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Volatile organic compound(VOC), ethylene gas, was characterized and quantified by GC/FID. 20-50 ppb levels were detected during the growth stages of radish. SPME could be a good analytical tool for the purpose. Low temperature trapping method using dry ice/diethyl ether and liquid nitrogen bath was recommended for the sampling process for GC/PID and GC/MS analysis.
Understanding the organic content of lunar regolith was an early priority upon the return of Apollo samples, with amino acids being of special interest because of their importance to life on Earth and their astrobiological relevance. Many initial studies focused on the detection of amino acids in these samples and attempts to determine the origin of those compounds. Although no consensus on the origin of the amino acids was reached in those early studies, more recent work determined that the detected amino acids originated from both terrestrial contamination and meteoritic or cometary in fall to the lunar surface. A majority of the amino acids in the Apollo samples studied originated from precursor molecules, either indigenous to the lunar samples or contaminants, that reacted during the water extraction and acid hydrolysis process for analysis in the laboratory, but the identities of the amino acid precursors still remain poorly understood. Such precursors could include hydrogen cyanide (HCN) and other volatile organic compounds such as amines, carboxylic acids, or aldehydes and ketones. The identities of these compounds, as well as the effects of years of curation on their abundances in lunar regolith samples stored at ambient temperature under nitrogen gas purge, are not clear. The specially curated samples available through the Apollo Next Generation Sample Analysis (ANGSA) program provide a unique opportunity to use state-of- the-art analytical techniques to examine previously unstudied lunar materials. The ANGSA samples include three types of samples: 1) samples stored frozen since <1 month after Earth arrival; 2) samples stored under helium; and 3) a double drive tube collected by Apollo 17 astronauts, with the bottom portion of the drive tube sealed under vacuum on the Moon and never opened. In contrast to the typically curated Apollo samples that have been kept for decades at room temperature under flowing nitrogen purge that may have significantly reduced the abundance of volatiles, the vacuum-sealed and frozen samples may have enhanced preservation of these volatiles. Our initial investigation examines amino acids and their potential volatile precursors, including hydrogen cyanide (HCN), aldehydes, ketones, amines, and mono-carboxylic acids, in a sample from the top portion of the Apollo 17 double drive tube. These results will aid in understanding the lunar abundances of these molecules and will also be compared to future analyses of other drive tube and frozen ANGSA samples.
Methane generation has been detected during thermolytic Hydrogen Generation Rate (HGR) testing of SRS tank waste and in simulant samples. Simulant testing has shown methane generation in the presence of trimethylsilanol (TMS) and radioactive sample testing has shown methane generation in presence of methylmercury, both of which are found within SRS waste tanks. The 2019 report Evaluation of the Current State of Knowledge for Thermolysis of Organics within SRS Waste Forming Volatile Organic Compounds (VOCs) reviewed historical data and assessed literature pertaining to thermolytic methane generation. That review recommended undertaking thermolysis studies on simulated waste to detect and quantify VOCs. The purpose of this assessment is to review chemistry and current knowledge of organics in SRS waste to recommend which organics in SRS waste tanks, if any, should be tested for thermolytic methane generation. An evaluation of observed methane generation rates has been performed to assess the implication for current CSTF controls. Based on the inputs used in this report, it was concluded that no methane generation data observed to date has challenged the existing 5% organic contribution to the Composite Lower Flammability Limit (CLFL) assumption in the CSTF tank farm at temperatures below 100 °C. Evidence shows that thermolytic pathways to methane generation become significant at temperatures >100 °C in caustic waste. Currently, the influences of thermolytic methane production on the flammability of vessels at >100 °C (e.g., evaporators) is unclear. It is recommended that testing should be undertaken using the HGR experimental approach for methane generation. The initial simulant testing should obtain quantitative methane generation rates at elevated temperatures for methylated siloxanes/silanes and methylmercury with the goal of determining the current mechanism for thermolytic methane generation seen in SRS tank waste. The results of this testing should then be compiled and analyzed to ascertain the risk of challenging the current projected organic contribution of 5% to the CLFL at elevated temperatures. Following this testing, an evaluation of possible flammable gas generation in the 2H and 3H Evaporators should be performed to assess the risk of methane generation at the high temperatures employed by the evaporators.
