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Diatom volatile organic compound production is driven by diel metabolism and the cell cycle

Introduction: Volatile organic compounds (VOCs) are small, low-vapor-pressure molecules emitted from the surface ocean into the atmosphere. In the atmosphere, VOCs can change OH reactivity and condense onto particles to become cloud condensation nuclei. VOCs are produced by phytoplankton, but the conditions leading to VOC accumulation in the surface ocean are poorly understood.Methods: In this study, VOC accumulation was measured in real time over a 12 h day−12 h night cycle in the model diatom Phaeodactylum tricornutum during exponential growth.Results: Sixty-three m/z signals were produced in higher concentrations than in cell-free controls. All VOCs, except methanol, were continuously produced over 24 h. All VOCs accumulated to higher concentrations during the day compared to the night, and 11 VOCs exhibited distinct accumulation patterns during the morning hours. Twenty-seven VOCs were associated with known metabolic pathways in P. tricornutum, with most VOCs involved in amino acid and fatty acid metabolism.Discussion: Patterns of VOC production were strongly associated with diel shifts in cell physiology and the cell cycle. Diel VOC production patterns give a fundamental understanding of the first steps in VOC accumulation in the surface ocean.

Biological and medical sciences↗

Harvest Initiated Volatile Organic Compound Emissions from In-Field Tall Wheatgrass

While crop and grassland usage continues to increase, the full diversity of plant-specific volatile organic compounds (VOCs) emitted from these ecosystems, including their implications for atmospheric chemistry and carbon cycling, remains poorly understood. It is particularly important to investigate VOCs in the context of potential biofuels: aside from the implications of largescale land use, harvest may shift both the flux and speciation of emitted VOCs. To this point, we evaluate the diversity of VOCs emitted both pre and postharvest from “Alkar” tall wheatgrass (Thinopyrum ponticum), a candidate biofuel that exhibits greater tolerance to frost and saline land compared to other grass varieties. Mature plants grown under field conditions (n = 6) were sampled for VOCs both pre- and postharvest (October 2022). Via hierarchical clustering of emitted VOCs from each plant, we observe distinct “volatilomes” (diversity of VOCs) specific to the pre- and postharvest conditions despite plant-to-plant variability. In total, 50 VOCs were found to be unique to the postharvest tall wheatgrass volatilome, and these unique VOCs constituted a significant portion (26%) of total postharvest signal. While green leaf volatiles (GLVs) dominate the speciation of postharvest emissions (e.g., 54% of unique postharvest VOC signal was due to 1-penten-3-ol), we demonstrate novel postharvest VOCs from tall wheatgrass that are under characterized in the context of carbon cycling and atmospheric chemistry (e.g., 3-octanone). Continuing evaluations will quantitatively investigate tall wheatgrass VOC fluxes, better informing the feasibility and environmental impact of tall wheatgrass as a biofuel.

09 BIOMASS FUELS↗

Species-Selective Detection of Volatile Organic Compounds by Ionic Liquid-Based Electrolyte Using Electrochemical Methods

The detection of volatile organic compounds (VOCs) is an important topic for environmental safety and public health. However, the current commercial VOC detectors suffer from cross-sensitivity and low reproducibility. In this work, we present species-selective detection for VOCs using an electrochemical cell based on ionic liquid (IL) electrolytes with features of high selectivity and reliability. The voltammograms measured with the IL-based electrolyte absorbing different VOCs exhibited species-selective features that were extracted and classified by linear discriminant analysis (LDA). The detection system could identify as many as four types of VOCs, including methanol, ethanol, acetone, formaldehyde, and additional water. A mixture of methanol and formaldehyde was detected as well. The sample required for the VOCs classification system was 50 μL, or 1.164 mmol, on average. The response time for each VOC measurement is as fast as 24 s. The volume of VOCs such as formaldehyde in solution could also be quantified by LDA and electrochemical impedance spectroscopy techniques, respectively. The system showed a tunable detection range for 1.6 and 16% (w/v) CH 2 O solution by adjusting the composition of the electrolyte. The limit of detection was as low as 1 μL. For the 1.6% CH 2 O solution, the linearity calibration range was determined to be from 5.30 to 53.00 μmol with a limit of detection at 0.53 μmol. The mechanisms for VOCs determination and quantification are also thoroughly discussed. Finally, it is expected that this work could provide a new insight into the concept of electrochemical detection of VOCs with machine learning analysis and be applied to both VOCs gas monitoring and fluid detection.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Technical Background and Validation Report on the Residential Water Inhalation Risk Calculator Presented in the Risk Assessment Information System

