Ambient Samples Research Articles

Distinct microbial communities in an ascidian-crustacean symbiosis.

Ascidians are marine invertebrates known to occasionally host symbiotic crustaceans. Although the microbiomes of both ascidians and free-living crustaceans have been characterized, there is no documentation of microbial communities in an ascidian-crustacean symbiosis. Samples of the solitary ascidian Ascidia sydneiensis and ambient seawater were collected in Belize. Four symbiotic amphipod crustaceans were retrieved from the branchial sac of the animal, and their microbiomes were compared with those from their ascidian host (tunic and branchial sac compartments) and seawater. Microbiome richness and diversity differed significantly between sample types, with amphipod microbiomes exhibiting significantly lower diversity than tunic and ambient seawater samples. Microbiome composition also differed significantly between sample types and among all pairwise comparisons, except for branchial sac and amphipod microbiomes. Differential operational taxonomic unit (OTU) analyses revealed that only 3 out of 2553 OTUs had significantly different relative abundances in amphipods compared with ascidian branchial sacs, whereas 72 OTUs differed between amphipod and tunic and 315 between amphipod and seawater samples. Thus, different body compartments of A. sydneiensis hosted distinct microbiomes, and symbiotic amphipods contained microbiomes resembling the region they inhabit (i.e., the branchial sac), suggesting that environmental filtering and co-evolutionary processes are determinants of microbiome composition within ascidian-crustacean symbioses.

Unambiguous Analysis and Systematic Mapping of Oxygenated Aromatic Compounds in Atmospheric Aerosols Using Ultrahigh-Resolution Mass Spectrometry.

Compositional analysis of organic aerosols (OAs) at the molecular level has been a long-standing challenge in field and laboratory studies. In this work, we applied different extraction protocols to aerosol samples collected from the ambient atmosphere and biomass burning sources, followed by Orbitrap mass spectrometric analysis with a soft electrospray ionization source operating in both positive and negative ionization modes. To systematically map the distribution of mono- and dioxygenated aromatic compounds (referred to as aromatic CHO1 and CHO2 formulas) in OA, we developed a unique two-dimensional Kendrick mass defect (2D KMD) framework. Our analysis unveiled a total of (76, 64, 70) aromatic CHO1 formulas and (103, 110, 106) CHO2 formulas, corresponding to samples obtained from ambient air, rice straw burning, and sugarcane leaf burning, respectively. These results reveal a significant number of additional distinct formulas exclusively present in ambient samples, suggesting a significant chemical transformation of OAs in the atmosphere. The analytical approach can be further extended to incorporate multiple layers of 2D KMD, enabling systematic mapping of the unexplored chemical space for complex environmental samples.

Preparation of Gold Nanoparticles via Anodic Stripping of Copper Underpotential Deposition in Bulk Gold Electrodeposition for High-Performance Electrochemical Sensing of Bisphenol A.

Bisphenol A is one of the most widely used industrial compounds. Over the years, it has raised severe concern as a potential hazard to the human endocrine system and the environment. Developing robust and easy-to-use sensors for bisphenol A is important in various areas, such as controlling and monitoring water purification and sewage water systems, food safety monitoring, etc. Here, we report an electrochemical method to fabricate a bisphenol A (BPA) sensor based on a modified Au nanoparticles/multiwalled carbon nanotubes composite electrocatalyst electrode (AuCu-UPD/MWCNTs/GCE). Firstly, the Au-Cu alloy was prepared via a convenient and controllable Cu underpotential/bulk Au co-electrodeposition on a multiwalled modified carbon nanotubes glassy carbon electrode (GCE). Then, the AuCu-UPD/MWCNTs/GCE was obtained via the electrochemical anodic stripping of Cu underpotential deposition (UPD). Our novel prepared sensor enables the high-electrocatalytic and high-performance sensing of BPA. Under optimal conditions, the modified electrode showed a two-segment linear response from 0.01 to 1 µM and 1 to 20 µM with a limit of detection (LOD) of 2.43 nM based on differential pulse voltammetry (DPV). Determination of BPA in real water samples using AuCu-UPD/MWCNTs/GCE yielded satisfactory results. The proposed electrochemical sensor is promising for the development of a simple, low-cost water quality monitoring system for the detection of BPA in ambient water samples.

