Polynuclear Speciation of Trivalent Cations near the Surface of an Electrolyte Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bera, Mrinal K.; Antonio, Mark R.

Despite long-standing efforts, there is no agreed upon structural model for electrolyte solutions at air-liquid interfaces. We report the simultaneous detection of the near-surface and bulk coordination environments of a trivalent metal cation (europium) in an aqueous solution by use of X-ray absorption spectroscopy. Within the first few nanometers of the liquid surface, the cations exhibit oxygen coordination typical of inner-sphere hydration of an aquated Eu3+ cation. Beyond that, outer-sphere ion-ion correlations are observed that are otherwise not present in the bulk electrolyte. The combination of near-surface and bulk sensitivities to probe metal ion speciation in electrolyte solutions is achievedmore » by detecting electron-yield and X-ray fluorescence signals from an inverted pendant drop. The results provide new knowledge about the near-surface chemistry of aqueous solutions of relevance to aerosols and ion transport processes in chemical separations and biological systems.« less

Extraordinarily rapid speciation in a marine fish

PubMed Central

Momigliano, Paolo; Jokinen, Henri; Fraimout, Antoine; Florin, Ann-Britt; Norkko, Alf; Merilä, Juha

2017-01-01

Divergent selection may initiate ecological speciation extremely rapidly. How often and at what pace ecological speciation proceeds to yield strong reproductive isolation is more uncertain. Here, we document a case of extraordinarily rapid speciation associated with ecological selection in the postglacial Baltic Sea. European flounders (Platichthys flesus) in the Baltic exhibit two contrasting reproductive behaviors: pelagic and demersal spawning. Demersal spawning enables flounders to thrive in the low salinity of the Northern Baltic, where eggs cannot achieve neutral buoyancy. We show that demersal and pelagic flounders are a species pair arising from a recent event of speciation. Despite having a parapatric distribution with extensive overlap, the two species are reciprocally monophyletic and show strongly bimodal genotypic clustering and no evidence of contemporary migration, suggesting strong reproductive isolation. Divergence across the genome is weak but shows strong signatures of selection, a pattern suggestive of a recent ecological speciation event. We propose that spawning behavior in Baltic flounders is the trait under ecologically based selection causing reproductive isolation, directly implicating a process of ecological speciation. We evaluated different possible evolutionary scenarios under the approximate Bayesian computation framework and estimate that the speciation process started in allopatry ∼2,400 generations ago, following the colonization of the Baltic by the demersal lineage. This is faster than most known cases of ecological speciation and represents the most rapid event of speciation ever reported for any marine vertebrate. PMID:28533412

Female Drosophila melanogaster gene expression and mate choice: the X chromosome harbours candidate genes underlying sexual isolation.

PubMed

Bailey, Richard I; Innocenti, Paolo; Morrow, Edward H; Friberg, Urban; Qvarnström, Anna

2011-02-28

The evolution of female choice mechanisms favouring males of their own kind is considered a crucial step during the early stages of speciation. However, although the genomics of mate choice may influence both the likelihood and speed of speciation, the identity and location of genes underlying assortative mating remain largely unknown. We used mate choice experiments and gene expression analysis of female Drosophila melanogaster to examine three key components influencing speciation. We show that the 1,498 genes in Zimbabwean female D. melanogaster whose expression levels differ when mating with more (Zimbabwean) versus less (Cosmopolitan strain) preferred males include many with high expression in the central nervous system and ovaries, are disproportionately X-linked and form a number of clusters with low recombination distance. Significant involvement of the brain and ovaries is consistent with the action of a combination of pre- and postcopulatory female choice mechanisms, while sex linkage and clustering of genes lead to high potential evolutionary rate and sheltering against the homogenizing effects of gene exchange between populations. Taken together our results imply favourable genomic conditions for the evolution of reproductive isolation through mate choice in Zimbabwean D. melanogaster and suggest that mate choice may, in general, act as an even more important engine of speciation than previously realized.

Trace metal speciation in natural waters: Computational vs. analytical

USGS Publications Warehouse

Nordstrom, D. Kirk

1996-01-01

Improvements in the field sampling, preservation, and determination of trace metals in natural waters have made many analyses more reliable and less affected by contamination. The speciation of trace metals, however, remains controversial. Chemical model speciation calculations do not necessarily agree with voltammetric, ion exchange, potentiometric, or other analytical speciation techniques. When metal-organic complexes are important, model calculations are not usually helpful and on-site analytical separations are essential. Many analytical speciation techniques have serious interferences and only work well for a limited subset of water types and compositions. A combined approach to the evaluation of speciation could greatly reduce these uncertainties. The approach proposed would be to (1) compare and contrast different analytical techniques with each other and with computed speciation, (2) compare computed trace metal speciation with reliable measurements of solubility, potentiometry, and mean activity coefficients, and (3) compare different model calculations with each other for the same set of water analyses, especially where supplementary data on speciation already exist. A comparison and critique of analytical with chemical model speciation for a range of water samples would delineate the useful range and limitations of these different approaches to speciation. Both model calculations and analytical determinations have useful and different constraints on the range of possible speciation such that they can provide much better insight into speciation when used together. Major discrepancies in the thermodynamic databases of speciation models can be evaluated with the aid of analytical speciation, and when the thermodynamic models are highly consistent and reliable, the sources of error in the analytical speciation can be evaluated. Major thermodynamic discrepancies also can be evaluated by simulating solubility and activity coefficient data and testing various chemical models for their range of applicability. Until a comparative approach such as this is taken, trace metal speciation will remain highly uncertain and controversial.

Chemical modeling of groundwater in the Banat Plain, southwestern Romania, with elevated As content and co-occurring species by combining diagrams and unsupervised multivariate statistical approaches.

PubMed

Butaciu, Sinziana; Senila, Marin; Sarbu, Costel; Ponta, Michaela; Tanaselia, Claudiu; Cadar, Oana; Roman, Marius; Radu, Emil; Sima, Mihaela; Frentiu, Tiberiu

2017-04-01

The study proposes a combined model based on diagrams (Gibbs, Piper, Stuyfzand Hydrogeochemical Classification System) and unsupervised statistical approaches (Cluster Analysis, Principal Component Analysis, Fuzzy Principal Component Analysis, Fuzzy Hierarchical Cross-Clustering) to describe natural enrichment of inorganic arsenic and co-occurring species in groundwater in the Banat Plain, southwestern Romania. Speciation of inorganic As (arsenite, arsenate), ion concentrations (Na + , K + , Ca 2+ , Mg 2+ , HCO 3 - , Cl - , F - , SO 4 2- , PO 4 3- , NO 3 - ), pH, redox potential, conductivity and total dissolved substances were performed. Classical diagrams provided the hydrochemical characterization, while statistical approaches were helpful to establish (i) the mechanism of naturally occurring of As and F - species and the anthropogenic one for NO 3 - , SO 4 2- , PO 4 3- and K + and (ii) classification of groundwater based on content of arsenic species. The HCO 3 - type of local groundwater and alkaline pH (8.31-8.49) were found to be responsible for the enrichment of arsenic species and occurrence of F - but by different paths. The PO 4 3- -AsO 4 3- ion exchange, water-rock interaction (silicates hydrolysis and desorption from clay) were associated to arsenate enrichment in the oxidizing aquifer. Fuzzy Hierarchical Cross-Clustering was the strongest tool for the rapid simultaneous classification of groundwaters as a function of arsenic content and hydrogeochemical characteristics. The approach indicated the Na + -F - -pH cluster as marker for groundwater with naturally elevated As and highlighted which parameters need to be monitored. A chemical conceptual model illustrating the natural and anthropogenic paths and enrichment of As and co-occurring species in the local groundwater supported by mineralogical analysis of rocks was established. Copyright © 2016 Elsevier Ltd. All rights reserved.

Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shukla, Anil; Bogdanov, Bogdan

2015-02-14

Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry. Singly as well as multiply charged clusters were formed with the general formulae, (HCOOLi)nLi+, (HCOOLi)nLimm+, (HCOOLi)nHCOO- and (HCOOLi)n(HCOO)mm-. Several magic number cluster ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi)3Li+ being the most abundant and stable cluster ions. Fragmentations of singly charged clusters proceed first by the loss of a dimer unit ((HCOOLi)2) followed by sequential loss of monomer units (HCOOLi). In the case ofmore » positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi)3Li+ at higher collision energies which later fragments to dimer and monomer ions in lower abundance. Quantum mechanical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability.« less

Influence of environmental conditions on the toxicokinetics of cadmium in the marine copepod Acartia tonsa.

PubMed

Pavlaki, Maria D; Morgado, Rui G; van Gestel, Cornelis A M; Calado, Ricardo; Soares, Amadeu M V M; Loureiro, Susana

2017-11-01

mMarine and estuarine ecosystems are highly productive areas that often act as a final sink for several pollutants, such as cadmium. Environmental conditions in these habitats can affect metal speciation, as well as its uptake and depuration by living organisms. The aim of this study was to assess cadmium uptake and depuration rates in the euryhaline calanoid copepod Acartia tonsa under different pH, salinity and temperature conditions. Cadmium speciation did not vary with changing pH or temperature, but varied with salinity. Free Cd 2+ ion activity increased with decreasing salinities resulting in increased cadmium concentrations in A. tonsa. However, uptake rate, derived using free Cd 2+ ion activity, showed no significant differences at different salinities indicating a simultaneous combined effect of Cd 2+ speciation and metabolic rates for osmoregulation. Cadmium concentration in A. tonsa and uptake rate increased with increasing pH, showing a peak at the intermediate pH of 7.5, while depuration rate fluctuated, thus suggesting that both parameters are mediated by metabolic processes (to maintain homeostasis at pH levels lower than normal) and ion competition at membrane binding sites. Cadmium concentration in A. tonsa, uptake and depuration rates increased with increasing temperature, a trend that can be attributed to an increase in metabolic energy demand at higher temperatures. The present study shows that cadmium uptake and depuration rates in the marine copepod A. tonsa is mostly affected by biological processes, mainly driven by metabolic mechanisms, and to a lesser extent by metal speciation in the exposure medium. Copyright © 2017 Elsevier Inc. All rights reserved.

Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shukla, Anil, E-mail: Anil.Shukla@pnnl.gov; Bogdanov, Bogdan

2015-02-14

Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry (collision-induced dissociation with N{sub 2}). Singly as well as multiply charged clusters were formed in both positive and negative ion modes with the general formulae, (HCOOLi){sub n}Li{sup +}, (HCOOLi){sub n}Li{sub m}{sup m+}, (HCOOLi){sub n}HCOO{sup −}, and (HCOOLi){sub n}(HCOO){sub m}{sup m−}. Several magic number cluster (MNC) ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi){sub 3}Li{sup +} being the most abundant and stable cluster ion. Fragmentations ofmore » singly charged positive clusters proceed first by the loss of a dimer unit ((HCOOLi){sub 2}) followed by the loss of monomer units (HCOOLi) although the former remains the dominant dissociation process. In the case of positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi){sub 3}Li{sup +} as the most abundant fragment ion at higher collision energies which then fragments further to dimer and monomer ions at lower abundances. In the negative ion mode, however, singly charged clusters dissociated via sequential loss of monomer units. Multiply charged clusters in both positive and negative ion modes dissociated mainly via Coulomb repulsion. Quantum chemical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the central lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability.« less

Effect of silver ions and clusters on the luminescence properties of Eu-doped borate glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiao, Qing, E-mail: jiaoqing@nbu.edu.cn; Wang, Xi; Qiu, Jianbei

2015-12-15

Highlights: • Ag{sup +} and Ag clusters are investigated in the borate glasses via ion exchange method. • The aggregation of silver ions to the clusters was controlled by the ion exchange concentration. • Eu{sup 3+}/Eu{sup 2+} ions emission was enhanced with the sensitization of the silver species. • Energy transfer process from Ag ions and Ag clusters to Eu ions is identified by the lifetime measurements. - Abstract: Silver ions and clusters were applied to Eu{sup 3+}-doped borate glasses via the Ag{sup +}–Na{sup +} ion exchange method. Eu{sup 3+}/Eu{sup 2+} ion luminescence enhancement was achieved after silver ion exchange.more » Absorption spectra showed no band at 420 nm, which indicates that silver nanoparticles can be excluded as a silver state in the glass. Silver ion aggregation into clusters during the ion exchange process may be inferred. The effect of silver ions and clusters on rare earth emissions was investigated using spectral information and lifetime measurements. Significant luminescence enhancements were observed from the energy transfer of Ag{sup +} ions and clusters to Eu{sup 3+}/Eu{sup 2+} ions, companied with the silver ions aggregated into the clusters state. The results of this research may extend the current understanding of interactions between rare-earth ions and Ag species.« less

Supersonic Bare Metal Cluster Beams. Technical Progress Report, March 16, 1984 - April 1, 1985

DOE R&D Accomplishments Database

Smalley, R. E.

1985-01-01

There have been four major areas of concentration for the study of bare metal cluster beams: neutral cluster, chemical reactivity, cold cluster ion source development (both positive and negative), bare cluster ion ICR (ion cyclotron resonance) development, and photofragmentation studies of bare metal cluster ions.

Chemical speciation of heavy metals by surface-enhanced Raman scattering spectroscopy: identification and quantification of inorganic- and methyl-mercury in water

NASA Astrophysics Data System (ADS)

Guerrini, Luca; Rodriguez-Loureiro, Ignacio; Correa-Duarte, Miguel A.; Lee, Yih Hong; Ling, Xing Yi; García de Abajo, F. Javier; Alvarez-Puebla, Ramon A.

2014-06-01

Chemical speciation of heavy metals has become extremely important in environmental and analytical research because of the strong dependence that toxicity, environmental mobility, persistence and bioavailability of these pollutants have on their specific chemical forms. Novel nano-optical-based detection strategies, capable of overcoming the intrinsic limitations of well-established analytic methods for the quantification of total metal ion content, have been reported, but the speciation of different chemical forms has not yet been achieved. Here, we report the first example of a SERS-based sensor for chemical speciation of toxic metal ions in water at trace levels. Specifically, the inorganic Hg2+ and the more toxicologically relevant methylmercury (CH3Hg+) are selected as analytical targets. The sensing platform consists of a self-assembled monolayer of 4-mercaptopyridine (MPY) on highly SERS-active and robust hybrid plasmonic materials formed by a dense layer of interacting gold nanoparticles anchored onto polystyrene microbeads. The co-ordination of Hg2+ and CH3Hg+ to the nitrogen atom of the MPY ring yields characteristic changes in the vibrational SERS spectra of the organic chemoreceptor that can be qualitatively and quantitatively correlated to the presence of the two different mercury forms.Chemical speciation of heavy metals has become extremely important in environmental and analytical research because of the strong dependence that toxicity, environmental mobility, persistence and bioavailability of these pollutants have on their specific chemical forms. Novel nano-optical-based detection strategies, capable of overcoming the intrinsic limitations of well-established analytic methods for the quantification of total metal ion content, have been reported, but the speciation of different chemical forms has not yet been achieved. Here, we report the first example of a SERS-based sensor for chemical speciation of toxic metal ions in water at trace levels. Specifically, the inorganic Hg2+ and the more toxicologically relevant methylmercury (CH3Hg+) are selected as analytical targets. The sensing platform consists of a self-assembled monolayer of 4-mercaptopyridine (MPY) on highly SERS-active and robust hybrid plasmonic materials formed by a dense layer of interacting gold nanoparticles anchored onto polystyrene microbeads. The co-ordination of Hg2+ and CH3Hg+ to the nitrogen atom of the MPY ring yields characteristic changes in the vibrational SERS spectra of the organic chemoreceptor that can be qualitatively and quantitatively correlated to the presence of the two different mercury forms. Electronic supplementary information (ESI) available: Representative TEM and ESEM images of AuNPs and PS@Au particles. Optical extinction spectra of AuNPs and PS@Au suspensions. SERS spectra of unmodified PS@Au suspension before and after the addition of CH3Hg+. SERS spectra of PS@Au-MPY upon addition of several metal solutions. Detailed SERS study of the MPY response to high concentration of CH3Hg+. See DOI: 10.1039/c4nr01464b

A comparison of the determination and speciation of inorganic arsenic using general HPLC methodology with UV, MS and MS/MS detection.

PubMed

Gilmartin, Gregory; Gingrich, Diane

2018-04-15

The determination and speciation of arsenic in natural resources such as drinking water and agricultural soils has been a growing concern in recent years due to its many toxicological effects [1-3]. To speciate and quantitate concentrations of <1 ppm of arsenic, typically an ion chromatograph (IC) interfaced to an inductively coupled plasma mass spectrometer (ICP-MS) is employed [4-9]. This methodology may be very robust and sensitive, but it is expensive and not as ubiquitous as high performance liquid chromatography (HPLC) with ultraviolet (UV) absorbance detection or electrospray ionization mass spectrometry (ESI-MS). Anion exchange chromatography is a well-documented means of speciating arsenite (As(III), As 2 O 3 ) and arsenate (As(V), AsO 4 ) using UV [10], conductivity [11], or ESI-MS detection [12,13]. This paper demonstrates the utilization of common liquid chromatographic instrumentation to speciate and determines inorganic Arsenic compounds using UV or MS via selected ion recording (SIR) or multiple reaction monitoring (MRM) detection. This paper describes the analysis of arsenite and arsenate samples prepared using both deionized and ground water. The limit of quantitation for the techniques described in this paper for samples spiked in ground water were 454 ppb (As(III)) and 562 ppb (As(V)) for UV detection, 45.4 ppb (As(III)) and 56.2 ppb (As(V)) for SIR detection, and 4.54 ppb (As(III)) and 5.62 ppb (As(V)) for MRM detection. Copyright © 2018 Elsevier B.V. All rights reserved.

Demonstrated Potential of Ion Mobility Spectrometry for Detection of Adulterated Perfumes and Plant Speciation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clark, Jared Matthew; Daum, Keith Alvin; Kalival, J. H.

2003-01-01

This initial study evaluates the use of ion mobility spectrometry (IMS) as a rapid test procedure for potential detection of adulterated perfumes and speciation of plant life. Sample types measured consist of five genuine perfumes, two species of sagebrush, and four species of flowers. Each sample type is treated as a separate classification problem. It is shown that discrimination using principal component analysis with K-nearest neighbors can distinguish one class from another. Discriminatory models generated using principal component regressions are not as effective. Results from this examination are encouraging and represent an initial phase demonstrating that perfumes and plants possessmore » characteristic chemical signatures that can be used for reliable identification.« less

Speciation of Mg in biogenic calcium carbonates

NASA Astrophysics Data System (ADS)

Farges, F.; Meibom, A.; Flank, A.-M.; Lagarde, P.; Janousch, M.; Stolarski, J.

2009-11-01

A selection of marine biominerals, mostly aragonitic coral skeletons were probed at the Mg K-edge by XANES spectroscopy coupled to μXRF methods and compared to an extensive set of relevant model compounds (silicates, carbonates, oxides and organic). Extensive methodologies are required to better describe the speciation of Mg in those minerals. A combination of ab-initio XANES calculations for defective clusters around Mg in aragonite together with wavelets analyzes of the XANES region are required to robustly interpret the spectra. When using those methodologies, the speciation of Mg ranges from a magnesite-type environment in some scleractinian corals to an organic-type environment. In all environments, the Mg-domains probed appear to be less than 1 nm in size.

Fertility depression among cheese‐making Penicillium roqueforti strains suggests degeneration during domestication

PubMed Central

Ropars, Jeanne; Lo, Ying‐Chu; Dumas, Emilie; Snirc, Alodie; Begerow, Dominik; Rollnik, Tanja; Lacoste, Sandrine; Dupont, Joëlle; Giraud, Tatiana; López‐Villavicencio, Manuela

2016-01-01

Genetic differentiation occurs when gene flow is prevented, due to reproductive barriers or asexuality. Investigating the early barriers to gene flow is important for understanding the process of speciation. Here, we therefore investigated reproductive isolation between different genetic clusters of the fungus Penicillium roqueforti, used for maturing blue cheeses, and also occurring as food spoiler or in silage. We investigated premating and postmating fertility between and within three genetic clusters (two from cheese and one from other substrates), and we observed sexual structures under scanning electron microscopy. All intercluster types of crosses showed some fertility, suggesting that no intersterility has evolved between domesticated and wild populations despite adaptation to different environments and lack of gene flow. However, much lower fertility was found in crosses within the cheese clusters than within the noncheese cluster, suggesting reduced fertility of cheese strains, which may constitute a barrier to gene flow. Such degeneration may be due to bottlenecks during domestication and/or to the exclusive clonal replication of the strains in industry. This study shows that degeneration has occurred rapidly and independently in two lineages of a domesticated species. Altogether, these results inform on the processes and tempo of degeneration and speciation. PMID:27470007

Hydrochemical characterization of groundwater in the Akyem area, Ghana

USGS Publications Warehouse

Banoeng-Yakubo, B.; Yidana, S.M.; Anku, Y.; Akabzaa, T.; Asiedu, D.

2008-01-01

The Akyem area is a small farming community located in southeastern Ghana. Groundwater samples from wells in the area were analyzed for concentrations of the major ions, silica, electrical conductivity and pH. The objective was to determine the main controls on the hydrochemistry of ground-water. Mass balance modeling was used together with multivariate R-mode hierarchical cluster analysis to determine the significant sources of variation in the hydrochemistry. Two water types exist in this area. The first is influenced most by the weathering of silicate minerals from the underlying geology, and is thus rich in silica, sodium, calcium, bicarbonate, and magnesium ions. The second is water that has been influenced by the effects of fertilizers and other anthropogenic activities in the area. Mineral speciation and silicate mineral stability diagrams suggest that montmorillonite, probably derived from the incongruent dissolution of feldspars and micas, is the most stable silicate phase in the groundwaters. The apparent incongruent weathering of silicate minerals in the groundwater system has led to the enrichment of sodium, calcium, magnesium and bicarbonate ions as well as silica, leading to the supersaturation of calcite, aragonite, dolomite and quartz. Stability in the montmorillonite field suggests restricted flow conditions and a long groundwater residence time, leading to greater exposure of the rock to weathering. Cation exchange processes appear to play minor roles in the hydrochemistry of groundwater.

Comparison of Se and Te clusters produced by ion bombardment

NASA Astrophysics Data System (ADS)

Trzyna, Małgorzata

2017-01-01

Nanostructures based on tellurium and selenium are materials used as components for the manufacturing topological insulators. Therefore it is crucial to precisely characterize these materials. In this work the emission of selenium and tellurium cluster ions, sputtered by Bi+ primary ion guns, was investigated by using Time-of-Flight Secondary Ion Mass Spectrometry (TOF SIMS). It has been found that BixTex and BixSex clusters appear in addition to Sex and Tex clusters in the mass range up to 1300 m/z. Local maxima or minima (magic numbers) are observed in the ion intensity versus a number of atoms per cluster for both positive and negative ions spectra for all types of clusters and primary ions used. These extrema can be attributed to different yield and stability of certain clusters but also to fragmentation of high-mass clusters.

Tracking niche variation over millennial timescales in sympatric killer whale lineages

PubMed Central

Foote, Andrew D.; Newton, Jason; Ávila-Arcos, María C.; Kampmann, Marie-Louise; Samaniego, Jose A.; Post, Klaas; Rosing-Asvid, Aqqalu; Sinding, Mikkel-Holger S.; Gilbert, M. Thomas P.

2013-01-01

Niche variation owing to individual differences in ecology has been hypothesized to be an early stage of sympatric speciation. Yet to date, no study has tracked niche width over more than a few generations. In this study, we show the presence of isotopic niche variation over millennial timescales and investigate the evolutionary outcomes. Isotopic ratios were measured from tissue samples of sympatric killer whale Orcinus orca lineages from the North Sea, spanning over 10 000 years. Isotopic ratios spanned a range similar to the difference in isotopic values of two known prey items, herring Clupea harengus and harbour seal Phoca vitulina. Two proxies of the stage of speciation, lineage sorting of mitogenomes and genotypic clustering, were both weak to intermediate indicating that speciation has made little progress. Thus, our study confirms that even with the necessary ecological conditions, i.e. among-individual variation in ecology, it is difficult for sympatric speciation to progress in the face of gene flow. In contrast to some theoretical models, our empirical results suggest that sympatric speciation driven by among-individual differences in ecological niche is a slow process and may not reach completion. We argue that sympatric speciation is constrained in this system owing to the plastic nature of the behavioural traits under selection when hunting either mammals or fish. PMID:23945688

Tracking niche variation over millennial timescales in sympatric killer whale lineages.