Indoor air quality (IAQ) is critical for human health. Poor IAQ is linked to respiratory issues, cardiovascular diseases, and cancer. Indoor pollutants are emitted by typical household items such as cleaning products, personal care items, building materials, and tap water - an understudied volatile organic compound (VOC) source. This document presents the Residential Water Inhalation Risk Calculator (RWIRC), which estimates daily VOC exposure concentrations from various household water uses, such as showering and dishwashing, to assess exposure risks for the most vulnerable occupant. Integrated into the Risk Assessment Information System (RAIS) and sponsored by the US Department of Energy (DOE), the calculator divides a house into three compartments: shower, bathroom, and other spaces, accounting for daily water usage patterns and calculating VOC concentrations. Exposure data generated using the calculator can assist health assessors in estimating excess lifetime cancer risk (ELCR) and hazard index (HI) from VOC inhalation. Unlike traditional exposure models that utilize Andelman’s constant, the RWIRC continuously assesses variability in VOC concentrations and environmental conditions using differential equations to track VOC concentrations and air exchange between compartments. The calculator also provides unique volatilization fractions for each chemical and appliance, enhancing accuracy of the exposure concentration estimation. The RWIRC is accessible online and allows users to customize parameters (i.e., number of bathrooms, water temperature, and exhaust fan conditions) and input VOC characteristics (i.e., tap water and ambient air concentrations). This document provides a step-by-step guide on implementing the calculator. It also provides comparisons with the ATSDR-SHOWER calculator, using eight VOCs with varying physicochemical properties to reveal differences in algorithms and output concentrations. Simulations also assess how bathroom door positions and exhaust fan usage affect VOC exposure. The calculator results can enhance EPA risk screening levels for inhalation exposure to VOCs from tap water, offering a sophisticated tool for assessing inhalation risks and improving public health protection.

54 ENVIRONMENTAL SCIENCES↗

Bioindicator “fingerprints” of methane-emitting thermokarst features in Alaskan soils

Permafrost thaw increases the bioavailability of ancient organic matter, facilitating microbial metabolism of volatile organic compounds (VOCs), carbon dioxide, and methane (CH 4 ). The formation of thermokarst (thaw) lakes in icy, organic-rich Yedoma permafrost leads to high CH 4 emissions, and subsurface microbes that have the potential to be biogeochemical drivers of organic carbon turnover in these systems. However, to better characterize and quantify rates of permafrost changes, methods that further clarify the relationship between subsurface biogeochemical processes and microbial dynamics are needed. In this study, we investigated four sites (two well-drained thermokarst mounds, a drained thermokarst lake, and the terrestrial margin of a recently formed thermokarst lake) to determine whether biogenic VOCs (1) can be effectively collected during winter, and (2) whether winter sampling provides more biologically significant VOCs correlated with subsurface microbial metabolic potential. During the cold season (March 2023), we drilled boreholes at the four sites and collected cores to simultaneously characterize microbial populations and captured VOCs. VOC analysis of these sites revealed “fingerprints” that were distinct and unique to each site. Total VOCs from the boreholes included > 400 unique VOC features, including > 40 potentially biogenic VOCs related to microbial metabolism. Subsurface microbial community composition was distinct across sites; for example, methanogenic archaea were far more abundant at the thermokarst site characterized by high annual CH 4 emissions. The results obtained from this method strongly suggest that ∼10% of VOCs are potentially biogenic, and that biogenic VOCs can be mapped to subsurface microbial metabolisms. By better revealing the relationship between subsurface biogeochemical processes and microbial dynamics, this work advances our ability to monitor and predict subsurface carbon turnover in Arctic soils.

anaerobic degradation↗

Air quality impacts from the development of unconventional oil and gas well pads: Air toxics and other volatile organic compounds

