Quantitative Hydrogen Chloride Detection in Combustion Environments Using Tunable Diode Laser Absorption Spectroscopy with Comprehensive Investigation of Hot Water Interference

Hydrogen chloride (HCl) monitoring during combustion/gasification of biomass fuels and municipal solid waste, such as polyvinyl chloride (PVC) and food residues, is demanded to avoid the adverse effect of HCl to furnace operation and to improve the quality of the gas products. Infrared tunable diode laser absorption spectroscopy (IR-TDLAS) is a feasible nonintrusive in-situ method for HCl measurements in harsh environments. In the present work, the measurement was performed using the R(3) line of the ν2 vibrational band of HCl at 5739.25 cm–1 (1742.4 nm). Water vapor is ubiquitous in combustion/gasification environments, and its spectral interference is one of the most common challenges for IR-TDLAS. Spectral analysis based on the current well-known databases was found to be insufficient to achieve an accurate measurement. The lack of accurate temperature-dependent water spectra can introduce thousands parts per million (ppm) HCl overestimation. For the first time, accurate spectroscopic data of temperature-dependent water spectra near 5739.3 cm–1 were obtained based on a systematic experimental investigation of the hot water lines in a well-controlled, hot flue gas with a temperature varying from 1100 to 1950 K. With the accurate knowledge of hot water interference, the HCl TDLAS system can achieve a detection limit of about 100 ppm⋅m at around 1500 K, and simultaneously the gas temperature can be derived. The technique was applied to measure the temporally resolved HCl release and local temperature over burning PVC particles in hot flue gas at 1790 K.

Comparison of airborne measurements of NO, NO₂, HONO, NO_y and CO during FIREX-AQ

We present a comparison of fast-response instruments installed onboard the NASA DC-8 aircraft that measured nitrogen oxides (NO and NO2), nitrous acid (HONO), total reactive odd nitrogen (measured both as the total (NOy) and from the sum of individually measured species (SNOy)) and carbon monoxide (CO) in the troposphere during the 2019 Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) campaign. By targeting smoke from summertime wildfires, prescribed fires and agricultural burns across the continental United States, FIREX-AQ provided a unique opportunity to investigate measurement accuracy in concentrated plumes where hundreds of species coexist. Here, we compare NO measurements by chemiluminescence (CL) and laser induced fluorescence (LIF); NO2 measurements by CL, LIF and cavity enhanced spectroscopy (CES); HONO measurements by CES and iodide-adduct chemical ionization mass spectrometry (CIMS); and CO measurements by tunable diode laser absorption spectrometry (TDLAS) and integrated cavity output spectroscopy (ICOS). Additionally, total NOy measurements using the CL instrument were compared with SNOy (= NO + NO2 + HONO + nitric acid (HNO3) + acyl peroxy nitrates (APNs) + submicron particulate nitrate (pNO3)). The aircraft instrument intercomparisons demonstrate the following: 1) NO measurements by CL and LIF agreed well within instrument uncertainties, but with potentially reduced time response for the CL instrument; 2) NO2 measurements by LIF and CES agreed well within instrument uncertainties, but CL NO2 was on average 10 % higher; 3) CES and CIMS HONO measurements were highly correlated in each fire plume transect, but the correlation slope of CES vs. CIMS for all 1 Hz data during FIREX-AQ was 1.8, which we attribute to a reduction in the CIMS sensitivity to HONO in high temperature environments; 4) NOy budget closure was demonstrated for all flights within the combined instrument uncertainties of 25 %. However, we used a fluid dynamic flow model to estimate that average pNO3 sampling fraction through the NOy inlet in smoke was variable from one flight to another and ranged between 0.36 and 0.99, meaning that approximately 0–24 % on average of the total measured NOy in smoke may have been unaccounted for and may be due to unmeasured species such as organic nitrates; 5) CO measurements by ICOS and TDLAS agreed well within combined instrument uncertainties, but with a systematic offset that averaged 2.87 ppbv; and 6) integrating smoke plumes followed by fitting the integrated values of each plume improved the correlation between independent measurements.

