Low-mass Ions Research Articles

Initial Experimental Results on Ion Cyclotron Resonance Heating Selectively Mixed Low Z Ions to Enhance Production Efficiency of Multicharged Ions on Electron Cyclotron Resonance Ion Source

According to the accessibility conditions of wave propagation in the magnetized plasma of an electron cyclotron resonance (ECR) ion source (ECRIS), it is speculated that the essential factor that determines the limitations in the multiply charged ion currents is the left-hand polarization wave cutoff (L-cutoff). It is necessary to overcome this limitation, we proposed the introduction of ion cyclotron resonance (ICR) or lower hybrid resonance (LHR) by lower frequency waves. We conduct heating low-mass ions selectively in enhanced producing multiply charged ion by mixing low-mass element gas, which has been conventionally performed in ECRIS, or relaxation of the potential well based on the existence of resonant electron particles by ECR. This paper will describe the initial experimental results of ICR application by introducing low-frequency RF electromagnetic waves in the ECRIS.

SpectiCal: m/z Calibration of MS2 Peptide Spectra Using Known Low Mass Ions.

Most tandem mass spectrometry fragmentation spectra have small calibration errors that can lead to suboptimal interpretation and annotation. We developed SpectiCal, a software tool that can read mzML files from data-dependent acquisition proteomics experiments in parallel, compute m/z calibrations for each file prior to identification analysis based on known low-mass ions, and produce information about frequently observed peaks and their explanations. Using calibration coefficients, the data can be corrected to generate new calibrated mzML files. SpectiCal was tested using five public data sets, creating a table of commonly observed low-mass ions and their identifications. Information about the calibration and individual peaks is written in PDF and TSV files. This includes information for each peak, such as the number of runs in which it appears, the percentage of spectra in which it appears, and a plot of the aggregated region surrounding each peak. SpectiCal can be used to compute MS run calibrations, examine MS runs for artifacts that might hinder downstream analysis, and generate tables of detected low-mass ions for further analysis. SpectiCal is freely available at https://github.com/PlantProteomes/SpectiCal.

Multiplexing Quadrupole and Ion Trap Operation Modes on a "Brick" Miniature Mass Spectrometer.

Although a quadruple mass analyzer and an ion trap mass analyzer have complementary analytical features, they usually have different geometries, operational modes, and electronic control systems. As a continuous effort to extend its coverage, both quadrupole and ion trap operation modes were realized on a "brick" miniature mass spectrometer with a single mass analyzer. In the quadrupole operation mode, low-mass ions ranging from 31 to 502 Th can be analyzed. On the other hand, the ion trap mode can be utilized to cover ions with higher mass to charge ratios (up to 922 Th), as well as performing tandem mass spectrometry. To realize the multiplexing of both operation modes, a printed circuit board (PCB)-based multi-electrode quadrupole-ion trap mass analyzer was designed and integrated in the system. To cover both volatile and non-volatile molecules, two ionization sources were also implemented, including a nano electrospray ionization source and an in-vacuum plasma ionization source. Performances of the instrument operated in these two modes were characterized, such as mass resolution, sensitivity, and mass range. Results demonstrate that the combination of the quadrupole and ion trap operation modes can provide new capabilities when solving analytical problems.

Development of novel isobaric tags enables accurate and sensitive multiplexed proteomics using complementary ions.

High-throughput quantitative analysis of the cells' proteomes across multiple conditions such as various perturbations and different time points is essential for gaining insights into treatment-induced biological responses or disease pathological states. The advancements in mass spectrometry instrumentation and isobaric labeling methods provided useful tools to help address such demands. However, the current widely adopted isobaric labeling methods such as tandem mass tag (TMT) and isobaric tags for relative and absolute quantitation (iTRAQ) are based on low-mass reporter ions, which are indistinguishable among different peptide analytes, to achieve relative quantification. Therefore, these methods intrinsically suffer from severe ratio distortion when analyzing complex samples due to peptide coelution and cofragmentation. Here, we developed a novel set of isobaric tags named dimethylated leucine complementary ion (DiLeuC) and relied on complementary ions for relative quantification, in which the complementary ions are the remanent peptide segments after fragmentation in the high-mass range. Since those residual peptide fragments are precursor-specific, they retain the relative abundance information in an interference-free manner even in a complex matrix environment. The quantification accuracy of our method was validated in a two-proteome model where the yeast proteome was spiked with a strong background human proteome as interference. In addition, we also applied this strategy to single-cell proteome analysis, demonstrating its potential utility for sensitive high-throughput quantitative proteomics.