Unconventional oil and natural gas development (UOGD) has expanded rapidly across the United States in recent decades and raised concerns about associated air quality impacts. While significant effort has been made to quantify methane emissions, relatively few observations have been made of Volatile Organic Compounds (VOCs), especially during drilling and completion of new wells. Extensive air monitoring during development of several large, multi-well pads in Broomfield, Colorado, in the Denver-Julesburg Basin, provides a novel opportunity to examine changes in local air toxics and other VOC concentrations during well drilling and completions and production. These operations offer an especially useful case to study as several management practices were implemented to reduce emissions (e.g., electrified, grid-powered drill rigs and closed loop fluid handling systems to reduce truck traffic and limit fluid handling on the pad). With simultaneous measurements of methane and 50 VOCs from October 2018 to December 2022 at as many as 19 sites near well pads, in adjacent neighborhoods, and at a more distant reference location, we identify impacts from each phase of well development and production. Use of weekly, time-integrated canisters, a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous photoionization detectors (PID) to trigger canister collection upon detection of VOC-rich plumes, and an instrumented vehicle, provided a powerful suite of measurements to characterize both transient plumes and longer-term changes in air quality. Prior to the start of well development, VOC gradients were small across Broomfield. Once drilling commenced, concentrations of oil and gas (O&G) related VOCs, including alkanes and aromatics, increased around active well pads. Concentration increases were clearly apparent during certain operations, including drilling, coil tubing/millout operations, and production tubing installation. Emissions of C 8 –C 10 n-alkanes during drilling operations highlighted the importance of VOC emissions from synthetic drilling mud chosen to reduce odor impacts. More than 90 samples were collected of transient plumes. Using composition measurements, meteorological data, and information about well pad activities, these plumes were connected with specific UOGD operations including drilling, flowback, and production equipment maintenance. The chemical signatures of these plumes differed by operation type (e.g., C 8 –C 10 n-alkanes constituted a larger fraction of measured VOCs in drilling-related plumes). Concentrations of individual, oil and gas-related VOCs in these plumes were often several orders of magnitude higher than in background air, with maximum ethane and benzene concentrations of 79,600 and 819 ppbv, respectively. Because these plumes typically impact a monitoring site for just several minutes, they are easily missed by slower-responding instruments. Study measurements highlight future emission mitigation opportunities during UOGD operations, including better control of emissions from shakers that separate drill cuttings from drilling mud, production separator maintenance operations, and periodic emptying of sand cans during flowback operations.

54 ENVIRONMENTAL SCIENCES↗

Measurement report: Extreme heat and wildfire emissions enhance volatile organic compounds in a temperate forest

Climate extremes are projected to cause unprecedented deviations in the emission and transformation of volatile organic compounds (VOCs), which trigger feedback mechanisms that will impact the atmospheric oxidation and formation of aerosols and clouds. However, the response of VOCs to future conditions such as extreme heat and wildfire events is still uncertain. This study explored the modification of the mixing ratio and distribution of several anthropogenic and biogenic VOCs in a temperate oak–hickory–juniper forest as a response to increased temperature and transported biomass burning plumes. A chemical ionization mass spectrometer was deployed on a tower at a height of 32 m in rural central Missouri, United States, for the continuous and in situ measurement of VOCs from June to August of 2023. The maximum observed temperature in the region was 38 °C, and during multiple episodes the temperature remained above 32 °C for several hours. Biogenic VOCs such as isoprene and monoterpene followed closely the temperature daily profile but at varying rates, whereas anthropogenic VOCs were insensitive to elevated temperature. During the measurement period, wildfire emissions were transported to the site and substantially increased the mixing ratios of acetonitrile and benzene, which are produced from burning of biomass. An in-depth analysis of the mass spectra revealed more than 250 minor compounds, such as formamide and methylglyoxal. Extreme heat and presence of wildfire plumes modified the overall volatility, reactivity, O : C, and H : C ratios of the extended list of VOCs. The calculated OH reactivities during extreme temperature condition and transport of biomass burning plumes were 106.37±4.27 and 106.22±5.15 s −1 , respectively, which are substantially higher than background level of 98.78±1.16 s −1 . Multivariate analysis also clustered the compounds into five factors, which highlighted the sources of the unaccounted-for VOCs. Ultimately, results here underscore the effect of extreme heat and wildfire emissions on the overall chemical properties VOC in a temperate forest.

