Pressure Chemical Ionization Mass Research Articles

Temperature dependent stochastic dynamics mass spectrometric analysis of configurationally locked polyenes

This paper derived relation between mass spectrometric variable intensity of analyte peaks and three-dimensional molecular structures of ions toward temperature utilising innovative stochastic dynamics equations, which provide exact analyte quantification and 3D structural analysis and are attractive formulas for modelling of mass spectrometric phenomena. The same equations are opened to develop new relations accounting for temperature; thus, providing argumentation about temperature dependent variables. High-temperature measurement of vapours are important tool, amongst others and use the Arrhenius’s plot. However, there is a variation between experimental and theoretical linear correlation toward temperature; thus, highlighting soft ionisation methods showing significant standard deviations. It could be explained with temperature perturbation of charge values. Descriptive models, so far, provide semi-quantification. This study, first shows validity of new functional model. Straightforwardly, its empirical proof is obtained determining 3D structurally protomers and isotopomers of configurationally locked polyenes via ultra-high resolution electrospray ionization and atmospheric pressure chemical ionization mass spectrometry within the temperature range T=300-450°C. There are used high accuracy quantum chemical static methods, molecular dynamics and chemometrics. There are excellent method performances (|r|=0.99978). The tool could be regarded as an actually honest alternative of available theoretical models.

The role of water in APCI-MS online monitoring of gaseous n-alkanes

In atmospheric pressure chemical ionization mass spectrometry (APCI-MS), [M−3H+H2O]+ ions can deliver analyte-specific signals that enable direct analysis of volatile n-alkane mixtures. The underlying ionization mechanisms have been the subject of open debate, and in particular the role of water is insufficiently clarified to allow for reliable process analytics when the humidity level changes over time. This can be a problem, particularly in online monitoring, where analyte accumulation in the ion source can also occur. Here, we investigated the role of water during APCI-MS of volatile n-alkanes by changing the carrier gas for sample injection from a dry to a wetted state as well as by using 18O-labeled water. This allowed for a distinction between gaseous and surface-adsorbed water molecules. While adsorbed water seems to be responsible for the desired [M−3H+H2O]+ signals through surface reactions with the analyte molecules, gaseous water was found to promote the formation of CnH2n+1O+ of different (and analyte-independent) hydrocarbons, revealing a reaction with hydrocarbon species which accumulated in the ion source during continuous operation. At the same time, gaseous water competed with analyte molecules for ionization and thus suppressed the formation of alkyl (CnH2n+1+) and alkenyl (CnH2n−1+) ions. The results reveal a memory effect due to hydrocarbon adsorption, which may cause severe interpretation difficulties when the ionization chamber undergoes sudden humidity changes. The use of [M−3H+H2O]+ for n-alkane analysis in alkane/water mixtures can be facilitated by constantly maintaining high humidity and hence stabilizing the ionization conditions.Graphical abstract

Heavy Water Microdroplet Surface Enriches the Lighter Isotopologue Impurities.

Water microdroplets promote unusual chemical reactions at the air-water interface. However, the interfacial structure of water microdroplets and its potential influence on chemical processes are still enigmatic. Here, we present evidence of in-droplet fractionation of water isotopologues. Employing a sonic spray, we atomized the heavy water (D2O, 99.9 atom % D) solution of three classes of organic compounds (basic, acidic, and neutral). The analytes were predominantly desorbed from the resulting droplet surface in protonated form rather than deuterated form, as detected by mass spectrometry. This result remained unaltered upon adding formic acid-d2 (DCOOD) to the droplet. Monitoring Dakin oxidation of benzaldehyde at the surface of binary microdroplets composed of 1:1 (v/v) D2O/H218O revealed the preferred formation of phenolate-16O over phenolate-18O. Atmospheric pressure chemical ionization mass spectrometric analysis of the vapor composition in the sprayed aerosol revealed the preferential evaporation of lighter water isotopologue impurities from the surface of heavy water microdroplets. These results indicate the enrichment of lighter water isotopologue impurities (HOD/H2O) on the surface of heavy water microdroplets, implying possible future developments for water isotopologue fractionation using microdroplets.

Nanoelectrode Atmospheric Pressure Chemical Ionization Mass Spectrometry.

