We present hourly online observations of molecular compositions (CxHyOzN0−1) and abundances of oxygenated organic species in gas and submicron particle phases from April to June of 2014 as part of ...the Biogenic Aerosols-Effects on Cloud and Climate (BAECC) campaign. Measurements were made using the Filter Inlet for Gases and AEROsols coupled to a high-resolution time-of-flight iodide-adduct ionization mass spectrometer (FIGAERO-CIMS) located atop a 35 m tall tower, about 10 m above a boreal forest canopy at the SMEAR II research station in Hyytiälä, Finland. Semi-volatile and highly oxygenated multifunctional (HOM) organic species possessing from 1 up to 20 carbon atoms, and with as few as 2 and as many as 16 oxygen atoms, were routinely observed. Utilizing non-negative matrix factorization, we determined that > 90 and > 99 % of the organic mass in the gas and particle phases, respectively, exhibited one of three distinct diel trends: one in which abundances were enhanced at daytime, another in the early morning hours, and thirdly during nighttime. Particulate organic nitrates contributed ∼ 35 % to the total organic aerosol mass loading at night during BAECC, much higher than observed by the same instrument package at a mixed-deciduous forest site in the southeastern US that experienced higher nighttime concentrations of nitrogen oxides. Unique HOM monomers (defined here as those with 10 carbon and 7 or more oxygen atoms) and dimers (at least 16 carbon atoms), with and without a nitrogen atom, were found in most of the three subgroups of both phases. We show the potential to connect these groupings of compounds based on their distinct behavior in time to the expected chemical conditions (biogenic VOC precursor, oxidant type, etc.) responsible for their production. A suite of nitrated dimer-like compounds was detected in both the gas and particle phases, suggesting a potential role for the formation of low-volatility organics from NO3-radical-driven, as well as daytime NO-influenced, monoterpene chemistry.
We evaluate monoterpene-derived peroxy radical (MT-RO2) unimolecular
autoxidation and self- and cross-reactions with other RO2 species in the
GEOS-Chem global chemical transport model. The formation ...of associated highly
oxygenated organic molecules (HOMs) and accretion products are tracked in
competition with other bimolecular reactions. Autoxidation is the dominant
fate up to 6–8 km for first-generation MT-RO2, which can undergo
unimolecular H shifts. Reaction with NO can be a more common fate for
H-shift rate constants < 0.1 s−1 or at altitudes higher than 8 km due to the imposed Arrhenius temperature dependence of unimolecular
H shifts. For MT-derived HOM-RO2, generated by multistep autoxidation
of first-generation MT-RO2, reaction with other RO2 species is predicted
to be the major fate throughout most of the boreal and tropical forest
regions, whereas reaction with NO dominates in the temperate and subtropical
forests of the Northern Hemisphere. The newly added reactions result in
an approximate 4 % global average decrease in HO2 and RO2,
mainly due to faster self-/cross-reactions of MT-RO2, but the impact
upon HO2, OH, and NOx abundances is only important in the planetary boundary layer (PBL) over portions of tropical forests. Predicted HOM
concentrations in MT-rich regions and seasons can exceed total organic
aerosol predicted by the standard version of the GEOS-Chem model depending on the
parameters used. Comparisons to observations reveal that large uncertainties
remain for key reaction parameters and processes, especially with respect to the
photochemical lifetime and volatility of HOMs as well as the rates and branching of
associated RO2 accretion products. Further observations and laboratory
studies related to MT-RO2-derived HOMs and gas-phase RO2 accretion
product formation kinetics – especially their atmospheric fate, such as
gas–particle partitioning, multiphase chemistry, and net secondary organic aerosol formation – are
needed.
Repeated phlebotomy for laboratory diagnostic testing is a known cause of iatrogenic anaemia and in critically ill neonates often leads to blood transfusion being required. This study has developed a ...spreadsheet clinical decision support tool to allow neonatal staff to determine the true minimum blood volume required to analyse groups of blood tests and modelled its potential benefit compared with the existing system in use.