Salvador, Christian Mark [Oak Ridge National Labor↗

Volatile Organic Compounds in Bankhead National Forest (AMF3). August to September, 2025

The formation of atmospheric aerosols through the transformation of volatile organic compounds (VOCs) is a fundamental process in aerosol-climate interactions, as these particles serve as cloud condensation nuclei and ultimately influence Earth’s radiative balance. However, there remains a critical need to quantify the effects of multiple coexisting VOC precursors on aerosol formation beyond the limitations of laboratory-scale studies. This research aims to advance the mechanistic understanding of secondary organic aerosol formation in the southeastern United States by investigating interactions among coexisting VOC precursors observed at the third ARM Mobile Facility located in the Bankhead National Forest. The dataset was generated from the deployment of Oak Ridge National Laboratory’s PTR-TOF 6000 X2 Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS) for the real-time, continuous monitoring of VOCs from August 21 to September 15, 2025. To minimize sampling artifacts and compound losses, the PTR-ToF-MS inlet was connected to the cabin flow line by replacing the existing Tygon tubing with 1/2-inch outer diameter perfluoroalkoxy (PFA) tubing. The instrument operated on an hourly measurement cycle consisting of 8 minutes of zero-air measurements followed by 52 minutes of ambient air sampling, with a temporal resolution of 10 seconds. The dataset includes concentrations, reported in ppb, of methanol, acetone, acetonitrile, isoprene, methyl vinyl ketone and methacrolein (MVK + MACR), monoterpenes, benzene, toluene, and catechol.

Atmospheric concentration of volatile organic comp↗

Bedroom Concentrations and Emissions of Volatile Organic Compounds during Sleep

Because humans spend about one-third of their time asleep in their bedrooms and are themselves emission sources of volatile organic compounds (VOCs), it is important to specifically characterize the composition of the bedroom air that they experience during sleep. This work uses real-time indoor and outdoor measurements of volatile organic compounds (VOCs) to examine concentration enhancements in bedroom air during sleep and to calculate VOC emission rates associated with sleeping occupants. Gaseous VOCs were measured with proton-transfer reaction time-of-flight mass spectrometry during a multiweek residential monitoring campaign under normal occupancy conditions. Results indicate high emissions of nearly 100 VOCs and other species in the bedroom during sleeping periods as compared to the levels in other rooms of the same residence. Air change rates for the bedroom and, correspondingly, emission rates of sleeping-associated VOCs were determined for two bounding conditions: (1) air exchange between the bedroom and outdoors only and (2) air exchange between the bedroom and other indoor spaces only (as represented by measurements in the kitchen). VOCs from skin oil oxidation and personal care products were present, revealing that many emission pathways can be important occupant-associated emission factors affecting bedroom air composition in addition to direct emissions from building materials and furnishings.

54 ENVIRONMENTAL SCIENCES↗

Application of Atmospheric Gases and Particulate Matter to the Assessment of Urban Heat Island

Background: Urban heat island (UHI), where built areas are warmer compared to non-urban regions, increases human related diseases and mortality. A key challenge in UHI analysis is the designation of sites as urban or suburban/rural; however, the growing complexity of green spaces in urban areas and the predominance of the transportation sector in nonurban areas creates a dilemma for distinct delineation. Objectives: This study aims to utilize the variability of atmospheric components such as particulate matter (PM), inorganic gases, and volatile organic compounds (VOCs) as direct tracers of the degree of urbanization for ground-based measurements to fully comprehend UHI in convoluted regions with indistinct delineation of urban and nonurban environments. Methods: Atmospheric gases and aerosols were used as direct tracers of urbanization for UHI analysis. Inorganic gases and particulate matter were monitored in two sites in a southeastern US city with varying degrees of urbanization. VOCs were analyzed using a proton transfer reaction time-of-flight mass spectrometer. Results: The more-urbanized site exhibited warmer night conditions and elevated total oxidant levels, leading to the formation of nanometer-sized particles. Machine learning analysis revealed similar atmospheric pollutant profiles for both sites, suggesting comparable sources and variability. Biogenic VOCs were enhanced at the less-urbanized site; however, levels of anthropogenic aromatic VOCs were comparable for both sites. A comprehensive mass spectra analysis revealed distinct molecular backbones per site that further affirmed the applicability of VOCs as indicators of urbanization. Conclusion: This study concludes that VOCs provide more direct and accurate information than typical inorganic gases and PM parameters for characterizing the degree of urbanization. Further exploration of VOCs can enhance our understanding of UHI dynamics and its interaction with vegetation in urban green spaces.

