Particle water and pH are predicted using meteorological observations (relative humidity (RH), temperature (T)), gas/particle composition, and thermodynamic modeling (ISORROPIA-II). A comprehensive ...uncertainty analysis is included, and the model is validated. We investigate mass concentrations of particle water and related particle pH for ambient fine-mode aerosols sampled in a relatively remote Alabama forest during the Southern Oxidant and Aerosol Study (SOAS) in summer and at various sites in the southeastern US during different seasons, as part of the Southeastern Center for Air Pollution and Epidemiology (SCAPE) study. Particle water and pH are closely linked; pH is a measure of the particle H+ aqueous concentration and depends on both the presence of ions and amount of particle liquid water. Levels of particle water, in turn, are determined through water uptake by both the ionic species and organic compounds. Thermodynamic calculations based on measured ion concentrations can predict both pH and liquid water but may be biased since contributions of organic species to liquid water are not considered. In this study, contributions of both the inorganic and organic fractions to aerosol liquid water were considered, and predictions were in good agreement with measured liquid water based on differences in ambient and dry light scattering coefficients (prediction vs. measurement: slope = 0.91, intercept = 0.5 μg m−3, R2 = 0.75). ISORROPIA-II predictions were confirmed by good agreement between predicted and measured ammonia concentrations (slope = 1.07, intercept = −0.12 μg m−3, R2 = 0.76). Based on this study, organic species on average contributed 35% to the total water, with a substantially higher contribution (50%) at night. However, not including contributions of organic water had a minor effect on pH (changes pH by 0.15 to 0.23 units), suggesting that predicted pH without consideration of organic water could be sufficient for the purposes of aqueous secondary organic aerosol (SOA) chemistry. The mean pH predicted in the Alabama forest (SOAS) was 0.94 ± 0.59 (median 0.93). pH diurnal trends followed liquid water and were driven mainly by variability in RH; during SOAS nighttime pH was near 1.5, while daytime pH was near 0.5. pH ranged from 0.5 to 2 in summer and 1 to 3 in the winter at other sites. The systematically low pH levels in the southeast may have important ramifications, such as significantly influencing acid-catalyzed reactions, gas–aerosol partitioning, and mobilization of redox metals and minerals. Particle ion balances or molar ratios, often used to infer pH, do not consider the dissociation state of individual ions or particle liquid water levels and do not correlate with particle pH.
Light absorbing organic carbon, often called brown carbon, has the potential to significantly contribute to the visible light-absorption budget, particularly at shorter wavelengths. Currently, the ...relative contributions of particulate brown carbon to light absorption, as well as the sources of brown carbon, are poorly understood. With this in mind size-resolved direct measurements of brown carbon were made at both urban (Atlanta), and rural (Yorkville) sites in Georgia. Measurements in Atlanta were made at both a representative urban site and a road-side site adjacent to a main highway. Fine particle absorption was measured with a multi-angle absorption photometer (MAAP) and seven-wavelength Aethalometer, and brown carbon absorption was estimated based on Mie calculations using direct size-resolved measurements of chromophores in solvents. Size-resolved samples were collected using a cascade impactor and analyzed for water-soluble organic carbon (WSOC), organic and elemental carbon (OC and EC), and solution light-absorption spectra of water and methanol extracts. Methanol extracts were more light-absorbing than water extracts for all size ranges and wavelengths. Absorption refractive indices of the organic extracts were calculated from solution measurements for a range of wavelengths and used with Mie theory to predict the light absorption by fine particles comprised of these components, under the assumption that brown carbon and other aerosol components were externally mixed. For all three sites, chromophores were predominately in the accumulation mode with an aerodynamic mean diameter of 0.5 μm, an optically effective size range resulting in predicted particle light absorption being a factor of 2 higher than bulk solution absorption. Mie-predicted brown carbon absorption at 350 nm contributed a significant fraction (20 to 40%) relative to total light absorption, with the highest contributions at the rural site where organic to elemental carbon ratios were highest. Brown carbon absorption, however, was highest by the roadside site due to vehicle emissions. The direct size-resolved measurement of brown carbon in solution definitively shows that it is present and optically important in the near-UV range in both a rural and urban environment during the summer when biomass burning emissions are low. These results allow estimates of brown carbon aerosol absorption from direct measurements of chromophores in aerosol extracts.
