Updates to instrumentation and protocols for isotopic analysis of nitrate by the denitrifier method.

RATIONALE: The denitrifier method allows for highly sensitive measurement of the (15) N/(14) N (δ(15) N value) and (18) O/(16) O (δ(18) O value) of nitrate dissolved in natural waters and for highly sensitive δ(15) N measurement of other N forms (e.g., organic N) that can be converted into nitrate. Here, updates to instrumentation and protocols are described, and improvements in data quality are demonstrated. METHODS: A 'heart cut' of the N2 O was implemented in the extraction system to (1) minimize introduction of contaminants into the mass spectrometer, reducing isotopic drift and (2) decrease the fraction of sample lost at the open split to improve sensitivity. Referencing protocols were updated, including a correction scheme for a weak dependence of nitrate δ(18) O values on nitrate concentration. Analyses of samples from the US GEOTRACES North Atlantic Program and of reference solutions from the same analysis batches were used to characterize performance. RESULTS: The drift is typically <0.1‰ for both δ(15) N and δ(18) O values. Within-batch and inter-batch replication yields 1 standard deviation (SD) of ≤0.06‰ for δ(15) N values and ≤0.14‰ for δ(18) O values down to 5 µM nitrate and ≤0.08‰ and ≤0.23‰ at 2 and 1 µM. The blank is typically 0.06 nmol N, 0.3% of the N in a 20 nmol N sample. Differences between reference materials in seawater are indistinguishable from reported differences for δ(15) N values, with a contraction for δ(18) O values of ≤5%. CONCLUSIONS: The new instrumentation and protocols yield nitrate isotopic data with external precision of ≤0.1‰ for large sample sets such as those derived from oceanographic sections. Further study should investigate the causes of (1) the weak dependence of nitrate δ(18) O values on nitrate concentration and (2) the inter-batch variation in the δ(18) O contraction (due mostly to oxygen atom exchange with water). Nevertheless, comprehensive correction schemes are in place for the measurement of both the δ(15) N and δ(18) O values of nitrate. Copyright © 2016 John Wiley & Sons, Ltd.

Genetic and morphometric evidence on a Galápagos Island exposes founder effects and diversification in the first-known (truly) feral western dog population.

Domesticated animals that revert to a wild state can become invasive and significantly impact native biodiversity. Although dogs can be problematic locally, only the Australasian dingo is known to occur in isolation from humans. Western dogs have experienced more intense artificial selection, which potentially limits their invasiveness. However, feral dogs eradicated from Isabela Island, Galápagos in the 1980s could be the first-known exception. We used DNA and morphometric data from 92 of these dogs to test the hypotheses that (i) these dogs persisted independently of humans for up to a century and a half since descending from a handful of dogs introduced in the early 1800s, vs. (ii) similarly to other western feral dog populations, they reflected continuous recruitment of strays from human settlements on a portion of the Island. We detected one dominant maternal lineage and one dominant paternal lineage shared by the three subpopulations, along with low autosomal genetic diversity, consistent with the hypothesized common origins from a small founder population. Genetic diversity patterns among the three island subpopulations were consistent with stepping-stone founder effects, while morphometric differentiation suggested rapid phenotypic divergence, possibly due to drift and reinforced by selection corresponding to distinct microclimates and habitats on Isabela. Despite the continued presence of free-ranging dogs in the vicinity of settlements on Isabela and other Galápagos Islands, feral populations have not reestablished in remote areas since the 1980s, emphasizing the rarity of conditions necessary for feralization of modern western dogs.

N2 fixation estimates in real-time by cavity ring-down laser absorption spectroscopy.

The most common currency for estimating N(2) fixation is acetylene reduction to ethylene. Real-time estimates of nitrogen fixation are needed to close the global nitrogen budget and these remain a critical gap in both laboratory and field experiments. We present a new method for continuous real-time measurements of ethylene production: Acetylene Reduction Assays by Cavity ring-down laser Absorption Spectroscopy (ARACAS). In ARACAS, air in the headspace of an incubation chamber is circulated with a diaphragm pump through a cavity ring-down ethylene spectrometer and back to the incubation chamber. This paper describes the new approach and its benefits compared to the conventional detection of ethylene by flame ionization detector gas chromatography. First, the detection of acetylene reduction to ethylene is non-intrusive and chemically non-destructive, allowing for real-time measurements of nitrogenase activity. Second, the measurements are made instantaneously and continuously at ppb levels, allowing for observation of real-time kinetics on time intervals as short as a few seconds. Third, the instrument can be automated for long time periods of measurement. Finally, the technique will be widely accessible by the research community as it can be readily adapted to most existing acetylene reduction protocols and is based on a modestly priced, commercially available instrument. We illustrate its use for measuring N(2) fixation using two species, the diazotrophic bacterium Azotobacter vinelandii and the lichen Peltigera praetextata. We also discuss potential limitations of the approach, primarily the implications of leaks in the analyzer, as well as future improvements.

Continuous high-frequency dissolved O2/Ar measurements by equilibrator inlet mass spectrometry.