Air quality sensor↗

Arrays of Functionalized Graphene Chemiresistors for Selective Sensing of Volatile Organic Compounds

Real-time detection of volatile organic compounds (VOCs) is being spotlighted for its importance in environmental monitoring and disease detection from the breath. However, the selective detection of VOCs in a small form factor gas sensor remains a challenge. Here, we present the VOC sensing performance of phthalocyanine (Pc)-functionalized graphene chemiresistors supported by the theoretical prediction of Pc's VOC interactions. Pc functionalization, with and without metalation, was studied parametrically with varying deposition parameters to explore impacts on the gas sensing response toward VOCs as a function of substrate coverage. Sensing data were collected to establish fingerprint signatures for a variety of VOCs. In conclusion, improvement in selectivity is shown by successfully differentiating the VOCs from each other when combined into a gas sensor array tested with acetone, ethanol, formaldehyde, and toluene.

2D materials↗

Demonstration of an Automated System for Vertical Profiles of Volatile Organic Compounds

Volatile organic compounds (VOCs) play important roles throughout the atmosphere, many of which are altitude dependent. This highlights the need for easily deployable devices to sample VOCs across different atmospheric layers. To address this, we present the design and initial application of a Time Resolved Automated Volatile organIc compounds Sampling system (TRAVIS). VOCs are collected on sorbent tubes, which are subsequently analyzed by a thermal desorption gas chromatography mass spectrometry pipeline. TRAVIS leverages a piezoelectric pump with an integrated pressure sensor for precise (0.1% flow rate relative standard deviation) and accurate (−3 ± 2% error in VOC quantitation) measurements. Via deployment on a tethered balloon system over an agricultural area, TRAVIS is used to show consistent vertically resolved VOC concentrations in a well-mixed (i.e., turbulent) atmosphere (e.g., 5% relative standard deviation for isoprene) and vertically dependent concentrations for a stratified atmosphere (e.g., prior to boundary layer development). Furthermore, we also show VOC information from an intermittent plume via both targeted and untargeted analysis, highlighting future applications for spurious events in agriculture, air quality monitoring, and environmental impact. Overall, the development of TRAVIS represents a lightweight, accurate, sensitive, and precise VOC sampling module for the scientific community.

Aerosols↗

Source Characterization of Volatile Organic Compounds at Carlsbad Caverns National Park

Carlsbad Caverns National Park (CAVE), located in southeastern New Mexico, experiences elevated ground-level ozone (O 3 ) exceeding the National Ambient Air Quality Standard (NAAQS) of 70 ppbv. It is situated adjacent to the Permian Basin, one of the largest oil and gas (O&G) producing regions in the US. In 2019, the Carlsbad Caverns Air Quality Study (CarCavAQS) was conducted to examine impacts of different sources on ozone precursors, including nitrogen oxides (NO x ) and volatile organic compounds (VOCs). Here, we use positive matrix factorization (PMF) analysis of speciated VOCs to characterize VOC sources at CAVE during the study. Seven factors were identified. Three factors composed largely of alkanes and aromatics with different lifetimes were attributed to O&G development and production activities. VOCs in these factors were typical of those emitted by O&G operations. Associated residence time analyses (RTA) indicated their contributions increased in the park during periods of transport from the Permian Basin. These O&G factors were the largest contributor to VOC reactivity with hydroxyl radicals (62%). Two PMF factors were rich in photochemically generated secondary VOCs; one factor contained species with shorter atmospheric lifetimes and one with species with longer lifetimes. RTA of the secondary factors suggested impacts of O&G emissions from regions farther upwind, such as Eagle Ford Shale and Barnett Shale formations. The last two factors were attributed to alkenes likely emitted from vehicles or other combustion sources in the Permian Basin and regional background VOCs, respectively.