Diversity, equity, and inclusivity in observational ambulatory assessment: Recommendations from two decades of Electronically Activated Recorder (EAR) research.

Ambient audio sampling methods such as the Electronically Activated Recorder (EAR) have become increasingly prominent in clinical and social sciences research. These methods record snippets of naturalistically assessed audio from participants' daily lives, enabling novel observational research about the daily social interactions, identities, environments, behaviors, and speech of populations of interest. In practice, these scientific opportunities are equaled by methodological challenges: researchers' own cultural backgrounds and identities can easily and unknowingly permeate the collection, coding, analysis, and interpretation of social data from daily life. Ambient audio sampling poses unique and significant challenges to cultural humility, diversity, equity, and inclusivity (DEI) in scientific research that require systematized attention. Motivated by this observation, an international consortium of 21 researchers who have used ambient audio sampling methodologies created a workgroup with the aim of improving upon existing published guidelines. We pooled formally and informally documented challenges pertaining to DEI in ambient audio sampling from our collective experience on 40+ studies (most of which used the EAR app) in clinical and healthy populations ranging from children to older adults. This article presents our resultant recommendations and argues for the incorporation of community-engaged research methods in observational ambulatory assessment designs looking forward. We provide concrete recommendations across each stage typical of an ambient audio sampling study (recruiting and enrolling participants, developing coding systems, training coders, handling multi-linguistic participants, data analysis and interpretation, and dissemination of results) as well as guiding questions that can be used to adapt these recommendations to project-specific constraints and needs.

Molecular characterization of diverse quinone analogs for discrimination of aerosol-bound persistent pyrolytic and photolytic radicals

Aerosol-bound organic radicals, including environmentally persistent free radicals (EPFRs), are key components that affect climate, air quality, and human health. While putative structures have been proposed, the molecular characteristics of EPFRs remain unknown. Here, we report a surrogate method to characterize EPFRs in real ambient samples using mass spectrometry. The method identifies chemically relevant oxygenated polycyclic aromatic hydrocarbons (OxPAH) that interconvert with oxygen-centered EPFR (OC-EPFR). We found OxPAH compounds most relevant to OC-EPFRs are structurally rich and diverse quinones, whose diversity is strongly associated with OC-EPFR levels. Both atmospheric oxidation and combustion contributed to OC-EPFR formation. Redundancy analysis and photochemical aging model show pyrolytic sources generated more oxidized OC-EPFRs than photolytic sources. Our study reveals the detailed molecular characteristics of OC-EPFRs and shows that oxidation states can be used to identify the origins of OC-EPFRs, offering a way to track the development and evolution of aerosol particles in the environment.

Repurposing dried blood spot device technology to examine bile acid profiles in human dried fecal spot samples.

Dried blood spot (DBS) analysis has existed for >50 years, but application of this technique to fecal analysis remains limited. To address whether dried fecal spots (DFS) could be used to measure fecal bile acids, we collected feces from five subjects for each of the following cohorts: 1) healthy individuals, 2) individuals with diarrhea, and 3) Clostridioides difficile-infected patients. Homogenized fecal extracts were loaded onto quantitative DBS (qDBS) devices, dried overnight, and shipped to the bioanalytical lab at ambient temperature. For comparison, source fecal extracts were shipped on dry ice and stored frozen. After 4 mo, frozen fecal extracts and ambient DFS samples were processed and subjected to targeted liquid chromatography-tandem mass spectrometry (LC-MS/MS)-based metabolomics with stable isotope-labeled standards. We observed no differences in the bile acid levels measured between the traditional extraction and the qDBS-based DFS methods. This pilot data demonstrates that DFS-based analysis is feasible and warrants further development for fecal compounds and microbiome applications.NEW & NOTEWORTHY Stool analysis in remote settings can be challenging, as the samples must be stored at -80°C and transported on dry ice for downstream processing. Our work indicates that dried fecal spots (DFS) on Capitainer quantitative DBS (qDBS) devices can be stored and shipped at ambient temperature and yields the same bile acid profiles as traditional samples. This approach has broad applications for patient home testing and sample collection in rural communities or resource-limited countries.

