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While plant δ15 N values have been applied to understand nitrogen (N) dynamics, uncertainties regarding intraspecific and temporal variability currently limit their application. We used a 28 yr record of δ15 N values from two Mojave Desert populations of Encelia farinosa to clarify sources of population-level variability. We leveraged > 3500 foliar δ15 N observations collected alongside structural, physiological, and climatic data to identify plant and environmental contributors to δ15 N values. Additional sampling of soils, roots, stems, and leaves enabled assessment of the distribution of soil N content and δ15 N, intra-plant fractionations, and relationships between soil and plant δ15 N values. We observed extensive within-population variability in foliar δ15 N values and found plant age and foliar %N to be the strongest predictors of individual δ15 N values. There were consistent differences between root, stem, and leaf δ15 N values (spanning c. 3‰), but plant and bulk soil δ15 N values were unrelated. Plant-level variables played a strong role in influencing foliar δ15 N values, and interannual relationships between climate and δ15 N values were counter to previously recognized spatial patterns. This long-term record provides insights regarding the interpretation of δ15 N values that were not available from previous large-scale syntheses, broadly enabling more effective application of foliar δ15 N values.

Plants make leaf-level trade-offs between photosynthetic carbon assimilation and water loss, and the optimal balance between the two is dependent, in part, on water availability. “Conservative” water-use strategies, in which minimizing water loss is prioritized over assimilating carbon, tend to be favored in arid environments, while “aggressive” water-use strategies, in which carbon assimilation is prioritized over water conservation, are often favored in mesic environments. When derived from foliar carbon isotope ratios, intrinsic water-use efficiency (iWUE) serves as a seasonally integrated indicator of the balance of carbon assimilation to water loss at the leaf level. Here, we used a multi-decadal record of annual iWUE, growth, and flowering from a single population of Encelia farinosa in the Mojave Desert to evaluate the effect of iWUE on plant performance across interannual fluctuations in water availability. We identified substantial variability in iWUE among individuals and found that iWUE interacted with water availability to significantly influence growth and flowering. However, the relationships between iWUE, water availability, and plant performance did not universally suggest that “conservative” water-use strategies were advantageous in dry years or that “aggressive” strategies were advantageous in wet years. iWUE was positively related to the odds of growth regardless of water availability and to the odds of flowering in dry years, but negatively related to growth rates in dry years. In addition, we found that leaf nitrogen content affected interannual plant performance and that an individual’s iWUE plasticity in response to fluctuations in aridity was negatively related to early life drought survival and growth.

Significance As Americans, our diets have among the highest protein consumption rates and we are experiencing increased rates of obesity across all age groups. Here we reveal that consumption of corn-fed animal proteins are more common among lower socioeconomic status populations, which places these populations at a potentially greater risk for increased health problems., Carbon and nitrogen isotope ratios in hair sampled from 65 communities across the central and intermountain regions of the United States and more intensively throughout 29 ZIP codes in the Salt Lake Valley, Utah, revealed a dietary divergence related to socioeconomic status as measured by cost of living, household income, and adjusted gross income. Corn-fed, animal-derived proteins were more common in the diets of lower socioeconomic status populations than were plant-derived proteins, with individual estimates of animal-derived protein diets as high as 75%; United States towns and cities averaged 57%. Similar patterns were seen across the socioeconomic status spectrum in the Salt Lake Valley. It is likely that corn-fed animal proteins were associated with concentrated animal-feeding operations, a common practice for industrial animal production in the United States today. Given recent studies highlighting the negative impacts of animal-derived proteins in our diets, hair carbon isotope ratios could provide an approach for scaling assessments of animal-sourced foods and health risks in communities across the United States.

While tree rings have enabled interannual examination of the influence of climate on trees, this is not possible for most shrubs. Here, we leverage a multidecadal record of annual foliar carbon isotope ratio collections coupled with 39 y of survey data from two populations of the drought-deciduous desert shrub Encelia farinosa to provide insight into water-use dynamics and climate. This carbon isotope record provides a unique opportunity to examine the response of desert shrubs to increasing temperature and water stress in a region where climate is changing rapidly. Population mean carbon isotope ratios fluctuated predictably in response to interannual variations in temperature, vapor pressure deficit, and precipitation, and responses were similar among individuals. We leveraged the well-established relationships between leaf carbon isotope ratios and the ratio of intracellular to ambient CO2 concentrations to calculate intrinsic water-use efficiency (iWUE) of the plants and to quantify plant responses to long-term environmental change. The population mean iWUE value increased by 53 to 58% over the study period, much more than the 20 to 30% increase that has been measured in forests [J. Penuelas, J. G. Canadell, R. Ogaya, Glob. Ecol. Biogeogr. 20, 597–608 (2011)]. Changes were associated with both increased CO2 concentration and increased water stress. Individuals whose lifetimes spanned the entire study period exhibited increases in iWUE that were very similar to the population mean, suggesting that there was significant plasticity within individuals rather than selection at the population scale.

Recent analyses on the length of drought recovery in forests have shown multi-year legacies, particularly in semi-arid, coniferous ecosystems. Such legacies are usually attributed to ecophysiological memory, although drought frequency itself, and its effect on overlapping recovery times, could also contribute. Here, we describe a multi-decadal study of drought legacies using tree-ring carbon-isotope ratios (δ13C) and ring-width index (RWI) in Pinus ponderosa at 13 montane sites traversing a winter–summer precipitation gradient in the Southwestern U.S. Sites and trees were selected to avoid collection biases that exist in archived tree-ring databanks. The spatial hydroclimate gradient and winter–summer seasonal patterns were well predicted by seasonal and inter-annual correlations between δ13C and atmospheric vapor pressure deficit (VPD). Using VPD, we found that the probability of extreme drought has increased up to 70% in this region during the past two decades. When the recent increase in drought frequency was not considered, multi-year legacies in both δ13C and RWI were observed at most sites. When the increase in drought frequency was detrended from tree-ring chronologies, some sites exhibited short legacies (1–2 years) in both δ13C and RWI, and there was a sight trend for longer legacies in RWI. However, when considered broadly across the region and multiple decades, no significant legacies were observed, which contrasts with past studies. Our results reveal that a contribution to observed multi-year legacies is related to shifts in the climate system itself, an exogenous factor, that must be considered along with physiological memory.

