Vacuum-Ultraviolet-Excited and CH2Cl2/H2O-Amplified Ionization-Coupled Mass Spectrometry for Oxygenated Organics Analysis.

The mass spectrometry analysis of oxygenated volatile organic compounds (OVOCs) remains challenging due to their limited ionization efficiencies. In this study, we surprisingly found that, under vacuum-UV (VUV) excitation, a gaseous mixture of CH2Cl2/H2O/analyte (OVOCs) in N2 buffer generated large amounts of H3O+ and protonated analyte even when the photon energy was lower than the ionization energy of the neutral species involved. In contrast to those obtained with VUV photoionization alone, the signal intensities of oxygenated organics can be amplified by more than 3 orders of magnitude. The isotope tracing experiment revealed that the proton donor is water, and the dependence of the signal intensities on the VUV photon intensities verified that the reaction was a single-photon process. The observed ionization process is assigned as an undocumented chemi-ionization reaction in which a complex formed from the ion-pair state CH2Cl2*, H2O, and analyte and then autoionized to produce the protonated analyte with the aid of the reorganization energy released from the formation of CH2O and HCl. Essentially, here we present an efficient chemi-ionization method for the direct protonation of oxygenated organics. By the method, the mass spectrometric sensitivities toward acetic acid, ethanol, aldehyde, diethyl ether, and acetone were determined to be 224 ± 17, 245 ± 5, 477 ± 14, 679 ± 11, and 684 ± 6 counts pptv-1, respectively, in 10 s acquisition time. In addition, the present ionization process provides a new method for the generation of a high-intensity H3O+ source (∼1011 ions s-1, measured by ion current) by which general organics can be indirectly protonated via a conventional proton-transfer reaction. These results open new aspects of chemi-ionization reactions and offer new technological applications that have the potential to greatly improve mass spectrometry sensitivity for detecting trace gaseous organics.

Gas-Phase Reactions of Methoxyphenols with NO3 Radicals: Kinetics, Products, and Mechanisms.

Methoxyphenols, a group of important tracers for wood smoke, are emitted to the atmosphere in large quantities, but their transformations are rarely studied. In this study, the kinetics and products of the gas-phase reactions of eugenol and 4-ethylguaiacol with NO3 radicals were investigated online using a vacuum ultraviolet photoionization gas time-of-flight mass spectrometer. The rate coefficients of the gaseous reactions of eugenol and 4-ethylguaiacol with NO3 radicals were (1.6 ± 0.4) × 10(-13) and (1.1 ± 0.2) × 10(-12) cm(3) molecule(-1) s(-1) (at 298 K), indicating that the atmospheric lifetimes of the NO3 radicals were 3.5 and 0.5 h, respectively. With the aid of gas-chromatography-mass-spectrometry analysis, several types of degradation products were identified with nitro derivatives as the major products. The configurations of the nitro-product isomers and their formation mechanisms were determined via theoretical calculations. On the basis of these products, degradation pathways of the methoxyphenols with NO3 radicals were proposed. This study determines the degradation rates and mechanisms of the methoxyphenols at night and implies the significant NO3 nighttime chemistry.

High organic aerosol in the low layer over a rural site in the North China Plain (NCP): Observations based on large tethered balloon.

High mass concentration of organic aerosol (OA) and its fraction in PM2.5 (particle matter with radius <2.5 µm) were observed in the low layer over a rural site of the North China Plain (NCP) in winter 2018. The mass fraction of OA in PM2.5 was 65.5 % at ground level (5 m above ground), and decreased to 37.1 % in layer of 200-1000 m. In addition, there was a sharp decrease of OA at around the top of planetary boundary layer (PBL), which was distinctly different from the vertical distributions of secondary inorganic aerosols (SIA, e.g., nitrate (NO3-), ammonium (NH4+), and sulfate (SO42-)). The altitude with sharp decrease of OA was very low in the morning and evening, e.g., the sharp decrease of OA occurred at a height <50 m at nighttime on Dec. 19, while was elevated in the noon with the PBL development. Furthermore, OA at ground level exhibited a distinct diurnal variation with a night-to-day ratio of 2.3, which was much larger than those of SIA and inactive CO. All the above results indicated the extremely high OA concentration at the rural site was mainly attributed to direct emission from local sources, such as the combustion of coal and biomass for heating. The extremely high OA could be expected in vest rural areas of the NCP in winter because the farmer activities are very similar to the investigated rural site, underscoring the urgency to mitigate OA emission in rural area for improving the local as well as the regional air quality.