The tool calculates the minimum blood volume accounting for novel factors including the current patient haematocrit for plasma/serum samples, instrument minimum test and dead volumes (including those where shared) and sharing of samples within/between laboratory departments. A year of neonatal unit laboratory requests were examined comparing the volumes and containers of blood recommended by the hospital information system with both the amount actually collected by staff and that recommended by the tool.
A total of 463 patients had 8481 blood draws for 23,899 tests or test profiles over the year. The hospital information system recommended collecting 11,222 mL of blood into 18,509 containers, while 17,734 containers were actually received (10,717 mL if fully filled). The tool recommended collecting 4915 mL of blood into 15,549 containers.
This tool allows neonatal intensive care unit staff to objectively determine the minimum blood volume required for a combination of tests and is generalizable between laboratory instruments. Compared with the hospital information system, use of the minimum blood volume clinical decision support tool could maximally reduce the volume of blood collected from this neonatal unit by more than a half. Neonatal intensive care unit staff had apparently already gone some way to determining their own minimum volumes required.
Eddy covariance fluxes of formic acid, HCOOH, were measured over a boreal forest canopy in spring/summer 2014. The HCOOH fluxes were bidirectional but mostly upward during daytime, in contrast to ...studies elsewhere that reported mostly downward fluxes. Downward flux episodes were explained well by modeled dry deposition rates. The sum of net observed flux and modeled dry deposition yields an upward gross flux of HCOOH, which could not be quantitatively explained by literature estimates of direct vegetative soil emissions nor by efficient chemical production from other volatile organic compounds, suggesting missing or greatly underestimated HCOOH sources in the boreal ecosystem. We implemented a vegetative HCOOH source into the GEOS-Chem chemical transport model to match our derived gross flux and evaluated the updated model against airborne and spaceborne observations. Model biases in the boundary layer were substantially reduced based on this revised treatment, but biases in the free troposphere remain unexplained.
Fine roots constitute a significant component of the net primary productivity (NPP) of forest ecosystems but are much less studied than aboveground NPP. Comparisons across sites and regions are also ...hampered by inconsistent methodologies, especially in tropical areas. Here, we present a novel dataset of fine root biomass, productivity, residence time, and allocation in tropical old‐growth rainforest sites worldwide, measured using consistent methods, and examine how these variables are related to consistently determined soil and climatic characteristics. Our pantropical dataset spans intensive monitoring plots in lowland (wet, semi‐deciduous, and deciduous) and montane tropical forests in South America, Africa, and Southeast Asia (n = 47). Large spatial variation in fine root dynamics was observed across montane and lowland forest types. In lowland forests, we found a strong positive linear relationship between fine root productivity and sand content, this relationship was even stronger when we considered the fractional allocation of total NPP to fine roots, demonstrating that understanding allocation adds explanatory power to understanding fine root productivity and total NPP. Fine root residence time was a function of multiple factors: soil sand content, soil pH, and maximum water deficit, with longest residence times in acidic, sandy, and water‐stressed soils. In tropical montane forests, on the other hand, a different set of relationships prevailed, highlighting the very different nature of montane and lowland forest biomes. Root productivity was a strong positive linear function of mean annual temperature, root residence time was a strong positive function of soil nitrogen content in montane forests, and lastly decreasing soil P content increased allocation of productivity to fine roots. In contrast to the lowlands, environmental conditions were a better predictor for fine root productivity than for fractional allocation of total NPP to fine roots, suggesting that root productivity is a particularly strong driver of NPP allocation in tropical mountain regions.
We present the largest global dataset to date on tropical forest fine root biomass, productivity, residence time, and allocation of total net primary productivity to fine roots, collected to a standardised protocol across 47 Global Ecosystems Monitoring plots in lowland and montane forests South America, Africa, and Southeast Asia. We observed large variability in fine root dynamics across sites and between lowland and montane forests. Soil physics and chemistry were the strongest drivers of fine root dynamics, whereas climate variables hardly featured as predictors.
Osseous genioplasty is a powerful procedure that can correct chin dysmorphology; however, traditional techniques may result in chin ptosis or a "witch's chin" deformity. Iatrogenic chin ptosis is ...thought to be caused by excessive degloving of soft tissue with a failure to reattach the mentalis muscle. In the authors' study, they compared the "no-degloving" technique (using a 90-degree plate with lag-screw fixation) to the "traditional" technique, for minimization of chin ptosis.