Globally, intrinsic water-use efficiency (iWUE) has risen dramatically over the past century in concert with increases in atmospheric CO(2) concentration. This increase could be further accelerated by long-term drought events, such as the ongoing multidecadal “megadrought” in the American Southwest. However, direct measurements of iWUE in this region are rare and largely constrained to trees, which may bias estimates of iWUE trends toward more mesic, high elevation areas and neglect the responses of other key plant functional types such as shrubs that are dominant across much of the region. Here, we found evidence that iWUE is increasing in the Southwest at one of the fastest rates documented due to the recent drying trend. These increases were particularly large across three common shrub species, which had a greater iWUE sensitivity to aridity than Pinus ponderosa, a common tree species in the western United States. The sensitivity of both shrub and tree iWUE to variability in atmospheric aridity exceeded their sensitivity to increasing atmospheric [CO(2)]. The shift to more water-efficient vegetation would be, all else being equal, a net positive for plant health. However, ongoing trends toward lower plant density, diminished growth, and increasing vegetation mortality across the Southwest indicate that this increase in iWUE is unlikely to offset the negative impacts of aridification.

International audience; Herd mobility is a key parameter of many agro-pastoral strategies. Sequential variationsof oxygen, carbon and strontium isotope ratios in ruminant teeth are commonly used forcharacterizing herd mobility along altitudinal gradients and across geological areas. Towhat extent is the variation and covariation of isotopic ratios along a tooth actuallyreflecting vertical and geological mobility? The interpretation of such data fomarchaeological material widely depends on our ability to answer to this question. Fewmodern baselines are available to assess covariation of oxygen and carbon isotope ratiosalong the tooth of modern sheep experiencing vertical mobilities. There are no suchbaselines for the covariation of strontium, oxygen and carbon isotope ratios. Our studyaimed at analyzing the variation and covariation of isotope ratios of oxygen, carbon, andstrontium in the teeth and guard hair of domestic ruminants experiencing differentpastoral mobilities along altitudinal gradients and across geological areas. We sampledlower molars from one cow and 17 sheep, as well as the guard hair from five goats, allgrazing in different mountainous areas of Azerbaijan (Nakhchivan, Ganja-Qazakh, andLankaran regions) at least part of the year. Our results suggest that the covariation ofthe isotope ratios of oxygen and carbon allow to spot easily the specimens movingseasonally between the plains and the highlands and also between the subalpine zoneand the highland meadows. To a lesser extent it is possible to sort two-staged annualmobility from four-staged annual mobility. The variations in strontium isotope ratiosduring the period of enamel formation also adequately reflect seasonal mobility but itdeeply depends on the number of samples analyzed along the tooth crown. These resultsallow us to interpret isotope ratio variations in archaeological domestic ruminant teeth inorder to analyze the role of herd mobilities in past agro-pastoral communities.

Accurate human provenancing using stable isotopes depends directly on solid understandings of the geographic and individual factors affecting isotope variability and incorporation into human tissues. Transfer of isotopic, and therefore spatial, information between environmental water and biological tissues is mediated by the isotopic composition of body water. Thus, there is a need to study body water isotope ratios at a population level and over a large isotopic and geographic range. We evaluated oxygen (δ18Obw) and hydrogen (δ2Hbw) isotope values of body water from 72 volunteers in 10 different cities across the US, and over a 5-10-day period. We analyzed covariates (e.g., water intake, physical activity, biometrics, gender) that might explain individual stable isotope ratio variations and tested a predictive model that incorporates the δ-values of drinking water, food, and O2 as well as individual variables to predict the δ-values of body water. The individual variability in body water isotope values overtime (mean 0.3‰ for δ18Obw and 2.3‰ for δ2Hbw) was lower than the intra-city variability (mean 0.9‰ for δ18Obw and 6.9‰ for δ2Hbw). Body water isotope values differed among cities (ANOVA: δ18ObwF = 97.2, p

Rationale Strontium isotope ratios (87 Sr/86 Sr) of hair may be a valuable tool to estimate human provenance. However, the systematics and mechanisms controlling spatial variation in 87 Sr/86 Sr of modern human hair remain unclear. Here, we measure 87 Sr/86 Sr of hair specimens from across the USA to assess the presence of geospatial relationships. Methods Ninety-eight human hair specimens were collected from salon/barbershop floors in 48 municipalities throughout the conterminous USA. [Sr] and 87 Sr/86 Sr ratios were measured from hair using quadrupole and multi-collector inductively coupled plasma mass spectrometers, respectively. The [Sr] and 87 Sr/86 Sr ratios of hair were compared with the measured [Sr] and 87 Sr/86 Sr ratios of tap waters from the collection locations. In addition, the 87 Sr/86 Sr ratio of hair was compared with the modeled ratios of bedrock and surface waters. Results Hair color was independent of the 87 Sr/86 Sr ratio, but related to [Sr]. The 87 Sr/86 Sr ratios of hair and leachate were not statistically different and were positively correlated; however, in several hair-leachate pairs, the ratios were conspicuously different. The 87 Sr/86 Sr ratios of both hair and leachate were linearly correlated with tap water. The 87 Sr/86 Sr ratio of hair was also significantly correlated with the modeled ratio of bedrock and surface waters, although the 87 Sr/86 Sr ratio of hair was most strongly correlated with the measured ratio of tap water. Conclusions The 87 Sr/86 Sr ratio of hair is related to the ratio of tap water, which varied geographically. The ratio of hair provided geographic information about an individual's recent residence. Differences in the 87 Sr/86 Sr ratios of hair and hair leachate may be concomitant with travel and could potentially be used as a screening tool to identify recent movements.