54 ENVIRONMENTAL SCIENCES↗

Intelligent Electrochemical Sensors for Precise Identification of Volatile Organic Compounds Enabled by Neural Network Analysis

The volatile organic compounds (VOCs) in a wide spectrum of categories were identified as biomarkers in aquatic environments, playing an important role in marine and freshwater ecology and global atmospheric chemistry. VOCs released from biofuel have also attracted increasing attention. Although the importance has been recognized, the portable detection and analysis methods of VOC in aquatic systems have not yet been well developed and understood. Here, in this work, we innovatively proposed an intelligent electrochemical sensing approach to classify and quantify VOCs in solution. Utilizing the cyclic voltammetry (CV) method with an ionic liquid (IL)-based electrolyte, we analyzed 50 μL samples of various VOC analytes, including acetic acid (AC), acetone, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethanol, formaldehyde, formic acid, methanol, methyl formate (MF), toluene, and a formaldehyde-methanol mixture, along with deionized water (DI water). The generated voltammograms were subsequently analyzed using our uniquely designed and optimized 1-D convolutional neural network (1D-CNN). This deep-learning algorithm achieved a 99.09% accuracy in VOC classification validated through fivefold cross-validation and demonstrated an impressive 94.4% test accuracy for methanol detection within a 10 μL error range. For quantification, the system accurately categorized methanol volumes ranging from 0 to 50 μL in 10 μL increments, achieving a 98.18% accuracy. A notable linear correlation (R2 = 95.56%) was found between max current density at the oxidation peak and methanol volume, with the limit of detection (LOD) at 9.3 μL. Such a sensing method exhibits potential for portability, high accuracy, and generalization in the classification and quantification, ultimately reshaping the realm of VOC analysis in solution.

42 ENGINEERING↗

Observations of ozone, acyl peroxy nitrates, and their precursors during summer 2019 at Carlsbad Caverns National Park, New Mexico

Carlsbad Caverns National Park (CAVE) is located in southeastern New Mexico and is adjacent to the Permian Basin, one of the most productive oil and natural gas (O&G) production regions in the United States. Since 2018, ozone (O 3 ) at CAVE has frequently exceeded the 70 ppbv 8-hour National Ambient Air Quality Standard. We examine the influence of regional emissions on O 3 formation using observations of O 3 , nitrogen oxides (NO x = NO + NO 2 ), a suite of volatile organic compounds (VOCs), peroxyacetyl nitrate (PAN), and peroxypropionyl nitrate (PPN). Elevated O 3 and its precursors are observed when the wind is from the southeast, the direction of the Permian Basin. We identify 13 days during the July 25 to September 5, 2019 study period when the maximum daily 8-hour average (MDA8) O 3 exceeded 65 ppbv; MDA8 O 3 exceeded 70 ppbv on 5 of these days. The results of a positive matrix factorization (PMF) analysis are used to identify and attribute source contributions of VOCs and NO x . On days when the winds are from the southeast, there are larger contributions from factors associated with primary O&G emissions; and, on high O 3 days, there is more contribution from factors associated with secondary photochemical processing of O&G emissions. The observed ratio of VOCs to NO x is consistently high throughout the study period, consistent with NO x -limited O 3 production. Finally, all high O 3 days coincide with elevated acyl peroxy nitrate abundances with PPN to PAN ratios > 0.15 ppbv ppbv -1 indicating that anthropogenic VOC precursors, and often alkanes specifically, dominate the photochemistry. Implications: The results above strongly indicate NO x -sensitive photochemistry at Carlsbad Caverns National Park indicating that reductions in NO x emissions should drive reductions in O 3 . However, the NO x -sensitivity is largely driven by emissions of NO x into a VOC-rich environment, and a high PPN:PAN ratio and its relationship to O 3 indicate substantial influence from alkanes in the regional photochemistry. Thus, simultaneous reductions in emissions of NO x and non-methane VOCs from the oil and gas sector should be considered for reducing O 3 at Carlsbad Caverns National Park. Reductions in non-methane VOCs will have the added benefit of reducing formation of other secondary pollutants and air toxics.

54 ENVIRONMENTAL SCIENCES↗