This article describes how the dimensions of nanowires affect the transmittance and sheet resistance of a random nanowire network. Silver nanowires with independently controlled lengths and diameters ...were synthesized with a gram-scale polyol synthesis by controlling the reaction temperature and time. Characterization of films composed of nanowires of different lengths but the same diameter enabled the quantification of the effect of length on the conductance and transmittance of silver nanowire films. Finite-difference time-domain calculations were used to determine the effect of nanowire diameter, overlap, and hole size on the transmittance of a nanowire network. For individual nanowires with diameters greater than 50 nm, increasing diameter increases the electrical conductance to optical extinction ratio, but the opposite is true for nanowires with diameters less than this size. Calculations and experimental data show that for a random network of nanowires, decreasing nanowire diameter increases the number density of nanowires at a given transmittance, leading to improved connectivity and conductivity at high transmittance (>90%). This information will facilitate the design of transparent, conducting nanowire films for flexible displays, organic light emitting diodes and thin-film solar cells.
Abstract
Solenoidal ionisers are a new class of highly efficient helium detectors that are increasingly important for high resolution atom scattering, molecular scattering and scanning helium ...microscopy. They operate via electron ionisation, where the electrons are trapped by the magnetic field of a solenoid and additional electrostatic potentials. Their ionisation efficiency scales with the electron population they contain, motivating large devices with high emission currents. However, these detectors typically become unstable at high electron densities, constraining their performance improvement. Through imaging the electron population at the exit of the ioniser, we demonstrate that these instabilities arise from non-uniformities in the electron distribution. Considering the ioniser as a non-neutral plasma leads to the proposal of the formation of a virtual cathode and a plasma instability as the origins of the non-uniformity.
The Indo-Gangetic Plain is a region of known high aerosol loading with substantial amounts of carbonaceous aerosols from a variety of sources, often dominated by biomass burning. Although black ...carbon has been shown to play an important role in the absorption of solar energy and hence direct radiative forcing (DRF), little is known regarding the influence of light absorbing brown carbon (BrC) on the radiative balance in the region. With this in mind, a study was conducted for a one month period during the winter–spring season of 2013 in Kanpur, India that measured aerosol chemical and physical properties that were used to estimate the sources of carbonaceous aerosols, as well as parameters necessary to estimate direct forcing by aerosols and the contribution of BrC absorption to the atmospheric energy balance. Positive matrix factorization analyses, based on aerosol mass spectrometer measurements, resolved organic carbon into four factors including low-volatile oxygenated organic aerosols, semivolatile oxygenated organic aerosols, biomass burning, and hydrocarbon like organic aerosols. Three-wavelength absorption and scattering coefficient measurements from a Photo Acoustic Soot Spectrometer were used to estimate aerosol optical properties and estimate the relative contribution of BrC to atmospheric absorption. Mean ± standard deviation values of short-wave cloud free clear sky DRF exerted by total aerosols at the top of atmosphere, surface and within the atmospheric column are −6.1 ± 3.2, −31.6 ± 11, and 25.5 ± 10.2 W/m2, respectively. During days dominated by biomass burning the absorption of solar energy by aerosols within the atmosphere increased by ∼35%, accompanied by a 25% increase in negative surface DRF. DRF at the top of atmosphere during biomass burning days decreased in negative magnitude by several W/m2 due to enhanced atmospheric absorption by biomass aerosols, including BrC. The contribution of BrC to atmospheric absorption is estimated to range from on average 2.6 W/m2 for typical ambient conditions to 3.6 W/m2 during biomass burning days. This suggests that BrC accounts for 10–15% of the total aerosol absorption in the atmosphere, indicating that BrC likely plays an important role in surface and boundary temperature as well as climate.