Urban areas are responsible for a substantial proportion of anthropogenic carbon emissions around the world. As global populations increasingly reside in cities, the role of urban emissions in determining the future trajectory of carbon emissions is magnified. Consequently, a number of research efforts have been started in the United States and beyond, focusing on observing atmospheric carbon dioxide (CO2) and relating its variations to carbon emissions in cities. Because carbon emissions are intimately tied to socioeconomic activity through the combustion of fossil fuels, and many cities are actively adopting emission reduction plans, such urban carbon research efforts give rise to opportunities for stakeholder engagement and guidance on other environmental issues, such as air quality.This paper describes a research effort centered in the Salt Lake City, Utah, metropolitan region, which is the locus for one of the longest-running urban CO2 networks in the world. The Salt Lake City area provides a rich environment for studying anthropogenic emissions and for understanding the relationship between emissions and socioeconomic activity when the CO2 observations are enhanced with a) air quality observations, b) novel mobile observations from platforms on light-rail public transit trains and a news helicopter, c) dense meteorological observations, and d) modeling efforts that include atmospheric simulations and high-resolution emission inventories.Carbon dioxide and other atmospheric observations are presented, along with associated modeling work. Examples in which the work benefited from and contributed to the interests of multiple stakeholders (e.g., policymakers, air quality managers, municipal government, urban planners, industry, and the general public) are discussed.

Summary • In this study, we tested the hypothesis that environmentally induced changes in the oxygen isotope ratio of leaf water are recorded in grass blade cellulose during leaf-blade expansion. • Grasses were grown hydroponically in chambers that allowed for control of relative humidity while keeping isotopic inputs (namely source water) constant. • In experiments where relative humidity was changed from 35% to 93% during grass blade expansion, a 10‰ shift in cellulose δ 18 O was observed along single grass blades of Lolium multiflorum . However, statistically significant changes were not detectable with relative humidity of 93% to 70%. • It is shown that grass blades, analogously to tree rings, record environmental change on an interseasonal basis. In light of this, care must be taken to compare leaves of the same developmental stage to avoid confusion of environmental effects with physiological effects in interpretations of leaf organic material δ 18 O. The results presented here confirm the ability of the current empirical models to predict the oxygen isotope ratio of cellulose in both grass blades that expanded in constant and variable growth conditions.

Isotope ratios of tree-ring cellulose are a prominent tool to reconstruct paleoclimate and plant responses to environmental variation. Current models for cellulose isotope ratios assume a transfer of the environmental signals recorded in bulk leaf water to carbohydrates and ultimately into stem cellulose. However, the isotopic signal of carbohydrates exported from leaf to branch may deviate from mean leaf values if spatial heterogeneity in isotope ratios exists in the leaf. We tested whether the isotopic heterogeneity previously observed along the length of a ponderosa pine (Pinus ponderosa) leaf water was preserved in photosynthetic products. We observed an increase in both sugar and bulk tissue δ

Detailed knowledge of the interactions between the atmosphere, biosphere and pedosphere is essential for an understanding of global carbon dynamics in terrestrial ecosystems. This chapter addresses ecosystem level variation of Δe, possible impacts of seasonality, of characteristic features of the dominant plant species within an ecosystem (life form, canopy structure, age) as well as the influence of climate and soil nutrient availability. It focuses on where to obtain tro-pospheric baseline data, and then discuss how to determine 13carbon of respired CO2. Canopy air should be collected dry, and stored in inert flasks that do not leak or exchange CO2, with seals that do not exchange with CO2. Natural landscapes comprise mosaics of evergreen and deciduous ecosystems, most pronounced in temperate and boreal regions. Information about the influence of different life forms on ecophysiological processes is therefore critical for understanding what controls carbon dynamics in evergreen and deciduous forest ecosystems, and how to integrate over diverse regions.

Significance As the proportion of land area covered by arid land vegetation continues to expand and water limitations for plants increase, understanding if and how desert shrubs are responding to environmental change has become more urgent. Among two populations of Mojave Desert shrubs, we found that intrinsic water-use efficiency has increased substantially over the last three decades in response to increasing aridity and CO2 concentration. While increases in intrinsic water-use efficiency have been widely assumed to mitigate negative effects of decreasing water availability, precise effects on plant productivity, reproduction, and survival remain unknown., While tree rings have enabled interannual examination of the influence of climate on trees, this is not possible for most shrubs. Here, we leverage a multidecadal record of annual foliar carbon isotope ratio collections coupled with 39 y of survey data from two populations of the drought-deciduous desert shrub Encelia farinosa to provide insight into water-use dynamics and climate. This carbon isotope record provides a unique opportunity to examine the response of desert shrubs to increasing temperature and water stress in a region where climate is changing rapidly. Population mean carbon isotope ratios fluctuated predictably in response to interannual variations in temperature, vapor pressure deficit, and precipitation, and responses were similar among individuals. We leveraged the well-established relationships between leaf carbon isotope ratios and the ratio of intracellular to ambient CO2 concentrations to calculate intrinsic water-use efficiency (iWUE) of the plants and to quantify plant responses to long-term environmental change. The population mean iWUE value increased by 53 to 58% over the study period, much more than the 20 to 30% increase that has been measured in forests [J. Peñuelas, J. G. Canadell, R. Ogaya, Glob. Ecol. Biogeogr. 20, 597–608 (2011)]. Changes were associated with both increased CO2 concentration and increased water stress. Individuals whose lifetimes spanned the entire study period exhibited increases in iWUE that were very similar to the population mean, suggesting that there was significant plasticity within individuals rather than selection at the population scale.

The Craig-Gordon type (C-G) leaf water isotope enrichment models assume a homogeneous distribution of enriched water across the leaf surface, despite observations that Δ18 O can become increasingly enriched from leaf base to tip. Datasets of this 'progressive isotope enrichment' are limited, precluding a comprehensive understanding of (a) the magnitude and variability of progressive isotope enrichment, and (b) how progressive enrichment impacts the accuracy of C-G leaf water model predictions. Here, we present observations of progressive enrichment in two conifer species that capture seasonal and diurnal variability in environmental conditions. We further examine which leaf water isotope models best capture the influence of progressive enrichment on bulk needle water Δ18 O. Observed progressive enrichment was large and equal in magnitude across both species. The magnitude of this effect fluctuated seasonally in concert with vapour pressure deficit, but was static in the face of diurnal cycles in meteorological conditions. Despite large progressive enrichment, three variants of the C-G model reasonably successfully predicted bulk needle Δ18 O. Our results thus suggest that the presence of progressive enrichment does not impact the predictive success of C-G models, and instead yields new insight regarding the physiological and anatomical mechanisms that cause progressive isotope enrichment.

