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Structure and reactive properties of Nb-impregnated two-dimensional pillared MWW zeolites for total oxidation of volatile organic compounds

In this work, the structure and reactive properties of niobium (Nb)-impregnated MWW-type materials were evaluated for gas-phase total oxidation of volatile organic compounds, including BTX (benzene, toluene and o -xylene). The role of the type of structure (two or three-dimensional) and the loading of Nb were considered. The results indicated most Nb species with a tetrahedral coordination on the external surfaces of both two- and three-dimensional zeolites, together with a minimal contribution of octahedral extra-framework Nb 2 O 5 species. The texture and Nb content played a key role in the gas-phase total oxidation of BTX. With the same Nb content (5 wt%), the pillared zeolite exhibited a higher specific surface, larger pore volume and mesopores between the MWW nanosheets when compared to the MCM-22 zeolites, which resulted in high accessibility of the reactant molecules to the active sites, reflected in higher BTX conversion at lower and higher temperatures (50–300 °C). The best performance was achieved with the pillared zeolite (10 wt% Nb), reaching a BTX conversion at 300 °C of 92%, 69% and 58%, respectively. Here, the catalyst was stable for up to 30 h of reaction.

36 MATERIALS SCIENCE↗

Henry’s Solubility and Diffusion Coefficients for 29 Volatile Organic Compounds in Polydimethylsiloxane Sylgard 184 at 293 K

Two-dimensional (2D) inverse gas chromatography (IGC) enables simultaneous determination of Henry’s solubility and Fickian diffusion coefficients for volatile organic compounds (VOCs) in polymer films. This technique offers a significant advantage over traditional cylindrical column IGC by providing precise control and measurement of the film thickness (here, 0.064 ± 0.002 mm), which is the critical length scale for accurate diffusivity determination. We apply this methodology to characterize VOC transport in Sylgard 184, a widely used polydimethylsiloxane (PDMS)-based polymer containing substantial silica filler content. At room temperature (20 °C), we measured solubility and diffusion coefficients for 29 common VOCs spanning diverse chemical functionalities, including alkanes, aromatics, chlorinated solvents, ketones, esters, and alcohols. Comparison with literature data for pure PDMS reveals that VOC solubility in Sylgard 184 is generally higher; for most non-hydrogen-bonding compounds it remains within a factor of 2 of pure PDMS, whereas alcohols are enhanced by roughly 1.8 to 3.7 times, which we attribute to favorable interactions with residual silanol groups on the silanized silica filler. Diffusion coefficients range from 1.0 × 10 –6 cm 2 /s (n-undecane) to 8.9 × 10–5 cm 2 /s (acetonitrile) and align well with extrapolated literature values for PDMS. This study provides essential thermodynamic and transport data for predicting VOC permeation in Sylgard 184 while demonstrating the utility of 2D IGC as a robust technique for characterizing rubbery polymer membranes across diverse industrial applications.

organic↗

A device for volatile organic compound (VOC) analysis from skin using heated dynamic headspace sampling

Abstract Human skin is an important source of volatile organic compounds (VOCs) offering noninvasive methods to gain clinical metabolite information. This work was focused on the development of a skin sampling device based on a dynamic headspace sampling method with the addition of temperature to increase VOC metabolite recovery. The device preconcentrates skin VOC emissions onto a sorbent substrate, which can either be preserved for offline analysis or attached to a real time sensor downstream. In this work, skin VOC samples were analyzed offline using thermal desorption-gas chromatography-mass spectrometry. A list of 10 common skin VOCs was pre-selected to optimize parameters of sampling time, sampling temperature, and sorbent selection. Overall, this study highlights an effective skin VOC sampling technology with a heating dimension (40 °C, rather than 30 °C or no heating) with a sampling time of 15 min (rather than 5 or 30 mins) and onto Tenax TA sorbent (rather than PDMS), which collectively increases the recovery of compounds with lower vapor pressure and decreases the observed variability in skin VOC measurements. Finally, a list of 79 skin VOC compounds were detected and identified within a cohort of 20 young, healthy volunteers.

