Atmospheric forcing dominates winter Barents-Kara sea ice variability on interannual to decadal time scales.

The last two decades have seen a dramatic decline and strong year-to-year variability in Arctic winter sea ice, especially in the Barents-Kara Sea (BKS), changes that have been linked to extreme midlatitude weather and climate. It has been suggested that these changes in winter sea ice arise largely from a combined effect of oceanic and atmospheric processes, but the relative importance of these processes is not well established. Here, we explore the role of atmospheric circulation patterns on BKS winter sea ice variability and trends using observations and climate model simulations. We find that BKS winter sea ice variability is primarily driven by a strong anticyclonic anomaly over the region, which explains more than 50% of the interannual variability in BKS sea-ice concentration (SIC). Recent intensification of the anticyclonic anomaly has warmed and moistened the lower atmosphere in the BKS by poleward transport of moist-static energy and local processes, resulting in an increase in downwelling longwave radiation. Our results demonstrate that the observed BKS winter sea-ice variability is primarily driven by atmospheric, rather than oceanic, processes and suggest a persistent role of atmospheric forcing in future Arctic winter sea ice loss.

A hydrogen isoscape for tracing the migration of herbivorous lepidopterans across the Afro-Palearctic range.

RATIONALE: Many insect species undertake multigenerational migrations in the Afro-tropical and Palearctic ranges, and understanding their migratory connectivity remains challenging due to their small size, short life span and large population sizes. Hydrogen isotopes (δ2 H) can be used to reconstruct the movement of dispersing or migrating insects, but applying δ2 H for provenance requires a robust isotope baseline map (i.e. isoscape) for the Afro-Palearctic. METHODS: We analyzed the δ2 H in the wings (δ2 Hwing ) of 142 resident butterflies from 56 sites across the Afro-Palearctic. The δ2 Hwing values were compared to the predicted local growing-season precipitation δ2 H values (δ2 HGSP ) using a linear regression model to develop an insect wing δ2 H isoscape. We used multivariate linear mixed models and high-resolution and time-specific remote sensing climate and environmental data to explore the controls of the residual δ2 Hwing variability. RESULTS: A strong linear relationship was found between δ2 Hwing and δ2 HGSP values (r2 = 0.53). The resulting isoscape showed strong patterns across the Palearctic but limited variation and high uncertainty for the Afro-tropics. Positive residuals of this relationship were correlated with dry conditions for the month preceding sampling whereas negative residuals were correlated with more wet days for the month preceding sampling. High intra-site δ2 Hwing variance was associated with lower relative humidity for the month preceding sampling and higher elevation. CONCLUSION: The δ2 Hwing isoscape is applicable for tracing herbivorous lepidopteran insects that migrate across the Afro-Palearctic range but has limited geolocation potential in the Afro-tropics. The spatial analysis of uncertainty using high-resolution climatic data demonstrated that many African regions with highly variable evaporation rates and relative humidity have δ2 Hwing values that are less related to δ2 HGSP values. Increasing geolocation precision will require new modeling approaches using more time-specific environmental data and/or independent geolocation tools.

Climate impacts on source contributions and evaporation to flow in the Snake River Basin using surface water isoscapes (δ2H and δ18O).

Rising global temperatures are expected to decrease the precipitation amount that falls as snow, causing greater risk of water scarcity, groundwater overdraft, and fire in areas that rely on mountain snowpack for their water supply. Streamflow in large river basins varies with the amount, timing, and type of precipitation, evapotranspiration, and drainage properties of watersheds; however, these controls vary in time and space making it difficult to identify the areas contributing most to flow and when. In this study, we separate the evaporative influences from source values of water isotopes from the Snake River Basin in the western United States (US) to relate source area to flow dynamics. We developed isoscapes (δ2H and δ18O) for the basin and found that isotopic composition of surface water in small watersheds is primarily controlled by longitude, latitude, and elevation. To examine temporal variability in source contributions to flow, we present a six-year record of Snake River water isotopes from King Hill, Idaho after removing evaporative influences. During periods of low flow, source water values were isotopically lighter indicating a larger contribution to flow from surface waters in the highest elevation, eastern portion of the basin. River evaporation increases were evident during summer likely reflecting climate, changing water availability, and management strategies within the basin. Our findings present a potential tool for identifying critical portions of basins contributing to river flow as climate fluctuations alter flow dynamics. This tool can be applied in other continental-interior basins where evaporation may obscure source water isotopic signatures.

