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At least 91 records · Page 5

Emerging technologies and radical collaboration to advance predictive understanding of watershed hydrobiogeochemistry

Increasing population and resource-intensive lifestyles are driving enhanced demands for clean water, food, and energy. In parallel, land-use change, climate change, and perturbations—including drought, floods, fires, and early snowmelt—are significantly reshaping interactions within watersheds throughout the world. While watersheds are the Earth's key functional unit for assessing and managing water resources, hydrological processes in watersheds also mediate biogeochemical interactions that support terrestrial life on Earth (Kaushal, Gold, Bernal, & Tank, 2018; National Research Council, 2012). Although society is dependent upon clean water availability, tractable prediction of watershed hydrobiogeochemical behavior, including watershed response to perturbations, remains a challenge. Central to the challenge are complex, multiscale interactions between plants, microorganisms, organic matter, minerals, dissolved constituents, and migrating fluids, which occur within and across bedrock-to-canopy compartments and along extensive lateral gradients of a watershed. Several recent community reports have synthesized formidable challenges associated with watershed science and technology (AGU, 2018; Blöschl et al., 2019). Here, we discuss emerging technologies and collaboration modes that are critical for developing generalizable insights about and predictive understanding of complex watershed hydrobiogeochemical behavior, which are important for underpinning optimized natural resource management.

54 ENVIRONMENTAL SCIENCES↗

Long-term hydrological, biogeochemical, and climatological data from Walker Branch Watershed, East Tennessee, USA

In 1967, the original Walker Branch Watershed (WBW) project was established to study elemental cycling and mass balances in a relatively unimpacted watershed. Over the next 50+ years, findings from additional experimental studies and long-term observations on WBW advanced understanding of catchment hydrology, biogeochemistry, and ecology and established WBW as a seminal site for catchment science. The 97.5-ha WBW is located in East Tennessee, USA, on the U.S. Department of Energy's Oak Ridge Reservation. Vegetation on the watershed is characteristic of an eastern deciduous, second-growth forest. The watershed is divided into two subcatchments: the West Fork (38.4 ha) and the East Fork (59.1 ha). Headwater streams draining these subcatchments are fed by multiple springs, and thus flow is perennial. Stream water is high in base cations due to weathering of dolomite bedrock and nutrient concentrations are low. Long-term observations of climate, hydrology, and biogeochemistry include daily (1969–2014) and 15-min (1994–2014) stream discharge and annual runoff (1969–2014); hourly, daily, and annual rainfall (1969–2012); daily climate and soil temperature (1993–2010); and weekly stream water chemistry (1989–2013). These long-term datasets are publicly available on the WBW website (https://walkerbranch.ornl.gov/long-term-data/). While collection of these data has ceased, related long-term measurements continue through the National Ecological Observatory Network (NEON), where WBW is the core terrestrial and aquatic site in the Appalachian and Cumberland Plateau region (NEON's Domain 7) of the United States. These long-term datasets have been and will continue to be important in evaluating the influence of climatic and environmental drivers on catchment processes.

54 ENVIRONMENTAL SCIENCES↗

Hidden Features: How Subsurface and Landscape Heterogeneity Govern Hydrologic Connectivity and Stream Chemistry in a Montane Watershed

