Gas Samples Research Articles

Wellbore cement alteration and roles of CO2 and shale during underground hydrogen storage

To mitigate climate change and adopt renewable energy, energy storage is crucial and can be done in the form of hydrogen gas (H2). Subsurface geologic reservoirs are positioned to store H2 on the largest scales for the longest terms of all potential options. However, H2 injection may boost reactions that consume hydrogen, generate undesired gases, and alter pore structures of geomedia. To explore the extent of H2-associated biotic reactions at a near wellbore location, four experiments were conducted under underground storage conditions with wellbore cement cores and, in most instances, shale samples submerged in synthetic formation brine. Post-reaction gas, aqueous, and solid phase samples were analyzed using olfactory screening and, later, gas chromatography (GC-MS), inductively coupled plasma optical emission spectroscopy (ICP-OES), scanning electron microscopy (SEM), and synchrotron micro-scale x-ray fluorescence (μ-XRF). Within a period of 16 weeks, hydrogen sulfide (H2S) was generated in systems containing both H2 and shale. XRF mapping identified a zone enriched in iron(II) and reduced sulfur along the rim of cement cross sections that was largely associated with CO2-induced cement carbonation. Shale did not show noticeable alteration, but there is evidence it contributed to the initial inoculation of the system and provided nutrients for microbes via water-rock interactions. This study considers both rock formations and wellbore cement not previously evaluated concurrently. Findings support understanding and modeling of H2-associated biogeochemical reactions during underground hydrogen storage.

Odor-Cued Grab Air Sampling for Improved Investigative Odorant Prioritization Assessment of Transient Downwind Environmental Odor Events.

A critical prelude to any community odor assessment should be the prioritization of specific chemical odorants that are most responsible for targeted downwind odors. Unfortunately, and historically, this is a step that has often been bypassed or overlooked. However, correct understanding of the specific impactful volatile organic compounds (VOCs) can inform the follow-on sampling, analytical, and remediation strategies that are most appropriate and efficient, based upon the chemistry behind the issue. With this understanding, the techniques and sampling strategies presented herein should be viewed as a qualitative prelude rather than an addendum to a follow-up routine, automated downwind odor monitoring. Downwind odor characteristics can vary depending upon the size of the upwind source, interim topography, and wind conditions. At one extreme, the downwind odor plume from a relatively large source located on a flat open plain and under stable, near-straight line wind conditions can be rather broad, sustained, and predictable. In contrast, the plume from a small point source (e.g., a roof vent stack) located on irregular topography and under rapidly shifting wind conditions can be intermittent and fleeting ("spikes" or "bursts"). These transient odor events can be surprisingly intense and offensive, despite their fleeting occurrence and perception. This work reports on improving and optimizing an environmental sampling strategy for odorant prioritization from such transient downwind odor conditions. This optimization addresses the challenges of (1) sampling of transient odor "spikes" and (2) prioritizing odors/odorants from multiple, closely colocated point sources under transient event conditions. Prioritizing is defined as identifying the key impactful odorants downwind. Grab air sampling protocol refinement has emerged from actual community environmental odor assessment projects. The challenge of assessing transient odor events has been mitigated by utilizing (a) rapid, odor-cued whole-air grab sampling (i.e., activated by and synchronous with the perceived sensory spikes) into metalized fluorinated ethylene polymer (m-FEP) gas sampling bags; (b) immediate transfer from bags onto solid-phase microextraction (SPME) fibers or sorbent tubes; and (c) maintaining refrigerated storage and shipment conditions between field collection and in-laboratory analysis. Results demonstrated approximately 11-fold increases in target odorant yields for 900 mL air sample capture on sorbent tube transfers from 2 to 3 s "burst" odor event bag captures compared to equivalent direct collections (with sorbent tubes) at the same downwind receptor location but during perceived (stable) odor "lull" periods. An application targeting general odor sampling and point-source differentiation utilizing tracer gases is also presented.