Biochemistry & Molecular Biology↗

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↗

A Rapid Decision Support Tool for Estimating Impacts of a Vadose Zone Volatile Organic Compound Source on Groundwater and Soil Gas

Diminishing rates of subsurface volatile contaminant removal by soil vapor extraction (SVE) oftentimes warrants an in‐depth performance assessment to guide remedy decision‐making processes. Such a performance assessment must include quantitative approaches to better understand the impact of remaining vadose zone contamination on soil gas and groundwater concentrations. The spreadsheet‐based Soil Vapor Extraction Endstate Tool (SVEET) software functionality has recently been expanded to facilitate quantitative performance assessments. The updated version, referred to as SVEET2, includes expansion of the input parameter ranges for describing a site (site geometry, source characteristics, etc.), an expanded list of contaminants, and incorporation of elements of the Vapor Intrusion Estimation Tool for Unsaturated‐zone Sources software to provide soil gas concentration estimates for use in vapor intrusion evaluation. As part of the update, SVEET2 was used to estimate the impact of a tetrachloroethene (PCE) vadose zone source on groundwater concentrations, comparing SVEET2 results to field‐observed values at an undisclosed site where SVE was recently terminated. PCE concentrations from three separate monitoring wells were estimated by SVEET2 to be within the range of 6.0–6.7 μg/L, as compared to actual field concentrations that ranged from 3 to 11 μg/L PCE. These data demonstrate that SVEET2 can rapidly provide representative quantitative estimates of impacts from a vadose zone contaminant source at field sites. Finally, in the context of the SVE performance assessment, such quantitative estimates provide a basis to support remedial and/or regulatory decisions regarding the continued need for vadose zone volatile organic compound remediation or technical justification for SVE termination, which can significantly reduce the cost to complete for a site.

54 ENVIRONMENTAL SCIENCES↗

Chemical ionization mass spectrometry utilizing benzene cations for measurements of volatile organic compounds and nitric oxide

We evaluate the capability of chemical ionization mass spectrometry (CIMS) using benzene cations as reagent ions (benzene CIMS) for detecting atmospheric trace gases. We characterize the ionization pathways and product ion distributions for 27 analytes spanning diverse chemical classes. To interpret the complex ion chemistry involving two reagent ions (C 6 H$^{+}_{6}$ and (C 6 H 6 )$^{+}_{2}$) and multiple ionization pathways (charge transfer, proton transfer, adduct formation, and hydride abstraction), we introduce a thermodynamics-based framework that classifies analytes into three categories based on their ionization energy (IE), relative to those of benzene monomer (9.24 eV) and dimer (8.69 eV). Each class exhibits distinct ionization mechanisms and product ions. Analytes with IE smaller than 8.69 eV (low IE) undergo charge transfer with both reagent ions; analytes with IE between 8.69 and 9.24 eV (mid IE) undergo charge transfer with C 6 H$^{+}_{6}$ and potential adduct formation with (C 6 H 6 )$^{+}_{2}$; analytes with IE larger than 9.24 eV (high IE) could undergo adduct formation, proton transfer, or hydride abstraction. Analytes within each class also show similar sensitivity, enabling sensitivity estimation for compounds lacking calibration standards. In addition to volatile organic compounds (VOCs), benzene CIMS detects nitric oxide (NO) with a detection limit of 5 pptv for 1 min integration time, exceeding the performance of most commercial NOx analyzers. Field deployments in Chicago and St. Louis demonstrate good agreement with reference NO measurements. Isoprene measurements show good agreement with a co-located gas chromatography–photoionization detector (GC-PID) in St. Louis, but exhibit substantial positive bias in Chicago, likely due to interferences from anthropogenic VOCs in the polluted urban environment. These results highlight the potential of benzene CIMS for concurrent measurements of NO, VOCs, and their oxidation products using a single instrument, while also underscoring challenges in complex atmospheric conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Architecture, catalysis and regulation of methylthio-alkane reductase for bacterial sulfur acquisition from volatile organic compounds