ABSTRACT Hydrologic connectivity is defined as the connection among stores of water within a watershed and controls the flux of water and solutes from the subsurface to the stream. Hydrologic connectivity is difficult to quantify because it is goverened by heterogeniety in subsurface storage and permeability and responds to seasonal changes in precipitation inputs and subsurface moisture conditions. How interannual climate variability impacts hydrologic connectivity, and thus stream flow generation and chemistry, remains unclear. Using a rare, four‐year synoptic stream chemistry dataset, we evaluated shifts in stream chemistry and stream flow source of Coal Creek, a montane, headwater tributary of the Upper Colorado River. We leveraged compositional principal component analysis and end‐member mixing to evaluate how seasonal and interannual variation in subsurface moisture conditions impacts stream chemistry. Overall, three main findings emerged from this work. First, three geochemically distinct end members were identified that constrained stream flow chemistry: reach inflows, and quick and slow flow groundwater contributions. Reach inflows were impacted by historic base and precious metal mine inputs. Bedrock fractures facilitated much of the transport of quick flow groundwater and higher‐storage subsurface features (e.g., alluvial fans) facilitated the transport of slow flow groundwater. Second, the contributions of different end members to the stream changed over the summer. In early summer, stream flow was composed of all three end members, while in late summer, it was composed predominantly of reach inflows and slow flow groundwater. Finally, we observed minimal differences in proportional composition in stream chemistry across all four years, indicating seasonal variability in subsurface moisture and spatial heterogeneity in landscape and geologic features had a greater influence than interannual climate fluctuation on hydrologic connectivity and stream water chemistry. These findings indicate that mechanisms controlling solute transport (e.g., hydrologic connectivity and flow path activation) may be resilient (i.e., able to rebound after perturbations) to predicted increases in climate variability. By establishing a framework for assessing compositional stream chemistry across variable hydrologic and subsurface moisture conditions, our study offers a method to evaluate watershed biogeochemical resilience to variations in hydrometeorological conditions.

Johnson, Keira [College of Earth, Ocean, and Atmos↗

Climatic controls on soil and saprock nitrogen distribution and persistence in the Sierra Nevada

Nitrogen (N) is an essential nutrient in soil that regulates plant growth, terrestrial sequestration of atmospheric carbon dioxide, and persistence of organic compounds. However, major knowledge gaps remain about how climate change may impact N accumulation and persistence, especially in deep soil and saprock (friable weakly weathered bedrock). Our objective was to understand how climate impacts the accumulation of N in soil and saprock and how climate impacts soil N distribution, persistence, and mechanisms of N persistence. We investigated N concentration in bulk soil and density fractions. We estimated N persistence along a bio-climatic sequence—sites range from a low-elevation oak savannah, mid-elevation pine-oak/mixed-conifer forest, to a high-elevation subalpine forest—in the southern Sierra Nevada in California. A combination of radiocarbon and elemental composition measurements along with a first-order kinetic model was used. The N concentration in the bulk soil and density fractions declined with depth, and there was a relatively greater mineral-associated heavy fraction (HF) N in deeper samples. The cooler/wetter mixed conifer site held 37% of profile N in saprock, which was greater than that of the entire soil profile at the drier/hotter oak savannah. The majority of N in soil, which was in the HF, was not influenced by climate proxies tested. However, both unprotected and occluded fractions of N were strongly influenced by climate. Soil N mean residence time (MRT) showed that drier/hotter climates have a shorter MRT, compared to mid-elevation sites with cooler/wetter climates. The effect of climate on deep saprock N storage might be indirect, primarily through climatic influence on the thickness of saprock. Overall, our findings suggest the mineral-associated HF N pool will not be vulnerable to changes in climate and will continue to contribute to the persistent soil N pool. The amount of topsoil and subsoil unprotected and occluded N can be explained by gross primary productivity and mean annual precipitation indicating that changes in climate can influence N partitioning. N stored in deep soil and saprock may be less vulnerable to climate than N stored in drier/hotter climates with less deeply stored N. It is critical to dig deeper to understand terrestrial ecosystems’ response to climate.

