) as well as classical turbidites (Facies C) with recognizable Bouma divisions, interbedded with approximately equal proportions of peri-platform ooze (Facies G). Seaward, aprons grade laterally into basinal facies of thin, base-cut-out carbonate turbidites (Facies D) that are subordinate to peri-platform oozes (Facies G). Carbonate base-of-slope aprons grade shelfward into an upper slope facies of fine-grained peri-platform ooze (Facies G) cut by numerous small canyons that are filled with coarse debris, as well as intraformational truncation surfaces which result from submarine sliding. In contrast, slope aprons grade shelfward immediately into shoal-water, platform-margin facies without an intervening by-pass slope. The two carbonate apron models presented here offer alternatives to the submarine-fan model for paleoenvironmental analysis and hydrocarbon exploration for mass-transported carbonate facies.

Sedimentary Geology

Significant results from using earth observation satellites for mineral and energy resource exploration

A large number of Earth-observation satellites orbit our world several times each day, providing new information about the land and sea surfaces and the overlying thin layer of atmosphere that makes our planet unique. Meteorological satellites have had the longest history of experimental use and most are now considered operational. The geologic information collected by the Landsat, Polar Orbiting Geophysical Observatory (POGO), Magsat, Heat Capacity Mapping Mission (HCMM) and Seasat land and ocean observation systems is being thoroughly tested, and some of these systems are now approaching operational use. Landsat multispectral images provide views of large areas of the Earth under uniform lighting conditions and can be obtained at a variety of scales and formats. Not only do the Landsat data provide highly useful images showing surficial materials and structures such as folds and faults, but also measurements and computer-derived ratios of the brightness of different rock types, alteration zones, and mineral associations. These data have led to the finding of a variety of new ore deposits. In addition, the combination of Landsat digital data and aeromagnetic data has extended the use of Landsat as an exploration tool which can be used to readily relate surface features to subsurface anomalies. Magsat data, now being collected, are helping refine information on major crustal anomalies that were first recognized during the analysis of POGO data. The more nearly circular orbit, lower altitude, and increased sophistication of its vector magnetometer enable Magsat to provide more precise information than POGO. Information of this type is required to develop crustal models. Although Magsat is designed to operate for only 4&ndash;8 months, the number of orbits that it should be able to make will be sufficient to accomplish its mission and to record a major magnetic storm expected in 1980. HCMM is a two-band visible to near-IR (0.55&ndash;1.1 &mu;m) and thermal infrared (10.2&ndash;12.5 &mu;m) system designed to measure reflected solar energy, determine the heat capacity of rocks and to monitor soil moisture, thermal effluents, plant canopy temperatures and snow cover. Launched in April 1978, it is in sun-synchronous, circular orbit at an altitude of 620 km. It is a relatively low-resolution system with an instantaneous field of view (IFOV) of 500&ndash;600 m and a swath width of 716 km. However, the system is designed to detect objects in the range of 260&deg;&ndash;340&deg; K with a sensitivity (NE&delta;T) of 0.4&deg;K at 280&deg;. Recording the thermal radiation of urban heat islands and high thermal inertia of quartzite strata in the Appalachian region are two examples of its land applications. Launched in June 1978, Seasat operated for only 100 days, but successfully acquired much information over both sea and land. The collection of synthetic aperture radar (SAR) imagery and radar altimetry was particularly important to geologists. Although there are difficulties in processing and distributing these data in a timely manner, initial evaluations indicate that the radar imagery supplements Landsat data by increasing the spectral range and offering a different look angle. The radar altimeter provides accurate profiles over narrow strips of land (1 km wide) and has demonstrated usefulness in measuring icecap surfaces (Greenland, Iceland, and Antarctica). The Salar of Uyuni in southern Bolivia served as a calibration site for the altimeter and has enabled investigators to develop a land-based smoothing algorithm that is believed to increase the accuracy of the system to 10 cm. Data from the altimeter are currently being used to measure subsidence resulting from ground water withdrawal in the Phoenix-Tucson area.