Associations of apparent temperature with acute cardiac events and subtypes of acute coronary syndromes in Beijing, China.

Limited evidence is available on apparent temperature (AT) and hospital admissions for acute cardiac events. We examined the associations of AT with admissions for acute cardiac events and acute coronary syndrome (ACS), and explored the effect difference between ST-elevation myocardial infarction (STEMI) and non-ST-elevation myocardial infarction ACS (NSTE-ACS). Poisson regression with distributed lag non-linear model was applied to examine the temperature-lag-admission associations. Stratified analyses were performed by gender and age-groups for acute cardiac events. A total of 11,657 acute cardiac events admissions were collected from hospital-based chest pain centers in Beijing, during 2017-2019. The single day effect of low AT (- 11 °C, 2.5th percentile) appeared on the 2nd day and persisted until the 11th day, with estimated relative risk (RR) ranging from 1.44 (95% CI: 1.159, 1.790) to 1.084 (95% CI: 1.022, 1.150) for acute cardiac events and from 1.034 (95% CI: 1.010, 1.059) to 1.006 (95% CI: 1.000, 1.011) for ACS. The single day effect of high AT (34 °C, 97.5th percentile) was only observed on the current day. The cold effect on acute cardiac events was more pronounced among female and older patients. The cumulative effect of high AT on STEMI admissions and low AT on NSTE-ACS reached a peak RR peak of 2.545 (95% CI: 1.016, 6.375) and 3.71 (95% CI: 1.315, 10.469) on lag 0-6 days, respectively. Both high and low ATs were associated with increased risk of acute cardiac events and ACS admissions. STEMI admissions may be more sensitive to high AT while NSTE-ACS to low AT.

Sulfide reduction can significantly enhance transport of biochar fine particles in saturated porous medium.

The release of fine particles from biochar materials applied in the environment may have important environmental implications, such as mobilization of environmental contaminants. In natural environments biochar fine particles can undergo various transformation processes, which may change their surface chemistry and consequently, the mobility of the particles. Here, we show that sulfide reduction can significantly alter the transport of wheat-straw- and pine-wood-derived biochar fine particles in saturated porous media. Counterintuitively, the sulfide-reduced biochar particles exhibited greater mobility in artificial groundwater than their non-reduced counterparts, even though reduction led to decrease of surface charge negativity and increase of hydrophobicity (from the removal of surface O-functional groups), both should favor particle deposition, as predicted based on extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory. Using transport experiments conducted in single-cation background solutions containing K+, Mg2+ or Ca2+ under different pH conditions, we show that the surprisingly greater mobility of sulfide-reduced biochar particles was attributable to the removal of surface carboxyl groups during reduction, as this markedly alleviated particle deposition through cation bridging, wherein Ca2+ acted as the bridging agent in linking the surface O-functional groups of biochar particles and quartz sand. These findings show the critical roles of surface properties in dictating the mobility of biochar fine particles and call for further understanding of their transport properties, which apparently cannot be simply extrapolated based on the findings of other (engineered) carbonaceous nanomaterials.

Transport of graphene oxide in saturated quartz sand containing iron oxides.

The environmental implications of graphene oxide (GO) have received much attention. Transport of GO in subsurface environment is a critical process affecting the migration and potential risks of this important class of carbonaceous nanomaterials. To date, the effects of heterogeneity in porous media, in particular, iron oxides, on GO transport are not well studied. In this study, we investigated the transport properties of GO in saturate quartz sand as affected by the presence of iron oxides, using goethite, hematite and ferrihydrite as the model iron oxide species, and applied a two-site transport model (which accounts for both attachment and straining) to fit the transport data. We found that iron oxide coating on sand surfaces markedly inhibited GO transport, mainly due to increased electrostatic attraction between particles and collectors, as the positively charged iron oxides provided favorable deposition sites for the negatively charged GO nanosheets. Additionally, increased surface roughness was likely an additional mechanism leading to the enhanced GO deposition. The extent of transport inhibition by iron oxides also depended on the morphology iron oxides, in that at the same Fe loading a larger effect was observed when iron oxides existed as the coating on sand surface than as discreet particles. The presence of iron oxide coatings (tested using goethite) could magnify the effects of cations on GO transport. Specifically, the presence of goethite facilitated the accumulation of cations on the surface of sand, and in the case of Ca2+, the binding of GO via the cation-bridging mechanism was enhanced, as goethite contained abundant surface hydroxyl groups that are strong metal-complexing moieties.