58 GEOSCIENCES↗

Early glacier advance in New Zealand during the Antarctic Cold Reversal

ABSTRACT Glacial landscapes preserve records of past climate change. Investigating the glacier–climate system over the Late Quaternary provides information about past climate change and context for present‐day glacier response to climate warming. Using 28 beryllium‐10 ( 10 Be) surface exposure dates and snowline reconstructions, we present glacier fluctuations and climate changes for the Antarctic Cold Reversal in the Ahuriri River catchment, Southern Alps of New Zealand (44°7′50″S, 169°38′29″E). Prominent terminal and lateral moraine features from the upper right tributary of the Ahuriri River valley have exposure ages of 14.5 ± 0.3, 13.6 ± 0.3 and 12.6 ± 0.2 ka, suggesting retreat of the glacier during the Antarctic Cold Reversal. Maximum elevation of lateral moraines (MELM) and accumulation area ratio (AAR) suggest snowline elevations at these ages were ≤700, ≤630 and ~360 m lower than today, respectively. This equates to air temperatures ≤3.9, ≤3.5 and 2.3 ± 0.7 °C lower than today (1981–2010), assuming no changes in past precipitation. Ice‐sculpted bedrock surfaces bound by a lateral moraine at nearby Canyon Creek have an age of 13.1 ± 0.3 ka, indicating the moraine correlates with those in the Ahuriri upper right tributary. MELM and AAR reconstructions from the Canyon Creek suggest that snowline elevations at 14.5–13.6 ka were ≤500 or ~380 m lower than today, corresponding to air temperatures ≤2.8 or 2.4 ± 0.7 °C lower than the present‐day (1981–2010). Our results provide insight into the structure of the Antarctic Cold Reversal in the Southern Alps, showing that the largest glacier advance occurred at the start of this interval at c . 14.5 ± 0.3 ka and was followed by gradual retreat. We hypothesize that the early cooling and glacier readvance in New Zealand at the onset of the Antarctic Cold Reversal were triggered by a latitudinal shift of the Southern Hemisphere westerly wind belt.

58 GEOSCIENCES↗

Factors influencing water quality in surface water and alluvial groundwaters downgradient of a reclaimed surface coal mine in the Powder River Basin of southeastern Montana, USA

Abstract Coal mining and reclamation can have a profound influence on hydrogeologic systems, with clear consequences for groundwater quality, yet their long-term influence on downgradient water quality over time following reclamation is less well documented. Geochemical trends were evaluated in water quality downgradient of a fully reclaimed landscape at the former Big Sky Mine in the Rosebud Creek watershed (southeastern Montana, USA), over a 3-year period (2020–2022), including bond release in 2022. Within 6 km downgradient from the reclaimed area, sulfate concentrations decreased from approximately 3500 to 1800 mg l −1 within the Miller Coulee alluvial aquifer. Major ions, δ 34 S SO4 values, and residence time tracers suggest that the observed decreases in sulfate concentration result from a combination of dilution by mixed-age inflows and incomplete transit of the high salinity plume from the mine boundary. Both bedrock and alluvial aquifers of the Rosebud Creek corridor contained contributions of millennia-old regional groundwater, which may serve to mitigate mine-derived high salinity waters. Rosebud Creek, which traverses the outflow zone of Miller Coulee in the study area, exhibited high sulfate concentrations during low flows and consistent downgradient increases in sulfate concentration. The possibility of plume dynamics in Miller Coulee suggests that the greatest water quality impacts may not yet have reached Rosebud Creek.

Keeshin, Skye I. (ORCID:0009000986449872)↗

A Geo-Data Science Method for Assessing Unconventional Rare-Earth Element Resources in Sedimentary Systems

Abstract Rare-earth elements (REEs) supply raw materials that constitute many of our modern critical infrastructure, defense, technology, and electrification needs. Despite REE accumulations occurring in conventional bedrock and ion-adsorption deposits sourced from weathering of igneous rocks, unconventional host materials such as coal and related sedimentary strata have been identified as promising sources of REEs to meet growing demand. To maximize the potential of unconventional resources such as REE-coal systems, new approaches are needed overcome challenges from mineral systems with no known deposits and areas with sparse geochemical data. This article presents a systematic knowledge-data resource assessment method for predicting and identifying REE resource potential and occurrence in these unconventional systems. The method utilizes a geologic and geospatial knowledge-data approach informed and guided by REE accumulation mechanisms to systematically assess and identify areas of higher enrichment. An assessment of the Powder River Basin is presented as a test case to demonstrate the method workflow and results. The key output is a potential enrichment score map reported with varying confidence levels based on the amount of supporting evidence. Results from the test case indicate several locations with promising potential for different types of coal-REE deposits, demonstrating the viability of the method for exploration and assessment of unconventional REE resources. The method is flexible by design and, with sufficient applicable knowledge and data, can be adapted for assessing critical mineral systems in other sedimentary systems as well.

