Mercury exposure of tidal marsh songbirds in the northeastern United States and its association with nest survival.

The biogeochemistry of tidal marsh sediments facilitates the transformation of mercury (Hg) into the biologically available form methylmercury (MeHg), resulting in elevated Hg exposures to tidal marsh wildlife. Saltmarsh and Acadian Nelson's sparrows (Ammospiza caudacutua and A. nelsoni subvirgatus, respectively) exclusively inhabit tidal marshes, potentially experiencing elevated risk to Hg exposure, and have experienced range-wide population declines. To characterize spatial and temporal variation of Hg exposure in these species, we sampled total mercury (THg) in blood collected from 9 populations spanning 560 km of coastline, including individuals resampled within and among years. Using concurrent nesting studies, we tested whether THg was correlated with nest survival probabilities, an index of fecundity. Blood THg ranged from 0.074-3.373 µg/g ww across 170 samples from 127 individuals. We detected high spatial variability in Hg exposure, observing differences of more than 45-fold across all individuals and 8-fold in mean blood THg among all study plots, including 4-fold between study plots within 4 km. Intraindividual changes in blood Hg exposure did not vary systematically in time but were considerable, varying by up to 2-fold within and among years. Controlling for both species differences and maximum water level, the dominant driver of fecundity in this system, nest survival probability decreased by 10% across the full range of female blood THg concentrations observed. We conclude that Hg has the potential to impair songbird reproduction, potentially exacerbating known climate-change driven population declines from sea-level rise in saltmarsh and Acadian Nelson's sparrows.

Using internet search data to understand information seeking behavior for health and conservation topics during the COVID-19 pandemic.

Emerging zoonotic diseases, such as COVID-19, exist at the intersection of human health and the environment. Public interest and support are required to maximize the effectiveness of policies to combat the current pandemic and prevent future outbreaks of zoonoses. Here, we use internet search data from the United States to investigate changes in public information seeking about topics at the intersection of health and the environment during the COVID-19 pandemic. Using breakpoint detection methods, we identify sharp increases in interest for 'wildlife trade', 'bats', and 'pangolins' in the early stages of the pandemic (on Jan. 12, Jan. 19, and Jan. 26, 2020, respectively). Network analyses also revealed increasing connectivity between terms related to human health and the environment, as well as the emergence of novel search terms pointing to a greater interest in wildlife trade and consumption. During the pandemic, the network connectivity between coronavirus keywords and conservation keywords increased, which we measured using the number of unique connections (edge connectivity, k' (G)) and the number of simple paths (Sp) between keywords. Both measures of network connectivity increased between 'coronavirus' and 'bats' or 'pangolins' (Δk' (G) = 1, ΔSp = 37), and between 'coronavirus' and 'conservation' (Δk' (G) = 1, ΔSp = 160). These findings suggest that policy and outreach efforts aimed at engaging public interest in intersectional approaches to pandemic prevention (eg: One Health, Planetary Health), may be able to take advantage of increases in public information seeking following catalyzing events during the pandemic. Further monitoring is needed to determine if these changes persist over time.

Landowner behavior can determine the success of conservation strategies for ecosystem migration under sea-level rise.

The human aspects of conservation are often overlooked but will be critical for identifying strategies for biological conservation in the face of climate change. We surveyed the behavioral intentions of coastal landowners with respect to various conservation strategies aimed at facilitating ecosystem migration for tidal marshes. We found that several popular strategies, including conservation easements and increasing awareness of ecosystem services, may not interest enough landowners to allow marsh migration at the spatial scales needed to mitigate losses from sea-level rise. We identified less common conservation strategies that have more support but that are unproven in practice and may be more expensive. Our results show that failure to incorporate human dimensions into ecosystem modeling and conservation planning could lead to the use of ineffective strategies and an overly optimistic view of the potential for ecosystem migration into human dominated areas.

