Secondary Ion Formation Research Articles

Effects of Hydrogen Dissociation During Gas Flooding on Formation of Metal Hydride Cluster Ions in Secondary Ion Mass Spectrometry

The application of hydrogen flooding was recently shown to be a simple and effective approach for improved layer differentiation and interface determination during secondary ion mass spectrometry (SIMS) depth profiling of thin films, as well as an approach with potential in the field of quantitative SIMS analyses. To study the effects of hydrogen further, flooding of H2 molecules was compared to reactions with atomic H on samples of pure metals and their alloys. H2 was introduced into the analytical chamber via a capillary, which was heated to approximately 2200 K to achieve dissociation. Dissociation of H2 up to 30% resulted in a significant increase in the intensity of the metal hydride cluster secondary ions originating from the metallic samples. Comparison of the time scales of possible processes provided insight into the mechanism of hydride cluster secondary ion formation. Cluster ions presumably form during the recombination of the atoms and molecules from the sample and atoms and molecules adsorbed from the gas. This process occurs on the surface or just above it during the sputtering process. These findings coincide with those of previous mechanistic and computational studies.

Role of Ammonia in Aerosol Liquid Water, pH, and Secondary Inorganic Aerosols Formation at an Ammonia-rich City in Changzhou

Ammonia （NH3） is an important alkaline reactive nitrogen, which, as a precursor of fine particulate matter, raises public health issues. In this study, online NH3, SO2, NO2, PM2.5, and its water-soluble inorganic ions were detected to deduce the influence of NH3 on aerosol liquid water content （AWC） and aerosol pH, including the formation of water-soluble secondary ions in PM2.5 in winter in Changzhou, an ammonia-rich city in the Yangtze River Delta area in winter. The results showed that NH4+ mainly existed in the form of NH4NO3 and （NH4）2SO4, and the remaining NH4+ existed as NH4Cl. Owing to the NH3-NH4+ buffer system, the aerosol pH values were found at 4.2 ± 0.4, which was positively correlated with the NH3 content. The aerosol pH value variation narrowed with the increase in PM2.5 concentration and tended to be between 4 to 5. AWC increased exponentially with the increase in humidity and SNA content, among which NH4NO3, （NH4）2SO4, and NH4Cl contributed 58.5%, 18.4%, and 8.3%, respectively, due to their hygroscopicity. Aerosol pH, AWC, and NH3-NH4+ conversion promoted the gas-to-particle conversion of SO2 and NO2. In Changzhou, rich NH3-NH4+ were found to maintain relatively high pH values, push up AWC, and promote the heterogeneous reaction of SO2, whereas NO3- generation was dominated by a homogeneous reaction, which was accelerated by NH3. According to the simulation results, relatively noticeable changes in aerosol pH and AWC could be found by the reduction of up to 30% of NH3.

SIMS analysis of the degradation pathways of methylammonium lead-halide perovskites

This study employed time-of-flight secondary ion mass spectrometry (TOF-SIMS) to investigate degradation pathways at the nanoscale, utilizing its capacity for in-depth chemical and structural analysis through various methods, including depth profiling and 3D analysis. A key focus is the matrix effect in ToF-SIMS, which alters secondary ion yields based on the sample matrix composition, influencing species identification and quantification. We show that this effect can be used to enhance the resolution of ToF-SIMS beyond its traditional limits, allowing for detailed imaging of the degradation process. Our findings indicate that the initial formation of PbI2 phases, a crucial step in the degradation pathway triggered by environmental factors, can be traced and visualized. By investigating the sputtering yields and secondary ion formation, we reveal the nonlinear sputtering regimes present in MAPI, contributing to our understanding of the mechanisms driving perovskite degradation. The application of this enhanced analytical technique paves the way for improved degradation studies.

A model for a Langmuir sheath in a stagnating dense plasma with secondary ion formation

This simplified model provides solutions for the current-voltage characteristics of a sheath in a dense flowing plasma when surface chemistry contributes secondary ions. The problem is motivated by the recent discovery that strong transient signals in industrial ion current sensors are caused by chemical reactions with carbon in the steel being cut or welded by oxyfuel processes. The one-dimensional model considers a quasi-uniform dense plasma flowing towards and stagnating on an absorbing surface, above which there is a source of secondary ions. Because the secondary ions are formed directly in the plasma sheath, they have strong impacts on the current-voltage characteristic. With ionic Reynolds number, R, and integral length scale, α, secondary ion formation rate, Ω, and length scale, β, saturation currents are simply R + βΩ until β ≪ 1, at which point, new electrons cannot escape the sheath, and secondary ions have no effect. Floating potential, ϕ ∞, scales like exp(ϕ∞)∝R−3/4 , and secondary ions have little impact unless β 2Ω > 1. Even then, floating potential is only weakly affected by secondary ion formation. The integral length scale, α, is not found to strongly affect the results.