Reactive health monitoring strategies during events like the COVID-19 pandemic highlighted the need for predictive, threat-agnostic diagnostics that can detect both known diseases and novel chemical or biological threats. To address this, we investigated an optical biosensor as a breath volatile organic compound (VOC) analyzer, aiming to emulate biological olfaction. We assembled and validated the device with thin film metal coated substrate-based sensors. We immobilized small biological recognition elements on the substrates and delivered controlled concentrations of target VOCs. The sensor was irradiated with a visible laser and the sensor signal was recorded. We characterized the laser performance and tested 3 recognition elements for 2 VOCs with varying concentrations (1-100 ppm). We also evaluated enhancement of the signal using nanostructures on the metal film in comparison with planar film substrate. We demonstrated detecting ethanol reliably at concentrations as low as ~2 ppm along with preliminary detection of acetone (<100 ppm). We also found several unexpected factors that influence the sensor behavior that should be addressed to further refine the device’s performance. The nanostructures were, as expected, found to amplify the sensor signals. These findings demonstrate the feasibility of the optical bio-sensing modality for breath VOC monitoring at physiologically relevant levels. This positions LLNL to develop a low-cost, scalable, broad-spectrum health monitoring capability aligned with the Early Detection thrust of the Bioresilience Mission Focus Area and attract external funding.
A brief overview of some of the analytical techniques currently used in monitoring and analyzing permanent gases and selected volatile organic compound in air are presented. Some of the analytical considerations in developing a specific method are discussed. Four broad groups of hardware are discussed: compound class specific personal monitors, gas chromatographic systems, infrared spectroscopic systems, and mass spectrometric residual gas analyzer systems. Three types of detectors are also discussed: catalytic sensor based systems, photoionization detectors, and wet or dry chemical reagent systems. Under gas chromatograph based systems five detector systems used in combination with a GC are covered: thermal conductivity detectors, photoionization detectors, Fourier transform infrared spectrophotometric systems, quadrapole mass spectrometric systems, and a relatively recent development, a surface acoustic wave vapor detector.
Gas-liquid chromatography (GLC) is a powerful and sensitive method for the separation and detection of organic compounds at nanogram levels. The primary requirement for successful analyses is that the compounds of interest must be volatile under the chromatographic conditions employed. Nonvolatile organic compounds must be converted to volatile derivatives prior to analysis. The derivatives of choice must be both amenable to chromatographic separation and be relatively stable. The condition of volatility necessitates the development of efficient derivatization reactions for important groups of compounds as amino acids, carbohydrates, nucleosides, etc. Trimethylsilylation and trifluoroacetylation represent specific areas of recent prominence. Some relevant practical aspects of GLC are discussed.
We adapted an existing, spaceflight-proven, robust “electronic nose” (E-Nose) that uses an array of electrical resistivity-based nanosensors mimicking aspects of mammalian olfaction to conduct on-site, rapid screening for COVID-19 infection by measuring the pattern of sensor responses to volatile organic compounds (VOCs) in exhaled human breath. We built and tested multiple copies of a hand-held prototype E-Nose sensor system, composed of 64 chemically sensitive nanomaterial sensing elements tailored to COVID-19 VOC detection; data acquisition electronics; a smart tablet with software (App) for sensor control, data acquisition and display; and a sampling fixture to capture exhaled breath samples and deliver them to the sensor array inside the E-Nose. The sensing elements detect the combination of VOCs typical in breath at parts-per-billion (ppb) levels, with repeatability of 0.02% and reproducibility of 1.2%; the measurement electronics in the E-Nose provide measurement accuracy and signal-to-noise ratios comparable to benchtop instrumentation. Preliminary clinical testing at Stanford Medicine with 63 participants, their COVID-19-positive or COVID-19-negative status determined by concomitant RT-PCR, discriminated between these two categories of human breath with a 79% correct identification rate using “leave-one-out” training-and-analysis methods. Analyzing the E-Nose response in conjunction with body temperature and other non-invasive symptom screening using advanced machine learning methods, with a much larger database of responses from a wider swath of the population, is expected to provide more accurate on-the-spot answers. Additional clinical testing, design refinement, and a mass manufacturing approach are the main steps toward deploying this technology to rapidly screen for active infection in clinics and hospitals, public and commercial venues, or at home.