Formulation of extracted soyabean starch based edible coatings by different methods and their impact on shelf life of sapota fruit

Sapota fruits were coated with soyabean starch extracted by two different methods and using three different methods of coating (dipping, spraying, and brushing) to determine their effectiveness starch on edible coating stored under ambient (28 ± 2 °C) and refrigerated (3 ± 1 °C) conditions. The samples based on the above six combinations of starch extraction and method of coating were analyzed for physiochemical changes on fruits at 5-day interval for 25 days. The results revealed that the maximum weight reduction was observed in Ambient Control (AC) and Refrigerated Control (RC) samples as 29.89 % and 17.26 % on the 15th day of storage even though RC sample lasted for 25th day. The value for sugar-acid ratio were found as 28.33 (RDT1), 31.88 (RDT2), 33.40 (RST1), 34.22(RST2), 36.44(RBT1), 36.90 (RBT2), and 51.90(RC) on the 15th day of storage for refrigerated storage and for ambient sample it was found as 12.2, 12.82, 13.08,13.30,13.68 and 13.98, respectively, for ADT1, ADT2, AST1, AST2, ABT1 and ABT2 respectively on the 15th day. The Titratable acidity (TA), Vitamin C, firmness, decay incidence, water activity and colour characteristics exhibited higher values for the sapota fruits treated with soyabean starch as compared to the control samples. The RDT1 sample found better results and enhanced the shelf-life of sapota fruit by 2 weeks in comparison to the control samples (AC&RC) at both storage conditions.

Anthropogenic emission controls organic aerosols at Gosan background site in the outflow from northeast Asia

Anthropogenic activities release substantial amounts of organic components into the atmosphere. In this study, eight groups of organic compounds such as polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, n-alkanes, fatty acids, fatty alcohols, phthalate esters, and lignin and resin acids were identified in the ambient aerosol samples collected from a regional background site in the Korean Climate Observatory at Gosan (KCOG), South Korea. The total identified organics were most abundant in winter (220 ± 60.3 ng m−3), followed by spring, autumn, and summer, with the predominance of n-fatty acids. All classes of aliphatic lipid components showed a significant positive correlation with fossil fuel-derived organic carbon (OC-FF) and biomass burning-derived organic carbon (OC-BB), indicating that they were abundantly emitted from anthropogenic sources such as fossil fuel combustion and biomass burning. The composition profiles and diagnostic ratios of PAHs indicate that they were largely derived from coal and/or biomass combustion in the continent. In contrast, hopanes are predominantly emitted from gasoline or diesel engines, particularly in the summer, from commercial ships. The high concentration of phthalates in the summer suggested that plastic emissions from the open ocean substantially contributed to the Gosan aerosols. The low ratios of unsaturated/saturated fatty acids indicate that Gosan organic aerosols were photochemically aged during atmospheric transport. The temporal and seasonal variations of organic species over KCOG provide crucial information on the emission strengths of different contributing sources in the East Asian outflow. Positive Matrix Factorization (PMF) results and 14C-based source apportionment studies demonstrated that anthropogenically derived organic aerosols largely contributed to the aerosol mass over KCOG. Thus, the East Asian continent might be the major source region for organic aerosols over the western North Pacific, except in the summer.