Seasonal Variations, Size Distributions, and Sources of Chemical Components of Submicron Particulate Matter in Nanjing

Size-segregated particulate matter (PM) samples were collected in different seasons from 2016 to 2017 at the Xianlin Campus of Nanjing University. Mass concentrations of water-soluble inorganic ions, carbonaceous components, and elements were analyzed for PM with an aerodynamic diameter ≤ 1.1 μm (PM1.1; <0.4 μm, 0.4-0.7 μm, and 0.7-1.1 μm). The results showed that PM1.1, OC, NO3-, SO42-, and NH4+ exhibited higher ambient levels in fall-winter than those in spring-summer, which was attributed to the changes in local diffusion conditions, evaporation, and decomposition of non-refractory components. Elemental carbon (EC) reached its maximum concentration[(1.87±0.98) μg·m-3]in spring due to the increase in industrial and road dust resuspension. According to the characteristic ratio between bulk components, the anions in PM1.1 were dominated by NO3-, SO42-, and Cl- in Nanjing, and the carbonaceous components were mainly from fossil fuel combustions and associated aging processes. As the ambient temperature increased, the size distributions of thermo-unstable components including NH4+, NO3-, and OC shifted towards finer particles, whereas EC became more enriched in coarse particles, possibly due to the increase in emission intensity of motor vehicles and fugitive dust contributions. Since high relative humidity (>70%) is often accompanied by high temperature (>20℃) and improved diffusion conditions, a relative humidity of 60%-70% was more conducive to the formation of secondary inorganic ions in PM1.1. Source apportionment results based on the speciation data of PM1.1 showed that secondary formation processes[(66.6±18.3)%]and dust resuspension[(16.8±14.8)%]were the main contributors to PM1.1 in Nanjing, and further control of the emissions of gaseous precursors and dust is necessary.

Sensitivity enhancement using chemically reactive gas cluster ion beams in secondary ion mass spectrometry (SIMS)

We report for the first time on significant molecular secondary ion yield increases by modifying the chemistry of a water cluster primary ion beam. This was demonstrated using 70‐keV ion beams of 0.15 eV/amu. For the neutral drug Bezafibrate, secondary ion yield enhancements ×5–10 were observed when replacing the Ar carrier gas in a water gas cluster ion beam (GCIB) source with a mixture containing 12% CO2 and 2% O2 in Ar. For the cationic drug Ranitidine, the ion yield enhancements using the CO2‐containing carrier gas were up to ×20–50 in positive mode and ×2–4 in negative mode. The extent of molecular fragmentation was very similar from both cluster beams. We conclude that additional chemically reactive species are present in the impact zone using the (H2O/CO2)n projectile, which promote the formation of secondary ions of both polarity through projectile impact‐induced chemical reactions. This methodology can be applied to further extend the capabilities of high‐resolution 3‐dimensional mass spectral imaging using reactive GCIB‐SIMS.

Insights into secondary ion formation during dynamic SIMS analysis: Evidence from sputtering of laboratory synthesized uranium compounds with a high-energy O− primary beam on a NanoSIMS 50L