The Soil Water Isotope Storage System (SWISS): An integrated soil water vapor sampling and multiport storage system for stable isotope geochemistry.

RATIONALE: Soil water stable isotopes are a powerful tool for tracking interactions among the hydrosphere, geosphere, atmosphere, and biosphere. The challenges associated with creating high-temporal-resolution soil water stable isotope datasets from a diversity of sites have limited the utility of stable isotope geochemistry in addressing a range of complex problems. A device that can enable further development of high-temporal-resolution soil water isotope datasets that are created with minimal soil profile disruption from remote sites would greatly expand the utility of soil water stable isotope analyses. METHODS: We designed a method for sampling and storing soil water vapor for stable isotope analysis that leverages recent advances in soil water sampling strategies. Here, we test the reliability of the storage system by introducing water vapor of known oxygen and hydrogen isotopic composition into the storage system, storing the water vapor for a predetermined amount of time, and then measuring the stable isotope composition of the vapor after the storage period. RESULTS: We demonstrate that water vapor stored in our flasks reliably maintains its isotope composition within overall system uncertainty (±0.5‰ for δ18 O values and ±2.4‰ for δ2 H values) for up to 30 days. CONCLUSIONS: This method has the potential to enable the collection of high-temporal-resolution soil water isotope datasets from remote sites that are not accessed daily in a time- and cost-effective manner. All the components used in the system can be easily controlled using open-source microcontrollers, which will be used in the future to automate sampling routines for remote field deployment. The system is designed to be an open-source tool for use by other researchers.

Pacific North American circulation pattern links external forcing and North American hydroclimatic change over the past millennium.

Land and sea surface temperatures, precipitation, and storm tracks in North America and the North Pacific are controlled to a large degree by atmospheric variability associated with the Pacific North American (PNA) pattern. The modern instrumental record indicates a trend toward a positive PNA phase in recent decades, which has led to accelerated warming and snowpack decline in northwestern North America. The brevity of the instrumental record, however, limits our understanding of long-term PNA variability and its directional or cyclic patterns. Here we develop a 937-y-long reconstruction of the winter PNA based on a network of annually resolved tree-ring proxy records across North America. The reconstruction is consistent with previous regional records in suggesting that the recent persistent positive PNA pattern is unprecedented over the past millennium, but documents patterns of decadal-scale variability that contrast with previous reconstructions. Our reconstruction shows that PNA has been strongly and consistently correlated with sea surface temperature variation, solar irradiance, and volcanic forcing over the period of record, and played a significant role in translating these forcings into decadal-to-multidecadal hydroclimate variability over North America. Climate model ensembles show limited power to predict multidecadal variation in PNA over the period of our record, raising questions about their potential to project future hydroclimatic change modulated by this circulation pattern.

Mechanistic model predicts tissue-environment relationships and trophic shifts in animal hydrogen and oxygen isotope ratios.

Statistical regression relationships between the hydrogen (H) and oxygen (O) isotope ratios (δ2H and δ18O, respectively) of animal organic tissues and those of environmental water have been widely used to reconstruct animal movements, paleoenvironments, and diet and trophic relationships. In natural populations, however, tissue-environment isotopic relationships are highly variable among animal types and geographic regions. No systematic understanding of the origin(s) of this variability currently exists, clouding the interpretation of isotope data. Here, we present and apply a model, based on fundamental metabolic relationships, to test the sensitivity of consumer tissue H and O isotope ratios, and thus tissue-environment relationships, to basic physiological, behavioral, and environmental parameters. We then simulate patterns in consumer tissue isotopic compositions under several 'real-world' scenarios, demonstrating that the new model can reproduce-and potentially explain-previously observed patterns in consumer tissue H isotope ratios, including between-continent differences in feather-precipitation relationships and 2H-enrichment with trophic level across species. The model makes several fundamental predictions about the organic O isotope system, which constitute hypotheses for future testing as new data are obtained. By highlighting potential sources of variability and bias in tissue-environment relationships and establishing a framework within which such effects can be predicted, these results should advance the application of H and O isotopes in ecological, paleoecological, and forensic research.

