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A stable isotope record of late Quaternary hydrologic change in the northwestern Brooks Range, Alaska (eastern Beringia)

A submillennial-resolution record of lake water oxygen isotope composition (δ 18 O) from chironomid head capsules is presented from Burial Lake, northwest Alaska. The record spans the Last Glacial Maximum (LGM; ~20–16k cal a bp ) to the present and shows a series of large lake δ 18 O shifts (~5‰). Relatively low δ 18 O values occurred during a period covering the LGM, when the lake was a shallow, closed-basin pond. Higher values characterize deglaciation (~16–11.5k cal a bp ) when the lake was still closed but lake levels were higher. A rapid decline between ~11 and 10.5k cal a bp indicates that lake levels rose to overflowing. Lake δ 18 O values are interpreted to reflect the combined effects of changes in lake hydrology, growing season temperature and meteoric source water as well as large-scale environmental changes impacting this site, including opening of the Bering Strait and shifts in atmospheric circulation patterns related to ice-sheet dynamics. The results indicate significant shifts in precipitation minus evaporation across the late Pleistocene to early Holocene transition, which are consistent with temporal patterns of vegetation change and paludification. This study provides new perspectives on the paleohydrology of eastern Beringia concomitant with human migration and major turnover in megafaunal assemblages.

Alaska↗

Use of upland and riparian areas by wintering bald eagles and implications for wind energy

Weather can shape movements of animals and alter their exposure to anthropogenic threats. Bald eagles ( Haliaeetus leucocephalus ) are increasingly at risk from collision with turbines used in onshore wind energy generation. In the midwestern United States, development of this energy source typically occurs in upland areas that bald eagles use only intermittently. Our objective was to determine the factors that cause wintering bald eagles to occupy riparian areas and riskier, upland areas. We tracked 20 bald eagles using telemetry in the Upper Midwest (MN, IA, MO, WI, IL, USA) during winter 2014–2015 and 2015–2016 and evaluated habitat use by eagles in response to variation in weather and time of year. Eagles used riparian areas more when wind speed and atmospheric pressure were low. Exclusive use of uplands was more frequent during weather systems with low pressure and high humidity and after long periods of cold weather. There was a non‐linear response to time of year (measured by days before migration) in the frequency of exclusive use of uplands or riparian areas. Probability of exclusive use of either landscape was generally constant within 95 days prior to migration. The probability of use of riparian areas, however, was markedly less during dates >100 days before migration. Our results suggest that eagles are most likely to be exposed to wind energy developments located in upland areas during low pressure systems, after long periods of cold weather, and several months before the onset of spring migration. This information helps to better understand the factors influencing bald eagle habitat use in winter and will be useful to managers and developers wishing to establish effective strategies to avoid, minimize, and mitigate take, and to survey for mortalities at wind energy developments.

Illinois, Iowa, Minnesota, Missouri, Wisconsin↗

Conservation implications of spatiotemporal variation in the terrestrial ecology of Western spadefoots

Conservation of species reliant on ephemeral resources can be especially challenging in the face of a changing climate. Western spadefoots ( Spea hammondii ) are small burrowing anurans that breed in ephemeral pools, but adults spend the majority of their lives underground in adjacent terrestrial habitat. Western spadefoots are of conservation concern throughout their range because of habitat loss, but little is known about the activity patterns and ecology of their terrestrial life stage. We conducted a radio-telemetry study of adult western spadefoots at 2 sites in southern California, USA, from December 2018 to November 2019 to characterize their survival, behavior, and movements from breeding through aestivation to refine conservation and management for the species. Western spadefoot survival varied seasonally, with risk of mortality higher in the active season than during aestivation. The probability of movement between successive observations was higher during the winter and spring and when atmospheric moisture was high and soil water content at 10-cm depth was low. The amount of rain between observations had the strongest effect on the probability of movement between observations; for every 20 mm of rainfall between observations, western spadefoots were 2.4 times more likely to move. When movements occurred, movement rates were highest when both relative humidity and soil water content at 10-cm depth were high. The conditions under which western spadefoots were likely active on the surface, likely to have moved, and moved at the highest rates are conditions that reduce the risk of desiccation of surface-active spadefoots. Western spadefoot home range areas varied between study sites and were mostly <1 ha, although 1 individual's home range area was >6 ha. Western spadefoots rapidly dispersed from the breeding pools, and asymptotic distances from the breeding pool were generally reached by June. The asymptotic distance from the breeding pool varied between sites, with the 95th percentile of the posterior predictive distribution reaching 486 m at 1 site and 187 m at the other. Western spadefoots did not select most habitat components disproportionately to their availability, but at Crystal Cove State Park, they avoided most evaluated vegetation types (graminoids, forbs, and shrubs). Spatial variation was evident in most evaluated western spadefoot behaviors; context-dependent behavior suggests that site-specific management is likely necessary for western spadefoots. Furthermore, comparison with an earlier study of western spadefoots at Crystal Cove State Park indicated substantial temporal variation in western spadefoot behavior. Therefore, basing management decisions on short-term studies might fail to meet conservation objectives. Better understanding the influences of spatial context and climatic variation on western spadefoot behavior will improve conservation efforts for this species.