In situ mass spectrometric investigation to probe GeSn growth dynamics and mechanisms in the chemical vapor deposition processes

GeSn has attracted increasing attention due to its tunable bandgap from indirect to direct resulting in unique electronic and optoelectronic capabilities. Chemical vapor deposition (CVD) is well acknowledged as an advanced growth method for GeSn, demonstrating its capability with grown materials for infrared lasers and detector development. As an in situ diagnostics of the CVD process, a residual gas analyzer (RGA) could enable the detection of all gaseous species during growth, thus probing the growth dynamics and mechanism. Therefore, it is highly desirable but is lacking in the (Si)GeSn research community. This work utilized an RGA equipped with a specialized differential vacuum pumping system to analyze the mass spectra of the GeSn CVD precursors of SnCl4, GeH4, and their combination. The spectra of SnCl4 collected from gas samples at a standard base pressure of 0.3 Torr display consistent fragments with central mass-to-charge ratios (m/z) of 78, 120, 155, 225, and 260, corresponding to Sn+, SnCl2+, SnCl+, SnCl2+, SnCl3+, and SnCl4+, respectively. These profiles closely resemble those observed in the National Institute of Standards and Technology and Wiley and Matsumoto et al. The simultaneous introduction of SnCl4 and GeH4 at a combined pressure of several tens of Torr yields spectra, indicating a chemical reaction that produces GeCl4 at room temperature in the vacuum chamber and tubing. Utilizing Gaussian16 and ORCA codes, the ab initio and density functional thermochemistry computations were employed to predict potential essential reactions and validate the experimental findings.

Natural Hydrogen in the Northern Perth Basin, WA Australia: Geospatial Analysis and Detection in Soil Gas for Early Exploration

The scope of this work is to empirically check and prove the practical applicability of the Primordially Hydridic Earth (PHE) concept for early exploration of the resources of naturally occurring hydrogen. With the PHE concept postulates interpreted within the local geological, tectonic, petrological and geophysical context, the reconnaissance plan, as well as the field exploration and data acquisition programs, were put together and implemented in the field. The results obtained from the surface (<1m deep) soil gas survey performed in Western Australia (WA) resulted in values of hundreds of ppm H<sub>2</sub>, including three samples with a concentration of hydrogen exceeding the gas sensor detection limit of 2,000 parts per million (ppm) (the all-Australia record). Similarly, several of the shallow soil samples used for obtaining headspace gas extracts yielded dozens % H<sub>2</sub>, which was established utilizing Gas Chromatography (GC) technology. The latter tests established the all-Australia record of 58.3% (norm.) H<sub>2</sub> concentration from 15 m depth, being the highest reading from the area of research. At one location, a concentration of He exceeding 8,000ppm was detected in a 1m surface soil gas sample analyzed by the independent lab. The most important outcome was finding natural hydrogen where it was expected and predicted. On the other hand, H<sub>2</sub> concentrations exceeding the natural background of 1-3ppm were not detected in the soil gas readings outside of the areas identified using the PHE concept as a theoretical foundation. It may be stated that overall, the practical application of the PHE concept along with the thoroughly planned utilization of carefully selected exploration techniques brings satisfactory results.

GEOCHEMISTRY OF OILS AND GASES FROM THE VERKHNECHONSKOYE FIELD, EAST SIBERIAN BASIN: APPLICATION OF ANALYTICAL RESULTS TO RESERVOIR CHARACTERISATION

A geochemical study was carried out on oil and gas samples from the Verkhnechonskoye field, located on the Nepa‐Botuoba Anteclise in the central‐southern part of the Siberian Platform. The goal of the study was to distinguish between fluids derived from the V10‐13 and B12 reservoir units in the Vendian (Neoproterozoic) Katanga and Nepa Formations and to identify the producing reservoir using geochemical data. The results of analyses of 12 oil and 13 associated gas samples from the two reservoirs showed that all the fluids have similar geochemical properties including: low Pr/Ph ratios (0.78‐1.00); a predominance of C29 over C27 and C28 steranes; a predominance of odd‐numbered C21‐C25 n‐alkylbenzenes over their even‐numbered homologues; the presence of 12‐ and 13‐methylalkanes; and a high relative abundance of tricyclic terpanes (cheilantanes). All these properties are consistent with those of the properties of petroleum from other fields on the Siberian Platform. The molecular and stable carbon isotope compositions of the oils and gases suggest that they were derived from marine organic matter with a high algal input deposited under reducing conditions. To date, specific source rocks which generated the oil and gas present at fields on the Nepa‐Botuaoba Anteclise have not conclusively been identified, but potential candidates include the Upper Riphean Iremeken and Ayan Formations and more probably the Vendian Zherbinskaya, Seralakh, Vanavara and Nepa Formations.The second part of the study demonstrates the application to reservoir geochemistry of C3‐ and C4‐ alkylbenzene compounds together with more conventional biomarkers. Key parameters were selected using statistical processing and displayed in graphic profiles. These profiles allowed the oil and gas samples to be classified according to the reservoir from which they were derived based on their geochemical properties. Parameters based on C3‐ and C4‐ alkylbenzene compounds were most effective in discriminating between oils from the two reservoirs. In addition, a new parameter is proposed based on the contents of 1‐methyl‐3‐isopropylbenzene, 1‐methyl‐2‐isopropylbenzene and 1‐methyl‐2‐propylbenzene; this parameter correlates closely with the pristane/phytane ratio and can be used as an additional indicator of the level of oxicity in the source rock depositional environment.

