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At least 613 records · Page 34

Evaluating marginal likelihood with thermodynamic integration method and comparison with several other numerical methods

Evaluating marginal likelihood is the most critical and computationally expensive task, when conducting Bayesian model averaging to quantify parametric and model uncertainties. The evaluation is commonly done by using Laplace approximations to evaluate semianalytical expressions of the marginal likelihood or by using Monte Carlo (MC) methods to evaluate arithmetic or harmonic mean of a joint likelihood function. This study introduces a new MC method, i.e., thermodynamic integration, which has not been attempted in environmental modeling. Instead of using samples only from prior parameter space (as in arithmetic mean evaluation) or posterior parameter space (as in harmonic mean evaluation), the thermodynamic integration method uses samples generated gradually from the prior to posterior parameter space. This is done through a path sampling that conducts Markov chain Monte Carlo simulation with different power coefficient values applied to the joint likelihood function. The thermodynamic integration method is evaluated using three analytical functions by comparing the method with two variants of the Laplace approximation method and three MC methods, including the nested sampling method that is recently introduced into environmental modeling. The thermodynamic integration method outperforms the other methods in terms of their accuracy, convergence, and consistency. The thermodynamic integration method is also applied to a synthetic case of groundwater modeling with four alternative models. The application shows that model probabilities obtained using the thermodynamic integration method improves predictive performance of Bayesian model averaging. As a result, the thermodynamic integration method is mathematically rigorous, and its MC implementation is computationally general for a wide range of environmental problems.

97 MATHEMATICS AND COMPUTING↗

Release Report for Building Debris for TA-21 Sewage Treatment Facility

ENV-ES finds that the materials associated with TA-21 Buildings 227 (superstructure only), and 229 (see Figure 1) meet the criteria for unrestricted release to the public for recycle or as sanitary/commercial waste. The interior and exterior of the metal shed, building 387, passed the release criteria collectively; however, results from the roof of the structure were above reference background measurements. Waste management should be consulted for waste disposition options for the roofing metal. These findings are consistent with the requirements of DOE Order 458.1 “Radiation Protection of the Public and the Environment” and LANL Policy 412 “Environmental Radiation Protection.” Sampling and data analysis, as described in this report, were sufficient to meet measurement objectives under the Multi-Agency Radiation Survey and Assessment of Materials and Equipment (MARSAME) manual (2009).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Detection and imaging of chemicals and hidden explosives using terahertz time-domain spectroscopy and deep learning

Detecting concealed chemicals and explosives remains a critical challenge in global security. Terahertz time-domain spectroscopy (THz-TDS) offers a promising non-invasive and stand-off detection technique owing to its ability to penetrate optically opaque materials without causing ionization damage. While many chemicals exhibit distinct spectral features in the terahertz range, conventional terahertz-based detection methods often struggle in real-world environments, where variations in sample geometry, thickness, and packaging can lead to inconsistent spectral responses. In this study, we present a chemical imaging system that integrates THz-TDS with deep learning to enable accurate pixel-level identification and classification of different explosives. Operating in reflection mode and enhanced with plasmonic nanoantenna arrays, our THz-TDS system achieves a peak dynamic range of 96 dB and a detection bandwidth of 4.5 THz, supporting practical, stand-off operation. By analyzing individual time-domain pulses with deep neural networks, the system exhibits strong resilience to environmental variations and sample inconsistencies. Blind testing across eight chemicals—including pharmaceutical excipients and explosive compounds—resulted in an average classification accuracy of 99.42% at the pixel level. Notably, the system maintained an average accuracy of 88.83% when detecting explosives concealed under opaque paper coverings, demonstrating its robust generalization capability. These results highlight the potential of combining advanced terahertz spectroscopy with neural networks for highly sensitive and specific chemical and explosive detection in diverse and operationally relevant scenarios.

Imaging and sensing↗

Effect of carbonyl iron particles composition on the physical characteristics of MR grease

Magnetorheological (MR) grease is an extension of the study of magnetorheological materials. The MR grease can help to reduce the particles sedimentation problem occurred in the MR fluids. Within this study, an effort has been taken to investigate the effect of different weight compositions of carbonyl iron particles on the physical and chemical characteristics of the MR grease under off-state condition (no magnetic field). The MR grease is prepared by mixing carbonyl iron particles having a size range of 1 to 10 µm with commercial NPC Highrex HD-3 grease. Characterizations of MR grease are investigated using Vibrating Sample Magnetometer (VSM), Environmental Scanning Electron Microscopy (ESEM), Differential Scanning Calorimeter (DSC) and rheometer. The dependency of carbonyl iron particles weight towards the magnetic properties of MR grease and other characterizations are investigated.