A small ionization needle with an ultrasharp, ultrafine tip is introduced. It is lab-fabricated from tungsten wire and serves as a corona discharge emitter in nanoelectrode atmospheric pressure chemical ionization mass spectrometry (nAPCI-MS). Tip radii ranged from 8 to 44 nm, up to 44× smaller than the sharpest previously reported corona needle. Because of this, nAPCI was able to operate at +1.0 kV with no auxiliary counter electrode. Alternatively, at +1.2 kV, nAPCI could be enclosed in a small plastic assembly for headspace analysis with a sampling tube attachment as long as 15 m. No added heat or gas flow was necessary. The efficacy of nAPCI-MS was demonstrated through needle durability studies and direct analysis of vapors from real-world samples. Provisional identifications include ibuprofen from a pharmaceutical tablet, albuterol aerosol sprayed from a medical inhaler, cocaine from paper currency, caffeine from a fingertip, and bisphenol E from a paper receipt.

On-site monitoring of nandrolone in cattle farming samples by portable atmospheric pressure chemical ionization mass spectrometry with ambient sampling

Nandrolone (NT) is a type of androgen anabolic steroid that is often illegally used in cattle farming, leading to unpredictable harm to human health via the food chain. In this study, a rapid detection method for NT in the samples of cattle farming was established using a portable mass spectrometer. The instrument parameters were optimized, including a thermal desorption temperature of 220 °C, a pump speed of 30 %, an APCI ionization voltage of 3900 v, and an injection volume of 6 μL. The samples of bovine urine, feed, sewage, and tissue were selected, and extracted using a solution of methanol:acetonitrile (1:1, v/v), followed by spiking a NT standard solution (1000 ng·mL−1) and ionization through the APCI ion source for detection. The results showed that NT could not be detected in beef and feed due to the complexity of the matrix, while clear signals of NT ions were observed in bovine urine and sewage samples, with LODs of 1000 and 100 ng·mL−1, respectively. Furthermore, quantitative analysis was attempted, and a good linear relationship (R2 = 0.9952) was observed for NT in sewage within the range of 100 to 1000 ng·mL−1. At spiked levels of 100, 500, 1000 and 2000 ng mL−1, the recovery rates ranged from 74.3 % to 92.8 %, with a relative standard deviation (n = 6) of less than 15 %. In conclusion, this detection method offers the advantages of simplicity, rapidity, strong timeliness, and specificity, making it suitable for on-site detection. It can be used for qualitative screening of nandrolone in bovine urine and quantitative analysis of nandrolone in sewage.

Rapid online analysis of n-alkanes in gaseous streams via APCI mass spectrometry.

Online monitoring of dynamic chemical processes involving a wide volatility range of hydrocarbon species is challenging due to long chromatographic measurement times. Mass spectrometry (MS) overcomes chromatographic delays. However, the analysis of n-alkane mixtures by MS is difficult because many fragment ions are formed, which leads to overlapping signals of the homologous series. Atmospheric pressure chemical ionization (APCI) is suitable for the analysis of saturated hydrocarbons and is the subject of current research. Still, although APCI is a "soft ionization" technique, fragmentation is typically inevitable. Moreover, it is usually applied for liquid samples, while an application for online gas-phase monitoring is widely unexplored. Here, we present an automated APCI-MS method for an online gas-phase analysis of volatile and semi-volatile n-alkanes. Mass spectra for n-heptane and n-decane reveal [M-H]+, [M-3H]+ and [M-3H+H2O]+ as abundant ions. While [M-H]+ and [M-3H]+ show an excessive fragmentation pattern to smaller CnH2n+1+ and CnH2n-1+ cations, [M-3H+H2O]+ is the only relevant signal within the CnH2n+1O+ ion group, i.e., no chain cleavage is observed. This makes [M-3H+H2O]+ an analyte-specific ion that is suitable for the quantification of n-alkane mixtures. A calibration confirms the linearity of C7 and C10 signals up to concentrations of ~1000-1500 ppm. Moreover, validated concentration profiles are measured for a binary C7/C10 mixture and a five-alkane C7/C10/C12/C14/C20 mixture. Compared to the 40-min sampling interval of the reference gas chromatograph, MS sampling is performed within 5 min and allows dynamic changesto be monitored.