Bacteria utilize methylthio-alkane reductase (MAR) to acquire sulfur from volatile organic sulfur compounds. Reductive cleavage of methylthio-ethanol and dimethylsulfide liberates methanethiol for methionine synthesis and concomitantly releases ethylene and methane, respectively. Here we show that the native MAR of Rhodospirillum rubrum is a two-component system composed of a MarH ATP-dependent reductase and a MarDK catalytic core, whose architecture parallels nitrogenase. MarS complexes with MarDK to downregulate MAR activity during cellular sulfate influx, based on chromatographic and activity analyses. MarDK possesses complex metallocofactors resembling, but not identical to, nitrogenase P- and iron-only M-clusters, designated as mar1 and mar2 clusters based on metal, spectroscopic and mutagenesis analyses. They exhibit electronic features similar to the iron-only nitrogenase under turnover and, remarkably, are matured by MarB or nitrogenase NifB, resulting in maturase-dependent activity profiles. Altogether, this suggests a broader scope of reactivity, mechanisms and regulation in microbial metabolism for the nitrogenase-like family of enzymes than previously considered.

09 BIOMASS FUELS↗

Metabolic Profiling of Volatile Organic Compounds (VOCs) Emitted by the Pathogens Francisella tularensis and Bacillus anthracis in Liquid Culture

We conducted comprehensive (untargeted) metabolic profiling of volatile organic compounds (VOCs) emitted in culture by bacterial taxa Francisella tularensis (F. tularensis) subspecies novicida and Bacillus anthracis (B. anthracis) Sterne, surrogates for potential bacterial bioterrorism agents, as well as selective measurements of VOCs from their fully virulent counterparts, F. tularensis subspecies tularensis strain SCHU S4 and B. anthracis Ames. F. tularensis and B. anthracis were grown in liquid broth for time periods that covered logarithmic growth, stationary, and decline phases. VOCs emitted over the course of the growth phases were collected from the headspace above the cultures using solid phase microextraction (SPME) and were analyzed using gas chromatography-mass spectrometry (GC-MS). We developed criteria for distinguishing VOCs originating from bacteria versus background VOCs (originating from growth media only controls or sampling devices). Analyses of collected VOCs revealed methyl ketones, alcohols, esters, carboxylic acids, and nitrogen- and sulfur-containing compounds that were present in the bacterial cultures and absent (or present at only low abundance) in control samples indicating that these compounds originated from the bacteria. Distinct VOC profiles where observed for F. tularensis when compared with B. anthracis while the observed profiles of each of the two F. tularensis and B. anthracis strains exhibited some similarities. Furthermore, the relative abundance of VOCs was influenced by bacterial growth phase. These data illustrate the potential for VOC profiles to distinguish pathogens at the genus and species-level and to discriminate bacterial growth phases. The determination of VOC profiles lays the groundwork for non-invasive probes of bacterial metabolism and offers prospects for detection of microbe-specific VOC biomarkers from two potential biowarfare agents.

59 BASIC BIOLOGICAL SCIENCES↗

Analyzing Tradeoffs Associated with the Manufacture of Refined Fuels by Comparing Volatile Organic Compound (VOC) Emissions Model Results with Carbon Impacts

A first-of-its kind, publicly-available model for estimating emissions of volatile organic compounds from operations along the supply chain of liquid fuels and refinery products is presented and demonstrated. This standardized model permits comprehensive, reproducible, and comparable evaluation of the supply chain/life cycle VOC emissions of liquid fuels and refinery products.