The Toxicology Laboratory at Johnson Space Center (JSC) has pioneered the use of gas chromatography-ion mobility spectrometry (GC/IMS) for measuring target volatile organic compounds (VOCs) aboard spacecraft. Graseby Dynamics, under contract to NASA/Wyle, has built several volatile organic analyzers (VOA) based on GC/IMS. Foremost among these have been the volatile organic analyzer-risk mitigation unit and the two flight VOA units for International Space Station (ISS). The development and evaluation of these instruments has been chronicled through presentations at the International Conference on Ion Mobility Spectrometry over the past three years. As the flight VOA from Graseby is prepared for operation on ISS at JSC, it is time to begin evaluations of technologies for the next generation VOA, Although the desired instrument characteristics for the next generation unit are the same as the current unit, the requirements are much more stringent. As NASA looks toward future missions beyond Earth environs, a premium will be placed upon small, light, reliable, autonomous hardware. It is with these visions in mind that the JSC Toxicology Laboratory began a search for the next generation VOA. One technology that is a candidate for the next generation VOA is GC/IMS. The recent miniaturization of IMS technology permits it to compete with other, inherently small, technologies such as chip-sized sensor arrays. This paper will discuss the lessons learned from the VOA experience and how that has shaped the design of a potential second generation VOA based upon GC/IMS technology. Data will be presented from preliminary evaluations of GC technology and the mini-IMS when exposed to VOCs likely to be detected aboard spacecraft. Results from the evaluation of an integrated GC/mini-IMS system will be shown if available.
Among the diverse metabolites produced by microbial communities, some are volatile. Volatile organic compounds (VOCs) are vigorously cycled by microbes as metabolic substrates and products and as signaling molecules. Yet, current microbial metabolomic studies predominantly focus on nonvolatile metabolites and overlook VOCs, which therefore represent a missing component of the metabolome. Advances in VOC detection now allow simultaneous observation of the numerous VOCs constituting the ‘volatilome’ of microbial systems. Here, we present a roadmap for integrating and advancing VOC and other ‘omics approaches and highlight the potential for realtime VOC measurements to help overcome limitations in discrete ‘omics sampling. Including volatile metabolites in metabolomics, both conceptually and in practice, will build a more comprehensive understanding of microbial processes across ecological communities.
The Mars Science Laboratory (MSL) Curiosity Rover carries a suite of instruments, one of which is the Sample Analysis at Mars (SAM) experiment. SAM is devoted to the in situ molecular analysis of gases evolving from solid samples collected by Curiosity on Mars surface/sub-surface. Among its three analytical devices, SAM has a gaschromatograph coupled to a quadrupole mass spectrometer (GC-QMS). The GC-QMS is devoted to the separation and identification of organic and inorganic material. Before proceeding to the GC-QMS analysis, the solid sample collected by Curiosity is subjected to a thermal treatment thanks to the pyrolysis oven to release the volatiles into the gas processing system. Depending on the sample, a derivatization method by wet chemistry: MTBSTFA of TMAH can also be applied to analyze the most refractory compounds. The GC is able to separate the organic molecules which are then detected and identified by the QMS (Figure 1). For the second time after the Viking landers in 1976, SAM detected chlorinated organic compounds with the pyrolysis GC-QMS experiment. The detection of perchlorates salts (ClO4-) in soil at the Phoenix Landing site suggests that the chlorohydrocarbons detected could come from the reaction of organics with oxychlorines. Indeed, laboratory pyrolysis experiments have demonstrated that oxychlorines decomposed into molecular oxygen and volatile chlorine (HCl and/or Cl2) when heated which then react with the organic matter in the solid samples by oxidation and/or chlorination processes.