Rationale Fraudulent region-of-origin labeling is a concern for high-value, globally traded commodities such as coffee. The oxygen isotope ratio of cellulose is a useful geographic tracer, as it integrates climate and source water signals. A predictive spatial model ("isoscape") of the δ18 O values of coffee bean cellulose is generated to evaluate coffee region-of-origin claims. Methods The oxygen isotope ratio of α-cellulose extracted from roasted coffee beans was measured via high-temperature conversion elemental analyzer/isotope ratio mass spectrometry (TC-EA/IRMS) and used to calculate the δ18 O value of coffee bean water. The 18 O enrichment of coffee bean water relative to the δ18 O value of local precipitation was modeled as a function of local temperature and humidity. This function was incorporated into a mechanistic model of cellulose δ18 O values to predict the δ18 O values of coffee bean cellulose across coffee-producing regions globally. Results The δ18 O values of analyzed coffee bean cellulose ranged from approximately +22‰ to +42‰ (V-SMOW). As expected, coffees grown in the same region tended to have similar isotope ratios, and the δ18 O value of coffee bean cellulose was generally higher than the δ18 O value of modeled stem cellulose for the region. Modeled δ18 O values of coffee cellulose were within ±2.3‰ of the measured δ18 O value of coffee cellulose. Conclusions The oxygen isotope ratio of coffee bean cellulose is a useful indicator of region-of-origin and varies predictably in response to climatic factors and precipitation isotope ratios. The isoscape of coffee bean cellulose δ18 O values from this study provides a quantitative tool that can be applied to region-of-origin verification of roasted coffee at the point-of-sale.

RATIONALE Strontium isotope ratios (87 Sr/86 Sr) in human fingernail keratin tissues have been underexplored for region of origin and travel history reconstruction studies. Here we investigated 87 Sr/86 Sr ratios in fingernail keratin to establish baseline measurements in a resident group and to examine how 87 Sr/86 Sr ratios changed with relocation. METHODS Fingernail clippings were collected from resident (n = 10) and non-resident/traveler groups (n = 4 and n = 4) that were part of a larger study in Salt Lake City (UT, USA) from 2015 to 2016. Strontium abundance and 87 Sr/86 Sr ratios were determined via multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). 87 Sr/86 Sr and oxygen (δ18 O) isotope ratios from the traveler participants were compared to examine temporal patterns. RESULTS Strontium abundance and 87 Sr/86 Sr ratios in fingernails from the resident group established a baseline against which we could evaluate potential differences in non-resident/traveler groups. Resident 87 Sr/86 Sr ratios remained constant over the study period and were consistent with previously measured tap waters for the area. 87 Sr/86 Sr ratio changes in non-resident/traveler groups were rapid and reflected the current location of the individual within 4-5 weeks of arrival. Lastly, δ18 O and 87 Sr/86 Sr ratios of the same fingernail clippings did not exhibit similar temporal patterns, since fingernail δ18 O ratios required more time to attain values characteristic of the new environment. CONCLUSIONS Our findings suggest that strontium is incorporated into fingernail tissues differently from hair and this could be advantageous to forensic investigations. We found that 87 Sr/86 Sr and δ18 O ratios of the same fingernail clippings revealed two different time points reflecting an individual's residence over short- (4-5 weeks, 87 Sr/86 Sr ratios) and long-term (3-5 months, δ18 O values) time scales. It is likely that the 87 Sr/86 Sr ratios of fingernail clippings reflect exogenous signals that are incorporated through bathing waters and that these signals change rapidly with movement to a new location. Our results may aid future forensic studies in the determination of region of origin in unidentified remains.

Anthropogenic emissions within urban environments are characterized by spatial heterogeneity and temporal variability that present challenges for measuring urban greenhouse gases and air pollutants. To address these challenges, we mounted instruments on public transit light-rail train cars that traverse the metropolitan Salt Lake Valley (SLV) in Utah, USA to observe the temporal and spatial variability of atmospheric species including carbon dioxide (CO2), methane (CH4), ozone (O3), fine particulate matter (PM2.5), and nitrogen dioxide (NO2). Utilizing electrified light-rail public transit as an observational platform enables real-time measurements with low operating costs while avoiding self-contamination from vehicle exhaust. We examine temporal averages and case studies of each species that reveal gradients, intermittent point sources, seasonal and diel changes, and complex relationships resulting from emissions, atmospheric chemistry, and meteorological conditions. CO2 and NO2 are related through the combustion of fossil fuel and we observed a broad spatial gradient across the city as well distinct plumes at traffic intersections and, for NO2, a large plume adjacent to a locomotive rail yard. Distributions of O3 were strongly correlated with NO2 due to atmospheric photochemical and titration processes. Episodes of high PM2.5 had distinct spatial patterns depending on meteorological conditions during wintertime persistent cold-air pool episodes. The spatial pattern of CH4 was characterized by distinct plumes associated with industrial and commercial facilities, some of which followed temporal patterns indicative of daytime working hours; other plumes were persistent throughout the whole day, suggestive of leak-related fugitive emissions. The ongoing multi-year record of spatial and temporal air quality observations provides a valuable data set for future air quality exposure studies. Our results suggest pollution and greenhouse gas emission monitoring and exposure assessment could be greatly enhanced by deploying instruments on public transit systems in urban centers worldwide.

Global travel has increased, and having a diagnostic tool to distinguish residents from visitors would be valuable. This study examined stable isotope biomarkers of fingernail tissues of resident (n = 26) and nonresident (n = 22) participants in Salt Lake City (SLC), UT, from 2015 to 2016. The purpose of this research was to determine whether fingernail isotopes could be used for reconstructing geolocation movements and to examine the convergence in nonresident fingernail isotopes to that of the resident signal following their arrival to SLC. Resident isotope values defined a baseline to make comparisons to. Initial nonresident hydrogen and oxygen isotope values were correlated with precipitation isotopes of their prior location. Fingernail isotope turnover rates were rapid and nonresident isotopes were indistinguishable from residents after ~71-90 days. The results of our study highlight the utility of stable isotope measurements of fingernail clippings to examine travel history reconstruction that could aid in identification of human remains.