Advanced data post-processing method for rapid identification and classification of the major triterpenoids of Alismatis rhizoma by ultra-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry.

Alismatis rhizoma (AR), a distinguished diuretic traditional Chinese herbal medicine, is widely used for the treatment of diarrhea, edema, nephropathy, hyperlipidemia, and tumors in clinical settings. Most beneficial effects of AR are attributed to the major triterpenoids, whose contents are relatively high in AR. To date, only 25 triterpenoids in AR have been characterized by LC-MS because the low-mass diagnostic ions are hardly triggered in MS, impeding structural identification. Herein, we developed an advanced data post-processing method with abundant characteristic fragments (CFs) and neutral losses (NLs) for rapid identification and classification of the major triterpenoids in AR by UPLC-Q-TOF-MSE . We aimed to establish a systematic method for rapid identification and classification of the major triterpenoids of AR. UPLC-Q-TOF-MSE coupled with an advanced data post-processing method was established to characterize the major triterpenoids of AR. The abundant CFs and NLs of different types of triterpenoids were discovered and systematically summarized. The rapid identification and classification of the major triterpenoids of AR were realized by processing the data and comparing with information described in the literature. In this study, a total of 44 triterpenoids were identified from AR, including three potentially new compounds and 41 known ones, which were classified into six types. The newly established approach is suitable for the chemical profiling of the major triterpenoids in AR, which could provide useful information about chemical constituents and a basis for further exploration of its active ingredients in vivo.

Field-Gradient-Focusing Ion Guide for Enhanced Transfer Efficiency of Low-Mass Ions.

Efficient transmission of low-mass ions in a rough vacuum pressure region has always been a challenging issue in mass spectrometry (MS). In this study, a novel ion guide, namely, field-gradient-focusing ion guide (FGF-IG), was proposed to improve the transfer efficiency of ions, especially low-mass ions in a rough vacuum region. The FGF-IG has 12 electrodes whose surfaces gradually narrowed and tilted inward, and its electric field gradually varies from dodecapole (or multipole) to quadrupole along the ion transfer route. The field radius was gradually decreased from 6 to 2 mm in the multipole region (65 mm in length) and finally remained unchanged as 2 mm in the quadrupole region (20 mm in length). By integrating into a miniature mass spectrometer (mini-MS) with a continuous atmospheric pressure interface, this ion guide was optimized in terms of inlet capillary position, radio frequency amplitude, and direct current voltage applied on it. Results showed that a reduced low-mass discrimination effect and improved efficiency of simultaneously transferring mid and low m/z ions were achieved for FGF-IG compared with a conventional ion funnel. Under optimized conditions, a limit of detection of 1 ng/mL was obtained for both reserpine (m/z 609) and arginine (m/z 175) ions by integrating FGF-IG into the mini-MS. The sensitivity of smaller arginine ions using FGF-IG was enhanced by ∼10 times than that obtained using the conventional ion funnel (10 ng/mL) in comparative experiments. The idea of smooth transfer from dodecapole to quadrupole fields could be extended to other multipole fields, as well as in lab-scale MS instruments.

Optimization of Higher-Energy Collisional Dissociation Fragmentation Energy for Intact Protein-Level Tandem Mass Tag Labeling.