PubMed

Foote, Andrew D; Newton, Jason; Ávila-Arcos, María C; Kampmann, Marie-Louise; Samaniego, Jose A; Post, Klaas; Rosing-Asvid, Aqqalu; Sinding, Mikkel-Holger S; Gilbert, M Thomas P

2013-10-07

Niche variation owing to individual differences in ecology has been hypothesized to be an early stage of sympatric speciation. Yet to date, no study has tracked niche width over more than a few generations. In this study, we show the presence of isotopic niche variation over millennial timescales and investigate the evolutionary outcomes. Isotopic ratios were measured from tissue samples of sympatric killer whale Orcinus orca lineages from the North Sea, spanning over 10 000 years. Isotopic ratios spanned a range similar to the difference in isotopic values of two known prey items, herring Clupea harengus and harbour seal Phoca vitulina. Two proxies of the stage of speciation, lineage sorting of mitogenomes and genotypic clustering, were both weak to intermediate indicating that speciation has made little progress. Thus, our study confirms that even with the necessary ecological conditions, i.e. among-individual variation in ecology, it is difficult for sympatric speciation to progress in the face of gene flow. In contrast to some theoretical models, our empirical results suggest that sympatric speciation driven by among-individual differences in ecological niche is a slow process and may not reach completion. We argue that sympatric speciation is constrained in this system owing to the plastic nature of the behavioural traits under selection when hunting either mammals or fish.

The effect of pH on phosphorus availability and speciation in an aquaponics nutrient solution.

PubMed

Cerozi, Brunno da Silva; Fitzsimmons, Kevin

2016-11-01

The interaction between the main ions in aquaponics nutrient solutions affects chemical composition and availability of nutrients, and nutrient uptake by plant roots. This study determined the effect of pH on phosphorus (P) speciation and availability in an aquaponics nutrient solution and used Visual MINTEQ to simulate P species and P activity. In both experimental and simulated results, P availability decreased with increase in pH of aquaponics nutrient solutions. According to simulations, P binds to several cations leaving less free phosphate ions available in solution. High pH values resulted in the formation of insoluble calcium phosphate species. The study also demonstrated the importance of organic matter and alkalinity in keeping free phosphate ions in solution at high pH ranges. It is recommended though that pH in aquaponics systems is maintained at a 5.5-7.2 range for optimal availability and uptake by plants. Copyright © 2016 Elsevier Ltd. All rights reserved.

Cesium Speciation in Dust from Municipal Solid Waste and Sewage Sludge Incineration by Synchrotron Radiation Micro-X-ray Analysis.

PubMed

Shiota, Kenji; Takaoka, Masaki; Fujimori, Takashi; Oshita, Kazuyuki; Terada, Yasuko

2015-11-17

The chemical behavior of Cs in waste incineration processes is important to consider when disposing of radionuclide-contaminated waste from the Fukushima Daiichi nuclear power plant accident in Japan. To determine the speciation of Cs, we attempted the direct speciation of trace amounts of stable Cs in the dust from municipal solid waste incineration (MSWI) and sewage sludge incineration (SSI) by micro-X-ray fluorescence (μ-XRF) and micro-X-ray absorption fine structure (μ-XAFS) at the SPring-8 facility. The μ-XRF results revealed that locally produced Cs was present in MSWI and SSI dust within the cluster size range of 2-10 μm. The μ-XAFS analysis confirmed that the speciation of Cs in MSWI dust was similar to that of CsCl, while in SSI dusts it was similar to pollucite. The solubility of Cs was considered to be influenced by the exact Cs species present in incineration residue.

Chemical Speciation Analysis of Sports Drinks by Acid-Base Titrimetry and Ion Chromatography: A Challenging Beverage Formulation Project

ERIC Educational Resources Information Center

Drossman, Howard

2007-01-01

Students have standardized a sodium hydroxide solution and analyzed commercially available sports drinks by titrimetric analysis of the triprotic citric acid, dihydrogen phosphate, and dihydrogen citrate and by ion chromatography for chloride, total phosphate and citrate. These experiments are interesting examples of analyzing real-world food and…

Mixed clusters from the coexpansion of C2F6 and n2 in a pulsed, supersonic expansion cluster ion source and beam deflection time-of-flight mass spectrometer: A first application

NASA Astrophysics Data System (ADS)

Thompson, Steven D.

The following topics are discussed: (1) cluster ion genesis; (2) cluster ion detection; (3) Ion source; (4) pulse valve; (5) e-gun; (6) Ion optics; (7) a first order model; and (8) a modified Bakker's model.

Investigation of Damage with Cluster Ion Beam Irradiation Using HR-RBS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seki, Toshio; Aoki, Takaaki; Matsuo, Jiro

2008-11-03

Cluster ion beam can process targets with shallow damage because of the very low irradiation energy per atom. However, it is needed to investigate the damage with cluster ion beam irradiation, because recent applications demand process targets with ultra low damage. The shallow damage can be investigated from depth profiles of specific species before and after ion irradiation. They can be measured with secondary ion mass spectrometry (SIMS) and Rutherford backscattering spectroscopy (RBS). High resolution Rutherford backscattering spectroscopy (HR-RBS) is a non destructive measurement method and depth profiles can be measured with nano-resolution. The cluster ion beam mixing of thinmore » Ni layer in carbon targets can be investigated with HR-RBS. The mixing depth with cluster ion irradiation at 10 keV was about 10 nm. The mixing depth with cluster ion irradiation at 1 keV and 5 keV were less than 1 nm and 5 nm, respectively. The number of displaced Ni atoms with cluster ion irradiation was very larger than that with monomer ion irradiation of same energy. This result shows that violent mixing occurs with single cluster impact.« less

REE speciation in low-temperature acidic waters and the competitive effects of aluminum

USGS Publications Warehouse

Gimeno, Serrano M.J.; Auque, Sanz L.F.; Nordstrom, D. Kirk

2000-01-01

The effect of simultaneous competitive speciation of dissolved rare earth elements (REEs) in acidic waters (pH 3.3 to 5.2) has been evaluated by applying the PHREEQE code to the speciation of water analyses from Spain, Brazil, USA, and Canada. The main ions that might affect REE are Al3+, F-, SO42-, and PO43-. Fluoride, normally a significant complexer of REEs, is strongly associated with Al3+ in acid waters and consequently has little influence on REEs. The inclusion of aluminum concentrations in speciation calculations for acidic waters is essential for reliable speciation of REEs. Phosphate concentrations are too low (10-4 to 10-7 m) to affect REE speciation. Consequently, SO42- is the only important complexing ligand for REEs under these conditions. According to Millero [Millero, F.J., 1992. Stability constants for the formation of rare earth inorganic complexes as a function of ionic strength. Geochim. Cosmochim. Acta, 56, 3123-3132], the lanthanide sulfate stability constants are nearly constant with increasing atomic number so that no REE fractionation would be anticipated from aqueous complexation in acidic waters. Hence, REE enrichments or depletions must arise from mass transfer reactions. (C) 2000 Elsevier Science B.V. All rights reserved.

Phytoextraction of cadmium by Ipomoea aquatica (water spinach) in hydroponic solution: effects of cadmium speciation.

PubMed

Wang, Kai-Sung; Huang, Lung-Chiu; Lee, Hong-Shen; Chen, Pai-Ye; Chang, Shih-Hsien

2008-06-01

Phytoextraction is a promising technique to remediate heavy metals from contaminated wastewater. However, the interactions of multi-contaminants are not fully clear. This study employed cadmium, Triton X-100 (TX-100), and EDTA to investigate their interactions on phytotoxicity and Cd phytoextraction of Ipomoea aquatica (water spinach) in simulated wastewater. The Cd speciation was estimated by a chemical equilibrium model and MINEQL+. Statistic regression was applied to evaluate Cd speciation on Cd uptake in shoots and stems of I. aquatica. Results indicated that the root length was a more sensitive parameter than root weight and shoot weight. Root elongation was affected by Cd in the Cd-EDTA solution and TX-100 in the Cd-TX-100 solution. Both the root length and the root biomass were negatively correlated with the total soluble Cd ions. In contrast, Cd phytoextraction of I. aquatic was correlated with the aqueous Cd ions in the free and complex forms rather than in the chelating form. Additionally, the high Cd bioconcentration factors of I. aquatica (375-2227 l kg(-1) for roots, 45-144 l kg(-1) for shoots) imply that I. aquatica is a potential aquatic plant to remediate Cd-contaminated wastewater.

Niche conservatism and phylogenetic clustering in a tribe of arid-adapted marsupial mice, the Sminthopsini.

PubMed

García-Navas, Vicente; Westerman, Michael

2018-05-28

The progressive expansion of the Australian arid zone during the last 20 Ma appears to have spurred the diversification of several families of plants, vertebrates and invertebrates, yet such taxonomic groups appear to show limited niche radiation. Here, we test whether speciation is associated with niche conservatism (constraints on ecological divergence) or niche divergence in a tribe of marsupial mice (Sminthopsini; 23 taxa) that includes the most speciose genus of living dasyurids, the sminthopsins. To that end, we integrated phylogenetic data with ecological niche modelling, to enable us to reconstruct the evolution of climatic suitability within Sminthopsini. Niche overlap among species was low-moderate (but generally higher than expected given environmental background similarity), and the degree of phylogenetic clustering increased with aridity. Climatic niche reconstruction illustrates that there has been little apparent evolution of climatic tolerance within clades. Accordingly, climatic disparity tends to be accumulated among clades, suggesting considerable niche conservatism. Our results also indicate that evolution of climatic tolerances has been heterogeneous across different dimensions of climate (temperature vs. precipitation) and across phylogenetic clusters (Sminthopsis murina group vs. other groups). Although some results point to the existence of shifts in climatic niches during the speciation of sminthopsins, our study provides evidence for substantial phylogenetic niche conservatism in the group. We conclude that niche diversification had a low impact on the speciation of this tribe of small, but highly mobile marsupials. © 2018 European Society For Evolutionary Biology. Journal of Evolutionary Biology © 2018 European Society For Evolutionary Biology.

Noble gas cluster ions

NASA Astrophysics Data System (ADS)

Kaya, Yunus; Kalkan, Yalçin; Veenhof, Rob

2018-02-01

In this work, a reaction mechanism of formation of noble gas (Ng) cluster ions has been theoretically investigated in detail. The kinetic studies of formation of Xe+Xe cluster in Xe, Ar+Ar cluster ions in Ar, and Ne+Ne cluster ions in Ne have been made as theoretically. The optimized structures in the ground state were calculated using the density functional theory (DFT) by the B3LYP method combined with the Stuttgart/Dresden effective core potential basis set (SDD). In addition, we calculated the rate constants of all cluster formations. The results are 1.15 × 10-31, 3.58 × 10-31, 0.23 × 10-31cm6/s, respectively for Neon, Argon, Xenon cluster ions.

Ion mobility spectrometry-mass spectrometry examination of the structures, stabilities, and extents of hydration of dimethylamine-sulfuric acid clusters.

PubMed

Thomas, Jikku M; He, Siqin; Larriba-Andaluz, Carlos; DePalma, Joseph W; Johnston, Murray V; Hogan, Christopher J

2016-08-17

We applied an atmospheric pressure differential mobility analyzer (DMA) coupled to a time-of-flight mass spectrometer to examine the stability, mass-mobility relationship, and extent of hydration of dimethylamine-sulfuric acid cluster ions, which are of relevance to nucleation in ambient air. Cluster ions were generated by electrospray ionization and were of the form: [H((CH3)2NH)x(H2SO4)y](+) and [(HSO4)((CH3)2NH)x(H2SO4)y](-), where 4 ≤ x ≤ 8, and 5 ≤ y ≤ 12. Under dry conditions, we find that positively charged cluster ions dissociated via loss of both multiple dimethylamine and sulfuric acid molecules after mobility analysis but prior to mass analysis, and few parent ions were detected in the mass spectrometer. Dissociation also occurred for negative ions, but to a lesser extent than for positive ions for the same mass spectrometer inlet conditions. Under humidified conditions (relative humidities up to 30% in the DMA), positively charged cluster ion dissociation in the mass spectrometer inlet was mitigated and occurred primarily by H2SO4 loss from ions containing excess acid molecules. DMA measurements were used to infer collision cross sections (CCSs) for all identifiable cluster ions. Stokes-Millikan equation and diffuse/inelastic gas molecule scattering predicted CCSs overestimate measured CCSs by more than 15%, while elastic-specular collision model predictions are in good agreement with measurements. Finally, cluster ion hydration was examined by monitoring changes in CCSs with increasing relative humidity. All examined cluster ions showed a modest amount of water molecule adsorption, with percentage increases in CCS smaller than 10%. The extent of hydration correlates directly with cluster ion acidity for positive ions.

Electrostatic effects on clustering and ion dynamics in ionomer melts

NASA Astrophysics Data System (ADS)

Ma, Boran; Nguyen, Trung; Pryamitsyn, Victor; Olvera de La Cruz, Monica

An understanding of the relationships between ionomer chain morphology, dynamics and counter-ion mobility is a key factor in the design of ion conducting membranes for battery applications. In this study, we investigate the influence of electrostatic coupling between randomly charged copolymers (ionomers) and counter ions on the structural and dynamic features of a model system of ionomer melts. Using coarse-grained molecular dynamics (CGMD) simulations, we found that variations in electrostatic coupling strength (Γ) remarkably affect the formation of ion-counter ion clusters, ion mobility, and polymer dynamics for a range of charged monomer fractions. Specifically, an increase in Γ leads to larger ionic cluster sizes and reduced polymer and ion mobility. Analysis of the distribution of the radius of gyration of the clusters further reveals that the fractal dimension of the ion clusters is nearly independent from Γ for all the cases studied. Finally, at sufficiently high values of Γ, we observed arrested heterogeneous ions mobility, which is correlated with an increase in ion cluster size. These findings provide insight into the role of electrostatics in governing the nanostructures formed by ionomers.

Evidence that Clouds of keV Hydrogen Ion Clusters Bounce Elastically from a Solid Surface

NASA Technical Reports Server (NTRS)

Lewis, R. A.; Martin, James J.; Chakrabarti, Suman; Rodgers, Stephen L. (Technical Monitor)

2002-01-01

The behavior of hydrogen ion clusters is tested by an inject/hold/extract technique in a Penning-Malmberg trap. The timing pattern of the extraction signals is consistent with the clusters bouncing elastically from a detector several times. The ion clusters behave more like an elastic fluid than a beam of ions.

Ion composition in a noctilucent cloud

NASA Technical Reports Server (NTRS)

Goldberg, R. A.; Witt, G.

1976-01-01

Ion composition at mesospheric altitudes was measured and compared between high and mid-latitude sites under summer daytime conditions. Rocket-borne measurements were made with pumped quadrupole ion mass spectrometers. The mid-latitude data were obtained at Wallops Island, Virginia on June 30, 1973, at 1510 LMT. Large quantities of hydronium cluster ions were observed through 109+, with maximum concentrations at 55+ and 73+. Also, cluster ions of nitric oxide were observed through 84+. The high latitude launch occurred at Kiruna, Sweden on August 2, 1973, at 0700 LMT following visual sighting of a noctilucent cloud on the prior evening. The data near mesopause shows cluster ions, but also a preponderance of heavy ions between 90 and 145 AMU, with groupings 18 AMU apart but unrelated to the more typical cluster ions. One possible set of consistent identifications leads to iron and iron oxide hydrates. These results may suggest the presence of metallic particulates and ions which form hydrated clusters ions.

[The progress in speciation analysis of trace elements by atomic spectrometry].

PubMed

Wang, Zeng-Huan; Wang, Xu-Nuo; Ke, Chang-Liang; Lin, Qin

2013-12-01

The main purpose of the present work is to review the different non-chromatographic methods for the speciation analysis of trace elements in geological, environmental, biological and medical areas. In this paper, the sample processing methods in speciation analysis were summarized, and the main strategies for non-chromatographic technique were evaluated. The basic principles of the liquid extractions proposed in the published literatures recently and their advantages and disadvantages were discussed, such as conventional solvent extraction, cloud point extraction, single droplet microextraction, and dispersive liquid-liquid microextraction. Solid phase extraction, as a non-chromatographic technique for speciation analysis, can be used in batch or in flow detection, and especially suitable for the online connection to atomic spectrometric detector. The developments and applications of sorbent materials filled in the columns of solid phase extraction were reviewed. The sorbents include chelating resins, nanometer materials, molecular and ion imprinted materials, and bio-sorbents. Other techniques, e. g. hydride generation technique and coprecipitation, were also reviewed together with their main applications.

Effects of calcium, magnesium, and sodium on alleviating cadmium toxicity to Hyalella azteca

USGS Publications Warehouse

Jackson, B.P.; Lasier, P.J.; Miller, W.P.; Winger, P.V.

2000-01-01

Toxicity of trace metal ions to aquatic organisms, arising through either anthropogenic inputs or acidification of surface waters, continues to be both a regulatory and environmental problem. It is generally accepted that the free metal ion is the major toxic species (Florence et a1.,1992) and that inorganic or organic complexation renders the metal ion non-bioavailable (Meador, 1991, Galvez and Wood, 1997). However, water chemistry parameters such as alkalinity, hardness, dissolved organic carbon and pH influence metal ion toxicity either directly by lowering free metal ion concentration or indirectly through synergistic or antagonistic effects. Alkalinity and salinity can affect the speciation of metal ions by increasing ion-pair formation, thus decreasing free metal ion concentration. For example, Cu was found to be less toxic to rainbow trout in waters of high alkalinity (Miller and Mackay, 1980), due to formation of CuCO3 ion pair, and corresponding reduction in free Cu2+ concentration. The influence of salinity on the toxicity of cadmium to various organisms has been demonstrated in a number of studies (Bervoets et al., 1995, Hall et al., 1995, Lin and Dunson, 1993, Blust et al., 1992). In all these studies the apparent toxicity of cadmium was lowered as salinity was increased due to increased formation of CdC1+ and CDCl2 aqueous complexes that are non-toxic or of much lower toxicity than the free Cd2+ ion. Changes in pH exert both a biological and chemical effect on metal ion toxicity (Campbell and Stokes, 1985). Low pH favors greater metal ion solubility, and, in the absence of complexing ions, reduced speciation of the metal ion, which tends to increase toxicity compared to higher pH. However, Iow pH also enhances competition between H+ and metal ion for cell surface binding sites, which tends to decrease metal ion toxicity.

Use of ion-pairing reagent for improving iodine speciation analysis in seaweed by pressure-driven capillary electrophoresis and ultraviolet detection.

PubMed

Sun, Jiannan; Wang, Dan; Cheng, Heyong; Liu, Jinhua; Wang, Yuanchao; Xu, Zigang

2015-01-30

This study achieved resolution improvement for iodine speciation in the presence of an ion-pairing reagent by a pressure-driven capillary electrophoresis (CE) system. Addition of 0.01mM tetrabutyl ammonium hydroxide (TBAH) as the ion-pairing reagent into the electrophoretic buffer resulted in the complete separation of four iodine species (I(-), IO3(-), mono-iodothyrosine-MIT and di-iodothyrosine-DIT), because of the electrostatic interaction between TBAH and the negatively charged analytes. A +16kV separation voltage was applied along the separation capillary (50μm i.d., 80cm total and 60cm effective) with the inlet grounded. The detection wavelength was fixed at 210nm, and the pressure-driven flow rate was set at 0.12mLmin(-1) with an injected volume of 2μL. The optimal electrolyte consisted of 2mM borate, 2mM TBAH and 80% methanol with pH adjusted to 8.5. Baseline separation of iodine species was achieved within 7min. The detection limits for I(-), IO3(-), MIT and DIT were 0.052, 0.040, 0.032 and 0.025mgL(-1), respectively. The relative standard deviations of peak heights and areas were all below 3% for 5mgL(-1) and 5% for 1mgL(-1). Application of the proposed method was demonstrated by speciation analysis of iodine in two seaweed samples. The developed method offered satisfactory recoveries in the 91-99% range and good precisions (<5%). Good agreement between the determined values by the proposed CE method and the HPLC-ICP-MS method was also obtained. All results proved its great potential in routine analysis of iodine speciation in environmental, food and biological samples. Copyright © 2014 Elsevier B.V. All rights reserved.

FAST TRACK COMMUNICATION: Inhomogeneous charge redistribution in Xe clusters exposed to an intense extreme ultraviolet free electron laser

NASA Astrophysics Data System (ADS)

Iwayama, H.; Sugishima, A.; Nagaya, K.; Yao, M.; Fukuzawa, H.; Motomura, K.; Liu, X.-J.; Yamada, A.; Wang, C.; Ueda, K.; Saito, N.; Nagasono, M.; Tono, K.; Yabashi, M.; Ishikawa, T.; Ohashi, H.; Kimura, H.; Togashi, T.

2010-08-01

The emission of highly charged ions from Xe clusters exposed to intense extreme ultraviolet laser pulses (λ ~ 52 nm) from the free electron laser in Japan was investigated using ion momentum spectroscopy. With increasing average cluster size, we observed multiply charged ions Xez + up to z = 3. From kinetic energy distributions, we found that multiply charged ions were generated near the cluster surface. Our results suggest that charges are inhomogeneously redistributed in the cluster to lower the total energy stored in the clusters.

Study on the coloration response of a radiochromic film to MeV cluster ion beams

NASA Astrophysics Data System (ADS)

Yuri, Yosuke; Narumi, Kazumasa; Chiba, Atsuya; Hirano, Yoshimi; Saitoh, Yuichi

2017-11-01

A radiochromic film, Gafchromic HD-V2, is applied to a possible method of measuring a two-dimensional (2D) spatial profile of MeV cluster ion beams. The coloration responses of the HD-V2 film to MeV carbon and gold cluster ion beams are experimentally investigated since some cluster effect may appear. The degree of the film coloration is quantified as a change in optical density (OD) by reading the films with an image scanner for high-resolution measurement of the 2D beam profile. The OD response of HD-V2 is characterized as a function of the ion and atom fluence for comparison. The dependences of the OD response on the cluster size, kinetic energy, and ion species are discussed. It is found that the sensitivity of the OD change is reduced when the cluster size is large. The beam profile of MeV cluster ion beams delivered from the tandem accelerator in TIARA is characterized from the measurement result using HD-V2 films. The present results show that the use of the Gafchromic HD-V2 film is suitable for the detail beam profile measurement of MeV cluster ions, especially C60 ions, whose available intensity is rather low in comparison with that of monatomic ion beams.

New perspectives in laser analytics: Resonance-enhanced multiphoton ionization in a Paul ion trap combined with a time-of-flight mass spectrometer

NASA Astrophysics Data System (ADS)

Bisling, Peter; Heger, Hans Jörg; Michaelis, Walfried; Weitkamp, Claus; Zobel, Harald

1995-04-01

A new laser analytical device has been developed that is based on resonance-enhanced multiphoton ionization in the very center of a radio-frequency quadrupole ion trap. Applications in speciation anlaysis of biological and enviromental samples and in materials science will all benefit from laser-optical selectivity in the resonance excitation process, combined with mass-spectropic sensivity which is further enhanced by the ion accumulation and storage capability.

Water quality characterization in some birimian aquifers of the Birim Basin, Ghana

USGS Publications Warehouse

Bruce, B.-Y.; Yidana, S.M.; Anku, Y.; Akabzaa, T.; Asiedu, D.

2009-01-01

The objective of this study was to determine the main controls on the hydrochemistry of groundwater in the study area. Mass balance modeling was used simultaneously with multivariate R-mode hierarchical cluster analysis to determine the significant sources of variation in the hydrochemistry. Two water types have been revealed in this area: (1) waters influenced more significantly by the weathering of silicate minerals from the underlying geology, and are rich in silica, sodium, calcium, bicarbonate, and magnesium ions, and (2) waters that have been influenced by the effects of fertilizers and other anthropogenic activities in the area. Mineral speciation and silicate mineral stability diagrams generated from the data suggest that montmorillonite, probably derived from the incongruent dissolution of feldspars and micas, is the most stable silicate phase in the groundwater. The apparent incongruent weathering of silicate minerals in the groundwater system has led to the enrichment of sodium, calcium, magnesium and bicarbonate ions as well as silica, leading to the supersaturation of calcite, aragonite, dolomite and quartz. Stability in the montmorillonite field suggests restricted flow conditions whereby groundwater residence time is relatively high, leading to greater contact of groundwater with the rock to enhance weathering. Cation exchange processes have also been determined to play minor roles in the hydrochemistry.