Selective Characterization of Olefins by Paternò-Büchi Reaction with Ultrahigh Resolution Mass Spectrometry.

Petroleum olefins play important roles in various secondary processing procedures and are important feedstocks for the modern organic chemical industry. It is quite challenging to analyze petroleum olefins beyond the gas chromatography (GC)-able range using mass spectrometry (MS) due to the difficulty of soft ionization and the matrix complexity. In this work, a Paternò-Büchi (PB) reaction combined with atmospheric pressure chemical ionization and ultrahigh resolution mass spectrometry (APCI-UHRMS) was developed for selective analysis of olefins. Through the PB reaction, C═C bonds were transformed into four-membered rings of oxetane with improved polarity so that soft ionization of olefins could be achieved. The systematic optimization of PB reaction conditions, as well as MS ionization conditions, ensured a high reaction yield and a satisfied MS response. Furthermore, a sound scheme was set up to discriminate the coexisting unsaturated alkanes in complex petroleum, including linear olefins, nonlinear olefins, cycloalkanes, and aromatics, making use of their different behaviors during the PB reaction and chemical ionization. The developed strategy was successfully applied to the analysis of olefins in fluid catalytic cracking oil slurry, a complex heavy oil sample. This method extended the characterization of petroleum olefins from lower to higher with high efficiency and selectivity to provide a comprehensive molecular library for heavy petroleum samples and process optimization.

TLC and HPTLC-APCI-MS for the rapid discrimination of plant resins frequently used for lacquers and varnishes by artists and conservators.

Depending on their terpenoid and phenolic constituents plant resins can be classified as diterpenoid, triterpenoid or phenolic resins; thereby the profile of diterpenes and triterpenes is considered as genus- or even species-specific. We aimed to develop a simple, rapid, inexpensive, sensitive and specific method for the identification of resin-specific triterpenoid and phenolic compounds in plant resins using (HP)TLC [(high-performance) thin-layer chromatography] combined with APCI-MS (atmospheric pressure chemical ionisation mass spectrometry) and post-chromatographic detection reactions. Twenty resin samples from different plant species were analysed. Different extraction procedures, post-chromatographic detection reagents as well as various sorbents and solvents for planar chromatography were tested. To evaluate the potential of the optimised (HP)TLC-APCI-MS methods, parameter such as limit of detection (LOD) was determined for selected marker compounds. Our protocol enabled qualitative analyses of chemotaxonomic molecular markers in natural resins such as dammar, mastic, olibanum and benzoin. For the first time, the application of thionyl chloride-stannic chloride reagent for a specific post-chromatographic detection of triterpenes is reported, sometimes even allowing discrimination between isomers based on their characteristic colour sequences. For triterpene acids, triterpene alcohols and phenolic compounds, detection limits of 2-20ng/TLC zone and a system precision with a relative standard deviation (RSD) in the range of 3.9%-7.0% were achieved by (HP)TLC-APCI-MS. The applicability of the method for the analysis of resin-based varnishes was successfully tested on a mastic-based varnish. Thus, the method we propose is a helpful tool for the discrimination of resins and resin-based varnishes with respect to their botanical origin.

Determination of astaxanthin and astaxanthin esters in three samples of shrimp waste (Parapenaeus longirostris) by high performance liquid chromatography coupled photo-diode array and mass spectrometry detection

The present study aimed to identify the content of astaxanthin and its esterified forms using high-performance liquid chromatography coupled with diode array and atmospheric pressure chemical ionisation mass spectrometry detection in three samples of shrimp waste. The analyses revealed twenty-one astaxanthin derivatives, including astaxanthin in free form, across all three extracts with the highest number of derivatives observed in the head extract. The shell extract had a lower content of astaxanthin and its esterified forms, with monoesterified astaxanthins being the major components, with contents ranging from 0.5–1 mg g−1. On the other hand, in both global waste and head extracts, astaxanthin diesters were found to be the dominant bioactive compounds, with contents ranging from 0.7–5.2 mg g−1 and 10.2–18.2 mg g−1, respectively. Notably, the astaxanthin content extracted from head was significantly higher compared to other extracts, indicating its potential as a valuable source of bioactive compounds.