Quartz Enhanced Photoacoustic Spectroscopy on Solid Samples.

Quartz-Enhanced Photoacoustic Spectroscopy (QEPAS) is a technique in which the sound wave is detected by a quartz tuning fork (QTF). It enables particularly high specificity with respect to the excitation frequency and is well known for an extraordinarily sensitive analysis of gaseous samples. We have developed the first photoacoustic (PA) cell for QEPAS on solid samples. Periodic heating of the sample is excited by modulated light from an interband cascade laser (ICL) in the infrared region. The cell represents a half-open cylinder that exhibits an acoustical resonance frequency equal to that of the QTF and, therefore, additionally amplifies the PA signal. The antinode of the sound pressure of the first longitudinal overtone can be accessed by the sound detector. A 3D finite element (FE) simulation confirms the optimal dimensions of the new cylindrical cell with the given QTF resonance frequency. An experimental verification is performed with an ultrasound micro-electromechanical system (MEMS) microphone. The presented frequency-dependent QEPAS measurement exhibits a low noise signal with a high-quality factor. The QEPAS-based investigation of three different solid synthetics resulted in a linearly dependent signal with respect to the absorption.

Design of a Rotating Disk Electrode setup operating under high pressure and temperature: Application to CO2 reduction on gold

We describe the design and development of a rotating disk electrode (RDE) cell capable of operating at pressures up to 200 bar and temperatures up to 200 °C. This setup enables electrochemical surface characterization through techniques such as voltammetry and impedance spectroscopy, under different mass transport regimes. Furthermore, evaluation of catalytic performance, including CO2 reduction, is possible as the system works in a semi-continuous mode interfaced with online gas sample measurements. As a proof of concept of the high-pressure cell designed, we examined the temperature-dependent changes in the cyclic voltammograms (CVs) of polycrystalline gold up to 150 °C and 50 bar. Additionally, online catalytic performance of CO2 reduction to CO on a rotating polycrystalline gold disk electrode was investigated under different pressure and temperature. Our results indicate a positive impact of temperature on the faradaic efficiency (FE) towards CO up to 50 °C, beyond which a rapid drop in performance was observed at atmospheric pressure. Conversely, increasing pressure positively affected CO2 solubility in the electrolyte, resulting in enhanced FE towards CO, reaching approximately 90 % at 6 bar compared to 40 % at atmospheric pressure. Notably, further increases in pressure did not significantly alter the FE, but led to higher current densities. Moreover, at pressures exceeding 6 bar, we observed a plateau in efficiency at temperatures higher than 50 °C. This observation suggests that increasing pressure can sustain CO2 electrolysis, validating the hypothesis that increasing CO2 solubility would suppress catalytic decay at higher temperatures. This study opens up promising avenues for future investigations in electrocatalysis, ranging from fundamental explorations of surface modifications induced by variations in temperature and pressure to the development of high-performance catalysts.

