scholarly journals Quantification of Isomer-Resolved Iodide CIMS Sensitivity and Uncertainty Using a Voltage Scanning Approach

2021 ◽  
Author(s):  
Chenyang Bi ◽  
Jordan E. Krechmer ◽  
Graham O. Frazier ◽  
Wen Xu ◽  
Andrew T. Lambe ◽  
...  
Keyword(s):  
Chemical Ionization ◽  
Maximum Deviation ◽  
Ionization Mass ◽  
Gas Chromatograph ◽  
Elemental Formula ◽  
Flame Ionization ◽  
Order Of Magnitude ◽  
The Individual ◽  
The Relationship ◽  
Voltage Scanning

Abstract. Chemical ionization mass spectrometry (CIMS) using iodide as a reagent ion has been widely used to classify organic compounds in the atmosphere by their elemental formula. Unfortunately, calibration of these instruments is challenging due to a lack of commercially available standards for many compounds, which has led to the development of methods for estimating CIMS sensitivity. By coupling a Thermal desorption Aerosol Gas chromatograph (TAG) simultaneously to a flame ionization detector (FID) and an iodide CIMS, we use the individual particle-phase analytes, quantified by the FID, to examine the sensitivity of the CIMS and its variability between isomers of the same elemental formula. Iodide CIMS sensitivities of isomers within a formula are found to generally vary by one order of magnitude with a maximum deviation of two orders of magnitude. Furthermore, we compare directly measured sensitivity to a method of estimating sensitivity based on declustering voltage (i.e., “voltage scanning”). This approach is found to carry high uncertainties for individual analytes (half to one order of magnitude), but represents a central tendency that can be used to estimate the sum of analytes with reasonable error (~30 % differences between predicted and measured moles). Finally, GC retention time, which is associated with vapor pressure and chemical functionality of an analyte, is found to qualitatively correlate with iodide CIMS sensitivity, but the relationship is not close enough to be quantitatively useful and could be explored further in the future as a potential calibration approach.

scholarly journals Coupling a gas chromatograph simultaneously to a flame ionization detector and chemical ionization mass spectrometer for isomer-resolved measurements of particle-phase organic compounds

2021 ◽  
Vol 14 (5) ◽  
pp. 3895-3907
Author(s):  
Chenyang Bi ◽  
Jordan E. Krechmer ◽  
Graham O. Frazier ◽  
Wen Xu ◽  
Andrew T. Lambe ◽  
...  
Keyword(s):  
Functional Groups ◽  
Organic Compounds ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Flame Ionization Detector ◽  
Ionization Mass ◽  
Particle Phase ◽  
Gas Chromatograph ◽  
Ionization Detector ◽  
Flame Ionization

Abstract. Atmospheric oxidation products of volatile organic compounds consist of thousands of unique chemicals that have distinctly different physical and chemical properties depending on their detailed structures and functional groups. Measurement techniques that can achieve molecular characterizations with details down to functional groups (i.e., isomer-resolved resolution) are consequently necessary to provide understandings of differences of fate and transport within isomers produced in the oxidation process. We demonstrate a new instrument coupling the thermal desorption aerosol gas chromatograph (TAG), which enables the separation of isomers, with the high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS), which has the capability of classifying unknown compounds by their molecular formulas, and the flame ionization detector (FID), which provides a near-universal response to organic compounds. The TAG-CIMS/FID is used to provide isomer-resolved measurements of samples from liquid standard injections and particle-phase organics generated in oxidation flow reactors. By coupling a TAG to a CIMS, the CIMS is enhanced with an additional dimension of information (resolution of individual molecules) at the cost of time resolution (i.e., one sample per hour instead of per minute). We found that isomers are prevalent in sample matrix with an average number of three to five isomers per formula depending on the precursors in the oxidation experiments. Additionally, a multi-reagent ionization mode is investigated in which both zero air and iodide are introduced as reagent ions, to examine the feasibility of extending the use of an individual CIMS to a broader range of analytes with still selective reagent ions. While this approach reduces iodide-adduct ions by a factor of 2, [M − H]− and [M + O2]− ions produced from lower-polarity compounds increase by a factor of 5 to 10, improving their detection by CIMS. The method expands the range of detected chemical species by using two chemical ionization reagents simultaneously, which is enabled by the pre-separation of analyte molecules before ionization.

scholarly journals Development of a photochemical source for the production and calibration of acyl peroxynitrate compounds

2015 ◽  
Vol 8 (5) ◽  
pp. 2225-2231 ◽  
Author(s):  
P. R. Veres ◽  
J. M. Roberts
Keyword(s):  
Dynamic System ◽  
Mass Spectroscopy ◽  
Chemical Ionization ◽  
Acyl Chloride ◽  
Ionization Mass ◽  
Gas Chromatograph ◽  
Iodide Ion ◽  
Ionization Mass Spectroscopy ◽  
Subsequent Separation ◽  
Standard Production