Determination of the Pesticides Ethoprophos and Atrazine in Water by T-Shaped Atmospheric Pressure Chemical Ionization (APCI) Mass Spectrometry (MS)

With the goal of enhancing the low sensitivity of the conventional atmospheric pressure chemical ionization (APCI) source due to the ion divergence, here is reported a T-shaped ion source to improve the sensitivity with a portable mass spectrometer for the rapid determination of the pesticides ethoprophos and atrazine in water. Compared with conventional APCI, the ion source improves the sensitivity for the analytes. The results show that the analysis requires less than 2 s, the limit of detection (LOD) is better than 0.1 and the relative standard deviation (RSD) is 16% at 1, 5, and 25 The recoveries of the analytes are between 80% and 130%, meeting the requirements for rapid pesticide determination in water.

Silver Ion High-Performance Liquid Chromatography-Atmospheric Pressure Chemical Ionization Mass Spectrometry: A Tool for Analyzing Cuticular Hydrocarbons.

Aliphatic hydrocarbons (HCs) are usually analyzed by gas chromatography (GC) or matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. However, analyzing long-chain HCs by GC is difficult because of their low volatility and the risk of decomposition at high temperatures. MALDI cannot distinguish between isomeric HCs. An alternative approach based on silver ion high-performance liquid chromatography (Ag-HPLC) is shown here. The separation of HC standards and cuticular HCs was accomplished using two ChromSpher Lipids columns connected in series. A gradient elution of the analytes was optimized using mobile phases prepared from hexane (or isooctane) and acetonitrile, 2-propanol, or toluene. HCs were detected by atmospheric pressure chemical ionization mass spectrometry (APCI-MS). Good separation of the analytes according to the number of double bonds, cis/trans geometry, and position of double bonds was achieved. The retention times increased with the number of double bonds, and trans isomers eluted ahead of cis isomers. The mobile phase significantly affected the mass spectra of HCs. Depending on the mobile phase composition, deprotonated molecules, molecular ions, protonated molecules, and various solvent-related adducts of HCs were observed. The optimized Ag-HPLC/APCI-MS was applied for characterizing cuticular HCs from a flesh fly, Neobellieria bullata, and cockroach, Periplaneta americana. The method made it possible to detect a significantly higher number of HCs than previously reported for GC or MALDI-MS. Unsaturated HCs were frequently detected as isomers differing by double-bond position(s). Minor HCs with trans double bonds were found beside the prevailing cis isomers. Ag-HPLC/APCI-MS has great potential to become a new tool in chemical ecology for studying cuticular HCs.

Positive Effect of Acetylation on Proteomic Analysis Based on Liquid Chromatography with Atmospheric Pressure Chemical Ionization and Photoionization Mass Spectrometry.

A typical bottom-up proteomic workflow comprises sample digestion with trypsin, separation of the hydrolysate using reversed-phase HPLC, and detection of peptides via electrospray ionization (ESI) tandem mass spectrometry. Despite the advantages and wide usage of protein identification and quantification, the procedure has limitations. Some domains or parts of the proteins may remain inadequately described due to inefficient detection of certain peptides. This study presents an alternative approach based on sample acetylation and mass spectrometry with atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI). These ionizations allowed for improved detection of acetylated peptides obtained via chymotrypsin or glutamyl peptidase I (Glu-C) digestion. APCI and APPI spectra of acetylated peptides often provided sequence information already at the full scan level, while fragmentation spectra of protonated molecules and sodium adducts were easy to interpret. As demonstrated for bovine serum albumin, acetylation improved proteomic analysis. Compared to ESI, gas-phase ionizations APCI and APPI made it possible to detect more peptides and provide better sequence coverages in most cases. Importantly, APCI and APPI detected many peptides which passed unnoticed in the ESI source. Therefore, analytical methods based on chymotrypsin or Glu-C digestion, acetylation, and APPI or APCI provide data complementary to classical bottom-up proteomics.