Optimization of the Polarized Imaging Nephelometer (PI-Neph) for continuous monitoring of multiwavelength aerosol phase functions in support of space polarimetry missions

This work deals with the set up and optimization of a commercial multiwavelength polarized imaging nephelometer (PI-Neph, Airphoton PIN100) designed to measure F11 (phase function) and –F12/F11 (polarized phase function) from ambient aerosol samples. Such measurements are critical for the success of upcoming satellite missions based on polarimetry measurements because they will support and validate retrieval techniques. The main novelty of the instrument with respect to previous versions consists of using only one beam instead of a mirror system to fold it, avoiding internal reflections of light and loss of energy within the laser beam. The instrument also includes the automatization of the imaging technique that makes possible continuous measurements in near real time of the aerosol phase functions at different states of linear polarization directly from ambient air. Laser emits at three different wavelengths (405, 515 and 660 nm) and the beam goes through a wire grid polarizer for linearly polarizing the light, followed by two liquid crystal retarders that control the state of linear polarization. The detector is a CMOS camera perpendicular to the beam which allows to obtain final phase functions in the range 5°–175° (losses of some angles by physical limitations and stray light). The calibration of the instrument is discussed and includes geometric calibration (to account for different light paths to the camera) plus absolute calibration (to obtain physical units). Temporal stability of calibrations is observed, and different data quality tests are presented in order to obtain reliable values of F11 and –F12/F11. For an automatic operation of the instrument that permits real time phase matrix measurements, a data quality check algorithm that avoids non-physical measurements and filters outliers has been developed. Validation of the scattering matrix elements based on monodisperse aerosol measurements is also done with polystyrene latex spheres (PSL), showing good agreement with Mie theory. Finally, first results of the instrument operating at the University of Granada (UGR) station from the Andalusian Global ObseRvatory of the Atmosphere (AGORA) since April 2022 are presented. Very good agreements of the integrated scattering coefficients with an integrating nephelometer (TSI, model 3563) were obtained with high correlation coefficients for the three wavelengths (R2 > 0.81). The calculated root-mean-square error (RMSE) reveals that the performance of the PI-Neph in the measurement of the scattering coefficient is better in the 660 nm and 515 nm wavelengths than in the 405 nm one, although differences between datasets are still low. The observed differences in phase functions and especially polarized phase functions (both in shape and spectral differences) under changing atmospheric scenarios (Saharan dust, pollution and background aerosol conditions) indicated that these variables are sensitive and reliable to classify the type of ambient aerosol. Particularly, the combined measurements of F11 and –F12/F11 shows a unique potential of the PI-Neph for aerosol typology.

Oyster reefs' control of carbonate chemistry-Implications for oyster reef restoration in estuaries subject to coastal ocean acidification.

Globally, oyster reef restoration is one of the most widely applied coastal restoration interventions. While reefs are focal points of processes tightly linked to the carbonate system such as shell formation and respiration, how these processes alter reef carbonate chemistry relative to the surrounding seawater is unclear. Moreover, coastal systems are increasingly impacted by coastal acidification, which may affect reef carbonate chemistry. Here, we characterized the growth of multiple constructed reefs as well as summer variations in pH and carbonate chemistry of reef-influenced seawater (in the middle of reefs) and ambient seawater (at locations ~50 m outside of reefs) to determine how reef chemistry was altered by the reef community and, in turn, impacts resident oysters. High frequency monitoring across three subtidal constructed reefs revealed reductions of daily mean and minimum pH (by 0.05-0.07 and 0.07-0.12 units, respectively) in seawater overlying reefs relative to ambient seawater (p < .0001). The proportion of pH measurements below 7.5, a threshold shown to negatively impact post-larval oysters, were 1.8×-5.2× higher in reef seawater relative to ambient seawater. Most reef seawater samples (83%) were reduced in total alkalinity relative to ambient seawater samples, suggesting community calcification was a key driver of modified carbonate chemistry. The net metabolic influence of the reef community resulted in reductions of CaCO3 saturation state in 78% of discrete samples, and juvenile oysters placed on reefs exhibited slower shell growth (p < .05) compared to oysters placed outside of reefs. While differences in survival were not detected, reef oysters may benefit from enhanced survival or recruitment at the cost of slowed growth rates. Nevertheless, subtidal restored reef communities modified seawater carbonate chemistry in ways that likely increased oyster vulnerability to acidification, suggesting that carbonate chemistry dynamics warrant consideration when determining site suitability for oyster restoration, particularly under continued climate change.