Isobaric chemical tag labeling (e.g., TMT) is a commonly used approach in quantitative proteomics, and quantification is enabled through detection of low-mass reporter ions generated after MS2 fragmentation. Recently, we have introduced and optimized an intact protein-level TMT labeling platform that demonstrated >90% labeling efficiency in complex samples with top-down proteomics. Higher-energy collisional dissociation (HCD) is commonly utilized for isobaric tag-labeled peptide fragmentation because it produces accurate reporter ion intensities and avoids loss of low mass ions. HCD energies have been optimized for isobaric tag labeled-peptides but have not been systematically evaluated for isobaric tag-labeled intact proteins. In this study, we report a systematic evaluation of normalized HCD fragmentation energies (NCEs) on TMT-labeled HeLa cell lysate using top-down proteomics. Our results suggested that reporter ions often result in higher ion intensities at higher NCEs. Optimal fragmentation of intact proteins for identification, however, required relatively lower NCE. We further demonstrated that a stepped NCE scheme with energies from 30% to 50% resulted in optimal quantification and identification of TMT-labeled HeLa proteins. These parameters resulted in an average reporter ion intensity of ∼4E4 and average proteoform spectrum matches (PrSMs) of >1000 per RPLC-MS/MS run with a 1% false discovery rate (FDR) cutoff.

Fragmentation dynamics and absolute dissociative electron attachment cross sections in the low energy electron collision with ethanol.

Dissociative electron attachment (DEA) to ethanol has been probed to study fragmentation dynamics using Time-of-Flight (ToF) mass spectrometric technique. Several fragment ions, namely, H-, O-, OH-, C2H3O- and C2H5O- have been observed. Extra effort has been made to detect low mass ions (here, H-). Absolute DEA cross sections for the formation of O- and OH- have been measured for the first time using relative flow technique (RFT). The threshold energy of different dissociation channels has been calculated using density functional theory (DFT) method. By combining the experimental and theoretical data, we found evidence of hydrogen migration in the production of O and C2H3O- ions.

Synchronized Reverse Scan Collision Induced Dissociation in Digital Ion Trap Mass Spectrometer for Improving Fragment Ion Detection

Development of fragment ion detection methods is of great importance for mass spectrometer advancement or substance identification. To date, collision induced dissociation (CID) remains the most commonly used ion activation method in MS/MS experiments, and the effectiveness of CID in an ion trap mass spectrometer is limited by low mass cutoff and weak fragmentation yields. Theoretically, controlling the q value is the key to maintain the fragment efficiency and trapping efficiency of MS/MS, thus improving the detection of fragment ion, while currently reported techniques usually require complex circuitry and often produce different CID patterns. In this paper, with the developed synchronized reversed scanning-collision induced dissociation (SRS-CID) technique, we demonstrate its effective improvement in fragment ion detection. The SRS-CID is implemented on a digital ion trap mass spectrometer (DITMS) by reverse scanning the q values during CID process, or specifically, the frequency is increased during the CID process. With the SRS-CID technique, the fragmentation efficiency of precursor ions can be slightly improved. For reserpine analyte, the trapping efficiency for low-mass fragment ions is improved at least 3 times, and for YGGFL, the trapping efficiency for low-mass fragment ions is improved at least 9 times. These experimental results can also be validated by simulations, and the kinetic energy variation plot suggests consecutive fragmentation occurs. In any case, the SRS-CID provides a solution to the low efficiency of fragment ion detection during tandem MS analysis, which will certainly be useful in the future.

Effects of substrate rotation during AlSi-HiPIMS/Ti-DCMS co-sputtering growth of TiAlSiN coatings on phase content, microstructure, and mechanical properties