36 MATERIALS SCIENCE↗

A progressive electrochemical sensor for food quality control: Reliable determination of theobromine in chocolate products using a miniaturized boron-doped diamond electrode

In the present paper, a miniaturized boron-doped diamond electrode (BDDE) is proposed as a progressive electrochemical sensor for simple, fast and reliable quantification of dimethylxanthine alkaloid, theobromine (TB). Using cyclic voltammetry, the studied xanthine provided one well-shaped, irreversible and diffusion-controlled oxidation peak at relatively high potentials (+1.2 V vs. Ag/AgCl/3 M KCl reference electrode) in the presence of 0.1 M H2SO4. After selection of suitable experimental conditions, the linear calibration curves for TB were obtained in the concentration range from 0.99 up to 54.5 μM with the sensitivity of 0.07 μA/μM providing both differential pulse (DPV) and square-wave voltammetric (SWV) techniques, respectively. The elaborated voltammetric protocol yielded low detection limits of 0.42 and 0.51 μM accompanied by adequate intra-day repeatability (relative standard deviation of 2.5 and 1.7%) using DPV and SWV procedure, respectively. The interference study revealed the reasonable selectivity when taking the target food samples into account. The practical applicability of the voltammetric protocol using a miniaturized BDDE was verified in the analysis of six commercially available brands of chocolate products with the determined mass percentages of TB ranging from 0.75 to 2.24% and from 0.69 to 2.15% using DPV and SWV procedure, respectively. The obtained results were also in a good agreement with those achieved by reference titration method with potentiometric indication. The progressive electrochemical sensor based on a miniaturized BDDE has appeared to be an attractive candidate for practical applications in food quality control. Besides, the proposed voltammetric protocol presents advantages when compared to others techniques (e.g. chromatography), concerning simplicity, cost, speed of analysis, waste generation (environmentally friendly) and samples pretreatment (only dilution in electrolyte solution prior to analysis). © 2018 Elsevier B.V.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scientific guidelines for preservation of samples collected from Mars

The maximum scientific value of Martian geologic and atmospheric samples is retained when the samples are preserved in the conditions that applied prior to their collection. Any sample degradation equates to loss of information. Based on detailed review of pertinent scientific literature, and advice from experts in planetary sample analysis, number values are recommended for key parameters in the environmental control of collected samples with respect to material contamination, temperature, head-space gas pressure, ionizing radiation, magnetic fields, and acceleration/shock. Parametric values recommended for the most sensitive geologic samples should also be adequate to preserve any biogenic compounds or exobiological relics.

Gooding, James L.↗

Role of paraoxonase 1 (PON1) in organophosphate metabolism: Implications in neurodegenerative diseases

Organophosphate pesticides are a class of compounds that are widely used in agricultural and rural areas. Paraoxonase 1 (PON1) is a phase-I enzyme that is involved in the hydrolysis of organophosphate esters. Environmental poisoning by organophosphate compounds has been the main driving force of previous research on PON1 enzymes. Recent discoveries in animal models have revealed the important role of the enzyme in lipid metabolism. However although PON1 function is well established in experimental models, the contribution of PON1 in neurodegenerative diseases remains unclear. In this minireview we summarize the involvement of PON1 genotypes in the occurrence of Parkinson's disease, Alzheimer's disease and amyotrophic lateral sclerosis. A brief overview of latest epidemiological studies, regarding the two most important PON1 coding region polymorphisms PON1-L55M and PON1-Q192R is presented. Positive and negative associations of PON1 with disease occurrence are reported. Notably the MM and RR alleles contribute a risk enhancing effect for the development of some neurodegenerative diseases, which may be explained by the reduced lipoprotein free radical scavenging activity that may give rise to neuronal damage, through distinct mechanism. Conflicting findings that fail to support this postulate may represent the human population ethnic heterogeneity, different sample size and environmental parameters affecting PON1 status. We conclude that further epidemiological studies are required in order to address the exact contribution of PON1 genome in combination with organophosphate exposure in populations with neurodegenerative diseases.