Constraining the Reaction Rate of Criegee Intermediates with Carboxylic Acids during the Multiphase Ozonolysis of Aerosolized Alkenes

Criegee intermediates (CIs) are central to the ozonolysis of unsaturated organic compounds, controlling the formation of small fragmentation reaction products and higher molecular weight oligomeric compounds through competing unimolecular and bimolecular pathways. In particular, the reaction of thermalized CI with carboxylic acids (RCOOH) to produce oligomeric α-acyloxyalkyl hydroperoxides (AAHPs) is of interest to the chemical transformation of organic compounds in the atmosphere. In the gas phase, the CI + RCOOH reaction proceeds at supercollisional rates, consistent with a barrierless reaction mechanism. However, the rate of this reaction in condensed phases remains uncertain. Here, we report the results of aerosol flow tube studies of the ozonolysis of submicron organic aerosol containing mixtures of an internal n-alkene (Z-9-tricosene, tri) and a saturated acid (2-hexyldecanoic acid, HDA). The decay of the reactants and formation of reaction products are monitored using atmospheric pressure chemical ionization mass spectrometry (APCI–MS). A 6-fold decrease in the reactive uptake of ozone is observed with increasing acid concentration, consistent with a previous study using alcohol additives. The decay of HDA with ozone exposure shows that HDA scavenges CIs at rates comparable to competing unimolecular pathways involving CIs. The decay kinetics of HDA are analyzed using a simple kinetic model in order to constrain the ratio of the CI + RCOOH and unimolecular CI rate constants. Empirical fitting to this model, combined with theoretical estimates of the unimolecular loss rate, yields a CI + RCOOH rate constant of 1.85 ± 0.27 × 10–19 cm3 molec–1 s–1, which is six orders of magnitude slower than the expected diffusion limit in a liquid organic matrix. Stochastic kinetic simulations are conducted with different values of the CI + RCOOH rate constant to validate this result and show that the diffusion-limited rate is indeed much too rapid to reproduce the experimental results.

Impact of Ambient Vapors on Spectra of 4-Nitroaniline Recorded under Atmospheric Solids Analysis Probe (ASAP) Mass Spectrometric Conditions.

Thermally desorbed 4-nitroaniline (4-NA), upon atmospheric pressure chemical ionization (APCI), generates gaseous ions for its protonated species. The APCI mass spectrum recorded under mild in-source ion-activating conditions from 4-NA showed a peak at m/z 139, whereas that acquired under high ion-activating conditions showed two additional peaks at m/z 122 (•OH loss) and 92 (•NO loss). The spectrum changed instantaneously when acetonitrile vapor was introduced to the source. In the new spectrum, both m/z 122 and 92 peaks were absent, while a new peak appeared at m/z 93. Ion-mobility separation carried out with the m/z 139 ion revealed that the initial ion represented the thermodynamically favored nitro-protonated tautomer. The ion population changed to an ensemble dominated by the less-favored amino-protomer when acetonitrile vapor was introduced to the ion source. The amino-protomer, upon collisional activation, loses •NO2 to generate an m/z 93 ion, which was confirmed to be the 4-dehydroanilinium ion. Ion mobility provided a practical way to monitor the changes secured by acetonitrile vapor because the two protomers showed different arrival times. Under spray-ionization conditions, the formation of the thermodynamically less favored protomer has been attributed to kinetic trapping. Our study demonstrated that the less favored amino-protomer could be generated by introducing acetonitrile vapor under nonspray conditions. Apparently, under APCI conditions, protonated water vapor attaches to the nitro group to generate a proton-bound heterodimer, which upon activation dissociates to yield the nitro-protomer. In contrast, protonated acetonitrile makes a tighter complex preferentially with the amino group, which upon activation breaks to the amino-protomer.