Framework for quantifying population responses to disturbance reveals that coastal birds are highly resilient to hurricanes.

Changes in the frequency and severity of extreme weather may introduce new threats to species that are already under stress from gradual habitat loss and climate change. We provide a probabilistic framework that quantifies potential threats by applying concepts from ecological resilience to single populations. Our approach uses computation to compare disturbance-impacted projections to a population's normal range of variation, quantifying the full range of potential impacts. We illustrate this framework with projection models for coastal birds, which are commonly depicted as vulnerable to disturbances, especially hurricanes and oil spills. We found that populations of coastal specialists are resilient to extreme disturbances, with high resistance to the effects of short-term reductions in vital rates and recovery within 20 years. Applying the general framework presented here across disturbance-prone species and ecosystems would improve understanding of population resilience and generate specific projections of resilience that are needed for effective conservation planning.

High-resolution tide projections reveal extinction threshold in response to sea-level rise.

Sea-level rise will affect coastal species worldwide, but models that aim to predict these effects are typically based on simple measures of sea level that do not capture its inherent complexity, especially variation over timescales shorter than 1 year. Coastal species might be most affected, however, by floods that exceed a critical threshold. The frequency and duration of such floods may be more important to population dynamics than mean measures of sea level. In particular, the potential for changes in the frequency and duration of flooding events to result in nonlinear population responses or biological thresholds merits further research, but may require that models incorporate greater resolution in sea level than is typically used. We created population simulations for a threatened songbird, the saltmarsh sparrow (Ammodramus caudacutus), in a region where sea level is predictable with high accuracy and precision. We show that incorporating the timing of semidiurnal high tide events throughout the breeding season, including how this timing is affected by mean sea-level rise, predicts a reproductive threshold that is likely to cause a rapid demographic shift. This shift is likely to threaten the persistence of saltmarsh sparrows beyond 2060 and could cause extinction as soon as 2035. Neither extinction date nor the population trajectory was sensitive to the emissions scenarios underlying sea-level projections, as most of the population decline occurred before scenarios diverge. Our results suggest that the variation and complexity of climate-driven variables could be important for understanding the potential responses of coastal species to sea-level rise, especially for species that rely on coastal areas for reproduction.

Seasonal fecundity is not related to geographic position across a species' global range despite a central peak in abundance.

The range of a species is determined by the balance of its demographic rates across space. Population growth rates are widely hypothesized to be greatest at the geographic center of the species range, but indirect empirical support for this pattern using abundance as a proxy has been mixed, and demographic rates are rarely quantified on a large spatial scale. Therefore, the texture of how demographic rates of a species vary over its range remains an open question. We quantified seasonal fecundity of populations spanning the majority of the global range of a single species, the saltmarsh sparrow (Ammodramus caudacutus), which demonstrates a peak of abundance at the geographic center of its range. We used a novel, population projection method to estimate seasonal fecundity inclusive of seasonal and spatial variation in life history traits that contribute to seasonal fecundity. We replicated our study over 3 years, and compared seasonal fecundity to latitude and distance among plots. We observed large-scale patterns in some life history traits that contribute to seasonal fecundity, such as an increase in clutch size with latitude. However, we observed no relationship between latitude and seasonal fecundity. Instead, fecundity varied greatly among plots separated by as little as 1 km. Our results do not support the hypothesis that demographic rates are highest at the geographic and abundance center of a species range, but rather they suggest that local drivers strongly influence saltmarsh sparrow fecundity across their global range.

Demographic analysis demonstrates systematic but independent spatial variation in abiotic and biotic stressors across 59 percent of a global species range.