Advances in Space Research

Fission-track dating applied to mineral exploration

The partial to total resetting of fission-track ages of minerals in country rock near a mineralized area can be used to (1) locate a thermal anomaly, and (2) date the mineralizing event. Two mining districts in Colorado have been studied - Rico and Gilman. Rico is a precious- and base-metal mining district. Initial fission-track dating of a sill located about 6 km from the center of the district gave ages of 20 Myr and 65 Myr for apatite and zircon, respectively. The Eagle Mine in the Gilman District is the largest producer of zinc in the state of Colorado. Fission-track dating of zircon from a 70 Myr-old sill shows partial resetting of the zircon (45 Myr). The thermal anomaly identified by fission-track dating is seen in both districts far outside the area affected by obvious alteration. Based on the results of these two pilot studies, fission-track dating can be a useful exploration method for thermal anomalies associated with buried or otherwise poorly expressed mineral deposits.

Nuclear Tracks and Radiation Measurements (1982)

Lead isotopes in iron and manganese oxide coatings and their use as an exploration guide for concealed mineralization

Lead isotopes from Fe and Mn oxides that coat stream pebbles from around the Mount Emmons porphyry molybdenum deposit in Colorado were studied to assess the feasibility of using Pb isotopes to detect concealed mineral deposits. The Fe/Mn oxide coatings were analyzed to determine their elemental concentrations using ICP-AES. The Pb isotope compositions of solutions from a selected suite of samples were measured, using both thermal ionization and ICP mass spectrometry, to compare results determined by the two analytical methods. Heavy mineral concentrates from the same sites were also analyzed to compare the Pb isotope compositions of the Fe/Mn coatings with those found in panned concentrates. The Fe/Mn and 206 Pb/ 204 Pb ratios of the oxide coatings are related to the lithology of the host rocks; Fe/Mn oxide coatings on pebbles of black shale have higher Fe/Mn values than do the coatings on either sandstone or igneous rocks. The shale host rocks have a more radiogenic signature (e.g. higher 206 Pb/ 204 Pb) than the sandstone or igneous host rocks. The Pb isotope data from sandstone and igneous hosts can detect concealed mineralized rock on both a regional and local scale, even though there are contributions from: (1) metals from the main-stage molybdenite ore deposit; (2) metals from the phyllic alteration zone which has a more radiogenic Pb isotope signature reflecting hydrothermal leaching of Pb from the Mancos Shale; (3) Pb-rich base metal veins with a highly variable Pb isotope signature; and (4) sedimentary country rocks which have a more radiogenic Pb isotope signature. An investigation of within-stream variation shows that the Pb isotope signature of the molybdenite ore zone is retained in the Fe/Mn oxide coatings and is not camouflaged by contributions from Pb-rich base-metal veins that crop out upstream. In another traverse, the Pb isotope data from Fe/Mn oxide coatings reflect a complex mixing of Pb from the molybdenite ore zone and its hornfels margin, Pb-rich base-metal veins, and sedimentary country rocks. Stream-sediment anomalies detected using oxalic acid leaches can be evaluated using Pb isotope analysesof selected geochemical anomalies. Such an evaluation procedure, given regional target Pb isotope signatures for concealed mineralization, can greatly reduce the cost of exploration for undiscovered ore deposits concealed beneath barren overburden. Lead isotope measurements on aliquots of the same solutions showed that ICP-MS determinations are of low precision and vary non-systematically when compared with the Pb isotope values of the higher precision thermal ionization method. These variations and lower precision of the ICP-MS measurements are attributed to matrix effects.

Colorado

A multiple-objective optimal exploration strategy

Exploration for natural resources is accomplished through partial sampling of extensive domains. Such imperfect knowledge is subject to sampling error. Complex systems of equations resulting from modelling based on the theory of correlated random fields are reduced to simple analytical expressions providing global indices of estimation variance. The indices are utilized by multiple objective decision criteria to find the best sampling strategies. The approach is not limited by geometric nature of the sampling, covers a wide range in spatial continuity and leads to a step-by-step procedure.

