Method development for thermal desorption-gas chromatography-tandem mass spectrometry (TD-GC-MS/MS) analysis of trace level fluorotelomer alcohols emitted from consumer products.

The scientific foundation for per- and polyfluoroalkyl substances (PFAS) measurements in water, soils, sediments, biosolids, biota, and outdoor air has rapidly expanded; however, there are limited efforts devoted to developing analytical methods to measure vapor-phase PFAS in indoor air. A gas chromatography-tandem mass spectrometry (GC-MS/MS) method coupled with thermal desorption (TD) sorbent tube analysis was developed to quantify trace levels of fluorotelomer alcohols (FTOHs) emitted from consumer products in the indoor environment. Method evaluation included determination of instrument detection limits (IDLs), quality assurance checks of target standards purchased from different vendors, sample loss during storage, and TD sorbent breakthrough with tubes coupled in-series. The IDLs for TD-GC-MS/MS analyses ranged from 0.07 - 0.09 ng/tube. No significant loss of FTOHs was observed during stability tests over 28 days with relative standard deviations (RSDs) of spiked TD tubes ranging from 3.1 - 7.7% and the RSDs of polypropylene copolymer vial storage of standard solutions ranging from 4.3 - 8.4%. TD tube breakthrough was minimal with recovered FTOHs in the second tubes <1% of the spiked concentrations in the first tubes with carrier gas volume up to 20 L. The method has been applied to determine FTOH emissions from three consumer products in micro-scale chambers. A liquid stone cleaner/sealer product contained the highest levels of 6:2, 8:2, and 10:2 FTOHs, while the mattress pad products contained lower levels of 8:2 and 10:2 FTOHs. The emission parameters, including the initial emission factors and first order decay rate constants, were obtained based on the experimental data. The developed methods are sensitive and specific for analysis of all four target FTOHs (4:2, 6:2, 8:2, 10:2 FTOHs) with chamber testing. The methods can be extended to indoor air sampling and could be applicable to ambient air sampling.

Integrating plant physiology into simulation of fire behavior and effects.

Wildfires are a global crisis, but current fire models fail to capture vegetation response to changing climate. With drought and elevated temperature increasing the importance of vegetation dynamics to fire behavior, and the advent of next generation models capable of capturing increasingly complex physical processes, we provide a renewed focus on representation of woody vegetation in fire models. Currently, the most advanced representations of fire behavior and biophysical fire effects are found in distinct classes of fine-scale models and do not capture variation in live fuel (i.e. living plant) properties. We demonstrate that plant water and carbon dynamics, which influence combustion and heat transfer into the plant and often dictate plant survival, provide the mechanistic linkage between fire behavior and effects. Our conceptual framework linking remotely sensed estimates of plant water and carbon to fine-scale models of fire behavior and effects could be a critical first step toward improving the fidelity of the coarse scale models that are now relied upon for global fire forecasting. This process-based approach will be essential to capturing the influence of physiological responses to drought and warming on live fuel conditions, strengthening the science needed to guide fire managers in an uncertain future.

Forecasting the influence of conservation strategies on landscape connectivity.

Maintaining and enhancing landscape connectivity reduces biodiversity declines due to habitat fragmentation. Uncertainty remains, however, about the effectiveness of conservation for enhancing connectivity for multiple species on dynamic landscapes, especially over long time horizons. We forecasted landscape connectivity from 2020 to 2100 under four common conservation land-acquisition strategies: acquiring the lowest cost land, acquiring land clustered around already established conservation areas, acquiring land with high geodiversity characteristics, and acquiring land opportunistically. We used graph theoretic metrics to quantify landscape connectivity across these four strategies, evaluating connectivity for four ecologically relevant species guilds that represent endpoints along a spectrum of vagility and habitat specificity: long- versus short-distance dispersal ability and habitat specialists versus generalists. We applied our method to central North Carolina and incorporated landscape dynamics, including forest growth, succession, disturbance, and management. Landscape connectivity improved for specialist species under all conservation strategies employed, although increases were highly variable across strategies. For generalist species, connectivity improvements were negligible. Overall, clustering the development of new protected areas around land already designated for conservation yielded the largest improvements in connectivity; increases were several orders of magnitude beyond current landscape connectivity for long- and short-distance dispersing specialist species. Conserving the lowest cost land contributed the least to connectivity. Our approach provides insight into the connectivity contributions of a suite of conservation alternatives prior to on-the-ground implementation and, therefore, can inform connectivity planning to maximize conservation benefit.