Inferring the source of evaporated waters using stable H and O isotopes.

Stable isotope ratios of H and O are widely used to identify the source of water, e.g., in aquifers, river runoff, soils, plant xylem, and plant-based beverages. In situations where the sampled water is partially evaporated, its isotope values will have evolved along an evaporation line (EL) in δ2H/δ18O space, and back-correction along the EL to its intersection with a meteoric water line (MWL) has been used to estimate the source water's isotope ratios. Here, we review the theory underlying isotopic estimation of source water for evaporated samples (iSWE). We note potential for bias from a commonly used regression-based approach for EL slope estimation and suggest that a model-based approach may be preferable if assumptions of the regression approach are not valid. We then introduce a mathematical framework that eliminates the need to explicitly estimate the EL-MWL intersection, simplifying iSWE analysis and facilitating more rigorous uncertainty estimation. We apply this approach to data from the US EPA's 2007 National Lakes Assessment. We find that data for most lakes are consistent with a water source similar to annual runoff, estimated from monthly precipitation and evaporation within the lake basin. Strong evidence for both summer- and winter-biased sources exists, however, with winter bias pervasive in most snow-prone regions. The new analytical framework should improve the rigor of iSWE in ecohydrology and related sciences, and our initial results from US lakes suggest that previous interpretations of lakes as unbiased isotope integrators may only be valid in certain climate regimes.

Applying the principles of isotope analysis in plant and animal ecology to forensic science in the Americas.

The heart of forensic science is application of the scientific method and analytical approaches to answer questions central to solving a crime: Who, What, When, Where, and How. Forensic practitioners use fundamentals of chemistry and physics to examine evidence and infer its origin. In this regard, ecological researchers have had a significant impact on forensic science through the development and application of a specialized measurement technique-isotope analysis-for examining evidence. Here, we review the utility of isotope analysis in forensic settings from an ecological perspective, concentrating on work from the Americas completed within the last three decades. Our primary focus is on combining plant and animal physiological models with isotope analyses for source inference. Examples of the forensic application of isotopes-including stable isotopes, radiogenic isotopes, and radioisotopes-span from cotton used in counterfeit bills to anthrax shipped through the U.S. Postal Service and from beer adulterated with cheap adjuncts to human remains discovered in shallow graves. Recent methodological developments and the generation of isotope landscapes, or isoscapes, for data interpretation promise that isotope analysis will be a useful tool in ecological and forensic studies for decades to come.

Vapor hydrogen and oxygen isotopes reflect water of combustion in the urban atmosphere.

Anthropogenic modification of the water cycle involves a diversity of processes, many of which have been studied intensively using models and observations. Effective tools for measuring the contribution and fate of combustion-derived water vapor in the atmosphere are lacking, however, and this flux has received relatively little attention. We provide theoretical estimates and a first set of measurements demonstrating that water of combustion is characterized by a distinctive combination of H and O isotope ratios. We show that during periods of relatively low humidity and/or atmospheric stagnation, this isotopic signature can be used to quantify the concentration of water of combustion in the atmospheric boundary layer over Salt Lake City. Combustion-derived vapor concentrations vary between periods of atmospheric stratification and mixing, both on multiday and diurnal timescales, and respond over periods of hours to variations in surface emissions. Our estimates suggest that up to 13% of the boundary layer vapor during the period of study was derived from combustion sources, and both the temporal pattern and magnitude of this contribution were closely reproduced by an independent atmospheric model forced with a fossil fuel emissions data product. Our findings suggest potential for water vapor isotope ratio measurements to be used in conjunction with other tracers to refine the apportionment of urban emissions, and imply that water vapor emissions associated with combustion may be a significant component of the water budget of the urban boundary layer, with potential implications for urban climate, ecohydrology, and photochemistry.

Persistent Urban Influence on Surface Water Quality via Impacted Groundwater.