Mathematical and Computer Modelling

Exploring the uncertainty of machine learning models and geostatistical mapping of rare earth element potential in Indiana coals, USA

Rare earth elements and yttrium (REEs) have a wide range of applications in high- and low-carbon technologies. The strategic significance of REEs has grown due to their expanding applications in manufacturing industries and the constrained availability of these essential resources. This research explores the applicability of machine learning models and their uncertainty for assessing the REE potential in coal beds using various coal parameters as inputs. The work focuses on developing a predictive model based on geological variables, excluding considerations related to potential shifts in the commodities market. The Indiana Coal Quality Database was used as the data source. The promising and unpromising indicators derived from the outlook coefficient of samples from the database were used as the REE potential indicator for machine learning classification models. The filter-based approach with bootstrap was used to evaluate the importance of the coal parameters and their prediction uncertainties. Four machine learning methods (linear discriminant analysis (LDA), random forest (RF), support vector machine (SVM), and artificial neural networks (ANN), a data balancing and augmentation approach (Synthetic Minority Over-sampling Technique), and bootstrap resampling techniques were used for building the models and evaluating their prediction capabilities under uncertainty. It was determined that the SVM bootstrap model with ten-times balanced and augmented data provided superior results compared with other models. Finally, stochastic spatial maps of the REE potential within the coal basin were generated using sequential indicator simulation. The spatial maps of the REE potential showed that a 29% area of the Indiana section of the Illinois coal basin has economic potential of REEs, with 90% confidence.

Indiana

Correlating multispectral imaging and compositional data from the Mars Exploration Rovers and implications for Mars Science Laboratory

In an effort to infer compositional information about distant targets based on multispectral imaging data, we investigated methods of relating Mars Exploration Rover (MER) Pancam multispectral remote sensing observations to in situ alpha particle X-ray spectrometer (APXS)-derived elemental abundances and Mössbauer (MB)-derived abundances of Fe-bearing phases at the MER field sites in Gusev crater and Meridiani Planum. The majority of the partial correlation coefficients between these data sets were not statistically significant. Restricting the targets to those that were abraded by the rock abrasion tool (RAT) led to improved Pearson’s correlations, most notably between the red–blue ratio (673 nm/434 nm) and Fe 3+ -bearing phases, but partial correlations were not statistically significant. Partial Least Squares (PLS) calculations relating Pancam 11-color visible to near-IR (VNIR; ∼400–1000 nm) “spectra” to APXS and Mössbauer element or mineral abundances showed generally poor performance, although the presence of compositional outliers led to improved PLS results for data from Meridiani. When the Meridiani PLS model for pyroxene was tested by predicting the pyroxene content of Gusev targets, the results were poor, indicating that the PLS models for Meridiani are not applicable to data from other sites. Soft Independent Modeling of Class Analogy (SIMCA) classification of Gusev crater data showed mixed results. Of the 24 Gusev test regions of interest (ROIs) with known classes, 11 had >30% of the pixels in the ROI classified correctly, while others were mis-classified or unclassified. k-Means clustering of APXS and Mössbauer data was used to assign Meridiani targets to compositional classes. The clustering-derived classes corresponded to meaningful geologic and/or color unit differences, and SIMCA classification using these classes was somewhat successful, with >30% of pixels correctly classified in 9 of the 11 ROIs with known classes. This work shows that the relationship between SWIR multispectral imaging data and APXS- and Mössbauer-derived composition/mineralogy is often weak, a perhaps not entirely unexpected result given the different surface sampling depths of SWIR imaging (uppermost few microns) vs. APXS (tens of μm) and MB measurements (hundreds of μm). Results from the upcoming Mars Science Laboratory (MSL) rover’s ChemCam Laser Induced Breakdown Spectroscopy (LIBS) instrument may show a closer relationship to Mastcam SWIR multispectral observations, however, because the initial laser shots onto a target will analyze only the upper few micrometers of the surface. The clustering and classification methods used in this study can be applied to any data set to formalize the definition of classes and identify targets that do not fit in previously defined classes.