The evolution of C4 photosynthesis requires an intermediate phase where photorespiratory glycine produced in the mesophyll cells must flow to the vascular sheath cells for metabolism by glycine decarboxylase. This glycine flux concentrates photorespired CO2 within the sheath cells, allowing it to be efficiently refixed by sheath Rubisco. A modest C4 biochemical cycle is then upregulated, possibly to support the refixation of photorespired ammonia in sheath cells, with subsequent increases in C4 metabolism providing incremental benefits until an optimized C4 pathway is established. ‘Why’ C4 photosynthesis evolved is largely explained by ancestral C3 species exploiting photorespiratory CO2 to improve carbon gain and thus enhance fitness. While photorespiration depresses C3 performance, it produces a resource (photorespired CO2) that can be exploited to build an evolutionary bridge to C4 photosynthesis. ‘Where’ C4 evolved is indicated by the habitat of species branching near C3-to-C4 transitions on phylogenetic trees. Consistent with the photorespiratory bridge hypothesis, transitional species show that the large majority of > 60 C4 lineages arose in hot, dry, and/or saline regions where photorespiratory potential is high. ‘When’ C4 evolved has been clarified by molecular clock analyses using phylogenetic data, coupled with isotopic signatures from fossils. Nearly all C4 lineages arose after 25 Ma when atmospheric CO2 levels had fallen to near current values. This reduction in CO2, coupled with persistent high temperature at low-to-mid-latitudes, met a precondition where photorespiration was elevated, thus facilitating the evolutionary selection pressure that led to C4 photosynthesis.

This study focuses on the examination of stable isotope biomarkers in human fingernails of travelers who ventured away from Salt Lake City, UT and subsequently returned. Here, we describe three case studies examining: individual travelers (n = 4), paired travelers (n = 2), and a traveler (n = 1) who repeatedly left and returned. Our case studies examined the influences of dietary and drinking water inputs on fingernail stable isotope profiles for reconstructing travel histories. Stable isotope data were compared with theoretical and predictive models that laid the groundwork for anthropological and forensic geospatial reconstruction of travel histories. Drinking water inputs strongly influenced stable isotope profiles and the patterns observed were consistent with reported travel histories. Finally, observed fingernail stable isotope ratio data were consistent with modeled rates of stable isotope turnover and transition to expected values for the new environment. The results of our study further support the use of fingernail tissues for travel history reconstruction.

Germination, establishment, phenology, and death among three drought-deciduous shrubs were influenced by ENSO/PDO and precipitation, based on 37 years of annual surveys. Encelia farinosa forms near monospecific stands on slopes, whereas E. frutescens and Ambrosia salsola dominate wash habitats. All shrubs exhibited phenological coherence. While germination, establishment, and mortality patterns were similar among wash species, these dynamics contrasted with E. farinosa on slopes. Germination was associated with El Niño years. Slope plant establishment was dependent on precipitation in the subsequent year, but not evidently so in wash species. Major mortality events were episodic, with Encelia mortality just as likely to occur in years with below or above average precipitation. In both Encelia species, mortality was associated with transitions to a cold PDO phase. In E. frutescens this response was more rapid, whereas in E. farinosa mortality lagged 1 year, resulting in contrasting slope-wash mortality patterns. 50% of newly established shrubs died within 5, 5, and 18 years for E. frutescens, E. farinosa, and A. salsola, respectively. The 90% mortality ages were 26 years for E. frutescens, 24 years for E. farinosa, and 51 years for A. salsola. While maximum life expectancies are unknown, estimated maximum life expectancies were 56, 66, and 86 years for E. frutescens, E. farinosa, and A. salsola, respectively. Overall, as the climate has become more arid over the past four decades, the populations in both slope and wash habitats have exhibited similar responses: reduced shrub abundances and reduced total supportable leaf areas.

Episodic multi-year droughts fundamentally alter the dynamics, functioning, and structure of Amazonian forests. However, the capacity of individual plant species to withstand intense drought regimes remains unclear. Here, we evaluated ecophysiological responses from a forest community where we sampled 83 woody plant species during 5 years of experimental drought (throughfall exclusion) in an eastern Amazonian terra firme forest. Overall, the experimental drought resulted in shifts of some, but not all, leaf traits related to photosynthetic carbon uptake and intrinsic water-use efficiency. Leaf δ13C values increased by 2–3‰ within the canopy, consistent with increased diffusional constraints on photosynthesis. Decreased leaf C:N ratios were also observed, consistent with lower investments in leaf structure. However, no statistically significant treatment effects on leaf nitrogen content were observed, consistent with a lack of acclimation in photosynthetic capacity or increased production of nitrogen-based secondary metabolites. The results of our study provide evidence of robust acclimation potential to drought intensification in the diverse flora of an Amazonian forest community. The results reveals considerable ability of several species to respond to intense drought and challenge commonly held perspectives that this flora has attained limited adaptive plasticity because of a long evolutionary history in a favorable and stable climate.

Cities are concentrated areas of CO2 emissions and have become the foci of policies for mitigation actions. However, atmospheric measurement networks suitable for evaluating urban emissions over time are scarce. Here we present a unique long-term (decadal) record of CO2 mole fractions from five sites across Utah's metropolitan Salt Lake Valley. We examine "excess" CO2 above background conditions resulting from local emissions and meteorological conditions. We ascribe CO2 trends to changes in emissions, since we did not find long-term trends in atmospheric mixing proxies. Three contrasting CO2 trends emerged across urban types: negative trends at a residential-industrial site, positive trends at a site surrounded by rapid suburban growth, and relatively constant CO2 over time at multiple sites in the established, residential, and commercial urban core. Analysis of population within the atmospheric footprints of the different sites reveals approximately equal increases in population influencing the observed CO2, implying a nonlinear relationship with CO2 emissions: Population growth in rural areas that experienced suburban development was associated with increasing emissions while population growth in the developed urban core was associated with stable emissions. Four state-of-the-art global-scale emission inventories also have a nonlinear relationship with population density across the city; however, in contrast to our observations, they all have nearly constant emissions over time. Our results indicate that decadal scale changes in urban CO2 emissions are detectable through monitoring networks and constitute a valuable approach to evaluate emission inventories and studies of urban carbon cycles.