Dual sorbent coating based magnet-integrated fabric phase sorptive extraction as a front-end to gas chromatography–mass spectrometry for multi-class pesticide determination in water samples

Magnet-integrated fabric phase sorptive extraction (MI-FPSE) is a sample preparation technique that has proved to be a powerful tool for environmental analysis. The fabrication and application of magnet-integrated dual sorbent-based FPSE membrane prepared by combining two different sol-gel sorbent-coated disks of different polarities together with a magnetic bar inserted between the two membranes to allow the stirring, was examined as novel preparation technique that not required samples pretreatments. The dual sorbent-based sample preparation platforms (made up of poly(tetrahydrofuran) and Carbowax 20M) were used for the extraction of seven classes of pesticides from ambient surface water samples prior to their determination by gas chromatography–mass spectrometry. Initially, different single and dual sol-gel sorbent-based MI-FPSE membranes were evaluated in terms of their extraction efficiency. The MI-FPSE with dual sol-gel sorbents were found to be superior to the single-materials MI-FPSE devices in terms of extraction recovery. The main parameters affecting the MI-FPSE extraction protocol (e.g., adsorption time, sample volume, stirring rate, salt addition, eluent type, desorption time and elution volume) were investigated. The selected extraction protocol enabled detection limits in the range between 0.001 and 0.16 ng mL−1. Furthermore, good relative standard deviation values for the intra-day and inter-day repeatability studies were obtained and were lower than 5.9 and 9.9 %, respectively. The proposed method was successfully used for the multi-class analysis of environmental surface water samples.

Sources of aeolian magnetite at a remote site in Japan: Dominantly Asian desert dust or anthropogenic emissions?

Asian dust (AD) profoundly impacts human health and the environment, and the soluble Fe in AD is essential for nutrient supply to the ocean and atmospheric chemistry. To accurately assess the impacts of AD, it must be separated from other natural and anthropogenic sources in the total aerosol loading. In this study, coarse aerosol samples (Dp > 2.5 μm) collected in Noto, a remote coastal area in Japan, were analyzed through an environmental magnetic analysis. A comparison of the metal content and Pb isotopic ratios revealed that the magnetization of aerosols, which reflects magnetite content, highly correlated with AD inflow. That is, aerosol magnetite is preferentially concentrated in atmospheric particles during AD events; therefore, AD-affected samples can easily be identified and distinguished from those primarily affected by transboundary air pollution by using magnetic measurements. Based on the magnetization intensity of an AD reference material (CJ-2), the AD loading for ambient samples was estimated to be 5.2–32 μg/m3, similar to that calculated based on the Al mass concentration. Moreover, magnetism is strongly linked with Fe solubility in the ambient samples. This is notable because such information has been obtained previously only through labor-intensive chemical speciation involving sequential extraction. Therefore, magnetism can be used as a new measure of both AD loading and Fe solubility via non-destructive measurements.

Active vs. passive isotopic analysis: Insights from urban Beijing field measurements and ammonia source signatures

Active collection methods such as ChemComb Speciation Cartridge samplers (CCSCs) are considered more accurate for determining the isotopic composition of NH3 (i.e., δ15N(NH3)), especially in ambient air. However, it is uncertain whether the difference in δ15N values remains consistent when comparing ALPHA to a lab-verified CCSCs with different filter types (Teflon, cellulose, and glass fiber). Here, we deployed two CCSCs and ALPHA side-by-side to collect ambient NH3 samples and compare their δ15N(NH3) values in urban Beijing during July 2019. Furthermore, NH3 source samples from urban traffic and livestock waste were collected using the ALPHA sampler under different scenarios, including various sampling locations, and sampling intervals to assess their representativeness. The results showed that NH3 concentrations measured by ALPHA were 27.6% and 8.5% lower than the concentrations measured by CCSCs A and B, respectively. CCSCs A showed lower δ15N(NH3) values (−16.4 ± 8.0‰) compared to CCSCs B, whereas the δ15N(NH3) values obtained from ALPHA (−23.9 ± 7.7‰) were not significantly different from CCSCs A. This variation in δ15N(NH3) values was attributed to reduced isotopic fractionation (31.5 ± 22.9‰) caused by decreased NH3 volatilization using Teflon and cellulose filter pack configurations. Moreover, this study revealed a consistent 15.1‰ lower δ15N(NH3) value with ALPHA compared to CCSCs B, when Teflon and glass fiber filter pack configurations were used for daily sampling. Additionally, this study revealed that ALPHA sampler might reach saturation when used for longer sampling durations, in contrast to shorter intervals of 8–12 h specifically for livestock waste. This saturation led to positive δ15N(NH3) values (2.9 ± 0.4‰), which were significantly higher compared to samples collected within the 8–12 h range. Further studies should conduct co-located measurements using both passive and active methods, enabling more accurate comparisons of sampling techniques at each location and ensuring representative samples for source apportionment studies.