Transport and retention of reduced graphene oxide materials in saturated porous media: Synergistic effects of enhanced attachment and particle aggregation.

The increasing production and use of graphene-based nanomaterials (e.g., graphene oxide (GO) and reduced graphene oxide (RGO)) will lead to their environmental release. To date, transport of RGOs in saturated porous media is poorly understood. Here, we examined the transport behaviors of three RGO materials obtained by reducing a GO product with commonly used reducing agents - N2H4, NaBH4 and L-ascorbic acid (referred to as N2H4-RGO, NaBH4-RGO and VC-RGO, respectively). When the dominant background cation was Na+, K+ or Mg2+, the mobility of the RGOs and GO in saturated quartz sand correlated well with their surface C/O ratio. Interestingly, the lower mobility of the more reduced materials (the ones with higher C/O values) was not only the results of their less negative surface charges and larger particle sizes, but also the outcome of their greater hydrophobicity, in line with the calculated extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) profiles. Counterintuitively, when the background cation was Ca2+, the least reduced material among the three RGOs, VC-RGO, exhibited the lowest mobility. Analysis of electrophoretic and aggregation properties, as well as pH-effect experiments, indicated that the surprisingly low mobility of VC-RGO was attributable to the strong cation-bridging effect (primarily Ca2+-bridging between RGO and quartz sand) associated with this material, as VC-RGO contained the highest amount of surface carboxyl group (a strong metal-binding moiety). Notably, enhanced attachment (due to increased hydrophobic effect and cation-bridging) and particle aggregation appeared to work synergistically to increase RGO retention, as the attachment of large RGO aggregates significantly enhanced particle straining by narrowing the flow path. These observations reveal a largely overlooked link between the mobility of graphene-based materials and their key physicochemical properties.

Ultrasensitive detection of volatile aldehydes with chemi-ionization-coupled time-of-flight mass spectrometry.

The chemi-ionization reaction is a high-efficiency pathway to produce molecular ions in plasma, however, it has rarely been applied in mass spectrometry to directly produce analyte ions. In this study, a novel chemi-ionization technique for mass spectrometry was applied for the direct and ultrasensitive detection of gaseous aldehydes. The ionization technique was enacted by a recently observed chemi-ionization reaction: the efficient proton transfer from H2O to oxygenated compounds was stimulated by vacuum ultraviolet (VUV)-excited CH2Cl2. By analyzing a series of aliphatic aldehydes (C2-C5) and benzaldehyde with different proton affinities (PAs) and polarities, the ionization features of the new ionization method were investigated for the first time. The chemi-ionization of aldehydes presented soft ionization characteristics with fragmentation patterns analogous to that of VUV photoionization. The method showed ultrahigh sensitivities toward aldehydes (up to 1108 ±â€¯6 counts pptv-1 for benzaldehyde in 10 s acquisition time). The corresponding 3σ limits of detection (LODs) achieved 0.30-0.69 pptv, which are equivalent of 1.35-1.92 ng m-3, for the compounds investigated. The humidity experiments revealed that the moisture in the sample gas had an evident impact on the detection efficiency of the analyte and the influence was PA dependent. In addition, the applicability of this ionization mode was further tested by analysis of aldehydes in cigarette smoke. This study provides a promising ionization method for greatly improving the current on-line detection sensitivity of volatile aldehydes.

Characterization of secondary organic aerosol from photo-oxidation of gasoline exhaust and specific sources of major components.