Hydrocarbon microseepages in the kerkennah islands, Eastern Tunisia: Integrated surface geochemical and geoelectrical prospecting approaches

Oil exploration is usually carried out using conventional techniques such as seismic reflection and exploratory drilling. However, these techniques are very costly with a high risk of dry holes or failure to find commercial quantities of hydrocarbons. Here we aim to evaluate surface geochemical prospection (SPG) methods which serve as preliminary step to derisk an area by exploring hydrocarbon micro-seeps. This approach helps to identify potential areas of interest when you have limited amount of money to explore a given area. This paper reports on surface gas micro-seepages in the Kerkennah archipelago, part of the Tunisian Pelagian Platform. 33 gas and soil samples were collected on a 1 × 1 km grid over Chergui Island. Both free gas and adsorbed soil gas techniques were used. Free hydrocarbon gas concentrations ranged from 0 to 21 ppm. Adsorbed gases showed concentrations up to 11 ppm. The presence of all light hydrocarbon gas components from methane to pentane, the values of the gas ratios C1/C2, C1/ΣC2+, (C3/C1) x 1000 and C1/(C2 + C3), and the Pixler and triangular diagrams together indicate that these gases are of thermogenic origin and have migrated from subsurface accumulations. Anomalous concentrations of hydrocarbon gases occurred in the middle and west of the study area. Both free and adsorbed gas anomalies have the same planar shape and form linear anomalies with a NW-SE trend. This orientation corresponds to that of the major fault system affecting the Kerkennah archipelago. Subsequent independent VES surveys and re-interpreted seismic lines confirmed the presence of a surface fault as suggested by the surface gas anomalies. In conclusion, our study has confirmed the presence of thermogenic hydrocarbon gas microseepage to the surface. The gases are interpreted to have migrated to the surface along faults. SPG methods were thus able to identify active hydrocarbon migration and can be considered as a useful low-cost approach to hydrocarbon exploration.

Photoabsorption cross section measurements of acetylene in the nonionizing region using the double-ion chamber method

The double-ion chamber (DIC) method has been used to measure photoabsorption cross sections in the ionization region of the sample gas. In this study, we introduce a method to extend the wavelength region of the DIC measurements beyond the ionization threshold wavelength by using the photoion currents from the impurities in the sample gas. To verify this method, the photoabsorption cross sections of C2H2 (ionization threshold wavelength λth = 108.8 nm) have been measured from 105 to 137 nm. The natural impurity, acetone (λth = 127.8 nm), contained 1% in high-purity grade acetylene (C2H2) sample gas, allowing for measurements in the non-ionizing region of C2H2 up to 127.7 nm. By adding 1% benzene (λth = 134.6 nm) in the sample gas, measurements were possible even further, to 134.5 nm. This new method enables the measurement of the photoabsorption cross section by photoions that are produced from the impurities in the sample gas in a substantial amount. The current measurement methodology aligns well with the previous measurements of Suto and Lee [Suto and Lee, J. Chem. Phys. 80, 4824 (1984)].

Novel differential pumping system with extended sampling range: Design and application in the EAST tokamak

A novel differential pumping system (DPS) with an adjustable sampling rate has been developed and implemented in the Experimental Advanced Superconducting Tokamak (EAST). This system is equipped with a high-resolution quadrupole mass spectrometer (QMS), covering a mass range of 1–16 atomic mass units (AMU), alongside a conventional QMS with a broader range of 1–200 AMU. The DPS features a dynamic pressure sampling capability from 10−2 to 105 Pa, utilizing a gas dosing valve and an angle valve, enabling a wide gas sampling ratio range of 10−9 to 3 × 10−2. The high-resolution QMS (QMG700) is adept at directly quantifying the partial pressures of deuterium and helium within mixtures, while the conventional QMS (RGA200) offers indirect measurement of D2 partial pressures above 2 × 10−5 Pa, complemented by direct wide-range mass analysis. During the EAST tokamak campaigns of 2023 and 2024, the DPS was effectively utilized for glow discharge cleaning (GDC) at a pressure of 3 Pa and ion cyclotron wall conditioning (ICWC) at approximately 3 × 10−3 Pa, accurately distinguishing deuterium pressure from the helium environment in the wide pressure range of vacuum vessel. Moreover, the DPS was successfully employed to trace the vacuum leak location in EAST campaign with a pressure of up to hundreds Pa. This DPS is a key tool for gas ingredient analysis and leak detection in the EAST campaigns, providing a valuable reference for the vacuum operation of future fusion reactors.