09 BIOMASS FUELS↗

The Effect of Adsorbed Volatile Organic Compounds on an Ultrathin Water Film Measurement

Using surface plasmon resonance imaging (SPRi), we have recently shown for the first time the existence of a monolayer water film between droplets during dropwise condensation. This study examines the effect of adsorbed volatile organic compounds (VOCs) on the ultrathin film measurement using SPRi. Further, the work presents the proper surface-treatment process that enables measurements of the ultrathin water layer during high-speed imaging of dropwise condensation at 3000 frame per second. In this study, two methods were applied for cleaning the surface (gold-coated glass)—(1) standard cleaning procedure (SCP) using acetone, isopropyl alcohol, and deionized water and (2) SCP followed by air plasma cleaning. This work discusses the effect of the cleaning procedures on surface roughness, contact angle, and surface chemistry using atomic force microscopy, optical microscopy, and an X-ray photoelectron spectroscope meter. The results showed that SCP before the SPRi is a proper surface-treatment method. The effect of adsorbed VOCs during dropwise condensation on a surface treated with SCP was measured to be 0.0025 (reflectivity unit), which was 70% smaller than the reflectance associated with a monolayer water film. The results of this work confirm a monolayer water film observation during the dropwise condensation, which has been reported before.

36 MATERIALS SCIENCE↗

Zero-Valent Iron Permeable Reactive Barrier to Remediate Volatile Organic Compounds in Groundwater - 20209

The US DOE-SRS, the US EPA, and the South Carolina Department of Health and Environmental Control determined it was appropriate to perform a non-time critical removal action at the P-Area Groundwater Operable Unit at the SRS to reduce the mass and downgradient transport of trichloroethylene in the P-Area groundwater plume. Contaminated groundwater discharges to a nearby stream, Steel Creek, within the SRS boundaries, resulting in trichloroethylene concentrations above the maximum contaminant level. Impact to surface water is limited in areal extent and supported by recently collected characterization data. The P-Area Groundwater Operable Unit encompasses the groundwater beneath an industrial area within SRS, P Area, where the P-Reactor once operated. The boundaries of the P-Area Groundwater Operable Unit extend northwest to Steel Creek, northeast toward PAR Pond, and southeast to Meyers Branch. Groundwater in the Upper Three Runs Aquifer of the P-Area Groundwater Operable Unit has been impacted by reactor and facility operations between 1954 and 1991, including tritium and volatile organic compounds. The P-Area surface units contributing to groundwater contamination were remediated as part of the P-Area Operable Unit in 2011. The P-Reactor closure is one of the first of its kind in the DOE Complex and is one of only a few full-sized production reactors in the US to undergo completion of final closure activities. The nature and extent of groundwater contamination was determined using a variety of investigative approaches such as groundwater monitoring wells, direct-push technology, and surface water samples. Groundwater contamination associated with trichloroethylene is primarily exhibited in a narrow plume that extends from the source area at P-Reactor and west to Steel Creek. Maximum contaminant level exceedances in groundwater occur over an area of ∼6.9 hectares for trichloroethylene with concentrations as high as 7.7 milligrams per liter. To the west of the P-Area facility area, the trichloroethylene groundwater plume is controlled by a buried geologic feature, assumed to be an old stream bed, that further narrows the groundwater plume in what has been designated as the 'neck area.' This narrowing of the groundwater plume provides an ideal location for a treatment barrier. The non-time critical removal action alternative chosen is to install a zero-valent iron permeable reactive barrier within the neck area of the trichloroethylene groundwater plume, perpendicular to groundwater flow direction. This technology will provide a treatment barrier that will reduce trichloroethylene groundwater concentrations by 90% and has an anticipated useful life of at least 25 years. A pre-design investigation was performed in the neck area to confirm site lithology, hydrogeology, geochemistry, and extent of trichloroethylene contamination prior to a final design. A treatability study, conducted as part of the pre-design investigation, indicated that the subsurface and groundwater in the PArea Groundwater Operable Unit is compatible with the zero-valent iron and will not lead to excessive buildup from mineralization/precipitation or biofouling. Probabilistic modeling was conducted using field and laboratory data to determine the expected performance of the zero-valent iron permeable reactive barrier. The model simulations indicated that a 3.81-centimeter thick barrier would provide greater than 90% reduction of trichloroethylene groundwater concentration. The final design of the zero-valent iron permeable reactive barrier is a barrier that will extend 80.5 linear meters in a 'zigzag' orientation to best transect the trichloroethylene plume and account for varying groundwater flow. The barrier will be installed from 13.7 meters below ground surface to 41.1 meters below ground surface for 65.8 linear meters and from 13.7 meters below ground surface to 36.6 meters below ground surface for 14.6 linear meters, the base of which is 'keyed' into a low permeability zone. The barrier is designed to a thickness of 10.2 centimeters, which was determined to reduce the trichloroethylene groundwater concentrations by greater than 90% with a safety factor of 2.67. A total of approximately 689 metric tons of zero-valent iron will be injected through 22 injection wells spaced 3.66 meters apart, using guar to suspend the zero-valent iron. Zero-valent iron permeable reactive barrier construction will be monitored through 23 installed resistivity receivers offset 7.32 meters from the zerovalent iron permeable reactive barrier. The zero-valent iron will be energized with a low-voltage 100 Hertz signal during injection and will be monitored using the resistivity receivers to ensure complete coalescence of the zero-valent iron permeable reactive barrier. The zero-valent iron was sized to have a hydraulic conductivity greater than the natural subsurface, thus promoting groundwater flow through the barrier. As contaminated groundwater contacts the zero-valent iron, volatile organic compounds, including trichloroethylene, are immediately degraded to harmless compounds such as ethylene. The performance of the zero-valent iron permeable reactive barrier will be monitored using three upgradient monitoring well clusters, six downgradient monitoring well clusters, and four in-wall monitoring wells. The in-wall monitoring wells will indicate immediate reduction of trichloroethylene mass in the groundwater and allow analyses of the zero-valent iron permeable reactive barrier health. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Low Molecular Weight Volatile Organic Compounds Indicate Grazing by the Marine Rotifer Brachionus plicatilis on the Microalgae Microchloropsis salina