We investigate the sputtering and ionization process that takes place during secondary ion mass spectrometry (SIMS) analysis in order to develop a better understanding of the underlying controls on elemental and molecular oxide secondary ion yields. Using data from a suite of uranium compounds that were sputtered with an O- primary beam on a NanoSIMS 50L, our goal is to understand whether a compound’s intrinsic properties, or processes operating at the sputtering site, exert the greatest influence over the relative abundances of uranium elemental and molecular oxide secondary ions observed during an analysis. While the observed 238U/238U16O and 238U/238U16O2 of the various compounds exhibit considerable overlap, there are relationships between the weighted mean 238U/238U16O and 238U/238U16O2 ratios for the various compounds and their enthalpies of formation. This reinforces the existing theory that the nature of the material being sputtered can influence relative ion yields (e.g. the SIMS matrix effect), but we also document significant evidence for the influence of processes operating at the sputtering site as a major factor. The existence of a strong relationship between the relative uranium molecular oxide production rate and the mass fractionation regimes taking place within an analysis, as well as the existence of sudden shifts in molecular oxide production rates taking place within an analysis, provide further evidence for the importance of processes related to the sputtering and ionization dynamics as exerting the most control over observed ion yields. Evaluation of our data within the context of existing models for secondary ion production during SIMS analysis highlights the need for additional models that consider the competing influences of a sample’s chemical and/or structural form, reactions taking place at the sputtering site, as well as the ionization and ion extraction dynamics of the various elemental and molecular oxide species.

Particles liquid water and acidity determine formation of secondary inorganic ions in Urumqi, NW China

Secondary atmospheric pollutants are an important component of the particles found in Urumqi city, China, Further, secondary inorganic aerosols, in particular, increase significantly during the winter heating period. In this study, samples collected from October 2017 to August 2018 from Urumqi were analyzed. Results showed that the average concentration of water-soluble inorganic ions (WSIs) in the heating period (86.9 ± 31.1 μg·m−3) was significantly higher than that in the non-heating period (14.1 ± 8.67 μg·m−3). SNA (SO42−, NO3−, NH4+) accounted for 90.7% of the total WSIs (TWSIs) in the heating period. Simulations revealed that the in situ pH (3.1) was higher in the heating period than that in non-heating period (0.66) when they were calculated by the aerosol thermodynamic model. The particles were found to be acidity during the entire period. The liquid water content of the particulates (LWC) was found to higher in the heating period (55.5 ± 51.8 μg·m−3) than the non-heating period (21.3 ± 40.3 μg·m−3). The average nitrogen oxidation rate (NOR) and sulfur oxidation rate (SOR) were 0.16 and 0.36, respectively, indicating a significant secondary formation of nitrate and sulfate in the atmosphere of Urumqi. Further analysis indicated that sulfate was significantly affected by the LWC and acidity of the particulates; nitrate was produced under ammonia-rich conditions in Urumqi, and the LWC facilitated the production of nitrate. This study provides information about the formation of secondary sulfate and nitrate aerosols during different periods in suburban Urumqi.

Ionization and fragmentation of methane, ethane, propane, and benzene induced by keV atomic cations

Collisions of keV atomic cations (He+, Ne+, Ar+, Kr+, Xe+, F+, Cl+, Br+, I+, Se+, Te+, Sb+, and Fe+) with neutral hydrocarbon molecules (methane, ethane, propane, and benzene) were measured using a modified sector type mass spectrometer. The atomic cations were produced in an electron ionization ion source, accelerated and mass selected by a magnetic sector. The beam of cations was subsequently guided into a collision chamber filled with the neutral hydrocarbon molecules. Secondary ions stemming from the ion/molecule interactions were analyzed by a quadrupole mass analyzer placed perpendicularly to the ion beam. Results presented in this paper show strong dependence of product ion formation and relative fragmentation yield (expressed as a Σ[F+i]/(Σ[F+i] + [M+]) ratio) on recombination energy of projectile ions. The influence of center-of-mass collision energy, as well as kinetic energy of the projectile, on secondary ion formation are also explored and discussed.

An evaluation of source apportionment of fine OC and PM2.5 by multiple methods: APHH-Beijing campaigns as a case study.