The balance of abiotic and biotic stressors experienced by a species likely varies across its range, resulting in spatially heterogeneous limitations on the species' demographic rates. Support for spatial variation in stressors (often latitudinal gradients) has been found in many species, usually with physiological or correlative occupancy data, but it has rarely been estimated directly with demographic data. We collected demographic data from 23 sites spanning the majority of the Saltmarsh Sparrow (Ammodramus caudacutus) breeding range. Using data from 837 nests, we quantified the abiotic and biotic variables most important to nest survival, which is the dominant driver of both fecundity and population growth rate in this species. We separately estimated daily nest failure probability due to nest depredation (biotic stressor) and nest flooding (abiotic stressor), which collectively account for almost all nest failure in the species. Nest depredation decreased with latitude, whereas nest flooding was not related to latitude. Instead, nest flooding was best predicted by a combination of maximum high tide, extremity of rare flooding events, and date. For a single vital rate, we observed predictable variation in competing biotic and abiotic stressors across this species range. We observed that biotic and abiotic stressors were geographically independent, both on a large spatial scale and locally. Our results suggest that stressors on the fecundity of Saltmarsh Sparrow vary systematically across its range, but independently. The observed patterns of biotic and abiotic stress provide information for efforts to conserve the Saltmarsh Sparrow, which is considered threatened. Further, understanding the effects that different stressors, and their interactions, have on demographic rates is necessary to unravel the processes that govern species distributions and to effectively conserve biodiversity in the face of global change.

El balance de factores de estrés abióticos y bióticos para una especie probablemente varía a través de su rango, dando como resultado limitaciones espaciales heterogéneas en las tasas demográficas de la especie. Se ha verificado la existencia de variación espacial en los factores de estrés (usualmente gradientes latitudinales) para muchas especies, usualmente con datos fisiológicos o de ocupación correlativa, pero raramente se ha estimado directamente con datos demográficos. Colectamos datos demográficos de 23 sitios abarcando la mayoría del rango reproductivo de Ammodramus caudacutus. Usando datos de 837 nidos, cuantificamos las variables abióticas y bióticas más importantes para la supervivencia del nido, que es la variable que determina tanto la fecundidad como la tasa de crecimiento poblacional en esta especie. Por otra parte, estimamos la probabilidad de fracaso diario del nido debido a la depredación del nido (factor de estrés biótico) e inundación del nido (factor de estrés abiótico), que juntos representaron casi todos los fracasos del nido en esta especie. La depredación del nido disminuyó con la latitud mientras que la inundación del nido no se relacionó con la latitud. En cambio, la inundación del nido se predijo mejor por una combinación del máximo superior de la marea, la extremidad de los eventos de inundación raros y la fecha. Considerando una sola tasa vital, observamos variación predecible en los factores de estrés biótico y abiótico que compiten a través del rango de la especie. Observamos que los factores de estrés biótico y abiótico fueron geográficamente independientes tanto a una escala espacial grande como a la escala local. Nuestros resultados sugieren que los factores de estrés relacionados a la fecundidad de A. caudacutus varían sistemática pero independientemente a través de su rango. Los patrones observados de estrés biótico y abiótico brindan información para los esfuerzos de conservación de A. caudacutus, una especie considerada amenazada. Más aún, es necesario entender los efectos que los diferentes factores de estrés y sus interacciones tienen en las tasas demográficas para desenmarañar los procesos que gobiernan las distribuciones de las especies y para conservar la biodiversidad de manera eficiente en miras al cambio global.

Trace Explosives Vapor Generation and Quantitation at Parts per Quadrillion Concentrations.