The environment of the HALOE assembly clean room at NASA Langley Research Center is analyzed to determine the background levels of airborne organic compounds. Sampling is accomplished by pumping the clean room air through absorbing cartridges. For volatile organics, cartridges are thermally desorbed and then analyzed by gas chromatography and mass spectrometry, compounds are identified by searching the EPA/NIH data base using an interactive operator INCOS computer search algorithm. For semivolatile organics, cartridges are solvent entracted and concentrated extracts are analyzed by gas chromatography-electron capture detection, compound identification is made by matching gas chromatogram retention times with known standards. The detection limits for the semivolatile organics are; 0.89 ng cu m for dioctylphlhalate (DOP) and 1.6 ng cu m for polychlorinated biphenyls (PCB). The detection limit for volatile organics ranges from 1 to 50 parts per trillion. Only trace quantities of organics are detected, the DOP levels do not exceed 2.5 ng cu m and the PCB levels do not exceed 454 ng cu m.
Volatile compounds in comets are the most pristine materials surviving from the time of formation of the Solar System, and thus potentially provide information about conditions that prevailed in the primitive solar material. Moreover, comets may have supplied a substantial fraction of the volatiles on the terrestrial planets, perhaps including organic compounds that played a role in the origin of life on Earth. Here we report the detection of hydrogen isocyanide (HNC) in comet Hyakutake. The abundance of HNC relative to hydrogen cyanide (HCN) is very similar to that observed in quiescent interstellar molecular clouds, and quite different from the equilibrium ratio expected in the outermost solar nebula, where comets are thought to form. Such a departure from equilibrium has long been considered a hallmark of gas-phase chemical processing in the interstellar medium, suggesting that interstellar gases have been incorporated into the comet's nucleus, perhaps as ices frozen onto interstellar grains. If this interpretation is correct, our results should provide constraints on the temperature of the solar nebula, and the subsequent chemical processes that occurred in the region where comets formed.
Volatile compounds in comets are the most pristine materials surviving from the time of formation of the Solar System, and thus potentially provide information about conditions that prevailed in the primitive solar nebula. Moreover, comets may have supplied a substantial fraction of the volatiles on the terrestrial planets, perhaps including organic compounds that played a role in the origin of life on Earth. Here we report the detection of hydrogen isocyanide (HNC) in comet Hyakutake. The abundance of HNC relative to hydrogen cyanide (HCN) is very similar to that observed in quiescent interstellar molecular clouds, and quite different from the equilibrium ratio expected in the outermost solar nebula, where comets are thought to form. Such a departure from equilibrium has long been considered a hallmark of gas-phase chemical processing in the interstellar medium, suggesting that interstellar gases have been incorporated into the comet's nucleus, perhaps as ices frozen onto interstellar grains. If this interpretation is correct, our results should provide constraints on the temperature of the solar nebula, and the subsequent chemical processes that occurred in the region where comets formed.