60 APPLIED LIFE SCIENCES↗

A Physically-Based Model for Thermo-Oxidative and Hydrolytic Aging of Elastomers

A computationally efficient model is proposed to capture the loss of mechanical performance due to chemical aging that are formed as the competition of chain scission and cross-link formation/dissolution, such as thermo-oxidative aging or hydrolytic aging. The model should be considered an extension of our recent models [1, 2, 3] which further simplifies the matrix behavior based on the assumption of independence of environmental and mechanical damage. The model uses this assumption to reduce the necessary material parameters needed to model constitutive and inelastic behavior of elastomers during aging. To this end, the model can provide accurate predictions of the material performance with the significantly fewer number of fitting parameters. The model is relevant for all decay mechanisms formed by the occurrence of two simultaneous micro-mechanisms; (i) formation/reduction of the cross-links, and (ii) chain scission, both of which are present in thermo-oxidation and hydrolytic aging. Assuming the alteration of the chain density along the aging trajectory is identical to the peroxide cross-link density for thermo-oxidation, and the change of the average molecular weight for hydrolysis, the strain energy of polymer matrix can be rewritten as a function of deformation, deformation history, storage time and aging temperature. Next, the modified network alteration model is formulated for implementation into Finite Element (FE) simulations. The model is built on the presumption of homogeneous and consistent oxygen/water absorption and thus is mainly relevant for relatively thin samples exposed to environmental loads for a long time. The proposed model includes only six physically inspired material parameters. Therefore, while it is computationally efficient, it shows good agreement with own experimental data, which performed on various range of accelerated aging temperatures and times. With respect to its computational efficiency, simplicity, accuracy, and interpret-ability, the model is the right choice for advanced implementations in FE programs.

42 ENGINEERING↗

Quality Control Analysis in Real-time (QC-ART): A Tool for Real-time Quality Control Assessment of Mass Spectrometry-based Proteomics Data

Liquid chromatography-mass spectrometry (LC-MS)-based proteomics studies of large sample cohorts can easily require from months to years to complete. Acquiring consistent, high-quality data in such large-scale studies is challenging because of normal variations in instrumentation performance over time, as well as artifacts introduced by the samples themselves, such as those due to collection, storage and processing. Existing quality control methods for proteomics data primarily focus on post-hoc analysis to remove low-quality data that would degrade downstream statistics; they are not designed to evaluate the data in near real-time, which would allow for interventions as soon as deviations in data quality are detected. In addition to flagging analyses that demonstrate outlier behavior, evaluating how the data structure changes over time can aide in understanding typical instrument performance or identify issues such as a degradation in data quality due to the need for instrument cleaning and/or re-calibration. To address this gap for proteomics, we developed Quality Control Analysis in Real-Time (QC-ART), a tool for evaluating data as they are acquired in order to dynamically flag potential issues with instrument performance or sample quality. QC-ART has similar accuracy as standard post-hoc analysis methods with the additional benefit of real-time analysis. We demonstrate the utility and performance of QC-ART in identifying deviations in data quality due to both instrument and sample issues in near real-time for LC-MS-based plasma proteomics analyses of a sample subset of The Environmental Determinants of Diabetes in the Young cohort. We also present a case where QC-ART facilitated the identification of oxidative modifications, which are often underappreciated in proteomic experiments.

Stanfill, Bryan A.↗

Monitoring Soil Erosion on a Burned Site in the Mojave-Great Basin Transition Zone: Final Report for the Jacob Fire Site