A simulation process of tunable open path diode laser spectrometer to detect a carbon monoxide gas in NIR region

By modifying the wavelength of the open path tunable diode laser spectrometer (TDLS) in the near infrared region, theoretical research was implemented to improve the detection limit of carbon monoxide gas. To adjust the correct wavelength in the NIR area, MatLab code was created. Following that, frequency domain measurements were performed in order to extract the second harmonic as an indicator of gas presence. According to the results, the correct wave length in the NIR area is (1584.877 nm), and the lowest limit of CO gas concentration is (0.012 ppb).

Emission Determination by Three Remote Sensing Methods in Two Release Trials

Concentrations of greenhouse gases such as carbon dioxide (CO2), nitrous dioxide (N2O) and methane (CH4) in the atmosphere are rising continuously. The first step to reduce emissions from landfills is to gain better knowledge about the quantities emitted. There are several ways to quantify CH4 emissions at landfills. Comprehensive quality analyses of individual methods for emission rate quantification at landfills are few to date. In the present paper, the authors conducted two field trials with three different remote sensing methods to gain more knowledge about the possibilities and challenges in quantification of CH4 emissions from landfills. One release trial was conducted with released N2O as tracer and CH4 for quality assessment of the methods. In the second trial, the N2O tracer was released on a landfill to gain experience under field conditions. The well-established inverse dispersion modelling method (IDMM) was used based on concentration data of TDLAS (Tunable Diode Laser Absorption Spectroscopy)-instruments and on concentration data of a partly drone based Fourier-Transformation-Infrared-Spectroscopy (FTIR)-instrument. Additionally, a tracer-method with N2O-tracer and FTIR measurements was conducted. In both trials, IDMM based on TDLAS data and FTIR data provided the best results for high emission rates (15% deviation) and low emission rates (47% deviation). However, both methods have advantages, depending on the field of application. IDMM based on TDLAS measurements is the best choice for long-term measurements over several hours with constant wind conditions (8% deviation). The IDMM based on drone based FTIR measurements is the means of choice for measurements under changing wind conditions and where no linear measurement distances are possible.

Development of an Online Detection Setup for Dissolved Gas in Transformer Insulating Oil

The type and concentration of dissolved gases in transformer insulating oil are used to assess transformer conditions. In this paper, an online detection setup for measuring the concentration of multicomponent gases dissolved in transformer insulating oil is developed, which consists of an oil-gas separation system and an optical system for acquiring the transformer status in real time. The oil-gas separation system uses low pressure, constant temperature, and low-frequency stirring as working conditions for degassing large-volume oil samples based on modified headspace degassing. The optical system uses tunable diode laser absorption spectroscopy (TDLAS) to determine the gas concentration. Six target gases (methane, ethylene, ethane, acetylene, carbon monoxide, and carbon dioxide) were detected by three near-infrared lasers (1569, 1684, and 1532 nm). The stability of the optical system was improved by the common optical path formed by time-division multiplexing (TDM) technology. The calibration experiments show that the second harmonics and the concentrations of the six gases are linear. A comparison experiment with gas chromatography (GC) demonstrates that the error of acetylene reaches the nL/L level, while the other gases reach the μL/L level. The data conforms to the power industry testing standards, and the state of the transformer is analyzed by the detected six characteristic gases. The setup provides an effective basis for the online detection of dissolved gas in transformer insulating oil.