Icarus

6th international conference on Mars polar science and exploration: Conference summary and five top questions

We provide a historical context of the International Conference on Mars Polar Science and Exploration and summarize the proceedings from the 6th iteration of this meeting. In particular, we identify five key Mars polar science questions based primarily on presentations and discussions at the conference and discuss the overlap between some of those questions. We briefly describe the seven scientific field trips that were offered at the conference, which greatly supplemented conference discussion of Mars polar processes and landforms. We end with suggestions for measurements, modeling, and laboratory and field work that were highlighted during conference discussion as necessary steps to address key knowledge gaps.

Icarus

Exploring the long-term balance between net precipitation and net groundwater exchange in Florida seepage lakes

The long-term balance between net precipitation and net groundwater exchange that maintains thousands of seepage lakes in Florida&rsquo;s karst terrain is explored at a representative lake basin and then regionally for the State&rsquo;s peninsular lake district. The 15-year water budget of Lake Starr includes El Ni&ntilde;o Southern Oscillation (ENSO)-related extremes in rainfall, and provides the longest record of Bowen ratio energy-budget (BREB) lake evaporation and lake-groundwater exchanges in the southeastern United States. Negative net precipitation averaging -25 cm/yr at Lake Starr overturns the previously-held conclusion that lakes in this region receive surplus net precipitation. Net groundwater exchange with the lake was positive on average but too small to balance the net precipitation deficit. Groundwater pumping effects and surface-water withdrawals from the lake widened the imbalance. Satellite-based regional estimates of potential evapotranspiration at five large lakes in peninsular Florida compared well with basin-scale evaporation measurements from seven open-water sites that used BREB methods. The regional average lake evaporation estimated for Lake Starr during 1996-2011 was within 5 percent of its measured average, and regional net precipitation agreed within 10 percent. Regional net precipitation to lakes was negative throughout central peninsular Florida and the net precipitation deficit increased by about 20 cm from north to south. Results indicate that seepage lakes farther south on the peninsula receive greater net groundwater inflow than northern lakes and imply that northern lakes are in comparatively leakier hydrogeologic settings. Findings reveal the peninsular lake district to be more vulnerable than was previously realized to drier climate, surface-water withdrawals from lakes, and groundwater pumping effects.

Florida

Exploring trip preference heterogeneity in away-from-home birdwatchers using a discrete choice experiment

Birdwatching has grown in popularity worldwide and birdwatchers have emerged as an important constituency for wildlife and habitat conservation. To help promote wetland conservation, agencies and managers need to understand birdwatchers' desired trip experiences. We conducted national web-based surveys of American and Canadian birdwatchers by employing a discrete choice experiment to explore birdwatching trip preferences. We also collected information about participation in birdwatching and recreation specialization. We used latent class analysis to identify groups of birdwatchers with similar preferences. Our analysis indicated that birdwatchers were not homogeneous in their preferences. The seven attributes and associated attribute levels that were presented to participants (travel distance, site naturalness, bird rarity, the presence of waterfowl and wetlands, ease of access, species diversity and the number of birds seen) were all relevant, to varying degrees, in decisions about whether to take a birdwatching trip. We identified five latent classes of birdwatchers in the United States and Canada. ‘Nature seekers’ prioritised setting naturalness; ‘local birdwatchers’ strongly preferred shorter travel distances; ‘list-focused birdwatchers’ prioritised bird rarity and diversity; whereas ‘site-focused birdwatchers’ prioritised on-site characteristics above bird-related characteristics; and ‘casual birdwatchers’ were most likely to opt out of taking a trip. We found variation in recreation specialization and avidity levels across all the classes. Some classes ( e.g. list-focused birdwatchers) tend to be more specialised and more avid than others ( e.g. casual and local birdwatchers). Recognising the diversity of birdwatcher trip preferences can help outdoor recreation and wildlife managers provide a variety of suitable settings, services, and experiences.