Generation of CsI cluster ions for mass calibration in matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Lou, Xianwen; van Dongen, Joost L J; Meijer, E W

2010-07-01

A simple method was developed for the generation of cesium iodide (CsI) cluster ions up to m/z over 20,000 in matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS). Calibration ions in both positive and negative ion modes can readily be generated from a single MALDI spot of CsI(3) with 2-[(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene] malononitrile (DCTB) matrix. The major cluster ion series observed in the positive ion mode is [(CsI)(n)Cs](+), and in the negative ion mode is [(CsI)(n)I](-). In both cluster series, ions spread evenly every 259.81 units. The easy method described here for the production of CsI cluster ions should be useful for MALDI MS calibrations. Copyright 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

From population connectivity to the art of striping Russian dolls: the lessons from Pocillopora corals.

PubMed

Gélin, Pauline; Fauvelot, Cécile; Bigot, Lionel; Baly, Joseph; Magalon, Hélène

2018-01-01

Here, we examined the genetic variability in the coral genus Pocillopora , in particular within the Primary Species Hypothesis PSH09, identified by Gélin, Postaire, Fauvelot and Magalon (2017) using species delimitation methods [also named Pocillopora eydouxi/meandrina complex sensu , Schmidt-Roach, Miller, Lundgren, & Andreakis (2014)] and which was found to split into three secondary species hypotheses (SSH09a, SSH09b, and SSH09c) according to assignment tests using multi-locus genotypes (13 microsatellites). From a large sampling (2,507 colonies) achieved in three marine provinces [Western Indian Ocean (WIO), Tropical Southwestern Pacific (TSP), and Southeast Polynesia (SEP)], genetic structuring analysis conducted with two clustering analyses (structure and DAPC) using 13 microsatellites revealed that SSH09a was restricted to the WIO while SSH09b and SSH09c were almost exclusively in the TSP and SEP. More surprisingly, each SSH split into two to three genetically differentiated clusters, found in sympatry at the reef scale, leading to a pattern of nested hierarchical levels (PSH > SSH > cluster), each level hiding highly differentiated genetic groups. Thus, rather than structured populations within a single species, these three SSHs, and even the eight clusters, likely represent distinct genetic lineages engaged in a speciation process or real species. The issue is now to understand which hierarchical level (SSH, cluster, or even below) corresponds to the species one. Several hypotheses are discussed on the processes leading to this pattern of mixed clusters in sympatry, evoking formation of reproductive barriers, either by allopatric speciation or habitat selection.

Measurements of ion energies from the explosion of large hydrogen iodide clusters irradiated by intense femtosecond laser pulses

NASA Astrophysics Data System (ADS)

Tisch, J. W. G.; Hay, N.; Springate, E.; Gumbrell, E. T.; Hutchinson, M. H. R.; Marangos, J. P.

1999-10-01

We present measurements of ion energies from the interaction of intense, femtosecond laser pulses with large mixed-species clusters. Multi-keV protons and ~100-keV iodine ions are observed from the explosion of HI clusters produced in a gas jet operated at room temperature. Clusters formed from molecular gases such as HI are thus seen to extend the advantages of the laser-cluster interaction to elements that do not readily form single-species clusters. In the light of recently reported nuclear fusion in laser-heated clusters, we also examine the possibility of boosting the explosion energies of low-Z ions through the use of mixed species clusters.

Secondary ion mass spectra of gold super clusters up to 140000 Dalton

NASA Astrophysics Data System (ADS)

Feld, H.; Leute, A.; Rading, D.; Benninghoven, A.; Schmid, G.

1990-03-01

The bombardment of a two-shell gold complex (Au55(PPh3)12Cl6) with 10 keV Xe+-ions results in the formation of secondary ion masses up to 140000 u. These are by far the largest secondary ions observed under primary particle bombardment. The detection and identification of these ions with a Time-Of-Flight Secondary Ion Mass Spectrometer (TOF-SIMS) gives important information about the behavior of naked full-shell clusters. Au13 particles, generated from the Au55 cluster, serve as building blocks for a series of super-clusters up to (Au13)55. The results for keV-ion bombardment are compared to those for MeV-ion bombardment.

Hybridization and differential introgression associated with environmental shifts in a mistletoe species complex.

PubMed

Baena-Díaz, Fernanda; Ramírez-Barahona, Santiago; Ornelas, Juan Francisco

2018-04-03

Host specialization after host shifting is traditionally viewed as the pathway to speciation in parasitic plants. However, geographical and environmental changes can also influence parasite speciation, through hybridization processes. Here we investigated the impact of past climatic fluctuations, environment, and host shifts on the genetic structure and patterns of hybridization and gene flow between Psittacanthus calyculatus and P. schiedeanus, a Mesoamerican species complex. Using microsatellites (408 individuals), we document moderate genetic diversity but high genetic differentiation between widespread parental clusters, calyculatus in dry pine-oak forests and schiedeanus in cloud forests. Bayesian analyses identified a third cluster, with admixture between parental clusters in areas of xeric and tropical dry forests and high levels of migration rates following secondary contact. Coincidently host associations in these areas differ from those in areas of parental species, suggesting that past hybridization played a role in environmental and host shifts. Overall, the observed genetic and geographic patterns suggest that these Psittacanthus populations could have entered a distinct evolutionary pathway. The results provide evidence for highlights on the importance of the Pleistocene climate changes, habitat differences, and potential host shifts in the evolutionary history of Neotropical mistletoes.

Speciation, population structure, and demographic history of the Mojave Fringe-toed Lizard (Uma scoparia), a species of conservation concern

PubMed Central

Gottscho, Andrew D; Marks, Sharyn B; Jennings, W Bryan

2014-01-01

The North American deserts were impacted by both Neogene plate tectonics and Quaternary climatic fluctuations, yet it remains unclear how these events influenced speciation in this region. We tested published hypotheses regarding the timing and mode of speciation, population structure, and demographic history of the Mojave Fringe-toed Lizard (Uma scoparia), a sand dune specialist endemic to the Mojave Desert of California and Arizona. We sampled 109 individual lizards representing 22 insular dune localities, obtained DNA sequences for 14 nuclear loci, and found that U. scoparia has low genetic diversity relative to the U. notata species complex, comparable to that of chimpanzees and southern elephant seals. Analyses of genotypes using Bayesian clustering algorithms did not identify discrete populations within U. scoparia. Using isolation-with-migration (IM) models and a novel coalescent-based hypothesis testing approach, we estimated that U. scoparia diverged from U. notata in the Pleistocene epoch. The likelihood ratio test and the Akaike Information Criterion consistently rejected nested speciation models that included parameters for migration and population growth of U. scoparia. We reject the Neogene vicariance hypothesis for the speciation of U. scoparia and define this species as a single evolutionarily significant unit for conservation purposes. PMID:25360285

Zn(II) and Hg(II) binding to a designed peptide that accommodates different coordination geometries.

PubMed

Szunyogh, Dániel; Gyurcsik, Béla; Larsen, Flemming H; Stachura, Monika; Thulstrup, Peter W; Hemmingsen, Lars; Jancsó, Attila

2015-07-28

Designed metal ion binding peptides offer a variety of applications in both basic science as model systems of more complex metalloproteins, and in biotechnology, e.g. in bioremediation of toxic metal ions, biomining or as artificial enzymes. In this work a peptide (HS: Ac-SCHGDQGSDCSI-NH2) has been specifically designed for binding of both Zn(II) and Hg(II), i.e. metal ions with different preferences in terms of coordination number, coordination geometry, and to some extent ligand composition. It is demonstrated that HS accommodates both metal ions, and the first coordination sphere, metal ion exchange between peptides, and speciation are characterized as a function of pH using UV-absorption-, synchrotron radiation CD-, (1)H-NMR-, and PAC-spectroscopy as well as potentiometry. Hg(II) binds to the peptide with very high affinity in a {HgS2} coordination geometry, bringing together the two cysteinates close to each end of the peptide in a loop structure. Despite the high affinity, Hg(II) is kinetically labile, exchanging between peptides on the subsecond timescale, as indicated by line broadening in (1)H-NMR. The Zn(II)-HS system displays more complex speciation, involving monomeric species with coordinating cysteinates, histidine, and a solvent water molecule, as well as HS-Zn(II)-HS complexes. In summary, the HS peptide displays conformational flexibility, contains many typical metal ion binding groups, and is able to accommodate metal ions with different structural and ligand preferences with high affinity. As such, the HS peptide may be a scaffold offering binding of a variety of metal ions, and potentially serve for metal ion sequestration in biotechnological applications.

Characterization of the reactive and dissociative behavior of transition metal oxide cluster ions in the gas phase.

PubMed

Maleknia, S; Brodbelt, J; Pope, K

1991-05-01

The reactive and dissociative behavior of molybdenum and tungsten oxide cluster ions has been studied in the gas phase using a triple quadrupole mass spectrometer. Cluster ions (MO3) n (-) were formed via a simple thermal desorption/electron capture negative ionization method, and their structures were characterized by collision-activated dissociation (CAD). Typically, the clusters fragment by losses of neutral (MO3) units. Reactions of the oxide cluster ions with ethylene oxide, cyclohexene oxide, ethylene sulfide cyclohexene sulfide, 2,3-butanedione, and 2,4-pentanedione were examined, and product ions were characterized by CAD. The clusters react with ethylene oxide by addition of ethylene oxide or net addition of oxygen, whereas the clusters react with ethylene sulfide via net addition of one or two sulfur atoms. Reactions of the clusters with the diones result in addition of one or two dione units, in some cases with dehydration.

Correlation between cation conduction and ionic morphology in a PEO-based single ion conductor

NASA Astrophysics Data System (ADS)

Lin, Kan-Ju; Maranas, Janna

2011-03-01

We use molecular dynamics simulation to study ion transport and backbone mobility of a PEO-based single ion conductor. Ion mobility depends on the chemical structure and the local environment of the ions, which consequently impact ionic conductivity. We characterize the aggregation state of the ions, and assess the role of ion complexes in ionomer dynamics. In addition to solvated cations and pairs, higher order ion clusters are found. Most of the ion clusters are in string-like structure and cross-link two or more different ionomer chains through ionic binding. Ionic crosslinks decrease mobility at the ionic co-monomer; hence the mobility of the adjacent PEO segment is influenced. Na ions show slow mobility when they are inside large clusters. The hopping timescale for Na varies from 20 ns to 200. A correlation is found between Na mobility and the number of hops from one coordination site to another. Besides ether oxygens, Na ions in the ionomer also use the anion and the edge of the cluster as hopping sites. The string-like structure of clusters provide less stable sites at the two ends thus ions are more mobile in those regions. We observed Grotthus like mechanism in our ionomer, in which the positive charge migrates within the string-like cluster without the cations actually moving.

Aluminum binding by humus

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benedetti, M.F.; Hiemstra, T.; Riemsdijk, W. van

The need for qualitative and quantitative description of the chemical speciation of Al, in particular and other metal ions in general, is stressed by the increased mobilization of metal ions in water and soils due to acid rain deposition. In this paper we present new data of Al binding to two humic acids. These new data sets and the some previously published data will be analyzed with the NICA-Donnan model using one set of parameters to describe the Al binding to the different humic substances. Once the experimental data is described with the NICA-Donnan approach, we will show the effectmore » of Ca on Al binding and surface speciation as well as the effect of Al on the charge of the humic particles. The parameters derived from the laboratory experiments will be used to describe the variation of the field based Al partition coefficient.« less

Tailoring Ion Charge State Distribution in Tetramethyltin Clusters under Influence of Moderate Intensity Picosecond Laser Pulse: Role of Laser Wavelength and Rate of Energy Deposition

NASA Astrophysics Data System (ADS)

Sharma, Pramod; Das, Soumitra; Vatsa, Rajesh K.

2017-07-01

Systematic manipulation of ionic-outcome in laser-cluster interaction process has been realized for studies carried out on tetramethyltin (TMT) clusters under picosecond laser conditions, determined by choice of laser wavelength and intensity. As a function of laser intensity, TMT clusters exhibit gradual enhancement in overall ionization of its cluster constituents, up to a saturation level of ionization, which was distinct for different wavelengths (266, 355, and 532 nm). Simultaneously, systematic appearance of higher multiply charged atomic ions and shift in relative abundance of multiply charged atomic ions towards higher charge state was observed, using time-of-flight mass spectrometer. At saturation level, multiply charged atomic ions up to (C2+, Sn2+) at 266 nm, (C4+, Sn4+) at 355 nm, and (C4+, Sn6+) at 532 nm were detected. In addition, at 355 nm intra-cluster ion chemistry within the ionized cluster leads to generation of molecular hydrogen ion (H2 +) and triatomic molecular hydrogen ion (H3 +). Generation of multiply charged atomic ions is ascribed to efficient coupling of laser pulse with the cluster media, facilitated by inner-ionized electrons produced within the cluster, at the leading edge of laser pulse. Role of inner-ionized electrons is authenticated by measuring kinetic energy distribution of electrons liberated upon disintegration of excessively ionized cluster, under the influence of picosecond laser pulse.

Lineage diversification of fringe-toed lizards (Phrynosomatidae: Uma notata complex) in the Colorado Desert: Delimiting species in the presence of gene flow

USGS Publications Warehouse

Gottscho, Andrew D.; Wood, Dustin A.; Vandergast, Amy; Lemos Espinal, Julio A.; Gatesy, John; Reeder, Tod

2017-01-01

Multi-locus nuclear DNA data were used to delimit species of fringe-toed lizards of theUma notata complex, which are specialized for living in wind-blown sand habitats in the deserts of southwestern North America, and to infer whether Quaternary glacial cycles or Tertiary geological events were important in shaping the historical biogeography of this group. We analyzed ten nuclear loci collected using Sanger sequencing and genome-wide sequence and single-nucleotide polymorphism (SNP) data collected using restriction-associated DNA (RAD) sequencing. A combination of species discovery methods (concatenated phylogenies, parametric and non-parametric clustering algorithms) and species validation approaches (coalescent-based species tree/isolation-with-migration models) were used to delimit species, infer phylogenetic relationships, and to estimate effective population sizes, migration rates, and speciation times. Uma notata, U. inornata, U. cowlesi, and an undescribed species from Mohawk Dunes, Arizona (U. sp.) were supported as distinct in the concatenated analyses and by clustering algorithms, and all operational taxonomic units were decisively supported as distinct species by ranking hierarchical nested speciation models with Bayes factors based on coalescent-based species tree methods. However, significant unidirectional gene flow (2NM >1) from U. cowlesi and U. notata into U. rufopunctata was detected under the isolation-with-migration model. Therefore, we conservatively delimit four species-level lineages within this complex (U. inornata, U. notata, U. cowlesi, and U. sp.), treating U. rufopunctata as a hybrid population (U. notata x cowlesi). Both concatenated and coalescent-based estimates of speciation times support the hypotheses that speciation within the complex occurred during the late Pleistocene, and that the geological evolution of the Colorado River delta during this period was an important process shaping the observed phylogeographic patterns.

Hybridization Reveals the Evolving Genomic Architecture of Speciation

PubMed Central

Kronforst, Marcus R.; Hansen, Matthew E.B.; Crawford, Nicholas G.; Gallant, Jason R.; Zhang, Wei; Kulathinal, Rob J.; Kapan, Durrell D.; Mullen, Sean P.

2014-01-01

SUMMARY The rate at which genomes diverge during speciation is unknown, as are the physical dynamics of the process. Here, we compare full genome sequences of 32 butterflies, representing five species from a hybridizing Heliconius butterfly community, to examine genome-wide patterns of introgression and infer how divergence evolves during the speciation process. Our analyses reveal that initial divergence is restricted to a small fraction of the genome, largely clustered around known wing-patterning genes. Over time, divergence evolves rapidly, due primarily to the origin of new divergent regions. Furthermore, divergent genomic regions display signatures of both selection and adaptive introgression, demonstrating the link between microevolutionary processes acting within species and the origin of species across macroevolutionary timescales. Our results provide a uniquely comprehensive portrait of the evolving species boundary due to the role that hybridization plays in reducing the background accumulation of divergence at neutral sites. PMID:24183670

The genomic bases of morphological divergence and reproductive isolation driven by ecological speciation in Senecio (Asteraceae).

PubMed

Chapman, M A; Hiscock, S J; Filatov, D A

2016-01-01

Ecological speciation, driven by adaptation to contrasting environments, provides an attractive opportunity to study the formation of distinct species, and the role of selection and genomic divergence in this process. Here, we focus on a particularly clear-cut case of ecological speciation to reveal the genomic bases of reproductive isolation and morphological differences between closely related Senecio species, whose recent divergence within the last ~200,000 years was likely driven by the uplift of Mt. Etna (Sicily). These species form a hybrid zone, yet remain morphologically and ecologically distinct, despite active gene exchange. Here, we report a high-density genetic map of the Senecio genome and map hybrid breakdown to one large and several small quantitative trait loci (QTL). Loci under diversifying selection cluster in three 5 cM regions which are characterized by a significant increase in relative (F(ST)), but not absolute (d(XY)), interspecific differentiation. They also correspond to some of the regions of greatest marker density, possibly corresponding to 'cold-spots' of recombination, such as centromeres or chromosomal inversions. Morphological QTL for leaf and floral traits overlap these clusters. We also detected three genomic regions with significant transmission ratio distortion (TRD), possibly indicating accumulation of intrinsic genetic incompatibilities between these recently diverged species. One of the TRD regions overlapped with a cluster of high species differentiation, and another overlaps the large QTL for hybrid breakdown, indicating that divergence of these species may have occurred due to a complex interplay of ecological divergence and accumulation of intrinsic genetic incompatibilities. © 2015 European Society For Evolutionary Biology. Journal of Evolutionary Biology © 2015 European Society For Evolutionary Biology.

Method of precisely modifying predetermined surface layers of a workpiece by cluster ion impact therewith

DOEpatents

Friedman, L.; Beuhler, R.J.; Matthew, M.W.; Ledbetter, M.

1984-06-25

A method of precisely modifying a selected area of a workpiece by producing a beam of charged cluster ions that is narrowly mass selected to a predetermined mean size of cluster ions within a range of 25 to 10/sup 6/ atoms per cluster ion, and accelerated in a beam to a critical velocity. The accelerated beam is used to impact a selected area of an outer surface of the workpiece at a preselected rate of impacts of cluster ions/cm/sup 2//sec in order to effect a precise modification in that selected area of the workpiece.

Method of precisely modifying predetermined surface layers of a workpiece by cluster ion impact therewith

DOEpatents

Friedman, Lewis; Buehler, Robert J.; Matthew, Michael W.; Ledbetter, Myron

1985-01-01

A method of precisely modifying a selected area of a workpiece by producing a beam of charged cluster ions that is narrowly mass selected to a predetermined mean size of cluster ions within a range of 25 to 10.sup.6 atoms per cluster ion, and accelerated in a beam to a critical velocity. The accelerated beam is used to impact a selected area of an outer surface of the workpiece at a preselected rate of impacts of cluster ions/cm.sup.2 /sec. in order to effect a precise modification in that selected area of the workpiece.

On Ion Clusters in the Interstellar Gas

NASA Technical Reports Server (NTRS)

Donn, Bertram

1960-01-01

In a recent paper V.I. Krassovsky (1958) predicts the occurrence of clusters of large numbers of atoms and molecules around ions in the interstellar gas. He then proposes a number of physicochemical processes that would be considerably enhanced by the high particle density in such clusters. In particular, he suggests that absorption by negative ions formed in the clusters would account for the interstellar extinction without any necessity for the presence of grains. Because of the important consequences that ion clusters could have, it is necessary to examine their occurrence more fully. This note re-examines the formation of ion clusters in space and shows that even ion-molecule pairs are essentially non-existent. Ion clusters have been considered by Bloom and Margenau (1952) from the same point of view as that used by Krassovsky, whose basic reference (Joffe and Semenov 1933) unfortunately is not available. A different approach has been used by Eyring, Hirschfelder, and Taylor (1936) following the methods of chemical equilibrium. Both the references cited here enable one to conclude that clustering is negligible. Therefore, the treatment of Eyring et al. is more appropriate than the method of Bloom and Margenau, which depends on the statistical equilibrium of an atmosphere in a force field.

Effect of low-oxygen-concentration layer on iron gettering capability of carbon-cluster ion-implanted Si wafer for CMOS image sensors

NASA Astrophysics Data System (ADS)

Onaka-Masada, Ayumi; Nakai, Toshiro; Okuyama, Ryosuke; Okuda, Hidehiko; Kadono, Takeshi; Hirose, Ryo; Koga, Yoshihiro; Kurita, Kazunari; Sueoka, Koji

2018-02-01

The effect of oxygen (O) concentration on the Fe gettering capability in a carbon-cluster (C3H5) ion-implanted region was investigated by comparing a Czochralski (CZ)-grown silicon substrate and an epitaxial growth layer. A high Fe gettering efficiency in a carbon-cluster ion-implanted epitaxial growth layer, which has a low oxygen region, was observed by deep-level transient spectroscopy (DLTS) and secondary ion mass spectroscopy (SIMS). It was demonstrated that the amount of gettered Fe in the epitaxial growth layer is approximately two times higher than that in the CZ-grown silicon substrate. Furthermore, by measuring the cathodeluminescence, the number of intrinsic point defects induced by carbon-cluster ion implantation was found to differ between the CZ-grown silicon substrate and the epitaxial growth layer. It is suggested that Fe gettering by carbon-cluster ion implantation comes through point defect clusters, and that O in the carbon-cluster ion-implanted region affects the formation of gettering sinks for Fe.

Ion-imprinted polymethacrylic microbeads as new sorbent for preconcentration and speciation of mercury.

PubMed

Dakova, Ivanka; Karadjova, Irina; Georgieva, Ventsislava; Georgiev, George

2009-04-30

Metal ion-imprinted polymer particles have been prepared by copolymerization of methacrylic acid as monomer, trimethylolpropane trimethacrylate as cross-linking agent and 2,2'-azobisisobutyronitrile as initiator, in the presence of Hg(II)-1-(2-thiazolylazo)-2-naphthol complex. The separation and preconcentration characteristics of the Hg-ion-imprinted microbeads for inorganic mercury have been investigated by batch procedure. The optimal pH value for the quantitative sorption is 7. The adsorbed inorganic mercury is easily eluted by 2 mL 4M HNO(3). The adsorption capacity of the newly synthesized Hg ion-imprinted microbeads is 32.0 micromol g(-1) for dry copolymer. The selectivity of the copolymer toward inorganic mercury (Hg(II)) ion is confirmed through the comparison of the competitive adsorptions of Cd(II), Co(II), Cu(II), Ni(II), Pb(II), Zn(II)) and high values of the selectivity and distribution coefficients have been calculated. Experiments performed for selective determination of inorganic mercury in mineral and sea waters showed that the interfering matrix does not influence the extraction efficiency of Hg ion-imprinted microbeads. The detection limit for inorganic mercury is 0.006 microg L(-1) (3 sigma), determined by cold vapor atomic adsorption spectrometry. The relative standard deviation varied in the range 5-9 % at 0.02-1 microg L(-1) Hg levels. The new Hg-ion-imprinted microbeads have been tested and applied for the speciation of Hg in river and mineral waters: inorganic mercury has been determined selectively in nondigested sample, while total mercury e.g. sum of inorganic and methylmercury, has been determined in digested sample.

The importance of extracellular speciation and corrosion of copper nanoparticles on lung cell membrane integrity.

PubMed

Hedberg, Jonas; Karlsson, Hanna L; Hedberg, Yolanda; Blomberg, Eva; Odnevall Wallinder, Inger

2016-05-01

Copper nanoparticles (Cu NPs) are increasingly used in various biologically relevant applications and products, e.g., due to their antimicrobial and catalytic properties. This inevitably demands for an improved understanding on their interactions and potential toxic effects on humans. The aim of this study was to investigate the corrosion of copper nanoparticles in various biological media and to elucidate the speciation of released copper in solution. Furthermore, reactive oxygen species (ROS) generation and lung cell (A549 type II) membrane damage induced by Cu NPs in the various media were studied. The used biological media of different complexity are of relevance for nanotoxicological studies: Dulbecco's modified eagle medium (DMEM), DMEM(+) (includes fetal bovine serum), phosphate buffered saline (PBS), and PBS+histidine. The results show that both copper release and corrosion are enhanced in DMEM(+), DMEM, and PBS+histidine compared with PBS alone. Speciation results show that essentially no free copper ions are present in the released fraction of Cu NPs in neither DMEM(+), DMEM nor histidine, while labile Cu complexes form in PBS. The Cu NPs were substantially more membrane reactive in PBS compared to the other media and the NPs caused larger effects compared to the same mass of Cu ions. Similarly, the Cu NPs caused much more ROS generation compared to the released fraction only. Taken together, the results suggest that membrane damage and ROS formation are stronger induced by Cu NPs and by free or labile Cu ions/complexes compared with Cu bound to biomolecules. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Uncertainty analysis of the nonideal competitive adsorption-donnan model: effects of dissolved organic matter variability on predicted metal speciation in soil solution.