Effects of storage conditions on the molecular-level composition of organic aerosol particles

Abstract. A significant fraction of atmospheric aerosol particles, which affect both the Earth's climate and human health, can be attributed to organic compounds and especially to secondary organic aerosol (SOA). To better understand the sources and processes generating organic aerosol particles, detailed chemical characterization is necessary, and particles are often collected onto filters and subsequently analyzed by liquid chromatography–mass spectrometry (LC–MS). A downside of such offline analysis techniques is the uncertainty regarding artifactual changes in composition occurring during sample collection, storage, extraction and analysis. The goal of this work was to characterize how storage conditions and storage time can affect the chemical composition of SOA generated from β-pinene and naphthalene, as well as from urban atmospheric aerosol samples. SOA samples were produced in the laboratory using an aerosol flow tube and were collected onto PTFE filters, whereas ambient samples were collected onto quartz filters with a high-volume air sampler. To characterize temporal changes in SOA composition, all samples were extracted and analyzed immediately after collection but were also stored as aqueous extracts or as filters for 24 h and up to 4 weeks at three different temperatures of +20, −20 or −80 ∘C in order to assess whether a lower storage temperature would be favorable. Analysis was conducted using ultra-high-performance liquid chromatography–high-resolution mass spectrometry (UHPLC–HRMS). Both principal component analysis (PCA) and time series of selected compounds were analyzed to identify the compositional changes over time. We show that the chemical composition of organic aerosols remained stable during low-temperature storage conditions, while storage at room temperature led to significant changes over time, even at short storage times of only 1 d. This indicates that it is necessary to freeze samples immediately after collection, and this requirement is especially important when automated ambient sampling devices are used where filters might be stored in the device for several days before being transferred to a laboratory.

SocialBit: protocol for a prospective observational study to validate a wearable social sensor for stroke survivors with diverse neurological abilities

IntroductionSocial isolation has been found to be a significant risk factor for health outcomes, on par with traditional risk factors. This isolation is characterised by reduced social interactions, which can...

Volatility Parametrization of Low-Volatile Components of Ambient Organic Aerosols Based on Molecular Formulas.

Evaluating the volatility of organic compounds based solely on their molecular formulas would avoid tough demands in deriving molecular structures. Here, we deployed an iodide-adduct Long Time-of-Flight Chemical Ionization Mass Spectrometry (LToF-CIMS) combined with a Filter Inlet for Gases and AEROsols (FIGAERO) to investigate molecular formulas and thermograms of organic compounds on ambient particulate samples collected in the summer of 2021 in a suburban site of Shanghai and to estimate saturation vapor pressures of low- and semivolatile components of ambient organic aerosols. Then, a hierarchical cluster analysis and a subsequent classification of obtained clusters by similarity calculation were applied to the measured data set of molecular formulas and saturation vapor pressures of organic aerosols with at least a 2/3 appearance frequency, together with a similar data set collected at a rural site in the Beijing-Tianjin-Hebei region during the winter of 2018 (Ren et al., 2018), to classify all compounds into multiple groups. For each group of compounds, parametrizations between volatility and elemental composition were derived, and then relationships between each group of parameters and the mean O:C were established to achieve a volatility-molecular formula parametrization with the O:C as a key input. Statistical comparison of estimated volatilities of low-volatile organic compounds shows a much better performance of our parametrization than previous molecular formula-based ones.