58 GEOSCIENCES↗

Quantifying the drivers of ecosystem fluxes and water potential across the soil-plant-atmosphere continuum in an arid woodland

Dryland ecosystems occupy a vast swath of the terrestrial land surface and exert a sizeable impact on the cycling of carbon and water globally. These biomes are characterized by tightly coupled carbon and water cycles that respond rapidly to transient pulses in water availability. However, there exist many mechanistic uncertainties regarding the environmental drivers of, and linkages between, plant and ecosystem processes. Thus, drylands are often poorly represented in many vegetation and land surface models. An enhanced understanding of dryland ecosystem function is limited by the lack of long-term, co-located, and frequent measurements of plant and ecosystem processes. At a piñon-juniper woodland in southeastern Utah, USA, we collected a continuous dataset of meteorological conditions, soil water potential from surface to bedrock, tree water potential, and ecosystem carbon and water fluxes from eddy covariance. We found that predawn and midday tree water potential and daily ecosystem fluxes were highly sensitive to fluctuations in soil water availability, particularly in shallower layers, and that daytime variability in atmospheric drivers only loosely controlled these processes. The strong connections between shallow soil water potential, tree water potential, and ecosystem fluxes occurred because of the dominant role of precipitation pulses in driving vegetation activity, as even small pulses of moisture stimulated shallow soil water potential, tree water potential, and evapotranspiration for between 1 and 2 weeks. Carbon fluxes (net ecosystem exchange and gross primary productivity) were sensitive to precipitation pulses for longer, up to 3 weeks. Our results highlight that improved monitoring and sensing of shallow soil moisture can greatly enhance our understanding of dryland ecosystem function. Here, a better mechanistic understanding of the impacts of precipitation pulses is also needed to improve vegetation modeling of dryland ecosystems.

54 ENVIRONMENTAL SCIENCES↗

Decoupling of particles and dissolved iron downstream of Greenlandic glacier outflows

Glaciers can be a significant and locally dominant source of iron (Fe), a biologically essential micronutrient, in high latitude coastal seas. The vast majority of this glacial Fe delivery is associated with particles, yet the speciation of the solid-phase Fe and specifically the relationships that govern exchange between particulate and dissolved Fe phases in these environments are poorly described. Here, in this work, we performed measurements of in situ dissolved Fe (dFe) along meltwater and particle plumes in three transects around Disko Bay and Ameralik Fjord (West Greenland). Measurements of dFe were combined with Fe K-edge X-ray absorption spectroscopy analysis of ~40 suspended sediment samples obtained from the same transects and from select depth profiles down to 300 m. We observed relatively constant dFe levels (4 to 10 nM for nearly all dFe measurements) across fjords with widely varying particulate Fe(II) contents (from 20 to 90% Fe(II)), indicating that dFe concentrations had little dependence on the oxidation state of Fe in the suspended sediment. Particulate Fe data were grouped by underlying bedrock geology, with suspended sediment consisting of 80-90% biotite-like Fe(II) in fjords with Precambrian shield geology and poorly-ordered Fe(III) particles (<20-30% Fe(II)) in one fjord with suspended sediments derived from tertiary basalts. Our characterization data indicated no significant change in the average Fe oxidation state and bonding environment of particles along the fjord transects, implying that Fe(II) in biotite-like coordination is not a readily labile Fe form on this spatial scale. Finally, our results suggest that dFe in these glacially-modified coastal waters is buffered at a relatively constant low nM concentration due to factors other than particle Fe mineralogy and that glacier-derived Fe phases are relatively inert on this spatial scale.

54 ENVIRONMENTAL SCIENCES↗

Solid-phase Mn speciation in suspended particles along meltwater-influenced fjords of West Greenland