Electric Drive and Automation of Sampling System for Chimney Fas Analyzer

To organize reliable control over emissions from chimneys of energy facilities, automatic monitoring systems are needed. Equipment is known for monitoring emissions from small-diameter chimneys, but for large-diameter pipes (15 m or more) available in our Republic, there are no corresponding technical solutions. The paper examines the problem of automating the sampling of flue gases based on an electric drive in large-diameter chimneys. To ensure the optimal trajectory of the sampler in the chimney section, it is necessary to use an asynchronous electric motor with a frequency converter and a position sensor. A functional diagram of the control system is proposed, which contains a programmable logic controller for generating the motion mode, as well as a method for calculating parameters and expressions for generating a task signal for continuous sampling mode. Since the range of speed control increases as the diameter of the chimney increases, depending on it, scalar or vector frequency control can be applied. An expression is proposed for calculating the optimal value of the parameter N of an incremental position and speed sensor (encoder), which contributes to a reasonable choice of sensor. The results of simulation modeling are presented, confirming the effectiveness of the proposed method for calculating the parameters of the sampler drive.

Performance of a Wearable Ring in Controlled Hypoxia: A Prospective Observational Study.

Over recent years, technological advances in wearables have allowed for continuous home monitoring of heart rate and oxygen saturation. These devices have primarily been used for sports and general wellness and may not be suitable for medical decision-making, especially in saturations below 90% and in patients with dark skin color. Wearable clinical-grade saturation of peripheral oxygen (SpO2) monitoring can be of great value to patients with chronic diseases, enabling them and their clinicians to better manage their condition with reliable real-time and trend data. This study aimed to determine the SpO2 accuracy of a wearable ring pulse oximeter compared with arterial oxygen saturation (SaO2) in a controlled hypoxia study based on the International Organization for Standardization (ISO) 80601-2-61:2019 standard over the range of 70%-100% SaO2 in volunteers with a broad range of skin color (Fitzpatrick I to VI) during nonmotion conditions. In parallel, accuracy was compared with a calibrated clinical-grade reference pulse oximeter (Masimo Radical-7). Acceptable medical device accuracy was defined as a maximum of 4% root mean square error (RMSE) per the ISO 80601-2-61 standard and a maximum of 3.5% RMSE per the US Food and Drug Administration guidance. We performed a single-center, blinded hypoxia study of the test device in 11 healthy volunteers at the Hypoxia Research Laboratory, University of California at San Francisco, under the direction of Philip Bickler, MD, PhD, and John Feiner, MD. Each volunteer was connected to a breathing apparatus for the administration of a hypoxic gas mixture. To facilitate frequent blood gas sampling, a radial arterial cannula was placed on either wrist of each participant. One test device was placed on the index finger and another test device was placed on the fingertip. SaO2 analysis was performed using an ABL-90 multi-wavelength oximeter. For the 11 participants included in the analysis, there were 236, 258, and 313 SaO2-SpO2 data pairs for the test device placed on the finger, the test device placed on the fingertip, and the reference device, respectively. The RMSE of the test device for all participants was 2.1% for either finger or fingertip placement, while the Masimo Radical-7 reference pulse oximeter RMSE was 2.8%, exceeding the standard (4% or less) and the Food and Drug Administration guidance (3.5% or less). Accuracy of SaO2-SpO2 paired data from the 4 participants with dark skin in the study was separately analyzed for both test device placements and the reference device. The test and reference devices exceeded the minimum accuracy requirements for a medical device with RMSE at 1.8% (finger) and 1.6% (fingertip) and for the reference device at 2.9%. The wearable ring meets an acceptable standard of accuracy for clinical-grade SpO2 under nonmotion conditions without regard to skin color. ClinicalTrials.gov NCT05920278; https://clinicaltrials.gov/study/NCT05920278.

Occurrence of organic ultraviolet absorbers in the particle and gas samples from plastic greenhouses: Human inhalation intake risk assessment

The environmental pollution of organic ultraviolet absorbers (UVAs) has attracted global attention. However, the distribution, sources and risk assessment of UVAs in air from plastic greenhouses are rarely reported. This study was the first to investigate the concentrations of ten UVAs in the air samples from plastic greenhouses. The total concentrations of ten UVAs (∑10UVAs) in the air samples ranged from 5.7 × 103 ng/m3 to 6.3 × 103 ng/m3 (median 5.7 × 103 ng/m3) in greenhouses covered with biodegradable mulch film, 288.2 ng/m3 to 376.4 ng/m3 (median 333.9 ng/m3) in greenhouses covered with PE mulch film, and 97.9 ng/m3 to 142.6 ng/m3 (median 114.9 ng/m3) in greenhouses covered without mulch film. The concentrations of ten UVAs in 65 commercial agricultural films were simultaneously analyzed. Additionally, the potential health risks for greenhouse workers exposed to UVAs were estimated. And the migration simulations showed that the health risk in greenhouses may be higher even if only one UVA is added to the biodegradable mulch film. Therefore, the exposure risk of UVAs in plastic greenhouses needs to be highly prioritized.

