Separating the rash from the chaff: novel clinical decision support deployed during the mpox outbreak.

A clinical decision support system, EvalMpox, was developed to apply person under investigation (PUI) criteria for patients presenting with rash and to recommend testing for PUIs. Of 668 patients evaluated, an EvalMpox recommendation for testing had a positive predictive value of 35% and a negative predictive value of 99% for a positive mpox test.

Direct Determination of Aerosol pH: Size-Resolved Measurements of Submicrometer and Supermicrometer Aqueous Particles.

Measuring the acidity of atmospheric aerosols is critical, as many key multiphase chemical reactions involving aerosols are highly pH-dependent. These reactions impact processes, such as secondary organic aerosol (SOA) formation, that impact climate and health. However, determining the pH of atmospheric particles, which have minute volumes (10-23-10-18 L), is an analytical challenge due to the nonconservative nature of the hydronium ion, particularly as most chemical aerosol measurements are made offline or under vacuum, where water can be lost and acid-base equilibria shifted. Because of these challenges, there have been no direct methods to probe atmospheric aerosol acidity, and pH has typically been determined by proxy/indirect methods, such as ion balance, or thermodynamic models. Herein, we present a novel and facile method for direct measurement of size-resolved aerosol acidity from pH 0 to 4.5 using quantitative colorimetric image processing of cellular phone images of (NH4)2SO4-H2SO4 aqueous aerosol particles impacted onto pH-indicator paper. A trend of increasing aerosol acidity with decreasing particle size was observed that is consistent with spectroscopic measurements of individual particle pH. These results indicate the potential for direct measurements of size-resolved atmospheric aerosol acidity, which is needed to improve fundamental understanding of pH-dependent atmospheric processes, such as SOA formation.

Extending surface enhanced Raman spectroscopy (SERS) of atmospheric aerosol particles to the accumulation mode (150-800 nm).

Due to their small size, measurements of the complex composition of atmospheric aerosol particles and their surfaces are analytically challenging. This is particularly true for microspectroscopic methods, where it can be difficult to optically identify individual particles smaller than the diffraction limit of visible light (∼350 nm) and measure their vibrational modes. Recently, surface enhanced Raman spectroscopy (SERS) has been applied to the study of aerosol particles, allowing for detection and characterization of previously undistinguishable vibrational modes. However, atmospheric particles analyzed via SERS have primarily been >1 µm to date, much larger than the diameter of the most abundant atmospheric aerosols (∼100 nm). To push SERS towards more relevant particle sizes, a simplified approach involving Ag foil substrates was developed. Both ambient particles and several laboratory-generated model aerosol systems (polystyrene latex spheres (PSLs), ammonium sulfate, and sodium nitrate) were investigated to determine SERS enhancements. SERS spectra of monodisperse, model aerosols between 400-800 nm were compared with non-SERS enhanced spectra, yielding average enhancement factors of 102 for both inorganic and organic vibrational modes. Additionally, SERS-enabled detection of 150 nm size-selected ambient particles represent the smallest individual aerosol particles analyzed by Raman microspectroscopy to date, and the first time atmospheric particles have been measured at sizes approaching the atmospheric number size distribution mode. SERS-enabled detection and identification of vibrational modes in smaller, more atmospherically-relevant particles has the potential to improve understanding of aerosol composition and surface properties, as well as their impact on heterogeneous and multiphase reactions involving aerosol surfaces.

Isoprene-Derived Organosulfates: Vibrational Mode Analysis by Raman Spectroscopy, Acidity-Dependent Spectral Modes, and Observation in Individual Atmospheric Particles.