Manganese (Mn) is an essential micro-nutrient that can limit or, along with iron (Fe), co-limit phytoplankton growth in the ocean. Glacier meltwater is thought to be a key source of trace metals to high latitude coastal systems, but little is known about the nature of Mn delivered to glacially-influenced fjords and adjacent coastal waters. In this work, we combine in-situ dissolved Mn (dMn) measurements of surface waters with Mn K-edge X-ray absorption spectroscopy (XAS) data of suspended particles in four fjords of West Greenland. Data were collected from transects of up to 100 km in fjords with different underlying bedrock geology from 64 to 70°N. We found that dMn concentrations generally decreased conservatively with increasing salinity (from 80 to 120 nM at salinity < 8 to < 40 nM at salinities > 25). Dissolved Fe (dFe) trends in these fjords similarly declined with increasing distance from glacier outflows (declining from > 20 nM to < 8 nM). However, the dMn/dFe ratio increased rapidly likely due to the greater stability of dMn at intermediate salinities (i.e. 10–20) compared to rapid precipitation of dFe across the salinity gradient. The XAS data indicated a widespread presence of Mn(II)-rich suspended particles near fjord surfaces, with structures akin to Mn(II)-bearing phyllosilicates. However, a distinct increase in Mn oxidation state with depth and the predominance of birnessite-like Mn(IV) oxides was observed for suspended particles in a fjord with tertiary basalt geology. The similar dMn behaviour in fjords with different suspended particle Mn speciation (i.e., Mn(II)-bearing phyllosilicates and Mn(IV)-rich birnessite) is consistent with the decoupling of dissolved and particulate Mn and suggests that dMn concentrations on the scale of these fjords are controlled primarily by dilution of a freshwater dMn source rather than exchange between dissolved and particle phases. This work provides new insights into the Mn cycle in high latitude coastal waters, where small changes in the relative availabilities of dMn, dFe and macronutrients may affect the identity of the nutrient(s) proximally limiting primary production.

58 GEOSCIENCES↗

Mineralogical, magnetic and geochemical data constrain the pathways and extent of weathering of mineralized sedimentary rocks

The oxidative weathering of sulfidic rock can profoundly impact watersheds through the resulting export of acidity and metals. Weathering leaves a record of mineral transformation, particularly involving minor redox-sensitive phases, that can inform the development of conceptual and quantitative models. In sulfidic sedimentary rocks, however, variations in depositional history, diagenesis and mineralization can change or overprint the distributions of these trace minerals, complicating the interpretation of weathering signatures. Here we show that a combination of bulk mineralogical and geochemical techniques, micrometer-resolution X-ray fluorescence microprobe analysis and rock magnetic measurements, applied to drill core samples and single weathered fractures, can provide data that enable the development of a geochemically consistent weathering model. This work focused on one watershed in the Upper Colorado River Basin sitting within the Mesaverde Formation, a sedimentary sandstone bedrock with disseminated sulfide minerals, including pyrite and sphalerite, that were introduced during diagenesis and subsequent magmatic-hydrothermal mineralization. Combined analytical methods revealed the pathways of iron (Fe), carbonate and silicate mineral weathering and showed how pH controls element retention or release from the actively weathering fractured sandstone. Drill core logging, whole rock X-ray diffraction, and geochemical measurements document the progression from unweathered rock at depth to weathered rock at the surface. X-ray microprobe analyses of a 1-cm size weathering profile along a fracture surface are consistent with the mobilization of Fe(II) and Fe(III) into acidic pore water from the dissolution of primary pyrite, Fe-sphalerite, chlorite, and minor siderite and pyrrhotite. These reactions are followed by the precipitation of secondary minerals such as of goethite and jarosite, a Fe-(oxyhydr)oxide and hydrous Fe(III) sulfate, respectively. Microscale analyses also helped explain the weathering reactions responsible for the mineralogical transformations observed in the top and most weathered section of the drill core. For example, dissolution of feldspar and chlorite neutralizes the acidity generated by Fe and sulfide mineral oxidation, oversaturating the solution in both Fe-oxides. The combination of X-ray spectromicroscopy and magnetic measurements show that the Fe(III) product is goethite, mainly present either as a coating on fracture surfaces in the actively weathering region of the core or more homogeneously contained within the unconsolidated regolith at the top of the core. Low-temperature magnetic data reveal the presence of ferromagnetic Fe-sulfide pyrrhotite that, although it occurs at trace concentrations, could provide a qualitative proxy for unweathered sulfide minerals because the loss of pyrrhotite is associated with the onset of oxidative weathering. Pyrrhotite loss and goethite formation are detectable through room-temperature magnetic coercivity changes, suggesting that rock magnetic measurements can determine weathering intensity in rock samples at many scales. In conclusion, this work contributes evidence that the weathering of sulfidic sedimentary rocks follows a geochemical pattern in which the abundance of sulfide minerals controls the generation of acidity and dissolved elements, and the pH-dependent mobility of these elements controls their export to the ground- and surface-water.