This study aims to critically evaluate the source apportionment of fine particles by multiple receptor modelling approaches, including carbon mass balance modelling of filter-based radiocarbon (14C) data, Chemical Mass Balance (CMB) and Positive Matrix Factorization (PMF) analysis on filter-based chemical speciation data, and PMF analysis on Aerosol Mass Spectrometer (AMS-PMF) or Aerosol Chemical Speciation Monitor (ACSM-PMF) data. These data were collected as part of the APHH-Beijing (Atmospheric Pollution and Human Health in a Chinese Megacity) field observation campaigns from 10th November to 12th December in winter 2016 and from 22nd May to 24th June in summer 2017. 14C analysis revealed the predominant contribution of fossil fuel combustion to carbonaceous aerosols in winter compared with non-fossil fuel sources, which is supported by the results from other methods. An extended Gelencsér (EG) method incorporating 14C data, as well as the CMB and AMS/ACSM-PMF methods, generated a consistent source apportionment for fossil fuel related primary organic carbon. Coal combustion, traffic and biomass burning POC were comparable for CMB and AMS/ACSM-PMF. There are uncertainties in the EG method when estimating biomass burning and cooking OC. The POC from cooking estimated by different methods was poorly correlated, suggesting a large uncertainty when differentiating this source type. The PM2.5 source apportionment results varied between different methods. Through a comparison and correlation analysis of CMB, PMF and AMS/ACSM-PMF, the CMB method appears to give the most complete and representative source apportionment of Beijing aerosols. Based upon the CMB results, fine aerosols in Beijing were mainly secondary inorganic ion formation, secondary organic aerosol formation, primary coal combustion and from biomass burning emissions.

A statistical model of secondary ion emission and attenuation clarifies disparities in quasi-simultaneous arrival coefficients measured with secondary ion mass spectrometry.

Secondary ion mass spectrometry data collected using electron multiplier detectors are subject to a correction for the quasi-simultaneous arrival (QSA) effect. Published Poisson statistical models indicate that the QSA coefficients, β, should have an invariant value of 0.5, whereas, with one exception, published experimental determinations vary between 0.6 and 1.0, with a mean value of 0.75. We developed a more complex model, combining both ion emission and attenuation, that predicts the observed range in measured β and elucidates the mechanism of secondary ion formation. For a given aperture setting, any secondary ion has an equal probability of successful transit to the electron multiplier. Binomial statistics can model pass-fail aperture attenuation but require probability distributions of the quasi-simultaneously emitted (QSE) ion tally, per primary ion, as input. Assuming (a) that each primary ion impact results in 0, 1, 2,… secondary ion emissions, randomly, with an average Ks and (b) that there is finite probability (P2) of a further emission process dependent on Ks , the required QSE probability distributions were generated via a combined Poisson-binomial statistical model. The value of β was output as a function of Ks and P2. For values of P2 > 0 and any value of Ks , β always exceeds 0.5. As P2 → 0, β → 0.5; for values of increasing P2 > 0.5 and decreasing Ks < 0.5, β → >1. Were the emission of one ion not to influence the probability of the formation of a second (i.e. model output for P2 = 0), β should always be 0.5. Yet measurements have never reported this value. Consequently, assuming that published β values are correct, emissions of QSE secondary ions do not occur independently, and it may be inferred that there are linked mechanisms of secondary ion formation as shown here.

High time-resolved PM2.5 composition and sources at an urban site in Yangtze River Delta, China after the implementation of the APPCAP

In this study, hourly concentrations of PM2.5 water-soluble inorganic ions, bulk organic carbon (OC), and elemental carbon (EC) were monitored from 1/1/2017 to 12/31/2017 and validated using filter-based offline analysis at an urban site in Nanjing, China. Compared with 2013 or before, the annual average of PM2.5 concentration (36.5 ± 32.9 μg m−3) in 2017 decreased by more than 40%, NO3− (12.8 ± 11.4 μg m−3) became the most abundant water-soluble ion instead of SO42− (9.29 ± 6.07 μg m−3), and the relative contribution of OC (5.92 ± 3.40 μg m−3) and EC (2.95 ± 1.53 μg m−3) to bulk PM2.5 (24.9 ± 9.31%) increased substantially, indicating the effectiveness of the control policy for reducing gaseous precursor emissions. Based on the diurnal variations of water-soluble ions and gaseous pollutants, NH4+, SO42−, and NO3− were secondarily formed and NH4NO3 dominated the composition of ammonium salts in PM2.5. The diurnal changes of OC, EC, and OC/EC ratios reflected prominent influences from local traffic patterns. Positive matrix factorization was performed using hourly data of PM2.5 components (PMF1-h), of which the results were justified by comparing to those using 23-h averaged data (PMF23-h). Given that the secondary ion formation was still the dominant source (68.2%) of PM2.5, and the average PM2.5 concentration in urban Nanjing remained higher than Tier II limit (35 μg m−3) of the Chinese National Ambient Air Quality Standard, controlling emissions of PM2.5 precursor gases should be continued after the completion of Air Pollution Prevention and Control Action Plan in 2017.