Journal of Outdoor Recreation and Tourism

Exploring the limits of identifying sub-pixel thermal features using ASTER TIR data

Understanding the characteristics of volcanic thermal emissions and how they change with time is important for forecasting and monitoring volcanic activity and potential hazards. Satellite instruments view volcanic thermal features across the globe at various temporal and spatial resolutions. Thermal features that may be a precursor to a major eruption, or indicative of important changes in an on-going eruption can be subtle, making them challenging to reliably identify with satellite instruments. The goal of this study was to explore the limits of the types and magnitudes of thermal anomalies that could be detected using satellite thermal infrared (TIR) data. Specifically, the characterization of sub-pixel thermal features with a wide range of temperatures is considered using ASTER multispectral TIR data. First, theoretical calculations were made to define a “thermal mixing detection threshold” for ASTER, which quantifies the limits of ASTER's ability to resolve sub-pixel thermal mixing over a range of hot target temperatures and % pixel areas. Then, ASTER TIR data were used to model sub-pixel thermal features at the Yellowstone National Park geothermal area (hot spring pools with temperatures from 40 to 90 °C) and at Mount Erebus Volcano, Antarctica (an active lava lake with temperatures from 200 to 800 °C). Finally, various sources of uncertainty in sub-pixel thermal calculations were quantified for these empirical measurements, including pixel resampling, atmospheric correction, and background temperature and emissivity assumptions.

Journal of Volcanology and Geothermal Research

Origin and evolution of mineralizing fluids and exploration of the Cerro Quema Au-Cu deposit (Azuero Peninsula, Panama) from a fluid inclusion and stable isotope perspective

Cerro Quema is a high sulfidation epithermal Au-Cu deposit with a measured, indicated and inferred resource of 35.98 Mt. @ 0.77 g/t Au containing 893,600 oz. Au (including 183,930 oz. Au equiv. of Cu ore). It is characterized by a large hydrothermal alteration zone which is interpreted to represent the lithocap of a porphyry system. The innermost zone of the lithocap is constituted by vuggy quartz with advanced argillic alteration locally developed on its margin, enclosed by a well-developed zone of argillic alteration, grading to an external halo of propylitic alteration. The mineralization occurs in the form of disseminations and microveinlets of pyrite, chalcopyrite, enargite, tennantite, and trace sphalerite, crosscut by quartz, barite, pyrite, chalcopyrite, sphalerite and galena veins. Microthermometric analyses of two phase (L + V) secondary fluid inclusions in igneous quartz phenocrysts in vuggy quartz and advanced argillically altered samples indicate low temperature (140–216 °C) and low salinity (0.5–4.8 wt% NaCl eq.) fluids, with hotter and more saline fluids identified in the east half of the deposit (Cerro Quema area). Stable isotope analyses (S, O, H) were performed on mineralization and alteration minerals, including pyrite, chalcopyrite, enargite, alunite, barite, kaolinite, dickite and vuggy quartz. The range of δ 34 S of sulfides is from − 4.8 to − 12.7‰, whereas δ 34 S of sulfates range from 14.1 to 17.4‰. The estimated δ 34 S ΣS of the hydrothermal fluid is − 0.5‰. Within the advanced argillic altered zone the δ 34 S values of sulfides and sulfates are interpreted to reflect isotopic equilibrium at temperatures of ~ 240 °C. The δ 18 O values of vuggy quartz range from 9.0 to 17.5‰, and the δ 18 O values estimated for the vuggy quartz-forming fluid range from − 2.3 to 3.0‰, indicating that it precipitated from mixing of magmatic fluids with surficial fluids. The δ 18 O of kaolinite ranges from 12.7 to 18.1‰ and δD from − 103.3 to − 35.2‰, whereas the δ 18 O of dickite varies between 12.7 and 16.3‰ and δD from − 44 to − 30. Based on δ 18 O and δD, two types of kaolinite/dickite can be distinguished, a supergene type and a hypogene type. Combined, the analytical data indicate that the Cerro Quema deposit formed from magmatic-hydrothermal fluids derived from a porphyry copper-like intrusion located at depth likely towards the east of the deposit. The combination of stable isotope geochemistry and fluid inclusion analysis may provide useful exploration vectors for porphyry copper targets in the high sulfidation/lithocap environment.