58 GEOSCIENCES↗

Comparison of fiber-optic distributed temperature sensing and high-sensitivity sensor spatial surveying of stream temperature

Measuring surface water temperature spatial variability is needed to estimate the interaction between surface water and groundwater, evaluate fish habitat and thermal inertia, and to estimate streamflow frequency and duration. Fiber optic distributed temperature sensing (FO-DTS) has been used in rivers and lakes, providing high-resolution and sensitive temperature monitoring over large temporal and spatial scales. However, in streams with cobbly or bedrock-lined streambeds and variable bathymetry, use of FO-DTS to measure temperature close to the surface water and groundwater interface can be challenging if even feasible. FO-DTS can also be costly, involve difficult installations, and require an advanced understanding of the technology, calibration, and data processing. In this study, we compared FO-DTS stream temperature survey results to an alternative temperature survey method employing a towed transect of high-resolution temperature loggers spaced at 1-m and transported in the stream along the study reach, to measure the spatial distribution of stream-water temperature in East Fork Poplar Creek near Oak Ridge, Tennessee, USA. We assessed the applicability and limitations of the two methods, and quantitatively compared in-situ temperature survey results measured simultaneously with each method. Regression results showed strong temporal and spatial correlation between the two methods. Differences were only elevated near the stream banks in areas that were coincident with correlation slope deviations from unity, which was attributed to shallower water and lower data density. Kriging standard errors were also low at channel center with minor increases near the stream banks. Furthermore, the results suggested that the array of the individual temperature sensors can provide a practical alternative to FO-DTS for thermal characterization of surface water, providing slightly lower spatial and temporal resolution, but with higher accuracy of temperature measurement, with greater simplicity, and with a broader range of conditions where it may be applied.

54 ENVIRONMENTAL SCIENCES↗

Dynamic coevolution of baseflow and multiscale groundwater flow system during prolonged droughts

Field and numerical studies suggest that baseflow is composed of waters from a spectrum of groundwater flow paths termed the Groundwater Flow System (GWFS) – from shallow hillslope contributions to watershed-scale deep circulation originating in headwaters and discharging into lowland rivers. Here, we explore the evolution of the GWFS under prolonged droughts to understand its dynamics and multiscale nature, and to elucidate its role in baseflow generation and recession at the watershed scale. In this work, we consider three drought scenarios of varying severity and simulate groundwater flow in a 2-D cross-section of an idealized watershed with deep permeable bedrock, tracking the evolution of flow paths, baseflow, and residence times during the recession process. We find that baseflow generation at different drainage stages, and within different subwatersheds, is influenced distinctly by flow paths of different scales, depending on the relative strength of the flow paths and the position of the subwatersheds relative to the recharge/discharge zones of the deeper watershed-scale groundwater circulation. Despite having the same local relief, geology, and climate, baseflow from each subwatershed has a distinct recession behavior and time-dependent residence time distribution. Also, the hydraulic and transport characteristics of baseflow generation co-evolve and are strongly affected by the connection state of the water table to subwatersheds. These findings suggest that asynchrony and dissimilarity of baseflow generation from hillslopes under the impact of the watershed-scale groundwater flow, and interactions with local-scale and intermediate-scale groundwater flow, must be taken into account when interpreting baseflow recession data and building conceptual baseflow models at the watershed scale.

54 ENVIRONMENTAL SCIENCES↗

Cosmogenic 10Be constraints on deglacial snowline rise in the Southern Alps, New Zealand