Microalgae produce specific chemicals indicative of stress and/or death. The aim of this study was to perform non-destructive monitoring of algal culture systems, in the presence and absence of grazers, to identify potential biomarkers of incipient pond crashes. Here, we report ten volatile organic compounds (VOCs) that are robustly generated by the marine alga, Microchloropsis salina, in the presence and/or absence of the marine grazer, Brachionus plicatilis. We cultured M. salina with and without B. plicatilis and collected in situ volatile headspace samples using thermal desorption tubes over the course of several days. Data from four experiments were aggregated, deconvoluted, and chromatographically aligned to determine VOCs with tentative identifications made via mass spectral library matching. VOCs generated by algae in the presence of actively grazing rotifers were confirmed via pure analytical standards to be pentane, 3-pentanone, 3-methylhexane, and 2-methylfuran. Six other VOCs were less specifically associated with grazing but were still commonly observed between the four replicate experiments. Through this work, we identified four biomarkers of rotifer grazing that indicate algal stress/death. This will aid machine learning algorithms to chemically define and diagnose algal mass production cultures and save algae cultures from imminent crash to make biofuel an alternative energy possibility.

headspace sampling↗

Enhanced detection of volatile organic compounds (VOCs) by caffeine modified carbon nanotube junctions

Detection of vapor phase analytes and gas molecules is primarily essential for numerous applications including medical diagnostic, environmental monitoring, chemical threat detection, food quality control, and chemical warfare agents. Here, we developed Caffeine functionalized carbon nanotubes (CNTs) random network based vapor quantum resistive sensors (vQRSs) for volatile organic compounds (VOCs) detection. The localized transmission electron microscopy (TEM) image and energy dispersive X-ray spectroscopy (EDS) confirm migration of caffeine to CNT–CNT junction (CNTj). We have recorded more than one order of magnitude higher sensitivity and unique selectivity towards selective VOCs (e.g., acetone, toluene, ethanol, methanol, etc.) with short response time (few seconds) for caffeine modified CNT junction (Caf-CNTj) vQRSs. Molecular dynamics (MD) calculations suggest that the sensitivity of the sensor is diffusion limited, with an advective contribution for ethanol. Furthermore, the designed Caf-CNTj sensors can potentially be important candidate to be a part of electronic nose used for various application such as breath analysis and food quality monitoring.