The generation of trace 2,4,6-trinitrotoluene (TNT), cyclotrimethylenetrinitramine (RDX), and pentaerythritol tetranitrate (PETN) vapors using a pneumatically modulated liquid delivery system (PMLDS) coupled to a polytetrafluoroethylene (PTFE) total-consumption micronebulizer is presented. The vapor generator operates in a continuous manner with final vapor concentrations proportional to the explosive concentration in aqueous solution delivered through the nebulizer and the diluent air flow rate. For quantitation of concentrations in the parts per billionvolume (ppbv) to parts per trillionvolume (pptrv) range, Tenax-TA thermal desorption tubes were used for vapor collection with subsequent analysis on a thermal-desorption system programmable-temperature vaporization gas chromatograph (TDS-PTV-GC) with a µ-ECD detector. With 30 min sample times and an average sampling rate of 100 mL min(-1), vapor concentrations of 38 pptrv for TNT, 25 pptrv for RDX, and 26 pptrv for PETN were determined. For parts per quadrillionvolume (ppqv) vapor quantitation of TNT and RDX, an online PTV-GC system with a negative-ion chemical ionization mass spectrometer (methane reagent gas) was used for direct sampling and capture of the vapor on the PTV inlet. Vapor concentrations as low as 160 ppqv and 710 ppqv for TNT and RDX were quantified, respectively, with an instrument duty cycle as low as 4 min.

Vapor detection performance of vertically aligned, ordered arrays of silicon nanowires with a porous electrode.

Vertically aligned, ordered arrays of silicon nanowires capped with a porous top electrode are used to detect gas phase ammonia and nitrogen dioxide in humidified air. The sensors had very fast response times and large signal-to-noise ratios. Calibration curves were created using both an initial slope method and a fixed-time point method. The initial-slope method had a power law dependence that correlates well with concentration, demonstrating a viable alternative for eventual quantitative vapor detection and enabling shorter sampling and regeneration times.

Periodically porous top electrodes on vertical nanowire arrays for highly sensitive gas detection.

Nanowires of various materials and configurations have been shown to be highly effective in the detection of chemical and biological species. In this paper, we report a novel, nanosphere-enabled approach to fabricating highly sensitive gas sensors based on ordered arrays of vertically aligned silicon nanowires topped with a periodically porous top electrode. The vertical array configuration helps to greatly increase the sensitivity of the sensor while the pores in the top electrode layer significantly improve sensing response times by allowing analyte gases to pass through freely. Herein, we show highly sensitive detection to both nitrogen dioxide (NO(2)) and ammonia (NH(3)) in humidified air. NO(2) detection down to 10 parts per billion (ppb) is demonstrated and an order-of-magnitude improvement in sensor response time is shown in the detection of NH(3).

Sample handling and chemical kinetics in an acoustically levitated drop microreactor.

Accurate measurement of enzyme kinetics is an essential part of understanding the mechanisms of biochemical reactions. The typical means of studying such systems use stirred cuvettes, stopped-flow apparatus, microfluidic systems, or other small sample containers. These methods may prove to be problematic if reactants or products adsorb to or react with the container's surface. As an alternative approach, we have developed an acoustically-levitated drop reactor eventually intended to study enzyme-catalyzed reaction kinetics related to free radical and oxidative stress chemistry. Microliter-scale droplet generation, reactant introduction, maintenance, and fluid removal are all important aspects in conducting reactions in a levitated drop. A three capillary bundle system has been developed to address these needs. We report kinetic measurements for both luminol chemiluminescence and the reaction of pyruvate with nicotinamide adenine dinucleotide, catalyzed by lactate dehydrogenase, to demonstrate the feasibility of using a levitated drop in conjunction with the developed capillary sample handling system as a microreactor.

Design and implementation of an efficient acoustically levitated drop reactor for in stillo measurements.

We present the details necessary for building an efficient acoustic drop levitator with reduced electrical power consumption and greater drop stability compared to previous designs. The system is optimized so that the levitated drop may be used as a chemical reactor. By introducing a temperature, pressure, and relative humidity sensor for feedback control of a linear actuator for adjusting resonator length, we have built a completely automated system capable of continuous levitation for extended periods of time. The result is a system capable of portable operation and interfacing with a variety of detection instrumentation for in stillo (in drop) measurements.

Trace explosives sensor testbed (TESTbed).