A historic return interval of 100 years for large fires in the U.S. southwestern deserts is being replaced by one where fires may reoccur as frequently as every 20 to 30 years. The shortened return interval, which translates to an increase in fires, has implications for management of Soil Corrective Action Units (CAUs) and Corrective Action Sites (CASs) for which the Department of Energy, National Nuclear Security Administration Nevada Field Office has responsibility. A series of studies was initiated at uncontaminated analog sites to better understand the possible impacts of erosion and transport by wind and water should contaminated soil sites burn. The first of these studies was undertaken at the Jacob Fire site approximately 12 kilometers (7.5 miles) north of Hiko, Nevada. A lightning-caused fire burned approximately 200 hectares during August 6-8, 2008. The site is representative of a transition between Mojave and Great Basin desert ecoregions on the Nevada National Security Site (NNSS), where the largest number of Soil CAUs/CASs are located. The area that burned at the Jacob Fire site was primarily a Coleogyne ramosissima (blackbrush) and Ephedra nevadensis (Mormon tea) community, also an abundant shrub assemblage in the similar transition zone on the NNSS. This report summarizes three years of measurements after the fire. Seven measurement campaigns at the Jacob Fire site were completed. Measurements were made on burned ridge (upland) and drainage sites, and on burned and unburned sites beneath and between vegetation. A Portable In-Situ Wind Erosion Lab (PI-SWERL) was used to estimate emissions of suspended particles at different wind speeds. Context for these measurements was provided through a meteorological tower that was installed at the Jacob Fire site to obtain local, relevant environmental parameters. Filter samples, collected from the exhaust of the PI-SWERL during measurements, were analyzed for chemical composition. Runoff and water erosion were quantified through a series of rainfall/runoff simulation tests in which controlled amounts of water were delivered to the soil surface in a specified amount of time. Runoff data were collected from understory and interspace soils on burned ridge and drainage areas. Runoff volume and suspended sediment in the runoff were sampled; the particle size distribution of the sediment was determined by laboratory analysis. Several land surface and soil characteristics associated with runoff were integrated by the calculation of site-specific curve numbers. Several vegetation surveys were conducted to assess post-burn recovery. Data from plots in both burned and unburned areas included species identification, counts, and location. Characterization of fire-affected area included measures at both the landscape scale and at specific sites. Although wind erosion measurements indicate that there are seasonal influences on almost all parameters measured, several trends were observed. PI-SWERL measurements indicated the potential for PM 10 windblown dust emissions was higher on areas that were burned compared to areas that were not. Among the burned areas, understory soils in drainage areas were the most emissive, and interspace soils along burned ridges were least emissive. By 34 months after the burn (MAB), at the end of the study, emissions from all burned soil sites were virtually indistinguishable from unburned levels. Like the amount of emissions, the chemical signature of the fire (indicated by the EC-Soil ratio) was elevated immediately after the fire and approached pre-burn levels by 24 MAB. Thus, the potential for wind erosion at the Jacob Fire site, as measured by the amount and type of emissions, increased significantly after the fire and returned to unburned levels by 24 MAB. The effect of fire on the potential for water erosion at the Jacob Fire site was more ambiguous. Runoff and sediment from ridge interspace soils and unburned interspace soils were similar throughout the study period. Seldom, if ever, did runoff and sediment occur in burned drainage area soils. For burned soils where runoff occurred at 1 MAB, the sediment size was finer than on unburned sites, but this effect disappeared by 3 MAB. For the three year study under the conditions tested at the Jacob Fire site, the potential for water erosion appeared relatively unaffected by the fire. Vegetation responses were documented for each year following the fire. By the end of the study, there was a substantial difference in plant densities and richness between drainage and ridge sites. Cheatgrass densities were higher in unburned plots, and cheatgrass was also more dominant in the community composition in unburned plots. Cheatgrass had increased in the burned area but so did other native species. Three years after the fire, the burned landscape continued to revegetate but had yet to approximate the condition of an unburned landscape. The results from the vegetation surveys support the wind erosion results, where the primary source of windborne particles originate from the understory, where lower plant diversity and densities were found. The soil appears to be more resilient and have a much shorter recovery time than the vegetation in this particular community.

54 ENVIRONMENTAL SCIENCES↗

Filling in the GAPS: evaluating completeness and coverage of open-access biodiversity databases in the United States