We report geochronological dating of glacial landforms, such as terminal and lateral moraines, is useful for determining the extent and timing of past glaciation and for reconstructing the magnitude and rate of past climate changes. In the Southern Alps of New Zealand, well-dated glacial geomorphological records constrain the last glacial cycle across much of the Waitaki River basin (e.g. Ōhau, Pukaki, Tekapo) but its southern sector such as the Ahuriri River valley remains comparatively unconstrained. Recently, there has been debate on the scale and rapidity of mountain glacier retreat during the last glacial termination, particularly the 20–17 ka period in New Zealand. Missing from this debate is well-constrained equilibrium-line altitude (ELA) and associated temperature reconstructions, particularly over the period around 17 ka, which can help us to develop a more complete picture of how past temperature changes drove glacier retreat. Here we report the first glacial chronology dataset from the Last Glacial Maximum (LGM) and subsequent deglaciation from the Ahuriri River valley, Southern Alps, New Zealand (44°23'54"S, 169°39'48"E) based on 38 beryllium-10 ( 10 Be) surface-exposure ages from terminal moraine systems and glaciated bedrock situated at the lower and middle sections of the valley. Our results show that the former Ahuriri Glacier reached its maximum extent at 19.8 ± 0.3 ka, which coincides with the global Last Glacial Maximum. By 16.7 ± 0.3 ka, the glacier had retreat ~18 km up-valley suggesting at least ~43% glacier-length loss relative to its full LGM extent. This deglaciation was accompanied by the formation of a shallow proglacial lake. Using the accumulation area ratio (AAR) method, we estimate that the ELA was lower than present by ~880 m (~1120 m a.s.l.) at 19.8 ± 0.3 ka, and ~770 m lower (~1230 m a.s.l.) at 16.7 ± 0.3 ka. Applying an estimate for temperature lapse rate, this ELA anomaly implies that local air temperature was 5 ± 1 °C colder than present (1981–2010) at 19.8 ± 0.3 ka, while it was 4.4 ± 0.9 °C colder at 16.7 ± 0.3 ka, assuming no change in precipitation. The substantial glacier retreat in response to a relatively small accompanying increases in ELA (110 m) and temperature (0.6 °C) may have been a result of the high glacier-length sensitivity of this glacier system due to its low gradient of former ice surface. Our low warming estimate differs markedly from other deglaciation studies, specifically from Rakaia River valley, which reports a much larger temperature increase at the onset of the last deglaciation. This precisely-dated moraine record along with reconstructed ELA as proxies for atmospheric conditions, provides new insight into post LGM glacier behaviour and climate conditions in New Zealand.

58 GEOSCIENCES↗

Quantification of manganese for ChemCam Mars and laboratory spectra using a multivariate model

In this work, we report a new calibration model for manganese using the laser-induced breakdown spectroscopy instrument that is part of the ChemCam instrument suite onboard the NASA Curiosity rover. The model has been trained using an expanded set of 523 manganese-bearing rock, mineral, metal ore, and synthetic standards. The optimal calibration model uses the Partial Least Squares (PLS) and Least Absolute Shrinkage and Selection Operator (LASSO) multivariate techniques, with a novel “double blending” technique. We determined the detection limit for manganese is 82 ppm using a method blank procedure and is possibly as low as 27 ppm based on visual inspection of the spectra. Based on a representative test set consisting of measurements on 93 standards, the double blended multivariate model shows a Root Mean Squared Error of Prediction (RMSEP) accuracy of 1.39 wt% MnO for the full blended model. Employing a local RMSEP estimate where the model performance is evaluated based on nearby test samples, the accuracy is 0.03 wt% at the quantification limit (0.05 wt% MnO), 0.4 wt% accuracy at 1.0 wt% MnO, and 4.4 wt% accuracy at 100 wt% MnO. Precision is estimated using the standard deviation of the test set measurements, and is ±0.01 wt% MnO at the quantification limit, ±0.09 wt% MnO at 1.0 wt% MnO, and ± 2.1 wt% MnO at 100 wt% MnO (all 1 standard deviation). This new calibration is important for understanding the variation of manganese in the bedrock with the Curiosity rover on Mars, which provides insight into past redox conditions on Mars.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improving ChemCam LIBS long-distance elemental compositions using empirical abundance trends