Growing urban environments stress hydrologic systems and impact downstream water quality. We examined a third-order catchment that transitions from an undisturbed mountain environment into urban Salt Lake City, Utah. We performed synoptic surveys during a range of seasonal baseflow conditions and utilized multiple lines of evidence to identify mechanisms by which urbanization impacts water quality. Surface water chemistry did not change appreciably until several kilometers into the urban environment, where concentrations of solutes such as chloride and nitrate increase quickly in a gaining reach. Groundwater springs discharging in this gaining system demonstrate the role of contaminated baseflow from an aquifer in driving stream chemistry. Hydrometric and hydrochemical observations were used to estimate that the aquifer contains approximately 18% water sourced from the urban area. The carbon and nitrogen dynamics indicated the urban aquifer also serves as a biogeochemical reactor. The evidence of surface water-groundwater exchange on a spatial scale of kilometers and time scale of months to years suggests a need to evolve the hydrologic model of anthropogenic impacts to urban water quality to include exchange with the subsurface. This has implications on the space and time scales of water quality mitigation efforts.

Stream Nitrogen Inputs Reflect Groundwater Across a Snowmelt-Dominated Montane to Urban Watershed.

Snowmelt dominates the hydrograph of many temperate montane streams, yet little work has characterized how streamwater sources and nitrogen (N) dynamics vary across wildland to urban land use gradients in these watersheds. Across a third-order catchment in Salt Lake City, Utah, we asked where and when groundwater vs shallow surface water inputs controlled stream discharge and N dynamics. Stream water isotopes (δ(2)H and δ(18)O) reflected a consistent snowmelt water source during baseflow. Near-chemostatic relationships between conservative ions and discharge implied that groundwater dominated discharge year-round across the montane and urban sites, challenging the conceptual emphasis on direct stormwater inputs to urban streams. Stream and groundwater NO3(-) concentrations remained consistently low during snowmelt and baseflow in most montane and urban stream reaches, indicating effective subsurface N retention or denitrification and minimal impact of fertilizer or deposition N sources. Rather, NO3(-) concentrations increased 50-fold following urban groundwater inputs, showing that subsurface flow paths potentially impact nutrient loading more than surficial land use. Isotopic composition of H2O and NO3(-) suggested that snowmelt-derived urban groundwater intercepted NO3(-) from leaking sewers. Sewer maintenance could potentially mitigate hotspots of stream N inputs at mountain/valley transitions, which have been largely overlooked in semiarid urban ecosystems.

Determining origin in a migratory marine vertebrate: a novel method to integrate stable isotopes and satellite tracking.

Stable isotope analysis is a useful tool to track animal movements in both terrestrial and marine environments. These intrinsic markers are assimilated through the diet and may exhibit spatial gradients as a result of biogeochemical processes at the base of the food web. In the marine environment, maps to predict the spatial distribution of stable isotopes are limited, and thus determining geographic origin has been reliant upon integrating satellite telemetry and stable isotope data. Migratory sea turtles regularly move between foraging and reproductive areas. Whereas most nesting populations can be easily accessed and regularly monitored, little is known about the demographic trends in foraging populations. The purpose of the present study was to examine migration patterns of loggerhead nesting aggregations in the Gulf of Mexico (GoM), where sea turtles have been historically understudied. Two methods of geographic assignment using stable isotope values in known-origin samples from satellite telemetry were compared: (1) a nominal approach through discriminant analysis and (2) a novel continuous-surface approach using bivariate carbon and nitrogen isoscapes (isotopic landscapes) developed for this study. Tissue samples for stable isotope analysis were obtained from 60 satellite-tracked individuals at five nesting beaches within the GoM. Both methodological approaches for assignment resulted in high accuracy of foraging area determination, though each has advantages and disadvantages. The nominal approach is more appropriate when defined boundaries are necessary, but up to 42% of the individuals could not be considered in this approach. All individuals can be included in the continuous-surface approach, and individual results can be aggregated to identify geographic hotspots of foraging area use, though the accuracy rate was lower than nominal assignment. The methodological validation provides a foundation for future sea turtle studies in the region to inexpensively determine geographic origin for large numbers of untracked individuals. Regular monitoring of sea turtle nesting aggregations with stable isotope sampling can be used to fill critical data gaps regarding habitat use and migration patterns. Probabilistic assignment to origin with isoscapes has not been previously used in the marine environment, but the methods presented here could also be applied to other migratory marine species.