Pronóstico de la Influencia de las Estrategias de Conservación sobre la Conectividad del Paisaje Resumen El mantenimiento y la mejora de la conectividad de paisaje reduce las declinaciones de biodiversidad causadas por la fragmentación del hábitat. Sin embargo, todavía existe incertidumbre sobre lo efectiva que es la conservación para la mejora de la conectividad para múltiples especies en paisajes dinámicos, especialmente durante periodos largos. Pronosticamos la conectividad de paisaje desde el 2020 hasta el 2100 bajo cuatro estrategias comunes de adquisición de tierras para conservación: adquisición de las tierras más baratas, adquisición de conjuntos de tierras adyacentes a áreas de conservación ya establecidas, adquisición de tierras con una gran diversidad de características geográficas, y adquisición oportunista de tierras. Después usamos medidas de teoría de grafos para cuantificar la conectividad de paisaje en estas cuatro estrategias y para evaluar la conectividad de cuatro gremios de especies con relevancia ecológica que representan los puntos finales en un espectro de movilidad y especificidad de hábitat: habilidad de dispersión de distancia corta versus larga y especialistas versus generalistas de hábitat. Aplicamos nuestro método en el centro de Carolina del Norte e incorporamos las dinámicas de paisaje, incluyendo el crecimiento, sucesión, alteración y gestión forestales. La conectividad del paisaje mejoró para las especies especialistas bajo todas las estrategias de conservación que se usaron, aunque los incrementos fueron muy variables según la estrategia. Para las especies generalistas, las mejoras en la conectividad fueron insignificantes. En general, agrupar al desarrollo de nuevas áreas protegidas alrededor de tierras ya designadas a la conservación produjo la mayor cantidad de mejoras en la conectividad; los incrementos estuvieron varias magnitudes más allá de la conectividad actual del paisaje para las especies especialistas con dispersión de corta y larga distancia. La conservación de las tierras más baratas contribuyó a la menor conectividad. Nuestra estrategia proporciona información sobre las contribuciones de conectividad de un conjunto de alternativas de conservación previas la implementación in situ y por lo tanto puede servir para orientar la planeación y maximizar el beneficio de conservación.

Warming increased bark beetle-induced tree mortality by 30% during an extreme drought in California.

Quantifying the responses of forest disturbances to climate warming is critical to our understanding of carbon cycles and energy balances of the Earth system. The impact of warming on bark beetle outbreaks is complex as multiple drivers of these events may respond differently to warming. Using a novel model of bark beetle biology and host tree interactions, we assessed how contemporary warming affected western pine beetle (Dendroctonus brevicomis) populations and mortality of its host, ponderosa pine (Pinus ponderosa), during an extreme drought in the Sierra Nevada, California, United States. When compared with the field data, our model captured the western pine beetle flight timing and rates of ponderosa pine mortality observed during the drought. In assessing the influence of temperature on western pine beetles, we found that contemporary warming increased the development rate of the western pine beetle and decreased the overwinter mortality rate of western pine beetle larvae leading to increased population growth during periods of lowered tree defense. We attribute a 29.9% (95% CI: 29.4%-30.2%) increase in ponderosa pine mortality during drought directly to increases in western pine beetle voltinism (i.e., associated with increased development rates of western pine beetle) and, to a much lesser extent, reductions in overwintering mortality. These findings, along with other studies, suggest each degree (°C) increase in temperature may have increased the number of ponderosa pine killed by upwards of 35%-40% °C-1 if the effects of compromised tree defenses (15%-20%) and increased western pine beetle populations (20%) are additive. Due to the warming ability to considerably increase mortality through the mechanism of bark beetle populations, models need to consider climate's influence on both host tree stress and the bark beetle population dynamics when determining future levels of tree mortality.

Epigenetic Markers Are Associated With Differences in Isocyanate Biomarker Levels in Exposed Spray-Painters.

Isocyanates are respiratory and skin sensitizers that are one of the main causes of occupational asthma globally. Genetic and epigenetic markers are associated with isocyanate-induced asthma and, before asthma develops, we have shown that genetic polymorphisms are associated with variation in plasma and urine biomarker levels in exposed workers. Inter-individual epigenetic variance may also have a significant role in the observed biomarker variability following isocyanate exposure. Therefore, we determined the percent methylation for CpG islands from DNA extracted from mononuclear blood cells of 24 male spray-painters exposed to 1,6-hexamethylene diisocyanate (HDI) monomer and HDI isocyanurate. Spray-painters' personal inhalation and skin exposure to these compounds and the respective biomarker levels of 1,6-diaminohexane (HDA) and trisaminohexyl isocyanurate (TAHI) in their plasma and urine were measured during three repeated industrial hygiene monitoring visits. We controlled for inhalation exposure, skin exposure, age, smoking status, and ethnicity as covariates and performed an epigenome-wide association study (EWAS) using likelihood-ratio statistical modeling. We identified 38 CpG markers associated with differences in isocyanate biomarker levels (Bonferroni < 0.05). Annotations for these markers included 18 genes: ALG1, ANKRD11, C16orf89, CHD7, COL27A, FUZ, FZD9, HMGN1, KRT6A, LEPR, MAPK10, MED25, NOSIP, PKD1, SNX19, UNC13A, UROS, and ZFHX3. We explored the functions of the genes that have been published in the literature and used GeneMANIA to investigate gene ontologies and predicted protein-interaction networks. The protein functions of the predicted networks include keratinocyte migration, cell-cell adhesions, calcium transport, neurotransmitter release, nitric oxide production, and apoptosis regulation. Many of the protein pathway functions overlap with previous findings on genetic markers associated with variability both in isocyanate biomarker levels and asthma susceptibility, which suggests there are overlapping protein pathways that contribute to both isocyanate toxicokinetics and toxicodynamics. These predicted protein networks can inform future research on the mechanism of allergic airway sensitization by isocyanates and aid in the development of mitigation strategies to better protect worker health.