The ChemCam instrument on the Curiosity rover provides chemical compositions of Martian rocks and soils using remote laser-induced breakdown spectroscopy (LIBS). The elemental calibration is stable as a function of distance for Ti, Fe, Mg, and Ca. The calibration shows small, systematically increasing abundance trends as a function of distance for Al, Na, K, and to some extent, Si. The distance effect is known to be due to a dependence with distance on the relative strengths of atomic transition lines. Emission lines representing transitions from relatively low energy levels remain intense at longer distances while emission lines representing transitions from higher energy levels decrease in intensity more rapidly as a function of distance. The multivariate algorithms used to determine elemental compositions rely on a large number of emission lines in many cases, so rather than trying to correct all emission lines, a study was made of the predicted compositions as a function of distance, in order to determine an empirical correction. Abundance trends can be well approximated by a linear trend with distance within the ranges of abundances and distances observed up to ~6 m. Data from 11 distinct geological members and data groups of the Murray formation in Gale crater, Mars, were used to form the model, selecting the members and data groups yielding the best statistics. The model was tested using data from several targets observed from two different distances, and using data from the Kimberley formation, the composition of which is significantly different from the Murray formation, showing that the model works on other compositions beyond those used to build the model. For long-distance observations up to ~6 m, corrections can be made back to an equivalent composition at the median distance of ChemCam observations (2.6 m). Finally, the model has been validated up to 6.2 m, although ChemCam is able to observe bedrock targets to >7 m, and iron meteorites to distances of >9 m.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterizing the diverse hydrogeology underlying rivers and estuaries using new floating transient electromagnetic methodology

We report the hydrogeology below large surface water features such as rivers and estuaries is universally under-informed at the long reach to basin scales (tens of km+). This challenge inhibits the accurate modeling of fresh/saline groundwater interfaces and groundwater/surface water exchange patterns at management-relevant spatial extents. Here we introduce a towed, floating transient electromagnetic (TEM) system (i.e. FloaTEM) for rapid (up to 15 km/h) high resolution electrical mapping of the subsurface below large water bodies to depths often a factor of 10 greater than other towed instruments. The novel FloaTEM system is demonstrated at a range of diverse 4th through 6th-order riverine settings across the United States including 1) the Farmington River, near Hartford, Connecticut; 2) the Upper Delaware River near Barryville, New York; 3) the Tallahatchie River near Shellmound, Mississippi; and, 4) the Eel River estuary, on Cape Cod, near Falmouth, Massachusetts. Airborne frequency-domain electromagnetic and land-based towed TEM data are also compared at the Tallahatchie River site, and streambed geologic scenarios are explored with forward modeling. A range of geologic structures and pore water salinity interfaces were identified. Process-based interpretation of the case study data indicated FloaTEM can resolve varied sediment-water interface materials, such as the accumulation of fines at the bottom of a reservoir and permeable sand/gravel riverbed sediments that focus groundwater discharge. Bedrock layers were mapped at several sites, and aquifer confining units were defined at comparable resolution to airborne methods. Terrestrial fresh groundwater discharge with flowpaths extending hundreds of meters from shore was also imaged below the Eel River estuary, improving on previous hydrogeological characterizations of that nutrient-rich coastal exchange zone. In summary, the novel FloaTEM system fills a critical gap in our ability to characterize the hydrogeology below surface water features and will support more accurate prediction of groundwater/surface water exchange dynamics and fresh-saline groundwater interfaces.

54 ENVIRONMENTAL SCIENCES↗

Intensity measure adequacy assessment for nonlinear site response using Information Theory

Nonlinear site response modeling is a crucial aspect of Probabilistic Seismic Hazard Analysis. Site amplification models routinely rely on a rock intensity measure to characterize the strength of the bedrock motion. However, the adequacy of such intensity measures towards predicting amplifications across the oscillator period range has not been investigated in the literature. This paper analyzes the adequacy of rock intensity measures using state of the art criterion established in Performance-Based Earthquake Engineering and techniques from Information Theory. The efficiency and the sufficiency of several rock intensity measure are assessed. It was found that spectral accelerations at low periods usually are adequate for predicting amplifications across the period range. This supports the current practice of using Peak Ground Acceleration in Ground Motion Models. However, for extremely soft sites, which demonstrate nonlinear effects well into the period range, it is better practice to ensure that amplification and spectral acceleration share the same oscillator period. Lastly, for predicting the peak shear strain (an important parameter that controls nonlinearity of site response), Peak Ground Velocity is generally adequate, and this conclusion is in line with the definition of proxy shear strain.

42 ENGINEERING↗