A combined high-power impulse and dc magnetron co-sputtering (HiPIMS/DCMS) technique is used to deposit Ti0.6Al0.32Si0.08N films with 1-fold substrate table rotation. Layers are grown at two different substrate-target separations, two different rotational speeds, and with different values of substrate bias. The aim is to study the role of (1) overlap between ion and neutral fluxes generated from HiPIMS and DCMS sources, respectively, and (2) the subplantation range of low-mass ions. Results from X-ray diffractometry highlight the necessity of flux intermixing in the formation of the metastable B1-structured TiAlSiN solid solutions. All films grown at short target-to-substrate distance contain the hexagonal AlN phase, as there is essentially no overlap between HiPIMS and DCMS fluxes, thus the Al+ and Si+ subplantation is very limited. Under conditions of high flux intermixing corresponding to larger target-to-substrate distance, no w-AlN forms irrespective of rotational speed (1 or 3 rpm) and bias amplitude (120 or 480 V), indicating that the role of Al+/Si+ and Ti flux overlap is crucial for the phase formation during film growth by HiPIMS/DCMS with substrate rotation. This conclusion is further supported by the fact that the reduction of the bilayer thickness with increasing the target-to-substrate distance (hence increasing flux overlap) is larger for films grown with higher amplitude of the substrate bias, indicative of more efficient Al+/Si+ subplantation into the c-TiN phase. Single-phase films with the hardness close to that of layers grown with stationary substrate table can be achieved, however, at the expense of higher compressive stress.

Different Metabolomic and Proteomic Profiles of Cerebrospinal Fluid in Ventricular and Lumbar Compartments in Relation to Leptomeningeal Metastases.

The different molecular profiles of cerebrospinal fluid (CSF) between ventricular and lumbar compartments remain elusive, especially in the context of leptomeningeal metastasis (LM), which affects CSF flow. We evaluated CSF metabolomic and proteomic profiles based on the compartments and the diagnosis of spinal LM, proved by MRI from 20 paired ventricular and lumbar CSF samples of LM patients, including 12 spinal LM (+) samples. In metabolome analysis, 9512 low-mass ions (LMIs) were identified—7 LMIs were abundant in all lumbar versus paired ventricular CSF samples, and 3 LMIs were significantly abundant in all ventricular CSF. In comparisons between spinal LM (+) CSF and LM (−) CSF, 105 LMIs were discriminative for spinal LM (+) CSF. In proteome analysis, a total of 1536 proteins were measured. A total of 18 proteins, including complement C3, were more highly expressed in all lumbar CSF, compared with paired ventricular CSF, while 82 proteins, including coagulation factor V, were higher in the ventricular CSF. Of 37 discriminative proteins, including uteroglobin and complement component C8 gamma chain, 4 were higher in all spinal LM (+) CSF versus spinal LM (−) CSF. We further evaluated metabolic pathways associated with these discriminative proteins using the Gene Ontology database. We found that 16/17 spinal LM (+) pathways, including complement activation, were associated with lumbar discriminative proteins, whereas only 2 pathways were associated with ventricular-discriminative proteins. In conclusion, we determined that metabolite and protein profiles differed between paired lumbar and ventricular CSF samples. The protein profiles of spinal LM (+) CSF showed more similarity with the lumbar CSF than the ventricular CSF. Thus, we suggest that CSF LMIs and proteins could reflect LM disease activity and that LM-associated differences in CSF are more likely to be present in the lumbar compartment.

Experimental Assessment of Leptomeningeal Metastasis Diagnosis in Medulloblastoma Using Cerebrospinal Fluid Metabolomic Profiles.

Diagnosing leptomeningeal metastasis (LM) in medulloblastoma is currently based on positive cerebrospinal fluid (CSF) cytology or magnetic resonance imaging (MRI) finding. However, the relevance of discordant results has not been established. We evaluated the diagnostic potential of CSF metabolomic profiles in the medulloblastoma LM assessment. A total of 83 CSF samples from medulloblastoma patients with documented MRI and CSF cytology results at the time of sampling for LM underwent low-mass ions (LMIs) analysis using liquid chromatography-mass spectrometry. Discriminating LMIs were selected by a summed sensitivity and specificity (>160%) and LMI discriminant equation (LOME) algorithms, evaluated by measuring diagnostic accuracy for verifying LM groups of different MRI/cytology results. Diagnostic accuracy of LM in medulloblastoma was 0.722 for cytology and 0.889 for MRI. Among 6572 LMIs identified in all sample, we identified 27 discriminative LMIs differentiating MRI (+)/cytology (+) from MRI (−)/cytology (−). Using LMI discriminant equation (LOME) analysis, we selected 9 LMIs with a sensitivity of 100% and a specificity of 93.6% for differentiating MRI (+)/cytology (+) from MRI (−)/cytology (−). Another LOME of 20 LMIs significantly differentiated sampling time relative to treatment (p = 0.007) and the presence or absence of LM-related symptoms (p = 0.03) in the MRI (+)/cytology (−) group. CSF metabolomics of medulloblastoma patients revealed significantly different profiles among LM diagnosed with different test results. We suggest that LM patients could be screened by appropriately selected LOME-generated LMIs to support LM diagnosis by either MRI or cytology alone.