36 MATERIALS SCIENCE↗

Bioremediation of Chlorinated Volatile Organic Compounds: DOE Experiences and Lessons Learned

From the mid-1980s to the present, the Department of Energy (DOE) has developed, tested, and deployed diverse bioremediation strategies for chlorinated volatile organic compounds (cVOCs). A systematic review of these projects after decades of activity provides an opportunity to identify crosscutting themes and lessons learned. The knowledge provided by a DOE bioremediation retrospective represents a resource to support current and future bioremediation operations, and future decisions related to cVOC bioremediation. This systematic review examined the design, objectives, performance and outcomes for remediation projects at DOE sites including Savannah River, Hanford, Idaho, Mound and Pinellas. The results were used to identify emergent themes to provide actionable insights. The bioremediation retrospective technical team first developed standardized criteria to support the systematic review. Then, the evaluation was performed using a sequential process that was informed by local technical experts who identified and provided the structured information that served as the basis for the evaluation. The participation of these experts was invaluable to the effort. Importantly, DOE cVOC bioremediation efforts were implemented based on the foundational knowledge developed by U.S. Department of Defense (DoD) strategic and applied environmental technology development and certification programs, as well as technical, policy and regulatory guidance from the U.S. Environmental Protection Agency (EPA), Interstate Technology and Regulatory Council (ITRC), U.S. Geological Survey (USGS), industry, and universities. To maximize the value of the DOE cVOC bioremediation retrospective, the systematic review strategy focused on identifying important DOE-specific experiences, trends and lessons learned that would extend the knowledge available from these other key entities.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Structural and Optical Response of Polymer-Stabilized Blue Phase Liquid Crystal Films to Volatile Organic Compounds

Engineering useful mechanical properties into stimuli-responsive soft materials without compromising their responsiveness is, in many cases, an unresolved challenge. For example, polymer networks formed within blue-phase liquid crystals (BPs) have been shown to form mechanically robust films, but the impact of polymer networks on the response of these soft materials to chemical stimuli has not been explored. In this work, we report on the response of polymer-stabilized BPs (PSBPs) to volatile organic compounds (VOCs, using toluene as a model compound) and compare the response to BPs without polymer stabilization and to polymerized nematic and cholesteric phases. We find that PSBPs generate an optical response to toluene vapor (change in reflection intensity under crossed polars) that is sixfold greater in sensitivity than the polymerized nematic or cholesteric phases and with a limit of detection (140 ± 10 ppm at 25 °C) that is relevant to the measurement of permissible exposure limits for humans. Additionally, when compared to BPs that have not been polymerized, PSBPs respond to a broader range of toluene vapor concentrations (5000 vs <1000 ppm) over a wider temperature interval (25–45 vs 45–53 °C). We place these experimental observations into the context of a simple thermodynamic model to explore how the PSBP response reflects the effect of toluene on competing contributions of double-twisted LC cylinders, disclinations, and polymer network to the free energy that controls the PSBP lattice spacing. Overall, we conclude that the mechanical and thermal stability of PSBPs, when combined with their optical responsiveness to toluene, make this class of self-supporting LCs a promising one as the basis of passive and compact (e.g., wearable) sensors for VOCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Abiotic and Biotic Damage of Microalgae Generate Different Volatile Organic Compounds (VOCs) for Early Diagnosis of Algal Cultures for Biofuel Production