Primary biodiversity data constitute observations of particular species at given points in time and space. Open-access electronic databases provide unprecedented access to these data, but their usefulness in characterizing species distributions and patterns in biodiversity depend on how complete species inventories are at a given survey location and how uniformly distributed survey locations are along dimensions of time, space, and environment. Our aim was to compare completeness and coverage among three open-access databases representing ten taxonomic groups (amphibians, birds, freshwater bivalves, crayfish, freshwater fish, fungi, insects, mammals, plants, and reptiles) in the contiguous United States. We compiled occurrence records from the Global Biodiversity Information Facility (GBIF), the North American Breeding Bird Survey (BBS), and federally administered fish surveys (FFS). In this study, we aggregated occurrence records by 0.1° × 0.1° grid cells and computed three completeness metrics to classify each grid cell as well-surveyed or not. Next, we compared frequency distributions of surveyed grid cells to background environmental conditions in a GIS and performed Kolmogorov–Smirnov tests to quantify coverage through time, along two spatial gradients, and along eight environmental gradients. The three databases contributed >13.6 million reliable occurrence records distributed among >190,000 grid cells. The percent of well-surveyed grid cells was substantially lower for GBIF (5.2%) than for systematic surveys (BBS and FFS; 82.5%). Still, the large number of GBIF occurrence records produced at least 250 well-surveyed grid cells for six of nine taxonomic groups. Coverages of systematic surveys were less biased across spatial and environmental dimensions but were more biased in temporal coverage compared to GBIF data. GBIF coverages also varied among taxonomic groups, consistent with commonly recognized geographic, environmental, and institutional sampling biases. Lastly, this comprehensive assessment of biodiversity data across the contiguous United States provides a prioritization scheme to fill in the gaps by contributing existing occurrence records to the public domain and planning future surveys.

59 BASIC BIOLOGICAL SCIENCES↗

Selective capture of radionuclides (U, Pu, Th, Am and Co) using functional nanoporous sorbents

Using our self-assembled silanol technology, we developed eight functional nanoporous silica sorbents for capturing two classes of radionuclides: the actinide uranium (U), thorium (Th), plutonium (Pu), americium (Am) and the transition metal cobalt (Co). We tested them in sea, ground, and river water that were adjusted to pH 0-8.0 and doped with competing metals (Mg, Ca, K, Se, Mn, Fe, Co, Cu, Zn, and Mo) at levels encountered in environmental or physiological samples. Sorbents having three analogs of hydroxypyridinones (HOPO) and acetamide phosphonate (Ac-Phos) were exceptional at capturing U, Th, and Pu from pH 2.0 to 8.0, and very good at capturing Am from pH 5.0 to 8.0 with the affinity ranged from 3,4-HOPO > 1,2-HOPO > 3,2-HOPO > Ac-Phos. However, the affinity is reversed at near zero pH. For capturing Co, a family of glycine derivatives on nanoporous silica has been developed and the affinity for Co ranged from IDAA ~ DE4A > ED3A between pH 5.0-8.0. Our materials significantly outperformed the commercially available cation sorbents such as Chelex-100 and activated carbon in terms of binding affinity and rate; thus demonstrating great potential to be used as decorporation agents for water treatment and recovery of valuable actinides.

uranium (U), thorium (Th), plutonium (Pu), americi↗

Use of Transmission Electron Microscopy for Analysis of Aerosol Particles and Strategies for Imaging Fragile Particles

For over 25 years, transmission electron microscopy (TEM) has provided a method for the study of aerosol particles with sizes from below the optical diffraction limit to several microns, resolving the particles as well as smaller features. The wide use of this technique to study aerosol particles has contributed important insights about environmental aerosol particle samples and model atmospheric systems. TEM produces an image that is a 2D projection of aerosol particles that have been impacted onto grids and, through associated techniques and spectroscopies, can contribute additional information such as the determination of elemental composition, crystal structure, and 3D particle structures. Soot, mineral dust, and organic/inorganic particles have all been analyzed using TEM and spectroscopic techniques. TEM, however, has limitations that are important to understand when interpreting data including the ability of the electron beam to damage and thereby change the structure and shape of particles, especially in the case of particles composed of organic compounds and salts. In this paper, we concentrate on the breadth of studies that have used TEM as the primary analysis technique. Another focus is on common issues with TEM and cryogenic-TEM. Insights for new users on best practices for fragile particles, that is, particles that are easily susceptible to damage from the electron beam, with this technique are discussed. Tips for readers on interpreting and evaluating the quality and accuracy of TEM data in the literature are also provided and explained.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Seeing through walls at the nanoscale: Microwave microscopy of enclosed objects and processes in liquids

Here, noninvasive in situ nanoscale imaging in liquid environments is a current imperative in the analysis of delicate biomedical objects and electrochemical processes at reactive liquid–solid interfaces. Microwaves of a few gigahertz frequencies offer photons with energies of ≈10 μeV, which can affect neither electronic states nor chemical bonds in condensed matter. Here, we describe an implementation of scanning near-field microwave microscopy for imaging in liquids using ultrathin molecular impermeable membranes separating scanning probes from samples enclosed in environmental cells. We imaged a model electroplating reaction as well as individual live cells. Through a side-by-side comparison of the microwave imaging with scanning electron microscopy, we demonstrate the advantage of microwaves for artifact-free imaging.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Minimum information about a marker gene sequence (MIMARKS) and minimum information about any (x) sequence (MIxS) specifications.