Azuero Peninsula

The northwestern slope valleys (NSVs) region, Mars: A prime candidate site for the future exploration of Mars

The northwestern slope valleys region is a prime candidate site for future science-driven Mars exploration because it records Noachian to Amazonian Tharsis development in a region that encapsulates (1) a diverse and temporally extensive stratigraphic record, (2) at least three distinct paleohydrologic regimes, (3) gargantuan structurally controlled flood valleys that generally correspond with gravity and magnetic anomalies, possibly marking ancient magnetized rock materials exposed by fluvial activity, (4) water enrichment, as indicated by Mars Odyssey and impact crater analyses, (5) long-lived magma and ground water/ice interactions that could be favorable for the development and sustenance of life, and (6) potential paleosol development. This region has high probability to yield significant geologic, climatic, and exobiologic information that could revolutionize our understanding of Mars. ?? 2003 Elsevier Ltd. All rights reserved.

Conference Paper

Water-quality trends in US rivers: Exploring effects from streamflow trends and changes in watershed management

We present a conceptual model that explores the relationship of streamflow trends to 15 water-quality parameters at 370 sites across the contiguous United States (US). Our analytical framework uses discrete water-quality data, daily streamflow records, and a statistical model to estimate water-quality trends between 1982 and 2012 and parse these trends into the amount of change attributed to trends in streamflow versus changes in watershed management , such as changes in point or non-point sources related to pollution control efforts. We conceptualize a water-quality trend as an additive function of these two trend components. We found that for most of these records the water-quality trends were more strongly affected by changes in watershed management as opposed to trends in streamflow. However, the importance of these trend components on water quality varied by estimate type (i.e. concentration versus load trends), parameter, and site. Trends in load were more influenced by changes in the streamflow regime than trends in concentration. Trends in major ions, salinity, and sediment were more sensitive to changes in streamflow than nutrients. When results were aggregated by site, 25% of the sites had at least 1 parameter where streamflow trends attributed >7.5% to the water-quality trend for concentrations. For loads, this was the case for 66% of the sites. The findings of this work have important implications for the analysis of water-quality trends. Understanding the relative role of streamflow and management changes can help to isolate the effects of pollution control efforts on water quality and provide clearer understanding of progress, or lack thereof, towards water-quality goals.

Science of the Total Environment

Fluid migration pathways to groundwater in mature oil fields: Exploring the roles of water injection/production and oil-well integrity in California, USA

Mature oil fields potentially contain multiple fluid migration pathways toward protected groundwater (total dissolved solids, TDS, in nonexempted aquifer <10,000 mg/L) because of their extensive development histories. Time-series data for water use, fluid pressures, oil-well construction, and geochemistry from the South Belridge and Lost Hills mature oil fields in California are used to explore the roles of injection/production of oil-field water and well-integrity issues in fluid migration. Injection/production of oil-field water modified hydraulic gradients in both oil fields, resulting in chemical transport from deeper groundwater and hydrocarbon-reservoir systems to aquifers in the oil fields. Those aquifers are used for water supply outside the oil-field boundaries. Oil wells drilled before 1976 can be fluid migration pathways because a relatively large percentage of them have >10 m of uncemented annulus that straddles oil-well casing damage and/or the base of groundwater with TDS <10,000 mg/L. The risk of groundwater-quality degradation is higher when wells with those risk factors occur in areas with upward hydraulic gradients created by positive net injection, groundwater withdrawals, or combinations of these variables. The complex changes in hydrologic conditions and groundwater chemistry likely would not have been discovered in the absence of years to decades of monitoring data for groundwater elevations and chemistry, and installation of monitoring wells in areas with overlapping risk factors. Important monitoring concepts based on results from this and other studies include monitoring hydrocarbon-reservoir and groundwater systems at multiple spatiotemporal scales and maintaining transparency and accessibility of data and analyses. This analysis focuses on two California oil fields, but the methods used and processes affecting fluid migration could be relevant in other oil fields where substantial injection/production of oil-field water occurs and oil-well integrity is of concern.