The oxygen (18O/16O) isotope analysis of hair is commonly applied to reconstruct an individual’s residence history. However, region-of-origin as determined from oxygen isotope values (δ18O) alone is often spatially indistinct. Adding additional geochemical recorders can refine region-of-origin estimates. In this capacity, strontium (87Sr/86Sr) isotope analysis has attracted increased interest. While 87Sr/86Sr reflects the influences of local geology, 87Sr/86Sr of hair includes both external environmental signals as well as the internal dietary indicators. To better understand the impact of these contributions to the spatial signal encoded within 87Sr/86Sr of hair, human hair was collected from three locations within Salt Lake City, Utah along with the donor’s sex. The 87Sr/86Sr and δ18O of hair and local tap water were measured. There were no significant relationships between sex and either δ18O or 87Sr/86Sr of hair, nor between collection location and the δ18O of hair. However, we found significant associations between collection location and 87Sr/86Sr of hair. These findings suggest that interactions with local water may be an important source of Sr to human hair and that the 87Sr/86Sr of hair may have the capacity to record differences in 87Sr/86Sr of tap waters on small spatial scales.

Two populations of the common shrub Encelia farinosa in the northern and southern portions of the Mojave Desert have been surveyed each spring for nearly 40 years, providing an opportunity to assess highly variable shrub mortality in an arid ecosystem. Most of the newly established shrubs experienced mortality during the juvenile stage, with median survival time of about three years in both populations yet, a small number of shrubs lived for at least a dozen years or even decades. Applying machine learning techniques, we predicted shrub mortality at different life-history stages using random forest and logistic regression. First, we examined seedling survival to become yearlings (one-year old plants), finding that less than 3% of seedlings in both populations survived to become established yearling shrubs. Second, we predicted whether or not yearlings would die prior to reaching the mature adult stage (four years old). The models achieved an Area Under the Receiver Operating Characteristic (AUC) in the 0.80 range for the Oatman population (southern Mojave Desert) and 0.90 range for the Death Valley population (northern Mojave Desert). We found yearling characteristics of smaller shrub size, low leaf coverage, and location in specific microsites associated with experiencing mortality before reaching the mature stage. Third, using only the average juvenile plant characteristics over the first four years of life, we predicted whether or not new adult shrubs were likely to experience mortality within the next eight years. The performance in this application achieved AUC in the 0.72 range for both populations. We found adult Encelia farinosa shrubs that had juvenile characteristics of smaller size, flowered less frequently, and had smaller inter-plant distances for the Oatman population were associated with increased mortality within the next eight years. Overall, the size of the shrub was the most important feature for the mortality modeling applications. No significant difference in AUC was found for random forest and logistic regression.

Black carbon (BC) and organic carbon (OC) aerosols are important components of fine particulate matter (PM2.5) in polluted urban environments. Quantifying the contribution of fossil fuel and biomass combustion to BC and OC concentrations is critical for developing and validating effective air quality control measures and climate change mitigation policy. We used radiocarbon (14C) to measure fossil and contemporary biomass contributions to BC and OC at three locations in Salt Lake City, Utah, USA during 2012-2014, including during winter inversion events. Aerosol filters were analyzed with the Swiss_4S thermal-optical protocol to isolate BC. We measured fraction modern (fM) of BC and total carbon in PM2.5 with accelerator mass spectrometry and derived the fM of OC using isotope mass balance. Combined with 14C information of endmember composition, our dataset of 31 14C aerosol measurements provided a baseline of the fossil and contemporary biomass components of carbonaceous aerosol. We show that fossil fuels were the dominant source of carbonaceous aerosol during winter, contributing 88% (80–98%) of BC and 58% (48–69%) of OC. While the concentration of both BC and OC increased during inversion events, the relative source contributions did not change. The sources of BC also did not vary throughout the year, while OC had a considerably higher contemporary biomass component in summer 62% (49-76%) and was more variable. Our results suggest that in order to reduce PM2.5 levels in Salt Lake City to meet national standards, a more stringent policy targeting mobile fossil fuel sources may be necessary.

Water availability and sustainability in the Western United States is a major flashpoint among expanding communities, growing industries, and productive agricultural lands. This issue came to a head in 2015 in the State of California, when the State mandated a 25% reduction in urban water use following a multi-year drought that significantly depleted water resources. Water demands and challenges in supplying water are only expected to intensify as climate perturbations, such as the 2012–2015 California Drought, become more common. As a consequence, there is an increased need to understand linkages between urban centers, water transport and usage, and the impacts of climate change on water resources. To assess if stable hydrogen and oxygen isotope ratios could increase the understanding of these relationships within a megalopolis in the Western United States, we collected and analyzed 723 tap waters across the San Francisco Bay Area during seven collection campaigns spanning 21 months during 2013–2015. The San Francisco Bay Area was selected as it has well-characterized water management strategies and the 2012–2105 California Drought dramatically affected its water resources. Consistent with known water management strategies and previously collected isotope data, we found large spatiotemporal variations in the δ2H and δ18O values of tap waters within the Bay Area. This is indicative of complex water transport systems and varying municipality-scale management decisions. We observed δ2H and δ18O values of tap water consistent with waters originating from snowmelt from the Sierra Nevada Mountains, local precipitation, ground water, and partially evaporated reservoir sources. A cluster analysis of the isotope data collected in this study grouped waters from 43 static sampling sites that were associated with specific water utility providers within the San Francisco Bay Area and known management practices. Various management responses to the drought, such as source switching, bringing in new sources, and water conservation, were observed in the isotope data. Finally, we estimated evaporative loss from one utility's reservoir system during the 2015 water year using a modified Craig-Gordon model to estimate the consequences of the drought on this resource. We estimated that upwards of 6.6% of the water in this reservoir system was lost to evaporation.