Isoprene, the most abundant biogenic volatile organic compound (BVOC) in the atmosphere, and its low-volatility oxidation products lead to secondary organic aerosol (SOA) formation. Isoprene-derived organosulfates formed from reactions of isoprene oxidation products with sulfate in the particle phase are a significant component of SOA and can hydrolyze forming polyols. Despite characterization by mass spectrometry, their basic structural and spectroscopic properties remain poorly understood. Herein, Raman microspectroscopy and density functional theory (DFT) calculations (CAM-B3LYP level of theory) were combined to analyze the vibrational modes of key organosulfates, 3-methyltetrol sulfate esters (racemic mixture of two isomers), and racemic 2-methylglyceric acid sulfate ester, and hydrolysis products, 2-methyltetrols, and 2-methylglyceric acid. Two intense vibrational modes were identified, ν(RO-SO3) (846 ± 4 cm-1) and νs(SO3) (1065 ± 2 cm-1), along with a lower intensity δ(SO3) mode (586 ± 2 cm-1). For 2-methylglyceric acid and its sulfate esters, deprotonation of the carboxylic acid at pH values above the pKa decreased the carbonyl stretch frequency (1724 cm-1), while carboxylate modes grew in for νs(COO-) and νa(COO-) at 1413 and 1594 cm-1, respectively. The ν(RO-SO3) and νs(SO3) modes were observed in individual atmospheric particles and can be used in future studies of complex SOA mixtures to distinguish organosulfates from inorganic sulfate or hydrolysis products.

Aerosol Emissions from Great Lakes Harmful Algal Blooms.

In freshwater lakes, harmful algal blooms (HABs) of Cyanobacteria (blue-green algae) produce toxins that impact human health. However, little is known about the lake spray aerosol (LSA) produced from wave-breaking in freshwater HABs. In this study, LSA were produced in the laboratory from freshwater samples collected from Lake Michigan and Lake Erie during HAB and nonbloom conditions. The incorporation of biological material within the individual HAB-influenced LSA particles was examined by single-particle mass spectrometry, scanning electron microscopy with energy-dispersive X-ray spectroscopy, and fluorescence microscopy. Freshwater with higher blue-green algae content produced higher number fractions of individual LSA particles that contained biological material, showing that organic molecules of biological origin are incorporated in LSA from HABs. The number fraction of individual LSA particles containing biological material also increased with particle diameter (greater than 0.5 µm), a size dependence that is consistent with previous studies of sea spray aerosol impacted by phytoplankton blooms. Similar to sea spray aerosol, organic carbon markers were most frequently observed in individual LSA particles less than 0.5 µm in diameter. Understanding the transfer of biological material from freshwater to the atmosphere via LSA is crucial for determining health and climate effects of HABs.

Inland Sea Spray Aerosol Transport and Incomplete Chloride Depletion: Varying Degrees of Reactive Processing Observed during SOAS.

Multiphase reactions involving sea spray aerosol (SSA) impact trace gas budgets in coastal regions by acting as a reservoir for oxidized nitrogen and sulfur species, as well as being a source of halogen gases (HCl, ClNO2, etc.). Whereas most studies of multiphase reactions on SSA have focused on marine environments, far less is known about SSA transported inland. Herein, single-particle measurements of SSA are reported at a site >320 km from the Gulf of Mexico, with transport times of 7-68 h. Samples were collected during the Southern Oxidant and Aerosol Study (SOAS) in June-July 2013 near Centreville, Alabama. SSA was observed in 93% of 42 time periods analyzed. During two marine air mass periods, SSA represented significant number fractions of particles in the accumulation (0.2-1.0 µm, 11%) and coarse (1.0-10.0 µm, 35%) modes. Chloride content of SSA particles ranged from full to partial depletion, with 24% of SSA particles containing chloride (mole fraction of Cl/Na ≥ 0.1, 90% chloride depletion). Both the frequent observation of SSA at an inland site and the range of chloride depletion observed suggest that SSA may represent an underappreciated inland sink for NOx/SO2 oxidation products and a source of halogen gases.

Spectroscopic Determination of Aerosol pH from Acid-Base Equilibria in Inorganic, Organic, and Mixed Systems.