A new ion funnel for improving the transmission of low mass ions

To solve the problem of low mass ion discrimination of conventional ion funnel and optimize ion transmission, a new ion funnel with a quadrupolar electrode configuration, was evaluated, based on the theoretical modeling, in this paper. The theoretical model was constructed by using the SIMION and the performance characteristics of the new ion funnel was simulated systematically by calculating the ion trajectory under different operating conditions. As the low mass ions lossed at the exit of ion funnel was mainly due to the opposite phase radio frequency (RF) voltage applied to the front and rear electrodes, the new ion funnel configuration rotated RF by 90 degrees and suppressed the axial potential wells near the ion funnel exit. The transmission efficiencies of the conventional and the new ion funnels for ions with low mass to charge ratio (m/z) were compared under the same operating conditions. The results showed that the new ion funnel configuration could improve the transmission efficiency by about 10% as compared to the conventional ion funnel in the m/z range below 70 while there was little differences in the transmission efficiency for high m/z ions.

Successive reactions in field induced fragmentation spectra from tandem ion mobility spectrometry at ambient pressure and their influence on classification by neural networks

Field-induced fragmentation (FIF) spectra were obtained for mobility isolated protonated monomers of volatile organic compounds from six chemical families at 130 to 157 Td in the reactive stage of a tandem ion mobility spectrometer at 98 °C. The extent of fragmentation at ambient pressure increased linearly with field strength for n-alcohols of carbon number 3 to 5, for n-akyl acetates of carbon numbers 4 to 11, and for n-aldehydes and ethers not previously fragmented at 129 Td and 93 °C. Efficiencies of fragmentation at 157 Td ranged from 57 to 100% for n-alcohols, 25–100% for n-alkyl acetates of carbon numbers 5 to 8 (10–29% for carbon numbers 9 to 11), 29–84% for ethers of carbon numbers 8 and below, and 7–57% for n-alkanes of carbon numbers 7 to 11. Multiple, low mass ions in FIF spectra were attributed to second and third levels of fragmentation with identical reduced mobility coefficients characteristic of a chemical class. Differences in fragment ion patterns between chemical classes were attributed to structural information from field-induced fragmentation. Classification by chemical class using neural networks was significantly improved for acetates and aldehydes with increased fragmentation at 157 Td. Spectra without fragmentation were poorly classified. Models of ion energy within the reactive stage suggested that ions undergoing decomposition were not symmetrically distributed between etched metal grids in the reactive stage.

Analysis of ethylene oxide in ice creams manufactured with contaminated carob bean gum (E410)

ABSTRACT Residues of ethylene oxide (EO), a banned fumigant in the EU, were found at amounts above the maximum residue limit (MRL) in carob (locust) bean gum (additive E410). The pesticide entered the food chain via stabiliser blends that are used as minor ingredients in the manufacture of ice cream. Consequently, all products that contained the non-compliant ingredient were withdrawn or recalled in several countries across the EU, in most cases irrespective of whether the pesticide residue was detectable or not in the final product. This is the first report of a reliable method to determine EO and its metabolite/marker compound 2-chloroethanol (2-CE), either together or independently in ice cream, with a limit of quantification at 0.01 mg EO/kg and recovery in the range of 87–104% across the levels investigated (0.01, 0.02 and 0.06 mg EO/kg). The method applies QuEChERS extraction and isotope dilution gas chromatography coupled with tandem mass spectrometry (GC-MS/MS). High resolution mass spectrometry (HRMS) confirmed the specificity of low mass ions. Data on the stability of EO and 2-CE under thermal conditions revealed that 2-CE is relatively stable in an ice cream matrix (ca. 80% recovery of spiked material). Importantly, this study also demonstrates that not EO, but 2-CE is the predominant analyte detected in the contaminated samples, which is new information of significance in terms of the overall risk assessment of EO in foodstuffs.