Influence of Genetic Variance on Biomarker Levels After Occupational Exposure to 1,6-Hexamethylene Diisocyanate Monomer and 1,6-Hexamethylene Diisocyanate Isocyanurate.

We evaluated the impact of genetic variance on biomarker levels in a population of workers in the automotive repair and refinishing industry who were exposed to respiratory sensitizers 1,6-hexamethylene diisocyanate (HDI) monomer and one of its trimers, HDI isocyanurate. The exposures and respective urine and plasma biomarkers 1,6-diaminohexane (HDA) and trisaminohexyl isocyanurate (TAHI) were measured in 33 workers; and genome-wide microarrays (Affymetrix 6.0) were used to genotype the workers' single-nucleotide polymorphisms (SNPs). Linear mixed model analyses have indicated that interindividual variations in both inhalation and skin exposures influenced these biomarker levels. Using exposure values as covariates and a false discovery rate < 0.10 to assess statistical significance, we observed that seven SNPs were associated with HDA in plasma, five were associated with HDA in urine, none reached significance for TAHI in plasma, and eight were associated with TAHI levels in urine. The different genotypes for the 20 significant SNPs accounted for 4- to 16-fold changes observed in biomarker levels. Associated gene functions include transcription regulation, calcium ion transport, vascular morphogenesis, and transforming growth factor beta signaling pathway, which may impact toxicokinetics indirectly by altering inflammation levels. Additionally, in an expanded analysis using a minor allele cutoff of 0.05 instead of 0.10, there were biomarker-associated SNPs within three genes that have been associated with isocyanate-induced asthma: ALK, DOCK2, and LHPP. We demonstrate that genetic variance impacts the biomarker levels in workers exposed to HDI monomer and HDI isocyanurate and that genetics can be used to refine exposure predictions in small cohorts when quantitative personal exposure and biomarker measurements are included in the models.

Trisaminohexyl isocyanurate, a urinary biomarker of HDI isocyanurate exposure.

Biological monitoring of occupational exposure to 1,6-hexamethylene diisocyanate (HDI)-containing spray-paints is limited to analysis of metabolites of HDI monomer although polymeric HDI isocyanurate constitutes the predominant inhalation and skin exposure for workers in the automotive paint industry. A novel method using nanoflow ultra-performance liquid chromatography coupled to nano-electrospray ionization tandem mass spectrometry (nano-UPLC-ESI-MS/MS) was developed to quantify trisaminohexyl isocyanurate (TAHI), a hydrolysis product of HDI isocyanurate, in the urine of spray-painters. Analytical and internal standards were synthesized in-house and weighted linear regression calibration curves were generated using spiked control urine from non-exposed persons (0.06-7.98 µg/L; N = 13; w = x-2; r = 0.998). Urine samples collected from 15 exposed workers (N = 111) were subjected to acid hydrolysis and extracted with dichloromethane, then derivatized with acetic anhydride. The derivatized product, trisacetamidohexyl isocyanurate (TAAHI), was analyzed using nano-UPLC-ESI-MS/MS. The protocol was sensitive and specific for analysis of TAHI in the urine of exposed workers with a method detection limit at 0.03 µg/L. TAHI was detected in 33 of 111 urine samples and in 11 of 15 workers. This biomarker for HDI isocyanurate is critical to determine the relative potency and dose-relationships between the monomer and oligomer exposure on the development of diisocyanate induced health effects in future studies.

Selected highlights in clinical anesthesia research.

STUDY OBJECTIVE: To review research highlights of manuscripts published in 2016 that pertain to all aspects of the clinical practice of anesthesiology. DESIGN: Narrative review. SETTING: N/A. MATERIALS: The major themes address broad categories of general anesthesia including airway management, abdominal surgery, and obstetrical and gynaecological anesthesia. In addition, recent advancements in specialties of anesthesiology including regional anesthesia are reviewed. INTERVENTIONS: N/A. MAIN RESULTS: N/A. CONCLUSIONS: This recent body of evidence will both help inform anesthesiologists of the developing trends in anesthesiology and will also pose new challenges for further studies.