Downstream natural gas composition across U.S. and Canada: implications for indoor methane leaks and hazardous air pollutant exposures

Previous research has shown that natural gas (NG) leaks from residential appliances are common, affecting greenhouse gas emission inventories and indoor air quality. To study these implications, we collected and analyzed 587 unburned NG samples from 481 residences over 17 North American cities for hydrocarbons, hazardous air pollutants, and organosulfur odorants. Nearly all (97% of) gas samples contained benzene (between-city mean: 2335 ppbv [95% CI: 2104, 2607]) with substantial variability between cities. Vancouver, Los Angeles, Calgary, and Denver had at least 2x higher mean benzene concentrations than other cities sampled, with Vancouver exhibiting a nearly 50x greater mean benzene level than the lowest-concentration city (Boston). We estimate that current U.S. and Canadian emissions inventories are missing an additional 25 000 [95% CI: 19 000, 34 000] and 4000 [95% CI: 3700, 5200] lbs benzene yr−1 through downstream NG leakage, respectively. Concentrations of odorants added for leak detection varied substantially across cities, indicating a lack of standardization. Houston, for instance, had 5x higher mean tert-butyl mercaptan levels than Toronto. Using these odorant measurements, we found that methane emissions as high as 0.0080–0.28 g h−1 and indoor benzene enhancements 0.0096–0.11 ppbv could go undetected by persons with an average sense of smell, with large uncertainties driven by smelling sensitivity, gas composition, and household conditions. We also observed larger leaks (>10 ppm ambient methane) in ∼4% of surveyed homes, confirming that indoor leakage occurs at varying degrees despite the presence of odorants. Overall, our results illustrate the importance of downstream NG composition to understand potential emissions, exposures, and odor-mediated leak detection levels. Given methane’s global warming potency, benzene’s toxicity, and wide variation in smelling abilities, our findings highlight the deficiencies regarding the sole reliance on odorization to alert and protect all occupants from indoor leaks.

Methane (CH4) Detection System Using The TGS2611 Sensor and MQ-4 Sensor

Abstract This research focused on cow dung digesters as measurement samples, utilizing the TGS2611 and MQ-4 sensors, both known for their affordability. The objective was to develop a low-cost gas sensor system for monitoring methane gas concentrations through a straightforward web-based data acquisition platform. The DHT11 sensor was employed to measure air temperature and humidity. The electronic sensor circuit in this research utilized a voltage divider circuit. Testing the performance of the low-cost gas sensor involved integrating it with an anaerobic digestion system. For both the TGS2611 and MQ-4 sensors, the graph illustrating the relationship between sensor voltage (volts) and methane gas concentration (ppm) formed a logarithmic or non-linear pattern. The measurement range for the system was around 4700 ppm to 6300 ppm for TGS2611 and 4000 ppm to 5100 ppm for MQ-4. The sensor sensitivity was determined as 0.5433 Volts/ppm for TGS2611 and 0.5639 Volt/ppm for MQ-4. The TGS2611 sensor exhibited a higher response to changes in methane gas concentration, while the MQ-4 sensor successfully detected methane gas within its designated range. Interestingly, the TGS2611 sensor accurately detected methane gas concentrations above its specified range. The gas sampling procedure involved automatic gas sampling in a vacuum chamber for measurement, a strategy potentially enhancing sensor robustness. This research successfully amalgamated sensor advantages, circuit control, and data analysis to realize an economical yet reliable monitoring system.