Stability assessment of organic sulfur and organosulfate compounds in filter samples for quantification by Fourier- transform infrared spectroscopy

Abstract. Organic sulfur and sulfate compounds, which are tracers for sources and atmospheric processes, are not currently measured in national monitoring networks such as the Interagency Monitoring of Protected Visual Environments (IMPROVE). The goal of this paper is to begin to assess the stability of organic sulfur and sulfate-containing compounds on polytetrafluoroethylene (PTFE) filters and the suitability of Fourier-transform infrared (FT-IR) spectroscopy to measure these compounds. Stability assessment is needed because PTFE samples collected by IMPROVE are typically stored 6–9 months prior to analysis. For this study, two organosulfur compounds, methanesulfonic acid (MSA) and hydroxymethanesulfonate ion (HMS), and two organosulfate compounds, methyl sulfate (MS) and 2-methyltetrol sulfate (2-MTS), are collected individually on PTFE filters. Gravimetric mass measurements are used to assess mass stability over time. FT-IR spectra are evaluated to assess the capability of measuring the compound from PTFE filters by assessing the compound stability or chemical changes over time. Ion chromatography (IC) and inductively coupled plasma optical emission spectroscopy (ICP-OES) are used as additional tools to assess stability or chemical changes over time. MS has the highest potential to be measured by FT-IR in IMPROVE samples. For MS, a simple organosulfate, the mass changes are within measurement uncertainty and FT-IR spectra indicate no compositional change over a 4-month period, suggesting that MS can be measured using FT-IR. IC and ICP-OES support the conclusion that MS is stable on the filter. However, for 2-MTS, the other organosulfate measured in this study, spectral changes after a month on the filter suggest that it decomposes into other organosulfates or an inorganic sulfate. MSA in IMPROVE samples can be measured, but only as a lower bound, due to volatility off the filter as indicated by FT-IR and gravimetry. FT-IR and IC both show that MSA does not chemically change over the course of the study. Measurements by all methods indicate that HMS is unstable on the PTFE filter, and IC and FT-IR indicate that it likely converts to inorganic sulfate. Future work includes the evaluation of these compounds in an ambient aerosol sample matrix to determine any differences in stability, identifying interference that could limit quantification, and developing calibrations to measure the compounds or functional groups in ambient samples.

In Situ Surface Tension Measurement of Deliquesced Aerosol Particles.

The surface tension of aerosol particles can potentially affect cloud droplet activation. Hence, direct measurement of the surface tensions of deliquesced aerosol particles is essential but is challenging. Here, we report in situ surface tension measurements based on a novel method that couples a linear quadrupole electrodynamic balance (EDB) with quasi-elastic light scattering (QELS). The EDB-QELS is validated using surface tension measurements of atmospherically relevant inorganic and organic droplets. The surface tension results reasonably agree with the reference values in the range of ∼50-90 mN m-1. We find a significant size dependence for sodium chloride droplets containing surface-active species (sodium dodecyl sulfate) in the size range of ∼5-18 μm. The surface tension increases from ∼55 to 80 mN m-1 with decreased size. Relative humidity (RH)-dependent surface tensions of mixed ammonium sulfate (AS) and polyethylene glycol droplets reveal the onset of liquid-liquid phase separation. Droplets containing water-soluble matter extracted from ambient aerosol samples and 2.3-2.9 M AS exhibit a ∼30% reduction in surface tension in the presence of ∼50 mmol-C L-1 water-soluble organic carbon, compared to pure water (∼72 mN m-1). The approach can offer size-resolved and RH-dependent surface tension measurements of deliquesced aerosol particles.