The authors compared genioplasty techniques for consecutive patients: group 1 (traditional) underwent degloving for fixation of a stair-step plate, whereas group 2 (no-degloving) underwent lag-screw fixation (n = 50; 25 patients per group). The authors compared operating room time, advancement, complications, preoperative-to-postoperative vertical height change of the pogonion and menton (obtained through cone beam computed tomographic scans), surgeons' assessment of witch's chin, and FACE-Q surveys.
No-degloving versus traditional groups had similar age and sex distributions, horizontal/vertical change (5 mm/2 mm versus 6 mm/2 mm), length of surgery, and complication rate (5 percent). The traditional group had more deviation from expected position for both the pogonion (3.4 mm versus 1.2 mm; p ≤ 0.05) and menton (2.9 mm versus 0.8 mm; p ≤ 0.05), and more occurrences of witch's chin (six versus zero). No-degloving was superior for several FACE-Q scales, including Chin Appearance, Quality of Life, Satisfaction with Decision to Undergo Procedure, and Satisfaction with Outcome.
No-degloving osseous genioplasty is a safe, reproducible technique that results in decreased soft-tissue ptosis and increased patient satisfaction.
Therapeutic, III.
We present measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation in an environmental simulation chamber at a variety of oxidant conditions and using dry ...neutral seed particles to suppress acid-catalyzed multiphase chemistry. A high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) utilizing iodide-adduct ionization coupled to the Filter Inlet for Gases and Aerosols (FIGAERO) allowed for simultaneous online sampling of the gas and particle composition. Under high-HO2 and low-NO conditions, highly oxygenated (O:C ≥ 1) C5 compounds were major components (∼ 50%) of SOA. The SOA composition and effective volatility evolved both as a function of time and as a function of input NO concentrations. Organic nitrates increased in both the gas and particle phases as input NO increased, but the dominant non-nitrate particle-phase components monotonically decreased. We use comparisons of measured and predicted gas-particle partitioning of individual components to assess the validity of literature-based group-contribution methods for estimating saturation vapor concentrations. While there is evidence for equilibrium partitioning being achieved on the chamber residence timescale (5.2h) for some individual components, significant errors in group-contribution methods are revealed. In addition, >30% of the SOA mass, detected as low-molecular-weight semivolatile compounds, cannot be reconciled with equilibrium partitioning. These compounds desorb from the FIGAERO at unexpectedly high temperatures given their molecular composition, which is indicative of thermal decomposition of effectively lower-volatility components such as larger molecular weight oligomers.
The apparent volatility of atmospheric organic aerosol (OA) particles is determined by their chemical composition and environmental conditions (e.g., ambient temperature). A quantitative, ...experimental assessment of volatility and the respective importance of these two factors remains challenging, especially in ambient measurements. We present molecular composition and volatility of oxygenated OA (OOA) particles in different rural, urban, and mountain environments (including Chacaltaya, Bolivia; Alabama, US; Hyytiälä, Finland; Stuttgart and Karlsruhe, Germany; and Delhi, India) based on deployments of a filter inlet for gases and aerosols coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (FIGAERO-CIMS). We find on average larger carbon numbers (nC) and lower oxygen-to-carbon (O : C) ratios at the urban sites (nC: 9.8 ± 0.7; O : C: 0.76 ± 0.03; average ±1 standard deviation) compared to the rural (nC: 8.8 ± 0.6; O : C: 0.80 ± 0.05) and mountain stations (nC: 8.1 ± 0.8; O : C: 0.91 ± 0.07), indicative of different emission sources and chemistry. Compounds containing only carbon, hydrogen, and oxygen atoms (CHO) contribute the most to the total OOA mass at the rural sites (79.9 ± 5.2 %), in accordance with their proximity to forested areas (66.2 ± 5.5 % at the mountain sites and 72.6 ± 4.3 % at the urban sites). The largest contribution of nitrogen-containing compounds (CHON) is found at the urban stations (27.1 ± 4.3 %), consistent with their higher NOx levels. Moreover, we parametrize OOA volatility (saturation mass concentrations, Csat) using molecular composition information and compare it with the bulk apparent volatility derived from thermal desorption of the OOA particles within the FIGAERO. We find differences in Csat values of up to ∼ 3 orders of magnitude and variation in thermal desorption profiles (thermograms) across different locations and systems. From our study, we draw the general conclusion that environmental conditions (e.g., ambient temperature) do not directly affect OOA apparent volatility but rather indirectly by influencing the sources and chemistry of the environment and thus the chemical composition. The comprehensive dataset provides results that show the complex thermodynamics and chemistry of OOA and their changes during its lifetime in the atmosphere. We conclude that generally the chemical description of OOA suffices to predict its apparent volatility, at least qualitatively. Our study thus provides new insights that will help guide choices of, e.g., descriptions of OOA volatility in different model frameworks such as air quality models and cloud parcel models.