California↗

Ecosystem variability along the estuarine salinity gradient: Examples from long-term study of San Francisco Bay

The salinity gradient of estuaries plays a unique and fundamental role in structuring spatial patterns of physical properties, biota, and biogeochemical processes. We use variability along the salinity gradient of San Francisco Bay to illustrate some lessons about the diversity of spatial structures in estuaries and their variability over time. Spatial patterns of dissolved constituents (e.g., silicate) can be linear or nonlinear, depending on the relative importance of river-ocean mixing and internal sinks (diatom uptake). Particles have different spatial patterns because they accumulate in estuarine turbidity maxima formed by the combination of sinking and estuarine circulation. Some constituents have weak or no mean spatial structure along the salinity gradient, reflecting spatially distributed sources along the estuary (nitrate) or atmospheric exchanges that buffer spatial variability of ecosystem metabolism (dissolved oxygen). The density difference between freshwater and seawater establishes stratification in estuaries stronger than the thermal stratification of lakes and oceans. Stratification is strongest around the center of the salinity gradient and when river discharge is high. Spatial distributions of motile organisms are shaped by species-specific adaptations to different salinity ranges (shrimp) and by behavioral responses to environmental variability (northern anchovy). Estuarine spatial patterns change over time scales of events (intrusions of upwelled ocean water), seasons (river inflow), years (annual weather anomalies), and between eras separated by ecosystem disturbances (a species introduction). Each of these lessons is a piece in the puzzle of how estuarine ecosystems are structured and how they differ from the river and ocean ecosystems they bridge.

California↗

Historical patterns of acidification and increasing CO2 flux associated with Florida springs

Florida has one of the highest concentrations of springs in the world, with many discharging into rivers and predominantly into eastern Gulf of Mexico coast, and they likely influence the hydrochemistry of these adjacent waters; however, temporal and spatial trends have not been well studied. We present over 20 yr of hydrochemical, seasonally sampled data to identify temporal and spatial trends of pH, alkalinity, partial pressure of carbon dioxide (pCO 2 ), and CO 2 flux from five first-order-magnitude (springs that discharge greater than 2.83 m 3 s −1 ) coastal spring groups fed by the Floridan Aquifer System that ultimately discharge into the Gulf of Mexico. All spring groups had pCO 2 levels (averages 3174.3–6773.2 μatm) that were much higher than atmospheric levels of CO 2 and demonstrated statistically significant temporal decreases in pH and increases in CO 2 flux, pCO 2 , and alkalinity. Total carbon flux emissions increased from each of the spring groups by between 3.48 × 10 7 and 2.856 × 10 8 kg C yr −1 over the time period. By 2013 the Springs Groups in total emitted more than 1.1739 × 10 9 kg C yr −1 . Increases in alkalinity and pCO 2 varied from 90.9 to 347.6 μmol kg −1 and 1262.3 to 2666.7 μatm, respectively. Coastal data show higher CO 2 evasion than the open Gulf of Mexico, which suggests spring water influences nearshore waters. The results of this study have important implications for spring water quality, dissolution of the Florida carbonate platform, and identification of the effect and partitioning of carbon fluxes to and within coastal and marine ecosystems.