A Comparison of Ambient Air Ethylene Oxide Modeling Estimates from Facility Stack and Fugitive Emissions to Canister-Based Ambient Air Measurements in Salt Lake City

Ethylene oxide (EtO) is a colorless, flammable gas at room temperature produced by the catalytic oxidation of ethylene. EtO is widely used by medical sterilization facilities to clean medical supplies and equipment. Recent epidemiological studies showed that EtO is a more potent carcinogen than previously documented, leading the Environmental Protection Agency (EPA) to update, in December 2016, the inhalation unit risk estimate for EtO. This resulted in the identification of EtO as a potential health concern in several areas across the US, including the state of Utah. The geography surrounding Salt Lake Valley creates a bowl, which is ideal for collecting air pollution emissions. The region often experiences inversion episodes which inhibit vertical mixing and cause an accumulation of air pollutants, leading to unhealthy pollution levels. Using the EPA’s dispersion modeling software, AERMOD, this study estimated EtO concentrations through facility stack and fugitive emissions modeling results. These values were compared with those of canister-based concentrations from ambient air samples taken near a medical device sterilization facility in Salt Lake Valley. Stainless steel whole-air passivated canisters were used to collect 24 h ambient concentration samples of EtO. Eight locations surrounding a Salt Lake Valley medical device sterilization facility and four background sites were chosen to measure the ambient concentrations. Accounting for potential atmospheric impacts on EtO, measurements were sampled in winter 2022 (January–March) and summer 2022 (July–September). The modeled EtO concentrations were adjusted to account for background values associated with the winter or summer data. Then, the two methodologies were compared using a Wilcoxon signed-ranked paired test. The statistical analysis resulted in six of the eight sample locations surrounding the sterilization facility being significantly different when comparing the canister-based measurements of ambient EtO to modeled estimates. Canister-based measurements taken at sites one, three, and four were statistically greater than the modeled estimates, while sites two, five, and seven were statistically less than the modeled estimates. Also, the summer background value calculated was almost 2.5 times greater than the winter one. The results do not suggest whether one method is more or less conservative than the other. In conclusion, the five of the closest sites and site seven were statistically different when comparing measured and modeled ambient concentrations of EtO. The comparison results do not clearly indicate if a correction factor could be derived for future human exposure to cancer risk assessment modeling. However, it is reasonable that the closer to the sterilization facility, the more total EtO exposure will be realized.

Isolated and solvated chiroptical behavior in conformationally flexible butanamines.

The nonresonant optical activity of two highly flexible aliphatic amines, (2R)-3-methyl-2-butanamine (R-MBA) and (2R)-(3,3)-dimethyl-2-butanamine (R-DMBA), has been probed under isolated and solvated conditions to examine the roles of conformational isomerism and to explore the influence of extrinsic perturbations. The optical rotatory dispersion (ORD) measured in six solvents presented uniformly negative rotatory powers over the 320-590 nm region, with the long-wavelength magnitude of chiroptical response growing nearly monotonically as the dielectric constant of the surroundings diminished. The intrinsic specific optical rotation, (in deg dm-1 [g/mL]-1 ), extracted for ambient vapor-phase samples of R-MBA [-11.031(98) and -2.29 (11)] and R-DMBA [-9.434 (72) and -1.350 (48)] at 355 and 633 nm were best reproduced by counterintuitive solvents of high polarity (yet low polarizability) like acetonitrile and methanol. Attempts to interpret observed spectral signatures quantitatively relied on the linear-response frameworks of density-functional theory (B3LYP, cam-B3LYP, and dispersion-corrected analogs) and coupled-cluster theory (CCSD), with variants of the polarizable continuum model (PCM) deployed to account for the effects of implicit solvation. Building on the identification of several low-lying equilibrium geometries (nine for R-MBA and three for R-DMBA), ensemble-averaged ORD profiles were calculated at T = 300K by means of the independent-conformer ansatz, which enabled response properties predicted for the optimized structure of each isomer to be combined through Boltzmann-weighted population fractions derived from corresponding relative internal-energy or free-energy values, the latter of which stemmed from composite CBS-APNO and G4 analyses. Although reasonable accord between theory and experiment was realized for the isolated (vapor-phase) species, the solution-phase results were less satisfactory and tended to degrade progressively as the solvent polarity increased. These trends were attributed to solvent-mediated changes in structural parameters and energy metrics for the transition states that separate and putatively isolate the equilibrium conformations supported by the ground electronic potential-energy surface, with the resulting displacement of barrier locations and/or decrease of barrier heights compromising the underlying premise of the independent-conformer ansatz.