Ionization probability of sputtered indium atoms under impact of slow highly charged ions

In order to investigate the different role of kinetic and potential projectile energy for secondary ion formation, the authors have measured the ionization probability of indium atoms sputtered from a clean indium surface under irradiation with rare gas (Xeq+) ions of different charge states q at the same kinetic impact energy of 20 keV. In this energy range, the kinetic energy of the projectile is predominantly deposited via nuclear stopping, leading to a collision-dominated sputtering process. The authors find that the ionization probability increases significantly if a highly charged ion is used as a projectile, where the ionization energy becomes comparable to or even exceeds the kinetic energy, indicating that a higher level of electronic substrate excitation induced by the potential energy stored in the projectile can boost the secondary ion formation process. This experimental result is discussed in terms of microscopic model calculations describing the secondary ion formation process. At the same time, the authors observe a significant change of the emission velocity distribution of the sputtered particles, leading to a pronounced low-energy contribution at higher projectile charge states. It is shown that this “potential sputtering” contribution strongly depends on surface chemistry even under conditions where the surface is dynamically cleaned by interleaved 5 keV Ar+ ion bombardment.

Seasonal Control of Water-Soluble Inorganic Ions in PM2.5 from Nanning, a Subtropical Monsoon Climate City in Southwestern China

In this study, we measured the daily water-soluble inorganic ions (WSIIs) concentration (including SO42−, NO3−, NH4+, Ca2+, K+, Cl−, Na+, Mg2+, and F−) of PM2.5 (particulate matter with a diameter smaller than 2.5 μm) throughout the year in Nanning (a typical subtropical monsoon climate city in southwestern China) to explore the influence of seasonal climate change on the properties of PM2.5 pollution. This suggested that SO42−, NO3−, and NH4+ were the main component of WSIIs in Nanning. Secondary inorganic ions from fossil fuel combustion, agricultural activities, and automobile emissions were the main contributors to PM2.5, contributing more than 60% to PM2.5. Compared with the wet season, the contributions of different sources increased in the dry season (including pollution days); of these sources, automobile emissions and coal combustion emissions increased the most (about nine times and seven times, respectively). Seasonal weather and climate change affected the concentration level of WSIIs. During the wet season, higher temperatures and abundant rainfalls contributed to the volatilization and removal of WSIIs in PM2.5, while in the dry season and on pollution days, lower temperatures and less precipitation, higher emissions, and poor diffusion conditions contributed to the accumulation of WSIIs in PM2.5. NH4HSO4, (NH4)2SO4 and NH4NO3 were the main chemical forms of secondary inorganic ions. Sufficient NH3, intense solar radiation, and moist particulate matter surface promoted the formation of secondary inorganic ions. The higher temperature contributed to the volatilization of secondary inorganic ions.

Ionization probability of sputtered coronene molecules

The formation of molecular secondary ions released from a Coronene film under irradiation with a 20-keV C60+ ion beam is investigated using combined time-of-flight Secondary Ion and Neutral Mass Spectrometry (ToF-SIMS/SNMS). More specifically, the charge state distribution of intact sputtered coronene molecules M is investigated by comparing the yield of molecular ions M+ with that of their neutral counterparts M0, with the latter being post-ionized after their ejection from the surface using single photon ionization in a pulsed vacuum-ultraviolet laser beam. A quantitative determination of the molecular ionization probability from such experiments requires precise information regarding the post-ionization efficiency as well as the laser induced photofragmentation of the sputtered neutral molecules, which is obtained from the laser intensity dependence of the measured ToF spectra. In order to assess the role of internal excitation encompassed during the sputter ejection process, the results obtained for sputtered molecules are compared with those obtained for thermally evaporated coronene molecules. As a result, we find an ionization probability of sputtered intact coronene molecules of the order of 10−3, which confirms previous data obtained in a similar experiment using a fundamentally different post-ionization scheme.