Florida↗

From forests to fish: Mercury in mountain lake food webs influenced by factors at multiple scales

Mountain lakes, while seemingly pristine, have been subjected to historical fish stocking practices and exposure to atmospherically deposited contaminants like mercury. Mercury bioaccumulation in these ecosystems varies widely due to strong environmental gradients, and there are complex, hierarchical factors that affect mercury transport and loading, methylmercury production, and food web biomagnification. We sought to assess how representative variables associated with watershed, lake, and food web‐scale processes—specifically, catchment tree cover, lake benthic primary production, and fish diet, respectively—are associated with mercury concentrations in mountain lake fish. Mean fish mercury concentrations varied threefold between lakes, with nearshore tree cover and fish diet accounting for the most variance in fish mercury. Tree cover was likely positively correlated to fish Hg due to its contributions to local deposition and its effect on lake biogeochemistry. Fish with benthic diets tended to have higher mercury concentrations, illustrating that food web processes are an important consideration when investigating drivers of contaminant bioaccumulation. Our results suggest that both landscape and ecological factors are determinants of fish mercury bioaccumulation, and thus variables at multiple scales should be considered when managing mountain lake food webs for mercury exposure risk.

Washington↗

Spatial and temporal variability in summertime dissolved carbon dioxide and methane in temperate ponds and shallow lakes

Small waterbodies have potentially high greenhouse gas emissions relative to their small footprint on the landscape, although there is high uncertainty in model estimates. Scaling their carbon dioxide (CO 2 ) and methane (CH 4 ) exchange with the atmosphere remains challenging due to an incomplete understanding and characterization of spatial and temporal variability in CO 2 and CH 4 . Here, we measured partial pressures of CO 2 ( p CO 2 ) and CH 4 ( p CH 4 ) across 30 ponds and shallow lakes during summer in temperate regions of Europe and North America. We sampled each waterbody in three locations at three times during the growing season, and tested which physical, chemical, and biological characteristics related to the means and variability of p CO 2 and p CH 4 in space and time. Summer means of p CO 2 and p CH 4 were inversely related to waterbody size and positively related to floating vegetative cover; p CO 2 was also positively related to dissolved phosphorus. Temporal variability in partial pressure in both gases weas greater than spatial variability. Although sampling on a single date was likely to misestimate mean seasonal p CO 2 by up to 26%, mean seasonal p CH 4 could be misestimated by up to 64.5%. Shallower systems displayed the most temporal variability in p CH 4 and waterbodies with more vegetation cover had lower temporal variability. Inland waters remain one of the most uncertain components of the global carbon budget; understanding spatial and temporal variability will ultimately help us to constrain our estimates and inform research priorities.

Limnology and Oceanography↗

Deep learning of estuary salinity dynamics is physically accurate at a fraction of hydrodynamic model computational cost

Salinity dynamics in the Delaware Bay estuary are a critical water quality concern as elevated salinity can damage infrastructure and threaten drinking water supplies. Current state-of-the-art modeling approaches use hydrodynamic models, which can produce accurate results but are limited by significant computational costs. We developed a machine learning (ML) model to predict the 250 mg L −1 Cl − isochlor, also known as the “salt front,” using daily river discharge, meteorological drivers, and tidal water level data. We use the ML model to predict the location of the salt front, measured in river miles (RM) along the Delaware River, during the period 2001–2020, and we compare predictions of the ML model to the hydrodynamic Coupled Ocean–Atmosphere-Wave-Sediment Transport (COAWST) model. The ML model predicts the location of the salt front with greater accuracy (root mean squared error [RMSE] = 2.52 RM) than the COAWST model does (RMSE = 5.36); however, the ML model struggles to predict extreme events. Furthermore, we use functional performance and expected gradients, tools from information theory and explainable artificial intelligence, to show that the ML model learns physically realistic relationships between the salt front location and drivers (particularly discharge and tidal water level). These results demonstrate how an ML modeling approach can provide predictive and functional accuracy at a significantly reduced computational cost compared to process-based models. In addition, these results provide support for using ML models in operational forecasting, scenario testing, management decisions, hindcasting, and resulting opportunities to understand past behavior and develop hypotheses.

Limnology and Oceanography↗

Increasing artificial light at night enhances salmonid predator foraging efficiency in an urbanized lake

Artificial light at night (ALAN) poses a threat to ecosystems globally. It includes both direct and indirect light, or skyglow, which occurs when ALAN scatters in the atmosphere, extending beyond its original source. We analyzed ALAN trends in Lake Washington, WA, from 2014 to 2023 using Visible Infrared Imaging Radiometer Suite (VIIRS) nighttime light measurements, evaluated the relationship between in situ and satellite measurements, and modeled predator search volumes for a juvenile salmon predator, cutthroat trout ( Oncorhynchus clarki ), as a function of ambient light and turbidity conditions. Open water regions experienced significant increases in ALAN, while nearshore areas primarily showed no or negative trends, revealing the role of skyglow in shaping open water light environments. Using a visual foraging model for cutthroat trout, we found that juvenile salmon at the shallow southern pelagic site experienced light 28 times brighter, resulting in a 168% greater predation vulnerability than those at the northern site. In the Ship Canal, a narrow corridor for outmigrating salmon, predator search volumes were 249% higher than at the southern site. These contrasts in predation vulnerability demonstrate how local conditions influence predator–prey dynamics and provide critical insight for targeting mitigation of both nearshore and distant light sources.