Open microalgal ponds used in industrial biomass production are susceptible to a number of biotic and abiotic environmental stressors (e.g., grazers, pathogens, pH, temperature, etc.) resulting in pond crashes with high economic costs. Identification of signature chemicals to aid in rapid, non-invasive, and accurate identification of the stressors would facilitate targeted and effective treatment to save the algal crop from a catastrophic crash. Specifically, we were interested in identifying volatile organic compounds (VOCs) that can be used to as an early diagnostic for algal crop damage. Cultures of Microchloropsis gaditana were subjected to two forms of algal crop damage: (1) active grazing by the marine rotifer, Brachionus plicatilis, or (2) repeated freeze–thaw cycles. VOCs emitted above the headspace of these algal cultures were collected using fieldable solid phase microextraction (SPME) fibers. An untargeted analysis and identification of VOCs was conducted using gas chromatography-mass spectrometry (GC-MS). Diagnostic VOCs unique to each algal crop damage mechanism were identified. Active rotifer grazing of M. gaditana was characterized by the appearance of carotenoid degradation products, including β-cyclocitral and various alkenes. Freeze–thaw algae produced a different set of VOCs, including palmitoleic acid. Both rotifer grazing and freeze–thawed algae produced β-ionone as a VOC, possibly suggesting a common stress-induced cellular mechanism. Importantly, these identified VOCs were all absent from healthy algal cultures of M. gaditana. Early detection of biotic or abiotic environmental stressors will facilitate early diagnosis and application of targeted treatments to prevent algal pond crashes. Thus, our work further supports the use of VOCs for monitoring the health of algal ponds to ultimately enhance algal crop yields for production of biofuel.

09 BIOMASS FUELS↗

Bacterial Volatile Organic Compounds as a Strategy to Increase Drought Tolerance in Maize (Zea mays L.): Influence on Plant Biochemistry

Maize is highly susceptible to drought, which affects growth and yield. This study investigated how bacterial volatile organic compounds (BVOCs) affect maize drought tolerance. Drought reduced shoot size but increased root length, an adaptation for accessing deeper soil moisture. BVOCs from strain D12 significantly increased root length and shoot growth under drought conditions. Drought also altered root biochemistry, decreasing enzyme activity, and increased osmolyte levels. BVOCs from strains F11 and FS4-14 further increased osmolyte levels but did not protect membranes from oxidative damage, while BVOCs from strains D12 and D7 strains reduced osmolyte levels and cell damage. In shoots, drought increased the levels of osmolytes and oxidative stress markers. BVOCs from FS4-14 had minimal effects on shoot biochemistry. BVOCs from D12 and F11 partially restored metabolic activity but did not reduce cell damage. BVOCs from D7 reduced metabolic activity and cell damage. These results suggest that BVOCs can modulate the biochemical response of maize to drought, with some strains evidencing the potential to enhance drought tolerance.

Lopes, Tiago (ORCID:0000000330603315)↗

Selective volatile organic compound gas sensor based on carbon nanotubes functionalized with ZnO nanoparticles

Here this paper describes the theory and results for a new class of low-cost chemoresistive gas sensors designed for selective hydrocarbon gas detection. The sensors utilize a multiwalled carbon nanotube (MWCNT) backbone functionalized with metal oxide nanocrystals. Specifically, nanoparticles were grown on the surface of the MWCNTs using atomic layer deposition. The crystallinity of the ZnO-MWCNTs' heterostructure was examined by using a high-resolution transmission electron microscope. The structure of the ZnO/MWCNTs was analyzed using a scanning electron microscope and energy dispersive x ray. The Hall effect measurement shows p-type characteristics of the MWCNTs, supporting the typical PN junction formation with n-type ZnO nanocrystals. The electron-donating ability of ZnO provided a strong response to the ppm levels of toluene at room temperature (25 °C) and showed strong selectivity with other volatile organic compound gases such as benzene, methane, and formaldehyde.

47 OTHER INSTRUMENTATION↗