Abstract. A dynamic system for the calibration of acyl peroxynitrate compounds (APNs) has been developed in the laboratory to reduce the difficulty, required time, and instability of laboratory-produced standards for difficult-to-synthesize APN species. In this work we present a photochemical source for the generation of APN standards: acetyl peroxynitrate (PAN), propionyl peroxynitrate (PPN), acryloyl peroxynitrate (APAN), methacryloyl peroxynitrate (MPAN), and crotonyl peroxynitrate (CPAN). APNs are generated via photolysis of a mixture of acyl chloride (RC(O)Cl) and ketone (RC(=O)R) precursor compounds in the presence of O2 and NO2. Subsequent separation by a prep-scale gas chromatograph and detection with a total NOy instrument serve to quantify the output of the APN source. Validation of the APN products was performed using iodide ion chemical ionization mass spectroscopy (I- CIMS). This method of standard production is an efficient and accurate technique for the calibration of instrumentation used to measure PAN, PPN, APAN, MPAN, and CPAN.

scholarly journals Correcting Bias in Log-Linear Instrument Calibrations in the Context of Chemical Ionization Mass Spectrometry

2021 ◽  
Author(s):  
Chenyang Bi ◽  
Jordan E. Krechmer ◽  
Manjula R. Canagaratna ◽  
Gabriel Isaacman-VanWertz
Keyword(s):  
Chemical Ionization ◽  
Correction Method ◽  
Operating Conditions ◽  
Oxidation Products ◽  
Mathematical Work ◽  
Ionization Mass ◽  
Individual Compound ◽  
Linear Calibration ◽  
Order Of Magnitude ◽  
Log Linear

Abstract. Quantitative calibration of analytes using chemical ionization mass spectrometers (CIMS) has been hindered by the lack of commercially available standards of atmospheric oxidation products. To accurately calibrate analytes without standards, techniques have been recently developed to log-linearly correlate analyte sensitivity with instrument operating conditions. However, there is an inherent bias when applying log-linear calibration relationships that is typically ignored. In this study, we examine the bias in a log-linear based calibration curve based on prior mathematical work. We quantify the potential bias within the context of a CIMS-relevant relationship between analyte sensitivity and instrument voltage differentials. Uncertainty in three parameters has the potential to contribute to the bias, specifically the inherent extent to which the nominal relationship can capture true sensitivity, the slope of the relationship, and the voltage differential below which maximum sensitivity is achieved. Using a prior published case study, we estimate an average bias of 30%, with one order of magnitude for less sensitive compounds in some circumstances. A parameter-explicit solution is proposed in this work for completely removing the inherent bias generated in the log-linear calibration relationships. A simplified correction method is also suggested for cases where a comprehensive bias correction is not possible due to unknown uncertainties of calibration parameters, which is shown to eliminate the bias on average but not for each individual compound.

scholarly journals Correcting bias in log-linear instrument calibrations in the context of chemical ionization mass spectrometry

2021 ◽  
Vol 14 (10) ◽  
pp. 6551-6560
Author(s):  
Chenyang Bi ◽  
Jordan E. Krechmer ◽  
Manjula R. Canagaratna ◽  
Gabriel Isaacman-VanWertz
Keyword(s):  
Chemical Ionization ◽  
Correction Method ◽  
Operating Conditions ◽  
Oxidation Products ◽  
Mathematical Work ◽  
Ionization Mass ◽  
Individual Compound ◽  
Linear Calibration ◽  
Order Of Magnitude ◽  
Log Linear

Abstract. Quantitative calibration of analytes using chemical ionization mass spectrometers (CIMSs) has been hindered by the lack of commercially available standards of atmospheric oxidation products. To accurately calibrate analytes without standards, techniques have been recently developed to log-linearly correlate analyte sensitivity with instrument operating conditions. However, there is an inherent bias when applying log-linear calibration relationships that is typically ignored. In this study, we examine the bias in a log-linear-based calibration curve based on prior mathematical work. We quantify the potential bias within the context of a CIMS-relevant relationship between analyte sensitivity and instrument voltage differentials. Uncertainty in three parameters has the potential to contribute to the bias, specifically the inherent extent to which the nominal relationship can capture true sensitivity, the slope of the relationship, and the voltage differential below which maximum sensitivity is achieved. Using a prior published case study, we estimate an average bias of 30 %, with 1 order of magnitude for less sensitive compounds in some circumstances. A parameter-explicit solution is proposed in this work for completely removing the inherent bias generated in the log-linear calibration relationships. A simplified correction method is also suggested for cases where a comprehensive bias correction is not possible due to unknown uncertainties of calibration parameters, which is shown to eliminate the bias on average but not for each individual compound.