PubMed

Groenenberg, Jan E; Koopmans, Gerwin F; Comans, Rob N J

2010-02-15

Ion binding models such as the nonideal competitive adsorption-Donnan model (NICA-Donnan) and model VI successfully describe laboratory data of proton and metal binding to purified humic substances (HS). In this study model performance was tested in more complex natural systems. The speciation predicted with the NICA-Donnan model and the associated uncertainty were compared with independent measurements in soil solution extracts, including the free metal ion activity and fulvic (FA) and humic acid (HA) fractions of dissolved organic matter (DOM). Potentially important sources of uncertainty are the DOM composition and the variation in binding properties of HS. HS fractions of DOM in soil solution extracts varied between 14 and 63% and consisted mainly of FA. Moreover, binding parameters optimized for individual FA samples show substantial variation. Monte Carlo simulations show that uncertainties in predicted metal speciation, for metals with a high affinity for FA (Cu, Pb), are largely due to the natural variation in binding properties (i.e., the affinity) of FA. Predictions for metals with a lower affinity (Cd) are more prone to uncertainties in the fraction FA in DOM and the maximum site density (i.e., the capacity) of the FA. Based on these findings, suggestions are provided to reduce uncertainties in model predictions.

Chemical fractionation and speciation modelling for optimization of ion-exchange processes to recover palladium from industrial wastewater.

PubMed

Folens, K; Van Hulle, S; Vanhaecke, F; Du Laing, G

2016-01-01

Palladium is used in several industrial applications and, given its high intrinsic value, intense efforts are made to recover the element. In this hydrometallurgic perspective, ion-exchange (IEX) technologies are principal means. Yet, without incorporating the chemical and physical properties of the Pd present in real, plant-specific conditions, the recovery cannot reach its technical nor economic optimum. This study characterized a relevant Pd-containing waste stream of a mirror manufacturer to provide input for a speciation model, predicting the Pd speciation as a function of pH and chloride concentration. Besides the administered neutral PdCl2 form, both positively and negatively charged [PdCln](2-n) species occur depending on the chloride concentration in solution. Purolite C100 and Relite 2AS IEX resins were selected and applied in combination with other treatment steps to optimize the Pd recovery. A combination of the cation and anion exchange resins was found successful to quantitatively recover Pd. Given the fact that Pd was also primarily associated with particles, laboratory-scale experiments focused on physical removal of the Pd-containing flow were conducted, which showed that particle-bound Pd can already be removed by physical pre-treatment prior to IEX, while the ionic fraction remains fully susceptible to the IEX mechanism.

Interactions Among Chemical Speciation, Algal Accumulation, and Biogeochemical Cycling of Toxic Metals in a Major U.S. Naval Harbor (Elizabeth River, VA)

DTIC Science & Technology

2000-09-30

the Elizabeth River/Hampton Roads system and algal species grown in metal ion buffer systems: Thalassiosira pseudonana, Emiliania huxleyi , and...metal ion concentration. 1 10 100 1000 -12 -11 -10 -9 -8 -7 Log [Zn2+] C el l Z n: C ( m ol /m ol ) T. pseudonana E. huxleyi I. galbana Elizabeth River

Potentiometric titration of metal ions in ethanol.

PubMed

Gibson, Graham T T; Mohamed, Mark F; Neverov, Alexei A; Brown, R S

2006-09-18

The potentiometric titrations of Zn2+, Cu2+ and 12 Ln3+ metal ions were obtained in ethanol to determine the titration constants (defined as the at which the [-OEt]/[Mx+]t ratios are 0.5, 1.5, and 2.5) and in two cases (La3+ and Zn2+) a complete speciation diagram. Several simple monobasic acids and aminium ions were also titrated to test the validity of experimental titration measurements and to establish new constants in this medium that will be useful for the preparation of buffers and standard solutions. The dependence of the titration constants on the concentration and type of metal ion and specific counterion effects is discussed. In selected cases, the titration profiles were analyzed using a commercially available fitting program to obtain information about the species present in solution, including La3+ for which a dimer model is proposed. The fitting provides the microscopic values for deprotonation of one to four metal-bound ethanol molecules. Kinetics for the La3+-catalyzed ethanolysis of paraoxon as a function of are presented and analyzed in terms of La3+ speciation as determined by the analysis of potentiometric titration curves. The stability constants for the formation of Zn2+ and Cu2+ complexes with 1,5,9-triazacyclododecane as determined by potentiometric titration are presented.

Chemical speciation and recovery of gold(I, III) from wastewater and silver by liquid-liquid extraction with the ion-pair reagent amiloride mono hydrochloride and AAS determination.

PubMed

El-Shahawi, M S; Bashammakh, A S; Bahaffi, S O

2007-06-15

A novel and low cost liquid-liquid extraction procedure for the separation of gold(III) at trace level from aqueous medium of pH 5-9 has been developed. The method has been based upon the formation of a yellow colored ternary complex ion associate of tetrachloro gold(III) complex anion, AuCl(4)(-) with the ion-pair reagent 1-(3,5-diamino-6-chloropyrazinecarboxyl) guanidine hydrochloride monohydrate, namely amiloride, DPG(+).Cl(-). The effect of various parameters, e.g. pH, organic solvent, shaking time, etc. on the preconcentration of gold(III) from the aqueous media by the DPG(+).Cl(-) reagent has been investigated. The colored gold species was quantitatively extracted into 4-methyl pentan-2-one. The chemical composition of the ion associate of DPG(+).Cl(-) with AuCl(4)(-) in the organic solvent has been determined by the Job's method. The molar absorptivity (2.19x10(4)Lmol(-1)cm(-1)) of the associate DPG(+).AuCl(4)(-) at 362nm enabled a convenient application of the developed extraction procedure for the separation and AAS determination of traces of aurate ions. Mono-valence gold ions after oxidation to gold(III) with bromine water in HCl (1.0molL(-1)) media have been also extracted quantitatively from the aqueous media by the developed procedure. The chemical speciation of mono- and/or tri-valence gold species spiked to fresh and industrial wastewater samples has been achieved. The method has been also applied successfully from the separation of gold(I) and gold(III) species from metallic ions and silver. The developed method has also the advantage of freedom from most diverse ions.

Arsenic distribution and valence state variation studied by fast hierarchical length-scale morphological, compositional, and speciation imaging at the Nanoscopium, Synchrotron Soleil

NASA Astrophysics Data System (ADS)

Somogyi, Andrea; Medjoubi, Kadda; Sancho-Tomas, Maria; Visscher, P. T.; Baranton, Gil; Philippot, Pascal

2017-09-01

The understanding of real complex geological, environmental and geo-biological processes depends increasingly on in-depth non-invasive study of chemical composition and morphology. In this paper we used scanning hard X-ray nanoprobe techniques in order to study the elemental composition, morphology and As speciation in complex highly heterogeneous geological samples. Multivariate statistical analytical techniques, such as principal component analysis and clustering were used for data interpretation. These measurements revealed the quantitative and valance state inhomogeneity of As and its relation to the total compositional and morphological variation of the sample at sub-μm scales.

Influence of dissolved organic matter and manganese oxides on metal speciation in soil solution: A modelling approach.

PubMed

Schneider, Arnaud R; Ponthieu, Marie; Cancès, Benjamin; Conreux, Alexandra; Morvan, Xavier; Gommeaux, Maxime; Marin, Béatrice; Benedetti, Marc F

2016-06-01

Trace element (TE) speciation modelling in soil solution is controlled by the assumptions made about the soil solution composition. To evaluate this influence, different assumptions using Visual MINTEQ were tested and compared to measurements of free TE concentrations. The soil column Donnan membrane technique (SC-DMT) was used to estimate the free TE (Cd, Cu, Ni, Pb and Zn) concentrations in six acidic soil solutions. A batch technique using DAX-8 resin was used to fractionate the dissolved organic matter (DOM) into four fractions: humic acids (HA), fulvic acids (FA), hydrophilic acids (Hy) and hydrophobic neutral organic matter (HON). To model TE speciation, particular attention was focused on the hydrous manganese oxides (HMO) and the Hy fraction, ligands not considered in most of the TE speciation modelling studies in soil solution. In this work, the model predictions of free ion activities agree with the experimental results. The knowledge of the FA fraction seems to be very useful, especially in the case of high DOM content, for more accurately representing experimental data. Finally, the role of the manganese oxides and of the Hy fraction on TE speciation was identified and, depending on the physicochemical conditions of the soil solution, should be considered in future studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Proceeding of the 18th Intl. Workshop on Inelastic Ion-Surface Collisions (IISC-18)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reinhold, Carlos O; Krstic, Predrag S; Meyer, Fred W

2011-01-01

The main topics of this proceedings were: (1) Energy loss of particles at surfaces; (2) Scattering of atoms, ions, molecules and clusters; (3) Charge exchange between particles and surfaces; (4) Ion induced desorption, electronic and kinetic sputtering; (5) Defect formation, surface modification and nanostructuring; (6) Electron, photon and secondary ion emission due to particle impact on surfaces; (7) Sputtering, fragmentation, cluster and ion formation in SIMS and SNMS; (8) Cluster/molecular and highly charged ion beams; and (9) Laser induced desorption.

Fibrous structure in GaSb surfaces irradiated with fast Cu cluster ions

NASA Astrophysics Data System (ADS)

Tsuchida, Hidetsugu; Nitta, Noriko; Yanagida, Yusuke; Okumura, Yuya; Murase, Ryu

2018-04-01

The effect of fast cluster irradiation on the formation of fibrous structures is investigated for single crystal GaSb surfaces irradiated by Cun+ ions (n = 1-3) with an energy of 0.4 MeV/atom at ion fluences up to 5 × 1015 cm-2. We study the cluster size dependence on the growth of fibrous network structures. With increasing cluster size, the shape of the fiber changed from rod-like to spherical. To quantitatively evaluate this cluster effect, a fiber diameter d in rod or spherical portion is examined as a function of ion fluence Φ and cluster size n. We find that the fiber diameter nonlinearly increases and follows the relation d ∝nα×Φ , with α≈2 . This evidently implies that the amount of defects generated by n-sized cluster bombardments varies as n2 for n ≤3 . Cluster ion irradiation enhances the defect generation owing to the overlap between cascades of individual cluster constituents and is therefore effective for the growth of nanofibers.

Novel size-dependent chemistry within ionized van der Waals clusters of 1,1-difluoroethane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coolbaugh, M.T.; Peifer, W.R.; Garvey, J.F.

1990-02-22

The authors present in this paper evidence for size-dependent cluster chemistry occurring in van der Waals clusters of 1,1-difluoroethane. Clusters of C{sub 2}H{sub 4}F{sub 2} are produced from a neat adiabatic expansion and are ionized via electron impact. In addition to the anticipated fragment ions, we observe ions with the general empirical formula of M{sub n}H{sup +} (where n {ge} 4). The reactive process that generates this species cannot be rationalized in terms of intramolecular analogues of known gas-phase bimolecular ion-molecular reactions. Hence, we fell the production of this product cluster ion represents an additional example of a brand newmore » class of ion-molecule reactions that can only occur within the unique solvated environment of the cluster.« less

Properties of ammonium ion-water clusters: analyses of structure evolution, noncovalent interactions, and temperature and humidity effects.

PubMed

Pei, Shi-Tu; Jiang, Shuai; Liu, Yi-Rong; Huang, Teng; Xu, Kang-Ming; Wen, Hui; Zhu, Yu-Peng; Huang, Wei

2015-03-26

Although ammonium ion-water clusters are abundant in the biosphere, some information regarding these clusters, such as their growth route, the influence of temperature and humidity, and the concentrations of various hydrated clusters, is lacking. In this study, theoretical calculations are performed on ammonium ion-water clusters. These theoretical calculations are focused on determining the following characteristics: (1) the pattern of cluster growth; (2) the percentages of clusters of the same size at different temperatures and humidities; (3) the distributions of different isomers for the same size clusters at different temperatures; (4) the relative strengths of the noncovalent interactions for clusters of different sizes. The results suggest that the dipole moment may be very significant for the ammonium ion-water system, and some new stable isomers were found. The nucleation of ammonium ions and water molecules is favorable at low temperatures; thus, the clusters observed at high altitudes might not be present at low altitudes. High humidity can contribute to the formation of large ammonium ion-water clusters, whereas the formation of small clusters may be favorable under low-humidity conditions. The potential energy surfaces (PES) of these different sized clusters are complicated and differ according to the distribution of isomers at different temperatures. Some similar structures are observed between NH4(+)(H2O)n and M(H2O)n (where M represents an alkali metal ion or water molecule); when n = 8, the clusters begin to form the closed-cage geometry. As the cluster size increases, these interactions become progressively weaker. The successive binding energy at the DF-MP2-F12/VDZ-F12 level is better than that at the PW91PW91/6-311++G(3df, 3pd) level and is consistent with the experimentally determined values.

A graph-theoretic approach for inparalog detection.

PubMed

Tremblay-Savard, Olivier; Swenson, Krister M

2012-01-01

Understanding the history of a gene family that evolves through duplication, speciation, and loss is a fundamental problem in comparative genomics. Features such as function, position, and structural similarity between genes are intimately connected to this history; relationships between genes such as orthology (genes related through a speciation event) or paralogy (genes related through a duplication event) are usually correlated with these features. For example, recent work has shown that in human and mouse there is a strong connection between function and inparalogs, the paralogs that were created since the speciation event separating the human and mouse lineages. Methods exist for detecting inparalogs that either use information from only two species, or consider a set of species but rely on clustering methods. In this paper we present a graph-theoretic approach for finding lower bounds on the number of inparalogs for a given set of species; we pose an edge covering problem on the similarity graph and give an efficient 2/3-approximation as well as a faster heuristic. Since the physical position of inparalogs corresponding to recent speciations is not likely to have changed since the duplication, we also use our predictions to estimate the types of duplications that have occurred in some vertebrates and drosophila.

Presumable incipient hybrid speciation of door snails in previously glaciated areas in the Caucasus.

PubMed

Koch, Eva L; Neiber, Marco T; Walther, Frank; Hausdorf, Bernhard

2016-04-01

Homoploid hybrid speciation, speciation by hybridization without a change in chromosome number, may be the result of an encounter of closely related species in a habitat that is different from that usually occupied by these species. In the northwestern Caucasus the land snail species Micropontica caucasica and M. circassica form two distinct entities with little admixture at low and intermediate altitudes. However, at higher altitudes in the Lagonaki plateau, which were repeatedly glaciated, Micropontica populations with intermediate characters occur. Admixture analyses based on AFLP data demonstrated that the populations from the Lagonaki plateau are homoploid hybrids that now form a cluster separate from the parental species. The Lagonaki populations are characterized by a mtDNA haplotype clade that has been found in the parental species only once. The fixation of this haplotype clade in most hybrid populations suggests that these haplotypes are better adapted to the cooler conditions in high altitude habitats and have replaced the haplotypes of the parental species in a selective sweep. The fixation of a presumably adaptive mitochondrial haplotype clade in the Lagonaki populations is an important step towards speciation under the differential fitness species concept. Copyright © 2015 Elsevier Inc. All rights reserved.

A plant-wide aqueous phase chemistry module describing pH variations and ion speciation/pairing in wastewater treatment process models.

PubMed

Flores-Alsina, Xavier; Kazadi Mbamba, Christian; Solon, Kimberly; Vrecko, Darko; Tait, Stephan; Batstone, Damien J; Jeppsson, Ulf; Gernaey, Krist V

2015-11-15

There is a growing interest within the Wastewater Treatment Plant (WWTP) modelling community to correctly describe physico-chemical processes after many years of mainly focusing on biokinetics. Indeed, future modelling needs, such as a plant-wide phosphorus (P) description, require a major, but unavoidable, additional degree of complexity when representing cationic/anionic behaviour in Activated Sludge (AS)/Anaerobic Digestion (AD) systems. In this paper, a plant-wide aqueous phase chemistry module describing pH variations plus ion speciation/pairing is presented and interfaced with industry standard models. The module accounts for extensive consideration of non-ideality, including ion activities instead of molar concentrations and complex ion pairing. The general equilibria are formulated as a set of Differential Algebraic Equations (DAEs) instead of Ordinary Differential Equations (ODEs) in order to reduce the overall stiffness of the system, thereby enhancing simulation speed. Additionally, a multi-dimensional version of the Newton-Raphson algorithm is applied to handle the existing multiple algebraic inter-dependencies. The latter is reinforced with the Simulated Annealing method to increase the robustness of the solver making the system not so dependent of the initial conditions. Simulation results show pH predictions when describing Biological Nutrient Removal (BNR) by the activated sludge models (ASM) 1, 2d and 3 comparing the performance of a nitrogen removal (WWTP1) and a combined nitrogen and phosphorus removal (WWTP2) treatment plant configuration under different anaerobic/anoxic/aerobic conditions. The same framework is implemented in the Benchmark Simulation Model No. 2 (BSM2) version of the Anaerobic Digestion Model No. 1 (ADM1) (WWTP3) as well, predicting pH values at different cationic/anionic loads. In this way, the general applicability/flexibility of the proposed approach is demonstrated, by implementing the aqueous phase chemistry module in some of the most frequently used WWTP process simulation models. Finally, it is shown how traditional wastewater modelling studies can be complemented with a rigorous description of aqueous phase and ion chemistry (pH, speciation, complexation). Copyright © 2015 Elsevier Ltd. All rights reserved.

COMPETITIVE INFLUENCE OF PHOSPHORUS AND CALCIUM ON PB IN-VITRO BIOAVAILABILITY

EPA Science Inventory

The bioavailability of a metal is heavily related to the speciation of the particular metal. Further, the complexity of examining metal bioavailability is compounded by the presence of competitive ions. Thus, equally contaminated soils with varying concentrations of competitive e...

Trojan-horse mechanism in the cellular uptake of silver nanoparticles verified by direct intra- and extracellular silver speciation analysis.

PubMed

Hsiao, I-Lun; Hsieh, Yi-Kong; Wang, Chu-Fang; Chen, I-Chieh; Huang, Yuh-Jeen

2015-03-17

The so-called "Trojan-horse" mechanism, in which nanoparticles are internalized within cells and then release high levels of toxic ions, has been proposed as a behavior in the cellular uptake of Ag nanoparticles (AgNPs). While several reports claim to have proved this mechanism by measuring AgNPs and Ag ions (I) in cells, it cannot be fully proven without examining those two components in both intra- and extracellular media. In our study, we found that even though cells take up AgNPs similarly to (microglia (BV-2)) or more rapidly than (astrocyte (ALT)) Ag (I), the ratio of AgNPs to total Ag (AgNPs+Ag (I)) in both cells was lower than that in outside media. It could be explained that H2O2, a major intracellular reactive oxygen species (ROS), reacts with AgNPs to form more Ag (I). Moreover, the major speciation of Ag (I) in cells was Ag(cysteine) and Ag(cysteine)2, indicating the possible binding of monomer cysteine or vital thiol proteins/peptides to Ag ions. Evidence we found indicates that the Trojan-horse mechanism really exists.

Range of plasma ions in cold cluster gases near the critical point

NASA Astrophysics Data System (ADS)

Zhang, G.; Quevedo, H. J.; Bonasera, A.; Donovan, M.; Dyer, G.; Gaul, E.; Guardo, G. L.; Gulino, M.; La Cognata, M.; Lattuada, D.; Palmerini, S.; Pizzone, R. G.; Romano, S.; Smith, H.; Trippella, O.; Anzalone, A.; Spitaleri, C.; Ditmire, T.

2017-05-01

We measure the range of plasma ions in cold cluster gases by using the Petawatt laser at the University of Texas-Austin. The produced plasma propagated in all directions some hitting the cold cluster gas not illuminated by the laser. From the ratio of the measured ion distributions at different angles we can estimate the range of the ions in the cold cluster gas. It is much smaller than estimated using popular models, which take only into account the slowing down of charged particles in uniform matter. We discuss the ion range in systems prepared near a liquid-gas phase transition.

Monoatomic and cluster beam effect on ToF-SIMS spectra of self-assembled monolayers on gold

NASA Astrophysics Data System (ADS)

Tuccitto, N.; Torrisi, V.; Delfanti, I.; Licciardello, A.

2008-12-01

Self-assembled monolayers represent well-defined systems that is a good model surface to study the effect of primary ion beams used in secondary ion mass spectrometry. The effect of polyatomic primary beams on both aliphatic and aromatic self-assembled monolayers has been studied. In particular, we analysed the variation of the relative secondary ion yield of both substrate metal-cluster (Au n-) in comparison with the molecular ions (M -) and clusters (M xAu y-) by using Bi +, Bi 3+, Bi 5+ beams. Moreover, the differences in the secondary ion generation efficiency are discussed. The main effect of the cluster beams is related to an increased formation of low-mass fragments and to the enhancement of the substrate related gold-clusters. The results show that, at variance of many other cases, the static SIMS of self-assembled monolayers does not benefit of the use of polyatomic primary ions.

FT-ICR mass spectrometric and density functional theory studies of sulfate prenucleation clusters

NASA Astrophysics Data System (ADS)

Lemke, K. H.

2012-12-01

Recent mass spectrometric1 and relaxation spectroscopic studies2 of metal sulfate salts have demonstrated that aqueous clusters play an important role in sulfate prenucleation processes. While such studies provide evidence that that ion clusters are nucleation relevant species, ultra-high resolution mass spectrumetry, in particular, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR/MS) can provide additional valuable information about the molecular composition and stability of individual ion clusters. Prompted by the above studies, our group has begun a systematic survey of metal sulfate clusters using FT-ICR mass spectrometry. Here, I report stoichiometries, structures and thermodynamic properties of calcium sulfate ion clusters, both "dry" and microsolvated, using electrospray ionization FT-ICR mass spectrometry in combination with semi-empirical methods and M062X/aug-cc-PVXZ level density functional theory calculations. In electrosprayed dilute aqueous solutions of CaSO4 (1-20mM), droplet desolvation results in the formation of stable doubly-charged clusters of [Ca(CaSO4)m(H2O)n]+2 (m≤10 & n≤9) as well as larger quadruply-charged ion clusters [Ca2(CaSO4)m(H2O)n]+4 with m≤23 and n≤10, demonstrating considerable sulfate nucleation potential in undersaturated electrolyte solutions. An attempt was also made to assess the extent of ion cluster aggregation in solution prior to electrospray ionization by measuring ion mass spectra at different solution concentrations. In brief, an increase in calcium sulfate concentration from 1-10mM results in a continuous increase in polynuclear ion cluster species, while smaller clusters, for instance, Ca[CaSO4]+2 and corresponding hydrated forms, become increasingly less abundant. Building on semi-empirical methods, M062X calculations have been applied to predict calcium sulfate cluster geometries, both "dry" and microsolvated, as well as the size-dependent evolution of clustering and hydration energies. 1Schoeder et al. (2011) J.Am.Chem.Soc., 133, 2444; 2Chen et al. (2005) J.Sol.Chem., 34, 1045;

A systematic investigation of aluminium ion speciation at high temperature. Part 1. Solution studies.

PubMed

Shafran, Kirill L; Perry, Carole C

2005-06-21

Speciation diagrams of aluminium ions in aqueous solution (0.2 M) at high temperature (90 degrees C) have been obtained from 48 h time-resolved multi-batch titration experiments monitored by 27Al NMR spectroscopy, potentiometry and dynamic light scattering. The quantitative speciation patterns and kinetic data obtained offer a dynamic picture of the distribution of soluble and insoluble Al species as a function of hydrolysis ratio h(h=[OH-]/[Al3+]) over a very broad range of conditions (-1.0 < or =h < or = 4.0). Monomeric, small oligomeric, tridecameric (the 'Al13-mer') and the recently characterised 30-meric aluminium species (the 'Al30-mer') as well as aluminium hydroxide have been identified and quantified. The Al13-mer species dominates over a relatively broad range of hydrolysis ratios (1.5 < or =h< or = 2.7) during the first 6 h of experiment, but are gradually replaced by Al30-mers at longer reaction times. Kinetic profiles indicate that the formation of the Al30-mer is limited by the disappearance of the Al13 species at mildly acidic conditions. The estimated rate constants of both hydrolytic processes show good internal correlation at h> or = 1.5. The effect of local perturbations leading to the formation of aluminium hydroxide below the electroneutrality point (h= 3.0) has been estimated quantitatively.