To further explore the composition and distribution of secondary organic aerosol (SOA) components from the photo-oxidation of light aromatic precursors (toluene, m-xylene, and 1,3,5-trimethylbenzene (1,3,5-TMB)) and idling gasoline exhaust, a vacuum ultraviolet photoionization mass spectrometer (VUV-PIMS) was employed. Peaks of the molecular ions of the SOA components with minimum molecular fragmentation were clearly observed from the mass spectra of SOA, through the application of soft ionization methods in VUV-PIMS. The experiments comparing the exhaust-SOA and light aromatic mixture-SOA showed that the observed distributions of almost all the predominant cluster ions in the exhaust-SOA were similar to that of the mixture-SOA. Based on the characterization experiments of SOA formed from individual light aromatic precursors, the SOA components with molecular weights of 98 and 110 amu observed in the exhaust-SOA resulted from the photo-oxidation of toluene and m-xylene; the components with a molecular weight of 124 amu were derived mainly from m-xylene; and the components with molecular weights of 100, 112, 128, 138, and 156 amu were mainly derived from 1,3,5-TMB. These results suggest that C7-C9 light aromatic hydrocarbons are significant SOA precursors and that major SOA components originate from gasoline exhaust. Additionally, some new light aromatic hydrocarbon-SOA components were observed for the first time using VUV-PIMS. The corresponding reaction mechanisms were also proposed in this study to enrich the knowledge base of the formation mechanisms of light aromatic hydrocarbon-SOA compounds.

Rapid detection of taste and odor compounds in water using the newly invented chemi-ionization technique coupled with time-of-flight mass spectrometry.

Taste and odor (T&O) compounds are widespread in water environments and have attracted considerable public attention. Nowadays, the standard detections of these chemicals rely mainly on off-line methods such as GC-MS or evaluation by trained analysts' senses. In this study, we report a method for the rapid detection of T&O compounds in water by exploiting a newly invented chemi-ionization source, in combination with headspace vapor measurement at room temperature. The calibrated limits of detection (LODs) of 2-methylbutyraldehyde, methyl tert-butyl ether (MTBE), methyl methacrylate (MMA), 2-isobutyl-3-methyoxypyrazine (IBMP), and 2-isopropyl-3-methoxypyrazine (IPMP) are in the range of 3.5-50.2 ng L-1, and the estimated LODs of 2-methylisoborneol (2-MIB) and geosmin (GSM) are 0.25 and 0.77 ng L-1, respectively. The calibration results reveal that the instrumental LODs for 2-methylbutyraldehyde, MTBE, MMA, ß-cyclocitral, 2-MIB, and GSM are 1-2 orders of magnitude better than the odor thresholds of humans. The accuracy, precision, recovery, and linearity (R2) of the method are tested. Water samples from city tap water and three rivers in Beijing are assessed using this technique, and the typical T&O compositions are observed with concentrations ranging from 0.2 to 297 ng L-1. The new ultra-sensitive rapid detection method shows comparable sensitivities to the existing off-line technique and displays great potential for real-time detection of T&O pollution in water environments.

A rapid detection method for policy-sensitive amines real-time supervision.

Many organic amines that comprise a benzene ring are policy-sensitive because of their toxicity and links to social harm. However, to date, detection of such compounds mainly relies on offline methods. This study proposes an online pptv (parts per trillion by volume) level of detection method for amines, using the recently-built vacuum ultraviolet photoionization mass spectrometer (VUV-PIMS) combined with a new doping technique. Thus, the dichloromethane doping-assisted photoionization mass spectra of aniline, benzylamine, phenethylamine, amphetamine, and their structural isomers were recorded. The dominant characteristic mass peaks for all amines are those afforded by protonated amines and the amino radical-loss. The signal intensities of the amines were enhanced by 60-130 times compared to those recorded without doping assistance. Under 10s detection time, the sensitivities of aniline and benzylamine in the gas phase were determined as 4.0 and 2.7 countspptv-1, with limits of detection (LODs) of 36 and 22 pptv, respectively. Notably, the detection efficiency of this method can be tenfold better in future applications since the ion transmission efficiency of the mass spectrometer was intentionally reduced to ~ 10% in this study. Therefore, dichloromethane doping-assisted photoionization mass spectrometry has proven to be a highly promising on-line approach to amine detection in environmental and judicial supervision and shows great potential for application in the biological field.

Formation mechanism of secondary organic aerosol from ozonolysis of gasoline vehicle exhaust.