The Representativeness of Subslab Soil Gas Collection as Effected by Probe Construction and Sampling Methods

AbstractSubslab soil gas (SSSG) samples were collected as part of an investigation to evaluate vapor intrusion (VI) into a building. The June 2015 Office of Solid Waste and Emergency Response (OSWER) VI Guide (U.S. Environmental Protection Agency [U.S. EPA] 2015) does not provide specific, detailed recommendations regarding how to collect SSSG samples. The data collected in this study will be used to provide input into future OSWER VI Guidance documents on SSSG sample collection. To this end, three different types of subslab sampling ports were constructed with various sampling techniques within a hexagon‐shaped grid in near proximity to each other. Conventional‐, Vapor Pin‐, and California‐style ports were established in duplicate for continual analysis by onsite gas chromatography‐electron capture detection (GC‐ECD). Triplicate ports were established to evaluate active and passive long‐term sampling methods to determine short range temporal differences. Active sampling methods included evacuated stainless‐steel canisters fitted with capillary flow controllers (Modified U.S. EPA Method TO‐15 [U.S. EPA 1999a]) and sorbent tubes collected using a syringe (Modified EPA TO‐17 [U.S. EPA 1999b]). The Passive sampling method used was sorbent tube samples collected following the EPA TO‐17 sampling method (Modified). This study did not identify any systematic differences in sample results between conventional, Vapor Pin, and CA‐style probes for used in SSSG sampling. The decisions for site management would probably be the same for data from any subslab port style, active or passive sampling techniques over durations less than 2 weeks.

A self-made tube cracker coupled to an EA-IRMS-AGE3 system

AbstractThe automatic graphitization system (AGE3) by IonPlus is very popular among radiocarbon dating laboratories. Usually, solid samples are burnt in an elemental analyzer (EA), and the gaseous CO2 is transferred for graphitization. Our system is coupled also with an isotope ratio mass spectrometer (IRMS), which measures the δ13C and δ15N of that gas. Some less routine pretreatment protocols require the production of gaseous samples and prevent the possibility of using the EA-AGE3 system, as the EA is used for solid samples only. In order to use that system, including the measurements of stable isotopes, we developed a glass tube cracker that connects to the EA. The device is routinely used in our laboratory and is mainly built from Swaglok catalog parts. We show that the background (blank) levels of a marble standard are indistinguishable between using the cracker and burning solid marble using the EA. We further demonstrate that the δ13C values are consistent and that the extraction efficiency when using the device is above 93%. Full descriptions, drawings, and working protocol are supplied.

Quantifying bimolecular reaction kinetics of isoprene hydroxy peroxy radical: From dry to highly humid atmospheric environment

Isoprene hydroxy peroxy radicals (ISOPOO), derived from isoprene oxidation by hydroxy radicals (OH), are key intermediates for ozone and secondary organic aerosol (SOA) formation in the atmosphere. Although ISOPOO-water complexes are ubiquitous, their impacts on ISOPOO chemistry remain obscure. Here the previously overlooked water effect on the bimolecular reaction kinetics of ISOPOO was investigated in an oxidative flow reactor. The major first-generation products of ISOPOO, isoprene hydroxy hydroperoxides (ISOPOOH), methacrolein (MACR), and methyl vinyl ketone (MVK), were measured simultaneously at various relative humidity (RH) with the help of a cold trap to avoid potential losses in direct gas sampling. We found that ISOPOO reactions were accelerated significantly under wet conditions, with a greater enhancement on 1,2-ISOPOO than 4,3-ISOPOO. 1,2-ISOPOOH yield appeared faster growth with RH than 4,3-ISOPOOH. MVK yield showed an upward-downward trend with RH, while MACR yield plateaued from 30% RH. To explain the enhancement in the ISOPOOH yield from 3% to 80% RH, the overall rate constants of 1,2-ISOPOO + HO2 and 4,3-ISOPOO + HO2 reactions at 80% RH should be 13 times and twice those at 3% RH, respectively. The empirical formulas were proposed for the first time to parameterize the water effect on ISOPOO + HO2 reactions. The updated kinetics of ISOPOO reactions were incorporated in a box model to simulate the RH-dependent ISOPOOH and C4 carbonyl yields under typical atmospheric conditions. High RH can enhance the ISOPOOH yield in urban, rural, and forest areas, and promote SOA formation correspondingly. Our findings shed light on the critical role of humidity in the reactions of ISOPOO and benefit evaluating the fate of isoprene and its impacts on air quality more accurately in the ambient atmosphere.