Effect of sweeteners and carbonation on aroma partitioning and release in beverage systems

The effect of monosaccharides (glucose, fructose and galactose) and disaccharides (sucrose and lactose) at 10, 20 and 30 % w/v on the in-vitro aroma partitioning of C4 – C10 aldehydes and ethyl esters, as well as limonene (concentration of aroma compounds at 1 μg mL−1), was studied using atmospheric pressure chemical ionisation–mass spectrometry. An increase in sugar concentration from 0 to 30 % w/v resulted in a significant increase in partitioning under static headspace conditions for the majority of the compounds (p < 0.05), an effect generally not observed when 10 % w/v sucrose was substituted with low-calorie sweeteners (p > 0.05). The complexity of the system was increased to model a soft drink design – comprising water, sucrose (10, 20 and 30 % w/v), acid (0.15 % w/v), carbonation (∼7.2 g/L CO2) and aroma compounds representative of an apple style flavouring, namely ethyl butanoate and hexanal (10 μg mL−1 each). Although the addition of sucrose had no significant in-vivo effect, carbonation significantly decreased breath-by-breath (in-vivo) aroma delivery (p < 0.05). To understand the physical mechanisms behind aroma release from the beverage matrix, the effect of sucrose on the kinetics of the matrix components was explored. An increase in sucrose concentration from 0 to 30 % w/v resulted in a significant decrease in water activity (p < 0.05), which accounted for the significantly slower rate of self-diffusion of aroma compounds (p < 0.05), measured using diffusion-ordered spectroscopy–nuclear magnetic resonance spectroscopy. No significant effect of sucrose on carbon dioxide volume flux was found (p > 0.05).

Deprotonation of trinitrotoluene by dichloromethane in atmospheric pressure chemical ionization mass spectrometry.

Trinitrotoluene (TNT) and its derivatives are found in the environment. Depending on the analysis conditions, TNT may be detected as a deprotonated molecule or a molecular ion through atmospheric pressure chemical ionization (APCI). Dichloromethane (CH2 Cl2 ) is used as an extraction solvent for TNT from environmental samples and as an ionizing agent to generate chlorinated species. APCI mass spectra of TNT dissolved in CH2 Cl2 revealed the presence of only the [TNT - H]- ion. This phenomenon was investigated by reactions with the CH2 Cl2 -related reactant ions. TNT in CH2 Cl2 was ionized through APCI, and CH2 Cl2 and acetone were used as the eluent. The vaporizing temperature was varied from 200 to 350°C. TNT-related ions and reactant ions were analyzed. Detection limits for TNT were determined under different conditions. Energy-minimized structures of the product ions were used to interpret the analysis results. Significant [TNT - H]- ion was observed, but the [TNT + Cl]- and TNT•- ions were not detected. The [HCl + Cl]- and [3acetone + Cl]- ions were detected as reactant ions when using CH2 Cl2 and acetone as eluent, respectively. Other potential reactant ions such as CH2 Cl2 •- and [CH2 Cl2 + Cl]- were not observed. The detection limit improved as the vaporizing temperature increased. The favorability of [TNT - H]- formation was explained on the basis of the heats of reactions. The [TNT - H]- ion was primarily produced by the deprotonation reaction between CH2 Cl2 •- and neutral TNT. This reaction was determined to be significantly exothermic. CH2 Cl2 can be helpful for the analysis of TNT in environmental samples through APCI mass spectrometry.

Group 6 germylidyne complexes in the gas phase by LIFDI and APCI mass spectrometry.

Although showing fascinating chemical properties and reactivity in solution, heavier tetrelylidyne complexes with M≡E triple bonds have not been studied in the gas phase before due to their high sensitivity towards air and moisture. We selected four group 6 germylidyne complexes, [Cp(PMe3)2M≡GeArMes] (M = Mo (1-Mo), W (1-W), ArMes = 2,6-dimesitylphenyl) and [Tp'(CO)2M≡GeArMes] (M = Mo (2-Mo), W (2-W), Tp' = κ3-N,N',N''-hydridotris(3,5-dimethylpyrazolyl) borate), for a mass-spectrometric study. Liquid Injection Field Desorption Ionization (LIFDI) proved to be a well-suited technique to ionize these sensitive compounds as the spectra show the molecular ions as radical cations and only minor traces of fragmentation or degradation products. In addition, Atmospheric Pressure Chemical Ionization (APCI) connected to a high-resolving tandem mass spectrometer allowed us to study the gas-phase fragmentation behaviour of these compounds. The fragmentation patterns not only comprise the expected losses of phosphane or carbonyl ligands, respectively, but also indicate C-H bond activation by the electron-deficient metal centre. An enhanced reactivity of the tungsten species is visible in a preferred methyl abstraction in the phosphane complex 1-W compared to 1-Mo. Although degradation in solution before ionization obviously can destroy the M≡Ge triple bond, the cleavage of the M≡Ge bond upon gas-phase activation is not observed for the Mo species and only as a minor pathway for the W compounds, highlighting the high bonding energy between metal and tetrel.