Gasoline vehicles are a major source of anthropogenic secondary organic aerosols (SOAs). However, current models based on known precursors fail to explain the substantial SOAs from vehicle emissions due to the inadequate understanding of the formation mechanism. To provide more information on this issue, the formation of SOAs from ozonolysis of four light-duty gasoline vehicle exhaust systems was investigated with a vacuum ultraviolet photoionization mass spectrometer (VUV-PIMS). Remarkable SOAs formation was observed and the SOAs were primarily aliphatic alkenes. PI mass spectra of the SOAs from all vehicles exhibited similar spectral patterns (a regular mass group with m/z at 98, 112, 126 …). Interestingly, most carbonyl products of aliphatic alkenes observed as major gaseous products have specific molecular weights, and the main formation pathway of SOAs can be explained well using aldol condensation reactions of these carbonyls. This is a direct observation of the aldol condensation as a dominated pathway for SOAs formation, and the first report on the composition and formation mechanism of the SOAs from the ozonolysis of gasoline vehicle exhaust is given. The study reveals that low molecular weight alkenes may play a more significant role in vehicle-induced SOAs formation than previously believed. More importantly, the PI mass spectra of SOAs from vehicles show similarities to the field aerosol sample mass spectra, suggesting the possible significance of the aldol condensation reactions in ambient aerosol formation. Since carbonyls are a major degradation product of biogenic and anthropogenic VOCs through atmospheric oxidation processes, the mechanism proposed in this study can be applied more generally to explain aerosol formation from the oxidation of atmospheric hydrocarbons.

[Effects of Arbuscular Mycorrhizal Fungi on the Growth and Ce Uptake of Maize Grown in Ce-contaminated Soils].

A greenhouse pot experiment was conducted to investigate the effects of arbuscular mycorrhizal (AM) fungi Glomus aggregatum (GA) and Funneliformis mosseae (FM) on AM colonization rate, biomass, nutrient uptake, C: N: P stoichiometric and Ce uptake and transport by maize (Zea mays L.) grown in soils with different levels of Ce-contaminated (100, 500 and 1000 mg x kg(-1)). The aim was to provide basic data and technical support for the treatment of soils contaminated by rare earth elements. The results indicated that symbiotic associations were successfully established between the two isolates and maize, and the average AM colonization rate ranged from 7. 12% to 74.47%. The increasing concentration of Ce in soils significantly decreased the mycorrhizal colonization rate, biomass, nutrition contents and transport rate of Ce from root to shoot of maize, and significantly increased C: P and N: P ratios and Ce contents in shoot and root of maize. Both AM fungi inoculations promoted the growth of maize, but the promoting role of FM was more significant than that of GA in severe Ce-contaminated soils. There were no significant differences in the growth of maize between two AM fungi in mild and moderate Ce-contaminated soils. Inoculation with AM fungi significantly improved nutritional status of maize by increasing nutrient uptake and decreasing C: N: P ratios. GA was more efficient than FM in enhancing nutrient uptake in mild and moderate Ce-contaminated soils, while FM was more efficient in severe Ce-contaminated soils. Moreover, inoculation with AM fungi significantly increased Ce contents of shoot and root in mild Ce-contaminated soils, but had no significant effect on Ce contents of maize in moderate and severe Ce-contaminated soils, and promoted the transport of Ce from root to shoot. The experiment demonstrates that AM fungi can alleviate toxic effects of Ce on plants and have a potential role in the phytoremediation of soils contaminated by rare earth elements.

Protonation enhancement by dichloromethane doping in low-pressure photoionization.

Doping has been used to enhance the ionization efficiency of analytes in atmospheric pressure photoionization, which is based on charge exchange. Compounds with excellent ionization efficiencies are usually chosen as dopants. In this paper, we report a new phenomenon observed in low-pressure photoionization: Protonation enhancement by dichloromethane (CH2Cl2) doping. CH2Cl2 is not a common dopant due to its high ionization energy (11.33 eV). The low-pressure photoionization source was built using a krypton VUV lamp that emits photons with energies of 10.0 and 10.6 eV and was operated at ~500-1000 Pa. Protonation of water, methanol, ethanol, and acetaldehyde was respectively enhanced by 481.7 ± 122.4, 197.8 ± 18.8, 87.3 ± 7.8, and 93.5 ± 35.5 times after doping 291 ppmv CH2Cl2, meanwhile CH2Cl2 almost does not generate noticeable ions itself. This phenomenon has not been documented in the literature. A new protonation process involving in ion-pair and H-bond formations was proposed to expound the phenomenon. The observed phenomenon opens a new prospect for the improvement of the detection efficiency of VUV photoionization.