Quantitation of Polychlorinated Biphenyl Residues by Electron Capture Gas-Liquid Chromatography: Reference Material Characterization and Preliminary Study

1978 ◽  
Vol 61 (2) ◽  
pp. 272-281
Author(s):  
Leon D Sawyer
Keyword(s):  
Electron Capture ◽  
Material Characterization ◽  
Chemical Ionization ◽  
Polychlorinated Biphenyl ◽  
Collaborative Study ◽  
Gas Liquid Chromatography ◽  
Ionization Mass ◽  
Preliminary Study ◽  
The Individual ◽  
Liquid Chromatographic

Abstract Weight per cent compositions of individual peaks of Aroclors 1016, 1242, 1248, 1254, and 1260 were determined under standard gas-liquid chromatographic (GLC) conditions. The GLC peak compositions were determined by using a Hall electrolytic conductivity detector for chlorine measurement and chemical ionization mass spectrometry with single ion monitoring for molecular weight characterization. The Aroclors used are available as reference materials for individual peak quantitation of polychlorinated biphenyl (PCB) residues by electron capture GLC. On the basis of a limited interlaboratory study and a collaborative study, the individual peak method shows improved interlaboratory precision and/or accuracy in PCB quantitation over existing methods.

scholarly journals Coupling a gas chromatograph simultaneously to a flame ionization detector and chemical ionization mass spectrometer for isomer-resolved measurements of particle-phase organic compounds

2020 ◽  
Author(s):  
Chenyang Bi ◽  
Jordan E. Krechmer ◽  
Graham O. Frazier ◽  
Wen Xu ◽  
Andrew T. Lambe ◽  
...  
Keyword(s):  
Functional Groups ◽  
Organic Compounds ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Measurement Techniques ◽  
Oxidation Products ◽  
Ionization Mass ◽  
Particle Phase ◽  
Gas Chromatograph ◽  
New Instrument

Abstract. Atmospheric oxidation products of volatile organic compounds consist of thousands of unique chemicals that have distinctly different physical and chemical properties depending on their detailed structures and functional groups. Measurement techniques that can achieve molecular characterizations with details down to functional groups (i.e., isomer-resolved resolution) are consequently necessary to provide understandings of differences of fate and transport within isomers produced in the oxidation process. We demonstrate a new instrument coupling the thermal desorption aerosol gas chromatograph (TAG), which enables the separation of isomers, with the high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS), which has the capability of classifying unknown compounds by their molecular formulas, and the flame ion detector (FID), which provide a near-universal response to organic compounds. The TAG-CIMS/FID is used to provide isomer-resolved measurements of samples from liquid standard injections and particle-phase organics generated in oxidation flow reactors. By coupling a TAG to a CIMS, the CIMS is enhanced with an additional dimension of information (resolution of individual molecules) at the cost of time resolution (i.e., one sample per hour instead of per minute). We found that isomers are prevalent in sample matrix with an average number of three to five isomers per formula depending on the precursors in the oxidation experiments. Additionally, a multi-reagent ionization mode is investigated in which both zero air and iodide are introduced as reagent ions, to examine the feasibility of extending the use of an individual CIMS to a broader range of analytes with still selective reagent ions. While this approach reduces iodide-adduct ions by a factor of two, [M−H]− and [M+O2]− ions produced from lower-polarity compounds increase by a factor of five to ten, improving their detection by CIMS. The method expands the range of detected chemical species by using two chemical ionization reagents simultaneously, enabled by the pre-separation of analyte molecules before ionization.

Multiresidue Screening by Negative Chemical Ionization Mass Spectrometry of Organic Polychlorides

1976 ◽  
Vol 59 (5) ◽  
pp. 1023-1027
Author(s):  
Ralph C Dougherty ◽  
Krystyna Piotrowska
Keyword(s):  
Mass Spectrometry ◽  
Chemical Ionization ◽  
Gel Permeation Chromatography ◽  
Ionization Mass Spectrometry ◽  
Chemical Ionization Mass Spectrometry ◽  
Ionization Mass ◽  
Negative Chemical Ionization ◽  
Gel Permeation ◽  
Order Of Magnitude ◽  
Nci Analysis

Abstract A multiresidue procedure, based on negative chemical ionization (NCI) mass spectrometry, for analyzing organochlorine residues in environmental substrates is described. The procedure is capable of routinely detecting about 1 ng unknown organochlorine residues. Semiquantitative data (order of magnitude) may be obtained for pentachlorophenol and 2,4,5-trichlorophenoxyacetic acid residues by calibration with internal p-chlorobenzophenone. Lipid-rich substrates were resolved into acidic and neutral fractions, and both fractions were further purified by gel permeation chromatography (GPC) prior to NCI analysis. In spite of the fact that recoveries were often low, the overall sensitivity for residues in lipid-rich substrates appeared to be higher than when the GPC step was omitted.

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