A novel vapor delivery testbed, referred to as the Trace Explosives Sensor Testbed, or TESTbed, is demonstrated that is amenable to both high- and low-volatility explosives vapors including nitromethane, nitroglycerine, ethylene glycol dinitrate, triacetone triperoxide, 2,4,6-trinitrotoluene, pentaerythritol tetranitrate, and hexahydro-1,3,5-trinitro-1,3,5-triazine. The TESTbed incorporates a six-port dual-line manifold system allowing for rapid actuation between a dedicated clean air source and a trace explosives vapor source. Explosives and explosives-related vapors can be sourced through a number of means including gas cylinders, permeation tube ovens, dynamic headspace chambers, and a Pneumatically Modulated Liquid Delivery System coupled to a perfluoroalkoxy total-consumption microflow nebulizer. Key features of the TESTbed include continuous and pulseless control of trace vapor concentrations with wide dynamic range of concentration generation, six sampling ports with reproducible vapor profile outputs, limited low-volatility explosives adsorption to the manifold surface, temperature and humidity control of the vapor stream, and a graphical user interface for system operation and testing protocol implementation.

Minimizing thermal degradation in gas chromatographic quantitation of pentaerythritol tetranitrate.

An analytical method for establishing calibration curves for the quantitation of pentaerythriol tetranitrate (PETN) from sorbent-filled thermal desorption tubes by gas chromatography with electron capture detection (TDS-GC-ECD) was developed. As PETN has been demonstrated to thermally degrade under typical GC instrument conditions, peaks corresponding to both PETN degradants and molecular PETN are observed. The retention time corresponding to intact PETN was verified by high-resolution mass spectrometry with a flowing atmospheric pressure afterglow (FAPA) ionization source, which enabled soft ionization of intact PETN eluting the GC and subsequent accurate-mass identification. The GC separation parameters were transferred to a conventional GC-ECD instrument where analytical method-induced PETN degradation was further characterized and minimized. A method calibration curve was established by direct liquid deposition of PETN standard solutions onto the glass frit at the head of sorbent-filled thermal desorption tubes. Two local, linear relationships between detector response and PETN concentration were observed, with a total dynamic range of 0.25-25ng.

Quantitative detection of trace explosive vapors by programmed temperature desorption gas chromatography-electron capture detector.

The direct liquid deposition of solution standards onto sorbent-filled thermal desorption tubes is used for the quantitative analysis of trace explosive vapor samples. The direct liquid deposition method yields a higher fidelity between the analysis of vapor samples and the analysis of solution standards than using separate injection methods for vapors and solutions, i.e., samples collected on vapor collection tubes and standards prepared in solution vials. Additionally, the method can account for instrumentation losses, which makes it ideal for minimizing variability and quantitative trace chemical detection. Gas chromatography with an electron capture detector is an instrumentation configuration sensitive to nitro-energetics, such as TNT and RDX, due to their relatively high electron affinity. However, vapor quantitation of these compounds is difficult without viable vapor standards. Thus, we eliminate the requirement for vapor standards by combining the sensitivity of the instrumentation with a direct liquid deposition protocol to analyze trace explosive vapor samples.

Dynamic headspace generation and quantitation of triacetone triperoxide vapor.

Two methods for quantitation of triacetone triperoxide (TATP) vapor using a programmable temperature vaporization (PTV) inlet coupled to a gas chromatography/mass spectrometer (GC/MS) have been demonstrated. The dynamic headspace of bulk TATP was mixed with clean humid air to produce a TATP vapor stream. Sampling via a heated transfer line to a PTV inlet with a Tenax-TA™ filled liner allowed for direct injection of the vapor stream to a GC/MS for vapor quantitation. TATP was extracted from the vapor stream and subsequently desorbed from the PTV liner for splitless injection on the GC column. Calibration curves were prepared using solution standards with a standard split/splitless GC inlet for quantitation of the TATP vapor. Alternatively, vapor was sampled onto a Tenax-TA™ sample tube and placed into a thermal desorption system. In this instance, vapor was desorbed from the tube and subsequently trapped on a liquid nitrogen cooled PTV inlet. Calibration curves for this method were prepared from direct liquid injection of standards onto samples tube with the caveat that a vacuum is applied to the tube during deposition to ensure that the volatile TATP penetrates into the tube. Vapor concentration measurements, as determined by either GC/MS analysis or mass gravimetry of the bulk TATP, were statistically indistinguishable. Different approaches to broaden the TATP vapor dynamic range, including diluent air flow, sample chamber temperature, sample vial orifice size, and sample size are discussed. Vapor concentrations between 50 and 5400ngL(-1) are reported, with stable vapor generation observed for as long as 60 consecutive hours.