Molecular Characterization of Olefins in Petroleum Fractions by Iodine Monochloride Addition and Atmospheric Pressure Chemical Ionization Mass Spectrometry

Molecular Characterization of Olefins in Petroleum Fractions by Iodine Monochloride Addition and Atmospheric Pressure Chemical Ionization Mass Spectrometry

Ion-Molecule Rate Constants for Reactions of Sulfuric Acid with Acetate and Nitrate Ions.

Atmospheric nucleation from precursor gases is a significant source of cloud condensation nuclei in the troposphere and thus can affect the Earth's radiative balance. Sulfuric acid, ammonia, and amines have been identified as key nucleation precursors in the atmosphere. Studies have also shown that atmospheric ions can react with sulfuric acid to form stable clusters in a process referred to as ion-induced nucleation (IIN). IIN follows similar reaction pathways as chemical ionization, which is used to detect and measure nucleation precursors via atmospheric pressure chemical ionization mass spectrometers. The rate at which ions form clusters depends on the ion-molecule rate constant. However, the rate constant varies based on the ion composition, which is often not known in the atmosphere. Previous studies have examined ion-molecule rate constants for sulfuric acid and nitrate ions but not for other atmospherically relevant ions like acetate. We report the relative rate constants of ion-molecule reactions between nitrate and acetate ions reacting with sulfuric acid. The ion-molecule rate constant for acetate and sulfuric acid is estimated to be a factor of 1.9-2.4 times higher than that of the known rate constant for nitrate and sulfuric acid. Using quantum chemistry, we find that acetate has a higher dipole moment and polarizability than nitrate. This may contribute to an increase in the collision cross-sectional area between acetate and sulfuric acid and lead to a greater reaction rate constant than nitrate. The ion-molecule rate constant for acetate with sulfuric acid will help quantify the contribution of acetate ions to atmospheric ion-induced new particle formation.

Contribution of atmospheric pressure chemical ionization mass spectrometry for the characterization of bio-oils from lignocellulosic biomass: Comparison with electrospray ionization and atmospheric pressure photoionization

Bio-oils obtained from lignocellulosic biomass pyrolysis present a very promising alternative to replace petroleum-based fuels. At the molecular level, these materials are highly complex organic mixtures comprising thousands of species covering a large range of mass and polarity. Compared to petroleum, they present a high amount of oxygen containing compounds, limiting their direct use in the classical refining system. To understand and improve both the conversion and upgrading processes, an advanced molecular description of the raw and upgraded bio-oils is required. The most powerful technique for the molecular characterization of such sample is Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), thanks to its very high mass accuracy and resolving power. It allows assigning unambiguously a unique molecular formula to each m/z signal. Besides, the use of different ionization sources ensures an extensive molecular description and enables to assess the efficiency of different catalytic chemical treatments. In this study, we report the characterization of a pine pyrolysis bio-oil by the three main atmospheric pressure ionization sources: electrospray (ESI), atmospheric pressure photoionization (APPI) and atmospheric pressure chemical ionization (APCI) in positive mode coupled to FTICR analyzer. In addition, different solvents and dopants were used to ensure a comprehensive description of the molecular content. Regardless of the atmospheric pressure ionization sources used, C0–100H0–300O0–15 molecular formulas are mainly obtained with lignocellulosic biomass-based bio-oils. Nevertheless, depending on the ionization source, the ions relative intensity are significantly different in respect with their double bound equivalent (DBE), oxygen to carbon ratio (O/C) and hydrogen to carbon ratio (H/C). For example, the APPI source has shown the efficient ionization of aromatic (high DBE and low H/C) less polar (low O/C) molecules compared to the ESI source which efficiency ionized more polar species with high oxygen atom content (high O/C). APCI source has proven to be particularly useful for bio-oil characterization as it demonstrates the presence of an aliphatic distribution in addition to the other bio-oil components also ionized by APPI and ESI.