Effects of particle size, storage conditions, and chemical pretreatments on carbon and oxygen isotopic measurements of modern tooth enamel.

Isotopic analysis of human tooth enamel can provide life history information useful in forensic identification. These applications depend on the availability of reference data documenting isotopic values for individuals with known life history and on the comparability of data from reference and case work samples. Here we build on previous methodological research, which has largely focused on paleontological and archaeological samples, and conduct experiments using enamel from modern human teeth targeting three sample preparation variables (sample particle size, storage conditions, and chemical pretreatments). Our results suggest that differences in particle size affect the efficiency of sample reactions during pretreatment and analysis, with coarse particles giving reduced loss of enamel carbonate during acid pretreatments but producing slightly higher oxygen isotope values than fine particles during analysis. Data for samples stored in dry and ambient environments following pretreatment were indistinguishable, suggesting no exchange of oxygen between samples and ambient water vapor. Finally, chemical pretreatments with a range of commonly used reactants and conditions showed a pervasive, moderate oxygen isotope shift associated with acetic acid treatment, which may be caused by exchange of enamel hydroxyl groups with reagents or rinse waters. Collectively, the results emphasize the importance of methodological standardization to improve comparability and reduce potential for bias in the forensic application of tooth enamel isotope data.

Oxygen Isotope and Fluorine Impurity Signatures during the Conversion of Uranium Ore Concentrates to Nuclear Fuel.

Within the front end of the nuclear fuel cycle, many processes impart forensic signatures. Oxygen-stable isotopes (δ18O values) of uranium-bearing materials have been theorized to provide the processing and geolocational signatures of interdicted materials. However, this signature has been minimally utilized due to a limited understanding of how oxygen isotopes are influenced during uranium processing. This study explores oxygen isotope exchange and fractionation between magnesium diuranate (MDU), ammonium diuranate (ADU), and uranyl fluoride (UO2F2) with steam (water vapor) during their reduction to UOx. The MDU was precipitated from two water sources, one enriched and one depleted in 18O. The UO2F2 was precipitated from a single water source and either directly reduced or converted to ADU prior to reduction. All MDU, ADU, and UO2F2 were reduced to UOx in a 10% hydrogen/90% nitrogen atmosphere that was dry or included steam. Powder X-ray diffraction (p-XRD) was used to verify the composition of materials after reduction as mixtures of primarily U3O8, U4O9, and UO2 with trace magnesium and fluorine phases in UOx from MDU and UO2F2, respectively. The bulk oxygen isotope composition of UOx from MDU was analyzed using fluorination to remove the lattice-bound oxygen, and then O2 was subsequently analyzed with isotope ratio mass spectrometry (IRMS). The oxygen isotope compositions of the ADU, UO2F2, and the resulting UOx were analyzed by large geometry secondary ion mass spectrometry (LG-SIMS). When reduced with steam, the MDU, ADU, and UO2F2 experienced significant oxygen isotope exchange, and the resulting δ18O values of UOx approached the values of the steam. When reduced without steam, the δ18O values of converted ADU, U3O8, and UOx products remained similar to those of the UO2F2 starting material. LG-SIMS isotope mapping of F impurity abundances and distributions showed that direct steam-assisted reduction from UO2F2 significantly removed F impurities while dry reduction from UO2F2 led to the formation of UOx that was enhanced in F impurities. In addition, when UO2F2 was processed via precipitation to ADU and calcination to U3O8, F impurities were largely removed, and reductions to UOx with and without steam each had low F impurities. Overall, these findings show promise for combining multiple signatures to predict the process history during the conversion of uranium ore concentrates to nuclear fuel.

Effects of chemical pretreatments on the hydrogen isotope composition of 2:1 clay minerals.