A new setup for low-temperature gas-phase ion fluorescence spectroscopy.

Here, we present a new instrument named LUNA2 (LUminescence iNstrument in Aarhus 2), which is purpose-built to measure dispersed fluorescence spectra of gaseous ions produced by electrospray ionization and cooled to low temperatures (<100K). LUNA2 is, as an earlier room-temperature setup (LUNA), optimized for a high collection efficiency of photons and includes improvements based on our operational experience with LUNA. The fluorescence cell is a cylindrical Paul trap made of copper with a hole in the ring electrode to permit laser light to interact with the trapped ions, and one end-cap electrode is a mesh grid combined with an aspheric condenser lens. The entrance and exit electrodes are both in physical contact with the liquid-nitrogen cooling unit to reduce cooling times. Mass selection is done in a two-step scheme where, first, high-mass ions are ejected followed by low-mass ions according to the Mathieu stability region. This scheme may provide a higher mass resolution than when only one DC voltage is used. Ions are irradiated by visible light delivered from a nanosecond 20-Hz pulsed laser, and dispersed fluorescence is measured with a spectrometer combined with an iCCD camera that allows intensification of the signal for a short time interval. LUNA2 contains an additional Paul trap that can be used for mass selection before ions enter the fluorescence cell, which potentially is relevant to diminishing RF heating in the cold trap. Successful operation of the setup is demonstrated from experiments with rhodamine dyes and oxazine-4, and spectral changes with temperature are identified.

Heavy Positive Ion Groups in Titan’s Ionosphere from Cassini Plasma Spectrometer IBS Observations

Abstract Titan’s ionosphere contains a plethora of hydrocarbons and nitrile cations and anions as measured by the Ion Neutral Mass Spectrometer and Cassini Plasma Spectrometer (CAPS) on board the Cassini spacecraft. Data from the CAPS Ion Beam Spectrometer (IBS) sensor have been examined for five close encounters of Titan during 2009. The high relative velocity of Cassini with respect to the cold ions in Titan’s ionosphere allows CAPS IBS to function as a mass spectrometer. Positive ion masses between 170 and 310 u/q are examined with ion mass groups identified between 170 and 275 u/q containing between 14 and 21 heavy (carbon/nitrogen/oxygen) atoms. These groups are the heaviest positive ion groups reported so far from the available in situ ion data at Titan. The ion group peaks are found to be consistent with masses associated with polycyclic aromatic compounds (PAC), including polycyclic aromatic hydrocarbon (PAH) and nitrogen-bearing polycyclic aromatic molecular ions. The ion group peak identifications are compared with previously proposed neutral PAHs and are found to be at similar masses, supporting a PAH interpretation. The spacing between the ion group peaks is also investigated, finding a spacing of 12 or 13 u/q indicating the addition of C or CH. Lastly, the occurrence of several ion groups is seen to vary across the five flybys studied, possibly relating to the varying solar radiation conditions observed across the flybys. These findings further the understanding between the low-mass ions and the high-mass negative ions, as well as with aerosol formation in Titan’s atmosphere.