The mass absorption efficiency (MAE) of elemental carbon (EC) in Beijing was quantified using a thermal-optical carbon analyzer. The MAE measured at 632 nm was 8.45±1.71 and 9.41±1.92 m2 g−1 during ...winter and summer respectively. The daily variation of MAE was found to coincide with the abundance of organic carbon (OC), especially the OC to EC ratio, perhaps due to the enhancement by coating with organic aerosol (especially secondary organic aerosol, SOA) or the artifacts resulting from the redistribution of liquid-like organic particles during the filter-based absorption measurements. Using a converting approach that accounts for the discrepancy caused by measurements methods of both light absorption and EC concentration, previously published MAE values were converted to the equivalent-MAE, which is the estimated value if using the same measurement methods as used in this study. The equivalent-MAE was found to be much lower in the regions heavily impacted by biomass burning (e.g., below 2.7 m2 g−1 for two Indian cities). Results from source samples (including diesel exhaust samples and biomass smoke samples) also demonstrated that emissions from biomass burning would decrease the MAE of EC. Moreover, optical properties of water-soluble organic carbon (WSOC) in Beijing were presented. Light absorption by WSOC exhibited strong wavelength (λ) dependence such that absorption varied approximately as λ−7, which was characteristic of the brown carbon spectra. The MAE of WSOC (measured at 365 nm) was 1.79±0.24 and 0.71±0.20 m2 g−1 during winter and summer respectively. The large discrepancy between the MAE of WSOC during winter and summer was attributed to the difference in the precursors of SOA such that anthropogenic volatile organic compounds (AVOCs) should be more important as the precursors of SOA in winter. The MAE of WSOC in Beijing was much higher than results from the southeastern United States which were obtained using the same method as used in this study, perhaps due to the stronger emissions of biomass burning in China.
Summary
Objective
Pathogenic variants involving the CDKL5 gene result in a severe epileptic encephalopathy, often later presenting with features similar to Rett syndrome. Cardinal features of ...epilepsy in the CDKL5 disorder include early onset at a median age of 6 weeks and poor response to antiepileptic drugs. The ketogenic diet (KD) was first introduced in the 1920s as a treatment option for refractory epilepsy in children. This study investigated use of the KD in the CDKL5 disorder and its influences on seizures.
Methods
The International CDKL5 Disorder Database, established in 2012, collects information on individuals with the CDKL5 disorder. Families have provided information regarding seizure characteristics, use, and side effects of the KD treatment. Descriptive statistics and time to event analyses were performed. Clinical vignettes were also provided on patients attending Boston Children's Hospital.
Results
Data regarding KD use were available for 204 individuals with a pathogenic CDKL5 variant. Median age of inclusion in the database was 4.8 years (range = 0.3–33.9 years), with median age of 6 weeks (range = 1 day–65 weeks) at seizure onset. History of KD use was reported for 51% (104 of 204) of individuals, with a median duration of use of 17 months (95% confidence interval = 9–24). Changes in seizure activity after commencing KD were reported for two‐thirds (69 of 104), with improvements in 88% (61 of 69). Nearly one‐third (31.7%) experienced side effects during the diet. At ascertainment, only one‐third (32%) remained on the diet, with lack of long‐term efficacy as the main reason for diet cessation (51%, 36 of 70).
Significance
Benefits of KD in the CDKL5 disorder are in keeping with previous trials on refractory epilepsies. However, poor long‐term efficacy remains as a significant barrier. In view of its side effect profile, KD administration should be supervised by a pediatric neurologist and specialist dietician.
Objective
In the absence of controlled trials, treatment of neonatal seizures has changed minimally despite poor drug efficacy. We tested bumetanide added to phenobarbital to treat neonatal seizures ...in the first trial to include a standard‐therapy control group.
Methods
A randomized, double‐blind, dose‐escalation design was employed. Neonates with postmenstrual age 33 to 44 weeks at risk of or with seizures were eligible. Subjects with electroencephalography (EEG)‐confirmed seizures after ≥20 and <40mg/kg phenobarbital were randomized to receive additional phenobarbital with either placebo (control) or 0.1, 0.2, or 0.3mg/kg bumetanide (treatment). Continuous EEG monitoring data from ≥2 hours before to ≥48 hours after study drug administration (SDA) were analyzed for seizures.