Đánh giá mức độ phát thải của các chất polyclodibenzo-p-dioxin và polyclodibenzofuran phát sinh không chủ định từ lò đốt rác chất thải sinh hoạt và rác thải công nghiệp ở Việt Nam

Polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) are the most toxic substances among the group of unintentional persistent organic pollutants (U - POP) generated from many sources, in which domestic and industrial waste incinerators are the highest emission risk. Assessment of pollution potential and dioxin/furan emissions from incinerators in developing countries, including Vietnam, is still limited; especially in-depth studies on the content and characteristics of PCDD/PCDF emitted into the atmosphere. Therefore, the research team evaluated the emission potential and characteristics of 07 PCDD and 10 PCDF, those are considered to be the most toxic isomers and congeners, from stack gas samples collected from incinerators at 33 facilities in 11 provinces in Vietnam. The total concentration of PCDD/PCDF in the industrial incinerators’ emission ranged from 37.3 to 3348.6 pg TEQs/m3 and domestic waste incinerators had lower total concentrations and fluctuated within about 37.3-1323.8 pg TEQs/m3. The characteristic of incinerator emissions is that the proportion of 2,3,7,8- TCDD accounts for 2.9 to 9.04%. The highest contributing concentrations were congeners 1,2,3,7,8-PeCDD, with its contributing percentage from 22.95-32.42%. The second largest contributor is congeners 2,3,4,7,8- PeCDF, accounting for 20.94- 21.50% of the total toxic congeners of PCDD/PCDF in both types of incinerators. However, in terms of toxic equivalency (TEQ), the concentration of industrial waste incinerators is much higher than that of domestic waste incinerators. The results of stack gas samples showed that the PCDD/PCDF content for domestic waste incinerators has 5/17 establishments that exceeded the permissible standard threshold: 0.6 ng/Nm3, according to QCVN 61-MT:2016/BTNMT. Industrial waste incinerators have 5/16 establishments that exceeded the permissible standard threshold: 0.6ng/Nm3 for furnaces with a capacity of 300kg/hour according to QCVN 30:2012/BTNMT.

The missing information of aliphatic-like & aromatic-like Unresolved Complex Mixtures (UCMs) in background oceanic atmosphere: occurrence, identification and deposition

Oceanic air samples (gas + particle phases) were collected over the Shanghai-Arctic background oceanic region during the Chinese Arctic Research expedition 2021. Full scan mode (semi-quantitative) and selective ion monitoring mode (quantitative) were used to analyze separately 72 polycyclic aromatic compounds (PACs) & C11–C35 n-Alkanes (n-Alks) and unresolved complex mixtures (UCMs, including aromatic-like and aliphatic-like compounds) in these samples. The concentration of ΣPACs in the gas-phase and particle-phase were 0.40–8.5 ng m−3 (2.4 ± 1.7 ng m−3) and 0.059–1.1 ng m−3 (0.21 ± 0.23 ng m−3), respectively. While Σn-Alks in the gas-phase and particle-phase were 2.2–80 ng m−3 (mean = 18 ± 24 ng m−3) and 2.2–20 ng m−3 (mean = 8.6 ± 5.0 ng m−3), respectively. The semi-quantitative result indicated that aromatic-like UCMs were 14–1400 times higher than those of ΣPACs in these two phases, while aliphatic-like UCMs were 1.2–25 times higher than those of Σn-Alks. Through three-dimensional identification of the one-dimensional GC-MS chromatogram (with the x-axis representing GC retention time, the y-axis representing m/z, and the z-axis representing peak intensity), we found that aromatic-like UCMs were primarily composed of phenanthrene & anthracene similar PACs, while aliphatic-like UCMs were predominated by long-chain alkanes. The source identification shows that oil-gas leakage was the dominant source of PACs, followed by petroleum & coal combustion and biomass combustion; n-Alks might be mainly originated from anthropogenic sources, while nature sources at high latitudes cannot be ignored as well. Aromatic-like UCMs had a decreasing latitude trend and the presence of 5–6 ring aromatic-like UCMs enclosed within organic aerosols could pose a significant ecological risk, particularly in high latitude regions. Net uptake of atmospheric carbon caused by dry deposition of aromatic-like & aliphatic-like UCMs varied significantly geographically with mid- and low-latitude seas. The non-polar and weakly polar substances were not the major components of organic carbon in oceanic air of high latitude areas.