California

Exploring spatial and temporal symptoms of the freshwater salinization syndrome in a rural to urban watershed

The freshwater salinization syndrome (FSS), a concomitant watershed-scale increase in salinity, alkalinity, and major-cation and trace-metal concentrations, over recent decades, has been described for major rivers draining extensive urban areas, yet few studies have evaluated temporal and spatial FSS variations, or causal factors, at the subwatershed scale in mixed-use landscapes. This study examines the potential influence of land-use practices and wastewater treatment plant (WWTP) effluent on the export of major ions and trace metals from the mixed-use East Branch Brandywine Creek watershed in southeastern Pennsylvania, during the 2019 water year. Separate analysis of baseflow and stormflow subsets revealed similar correlations among land-use characteristics and streamwater chemistry. Positive associations between percent impervious surface cover, which ranged from 1.26 % to 21.9 % for the 13 sites sampled, and concentrations of Ca 2+ , Mg 2+ , Na + , and Cl − are consistent with road-salt driven reverse cation exchange and weathering of the built environment. The relative volume of upstream WWTP was correlated with Cu and Zn, which may be derived in part from corroded water-conveyance infrastructure; chloride to sulfate mass ratios (CSMR) ranged from ~6.3 to ~7.7× the 0.5 threshold indicating serious corrosivity potential. Observed exceedances of U.S. Environmental Protection Agency Na + and Cl − drinking water and aquatic life criteria occurred in winter months. Finally, correlations between percent cultivated cropland and As and Pb concentrations may be explained by the persistence of agricultural pesticides that had been used historically. Study results contribute to the understanding of FSS solute origin, fate, and transport in mixed-use watersheds, particularly those in road salt-affected regions. Study results also emphasize the complexity of trace-metal source attribution and explore the potential for FSS solutes to affect human health, aquatic life, and infrastructure.

Pennsylvania

Exploring behavior of an unusual megaherbivore: A spatially explicit foraging model of the hippopotamus

Herbivore foraging theories have been developed for and tested on herbivores across a range of sizes. Due to logistical constraints, however, little research has focused on foraging behavior of megaherbivores. Here we present a research approach that explores megaherbivore foraging behavior, and assesses the applicability of foraging theories developed on smaller herbivores to megafauna. With simulation models as reference points for the analysis of empirical data, we investigate foraging strategies of the common hippopotamus (Hippopotamus amphibius). Using a spatially explicit individual based foraging model, we apply traditional herbivore foraging strategies to a model hippopotamus, compare model output, and then relate these results to field data from wild hippopotami. Hippopotami appear to employ foraging strategies that respond to vegetation characteristics, such as vegetation quality, as well as spatial reference information, namely distance to a water source. Model predictions, field observations, and comparisons of the two support that hippopotami generally conform to the central place foraging construct. These analyses point to the applicability of general herbivore foraging concepts to megaherbivores, but also point to important differences between hippopotami and other herbivores. Our synergistic approach of models as reference points for empirical data highlights a useful method of behavioral analysis for hard-to-study megafauna. ?? 2003 Elsevier B.V. All rights reserved.

Ecological Modelling

Exploring the potential of electrospray-Orbitrap for stable isotope analysis using nitrate as a model

Widely used isotope ratio mass spectrometers have limited capabilities to measure metabolites, drugs, or small polyatomic ions without the loss of structural isotopic information. A new approach has recently been introduced that uses electrospray ionization Orbitrap to measure multidimensional isotope signatures of intact polar compounds. Using nitrate as a model compound, this study aims to establish performance metrics for comparisons with conventional IRMS at the natural abundance level. We present a framework on how to convert isotopolog intensities to δ values that are commonly used in the isotope geochemistry community. The quantification of seven nitrate isotopologs provides multiple pathways for obtaining the primary N and O δ values including non-mass-dependent O isotope variations, as well as opportunities to explore nonrandom isotopic distributions (i.e., clumping effects) within molecular nitrate. Using automation and the adaptation of measurement principles that are specific to isotope ratio analysis, nitrate δ15NAIR, δ18OVSMOW, and δ17OVSMOW were measured with a long-term precision of 0.4‰ or better for isotopic reference materials and purified nitrate from environmental samples. In addition, we demonstrate promising results for unpurified environmental samples in liquid form. With these new developments, this study connects the two largely disparate mass spectrometry fields of bioanalytical MS and isotope ratio MS, thus providing a route to measure new isotopic signatures in diverse organic and inorganic solutes.

Analytical Chemistry