A simple and low cost dual-wavelength β-correction spectrophotometric determination and speciation of mercury(II) in water using chromogenic reagent 4-(2-thiazolylazo) resorcinol

NASA Astrophysics Data System (ADS)

Al-Bagawi, A. H.; Ahmad, W.; Saigl, Z. M.; Alwael, H.; Al-Harbi, E. A.; El-Shahawi, M. S.

2017-12-01

The most common problems in spectrophotometric determination of various complex species originate from the background spectral interference. Thus, the present study aimed to overcome the spectral matrix interference for the precise analysis and speciation of mercury(II) in water by dual-wavelength β-correction spectrophotometry using 4-(2-thiazolylazo) resorcinol (TAR) as chromogenic reagent. The principle was based on measuring the correct absorbance for the formed complex of mercury(II) ions with TAR reagent at 547 nm (lambda max). Under optimized conditions, a linear dynamic range of 0.1-2.0 μg mL- 1 with correlation coefficient (R2) of 0.997 were obtained with lower limits of detection (LOD) of 0.024 μg mL- 1 and limit of quantification (LOQ) of 0.081 μg mL- 1. The values of RSD and relative error (RE) obtained for β-correction method and single wavelength spectrophotometry were 1.3, 1.32% and 4.7, 5.9%, respectively. The method was validated in tap and sea water in terms of the data obtained from inductively coupled plasma-optical emission spectrometry (ICP-OES) using student's t and F tests. The developed methodology satisfactorily overcomes the spectral interference in trace determination and speciation of mercury(II) ions in water.

The role of different network modifying cations on the speciation of the Co2 + complex in silicates and implication in the investigation of historical glasses

NASA Astrophysics Data System (ADS)

Fornacelli, Cristina; Ceglia, Andrea; Bracci, Susanna; Vilarigues, Marcia

2018-01-01

In the last decades the speciation of the cobalt complex in a glass matrix has been extensively studied. Bivalent cobalt ions in glasses of different composition commonly adopt a tetrahedral coordination, though hexa- or penta-coordinated species are also possible. Changes in the absorbance spectrum of Co-doped glasses were attested in previous studies according to the introduction of different modifying cations. A shifting of the first sub-band characterizing the typical triplets of tetrahedral Co2 + ions in both the visible and near infrared regions was observed, but discrepancies in literature suggested a relevant role of glass composition on the definition of the optical signature of cobalt. Co-doped glasses with different composition (soda-lime, potash-lime, mixed alkali and ZnO-Na2O-CaO-SiO2) were studied via Fiber Optic Reflectance Spectroscopy (FORS). Pseudo-Voigt functions were used for the deconvolution of the absorbance spectra and the features of the bands characteristic of each cobalt complex were investigated. The structural role played by each modifying cation and the fundamental implications of glass basicity on the speciation of different Co-complexes were stressed. Changes in glass structure resulted in different equilibria between the three absorbing species whose specific optical signatures in the 480-530 nm region interact to determine the resulting absorbance spectrum.

A simple method using on-line continuous leaching and ion exchange chromatography coupled to inductively coupled plasma mass spectrometry for the speciation analysis of bio-accessible arsenic in rice.

PubMed

Horner, Nolan S; Beauchemin, Diane

2012-03-02

A simple method for the speciation analysis of bio-accessible arsenic (As) in rice was developed using a continuous on-line leaching method to release the bio-accessible fraction. The continuous on-line leaching method has several advantages over commonly used batch methods including quicker and easier sample preparation, reduced risk of contamination and access to real time leaching data. The bio-accessibility of As in the samples was monitored using inductively coupled plasma mass spectrometry (ICP-MS). Results from a certified reference material as well as cooked and uncooked white rice showed that the majority of As was leached by saliva. Results obtained using the continuous on-line leaching method were comparable to those obtained using a batch method. Speciation analysis of the saliva leachate was performed using ion exchange chromatography coupled to ICP-MS. The four most toxic forms of As (As(III), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and As(V)) were clearly separated within 5 min in a single chromatographic run. Over 92% of bio-accessible As in the certified reference material and uncooked white rice sample was in the form of DMA and As(V), whereas it was present as DMA and As(III) in the cooked white rice. Copyright © 2011 Elsevier B.V. All rights reserved.

Interaction of boron cluster ions with water: Single collision dynamics and sequential etching

NASA Astrophysics Data System (ADS)

Hintz, Paul A.; Ruatta, Stephen A.; Anderson, Scott L.

1990-01-01

Reactions of mass-selected, cooled, boron cluster ions (B+n, n=1-14) with water have been studied for collision energies from 0.1 to 6.0 eV. Most work was done with D2O, however isotope effects were examined for selected reactant cluster ions. For all size clusters there are exoergic product channels, which in most cases have no activation barriers. Cross sections are generally large, however there are fluctuations with cluster size in total reactivity, collision energy dependences, and in product distributions. For small cluster ions, there is a multitude of product channels. For clusters larger than B+6, the product distributions are dominated by a single channel: Bn-1D++DBO. Under multiple collision conditions, the primary products undergo a remarkable sequence of secondary ``etching'' reactions. As these occur, boron atoms are continuously replaced by hydrogen, and the intermediate products retain the composition: Bn-mH+m. This highly efficient chemistry appears to continue unchanged as the composition changes from pure boron to mostly hydrogen. Comparison of these results is made with boron cluster ion reactions with O2 and D2, as well as reactions with water of aluminum and silicon cluster ions. Some discussion is given of the thermochemistry for these reactions, and a possible problem with the thermochemical data in the BOD/DBO system is discussed.

Observation of different core water cluster ions Y-(H2O)n (Y = O2, HCN, HOx, NOx, COx) and magic number in atmospheric pressure negative corona discharge mass spectrometry

NASA Astrophysics Data System (ADS)

Sekimoto, K.; Takayama, M.

2010-12-01

Atmospheric ion water clusters have been of long-standing interest in the field of atmospheric sciences, because of them playing a central role in the formation of tropospheric aerosols which affect the photochemistry, radiation budget of the atmosphere and climate. On the basis of a mechanism of aerosol formation in the troposphere proposed by Yu and Turco, termed “ion-mediated nucleation” (Geophys. Res. Lett. 2000, 27, 883), atmospheric ion water clusters are most likely to be produced via two processes; 1) direct attachment of polar solvent molecules H2O to atmospheric ions due to them having strong binding energy via ion-dipole interactions, and 2) growth of ion-induced hydrates into larger water clusters bound via hydrogen-bonding networks by condensation with H2O molecules. The stability and growth rates of water clusters are strongly dependent on the thermochemical properties of individual atmospheric core ions. A large number of thermochemical information of the positive atmospheric ion H3O+ and its hydrates H3O+(H2O)n have been reported so far, while there has been little information of the water clusters with the negative atmospheric core ions. Therefore, fundamental studies of the thermochemistry of various negative atmospheric ion water clusters will contribute towards furthering an understanding of their unique role in atmospheric sciences and climate change. We have recently established an atmospheric pressure DC corona discharge device containing a specific corona needle electrode that made it possible to reproducibly generate negative core ions Y- originating from ambient air (Int. J. Mass Spectrom. 2007, 261, 38; Eur. Phys. J. D 2008, 50, 297). The change in electric field strength on the needle tip resulted in the formation of negative atmospheric core ions Y- with various different lifetimes in air. The low field strength brought about the dominant formation of core ions with short lifetimes in air such as O2- and HOx-, while the longer-lived core ions HCN-, NOx- and COx- were mainly produced at higher field strength. Furthermore, the use of the discharge system coupled to mass spectrometers led to the stable formation of large water clusters Y-(H2O)n due to adiabatic expansion caused by the pressure difference between the ambient discharge area (760 torr) and vacuum region in the mass spectrometers (≈ 1 torr). Here we show the resulting mass spectra of large water clusters Y-(H2O)n (0 ≤ n ≥ 80) with the dominant negative core ion Y- such as O2-, HO-, HO2-, HCN-, NO2-, NO3-, NO3-(HNO3)2, CO3- and HCO4- which play a central role in tropospheric ion chemistry, as well as the detailed mechanism of formation of those negative ion water clusters by atmospheric pressure DC corona discharge mass spectrometry. Here we also provide new thermochemical information about magic numbers and first hydrated shells for individual negative core ions Y-, which have particular stability in the Y-(H2O)n cluster series, by using the reliable mass spectrometry data obtained and the relationship between the temperature condition in a reaction chamber and the resulting cluster distribution.

Comparative study of energy of particles ejected from coulomb explosion of rare gas and metallic clusters irradiated by intense femtosecond laser field

NASA Astrophysics Data System (ADS)

Boucerredj, N.; Beggas, K.

2016-10-01

We present our study of high intensity femtosecond laser field interaction with large cluster of Kr and Na (contained 2.103 to 2.107 atoms). When laser intensity is above a critical value, it blows off all of electrons from the cluster and forms a non neutral ion cloud. The irradiation of these clusters by the intense laser field leads to highly excitation energy which can be the source of energetic electrons, electronic emission, highly charge, energetic ions and fragmentation process. During the Coulomb explosion of the resulting highly ionized, high temperature nanoplasma, ions acquire again their energy. It is shown that ultra fast ions are produced. The goal of our study is to investigate in detail a comparative study of the expansion and explosion then the ion energy of metallic and rare gas clusters irradiated by an intense femtosecond laser field. We have found that ions have a kinetic energy up to 105 eV and the Coulomb pressure is little than the hydrodynamic pressure. The Coulomb explosion of a cluster may provide a new high energy ion source.

Culturing Selenastrum capricornutum (Chlorophyta) in a synthetic algal nutrient medium with defined mineral particulates

USGS Publications Warehouse

Kuwabara, J.S.; Davis, J.A.; Chang, Cecily C.Y.

1985-01-01

Algal nutrient studies in chemically-defined media typically employ a synthetic chelator to prevent iron hydroxide precipitation. Micronutrient-particulate interactions may, however, significantly affect chemical speciation and hence biovailability of these nutrients in natural waters. A technique is described by which Selenastrum capricornutum Printz (Chlorophyta) may be cultured in a medium where trace metal speciation (except iron) is controlled, not by organic chelation, but by sorption onto titanium dioxide. Application of this culturing protocol in conjunction with results from sorption studies of nutrient ions on mineral particles provides a means of studying biological impacts of sorptive processes in aquatic environments. ?? 1985 Dr W. Junk Publishers.

Electrochemical Properties and Speciation in Mg(HMDS)2-Based Electrolytes for Magnesium Batteries as a Function of Ethereal Solvent Type and Temperature.

PubMed

Merrill, Laura C; Schaefer, Jennifer L

2017-09-19

Magnesium batteries are a promising alternative to lithium-ion batteries due to the widespread abundance of magnesium and its high specific volumetric energy capacity. Ethereal solvents such as tetrahydrofuran (THF) are commonly used for magnesium-ion electrolytes due to their chemical compatibility with magnesium metal, but the volatile nature of THF is a concern for practical application. Herein, we investigate magnesium bis(hexamethyldisilazide) plus aluminum chloride (Mg(HMDS) 2 -AlCl 3 ) electrolytes in THF, diglyme, and tetraglyme at varying temperature. We find that, despite the higher thermal stability of the glyme-based electrolytes, THF-based electrolytes have better reversibility at room temperature. Deposition/stripping efficiency is found to be a strong function of temperature. Diglyme-based Mg(HMDS) 2 -AlCl 3 electrolytes are found to not exchange as quickly as THF and tetraglyme, stabilizing AlCl 2 + and facilitating undesired aluminum deposition. Raman spectroscopy, 27 Al NMR, and mass spectrometry are used to identify solution speciation.

A linkage disequilibrium perspective on the genetic mosaic of speciation in two hybridizing Mediterranean white oaks

PubMed Central

Goicoechea, P G; Herrán, A; Durand, J; Bodénès, C; Plomion, C; Kremer, A

2015-01-01

We analyzed the genetic mosaic of speciation in two hybridizing Mediterranean white oaks from the Iberian Peninsula (Quercus faginea Lamb. and Quercus pyrenaica Willd.). The two species show ecological divergence in flowering phenology, leaf morphology and composition, and in their basic or acidic soil preferences. Ninety expressed sequence tag-simple sequence repeats (EST-SSRs) and eight nuclear SSRs were genotyped in 96 trees from each species. Genotyping was designed in two steps. First, we used 69 markers evenly distributed over the 12 linkage groups (LGs) of the oak linkage map to confirm the species genetic identity of the sampled genotypes, and searched for differentiation outliers. Then, we genotyped 29 additional markers from the chromosome bins containing the outliers and repeated the multilocus scans. We found one or two additional outliers within four saturated bins, thus confirming that outliers are organized into clusters. Linkage disequilibrium (LD) was extensive; even for loosely linked and for independent markers. Consequently, score tests for association between two-marker haplotypes and the ‘species trait' showed a broad genomic divergence, although substantial variation across the genome and within LGs was also observed. We discuss the influence of several confounding effects on neutrality tests and review the evolutionary processes leading to extensive LD. Finally, we examine how LD analyses within regions that contain outlier clusters and quantitative trait loci can help to identify regions of divergence and/or genomic hitchhiking in the light of predictions from ecological speciation theory. PMID:25515016

Effects of inorganic electrolyte anions on enrichment of Cu(II) ions with aminated Fe3O4/graphene oxide: Cu(II) speciation prediction and surface charge measurement.

PubMed

Hu, Xin-jiang; Liu, Yun-guo; Zeng, Guang-ming; Wang, Hui; You, Shao-hong; Hu, Xi; Tan, Xiao-fei; Chen, An-wei; Guo, Fang-ying

2015-05-01

The present work evaluated the effects of six inorganic electrolyte anions on Cu(II) removal using aminated Fe3O4/graphene oxide (AMGO) in single- and multi-ion systems. A 2(6-2) fractional factorial design (FFD) was employed for assessing the effects of multiple anions on the adsorption process. The results indicated that the Cu(II) adsorption was strongly dependent on pH and could be significantly affected by inorganic electrolyte anions due to the changes in Cu(II) speciation and surface charge of AMGO. In the single-ion systems, the presence of monovalent anions (Cl(-), ClO4(-), and NO3(-)) slightly increased the Cu(II) adsorption onto AMGO at low pH, while the Cu(II) adsorption was largely enhanced by the presence of SO4(2-), CO3(2-), and HPO4(2-). Based on the estimates of major effects and interactions from FFD, the factorial effects of the six selected species on Cu(II) adsorption in multi-ion system were in the following sequence: HPO4(2-)>CO3(2-)>Cl(-)>SO4(2-)>NO3(-)=ClO4(-), and the combined factors of AD (Cl(-)×SO4(2-)) and EF (Cl(-)×SO4(2-)) had significant effects on Cu(II) removal. Copyright © 2015 Elsevier Ltd. All rights reserved.

Extending a Tandem Mass Spectral Library to Include MS2 Spectra of Fragment Ions Produced In-Source and MSn Spectra.

PubMed

Yang, Xiaoyu; Neta, Pedatsur; Stein, Stephen E

2017-11-01

Tandem mass spectral library searching is finding increased use as an effective means of determining chemical identity in mass spectrometry-based omics studies. We previously reported on constructing a tandem mass spectral library that includes spectra for multiple precursor ions for each analyte. Here we report our method for expanding this library to include MS 2 spectra of fragment ions generated during the ionization process (in-source fragment ions) as well as MS 3 and MS 4 spectra. These can assist the chemical identification process. A simple density-based clustering algorithm was used to cluster all significant precursor ions from MS 1 scans for an analyte acquired during an infusion experiment. The MS 2 spectra associated with these precursor ions were grouped into the same precursor clusters. Subsequently, a new top-down hierarchical divisive clustering algorithm was developed for clustering the spectra from fragmentation of ions in each precursor cluster, including the MS 2 spectra of the original precursors and of the in-source fragments as well as the MS n spectra. This algorithm starts with all the spectra of one precursor in one cluster and then separates them into sub-clusters of similar spectra based on the fragment patterns. Herein, we describe the algorithms and spectral evaluation methods for extending the library. The new library features were demonstrated by searching the high resolution spectra of E. coli extracts against the extended library, allowing identification of compounds and their in-source fragment ions in a manner that was not possible before. Graphical Abstract ᅟ.

Genetic structure and bio-climatic modeling support allopatric over parapatric speciation along a latitudinal gradient.

PubMed

Rossetto, Maurizio; Allen, Chris B; Thurlby, Katie A G; Weston, Peter H; Milner, Melita L

2012-08-20

Four of the five species of Telopea (Proteaceae) are distributed in a latitudinal replacement pattern on the south-eastern Australian mainland. In similar circumstances, a simple allopatric speciation model that identifies the origins of genetic isolation within temporal geographic separation is considered as the default model. However, secondary contact between differentiated lineages can result in similar distributional patterns to those arising from a process of parapatric speciation (where gene flow between lineages remains uninterrupted during differentiation). Our aim was to use the characteristic distributional patterns in Telopea to test whether it reflected the evolutionary models of allopatric or parapatric speciation. Using a combination of genetic evidence and environmental niche modelling, we focused on three main questions: do currently described geographic borders coincide with genetic and environmental boundaries; are there hybrid zones in areas of secondary contact between closely related species; did species distributions contract during the last glacial maximum resulting in distributional gaps even where overlap and hybridisation currently occur? Total genomic DNA was extracted from 619 individuals sampled from 36 populations representing the four species. Seven nuclear microsatellites (nSSR) and six chloroplast microsatellites (cpSSR) were amplified across all populations. Genetic structure and the signature of admixture in overlap zones was described using the Bayesian clustering methods implemented in STUCTURE and NewHybrids respectively. Relationships between chlorotypes were reconstructed as a median-joining network. Environmental niche models were produced for all species using environmental parameters from both the present day and the last glacial maximum (LGM).The nSSR loci amplified a total of 154 alleles, while data for the cpSSR loci produced a network of six chlorotypes. STRUCTURE revealed an optimum number of five clusters corresponding to the four recognised species with the additional division of T. speciosissima into populations north and south of the Shoalhaven River valley. Unexpectedly, the northern disjunct population of T. oreades grouped with T. mongaensis and was identified as a hybrid swarm by the Bayesian assignment test implemented in NewHybrids. Present day and LGM environmental niche models differed dramatically, suggesting that distributions of all species had repeatedly expanded and contracted in response to Pleistocene climatic oscillations and confirming strongly marked historical distributional gaps among taxes. Genetic structure and bio-climatic modeling results are more consistent with a history of allopatric speciation followed by repeated episodes of secondary contact and localised hybridisation, rather than with parapatric speciation. This study on Telopea shows that the evidence for temporal exclusion of gene flow can be found even outside obvious geographical contexts, and that it is possible to make significant progress towards excluding parapatric speciation as a contributing evolutionary process.

Computational scheme for the prediction of metal ion binding by a soil fulvic acid

USGS Publications Warehouse

Marinsky, J.A.; Reddy, M.M.; Ephraim, J.H.; Mathuthu, A.S.

1995-01-01

The dissociation and metal ion binding properties of a soil fulvic acid have been characterized. Information thus gained was used to compensate for salt and site heterogeneity effects in metal ion complexation by the fulvic acid. An earlier computational scheme has been modified by incorporating an additional step which improves the accuracy of metal ion speciation estimates. An algorithm is employed for the prediction of metal ion binding by organic acid constituents of natural waters (once the organic acid is characterized in terms of functional group identity and abundance). The approach discussed here, currently used with a spreadsheet program on a personal computer, is conceptually envisaged to be compatible with computer programs available for ion binding by inorganic ligands in natural waters.

Characterization of high explosive particles using cluster secondary ion mass spectrometry.

PubMed

Gillen, Greg; Mahoney, Christine; Wight, Scott; Lareau, Richard

2006-01-01

The use of secondary ion mass spectrometry (SIMS) for the detection and spatially resolved analysis of individual high explosive particles is described. A C(8) (-) carbon cluster primary ion beam was used in a commercial SIMS instrument to analyze samples of high explosives dispersed as particles on silicon substrates. In comparison with monatomic primary ion bombardment, the carbon cluster primary ion beam was found to greatly enhance characteristic secondary ion signals from the explosive compounds while causing minimal beam-induced degradation. The resistance of these compounds to degradation under ion bombardment allows explosive particles to be analyzed under high primary ion dose bombardment (dynamic SIMS) conditions, facilitating the rapid acquisition of spatially resolved molecular information. The use of cluster SIMS combined with computer control of the sample stage position allows for the automated identification and counting of explosive particle distributions on silicon surfaces. This will be useful for characterizing the efficiency of transfer of particulates in trace explosive detection portal collectors and/or swipes utilized for ion mobility spectrometry applications.

On the Surface Mapping using Individual Cluster Impacts

PubMed Central

Fernandez-Lima, F.A.; Eller, M.J.; DeBord, J.D.; Verkhoturov, S.V.; Della-Negra, S.; Schweikert, E.A.

2011-01-01

This paper describes the advantages of using single impacts of large cluster projectiles (e.g. C60 and Au400) for surface mapping and characterization. The analysis of co-emitted time-resolved photon spectra, electron distributions and characteristic secondary ions shows that they can be used as surface fingerprints for target composition, morphology and structure. Photon, electron and secondary ion emission increases with the projectile cluster size and energy. The observed, high abundant secondary ion emission makes cluster projectiles good candidates for surface mapping of atomic and fragment ions (e.g., yield >1 per nominal mass) and molecular ions (e.g., few tens of percent in the 500 < m/z < 1500 range). PMID:22393269

The quantitative analysis of silicon carbide surface smoothing by Ar and Xe cluster ions

NASA Astrophysics Data System (ADS)

Ieshkin, A. E.; Kireev, D. S.; Ermakov, Yu. A.; Trifonov, A. S.; Presnov, D. E.; Garshev, A. V.; Anufriev, Yu. V.; Prokhorova, I. G.; Krupenin, V. A.; Chernysh, V. S.

2018-04-01

The gas cluster ion beam technique was used for the silicon carbide crystal surface smoothing. The effect of processing by two inert cluster ions, argon and xenon, was quantitatively compared. While argon is a standard element for GCIB, results for xenon clusters were not reported yet. Scanning probe microscopy and high resolution transmission electron microscopy techniques were used for the analysis of the surface roughness and surface crystal layer quality. The gas cluster ion beam processing results in surface relief smoothing down to average roughness about 1 nm for both elements. It was shown that xenon as the working gas is more effective: sputtering rate for xenon clusters is 2.5 times higher than for argon at the same beam energy. High resolution transmission electron microscopy analysis of the surface defect layer gives values of 7 ± 2 nm and 8 ± 2 nm for treatment with argon and xenon clusters.

Generation and collision-induced dissociation of ammonium tetrafluoroborate cluster ions.

PubMed

Dain, Ryan P; Van Stipdonk, Michael J

2008-07-01

Singly and doubly charged cluster ions of ammonium tetrafluoroborate (NH4BF4) with general formula [(NH4BF4)nNH4]+ and [(NH4BF4)m(NH4)2]2+, respectively, were generated by electrospray ionization (ESI) and their fragmentation examined using collision-induced dissociation (CID) and ion-trap tandem mass spectrometry. CID of [(NH4BF4)nNH4]+ caused the loss of one or more neutral NH4BF4 units. The n = 2 cluster, [(NH4BF4)2NH4]+, was unique in that it also exhibited a dissociation pathway in which HBF4 was eliminated to create [(NH4BF4)(NH3)NH4]+. Dissociation of [(NH4BF4)m(NH4)2]2+ occurred through two general pathways: (a) 'fission' to produce singly charged cluster ions and (b) elimination of one or more neutral NH4BF4 units to leave doubly charged product ions. CID profiles, and measurements of changing precursor and product ion signal intensity as a function of applied collision voltage, were collected for [(NH4BF4)nNH4]+ and compared with those for analogous [(NaBF4)nNa]+ and [(KBF4)nK]+ ions to determine the influence of the cation on the relative stability of cluster ions. In general, the [(NH4BF4)nNH4]+ clusters were found to be easier to dissociate than both the sodium and potassium clusters of comparable size, with [(KBF4)nK]+ ions the most difficult to dissociate.

Comparison of soil solution speciation and diffusive gradients in thin-films measurement as an indicator of copper bioavailability to plants.