Mars is an important target for Astrobiology. A key goal of the MSL mission was to determine whether Mars was habitable in the past, a que-tion that has now been definitely determined to be yes. Another key goal for Mars exploration is to understand the origin and distribution of organic material on Mars; this question is being addressed by the SAM instrument on MSL, and will also be informed by two upcoming Mars exploration missions, ExoMars and Mars 2020. These latter two missions have instrumentation capable of detecting and characterize organic molecules. Over the next decade, these missions will analyze organics in surface, near-surface and sub-surface samples. Each mission has the capability to analyze organics by different methods (pyrolysis gas chromatography-mass spectrometry [py-GC-MS]; laser desorption and thermal volatilization GC-MS; and Raman spectroscopy). Plausibly extraterrestrial organics were recently discovered by the Mars Science Laboratory (MSL), providing an important first step towards understanding the organic inventory on Mars [1]. The compounds detected were chlorobenzenes and chloroalkanes, but it was argued that chlorination of these compounds occurred during pyrolysis of samples containing unchlorinated organics in the presence of perchlorate. A recent report analyzed a suite of aromatic (benzene, toluene, benzoic acid, phthalic acid, and mellitic acid) and aliphatic (acetic acid, propane, propanol, and hexane) by pyrolysis under SAM-like conditions in the presence of perchlorate to attempt to constrain possible precursor molecules for the organic molecules detected on Mars. For aromatic compounds, the aromatic acids all readily produced SAM-relevant chlorobenzes, whereas benzene and toluene did not. This observation suggests that the chlorobenzene detected on Mars could have derived from compounds like mellitic acid, consistent with the previous hypothesis by Benner et al. [3]. Among the aliphatic molecules, it was shown that pyrolysis of alkanes and alcohols in the presence of perchlorates produced polychlorine containing chloro-alkanes similar to what was observed on Mars. Surpris-ingly, however, similar treatment of acetic acid pro-duced chloroketones, instead, and no chloroalkanes were reported. This suggests that the chloroalkanes detected in the Sheepbed mudstone were not derived from aliphatic carboxylic acids, but instead were from more reduced alcohols or even alkanes, or perhaps were degradation products of more complicated organic material. Because organics analyses on mars will rely heavily on py-GC-MS of perchlorate-containing samples over the next decade, it is important to understand the fate of organic molecules of biotic and abiotic origin under such conditions. In this work we begin a series of experiments to improve our understanding of products generated during py-GC-MS of increasingly complex organic molecules (esters, amides, peptides, nucleic acids, fatty acids) in the presence of perchlorate.
The accumulation of carbon dioxide (CO 2 ) within enclosed spaces, along with volatile organic compounds, under certain humidity, temperature, and ventilation conditions is associated with detrimental human health symptoms such as fatigue. Color-based chemical sensing is a promising approach to detect CO 2 levels relevant to indoor air quality through producing fast, quantifiable output visible to the naked eye. In a prior work, a colorimetric gas sensor was fabricated through synthesizing the metal-organic framework, ZIF-8, as the adsorbent, followed by post-synthetic mixing with a dye, phenol red (PSP), and primary amine, ethylenediamine (ED). While this sensor (termed PSP-ED/ZIF-8) maintained its structural integrity in atmospheric conditions and exhibited an increasing fuchsia-to-yellow color change with increasing CO 2 levels in dry environment, the colorimetric response greatly suffered in the presence of humid CO 2 . Here in this work, a significantly improved colorimetric CO 2 sensor (referred to as ED/PSP:ZIF-8) is accomplished through directly incorporating phenol red in the ZIF-8 metal and linker precursor solutions and then blending with ethylenediamine. MATLAB-generated color distributions and in-situ ultraviolet-visible (UV-Vis) spectroscopic studies quantitatively demonstrate an enhanced colorimetric gas response of ED/PSP:ZIF-8 compared to that of PSP-ED/ZIF-8 across an important range of CO 2 for indoor air quality monitoring (500 – 3500 ppm) and across a range of humidity. The new sensor also exhibits high selectivity to CO 2 compared to select volatile organic compounds, such as acetone and ethanol, which contribute to human health symptoms experienced indoors. The enhanced performance is attributed to the proposed incorporation of phenol red within ZIF-8, while maintaining the chemical stability of the MOF.
We measured stable and reactive trace gases with an airborne Fourier transform infrared spectrometer (AFTIR) on the University of Washington Convair-580 research aircraft in August/September 2000 during the SAFARI 2000 dry season campaign in Southern Africa. The measurements included vertical profiles of C02, CO, H20, and CH4 up to 5.5 km on six occasions above instrumented ground sites and below the TERRA satellite and ER-2 high-flying research aircraft. We also measured the trace gas emissions from 10 African savanna fires. Five of these fires featured extensive ground-based fuel characterization, and two were in the humid savanna ecosystem that accounts for most African biomass burning. The major constituents we detected in nascent CH3OOH, HCHO, CH30H, HCN, NH3, HCOOH, and C2H2. These are the first quantitative measurements of the initial emissions of oxygenated volatile organic compounds (OVOC), NH3, and HCN from African savanna fires. On average, we measured 5.3 g/kg of OVOC and 3.6 g/kg of hydrocarbons (including CH4) in the initial emissions from the fires. Thus, the OVOC will have profound, largely unexplored effects on tropical tropospheric chemistry. The HCN emission factor was only weakly dependent on fire type; the average value (0.53 g/kg) is about 20 times that of a previous recommendation. HCN may be useful as a tracer for savanna fires. Delta O3/Delta CO and Delta CH3COO/Delta CO increased to as much as 9% in <1 h of photochemical processing downwind of fires. Direct measurements showed that cloud processing of smoke greatly reduced CH30H, NH3, CH3COOH, SO2, and NO2 levels, but significantly increased HCHO and NO.