Analysis of Pollution Characteristics and Sources of PM2.5 Chemical Components in Chengdu in Winter

Day-night PM2.5 samples were continuously collected in Chengdu from January 1 to 20, 2017, and the concentrations of major chemical components (water-soluble ions and carbonaceous components) were measured in the laboratory. During the observation period, the average mass concentration of PM2.5 was (127.1±59.9) μg·m-3. The mass concentration of water-soluble ions was (56.5±25.7) μg·m-3 and SO42-, NO3-, and NH4+ were the most dominant ions with a concentration of (13.6±5.5), (21.4±12.0), and (13.3±5.7) μg·m-3, respectively, accounting for 85.6% of the water-soluble ions. The average mass concentrations of organic carbon (OC) and elemental carbon (EC) were 34.0 and 6.1 μg·m-3, respectively, accounting for 26.8% and 4.8% of the PM2.5 mass concentration, respectively. The comparison of the average day-night concentration shows that the daytime and nighttime mass concentrations of PM2.5 are (120.4±56.4) and (133.8±64.0) μg·m-3, respectively, and that the nighttime pollution is more serious. The SO42-, NO3-, and NH4+ concentrations are higher during the day than at night, which is related to daytime light, which promotes the formation of secondary ions. The Cl-, K+, OC, and EC concentrations increase significantly, which may be affected by increased emissions from coal and material combustion. Based on the literature review and comparison of the winter chemical composition of PM2.5 in Chengdu in recent years, the SO42- concentration significantly decreases from 50.6 μg·m-3 in 2010 to 13.6 μg·m-3 in 2017. The NO3- concentration changes little; it is maintained at~20 μg·m-3. The analysis of the acid-alkali ion balance shows that PM2.5 in Chengdu is alkaline due to the relative overgrowth of NH4+, which is different from previous partially acidic results. The average value of NO3-/SO42- is 1.57. Mobile sources have a greater impact on the PM2.5 pollution in Chengdu in winter. The correlation coefficients of OC and EC between daytime and nighttime are 0.82 and 0.90, respectively (P<0.01), which indicates that the OC and EC sources are consistent. The SOC estimation shows that the SOC concentrations during the day and night are 8.5 μg·m-3 and 11.9 μg·m-3, respectively, accounting for 28.1% and 30.8% of the OC, respectively. The K+/EC average value is 0.31 and the correlation coefficient between K+ and OC is 0.87 (P<0.01), indicating that biomass combustion has a certain influence on the carbonaceous aerosol in Chengdu in winter. The principal component analysis shows that the winter PM2.5 in Chengdu mainly originates from combustion sources (coal burning, biomass burning, etc.), secondary inorganic sources, and soil and dust sources. The contribution rates are 32.8%, 34.5%, and 21.5%, respectively.

Seasonal Variation and Source Analysis of Water-soluble Inorganic Salts in PM2.5 in the Southern Suburbs of Beijing

In order to study the variation of water-soluble inorganic ions in the four suburbs of Beijing using the atmospheric fine particulate matter rapid trapping system and chemical composition analysis system (RCFP-IC), we carried out measurements for nine water-soluble inorganic ions (Cl-, NO2-, NO3-, SO42-, Na+, NH4+, K+, Mg2+, Ca2+) in PM2.5 with continuous on-line observations for one year in Beijing's southern suburbs in 2016. The transport process of pollutants and the potential sources of pollutants were evaluated by combining a trajectory clustering method and potential source contribution factor analysis method (PSCF). During the observation period, the total concentration of the nine water-soluble inorganic ions was 38.6 μg ·m-3, and results showed that the concentration in winter and spring was high and in summer and autumn was low. The order of the concentration from high to low was SO42- > NO3- > NH4+ > Ca2+ > NO2- > Cl- > Na+ > K+ > Mg2+. In winter, the SO42-, NO3- and NH4+ accounted for 75.7% of the total measured water-soluble ions, followed by 72.8% in spring and 60.2% in summer. With an increase in air pollution, the concentrations of SO42-, NO3-, and NH4+ increased significantly, indicating that SO42-, NO3-, and NH4+ were closely related to the deterioration of air quality. SO42- was dominant in the formation of secondary ions compared to NO3- and NH4+; and SO42-, NO3-, and NH4+ had significant diurnal variations. The diurnal variation of the SO42- statistic (hours) was bimodal, and the peak values were at about 10:00 and 18:00. The diurnal variation of NO3- and NH4+ had single peaks, with the peak appearing at 10:00. The trend of the diurnal variation for these two ions was similar. Finally, the sources of pollution in the southern suburbs of Beijing mainly included secondary sources, coal-fired sources, and mixed sources of dust and dust. The main potential source of pollution in the southern suburbs was in the southeastern part of the observation site, while the northeastern airflow was favorable for the diffusion and dilution of pollutants.