MBRS-56. RE-EVALUATION OF LEPTOMENINGEAL METASTASIS IN MEDULLOBLASTOMA WITH MAGNETIC RESONANCE IMAGING, RELATED SYMPTOMS AND CEREBROSPINAL FLUID METABOLOMIC PROFILES

BACKGROUNDDiagnosis of leptomeningeal metastasis (LM) in medulloblastoma is made by positive findings in either MRI or CSF cytology. We studied if CSF metabolomics profile can differentiate the discordant results between MRI and CSF cytology and reflect the sampling time related to treatment.MATERIALS AND METHODSWe prospectively collected 83 CSF samples from 45 medulloblastoma patients. A total of 6,527 low-mass ions (LMIs) were detected using liquid chromatography tandem mass spectrometry (LC-MS/MS). Discriminative low-mass ions (LMIs) between four different MRI and cytology results groups were evaluated and representative LMIs were identified.RESULTSCSF cytology and MRI finding were both positive for LM in 8 samples and both negative for 47 samples. Tests were cytology (-) and MRI (+) in 20 samples, whereas cytology (+) and MRI (-) status were in the remaining 8 samples. The diagnostic accuracy by area under the curve (AUC) was 0.722 for cytology and 0.888 for MRI each. Based on the exclusiveness of LMI between groups, we verified 27 discriminative LMIs in MRI (+)/ cytology (+), 9 LMIs in MRI (+)/ cytology (-), and 12 LMIs in MRI (-) and cytology (+) group, separately. Metabolic pathways involved in MRI (+)/ cytology (+) group were linoleic acid, phenylalanine, TCA cycle, retinol, arginine-ornithine, nicotinate-nicotinamide, etc. Low-mass-ion discriminant equation (LOME), which could differentiate both different MRI and cytology results and the sampling time or presence of LM-related symptoms was found.CONCLUSIONNon-targeted MSanalysis CSF metabolite in medulloblastomas revealed significantly different profiles, and these results suggest LMI profiles might have a higher sensitivity for LM diagnosis than either MRI or cytology.

Dynamics of Molecules Observed at Crude-Oil-Gas Interfaces by Time-of-Flight Secondary Ion Mass Spectrometry Imaging.

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) imaging provides molecular speciation at the micrometer scale, while the penetration depth of the primary ion beam is limited to the top-layers of a sample. These combined properties make TOF-SIMS potentially an ideal technique to study oil–gas interfaces. TOF-SIMS spectra of three crude oils were evaluated, and only low-mass fragment ions could be assigned to molecular structures unambiguously. Films of crude oils were incubated under air, oil vapor, or water vapor for various times. TOF-SIMS images of a polar crude oil revealed feeble structures of ∼10 μm large round patches that grew to ∼30 μm large crystals when incubated under air and oil vapor, respectively. Principal component analysis of the images showed that the continuous phase had typical aromatic signatures, while the patches and crystals had alkane-like characteristics. No features showed up when the oil film was incubated under water vapor, which indicated that saturated water vapor prevented the accumulation of nonpolar alkane-like compounds at the oil–gas interface. These examples showed that crude oils do not behave as dead fluids but that their constituents accumulate at the oil–gas interfaces in a dynamic way.

Spatial Variations of Low-mass Negative Ions in Titan’s Upper Atmosphere

Abstract Observations with Cassini’s Electron Spectrometer discovered negative ions in Titan’s ionosphere, at altitudes between 1400 and 950 km. Within the broad mass distribution extending up to several thousand amu, two distinct peaks were identified at 25.8–26.0 and 49.0–50.1 amu/q, corresponding to the carbon chain anions CN− and/or for the first peak and C3N− and/or C4H− for the second peak. In this study we present the spatial distribution of these low-mass negative ions from 28 Titan flybys with favorable observations between 2004 October 26 and 2012 May 22. We report a trend of lower densities on the night side and increased densities up to twice as high on the day side at small solar zenith angles. To further understand this trend, we compare the negative ion densities to the total electron density measured by Cassini’s Langmuir Probe. We find the low-mass negative ion density and the electron density to be proportional to each other on the day side but independent of each other on the night side. This indicates photochemical processes and is in agreement with the primary production route for the low-mass negative ions being initiated by dissociative reactions with suprathermal electron populations produced by photoionisation. We also find the ratio of to to be highly constrained on the day side, in agreement with this production channel, but notably displaying large variations on the night side.