Center for High Performance Computing at the University of Utah; US Department of Energy (DOE), Office of Science, Office of Biological and Environmental Research, Terrestrial Ecosystem Science (TES) Program [DE-SC0010625]; US National Science Foundation Macrosystems Biology Program [EF-1137336]; Atmospheric Radiation Measurement Program (ARM) [DE-AC02-05CH11231]; NOAA Climate Program Office's Atmospheric Chemistry, Carbon Cycle, and Climate Program [NA14OAR4310178]; U.S. Department of Energy's Office of Science; NSF as part of the Harvard Forest LTER; DOE TES program [DE-SC0006741]

RATIONALE Oxygen isotope ratios (δ18 O values) of hair largely reflect features of regional hydrology while strontium isotope ratios (87 Sr/86 Sr) are thought to reflect bedrock geology; combination of both isotope signatures may provide greater capacity for determining provenance and reconstructing travel history of an organism. To test this hypothesis, we compared the O-Sr isotope profiles of hair from domestic horses with known residency histories. METHODS Tail hairs were collected from a pair of horses pastured together for a period of 16 months, one of which lived in a different location for the 8 months prior. Hair samples were washed with solvents to remove external contaminants prior to sequential sampling for δ18 O and 87 Sr/86 Sr analysis via TC/EA-IRMS and MC-ICP-MS, respectively. Hair digests were concentrated and analyzed employing low-flow natural aspiration to measure 87 Sr/86 Sr. RESULTS Tail hair from the control and transported horses had mean δ18 O values of 11.25 ± 1.62 ‰ and 10.96 ± 1.53 ‰, and mean 87 Sr/86 Sr of 0.7101 ± 0.0006 and 0.7109 ± 0.0020, respectively. The δ18 O and 87 Sr/86 Sr profiles for the control and transported horses were indistinguishable when they were pastured together. The 87 Sr/86 Sr profiles were significantly different during the period that the horses were living apart, while the δ18 O values were indistinguishable during that period. CONCLUSIONS By comparing the O-Sr isotope profiles of a control and transported horse, we investigated isotopic signal(s) potentially useful for reconstructing travel histories via high-resolution sequential sampling along single strands of tail hair. Improved analytical capabilities allowed for extremely low Sr abundance samples to be analyzed for 87 Sr/86 Sr and proved capable of resolving a horse's movement between distinct regions. Copyright © 2017 John Wiley & Sons, Ltd.

Isotope ratio mass spectrometry (IRMS) techniques have been used for decades to characterize explosives alongside traditional chemical analyses. We present here a broadly applicable framework for methodologically applying a variety of separation techniques to explosive mixtures and preparing different explosive components for stable isotope analysis. This framework allows an analyst to collect the most characteristic information possible from an explosive sample, by analyzing multiple components with independent isotope signatures to produce multivariate datasets for discrimination. A case illustration demonstrating the application of methods in the framework to plastic explosives (specifically C-4 and Semtex) has been prepared separately. In developing this framework, we focused on explosives samples that may contain RDX, HMX, PETN, TNT, AN, and/or nitrocellulose along with various binders, plasticizers, oils, and other additives. This paper describes the theory and processes used to develop a component-specific approach to prepare explosives samples for isotope ratio analysis, focusing specifically on optimization of solvent extraction methods. Other methods used in framework development include gravimetric analysis and HPLC.

Canopy and aerodynamic conductances (gC and gA) are two of the key land surface biophysical variables that control the land surface response of land surface schemes in climate models. Their representation is crucial for predicting transpiration (λET) and evaporation (λEE) flux components of the terrestrial latent heat flux (λE), which has important implications for global climate change and water resource management. By physical integration of radiometric surface temperature (TR) into an integrated framework of the Penman–Monteith and Shuttleworth–Wallace models, we present a novel approach to directly quantify the canopy-scale biophysical controls on λET and λEE over multiple plant functional types (PFTs) in the Amazon Basin. Combining data from six LBA (Large-scale Biosphere-Atmosphere Experiment in Amazonia) eddy covariance tower sites and a TR-driven physically based modeling approach, we identified the canopy-scale feedback-response mechanism between gC, λET, and atmospheric vapor pressure deficit (DA), without using any leaf-scale empirical parameterizations for the modeling. The TR-based model shows minor biophysical control on λET during the wet (rainy) seasons where λET becomes predominantly radiation driven and net radiation (RN) determines 75 to 80 % of the variances of λET. However, biophysical control on λET is dramatically increased during the dry seasons, and particularly the 2005 drought year, explaining 50 to 65 % of the variances of λET, and indicates λET to be substantially soil moisture driven during the rainfall deficit phase. Despite substantial differences in gA between forests and pastures, very similar canopy–atmosphere "coupling" was found in these two biomes due to soil moisture-induced decrease in gC in the pasture. This revealed the pragmatic aspect of the TR-driven model behavior that exhibits a high sensitivity of gC to per unit change in wetness as opposed to gA that is marginally sensitive to surface wetness variability. Our results reveal the occurrence of a significant hysteresis between λET and gC during the dry season for the pasture sites, which is attributed to relatively low soil water availability as compared to the rainforests, likely due to differences in rooting depth between the two systems. Evaporation was significantly influenced by gA for all the PFTs and across all wetness conditions. Our analytical framework logically captures the responses of gC and gA to changes in atmospheric radiation, DA, and surface radiometric temperature, and thus appears to be promising for the improvement of existing land–surface–atmosphere exchange parameterizations across a range of spatial scales.