RATIONALE: Clays are a commonly occurring authigenic mineral within soils, and the hydrogen isotope ratios of their structural hydroxyl groups can serve as a useful environmental proxy. Chemical and physical treatments are necessary to eliminate contaminating materials from clays, but they have the potential to alter their isotopic composition. METHODS: Several pure, commonly occurring 2:1 clay mineralogies were treated with typical chemical procedures for the removal of carbonates, organic matter, and amorphous hydroxides. Samples were heated under vacuum to remove the adsorbed and interlayer water that occurs universally in natural clays. The samples were then analyzed for hydrogen content and isotope ratios through thermal conversion elemental analyzer/isotope ratio mass spectrometry (TC-EA/IRMS). RESULTS: No effects on hydrogen composition were found for most of the analyzed mineralogies. Smectite samples showed significant alteration following treatments for carbonate and organic matter. In addition, the smectites showed variable levels of hydrogen exchange with isotopically labeled H2 O. CONCLUSIONS: Smectites show significant and highly variable alteration following common chemical treatments, and analysis for paleoclimate reconstruction is problematic. A minor amount of H isotope exchange is likely at temperatures sufficient to remove adsorbed water, and efforts must be made to minimize and quantify this exchange during analyses of clay samples.

Toward a Cenozoic history of atmospheric CO2.

The geological record encodes the relationship between climate and atmospheric carbon dioxide (CO2) over long and short timescales, as well as potential drivers of evolutionary transitions. However, reconstructing CO2 beyond direct measurements requires the use of paleoproxies and herein lies the challenge, as proxies differ in their assumptions, degree of understanding, and even reconstructed values. In this study, we critically evaluated, categorized, and integrated available proxies to create a high-fidelity and transparently constructed atmospheric CO2 record spanning the past 66 million years. This newly constructed record provides clearer evidence for higher Earth system sensitivity in the past and for the role of CO2 thresholds in biological and cryosphere evolution.

A 3-D groundwater isoscape of the contiguous USA for forensic and water resource science.

A wide range of hydrological, ecological, environmental, and forensic science applications rely on predictive "isoscape" maps to provide estimates of the hydrogen or oxygen isotopic compositions of environmental water sources. Many water isoscapes have been developed, but few studies have produced isoscapes specifically representing groundwaters. None of these have represented distinct subsurface layers and isotopic variations across them. Here we compiled >6 million well completion records and >27,000 groundwater isotope datapoints to develop a space- and depth-explicit water isoscape for the contiguous United States. This 3-dimensional model shows that vertical isotopic heterogeneity in the subsurface is substantial in some parts of the country and that groundwater isotope delta values often differ from those of coincident precipitation or surface water resources; many of these patterns can be explained by established hydrological and hydrogeological mechanisms. We validate the groundwater isoscape against an independent data set of tap water values and show that the model accurately predicts tap water values in communities known to use groundwater resources. This new approach represents a foundation for further developments and the resulting isoscape should provide improved predictions of water isotope values in systems where groundwater is a known or potential water source.

Multi-isotopes in human hair: A tool to initiate cross-border collaboration in international cold-cases.

Unidentified human remains have historically been investigated nationally by law enforcement authorities. However, this approach is outdated in a globalized world with rapid transportation means, where humans easily move long distances across borders. Cross-border cooperation in solving cold-cases is rare due to political, administrative or technical challenges. It is fundamental to develop new tools to provide rapid and cost-effective leads for international cooperation. In this work, we demonstrate that isotopic measurements are effective screening tools to help identify cold-cases with potential international ramifications. We first complete existing databases of hydrogen and sulfur isotopes in human hair from residents across North America by compiling or analyzing hair from Canada, the United States (US) and Mexico. Using these databases, we develop maps predicting isotope variations in human hair across North America. We demonstrate that both δ2H and δ34S values of human hair are highly predictable and display strong spatial patterns. Multi-isotope analysis combined with dual δ2H and δ34S geographic probability maps provide evidence for international travel in two case studies. In the first, we demonstrate that multi-isotope analysis in bulk hair of deceased border crossers found in the US, close to the Mexico-US border, help trace their last place of residence or travel back to specific regions of Mexico. These findings were validated by the subsequent identification of these individuals through the Pima County Office of the Medical Examiner in Tucson, Arizona. In the second case study, we demonstrate that sequential multi-isotope analysis along the hair strands of an unidentified individual found in Canada provides detailed insights into the international mobility of this individual during the last year of life. In both cases, isotope data provide strong leads towards international travel.