Direct liquid deposition calibration method for trace cyclotrimethylenetrinitramine using thermal desorption instrumentation.

A simple method for establishing calibration curves with sorbent-filled thermal desorption tubes has been demonstrated for nitroaromatic and nitramine vapor samples using a thermal desorption system with a cooled inlet system (TDS-CIS), which was coupled to a gas chromatograph (GC) with an electron capture detector (ECD). The method relies upon the direct liquid deposition of standard solutions onto the glass frit at the head of sorbent-filled thermal desorption tubes. Linear calibration results and ideal system conditions for the TDS-CIS-GC-ECD were established for mixtures containing both cyclotrimethylenetrinitramine, a.k.a. RDX, and 2,4,6-trinitrotoluene (TNT). Because of the chemical characteristics of RDX, a higher TDS-CIS flow rate relative to the optimized approach for TNT was required for efficient RDX desorption. Simultaneous quantitation of TNT and RDX using the direct liquid deposition method with optimized instrumentation parameters for RDX were compared to results from a standard split/splitless GC inlet and a CIS.

Characterization of thermal desorption instrumentation with a direct liquid deposition calibration method for trace 2,4,6-trinitrotoluene quantitation.

The use of thermal desorption systems for the analysis of trace vapors typically requires establishing a calibration curve from vapors generated with a permeation tube. The slow equilibration time of permeation tubes causes such an approach to become laborious when covering a wide dynamic range. Furthermore, many analytes of interest, such as explosives, are not available as permeation tubes. A method for easily and effectively establishing calibration curves for explosive vapor samples via direct deposition of standard solutions on thermal desorption tubes was investigated. The various components of the thermal desorption system were compared to a standard split/splitless inlet. Calibration curves using the direct liquid deposition method with a thermal desorption unit coupled to a cryo-focusing inlet were compared to a standard split/splitless inlet, and a statistical difference was observed but does not eliminate or deter the use of the direct liquid deposition method for obtaining quantitative results for explosive vapors.

Fast carbon nanotube detectors for micro gas chromatographs.

Highly sensitive and completely reversible chemiresistor detectors based on carbon nanotubes (CNTs) were fabricated for multi-component chemical analysis. CNT detectors were used in a series configuration with a gas chromatography column and exposed to a mixture of nine different compounds. It is shown that CNT detectors were able to show parts per billion (pbb) sensitivity responses to each individual component of the mixture and detect nine distinct chemical compounds in roughly 210 s when the detector operates in current stimulated desorption (CSD) mode. This is the first demonstration of an uncoated CNT detector to analyze multi-component chemical mixtures providing an alternative yet simple sensing approach for online air quality control and health monitoring applications.

Nonthermal current-stimulated desorption of gases from carbon nanotubes.

The desorption of gases from carbon nanotubes is usually a slow process that limits the nanotubes' utility as sensors or as memristors. Here, we demonstrate that flow in the nanotube above the Poole-Frenkel conduction threshold can stimulate adsorbates to desorb without heating the sensor substantially. The method is general: alcohols, aromatics, amines, and phosphonates were all found to desorb. We postulate that the process is analogous to electron-stimulated desorption, but with an internally conducted rather than externally applied source of electrons.