We present testing results for developmental hardware of the Spacecraft Water Impurity Monitor (SWIM) Organic Water Module (OWM). SWIM-OWM will monitor spacecraft potable water and system water for trace organic contaminants. The system will detect and identify the specific organic chemical that makes up a given total organic carbon reading. We have built a first development unit (1DU) for SWIM-OWM, which directly injects aqueous water samples and detects chemicals with both a thermal conductivity detector and mass spectrometer sensor. The gas chromatography mass spectrometer (GCMS) system that comprises SWIM-OWM draws on the success of ISS-proven mass spectrometer hardware, and the demonstration of GCMS detection of trace organic contaminants in ISS cabin air. SWIM-OWM benefits from the excellent sensitivity and specificity afforded by GCMS. We have demonstrated detection of a set of chemicals relevant to both crew health and performance as well as system monitoring; these target chemicals range from light, volatile organics such as acetone and ethanol, to heavier, very non-volatile compounds such as dimethyl sulfone and o-phthalaldehyde. Direct aqueous injection was chosen for the general applicability of the technique to clean water sampling and to preclude sample pre-processing, which facilitates an on-line implementation of the SWIM-OWM when deployed in a spacecraft or habitation module. A specific advantage of direct aqueous injection when coupled with appropriate methods is that both the light, volatile organics and heavier non-volatiles can be detected from a single injection, in a single chromatogram. Results from 1DU testing will be discussed, and forward plans will be outlined for continued maturation of SWIM-OWM with the goal of implementing a technology demonstration for the purposes of maturing the engineering design and operations in an environment relevant to NASA’s future goals of exploring and setting up habitation on the Moon and Mars.
We present testing results for developmental hardware of the Spacecraft Water Impurity Monitor (SWIM) Organic Water Module (OWM). SWIM-OWM will monitor spacecraft potable water and system water for trace organic contaminants. The system will detect and identify the specific organic chemical that makes up a given total organic carbon reading. We have built a first development unit (1DU) for SWIM-OWM, which directly injects aqueous water samples and detects chemicals with both a thermal conductivity detector and mass spectrometer sensor. The gas chromatography mass spectrometer (GCMS) system that comprises SWIM-OWM draws on the success of ISS-proven mass spectrometer hardware, and the demonstration of GCMS detection of trace organic contaminants in ISS cabin air. SWIM-OWM benefits from the excellent sensitivity and specificity afforded by GCMS. We have demonstrated detection of a set of chemicals relevant to both crew health and performance as well as system monitoring; these target chemicals range from light, volatile organics such as acetone and ethanol, to heavier, very non-volatile compounds such as dimethyl sulfone and o-phthalaldehyde. Direct aqueous injection was chosen for the general applicability of the technique to clean water sampling and to preclude sample pre-processing, which facilitates an on-line implementation of the SWIM-OWM when deployed in a spacecraft or habitation module. A specific advantage of direct aqueous injection when coupled with appropriate methods is that both the light, volatile organics and heavier non-volatiles can be detected from a single injection, in a single chromatogram. Results from 1DU testing will be discussed, and forward plans will be outlined for continued maturation of SWIM-OWM with the goal of implementing a technology demonstration for the purposes of maturing the engineering design and operations in an environment relevant to NASA’s future goals of exploring and setting up habitation on the Moon and Mars.