Results
Subjects were randomized to treatment (n = 27) and control (n = 16) groups. Pharmacokinetics were highly variable among subjects and altered by hypothermia. The only statistically significant adverse event was diuresis in treated subjects (48% vs 13%, p = 0.02). One treated (4%) and 3 control subjects died (19%, p = 0.14). Among survivors, 2 of 26 treated subjects (8%) and 0 of 13 control subjects had hearing impairment, as did 1 nonrandomized subject. Total seizure burden varied widely, with much higher seizure burden in treatment versus control groups (median = 3.1 vs 1.2 min/h, p = 0.006). There was significantly greater reduction in seizure burden 0 to 4 hours and 2 to 4 hours post‐SDA (both p < 0.01) compared with 2‐hour baseline in treatment versus control groups with adjustment for seizure burden.
Interpretation
Although definitive proof of efficacy awaits an appropriately powered phase 3 trial, this randomized, controlled, multicenter trial demonstrated an additional reduction in seizure burden attributable to bumetanide over phenobarbital without increased serious adverse effects. Future trials of bumetanide and other drugs should include a control group and balance seizure severity. ANN NEUROL 2021;89:327–340
The current model of murine innate lymphoid cell (ILC) development holds that mouse ILCs are derived downstream of the common lymphoid progenitor through lineage-restricted progenitors. However, ...corresponding lineage-restricted progenitors in humans have yet to be discovered. Here we identified a progenitor population in human secondary lymphoid tissues (SLTs) that expressed the transcription factor RORγt and was unique in its ability to generate all known ILC subsets, including natural killer (NK) cells, but not other leukocyte populations. In contrast to murine fate-mapping data, which indicate that only ILC3s express Rorγt, these human progenitor cells as well as human peripheral blood NK cells and all mature ILC populations expressed RORγt. Thus, all human ILCs can be generated through an RORγt+ developmental pathway from a common progenitor in SLTs. These findings help establish the developmental signals and pathways involved in human ILC development.
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•All human innate lymphoid cell subsets express RORγt•RORγt is expressed in a subset of CD34+CD45RA+ progenitors found in human SLT•The human RORγt+CD34+CD45RA+ progenitor is restricted to ILC development
Human innate lymphoid cells (ILCs) mediate responses against pathogens and cancer; how they develop is unclear. Freud and colleagues identify a human RORγt+ progenitor that selectively resides in secondary lymphoid tissues and exclusively generates all ILCs, including NK cells. These findings help define the pathways involved in human ILC development.
It has been shown that sunlit snow and ice plays an important role in processing atmospheric species. Photochemical production of a variety of chemicals has recently been reported to occur in ...snow/ice and the release of these photochemically generated species may significantly impact the chemistry of the overlying atmosphere. Nitrogen oxide and oxidant precursor fluxes have been measured in a number of snow covered environments, where in some cases the emissions significantly impact the overlying boundary layer. For example, photochemical ozone production (such as that occurring in polluted mid-latitudes) of 3–4 ppbv/day has been observed at South Pole, due to high OH and NO levels present in a relatively shallow boundary layer. Field and laboratory experiments have determined that the origin of the observed NOx flux is the photochemistry of nitrate within the snowpack, however some details of the mechanism have not yet been elucidated. A variety of low molecular weight organic compounds have been shown to be emitted from sunlit snowpacks, the source of which has been proposed to be either direct or indirect photo-oxidation of natural organic materials present in the snow. Although myriad studies have observed active processing of species within irradiated snowpacks, the fundamental chemistry occurring remains poorly understood. Here we consider the nature of snow at a fundamental, physical level; photochemical processes within snow and the caveats needed for comparison to atmospheric photochemistry; our current understanding of nitrogen, oxidant, halogen and organic photochemistry within snow; the current limitations faced by the field and implications for the future.
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