Secondary ion formation during electronic and nuclear sputtering of germanium

Abstract Using a time-of-flight mass spectrometer attached to the UNILAC beamline located at the GSI Helmholtz Centre for Heavy Ion Research, we investigate the formation of secondary ions sputtered from a germanium surface under irradiation by swift heavy ions (SHI) such as 5 MeV/u Au by simultaneously recording the mass spectra of the ejected secondary ions and their neutral counterparts. In these experiments, the sputtered neutral material is post-ionized via single photon absorption from a pulsed, intensive VUV laser. After post-ionization, the instrument cannot distinguish between secondary ions and post-ionized neutrals, so that both signals can be directly compared in order to investigate the ionization probability of different sputtered species. In order to facilitate an in-situ comparison with typical nuclear sputtering conditions, the system is also equipped with a conventional rare gas ion source delivering a 5 keV argon ion beam. For a dynamically sputter cleaned surface, it is found that the ionization probability of Ge atoms and Gen clusters ejected under electronic sputtering conditions is by more than an order of magnitude higher than that measured for keV sputtered particles. In addition, the mass spectra obtained under SHI irradiation show prominent signals of GenOm clusters, which are predominantly detected as positive or negative secondary ions. From the m-distribution for a given Ge nuclearity n, one can deduce that the sputtered material must originate from a germanium oxide matrix with approximate GeO stoichiometry, probably due to residual native oxide patches even at the dynamically cleaned surface. The results clearly demonstrate a fundamental difference between the ejection and ionization mechanisms in both cases, which is interpreted in terms of corresponding model calculations.

Impact of mixed anthropogenic and natural emissions on air quality and eco-environment—the major water-soluble components in aerosols from northwest to offshore isle

Based on more than 300 atmospheric TSP and PM2.5 samples collected at five sites over China in 2007 and 2008, characteristics, sources, and interactions of the major water-soluble species were investigated for a better understanding of their role in urban air quality and offshore eco-environment. From the dust source regions in Northwestern China to an offshore isle over the East China Sea, concentration levels and fine/coarse particle distributions of five representative water-soluble components were well elucidated, reflecting the distinct differences of geo-history, location, and present economic situation among the target areas. NO3−/SO42− mass ratios reflected significant divergence of motorization among the studied regions. Specifically, a case study during the World Car-Free Day proved that traffic restriction measures could indeed help mitigate the aerosol species formed from vehicle emissions. Investigation on the molar concentration stoichiometry and mass percentage variations of particulate NO3−, SO42−, and NH4+ revealed that NH3 was a driving factor in the formation of major secondary water-soluble ions in atmospheric fine particles over urban areas. Based on the prevailing wind analysis, observation over an offshore isle clearly indicated the influence of the relative strength of anthropogenic sources and ocean-related natural sources on the formation and size distribution of MSA (methanesulfonic acid), a major water-soluble organic component in aerosol. Annual dry deposition flux of particulate NO3− and NH4+ over the East China Sea was estimated based on the strength of an improved calculation formula. Reductive nitrogen was found to be the major form of the deposited atmospheric inorganic nitrogen, accounting for ~ 69% of the total nitrogen depositions.

Molecular ionization probability in cluster-SIMS

The ionization efficiency of molecular species sputtered under bombardment with cluster ion beams is generally assumed to be rather low, but hard experimental evidence for this notion is still lacking. In order to estimate the prospects for possible sensitivity improvements in molecular secondary ion mass spectrometry (SIMS) experiments, the author therefore reports on recent experiments utilizing laser postionization (LPI) in order to determine an absolute ionization probability value for a few organic molecules sputtered under C60 cluster ion bombardment. The results show that the molecular ionization efficiency obtained under these bombarding conditions is of the order of 10−3, leaving at least 2 orders of magnitude for possible enhancement of the physical or a chemical ionization mechanism leading to the formation of (quasi-) molecular secondary ions. Analyzing the measured molecular LPI signal, the author demonstrates that about the same headroom exists for improvement of the currently achieved postionization efficiency. Using trehalose as a model system, the author then illustrates the level of improvement achieved by different attempts to utilize projectile induced surface chemistry in order to enhance the ionization efficiency. The results may be useful to guide new developments aimed at enhancing the detection sensitivity in molecular cluster-SIMS experiments.