The oxygen (O(2)) concentration in the surface ocean is influenced by biological and physical processes. With concurrent measurements of argon (Ar), which has similar solubility properties as oxygen, we can remove the physical contribution to O(2) supersaturation and determine the biological oxygen supersaturation. Biological O(2) supersaturation in the surface ocean reflects the net metabolic balance between photosynthesis and respiration, i.e., the net community productivity (NCP). We present a new method for continuous shipboard measurements of O(2)/Ar by equilibrator inlet mass spectrometry (EIMS). From these measurements and an appropriate gas exchange parametrization, NCP can be estimated at high spatial and temporal resolution. In the EIMS configuration, seawater from the ship's continuous intake flows through a cartridge enclosing a gas-permeable microporous membrane contactor. Gases in the headspace of the cartridge equilibrate with dissolved gases in the flowing seawater. A fused-silica capillary continuously samples headspace gases, and the O(2)/Ar ratio is measured by mass spectrometry. The ion current measurements on the mass spectrometer reflect the partial pressures of dissolved gases in the water flowing through the equilibrator. Calibration of the O(2)/Ar ion current ratio (32/40) is performed automatically every 2 h by sampling ambient air through a second capillary. A conceptual model demonstrates that the ratio of gases reaching the mass spectrometer is dependent on several parameters, such as the differences in molecular diffusivities and solubilities of the gases. Laboratory experiments and field observations performed by EIMS are discussed. We also present preliminary evidence that other gas measurements, such as N(2)/Ar and pCO(2) measurements, may potentially be performed with EIMS. Finally, we compare the characteristics of the EIMS with the previously described membrane inlet mass spectrometry (MIMS) approach.

Usual interstitial pneumonia in an adolescent with ABCA3 mutations.

Many diverse and frequently idiopathic disorders cause interstitial lung disease (ILD) in children. Although the histologic patterns of ILD in children and adults share similar features, important differences exist in etiology, clinical manifestations, and outcome. Usual interstitial pneumonia (UIP) is the most frequent histologic pattern in adult ILD; however, the characteristic histologic features of UIP have yet to be demonstrated in a child. We report a 15-year-old boy with the UIP pattern of pulmonary fibrosis who had mutations in the adenosine triphosphate-binding-cassette-A3 gene. Discovery of how genetic mutations of proteins involved in surfactant biosynthesis lead to progressive fibrosis will have implications for the understanding of the pathogenesis and clinical manifestations of ILD in both adults and children.

The contemporary degassing rate of 40Ar from the solid Earth.

Knowledge of the outgassing history of radiogenic (40)Ar, derived over geologic time from the radioactive decay of (40)K, contributes to our understanding of the geodynamic history of the planet and the origin of volatiles on Earth's surface. The (40)Ar inventory of the atmosphere equals total (40)Ar outgassing during Earth history. Here, we report the current rate of (40)Ar outgassing, accessed by measuring the Ar isotope composition of trapped gases in samples of the Vostok and Dome C deep ice cores dating back to almost 800 ka. The modern outgassing rate (1.1 +/- 0.1 x 10(8) mol/yr) is in the range of values expected by summing outgassing from the continental crust and the upper mantle, as estimated from simple calculations and models. The measured outgassing rate is also of interest because it allows dating of air trapped in ancient ice core samples of unknown age, although uncertainties are large (+/-180 kyr for a single sample or +/-11% of the calculated age, whichever is greater).

The Southern Ocean biological response to aeolian iron deposition.

Biogeochemical rate processes in the Southern Ocean have an important impact on the global environment. Here, we summarize an extensive set of published and new data that establishes the pattern of gross primary production and net community production over large areas of the Southern Ocean. We compare these rates with model estimates of dissolved iron that is added to surface waters by aerosols. This comparison shows that net community production, which is comparable to export production, is proportional to modeled input of soluble iron in aerosols. Our results strengthen the evidence that the addition of aerosol iron fertilizes export production in the Southern Ocean. The data also show that aerosol iron input particularly enhances gross primary production over the large area of the Southern Ocean downwind of dry continental areas.

Challenges to improving chronic disease care and training in residencies.

PURPOSE: To improve quality of care for chronic disease, professional organizations and medical providers are adopting new care models. The transition to better delivery systems is not easy and there are many barriers under the best of circumstances. This study investigated residency-based experiences with changes in teaching and delivery of chronic disease care. METHOD: In 2004-05 at the University of Southern California, the authors conducted qualitative cross-sectional in-depth interviews with directors of grant-funded residency-based chronic care projects. Open- and closed-ended questions explored the intent of and the challenges encountered by primary care residencies implementing improvements in chronic disease care and training. RESULTS: Six out of 14 program director responded, reporting that rotation-based and longitudinal experiences were used to teach and deliver improved chronic disease care. Common challenges were identified across residency sites, as well as challenges unique to particular residency settings. Among these challenges were engaging faculty and residents who spend limited time in the practice center, as well as institutional barriers related to authority, competing priorities, process, and resources. CONCLUSIONS: Successful innovations for chronic disease care and training are possible in residencies, but their implementation cannot be taken lightly. There are predictable barriers that can be dealt with locally, but also others that would benefit from coordinated national attention.