Cities generate 70% of anthropogenic greenhouse gas emissions, a fraction that is growing with global urbanization. While cities play an important role in climate change mitigation, there has been little focus on reducing urban methane emissions. Here we develop a conceptual framework for methane mitigation in cities by describing emission processes, the role of measurements, and a need for new institutional partnerships. Urban methane emissions are likely to grow with expanding use of natural gas and organic waste disposal systems in growing population centers; however, we currently lack the ability quantify this increase. We also lack systematic knowledge of the relative contribution of these distinct source sectors on emissions. We present new observations from 4 North American cities to demonstrate that methane emissions vary in magnitude and sector from city to city, and hence require different mitigation strategies. Detections of fugitive emissions from these systems suggest that current mitigation approaches are absent or ineffective. These findings illustrate that tackling urban methane emissions will require research efforts to identify mitigation targets, develop and implement new mitigation strategies, and monitor atmospheric methane levels to ensure the success of mitigation efforts. This research will require a variety of techniques to achieve these objectives, and should be deployed in cities globally. We suggest that metropolitan-scale partnerships may effectively coordinate systematic measurements and actions focused on emission reduction goals.

The extent to which atmospheric nitrogen (N) deposition reflects land use differences and biogenic versus fossil fuel reactive N sources remains unclear yet represents a critical uncertainty in ecosystem N budgets. We compared N concentrations and isotopes in precipitation-event bulk (wet + dry) deposition across nearby valleys in northern Utah with contrasting land use (highly urban versus intensive agriculture/low-density urban). We predicted greater nitrate (NO3−) versus ammonium (NH4+) and higher δ15N of NO3− and NH4+ in urban valley sites. Contrary to expectations, annual N deposition (3.5–5.1 kg N ha−1 yr−1) and inorganic N concentrations were similar within and between valleys. Significant summertime decreases in δ15N of NO3− possibly reflected increasing biogenic emissions in the agricultural valley. Organic N was a relatively minor component of deposition (~13%). Nearby paired wildland sites had similar bulk deposition N concentrations as the urban and agricultural sites. Weighted bulk deposition δ15N was similar to natural ecosystems (−0.6 ± 0.7‰). Fine atmospheric particulate matter (PM2.5) had consistently high values of bulk δ15N (15.6 ± 1.4‰), δ15N in NH4+ (22.5 ± 1.6‰), and NO3− (8.8 ± 0.7‰), consistent with equilibrium fractionation with gaseous species. The δ15N in bulk deposition NH4+ varied by more than 40‰, and spatial variation in δ15N within storms exceeded 10‰. Sporadically high values of δ15N were thus consistent with increased particulate N contributions as well as potential N source variation. Despite large differences in reactive N sources, urban and agricultural landscapes are not always strongly reflected in the composition and fluxes of local N deposition—an important consideration for regional-scale ecosystem models.

An improved method for the separation of the components of plastic explosives is described with the goal of stable isotope ratio analysis of each isolated component. The binder and plasticizer of a plastic explosive were extracted into cyclohexane, leaving the explosive components and other insoluble material. The plasticizers, oils, and additives were next extracted from the dried cyclohexane-soluble fraction into acetone, leaving the polymeric binder. Plasticizers, oils, and additives were identified by GC–MS and individual plasticizers, oils, dyes, and antioxidants were isolated by GC and/or flash chromatography free of interfering materials. The explosive components were extracted from the cyclohexane-insoluble fraction with acetone, and then quantitatively analyzed for individual explosive compounds via HPLC-UV/Vis spectroscopy. Individual explosive compounds were isolated via preparative HPLC. The separation process was validated by gravimetric, HPLC-UV/Vis, EA, GC–MS, TC/EA, and FTIR results consistent with the expected formulation of the plastic explosives. The isolated components were analyzed for component-specific stable isotope ratios. Control mixtures of previously characterized components of two common plastic explosive formulations were also separated and analyzed. These isolated components retained the isotope ratios prior to mixture, demonstrating the robustness and reliability of the technique. Two example C-4 explosives from different sources, with indistinguishable chemical composition and raw explosive 13 C/ 12 C and 15 N/ 14 N isotope ratios, were extracted and analyzed. The resultant binder and plasticizer 2 H/ 1 H and 13 C/ 12 C results were used to discriminate between the two C-4 samples that were otherwise apparently identical.

Water extraction for anthropogenic use has become a major flux in the hydrological cycle. With increasing demand for water and challenges supplying it in the face of climate change, there is a pressing need to better understand connections between human populations, climate, water extraction, water use, and its impacts. To understand these connections, we collected and analyzed stable isotopic ratios of more than 800 urban tap water samples in a series of semiannual water surveys (spring and fall, 2013 to 2015) across the Salt Lake Valley (SLV) of northern Utah. Consistent with previous work, we found that mean tap water had a lower 2H and 18O concentration than local precipitation, highlighting the importance of nearby montane winter precipitation as source water for the region. However, we observed strong and structured spatiotemporal variation in tap water isotopic compositions across the region which we attribute to complex distribution systems, varying water management practices and multiple sources used across the valley. Water from different sources was not used uniformly throughout the area and we identified significant correlation between water source and demographic parameters including population and income. Isotopic mass balance indicated significant inter- and intra-annual variability in water losses within the distribution network due to evaporation from surface water resources supplying the SLV. Our results demonstrate the effectiveness of isotopes as an indicator of water management strategies and climate impacts within regional urban water systems, with potential utility for monitoring, regulation, forensic and a range of water resource research. This article is protected by copyright. All rights reserved.

Macrosystems program in the Emerging Frontiers section of the U.S. National Science Foundation (NSF) [1065790]; Interuniversity Training Program in Continental-scale Ecology (NSF) [1137336]; Swiss National Science Foundation [P300P2_154543]

Stable isotopes are being used for forensic science studies, with applications to both natural and manufactured products. In this review we discuss how scientific evidence can be used in the legal context and where the scientific progress of hypothesis revisions can be in tension with the legal expectations of widely used methods for measurements. Although this review is written in the context of US law, many of the considerations of scientific reproducibility and acceptance of relevant scientific data span other legal systems that might apply different legal principles and therefore reach different conclusions. Stable isotopes are used in legal situations for comparing samples for authenticity or evidentiary considerations, in understanding trade patterns of illegal materials, and in understanding the origins of unknown decedents. Isotope evidence is particularly useful when considered in the broad framework of physiochemical processes and in recognizing regional to global patterns found in many materials, including foods and food products, drugs, and humans. Stable isotopes considered in the larger spatial context add an important dimension to forensic science.