Washington↗

Validity of the Landsat surface reflectance archive for aquatic science: Implications for cloud-based analysis

Originally developed for terrestrial science and applications, the US Geological Survey Landsat surface reflectance (SR) archive spanning ~ 40 yr of observations has been increasingly utilized in large-scale water-quality studies. These products, however, have not been rigorously validated using in situ measured reflectance. This letter quantifies and demonstrates the quality of the SR products by harnessing a sizeable global dataset ( N = 1100). We found that the Landsat 8/9 SR in the green and red bands marginally meet the targeted accuracy requirements (30%), whereas the uncertainties in the blue and coastal-aerosol bands ranged from 48% to 110%. We further observed > +25% biases in the visible bands of Landsat 5/7 SR, which can introduce an apparent downward trend when applied in time-series analyses combined with Landsat 8/9. Users must exercise caution when using this archive for trend analyses, and progress in atmospheric correction is required to foster advanced applications of the Landsat archive for aquatic science.

Limnology and Oceanography Letters↗

Arctic fishes reveal patterns in radiocarbon age across habitats and with recent climate change

Climate change alters the sources and age of carbon in Arctic food webs by fostering the release of older carbon from degrading permafrost. Radiocarbon ( 14 C) traces carbon sources and age, but data before rapid warming are rare and limit assessments over time. We capitalized on 14 C data collected ~ 40 years ago that used fish as natural samplers by resampling the same species today. Among resampled fish, those using freshwater food webs had the oldest 14 C ages (> 1000 yr BP), while those using marine food webs had the youngest 14 C ages (near modern). One migratory species encompassed the entire range of 14 C ages because juveniles fed in freshwater streams and adults fed in offshore marine habitats. Over ~ 40 yr, average 14 C ages of freshwater and marine feeding fish shifted closer to atmospheric values, suggesting a potential influence from “greening of the Arctic.”

Alaska↗

Spatial mapping of dissolved methane using an in situ sensor in Puget Sound

Release of methane, as gas bubbles or in the dissolved phase, from the seafloor has been observed in coastal waters (< 200 m) and deep ocean basins (> 1000 m). Methane dissolution within the water column affects the geochemistry of the surrounding water, leading to localized oxygen loss and potential escape to the atmosphere, particularly from shallower sites. Traditional methods for detecting and quantifying dissolved methane rely on collecting discrete water samples for ship- or land-based ex situ analysis and post processing. Here, we report on the use of a reduced response time, in situ methane sensor, the Sensor for Aqueous Gases in the Environment (SAGE), for detecting and quantifying dissolved methane concentrations in a wide range of seafloor environments. During a Fall 2022 research cruise on the R/V Thomas G. Thompson in Puget Sound, SAGE was integrated onto a towed conductivity/temperature/depth rosette and deep-sea camera system with live-stream 1 Hz telemetry and used to spatially map the concentration of methane approximately 1 m above the seafloor. The site had been previously identified as an active methane plume field characterized by gas bubbles, fluid venting, and a faulted seabed. The widespread background dissolved concentration of methane measured by SAGE was 83 nM, and a range of 78–670 nM was observed throughout the survey. The results highlight the capacity of SAGE to map the spatial and temporal variability of dissolved methane concentrations in situ and to identify and localize sites of variable methane emissions from the seafloor.

Washington↗

Phenological variation in spring migration timing of adult alewife (Alosa pseudoharengus) in coastal Massachusetts

The timing of biological events in plants and animals, such as migration and reproduction, is shifting due to climate change. Anadromous fishes are particularly susceptible to these shifts as they are subject to strong seasonal cycles when transitioning between marine and freshwater habitats to spawn. We used linear models to determine the extent of phenological shifts in adult Alewife Alosa pseudoharengus as they migrated from ocean to freshwater environments during spring to spawn at 12 sites along the northeastern USA. We also evaluated broadscale oceanic and atmospheric drivers that trigger their movements from offshore to inland habitats, including sea surface temperature, North Atlantic Oscillation index, and Gulf Stream index. Run timing metrics of initiation, median (an indicator of peak run timing), end, and duration were found to vary among sites. Although most sites showed negligible shifts towards earlier timing, statistically significant changes were detected in three systems. Overall, winter sea surface temperature, spring and fall transition dates, and annual run size were the strongest predictors of run initiation and median dates, while a combination of within-season and seasonal-lag effects influenced run end and duration timing. Disparate results observed across the 12 spawning runs suggest that regional environmental processes were not consistent drivers of phenology and local environmental and ecological conditions may be more important. Additional years of data to extend time series and monitoring of Alewife timing and movements in nearshore habitats may provide important information about staging behaviors just before adults transition between ocean and freshwater habitats.