PubMed

Zhao, Fang-Jie; Rooney, Corinne P; Zhang, Hao; McGrath, Steve P

2006-03-01

The toxicity effect concentrations (10% effective concentration [EC10] and 50% effective concentration [EC50]) of total added Cu derived from barley root elongation and tomato growth assays varied widely among 18 European soils. We investigated whether this variation could be explained by the solubility or speciation of Cu in soil solutions or the diffusive gradients in thin-films (DGT) measurement. Solubility and Cu speciation varied greatly among the soils tested. However, the EC10 and EC50 of soil solution Cu or free Cu2+ activity varied even more widely than those based on the total added Cu, indicating that solubility or soil solution speciation alone could not explain intersoil variation in Cu toxicity. Estimated EC10 and EC50 of free Cu2+ activity correlated closely and negatively with soil pH, indicating a protective effect of H+, which is consistent with the biotic ligand model concept. The DGT measurement was found to narrow the intersoil variation in EC50 considerably and to be a better predictor of plant Cu concentrations than either soil solution Cu or free Cu2+ activity. We conclude that plant bioavailability of Cu in soil depends on Cu speciation, interactions with protective ions (particularly H+), and the resupply from the solid phase, and we conclude that the DGT measurement provides a useful indicator of Cu bioavailability in soil.

Observations of different core water cluster ions Y-(H2O)n (Y = O2, HOx, NOx, COx) and magic number in atmospheric pressure negative corona discharge mass spectrometry.

PubMed

Sekimoto, Kanako; Takayama, Mitsuo

2011-01-01

Reliable mass spectrometry data from large water clusters Y(-)(H(2)O)(n) with various negative core ions Y(-) such as O(2)(-), HO(-), HO(2)(-), NO(2)(-), NO(3)(-), NO(3)(-)(HNO(3))(2), CO(3)(-) and HCO(4)(-) have been obtained using atmospheric pressure negative corona discharge mass spectrometry. All the core Y(-) ions observed were ionic species that play a central role in tropospheric ion chemistry. These mass spectra exhibited discontinuities in ion peak intensity at certain size clusters Y(-)(H(2)O)(m) indicating specific thermochemical stability. Thus, Y(-)(H(2)O)(m) may correspond to the magic number or first hydrated shell in the cluster series Y(-)(H(2)O)(n). The high intensity discontinuity at HO(-)(H(2)O)(3) observed was the first mass spectrometric evidence for the specific stability of HO(-)(H(2)O)(3) as the first hydrated shell which Eigen postulated in 1964. The negative ion water clusters Y(-)(H(2)O)(n) observed in the mass spectra are most likely to be formed via core ion formation in the ambient discharge area (760 torr) and the growth of water clusters by adiabatic expansion in the vacuum region of the mass spectrometers (≈1 torr). The detailed mechanism of the formation of the different core water cluster ions Y(-)(H(2)O)(n) is described. Copyright © 2010 John Wiley & Sons, Ltd.

Racetrack-shape fixed field induction accelerator for giant cluster ions

NASA Astrophysics Data System (ADS)

Takayama, Ken; Adachi, Toshikazu; Wake, Masayoshi; Okamura, Katsuya

2015-05-01

A novel scheme for a racetrack-shape fixed field induction accelerator (RAFFIA) capable of accelerating extremely heavy cluster ions (giant cluster ions) is described. The key feature of this scheme is rapid induction acceleration by localized induction cells. Triggering the induction voltages provided by the signals from the circulating bunch allows repeated acceleration of extremely heavy cluster ions. The given RAFFIA example is capable of realizing the integrated acceleration voltage of 50 MV per acceleration cycle. Using 90° bending magnets with a reversed field strip and field gradient is crucial for assuring orbit stability in the RAFFIA.

Bio-metals imaging and speciation in cells using proton and synchrotron radiation X-ray microspectroscopy

PubMed Central

Ortega, Richard; Devès, Guillaume; Carmona, Asunción

2009-01-01

The direct detection of biologically relevant metals in single cells and of their speciation is a challenging task that requires sophisticated analytical developments. The aim of this article is to present the recent achievements in the field of cellular chemical element imaging, and direct speciation analysis, using proton and synchrotron radiation X-ray micro- and nano-analysis. The recent improvements in focusing optics for MeV-accelerated particles and keV X-rays allow application to chemical element analysis in subcellular compartments. The imaging and quantification of trace elements in single cells can be obtained using particle-induced X-ray emission (PIXE). The combination of PIXE with backscattering spectrometry and scanning transmission ion microscopy provides a high accuracy in elemental quantification of cellular organelles. On the other hand, synchrotron radiation X-ray fluorescence provides chemical element imaging with less than 100 nm spatial resolution. Moreover, synchrotron radiation offers the unique capability of spatially resolved chemical speciation using micro-X-ray absorption spectroscopy. The potential of these methods in biomedical investigations will be illustrated with examples of application in the fields of cellular toxicology, and pharmacology, bio-metals and metal-based nano-particles. PMID:19605403

Thermal and log-normal distributions of plasma in laser driven Coulomb explosions of deuterium clusters

NASA Astrophysics Data System (ADS)

Barbarino, M.; Warrens, M.; Bonasera, A.; Lattuada, D.; Bang, W.; Quevedo, H. J.; Consoli, F.; de Angelis, R.; Andreoli, P.; Kimura, S.; Dyer, G.; Bernstein, A. C.; Hagel, K.; Barbui, M.; Schmidt, K.; Gaul, E.; Donovan, M. E.; Natowitz, J. B.; Ditmire, T.

2016-08-01

In this work, we explore the possibility that the motion of the deuterium ions emitted from Coulomb cluster explosions is highly disordered enough to resemble thermalization. We analyze the process of nuclear fusion reactions driven by laser-cluster interactions in experiments conducted at the Texas Petawatt laser facility using a mixture of D2+3He and CD4+3He cluster targets. When clusters explode by Coulomb repulsion, the emission of the energetic ions is “nearly” isotropic. In the framework of cluster Coulomb explosions, we analyze the energy distributions of the ions using a Maxwell-Boltzmann (MB) distribution, a shifted MB distribution (sMB), and the energy distribution derived from a log-normal (LN) size distribution of clusters. We show that the first two distributions reproduce well the experimentally measured ion energy distributions and the number of fusions from d-d and d-3He reactions. The LN distribution is a good representation of the ion kinetic energy distribution well up to high momenta where the noise becomes dominant, but overestimates both the neutron and the proton yields. If the parameters of the LN distributions are chosen to reproduce the fusion yields correctly, the experimentally measured high energy ion spectrum is not well represented. We conclude that the ion kinetic energy distribution is highly disordered and practically not distinguishable from a thermalized one.

A dual cryogenic ion trap spectrometer for the formation and characterization of solvated ionic clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marsh, Brett M.; Voss, Jonathan M.; Garand, Etienne, E-mail: egarand@chem.wisc.edu

2015-11-28

A new experimental approach is presented in which two separate cryogenic ion traps are used to reproducibly form weakly bound solvent clusters around electrosprayed ions and messenger-tag them for single-photon infrared photodissociation spectroscopy. This approach thus enables the vibrational characterization of ionic clusters comprised of a solvent network around large and non-volatile ions. We demonstrate the capabilities of the instrument by clustering water, methanol, and acetone around a protonated glycylglycine peptide. For water, cluster sizes with greater than twenty solvent molecules around a single ion are readily formed. We further demonstrate that similar water clusters can be formed around ionsmore » having a shielded charge center or those that do not readily form hydrogen bonds. Finally, infrared photodissociation spectra of D{sub 2}-tagged GlyGlyH{sup +} ⋅ (H{sub 2}O){sub 1−4} are presented. They display well-resolved spectral features and comparisons with calculations reveal detailed information on the solvation structures of this prototypical peptide.« less

Adsorption and Formation of Small Na Clusters on Pristine and Double-Vacancy Graphene for Anodes of Na-Ion Batteries.

PubMed

Liang, Zhicong; Fan, Xiaofeng; Zheng, Weitao; Singh, David J

2017-05-24

Layered carbon is a likely anode material for Na-ion batteries (NIBs). Graphitic carbon has a low capacity of approximately 35 (mA h)/g due to the formation of NaC 64 . Using first-principles methods including van der Waals interactions, we analyze the adsorption of Na ions and clusters on graphene in the context of anodes. The interaction between Na ions and graphene is found to be weak. Small Na clusters are not stable on the surface of pristine graphene in the electrochemical environment of NIBs. However, we find that Na ions and clusters can be stored effectively on defected graphene that has double vacancies. In addition, the adsorption energy of small Na clusters near a double vacancy is found to decrease with increasing cluster size. With high concentrations of vacancies the capacity of Na on defective graphene is found to be as much as 10-30 times higher than that of graphitic carbon.

A dual cryogenic ion trap spectrometer for the formation and characterization of solvated ionic clusters

DOE PAGES

Marsh, Brett M.; Voss, Jonathan M.; Garand, Etienne

2015-11-24

A new experimental approach is presented in which two separate cryogenic ion traps are used to reproducibly form weakly bound solvent clusters around electrosprayed ions and messenger-tag them for single-photon infrared photodissociation spectroscopy. This approach thus enables the vibrational characterization of ionic clusters comprised of a solvent network around large and non-volatile ions. We demonstrate the capabilities of the instrument by clustering water, methanol, and acetone around a protonated glycylglycine peptide. For water, cluster sizes with greater than twenty solvent molecules around a single ion are readily formed. We further demonstrate that similar water clusters can be formed around ionsmore » having a shielded charge center or those that do not readily form hydrogen bonds. Finally, infrared photodissociation spectra of D 2-tagged GlyGlyH +·(H 2O) 1–4 are presented. As a result, they display well-resolved spectral features and comparisons with calculations reveal detailed information on the solvation structures of this prototypical peptide.« less

Are clusters important in understanding the mechanisms in atmospheric pressure ionization? Part 1: Reagent ion generation and chemical control of ion populations.

PubMed

Klee, Sonja; Derpmann, Valerie; Wißdorf, Walter; Klopotowski, Sebastian; Kersten, Hendrik; Brockmann, Klaus J; Benter, Thorsten; Albrecht, Sascha; Bruins, Andries P; Dousty, Faezeh; Kauppila, Tiina J; Kostiainen, Risto; O'Brien, Rob; Robb, Damon B; Syage, Jack A

2014-08-01

It is well documented since the early days of the development of atmospheric pressure ionization methods, which operate in the gas phase, that cluster ions are ubiquitous. This holds true for atmospheric pressure chemical ionization, as well as for more recent techniques, such as atmospheric pressure photoionization, direct analysis in real time, and many more. In fact, it is well established that cluster ions are the primary carriers of the net charge generated. Nevertheless, cluster ion chemistry has only been sporadically included in the numerous proposed ionization mechanisms leading to charged target analytes, which are often protonated molecules. This paper series, consisting of two parts, attempts to highlight the role of cluster ion chemistry with regard to the generation of analyte ions. In addition, the impact of the changing reaction matrix and the non-thermal collisions of ions en route from the atmospheric pressure ion source to the high vacuum analyzer region are discussed. This work addresses such issues as extent of protonation versus deuteration, the extent of analyte fragmentation, as well as highly variable ionization efficiencies, among others. In Part 1, the nature of the reagent ion generation is examined, as well as the extent of thermodynamic versus kinetic control of the resulting ion population entering the analyzer region.

Development of the ion source for cluster implantation

NASA Astrophysics Data System (ADS)

Kulevoy, T. V.; Seleznev, D. N.; Kozlov, A. V.; Kuibeda, R. P.; Kropachev, G. N.; Alexeyenko, O. V.; Dugin, S. N.; Oks, E. M.; Gushenets, V. I.; Hershcovitch, A.; Jonson, B.; Poole, H. J.

2014-02-01

Bernas ion source development to meet needs of 100s of electron-volt ion implanters for shallow junction production is in progress in Institute for Theoretical and Experimental Physics. The ion sources provides high intensity ion beam of boron clusters under self-cleaning operation mode. The last progress with ion source operation is presented. The mechanism of self-cleaning procedure is described.

Uniform deposition of size-selected clusters using Lissajous scanning

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beniya, Atsushi; Watanabe, Yoshihide, E-mail: e0827@mosk.tytlabs.co.jp; Hirata, Hirohito

2016-05-15

Size-selected clusters can be deposited on the surface using size-selected cluster ion beams. However, because of the cross-sectional intensity distribution of the ion beam, it is difficult to define the coverage of the deposited clusters. The aggregation probability of the cluster depends on coverage, whereas cluster size on the surface depends on the position, despite the size-selected clusters are deposited. It is crucial, therefore, to deposit clusters uniformly on the surface. In this study, size-selected clusters were deposited uniformly on surfaces by scanning the cluster ions in the form of Lissajous pattern. Two sets of deflector electrodes set in orthogonalmore » directions were placed in front of the sample surface. Triangular waves were applied to the electrodes with an irrational frequency ratio to ensure that the ion trajectory filled the sample surface. The advantages of this method are simplicity and low cost of setup compared with raster scanning method. The authors further investigated CO adsorption on size-selected Pt{sub n} (n = 7, 15, 20) clusters uniformly deposited on the Al{sub 2}O{sub 3}/NiAl(110) surface and demonstrated the importance of uniform deposition.« less

Insights into water-mediated ion clustering in aqueous CaSO4 solutions: pre-nucleation cluster characteristics studied by ab initio calculations and molecular dynamics simulations.

PubMed

Li, Hui-Ji; Yan, Dan; Cai, Hou-Qin; Yi, Hai-Bo; Min, Xiao-Bo; Xia, Fei-Fei

2017-05-10

The molecular structure of growth units building crystals is a fundamental issue in the crystallization processes from aqueous solutions. In this work, a systematic investigation of pre-nucleation clusters and their hydration characteristics in aqueous CaSO 4 solutions was performed using ab initio calculations and molecular dynamics (MD) simulations. The results of ab initio calculations and MD simulations indicate that the dominant species in aqueous CaSO 4 solutions are monodentate ion-associated structures. Compared with charged ion clusters, neutral clusters are more likely to be present in an aqueous CaSO 4 solution. Neutral (CaSO 4 ) m clusters are probably the growth units involved in the pre-nucleation or crystallization processes. Meanwhile, hydration behavior around ion associated species in aqueous CaSO 4 solutions plays an important role in related phase/polymorphism selections. Upon ion clustering, the residence of some water molecules around Ca 2+ in ion-associated species is weakened while that of some bridging waters is enhanced due to dual interaction by Ca 2+ and SO 4 2- . Some phase/polymorphism selections can be achieved in aqueous CaSO 4 solutions by controlling the hydration around pre-nucleation clusters. Moreover, the association trend between calcium and sulfate is found to be relatively strong, which hints at the low solubility of calcium sulfate in water.

Recombination-enhanced surface expansion of clusters in intense soft x-ray laser pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rupp, Daniela; Flückiger, Leonie; Adolph, Marcus

Here, we studied the nanoplasma formation and explosion dynamics of single large xenon clusters in ultrashort, intense x-ray free-electron laser pulses via ion spectroscopy. The simultaneous measurement of single-shot diffraction images enabled a single-cluster analysis that is free from any averaging over the cluster size and laser intensity distributions. The measured charge state-resolved ion energy spectra show narrow distributions with peak positions that scale linearly with final ion charge state. These two distinct signatures are attributed to highly efficient recombination that eventually leads to the dominant formation of neutral atoms in the cluster. The measured mean ion energies exceed themore » value expected without recombination by more than an order of magnitude, indicating that the energy release resulting from electron-ion recombination constitutes a previously unnoticed nanoplasma heating process. This conclusion is supported by results from semiclassical molecular dynamics simulations.« less

Recombination-enhanced surface expansion of clusters in intense soft x-ray laser pulses

DOE PAGES

Rupp, Daniela; Flückiger, Leonie; Adolph, Marcus; ...

2016-10-07

Here, we studied the nanoplasma formation and explosion dynamics of single large xenon clusters in ultrashort, intense x-ray free-electron laser pulses via ion spectroscopy. The simultaneous measurement of single-shot diffraction images enabled a single-cluster analysis that is free from any averaging over the cluster size and laser intensity distributions. The measured charge state-resolved ion energy spectra show narrow distributions with peak positions that scale linearly with final ion charge state. These two distinct signatures are attributed to highly efficient recombination that eventually leads to the dominant formation of neutral atoms in the cluster. The measured mean ion energies exceed themore » value expected without recombination by more than an order of magnitude, indicating that the energy release resulting from electron-ion recombination constitutes a previously unnoticed nanoplasma heating process. This conclusion is supported by results from semiclassical molecular dynamics simulations.« less

Transcriptomic Responses During Early Development Following Arsenic Exposure in Western Clawed Frogs, Silurana tropicalis.

PubMed

Zhang, Jing; Koch, Iris; Gibson, Laura A; Loughery, Jennifer R; Martyniuk, Christopher J; Button, Mark; Caumette, Guilhem; Reimer, Kenneth J; Cullen, William R; Langlois, Valerie S

2015-12-01

Arsenic compounds are widespread environmental contaminants and exposure elicits serious health issues, including early developmental anomalies. Depending on the oxidation state, the intermediates of arsenic metabolism interfere with a range of subcellular events, but the fundamental molecular events that lead to speciation-dependent arsenic toxicity are not fully elucidated. This study therefore assesses the impact of arsenic exposure on early development by measuring speciation and gene expression profiles in the developing Western clawed frog (Silurana tropicalis) larvae following the environmental relevant 0.5 and 1 ppm arsenate exposure. Using HPLC-ICP-MS, arsenate, dimethylarsenic acid, arsenobetaine, arsenocholine, and tetramethylarsonium ion were detected. Microarray and pathway analyses were utilized to characterize the comprehensive transcriptomic responses to arsenic exposure. Clustering analysis of expression data showed distinct gene expression patterns in arsenate treated groups when compared with the control. Pathway enrichment revealed common biological themes enriched in both treatments, including cell signal transduction, cell survival, and developmental pathways. Moreover, the 0.5 ppm exposure led to the enrichment of pathways and biological processes involved in arsenic intake or efflux, as well as histone remodeling. These compensatory responses are hypothesized to be responsible for maintaining an in-body arsenic level comparable to control animals. With no appreciable changes observed in malformation and mortality between control and exposed larvae, this is the first study to suggest that the underlying transcriptomic regulations related to signal transduction, cell survival, developmental pathways, and histone remodeling may contribute to maintaining ongoing development while coping with the potential arsenic toxicity in S. tropicalis during early development. © The Author 2015. Published by Oxford University Press on behalf of the Society of Toxicology. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Processes Driving the Adaptive Radiation of a Tropical Tree ( Diospyros , Ebenaceae) in New Caledonia, a Biodiversity Hotspot

PubMed Central

Paun, Ovidiu; Turner, Barbara; Trucchi, Emiliano; Munzinger, Jérôme; Chase, Mark W.; Samuel, Rosabelle

2016-01-01

Abstract Due to its special geological history, the New Caledonian Archipelago is a mosaic of soil types, and in combination with climatic conditions this results in a heterogeneous environment across relatively small distances. A group of over 20 endemic species of Diospyros (Ebenaceae) has rapidly and recently radiated on the archipelago after a single long-distance dispersal event. Most of the Diospyros species in the radiating group are morphologically and ecologically well differentiated, but they exhibit low levels of DNA variability. To investigate the processes that shaped the diversification of this group we employed restriction site associated DNA sequencing (RADseq). Over 8400 filtered SNPs generally confirm species delimitations and produce a well-supported phylogenetic tree. Our analyses document local introgression, but only a limited potential for gene flow over longer distances. The phylogenetic relationships point to an early regional clustering among populations and species, indicating that allopatric speciation with respect to macrohabitat (i.e., climatic conditions) may have had a role in the initial differentiation within the group. A later, more rapid radiation involved divergence with respect to microhabitat (i.e., soil preference). Several sister species in the group show a parallel divergence in edaphic preference. Searches for genomic regions that are systematically differentiated in this replicated phenotypic divergence pointed to loci potentially involved in ion binding and cellular transport. These loci appear meaningful in the context of adaptations to soil types that differ in heavy-metal and mineral content. Identical nucleotide changes affected only two of these loci, indicating that introgression may have played a limited role in their evolution. Our results suggest that both allopatric diversification and (parapatric) ecological divergence shaped successive rounds of speciation in the Diospyros radiation on New Caledonia. PMID:26430059

Dynamic secondary ion mass spectroscopy of Au nanoparticles on Si wafer using Bi3+ as primary ion coupled with surface etching by Ar cluster ion beam: The effect of etching conditions on surface structure

NASA Astrophysics Data System (ADS)

Park, Eun Ji; Choi, Chang Min; Kim, Il Hee; Kim, Jung-Hwan; Lee, Gaehang; Jin, Jong Sung; Ganteför, Gerd; Kim, Young Dok; Choi, Myoung Choul

2018-01-01

Wet-chemically synthesized Au nanoparticles were deposited on Si wafer surfaces, and the secondary ions mass spectra (SIMS) from these samples were collected using Bi3+ with an energy of 30 keV as the primary ions. In the SIMS, Au cluster cations with a well-known, even-odd alteration pattern in the signal intensity were observed. We also performed depth profile SIMS analyses, i.e., etching the surface using an Ar gas cluster ion beam (GCIB), and a subsequent Bi3+ SIMS analysis was repetitively performed. Here, two different etching conditions (Ar1600 clusters of 10 keV energy or Ar1000 of 2.5 keV denoted as "harsh" or "soft" etching conditions, respectively) were used. Etching under harsh conditions induced emission of the Au-Si binary cluster cations in the SIMS spectra of the Bi3+ primary ions. The formation of binary cluster cations can be induced by either fragmentation of Au nanoparticles or alloying of Au and Si, increasing Au-Si coordination on the sample surface during harsh GCIB etching. Alternatively, use of the soft GCIB etching conditions resulted in exclusive emission of pure Au cluster cations with nearly no Au-Si cluster cation formation. Depth profile analyses of the Bi3+ SIMS combined with soft GCIB etching can be useful for studying the chemical environments of atoms at the surface without altering the original interface structure during etching.

Chemodynamics of heavy metals in long-term contaminated soils: metal speciation in soil solution.

PubMed

Kim, Kwon-Rae; Owens, Gary

2009-01-01

The concentration and speciation of heavy metals in soil solution isolated from long-term contaminated soils were investigated. The soil solution was extracted at 70% maximum water holding capacity (MWHC) after equilibration for 24 h. The free metal concentrations (Cd2+, CU2+, Pb2+, and Zn2+) in soil solution were determined using the Donnan membrane technique (DMT). Initially the DMT was validated using artificial solutions where the percentage of free metal ions were significantly correlated with the percentages predicted using MINTEQA2. However, there was a significant difference between the absolute free ion concentrations predicted by MINTEQA2 and the values determined by the DMT. This was due to the significant metal adsorption onto the cation exchange membrane used in the DMT with 20%, 28%, 44%, and 8% mass loss of the initial total concentration of Cd, Cu, Pb, and Zn in solution, respectively. This could result in a significant error in the determination of free metal ions when using DMT if no allowance for membrane cation adsorption was made. Relative to the total soluble metal concentrations the amounts of free Cd2+ (3%-52%) and Zn2+ (11%-72%) in soil solutions were generally higher than those of Cu2+ (0.2%-30%) and Pb2+ (0.6%-10%). Among the key soil solution properties, dissolved heavy metal concentrations were the most significant factor governing free metal ion concentrations. Soil solution pH showed only a weak relationship with free metal ion partitioning coefficients (K(p)) and dissolved organic carbon did not show any significant influence on K(p).

COMPETITIVE INFLUENCE OF PHOSPHORUS AND CALCIUM ON PB IN-VITRO BIOAVAILABILITY (S11-SCHECKEL101231-POSTER)

EPA Science Inventory

The bioavailability of a metal is heavily related to the speciation of the particular metal. Further, the complexity of examining metal bioavailability is compounded by the presence of competitive ions. Thus, equally contaminated soils with varying concentrations of competitive e...

COMPLEMENTARY APPROACHES TO THE DETERMINATION OF ARSENIC SPECIES RELEVANT TO CONCENTRATED ANIMAL FEEDING OPERATIONS

EPA Science Inventory

Ion-exchange chromatography is the most often used analytical approach for arsenic

speciation, due to the weak-acid nature of several of its species. However, no single

technique can determine all potentially occurring arsenic species, especially in complex

e...

New gas phase inorganic ion cluster species and their atmospheric implications

NASA Technical Reports Server (NTRS)

Maerk, T. D.; Peterson, K. I.; Castleman, A. W., Jr.