Atmospheric aerosol acidity impacts key multiphase processes, such as acid-catalyzed reactions leading to secondary organic aerosol formation, which impact climate and human health. However, traditional indirect methods of estimating aerosol pH often disagree with thermodynamic model predictions, resulting in aerosol acidity still being poorly understood in the atmosphere. Herein, a recently developed method coupling Raman microspectroscopy with extended Debye-Hückel activity calculations to directly determine the acidity of individual particles (1-15 µm projected area diameter, average 6 µm) was applied to a range of atmospherically relevant inorganic and organic acid-base equilibria systems (HNO3/NO3-, HC2O4-/C2O42-, CH3COOH/CH3COO-, and HCO3-/CO32-) covering a broad pH range (-1 to 10), as well as an inorganic-organic mixture (sulfate-oxalate). Given the ionic strength of the inorganic solutions, the H+ activity, γ(H+), yielded lower values (0.68-0.75) than the organic and mixed systems (0.72-0.80). A consistent relationship between increasing peak broadness with decreasing pH was observed for acidic species, but not their conjugate bases. Greater insight into spectroscopic responses to acid-base equilibria for more complicated mixtures is still needed to understand the behavior of atmospheric aerosols.

Direct Measurement of pH in Individual Particles via Raman Microspectroscopy and Variation in Acidity with Relative Humidity.

Atmospheric aerosol acidity is an important characteristic of aqueous particles, which has been linked to the formation of secondary organic aerosol by catalyzing reactions of oxidized organic compounds that have partitioned to the particle phase. However, aerosol acidity is difficult to measure and traditionally estimated using indirect methods or assumptions based on composition. Ongoing disagreements between experiments and thermodynamic models of particle acidity necessitate improved fundamental understanding of pH and ion behavior in high ionic strength atmospheric particles. Herein, Raman microspectroscopy was used to determine the pH of individual particles (H2SO4+MgSO4) based on sulfate and bisulfate concentrations determined from νs(SO4(2-)) and νs(HSO4(-)), the acid dissociation constant, and activity coefficients from extended Debye-Hückel calculations. Shifts in pH and peak positions of νs(SO4(2-)) and νs(HSO4(-)) were observed as a function of relative humidity. These results indicate the potential for direct spectroscopic determination of pH in individual particles and the need to improve fundamental understanding of ion behavior in atmospheric particles.

Surface Enhanced Raman Spectroscopy Enables Observations of Previously Undetectable Secondary Organic Aerosol Components at the Individual Particle Level.

The first use of surface enhanced Raman spectroscopy (SERS) to detect trace organic and/or inorganic species in ambient atmospheric aerosol particles is presented. This new analytical method provides direct, spectroscopic detection of species present at attogram to femtogram levels in individual submicrometer atmospheric particles. An array of spectral features resulting from organic functional groups in secondary organic aerosol (SOA) material were observed in individual particles impacted on silver nanoparticle-coated substrates. The results demonstrate the complexity of organic and inorganic species in SOA formed by oxidation of biogenic volatile organic compounds (BVOCs) at the single particle level. While SOA composition is frequently assumed to be homogeneous between and within individual particles, substantial particle-to-particle variability in SOA composition and changes on scales <1 µm were observed. The observations obtained with this new method demonstrate the power of SERS to probe difficult to detect inter- and intraparticle variability in ambient SOA particles.

Indirect behavioral measures of cognition among sexual offenders.

Indirect measures of cognition have become an important tool in research on sexual offending. Such methods allow the exploration and testing of models of cognitive processes that might underpin sexual preferences and, in turn, sexual offending. The article reviews studies that have used a large range of indirect techniques (e.g., Implicit Association Test, Implicit Relational Assessment Procedure, Choice Reaction Times, Stroop Interference, Rapid Serial Visual Presentation, Lexical Decision Priming Task, and Viewing Times), and aims to discuss the strengths and weaknesses of this research.