Massachusetts↗

Data-limited fishery assessment methods shed light on the exploitation history and population dynamics of Endangered Species Act-listed Yelloweye Rockfish in Puget Sound, Washington

Objective The distinct population segment (DPS) of Yelloweye Rockfish Sebastes ruberrimus inhabiting the Puget Sound/Georgia Basin was listed under the Endangered Species Act (ESA) in 2010, and a formal recovery plan for the DPS was published by National Oceanic and Atmospheric Administration Fisheries in 2017. In this recovery plan, the biological criteria for delisting or downlisting were specified as certain levels of spawning potential ratio (SPR), a commonly used metric of equilibrium stock status for commercially exploited fishes. Although this metric can be estimated from length compositions, the combination of length data with a catch history (which was not previously available for this DPS) improves our understanding of population dynamics over time and allows us to estimate a different measure of stock status, relative (to unfished) spawning stock biomass (SSB), rather than only SPR. Methods To estimate relative SSB and reconstruct the historical dynamics of this DPS, we reconstructed the catch history from fisheries records, collated length data from historical and contemporary hook-and-line surveys, and fitted a data-limited version of a statistical catch-at-age model. Result Despite a high level of uncertainty, we estimated that Yelloweye Rockfish in Puget Sound are above 25% of unfished biomass (a reference point detailed in the recovery criteria) under the assumption of deterministic recruitment, presenting the first direct estimates of Yelloweye Rockfish population status in Puget Sound. Conclusion However, as informed by recent genetic studies, the DPS boundaries of ESA-listed Yelloweye Rockfish extend from South Puget Sound to Queen Charlotte Strait in British Columbia. The Canadian portion of this population is managed separately and is currently estimated to be at 32% of unfished biomass (95% quantiles = 15%–68%). Thus, the disjunction between the biological boundaries of the population and the jurisdictional boundaries between Canada and the United States presents an additional source of uncertainty in assessing recovery that must be addressed to achieve DPS-wide recovery goals.

Washington↗

Review: Endophytic microbes and their potential applications in crop management

Endophytes are microbes (mostly bacteria and fungi) present in plants. Endophytic microbes are often functional in that they may carry nutrients from the soil into plants, modulate plant development, increase stress tolerance of plants, suppress virulence in pathogens, increase disease resistance in plants, and suppress development of competitor plant species. Endophytic microbes have been shown: 1) obtain nutrients in soils and transfer nutrients to plants in the rhizophagy cycle and other nutrient‐transfer symbioses; 2) increase plant growth and development; 3) reduce oxidative stress of hosts; 4) protect plants from disease; 5) deter feeding by herbivores; and 6) suppress growth of competitor plant species. Because of the effective functions of endophytic microbes, we suggest that endophytic microbes may significantly reduce use of agrochemicals (fertilizers, fungicides, insecticides, and herbicides) in the cultivation of crop plants. The loss of endophytic microbes from crop plants during domestication and long‐term cultivation could be remedied by transfer of endophytes from wild relatives of crops to crop species. Increasing atmospheric carbon dioxide levels could reduce the efficiency of the rhizophagy cycle due to repression of reactive oxygen used to extract nutrients from microbes in roots.