1980-01-01

Recent experimental laboratory observations, with high-pressure mass spectroscopy, have revealed the existence of previously unreported species involving water clustered to sodium dimer ions, and alkali metal hydroxides clustered to alkali metal ions. The important implications of these results concerning the existence of such species are here discussed, as well as how from a practical aspect they confirm the stability of certain cluster species proposed by Ferguson (1978) to explain masses recently detected at upper altitudes using mass spectrometric techniques.

Study of shallow junction formation by boron-containing cluster ion implantation of silicon and two-stage annealing

NASA Astrophysics Data System (ADS)

Lu, Xin-Ming

Shallow junction formation made by low energy ion implantation and rapid thermal annealing is facing a major challenge for ULSI (ultra large scale integration) as the line width decreases down to the sub micrometer region. The issues include low beam current, the channeling effect in low energy ion implantation and TED (transient enhanced diffusion) during annealing after ion implantation. In this work, boron containing small cluster ions, such as GeB, SiB and SiB2, was generated by using the SNICS (source of negative ion by cesium sputtering) ion source to implant into Si substrates to form shallow junctions. The use of boron containing cluster ions effectively reduces the boron energy while keeping the energy of the cluster ion beam at a high level. At the same time, it reduces the channeling effect due to amorphization by co-implanted heavy atoms like Ge and Si. Cluster ions have been used to produce 0.65--2keV boron for low energy ion implantation. Two stage annealing, which is a combination of low temperature (550°C) preannealing and high temperature annealing (1000°C), was carried out to anneal the Si sample implanted by GeB, SiBn clusters. The key concept of two-step annealing, that is, the separation of crystal regrowth, point defects removal with dopant activation from dopant diffusion, is discussed in detail. The advantages of the two stage annealing include better lattice structure, better dopant activation and retarded boron diffusion. The junction depth of the two stage annealed GeB sample was only half that of the one-step annealed sample, indicating that TED was suppressed by two stage annealing. Junction depths as small as 30 nm have been achieved by two stage annealing of sample implanted with 5 x 10-4/cm2 of 5 keV GeB at 1000°C for 1 second. The samples were evaluated by SIMS (secondary ion mass spectrometry) profiling, TEM (transmission electron microscopy) and RBS (Rutherford Backscattering Spectrometry)/channeling. Cluster ion implantation in combination with two-step annealing is effective in fabricating ultra-shallow junctions.

Group additivity-Pourbaix diagrams advocate thermodynamically stable nanoscale clusters in aqueous environments

PubMed Central

Wills, Lindsay A.; Qu, Xiaohui; Chang, I-Ya; Mustard, Thomas J. L.; Keszler, Douglas A.; Persson, Kristin A.; Cheong, Paul Ha-Yeon

2017-01-01

The characterization of water-based corrosion, geochemical, environmental and catalytic processes rely on the accurate depiction of stable phases in a water environment. The process is aided by Pourbaix diagrams, which map the equilibrium solid and solution phases under varying conditions of pH and electrochemical potential. Recently, metastable or possibly stable nanometric aqueous clusters have been proposed as intermediate species in non-classical nucleation processes. Herein, we describe a Group Additivity approach to obtain Pourbaix diagrams with full consideration of multimeric cluster speciation from computations. Comparisons with existing titration results from experiments yield excellent agreement. Applying this Group Additivity-Pourbaix approach to Group 13 elements, we arrive at a quantitative evaluation of cluster stability, as a function of pH and concentration, and present compelling support for not only metastable but also thermodynamically stable multimeric clusters in aqueous solutions. PMID:28643782

Group additivity-Pourbaix diagrams advocate thermodynamically stable nanoscale clusters in aqueous environments

NASA Astrophysics Data System (ADS)

Wills, Lindsay A.; Qu, Xiaohui; Chang, I.-Ya; Mustard, Thomas J. L.; Keszler, Douglas A.; Persson, Kristin A.; Cheong, Paul Ha-Yeon

2017-06-01

The characterization of water-based corrosion, geochemical, environmental and catalytic processes rely on the accurate depiction of stable phases in a water environment. The process is aided by Pourbaix diagrams, which map the equilibrium solid and solution phases under varying conditions of pH and electrochemical potential. Recently, metastable or possibly stable nanometric aqueous clusters have been proposed as intermediate species in non-classical nucleation processes. Herein, we describe a Group Additivity approach to obtain Pourbaix diagrams with full consideration of multimeric cluster speciation from computations. Comparisons with existing titration results from experiments yield excellent agreement. Applying this Group Additivity-Pourbaix approach to Group 13 elements, we arrive at a quantitative evaluation of cluster stability, as a function of pH and concentration, and present compelling support for not only metastable but also thermodynamically stable multimeric clusters in aqueous solutions.

Anomalous X-Ray Reflectivity Characterization of Ion Distribution at Biomimetic Membranes

NASA Astrophysics Data System (ADS)

Vaknin, David; Krüger, Peter; Lösche, Mathias

2003-05-01

Anomalous x-ray reflectivity measurements provides detailed information on ion binding to biomembrane surfaces. Using a monochromatic beam tuned to various x-ray energies at the Argonne National Laboratory Advanced Photon Source and utilizing a newly commissioned x-ray liquid surfaces reflectometer, measurements at and away from ion absorption edges allow determination of the distribution of these ions as they accumulate near lipid membranes. As a model, the interaction of Ba2+ ions with DMPA- (1,2-dimyristoyl-sn-glycero-3-phosphatidic acid) monolayers at the aqueous surface is studied. We find an unexpectedly large concentration of barium at the interface, ≈1.5 per DMPA-, forming a Stern layer of bound ions and a cloud of less densely bound ions near the lipid headgroups. This result can be understood only if one assumes that bound cations are partially speciated, e.g., as BaOH+.

A null model for microbial diversification

PubMed Central

Straub, Timothy J.

2017-01-01

Whether prokaryotes (Bacteria and Archaea) are naturally organized into phenotypically and genetically cohesive units comparable to animal or plant species remains contested, frustrating attempts to estimate how many such units there might be, or to identify the ecological roles they play. Analyses of gene sequences in various closely related prokaryotic groups reveal that sequence diversity is typically organized into distinct clusters, and processes such as periodic selection and extensive recombination are understood to be drivers of cluster formation (“speciation”). However, observed patterns are rarely compared with those obtainable with simple null models of diversification under stochastic lineage birth and death and random genetic drift. Via a combination of simulations and analyses of core and phylogenetic marker genes, we show that patterns of diversity for the genera Escherichia, Neisseria, and Borrelia are generally indistinguishable from patterns arising under a null model. We suggest that caution should thus be taken in interpreting observed clustering as a result of selective evolutionary forces. Unknown forces do, however, appear to play a role in Helicobacter pylori, and some individual genes in all groups fail to conform to the null model. Taken together, we recommend the presented birth−death model as a null hypothesis in prokaryotic speciation studies. It is only when the real data are statistically different from the expectations under the null model that some speciation process should be invoked. PMID:28630293

Implications of mercury speciation in thiosulfate treated plants.

PubMed

Wang, Jianxu; Feng, Xinbin; Anderson, Christopher W N; Wang, Heng; Zheng, Lirong; Hu, Tiandou

2012-05-15

Mercury uptake was induced in two cultivars of Brassica juncea under field conditions using thiosulfate. Analysis was conducted to better understand the mechanism of uptake, speciation of mercury in plants, and redistribution of mercury in the soil. Plant mercury and sulfur concentrations were increased after thiosulfate treatment, and a linear correlation between mercury and sulfur was observed. Mercury may be absorbed and transported in plants as the Hg-thiosulfate complex. The majority of mercury in treated plant tissues (two cultivars) was bound to sulfur in a form similar to β-HgS (66-94%). Remaining mercury was present in forms similar to Hg-cysteine (1-10%) and Hg-dicysteine (8-28%). The formation of β-HgS may relate to the transport and assimilation of sulfate in plant tissues. Mercury-thiosulfate complex could decompose to mercuric and sulfate ions in the presence of free protons inside the plasma membrane, while sulfide ions would be produced by the assimilation of sulfate. The concomitant presence of mercuric ions and S(2-) would precipitate β-HgS. The mercury concentration in the rhizosphere decreased in the treated relative to the nontreated soil. The iron/manganese oxide and organic-bound fractions of soil mercury were transformed to more bioavailable forms (soluble and exchangeable and specifically sorbed) and taken up by plants.

Transformation of metals speciation in a combined landfill leachate treatment.

PubMed

Wu, Yanyu; Zhou, Shaoqi; Chen, Dongyu; Zhao, Rong; Li, Huosheng; Lin, Yiming

2011-04-01

Landfill leachate was treated by a combined sequential batch reactor (SBR), coagulation, Fenton oxidation and biological aerated filter (BAF) technology. The metals in treatment process were fractionated into three fractions: particulate and colloidal (size charge filtration), free ion/labile (cation exchange) and non-labile fractions. Fifty percent to 66% Cu, Ni, Zn, Mn, Pb and Cd were present as particulate/colloidal matter in raw leachate, whereas Cr was present 94.9% as non-labile complexes. The free ion/labile fractions of Ni, Zn, Mg, Mn, Pb and Cd increased significantly after treatment except Cr. Fifty-nine percent to 100% of Al was present mainly as particulate/colloidal matter >0.45 μm and the remaining portions were predicted as non-labile complexes except in coagulation effluent. The speciation of Fe varied significantly in various individual processes. Visual MINTEQ simulation showed that 95-100% colloidal species for Cu, Cd and Pb were present as metal-humic complexes even with the lower dissolved organic carbon. Optimum agreements for the free ion/labile species were within acidic solution, whereas under-estimated in alkaline effluents. Overestimated particulate/colloidal fraction consisted with the hypothesis that a portion of colloids in fraction <0.45 μm were considered as dissolved. Copyright © 2011 Elsevier B.V. All rights reserved.

WATEQF; a FORTRAN IV version of WATEQ : a computer program for calculating chemical equilibrium of natural waters

USGS Publications Warehouse

Plummer, Niel; Jones, Blair F.; Truesdell, Alfred Hemingway

1976-01-01

WATEQF is a FORTRAN IV computer program that models the thermodynamic speciation of inorganic ions and complex species in solution for a given water analysis. The original version (WATEQ) was written in 1973 by A. H. Truesdell and B. F. Jones in Programming Language/one (PL/1.) With but a few exceptions, the thermochemical data, speciation, coefficients, and general calculation procedure of WATEQF is identical to the PL/1 version. This report notes the differences between WATEQF and WATEQ, demonstrates how to set up the input data to execute WATEQF, provides a test case for comparison, and makes available a listing of WATEQF. (Woodard-USGS)

CO2 Cluster Ion Beam, an Alternative Projectile for Secondary Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Tian, Hua; Maciążek, Dawid; Postawa, Zbigniew; Garrison, Barbara J.; Winograd, Nicholas

2016-09-01

The emergence of argon-based gas cluster ion beams for SIMS experiments opens new possibilities for molecular depth profiling and 3D chemical imaging. These beams generally leave less surface chemical damage and yield mass spectra with reduced fragmentation compared with smaller cluster projectiles. For nanoscale bioimaging applications, however, limited sensitivity due to low ionization probability and technical challenges of beam focusing remain problematic. The use of gas cluster ion beams based upon systems other than argon offer an opportunity to resolve these difficulties. Here we report on the prospects of employing CO2 as a simple alternative to argon. Ionization efficiency, chemical damage, sputter rate, and beam focus are investigated on model compounds using a series of CO2 and Ar cluster projectiles (cluster size 1000-5000) with the same mass. The results show that the two projectiles are very similar in each of these aspects. Computer simulations comparing the impact of Ar2000 and (CO2)2000 on an organic target also confirm that the CO2 molecules in the cluster projectile remain intact, acting as a single particle of m/z 44. The imaging resolution employing CO2 cluster projectiles is improved by more than a factor of two. The advantage of CO2 versus Ar is also related to the increased stability which, in addition, facilitates the operation of the gas cluster ion beams (GCIB) system at lower backing pressure.

The adsorption of helium atoms on small cationic gold clusters.

PubMed

Goulart, Marcelo; Gatchell, Michael; Kranabetter, Lorenz; Kuhn, Martin; Martini, Paul; Gitzl, Norbert; Rainer, Manuel; Postler, Johannes; Scheier, Paul; Ellis, Andrew M

2018-04-04

Adducts formed between small gold cluster cations and helium atoms are reported for the first time. These binary ions, Aun+Hem, were produced by electron ionization of helium nanodroplets doped with neutral gold clusters and were detected using mass spectrometry. For a given value of n, the distribution of ions as a function of the number of added helium atoms, m, has been recorded. Peaks with anomalously high intensities, corresponding to so-called magic number ions, are identified and interpreted in terms of the geometric structures of the underlying Aun+ ions. These features can be accounted for by planar structures for Aun+ ions with n ≤ 7, with the addition of helium having no significant effect on the structures of the underlying gold cluster ions. According to ion mobility studies and some theoretical predictions, a 3-D structure is expected for Au8+. However, the findings for Au8+ in this work are more consistent with a planar structure.

A DIM model for sodium cluster-ions interacting with a charged conducting sphere

NASA Astrophysics Data System (ADS)

Kuntz, P. J.

A diatomics-in-molecules (DIM) model for the energy, shape and charge distribution of metal cluster ions in the presence of a charged insulated conducting sphere is presented. The electrostatic interaction between the sphere and the cluster-ion is introduced in a self-consistent manner which allows the sphere to be polarized by the ion and the ion by the sphere. This interaction appears in the diagonal elements of the model Hamiltonian matrix in such a way that the lowest eigenvalue includes the correct electrostatic energy for the charge distribution in the ground state. The model is applied to the calculation of fusion barriers for Na+2 and Na+3 ions. When both the charge distribution and the geometric configuration of the cluster-ion are allowed to relax freely, the energy as a function of distance from the sphere is nearly the same as that calculated from the electrostatic energy alone, which implies that details of the molecular structure of the cluster-ion can be neglected in calculating fusion barriers from charge polarization alone. That the fusion barriers lie sufficiently far away from the sphere so that the molecule does not dissociate under the influence of the Coulomb interaction confirms that it is meaningful to speak of two separate entities at the barrier position.

The role of different network modifying cations on the speciation of the Co2+ complex in silicates and implication in the investigation of historical glasses.

PubMed

Fornacelli, Cristina; Ceglia, Andrea; Bracci, Susanna; Vilarigues, Marcia

2018-01-05

In the last decades the speciation of the cobalt complex in a glass matrix has been extensively studied. Bivalent cobalt ions in glasses of different composition commonly adopt a tetrahedral coordination, though hexa- or penta-coordinated species are also possible. Changes in the absorbance spectrum of Co-doped glasses were attested in previous studies according to the introduction of different modifying cations. A shifting of the first sub-band characterizing the typical triplets of tetrahedral Co 2+ ions in both the visible and near infrared regions was observed, but discrepancies in literature suggested a relevant role of glass composition on the definition of the optical signature of cobalt. Co-doped glasses with different composition (soda-lime, potash-lime, mixed alkali and ZnO-Na 2 O-CaO-SiO 2 ) were studied via Fiber Optic Reflectance Spectroscopy (FORS). Pseudo-Voigt functions were used for the deconvolution of the absorbance spectra and the features of the bands characteristic of each cobalt complex were investigated. The structural role played by each modifying cation and the fundamental implications of glass basicity on the speciation of different Co-complexes were stressed. Changes in glass structure resulted in different equilibria between the three absorbing species whose specific optical signatures in the 480-530nm region interact to determine the resulting absorbance spectrum. Copyright © 2017 Elsevier B.V. All rights reserved.

Electron-induced chemistry in microhydrated sulfuric acid clusters

NASA Astrophysics Data System (ADS)

Lengyel, Jozef; Pysanenko, Andriy; Fárník, Michal

2017-11-01

We investigate the mixed sulfuric acid-water clusters in a molecular beam experiment with electron attachment and negative ion mass spectrometry and complement the experiment by density functional theory (DFT) calculations. The microhydration of (H2SO4)m(H2O)n clusters is controlled by the expansion conditions, and the electron attachment yields the main cluster ion series (H2SO4)m(H2O)nHSO4- and (H2O)nH2SO4-. The mass spectra provide an experimental evidence for the onset of the ionic dissociation of sulfuric acid and ion-pair (HSO4- ṡ ṡ ṡ H3O+) formation in the neutral H2SO4(H2O)n clusters with n ≥ 5 water molecules, in excellent agreement with the theoretical predictions. In the clusters with two sulfuric acid molecules (H2SO4)2(H2O)n this process starts as early as n ≥ 2 water molecules. The (H2SO4)m(H2O)nHSO4- clusters are formed after the dissociative electron attachment to the clusters containing the (HSO4- ṡ ṡ ṡ H3O+) ion-pair structure, which leads to the electron recombination with the H3O+ moiety generating H2O molecule and the H-atom dissociation from the cluster. The (H2O)nH2SO4- cluster ions point to an efficient caging of the H atom by the surrounding water molecules. The electron-energy dependencies exhibit an efficient electron attachment at low electron energies below 3 eV, and no resonances above this energy, for all the measured mass peaks. This shows that in the atmospheric chemistry only the low-energy electrons can be efficiently captured by the sulfuric acid-water clusters and converted into the negative ions. Possible atmospheric consequences of the acidic dissociation in the clusters and the electron attachment to the sulfuric acid-water aerosols are discussed.

The formation of magnetic silicide Fe3Si clusters during ion implantation

NASA Astrophysics Data System (ADS)

Balakirev, N.; Zhikharev, V.; Gumarov, G.

2014-05-01

A simple two-dimensional model of the formation of magnetic silicide Fe3Si clusters during high-dose Fe ion implantation into silicon has been proposed and the cluster growth process has been computer simulated. The model takes into account the interaction between the cluster magnetization and magnetic moments of Fe atoms random walking in the implanted layer. If the clusters are formed in the presence of the external magnetic field parallel to the implanted layer, the model predicts the elongation of the growing cluster in the field direction. It has been proposed that the cluster elongation results in the uniaxial magnetic anisotropy in the plane of the implanted layer, which is observed in iron silicide films ion-beam synthesized in the external magnetic field.

Predicting Metal Speciation & Bioavailability via Estimation of Metal-Organic Thermodynamic Properties

NASA Astrophysics Data System (ADS)

Prasad, A.; Howells, A. E.; Shock, E.

2017-12-01

The biological fate of any metal depends on its chemical form in the environment. Arsenic for example, is extremely toxic in the form of inorganic As+3 but completely benign in the organic form of arsenobetaine. Thus, given an exhaustive set of reactions and their equilibrium constants (logK), the bioavailability of any metal can be obtained for blood plasma, hydrothermal fluids or any system of interest. While many data exist for metal-inorganic ligands, logK data covering the temperature range of life for metal-organic complexes are sparse. Hence, we decided to estimate metal-organic logK values from correlations with the commonly available values of ligand pKa. Metal ion specific correlations were made with ligands classified according to their electron donor atoms, denticity and other chemical factors. While this approach has been employed before (Carbonaro et al. 2007, GCA 71, 3958-3968), new correlations were developed that provide estimates even when no metal-organic logK is available. In addition, we have used the same methods to make estimates of metal-organic entropy of association (ΔaS), which can provide logK for any temperature of biological relevance. Our current correlations employ logK and ΔaS data from 30 metal ions (like the biologically relevant Fe+3 & Zn+2) and 74 ligands (like formate and ethylenediamine), which can be expanded to estimate the metal-ligand reaction properties for these 30 metal ions with a possibly limitless number of ligands that may belong to our categories of ligands. With the help of such data, copper speciation was obtained for a defined growth medium for methanotrophs employed by Morton et al. (2000, AEM 66, 1730-1733) that agrees with experimental measurements showing that the free metal ion may not be the bioavailable form in all conditions. These results encourage us to keep filling the gaps in metal-organic logK data and continue finding relationships between biological responses (like metal-accumulation ratios & metal-induced toxicity) and metal speciation.

Relationship between metal speciation in soil solution and metal adsorption at the root surface of ryegrass.

PubMed

Kalis, Erwin J J; Temminghoff, Erwin J M; Town, Raewyn M; Unsworth, Emily R; van Riemsdijk, Willem H

2008-01-01

The total metal content of the soil or total metal concentration in the soil solution is not always a good indicator for metal availability to plants. Therefore, several speciation techniques have been developed that measure a defined fraction of the total metal concentration in the soil solution. In this study the Donnan Membrane Technique (DMT) was used to measure free metal ion concentrations in CaCl(2) extractions (to mimic the soil solution, and to work under standardized conditions) of 10 different soils, whereas diffusive gradients in thin-films (DGT) and scanning chronopotentiometry (SCP) were used to measure the sum of free and labile metal concentrations in the CaCl(2) extracts. The DGT device was also exposed directly to the (wetted) soil (soil-DGT). The metal concentrations measured with the speciation techniques are related to the metal adsorption at the root surface of ryegrass (Lolium perenne L.), to be able to subsequently predict metal uptake. In most cases the metal adsorption related pH-dependently to the metal concentrations measured by DMT, SCP, and DGT in the CaCl(2) extract. However, the relationship between metal adsorption at the root surface and the metal concentrations measured by the soil-DGT was not-or only slightly-pH dependent. The correlations between metal adsorption at the root surface and metal speciation detected by different speciation techniques allow discussion about rate limiting steps in biouptake and the contribution of metal complexes to metal bioavailability.

Accessing the Vibrational Signatures of Amino Acid Ions Embedded in Water Clusters

DOE PAGES

Voss, Jonathan M.; Fischer, Kaitlyn C.; Garand, Etienne

2018-04-16

We present an infrared predissociation (IRPD) study of microsolvated GlyH +(H 2O) n and GlyH +(D 2O) n clusters, formed inside of a cryogenic ion trap via condensation of H 2O or D 2O onto the protonated glycine ions. The resulting IRPD spectra, showing characteristic O–H and O–D stretches, indicate that H/D exchange reactions are quenched when the ion trap is held at 80 K, minimizing the presence of isotopomers. Comparisons of GlyH +(H 2O) n and GlyH +(D 2O) n spectra clearly highlight and distinguish the vibrational signatures of the water solvent molecules from those of the core GlyHmore » + ion, allowing for quick assessment of solvation structures. Without the aid of calculations, we can already infer solvation motifs and the presence of multiple conformations. Furthermore, the use of a cryogenic ion trap to cluster solvent molecules around ions of interest and control H/D exchange reactions is broadly applicable and should be extendable to studies of more complex peptidic ions in large solvated clusters.« less

Accessing the Vibrational Signatures of Amino Acid Ions Embedded in Water Clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Voss, Jonathan M.; Fischer, Kaitlyn C.; Garand, Etienne

We present an infrared predissociation (IRPD) study of microsolvated GlyH +(H 2O) n and GlyH +(D 2O) n clusters, formed inside of a cryogenic ion trap via condensation of H 2O or D 2O onto the protonated glycine ions. The resulting IRPD spectra, showing characteristic O–H and O–D stretches, indicate that H/D exchange reactions are quenched when the ion trap is held at 80 K, minimizing the presence of isotopomers. Comparisons of GlyH +(H 2O) n and GlyH +(D 2O) n spectra clearly highlight and distinguish the vibrational signatures of the water solvent molecules from those of the core GlyHmore » + ion, allowing for quick assessment of solvation structures. Without the aid of calculations, we can already infer solvation motifs and the presence of multiple conformations. Furthermore, the use of a cryogenic ion trap to cluster solvent molecules around ions of interest and control H/D exchange reactions is broadly applicable and should be extendable to studies of more complex peptidic ions in large solvated clusters.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laskin, Julia; Johnson, Grant E.; Prabhakaran, Venkateshkumar

Immobilization of complex molecules and clusters on supports plays an important role in a variety of disciplines including materials science, catalysis and biochemistry. In particular, deposition of clusters on surfaces has attracted considerable attention due to their non-scalable, highly size-dependent properties. The ability to precisely control the composition and morphology of clusters and small nanoparticles on surfaces is crucial for the development of next generation materials with rationally tailored properties. Soft- and reactive landing of ions onto solid or liquid surfaces introduces unprecedented selectivity into surface modification by completely eliminating the effect of solvent and sample contamination on the qualitymore » of the film. The ability to select the mass-to-charge ratio of the precursor ion, its kinetic energy and charge state along with precise control of the size, shape and position of the ion beam on the deposition target makes soft-landing an attractive approach for surface modification. High-purity uniform thin films on surfaces generated using mass-selected ion deposition facilitate understanding of critical interfacial phenomena relevant to catalysis, energy generation and storage, and materials science. Our efforts have been directed toward understanding charge retention by soft-landed metal and metal-oxide cluster ions, which may affect both their structure and reactivity. Specifically, we have examined the effect of the surface on charge retention by both positively and negatively charged cluster ions. We found that the electronic properties of the surface play an important role in charge retention by cluster cations. Meanwhile, the electron binding energy is a key factor determining charge retention by cluster anions. These findings provide the scientific foundation for the rational design of interfaces for advanced catalysts and energy storage devices. Further optimization of electrode-electrolyte interfaces for applications in energy storage and electrocatalysis may be achieved by understanding and controlling the properties of soft-landed cluster ions.« less

Analysis of heterogeneous water vapor uptake by metal iodide cluster ions via differential mobility analysis-mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oberreit, Derek; Fluid Measurement Technologies, Inc., Saint Paul, Minnesota 55110; Rawat, Vivek K.