Here we present a standard developed by the Genomic Standards Consortium (GSC) for reporting marker gene sequences - the minimum information about a marker gene sequence (MIMARKS). We also introduce a system for describing the environment from which a biological sample originates. The 'environmental packages' apply to any genome sequence of known origin and can be used in combination with MIMARKS and other GSC checklists. Finally, to establish a unified standard for describing sequence data and to provide a single point of entry for the scientific community to access and learn about GSC checklists, we present the minimum information about any (x) sequence (MIxS). Adoption of MIxS will enhance our ability to analyze natural genetic diversity documented by massive DNA sequencing efforts from myriad ecosystems in our ever-changing biosphere.

59 BASIC BIOLOGICAL SCIENCES↗

Covalent adaptable polymer networks with CO 2 -facilitated recyclability

Cross-linked polymers with covalent adaptable networks (CANs) can be reprocessed under external stimuli owing to the exchangeability of dynamic covalent bonds. Optimization of reprocessing conditions is critical since increasing the reprocessing temperature costs more energy and even deteriorates the materials, while reducing the reprocessing temperature via molecular design usually narrows the service temperature range. Exploiting CO 2 gas as an external trigger for lowering the reprocessing barrier shows great promise in low sample contamination and environmental friendliness. Herein, we develop a type of CANs incorporated with ionic clusters that achieve CO 2 -facilitated recyclability without sacrificing performance. The presence of CO 2 can facilitate the rearrangement of ionic clusters, thus promoting the exchange of dynamic bonds. The effective stress relaxation and network rearrangement enable the system with rapid recycling under CO 2 while retaining excellent mechanical performance in working conditions. This work opens avenues to design recyclable polymer materials with tunable dynamics and responsive recyclability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scalable fabrication of an array-type fixed-target device for automated room temperature X-ray protein crystallography

X-ray crystallography is one of the leading tools to analyze the 3-D structure, and therefore, function of proteins and other biological macromolecules. Traditional methods of mounting individual crystals for X-ray diffraction analysis can be tedious and result in damage to fragile protein crystals. Furthermore, the advent of multi-crystal and serial crystallography methods explicitly require the mounting of larger numbers of crystals. To address this need, we have developed a device that facilitates the straightforward mounting of protein crystals for diffraction analysis, and that can be easily manufactured at scale. Inspired by grid-style devices that have been reported in the literature, we have developed an X-ray compatible microfluidic device that can be used to trap protein crystals in an array configuration, while also providing excellent optical transparency, a low X-ray background, and compatibility with the robotic sample handling and environmental controls used at synchrotron macromolecular crystallography beamlines. At the Stanford Synchrotron Radiation Lightsource (SSRL), these capabilities allow for fully remote-access data collection at controlled humidity conditions. Furthermore, we have demonstrated continuous manufacturing of these devices via roll-to-roll fabrication to enable cost-effective and efficient large-scale production.

chemical engineering↗

An omnipresent diversity and variability in the chemical composition of atmospheric functionalized organic aerosol

Abstract The atmospheric evolution of organic compounds encompasses many thousands of compounds with varying volatility, polarity, and water solubility. The molecular-level chemical composition of this mixture plays a major, yet uncertain, role in its transformations and impacts. Here we perform a non-targeted molecular-level intercomparison of functionalized organic aerosol from three diverse field sites and a chamber. Despite similar bulk composition, we report large molecular-level variability between multi-hour organic aerosol samples at each site, with 66 ± 13% of functionalized compounds differing between consecutive samples. Single precursor environmental laboratory chamber experiments and fully chemically-explicit modeling confirm this variability is due to changes in emitted precursors, chemical age, and/or oxidation conditions. These molecular-level results demonstrate greater compositional variability than is typically observed in less-speciated measurements, such as bulk elemental composition, which tend to show less daily variability. These observations should inform future field and laboratory studies, including assessments of the effects of variability on aerosol properties and ultimately the development of strategic organic aerosol parameterizations for air quality and climate models.

Ditto, Jenna C.↗