Pest Management Science↗

Analysis of the surface hydrology in a regional climate model

This paper discusses the surface hydrology of a multi‐year simulation of present day climate over the United States (US) conducted with a regional climate model (RegCM) nested within a general circulation model (GCM). The RegCM, which is run with a 60 km gridpoint spacing is interactively coupled with a state‐of‐the‐art surface physics package that includes full surface hydrology calculations (the Biosphere‐Atmosphere Transfer Scheme or BATS). The hydrologic budgets of ten regional drainage basins in the US are analysed. Model results are compared with available observations and with results from previous modelling experiments to evaluate the feasibility of using nested RegCM/GCM models for hydrology studies. In our experiment, the model captures the basic seasonality of the basin hydrologic budgets, although the simulated precipitation amounts are too high over the western US and too low over the eastern US. As a result, runoff, snow cover and soil water content are underestimated over the eastern US basins, while evaporation and runoff are overestimated in some of the western US basins. Topographically induced characteristics of precipitation, snow cover and runoff are well simulated over the mountainous western regions. Also well captured is the inter‐basin variation of hydrologic budgets which occurs in response to different climatic settings. The springtime snowmelt and peak runoff season generally occurs in the model earlier in the year than is observed. Although our work indicates that the coupled regional modelling system can be useful in applications to hydrological studies, results from this experiment indicate that better accuracy in the simulation of regional climatic variables and more detailed representation of some hydrologic processes would be required before the coupled modelling system could be used to provide accurate assessments of hydrologic responses to climate change.

Quarterly Journal of the Royal Meteorological Soci↗

Oxygen isotopes in nitrate: New reference materials for 18O:17O:16O measurements and observations on nitrate-water equilibration

Despite a rapidly growing literature on analytical methods and field applications of O isotope-ratio measurements of NO 3 − in environmental studies, there is evidence that the reported data may not be comparable because reference materials with widely varying δ 18 O values have not been readily available. To address this problem, we prepared large quantities of two nitrate salts with contrasting O isotopic compositions for distribution as reference materials for O isotope-ratio measurements: USGS34 (KNO 3 ) with low δ 18 O and USGS35 (NaNO 3 ) with high δ 18 O and ‘mass-independent’ δ 17 O. The procedure used to produce USGS34 involved equilibration of HNO 3 with 18 O-depleted meteoric water. Nitric acid equilibration is proposed as a simple method for producing laboratory NO 3 − reference materials with a range of δ 18 O values and normal (mass-dependent) 18 O: 17 O: 16 O variation. Preliminary data indicate that the equilibrium O isotope-fractionation factor ( α ) between [NO 3 − ] and H 2 O decreases with increasing temperature from 1.0215 at 22°C to 1.0131 at 100°C. USGS35 was purified from the nitrate ore deposits of the Atacama Desert in Chile and has a high 17 O: 18 O ratio owing to its atmospheric origin. These new reference materials, combined with previously distributed NO 3 − isotopic reference materials IAEA-N3 (=IAEA-NO-3) and USGS32, can be used to calibrate local laboratory reference materials for determining offset values, scale factors, and mass-independent effects on N and O isotope-ratio measurements in a wide variety of environmental NO 3 − samples. Preliminary analyses yield the following results (normalized with respect to VSMOW and SLAP, with reproducibilities of ±0.2–0.3‰, 1 σ ): IAEA-N3 has δ 18 O = +25.6‰ and δ 17 O = +13.2‰; USGS32 has δ 18 O = +25.7‰; USGS34 has δ 18 O = −27.9‰ and δ 17 O = −14.8‰; and USGS35 has δ 18 O = +57.5‰ and δ 17 O = +51.5‰.

Rapid Communications in Mass Spectrometry↗

Using dual-bacterial denitrification to improve δ15N determinations of nitrates containing mass-independent 17O

The bacterial denitrification method for isotopic analysis of nitrate using N 2 O generated from Pseudomonas aureofaciens may overestimate δ 15 N values by as much as 1–2‰ for samples containing atmospheric nitrate because of mass-independent 17 O variations in such samples. By analyzing such samples for δ 15 N and δ 18 O using the denitrifier Pseudomonas chlororaphis , one obtains nearly correct δ 15 N values because oxygen in N 2 O generated by P. chlororaphis is primarily derived from H 2 O. The difference between the apparent δ 15 N value determined with P. aureofaciens and that determined with P. chlororaphis , assuming mass-dependent oxygen isotopic fractionation, reflects the amount of mass-independent 17 O in a nitrate sample. By interspersing nitrate isotopic reference materials having substantially different δ 18 O values with samples, one can normalize oxygen isotope ratios and determine the fractions of oxygen in N 2 O derived from the nitrate and from water with each denitrifier. This information can be used to improve δ 15 N values of nitrates having excess 17 O. The same analyses also yield estimates of the magnitude of 17 O excess in the nitrate (expressed as Δ 17 O) that may be useful in some environmental studies. The 1- σ uncertainties of δ 15 N, δ 18 O and Δ 17 O measurements are ±0.2, ±0.3 and ±5‰, respectively.

Rapid Communications in Mass Spectrometry↗