Nitrous acid (HONO) mixing ratios measured in aged wildfire smoke plumes were higher than expected from known homogeneous chemical reactions. In a representative smoke plume, intercepted hours to ...days downwind of the source, the missing HONO source was highly correlated to particulate nitrate photolysis and NO2 reactive uptake to particles. Using a multilinear regression involving these two sources, we could explain the missing HONO production in this plume (R2 = 0.77). The resulting fit parameters from this plume had good explanatory power (R2 = 0.64) for missing HONO production in other fire plumes. The mean enhancement factor for particulate nitrate photolysis relative to gas‐phase nitric acid photolysis was 63 and the mean NO2 reactive uptake coefficient to submicron aerosol surface area forming HONO was 4.9 × 10−4. Given the likelihood of other neglected secondary HONO sources, these values are upper‐limits, suggesting a need to revisit HONO formation mechanisms in aged wildfire smoke.
Plain Language Summary
A river of smoke from multiple wildfires was sampled far downwind and served as a natural laboratory for evaluating sources of nitrous acid (HONO) in aged wildfire smoke. HONO photolysis is an important source of reactive oxidants that initiate chemical transformations of wildfire emissions. We demonstrate that sources of HONO from chemical processes, known as secondary HONO sources, can largely be explained by two processes – the photolysis of particulate nitrate and the reactive uptake of nitrogen dioxide (NO2) to smoke aerosol particles. High time resolution in situ observations of HONO and auxiliary measurements were used to map out variations in the missing HONO source across a wide span of wildfire characteristics. The results place an upper limit on the magnitude of HONO sources from particulate nitrate photolysis, and suggest that the heterogeneous NO2 reactive uptake to smoke particles could be more important than previous field studies have indicated. These findings demonstrate the existence of additional processes other than direct emissions responsible for HONO formation in fire smoke. This secondary HONO source could increase the oxidizing capacity of wildfire smoke plumes significantly downwind of the emission source and therefore affect the formation and lifetime of other secondary wildfire smoke components.
Key Points
Secondary multi‐phase processes dominate daytime HONO levels in aged (>3 hr) fire smoke
The inferred strength of secondary HONO production is most correlated to NO2, aerosol surface area, and particulate nitrate
We find significantly weaker HONO formation from particulate nitrate photolysis than previous reports
Pharmaceuticals have extensive reciprocal interactions with the microbiome, but whether bacterial drug sensitivity and metabolism is driven by pathways conserved in host cells remains unclear. Here ...we show that anti-cancer fluoropyrimidine drugs inhibit the growth of gut bacterial strains from 6 phyla. In both Escherichia coli and mammalian cells, fluoropyrimidines disrupt pyrimidine metabolism. Proteobacteria and Firmicutes metabolized 5-fluorouracil to its inactive metabolite dihydrofluorouracil, mimicking the major host mechanism for drug clearance. The preTA operon was necessary and sufficient for 5-fluorouracil inactivation by E. coli, exhibited high catalytic efficiency for the reductive reaction, decreased the bioavailability and efficacy of oral fluoropyrimidine treatment in mice and was prevalent in the gut microbiomes of colorectal cancer patients. The conservation of both the targets and enzymes for metabolism of therapeutics across domains highlights the need to distinguish the relative contributions of human and microbial cells to drug efficacy and side-effect profiles.
PDF