Das ACTRIS-Kalibrierzentrum für Stickoxid-Messungen am Forschungszentrum Jülich

<p>Langzeitmessungen der atmosphärischen Zusammensetzung sind von zentraler Bedeutung, um die Atmosphärenchemie und den Klimawandel zu verstehen. ACTRIS (Aerosol, Cloud and Trace Gases Research Infrastructure) hat sich zum Ziel gesetzt, ein europaweites Netzwerk von Beobachtungsstationen aufzubauen, die qualitativ hochwertige Daten und Informationen zu kurzlebigen atmosphärischen Bestandteilen liefern und für Nutzer auf der ganzen Welt offen zugänglich machen. Stickstoffmonoxid (NO) und Stickstoffdioxid (NO<sub>2</sub>), die sogenannten Stickoxide (NO<sub>x</sub>), spielen eine Schlüsselrolle in der Atmosphärenchemie, da sie zur Bildung von troposphärischem Ozon, Smog und saurem Regen beitragen. Darüber hinaus ist die kurz- und langfristige Exposition mit NO<sub>2</sub> mit negativen Auswirkungen auf das menschliche Atmungssystem in Verbindung gebracht worden. Die Hauptquellen von NO<sub>x</sub> in bewohnten Gebieten sind Verbrennungsprozesse, z.B. von Fahrzeugen und bei industriellen Aktivitäten. NO<sub>x</sub>-Messungen werden derzeit meist indirekt über Chemilumineszenz-Instrumente durchgeführt, die Korrekturen für Feuchte und Ozon erfordern. Jüngste technologische Fortschritte (z. B. Cavity Attenuated Phase Shift, CAPS, oder Tunable Diode Laser Systeme) erlauben die direkte Detektion von NO<sub>x</sub>-Komponenten, was Interferenzen vermeidet, die durch die Umwandlung von NO<sub>2</sub> in NO hervorgerufen werden. Messvergleiche zeigen aber, dass auch hier neben bekannten Problemen wie Reaktionen in den Einlassleitungen auch unerwartete Artefakte beobachtet werden können. Messvergleiche aber zeigen auch hier, dass neben bekannten Problemen wie Reaktionen in den Einlassleitungen auch unerwartete auftreten können. Um genaue und präzise NO<sub>x</sub> Messungen mit einer Vielzahl von NO<sub>x</sub>-Messsystemen in verschiedenen Stationen sicherzustellen, müssen neben der Standardisierung von Messprotokollen und Kalibrierungsverfahren auch an zentraler Stelle durch Messvergleiche und Auditierungen Unterschiede der verschiedenen Messverfahren dokumentiert werden.</p> <p>ACTRIS setzt sich aus central facilities (CFs) und national facilities (NFs) zusammen. Die NFs bilden den explorativen und beobachtenden Teil der Forschungsinfrastruktur. Die CFs sind von grundlegender Bedeutung für die Bereitstellung von harmonisierten und hochpräzisen Daten und stellen eine Vielzahl von Dienstleistungen zur Verfügung. Eines der CFs ist das Reactive Trace Gases In Situ Measurements (CiGas), das für die Überwachung der Datenqualität reaktiver Spurengase verantwortlich ist. Für die Qualitätssicherung (QA) und Qualitätskontrolle (QC) der Stickoxidmessungen an den NFs innerhalb von CiGas ist das Forschungszentrum Jülich (FZJ) zuständig, das auch das World Calibration Center (WCC) für Stickoxide im Global Atmosphere Watch (GAW) Netzwerk beheimatet. Seine Aufgaben umfassen i) die Verbindung von Spurengasmessungen von ACTRIS mit denen anderer Netzwerke, ii) die Beratung und Organisation von Schulungen, iii) die Bereitstellung von Mess- und Auswerteverfahren, iv) das Labelling und die Auditierung von NFs, v) die Implementierung neuer wissenschaftlicher und technologischer Entwicklungen.</p> <p>Es ist vorgesehen, bis 2025 ein zertifiziertes und funktionsfähiges Netzwerk von ACTRIS-Stationen aufzubauen. Es soll der wissenschaftlichen Gemeinschaft qualitativ hochwertige Daten liefern, die die Grundlage für fundierte Entscheidungen der politischen Entscheidungsträger bilden können.</p>