The sorption of vapor molecules onto pre-existing nanometer sized clusters is of importance in understanding particle formation and growth in gas phase environments and devising gas phase separation schemes. Here, we apply a differential mobility analyzer-mass spectrometer based approach to observe directly the sorption of vapor molecules onto iodide cluster ions of the form (MI){sub x}M{sup +} (x = 1-13, M = Na, K, Rb, or Cs) in air at 300 K and with water saturation ratios in the 0.01-0.64 range. The extent of vapor sorption is quantified in measurements by the shift in collision cross section (CCS) for eachmore » ion. We find that CCS measurements are sensitive enough to detect the transient binding of several vapor molecules to clusters, which shift CCSs by only several percent. At the same time, for the highest saturation ratios examined, we observed CCS shifts of up to 45%. For x < 4, cesium, rubidium, and potassium iodide cluster ions are found to uptake water to a similar extent, while sodium iodide clusters uptake less water. For x ≥ 4, sodium iodide cluster ions uptake proportionally more water vapor than rubidium and potassium iodide cluster ions, while cesium iodide ions exhibit less uptake. Measured CCS shifts are compared to predictions based upon a Kelvin-Thomson-Raoult (KTR) model as well as a Langmuir adsorption model. We find that the Langmuir adsorption model can be fit well to measurements. Meanwhile, KTR predictions deviate from measurements, which suggests that the earliest stages of vapor uptake by nanometer scale species are not well described by the KTR model.« less

Ion induced electron emission statistics under Agm- cluster bombardment of Ag

NASA Astrophysics Data System (ADS)

Breuers, A.; Penning, R.; Wucher, A.

2018-05-01

The electron emission from a polycrystalline silver surface under bombardment with Agm- cluster ions (m = 1, 2, 3) is investigated in terms of ion induced kinetic excitation. The electron yield γ is determined directly by a current measurement method on the one hand and implicitly by the analysis of the electron emission statistics on the other hand. Successful measurements of the electron emission spectra ensure a deeper understanding of the ion induced kinetic electron emission process, with particular emphasis on the effect of the projectile cluster size to the yield as well as to emission statistics. The results allow a quantitative comparison to computer simulations performed for silver atoms and clusters impinging onto a silver surface.

Properties of small Ar sub N-1 K/+/ ionic clusters

NASA Technical Reports Server (NTRS)

Etters, R. D.; Danilowicz, R.; Dugan, J.

1977-01-01

A self-consistent formalism is developed that, based upon a many-body potential, dynamically determines the thermodynamic properties of ionic clusters without an a priori designation of the equilibrium structures. Aggregates consisting of a single closed shell K(+) ion and N-1 isoelectronic argon atoms were studied. The clusters form crystallites at low temperatures, and melting transitions and spontaneous dissociations are indicated. The results confirm experimental evidence that shows that ionic clusters become less stable with increasing N. The crystallite structures formed by four different clusters are isosceles triangle, skewed form, octahedron with ion in the middle, and icosahedron with the ion in the middle.

Atomically precise (catalytic) particles synthesized by a novel cluster deposition instrument

DOE PAGES

Yin, C.; Tyo, E.; Kuchta, K.; ...

2014-05-06

Here, we report a new high vacuum instrument which is dedicated to the preparation of well-defined clusters supported on model and technologically relevant supports for catalytic and materials investigations. The instrument is based on deposition of size selected metallic cluster ions that are produced by a high flux magnetron cluster source. Furthermore, we maximize the throughput of the apparatus by collecting and focusing ions utilizing a conical octupole ion guide and a linear ion guide. The size selection is achieved by a quadrupole mass filter. The new design of the sample holder provides for the preparation of multiple samples onmore » supports of various sizes and shapes in one session. After cluster deposition onto the support of interest, samples will be taken out of the chamber for a variety of testing and characterization.« less

Correspondence between ion-cluster and bulk thermodynamics: on the validity of the cluster pair approximation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vlcek, Lukas; Chialvo, Ariel; Simonson, J Michael

2013-01-01

Molecular models and experimental estimates based on the cluster pair approximation (CPA) provide inconsistent predictions of absolute single-ion hydration properties. To understand the origin of this discrepancy we used molecular simulations to study the transition between hydration of alkali metal and halide ions in small aqueous clusters and bulk water. The results demonstrate that the assumptions underlying the CPA are not generally valid as a result of a significant shift in the ion hydration free energies (~15 kJ/mol) and enthalpies (~47 kJ/mol) in the intermediate range of cluster sizes. When this effect is accounted for, the systematic differences between modelsmore » and experimental predictions disappear, and the value of absolute proton hydration enthalpy based on the CPA gets in closer agreement with other estimates.« less

Method and apparatus for the production of cluster ions

DOEpatents

Friedman, Lewis; Beuhler, Robert J.

1988-01-01

A method and apparatus for the production of cluster ions, and preferably isotopic hydrogen cluster ions is disclosed. A gas, preferably comprising a carrier gas and a substrate gas, is cooled to about its boiling point and expanded through a supersonic nozzle into a region maintained at a low pressure. Means are provided for the generation of a plasma in the gas before or just as it enters the nozzle.

Method and apparatus for the production of cluster ions

DOEpatents

Friedman, L.; Beuhler, R.J.

A method and apparatus for the production of cluster ions, and preferably isotopic hydrogen cluster ions is disclosed. A gas, preferably comprising a carrier gas and a substrate gas, is cooled to about its boiling point and expanded through a supersonic nozzle into a region maintained at a low pressure. Means are provided for the generation of a plasma in the gas before or just as it enters the nozzle.

Development of Wien filter for small ion gun of surface analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bahng, Jungbae; Busan Center, Korea Basic Science Institute, Busan 609-735; Hong, Jonggi

The gas cluster ion beam (GCIB) and liquid metal ion beam have been studied in the context of ion beam usage for analytical equipment in applications such as X-ray photoelectron spectroscopy and secondary ion mass spectroscopy (SIMS). In particular, small ion sources are used for the secondary ion generation and ion etching. To set the context to this study, the SIMS project has been launched to develop ion-gun based analytical equipment for the Korea Basic Science Institute. The objective of the first stage of the project is the generation of argon beams with a GCIB system [A. Kirkpatrick, Nucl. Instrum.more » Methods Phys. Res., Sect. B 206, 830–837 (2003)] that consists of a nozzle, skimmer, ionizer, acceleration tube, separation system, transport system, and target. The Wien filter directs the selected cluster beam to the target system by exploiting the velocity difference of the generated particles from GCIB. In this paper, we present the theoretical modeling and three-dimensional electromagnetic analysis of the Wien filter, which can separate Ar{sup +}{sub 2500} clusters from Ar{sup +}{sub 2400} to Ar{sup +}{sub 2600} clusters with a 1-mm collimator.« less

Effects of aqueous uranyl speciation on the kinetics of microbial uranium reduction

DOE PAGES

Belli, Keaton M.; DiChristina, Thomas J.; Van Cappellen, Philippe; ...

2015-02-16

The ability to predict the success of the microbial reduction of soluble U(VI) to highly insoluble U(IV) as an in situ bioremediation strategy is complicated by the wide range of geochemical conditions at contaminated sites and the strong influence of aqueous uranyl speciation on the bioavailability and toxicity of U(VI) to metal-reducing bacteria. In order to determine the effects of aqueous uranyl speciation on uranium bioreduction kinetics, incubations and viability assays with Shewanella putrefaciens strain 200 were conducted over a range of pH and dissolved inorganic carbon (DIC), Ca 2+, and Mg 2+ concentrations. A speciation-dependent kinetic model was developedmore » to reproduce the observed time series of total dissolved uranium concentration over the range of geochemical conditions tested. The kinetic model yielded the highest rate constant for the reduction of uranyl non-carbonate species (i.e., the ‘free’ hydrated uranyl ion, uranyl hydroxides, and other minor uranyl complexes), indicating that they represent the most readily reducible fraction of U(VI) despite being the least abundant uranyl species in solution. In the presence of DIC, Ca 2+, and Mg 2+ is suppressed during the formation of more bioavailable uranyl non-carbonate species and resulted in slower bioreduction rates. At high concentrations of bioavailable U(VI), however, uranium toxicity to S. putrefaciens inhibited bioreduction, and viability assays confirmed that the concentration of non-carbonate uranyl species best predicts the degree of toxicity. The effect of uranium toxicity was accounted for by incorporating the free ion activity model of metal toxicity into the bioreduction rate law. These results demonstrate that, in the absence of competing terminal electron acceptors, uranium bioreduction kinetics can be predicted over a wide range of geochemical conditions based on the bioavailability and toxicity imparted on U(VI) by solution composition. Finally, these findings also imply that the concentration of uranyl non-carbonate species, despite being extremely low, is a determining factor controlling uranium bioreduction at contaminated sites.« less

Ion Mobility Mass Spectrometry Analysis of Isomeric Disaccharide Precursor, Product and Cluster Ions

PubMed Central

Li, Hongli; Bendiak, Brad; Siems, William F.; Gang, David R.; Hill, Herbert H.

2015-01-01

RATIONALE Carbohydrates are highly variable in structure owing to differences in their anomeric configurations, monomer stereochemistry, inter-residue linkage positions and general branching features. The separation of carbohydrate isomers poses a great challenge for current analytical techniques. METHODS The isomeric heterogeneity of disaccharide ions and monosaccharideglycolaldehyde product ions evaluated using electrospray traveling wave ion mobility mass spectrometry (Synapt G2 high definition mass spectrometer) in both positive and negative ion modes investigation. RESULTS The separation of isomeric disaccharide ions was observed but not fully achieved based on their mobility profiles. The mobilities of isomeric product ions, the monosaccharide-glycolaldehydes, derived from different disaccharide isomers were measured. Multiple mobility peaks were observed for both monosaccharide-glycolaldehyde cations and anions, indicating that there was more than one structural configuration in the gas phase as verified by NMR in solution. More importantly, the mobility patterns for isomeric monosaccharide-glycolaldehyde product ions were different, which enabled partial characterization of their respective disaccharide ions. Abundant disaccharide cluster ions were also observed. The Results showed that a majority of isomeric cluster ions had different drift times and, moreover, more than one mobility peak was detected for a number of specific cluster ions. CONCLUSIONS It is demonstrated that ion mobility mass spectrometry is an advantageous method to assess the isomeric heterogeneity of carbohydrate compounds. It is capable of differentiating different types of carbohydrate ions having identical m/z values as well as multiple structural configurations of single compounds. PMID:24591031

Self-confinement of finite dust clusters in isotropic plasmas.

PubMed

Miloshevsky, G V; Hassanein, A

2012-05-01

Finite two-dimensional dust clusters are systems of a small number of charged grains. The self-confinement of dust clusters in isotropic plasmas is studied using the particle-in-cell method. The energetically favorable configurations of grains in plasma are found that are due to the kinetic effects of plasma ions and electrons. The self-confinement phenomenon is attributed to the change in the plasma composition within a dust cluster resulting in grain attraction mediated by plasma ions. This is a self-consistent state of a dust cluster in which grain's repulsion is compensated by the reduced charge and floating potential on grains, overlapped ion clouds, and depleted electrons within a cluster. The common potential well is formed trapping dust clusters in the confined state. These results provide both valuable insights and a different perspective to the classical view on the formation of boundary-free dust clusters in isotropic plasmas.

Rumsey and Walker_AMT_2016_Table 1

EPA Pesticide Factsheets

Table summarizes instrument analytical detection limits, including liquid and equivalent air concentrations.This dataset is associated with the following publication:Rumsey, I. Application of an online ion chromatography-based instrument for gradient flux measurements of speciated nitrogen and sulfur. ENVIRONMENTAL SCIENCE & TECHNOLOGY. American Chemical Society, Washington, DC, USA, 9(6): 2581-2592, (2016).

Total Arsenic Determination and Speciation in Infant Food Products by Ion Chromatography Inductively Coupled Plasma Mass Spectrometry

EPA Science Inventory

Health risk associated with dietary arsenic intake may be different for infants and adults. Seafood is the main contributor to arsenic intake for adults while terrestrial-based food is the primary source for infants. Processed infant food products such as rice-based cereals, mi...

Effect of Ocean Acidification on Organic and Inorganic Speciation of Trace Metals.

PubMed

Stockdale, Anthony; Tipping, Edward; Lofts, Stephen; Mortimer, Robert J G

2016-02-16

Rising concentrations of atmospheric carbon dioxide are causing acidification of the oceans. This results in changes to the concentrations of key chemical species such as hydroxide, carbonate and bicarbonate ions. These changes will affect the distribution of different forms of trace metals. Using IPCC data for pCO2 and pH under four future emissions scenarios (to the year 2100) we use a chemical speciation model to predict changes in the distribution of organic and inorganic forms of trace metals. Under a scenario where emissions peak after the year 2100, predicted free ion Al, Fe, Cu, and Pb concentrations increase by factors of up to approximately 21, 2.4, 1.5, and 2.0 respectively. Concentrations of organically complexed metal typically have a lower sensitivity to ocean acidification induced changes. Concentrations of organically complexed Mn, Cu, Zn, and Cd fall by up to 10%, while those of organically complexed Fe, Co, and Ni rise by up to 14%. Although modest, these changes may have significance for the biological availability of metals given the close adaptation of marine microorganisms to their environment.

Speciation of Mn(II), Mn(VII) and total manganese in water and food samples by coprecipitation-atomic absorption spectrometry combination.

PubMed

Citak, Demirhan; Tuzen, Mustafa; Soylak, Mustafa

2010-01-15

A speciation procedure based on the coprecipitation of manganese(II) with zirconium(IV) hydroxide has been developed for the investigation of levels of manganese species. The determination of manganese levels was performed by flame atomic absorption spectrometry (FAAS). Total manganese was determined after the reduction of Mn(VII) to Mn(II) by ascorbic acid. The analytical parameters including pH, amount of zirconium(IV), sample volume, etc., were investigated for the quantitative recoveries of manganese(II). The effects of matrix ions were also examined. The recoveries for manganese(II) were in the range of 95-98%. Preconcentration factor was calculated as 50. The detection limit for the analyte ions based on 3 sigma (n=21) was 0.75 microg L(-1) for Mn(II). The relative standard deviation was found to be lower than 7%. The validation of the presented procedure was performed by analysis of certified reference material having different matrices, NIST SRM 1515 (Apple Leaves) and NIST SRM 1568a (Rice Flour). The procedure was successfully applied to natural waters and food samples.

Identification and dynamics of a cryptic suture zone in tropical rainforest

PubMed Central

Moritz, C.; Hoskin, C.J.; MacKenzie, J.B.; Phillips, B.L.; Tonione, M.; Silva, N.; VanDerWal, J.; Williams, S.E.; Graham, C.H.

2009-01-01

Suture zones, shared regions of secondary contact between long-isolated lineages, are natural laboratories for studying divergence and speciation. For tropical rainforest, the existence of suture zones and their significance for speciation has been controversial. Using comparative phylogeographic evidence, we locate a morphologically cryptic suture zone in the Australian Wet Tropics rainforest. Fourteen out of 18 contacts involve morphologically cryptic phylogeographic lineages, with mtDNA sequence divergences ranging from 2 to 15 per cent. Contact zones are significantly clustered in a suture zone located between two major Quaternary refugia. Within this area, there is a trend for secondary contacts to occur in regions with low environmental suitability relative to both adjacent refugia and, by inference, the parental lineages. The extent and form of reproductive isolation among interacting lineages varies across species, ranging from random admixture to speciation, in one case via reinforcement. Comparative phylogeographic studies, combined with environmental analysis at a fine-scale and across varying climates, can generate new insights into suture zone formation and to diversification processes in species-rich tropical rainforests. As arenas for evolutionary experimentation, suture zones merit special attention for conservation. PMID:19203915

Suppression of vacancy cluster growth in concentrated solid solution alloys

DOE PAGES

Zhao, Shijun; Velisa, Gihan; Xue, Haizhou; ...

2016-12-13

Large vacancy clusters, such as stacking-fault tetrahedra, are detrimental vacancy-type defects in ion-irradiated structural alloys. Suppression of vacancy cluster formation and growth is highly desirable to improve the irradiation tolerance of these materials. In this paper, we demonstrate that vacancy cluster growth can be inhibited in concentrated solid solution alloys by modifying cluster migration pathways and diffusion kinetics. The alloying effects of Fe and Cr on the migration of vacancy clusters in Ni concentrated alloys are investigated by molecular dynamics simulations and ion irradiation experiment. While the diffusion coefficients of small vacancy clusters in Ni-based binary and ternary solid solutionmore » alloys are higher than in pure Ni, they become lower for large clusters. This observation suggests that large clusters can easily migrate and grow to very large sizes in pure Ni. In contrast, cluster growth is suppressed in solid solution alloys owing to the limited mobility of large vacancy clusters. Finally, the differences in cluster sizes and mobilities in Ni and in solid solution alloys are consistent with the results from ion irradiation experiments.« less

Systematization of the mass spectra for speciation of inorganic salts with static secondary ion mass spectrometry.

PubMed

Van Ham, Rita; Van Vaeck, Luc; Adams, Freddy C; Adriaens, Annemie

2004-05-01

The analytical use of mass spectra from static secondary ion mass spectrometry for the molecular identification of inorganic analytes in real life surface layers and microobjects requires an empirical insight in the signals to be expected from a given compound. A comprehensive database comprising over 50 salts has been assembled to complement prior data on oxides. The present study allows the systematic trends in the relationship between the detected signals and molecular composition of the analyte to be delineated. The mass spectra provide diagnostic information by means of atomic ions, structural fragments, molecular ions, and adduct ions of the analyte neutrals. The prediction of mass spectra from a given analyte must account for the charge state of the ions in the salt, the formation of oxide-type neutrals from oxy salts, and the occurrence of oxidation-reduction processes.

CO2 Cluster Ion Beam, an Alternative Projectile for Secondary Ion Mass Spectrometry.

PubMed

Tian, Hua; Maciążek, Dawid; Postawa, Zbigniew; Garrison, Barbara J; Winograd, Nicholas

2016-09-01

The emergence of argon-based gas cluster ion beams for SIMS experiments opens new possibilities for molecular depth profiling and 3D chemical imaging. These beams generally leave less surface chemical damage and yield mass spectra with reduced fragmentation compared with smaller cluster projectiles. For nanoscale bioimaging applications, however, limited sensitivity due to low ionization probability and technical challenges of beam focusing remain problematic. The use of gas cluster ion beams based upon systems other than argon offer an opportunity to resolve these difficulties. Here we report on the prospects of employing CO2 as a simple alternative to argon. Ionization efficiency, chemical damage, sputter rate, and beam focus are investigated on model compounds using a series of CO2 and Ar cluster projectiles (cluster size 1000-5000) with the same mass. The results show that the two projectiles are very similar in each of these aspects. Computer simulations comparing the impact of Ar2000 and (CO2)2000 on an organic target also confirm that the CO2 molecules in the cluster projectile remain intact, acting as a single particle of m/z 44. The imaging resolution employing CO2 cluster projectiles is improved by more than a factor of two. The advantage of CO2 versus Ar is also related to the increased stability which, in addition, facilitates the operation of the gas cluster ion beams (GCIB) system at lower backing pressure. Graphical Abstract ᅟ.

Single photon ionization of van der Waals clusters with a soft x-ray laser: (CO2)n and (CO2)n(H2O)m.

PubMed

Heinbuch, S; Dong, F; Rocca, J J; Bernstein, E R

2006-10-21

Pure neutral (CO2)n clusters and mixed (CO2)n(H2O)m clusters are investigated employing time of flight mass spectroscopy and single photon ionization at 26.5 eV. The distribution of pure (CO2)n clusters decreases roughly exponentially with increasing cluster size. During the ionization process, neutral clusters suffer little fragmentation because almost all excess cluster energy above the vertical ionization energy is taken away by the photoelectron and only a small part of the photon energy is deposited into the (CO2)n cluster. Metastable dissociation rate constants of (CO2)n+ are measured in the range of (0.2-1.5) x 10(4) s(-1) for cluster sizes of 5< or =n< or =16. Mixed CO2-H2O clusters are studied under different generation conditions (5% and 20% CO2 partial pressures and high and low expansion pressures). At high CO2 concentration, predominant signals in the mass spectrum are the (CO2)n+ cluster ions. The unprotonated cluster ion series (CO2)nH2O+ and (CO2)n(H2O)2+ are also observed under these conditions. At low CO2 concentration, protonated cluster ions (H2O)nH+ are the dominant signals, and the protonated CO2(H2O)nH+ and unprotonated (H2O)n+ and (CO2)(H2O)n+ cluster ion series are also observed. The mechanisms and dynamics of the formation of these neutral and ionic clusters are discussed.

Active spacecraft potential control: An ion emitter experiment. [Cluster mission

NASA Technical Reports Server (NTRS)

Riedler, W.; Goldstein, R.; Hamelin, M.; Maehlum, B. N.; Troim, J.; Olsen, R. C.; Pedersen, A.; Grard, R. J. L.; Schmidt, R.; Rudenauer, F.

1988-01-01

The cluster spacecraft are instrumented with ion emitters for charge neutralization. The emitters produce indium ions at 6 keV. The ion current is adjusted in a feedback loop with instruments measuring the spacecraft potential. The system is based on the evaporation of indium in the apex field of a needle. The design of the active spacecraft potential control instruments, and the ion emitters is presented.

Mass spectrometric study of the negative and positive secondary ions emitted from ethanol microdroplets by MeV-energy heavy ion impact

NASA Astrophysics Data System (ADS)

Kitajima, Kensei; Majima, Takuya; Nishio, Tatsuya; Oonishi, Yoshiki; Mizutani, Shiori; Kohno, Jun-ya; Saito, Manabu; Tsuchida, Hidetsugu

2018-06-01

We have investigated the negative and positive secondary ions emitted from ethanol droplets by 4.0-MeV C3+ impact to reveal the characteristic features of the reaction processes induced by fast heavy ions at the liquid ethanol surface. Analysis of the secondary ions was performed by time-of-flight mass spectrometry for microdroplet targets in a high vacuum environment. Fragment ions, deprotonated cluster ions, and trace amounts of the reaction product ions are observed in the negative secondary ions. The main fragment anions are C2HmO- (m = 1, 3, and 5) and C2H- generated by loss of hydrogen and oxygen atoms. The reaction product anions include deprotonated glycols, larger alcohols, and their dehydrated and dehydrogenated forms generated by secondary reactions between fragments and radicals. Furthermore, C3Hm- (m = 0-2) and C4Hm- (m = 0 and 1) are observed, which could be produced through a plasma state generated in the heavy ion track. Deprotonated ethanol cluster ions, [(EtOH)n - H]-, are observed up to about n = 25. [(EtOH)n - H]- have smaller kinetic energies than the protonated cluster ions (EtOH)nH+. This probably represents the effect of the positive Coulomb potential transiently formed in the ion track. We also discuss the size distributions and structures of the water- and CH2OH-radical-attached ethanol cluster ions.

Transmission of cluster ions through a tandem accelerator of several stripper gases.

PubMed

Saitoh, Yuichi; Chiba, Atsuya; Narumi, Kazumasa

2009-10-01

The transmissions of carbon cluster ion beams through a tandem accelerator using several stripper gases (He, N2, CO2, and SF6) with a terminal voltage of 2.5 MV were measured as a function of the gas pressure in investigating the most suitable gas for cluster ion acceleration. This resulted in it being demonstrated that the highest transmission could be obtained using the smaller size gas, i.e., helium displayed the best performance of the four gases used. In addition, the ratio of transmissions of C(n) with helium and nitrogen increased with increases in the n, thus revealing that helium gas should prove the most effective in larger cluster ion acceleration using the same energy.

Ligand induced structural isomerism in phosphine coordinated gold clusters revealed by ion mobility mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ligare, Marshall R.; Baker, Erin S.; Laskin, Julia

Structural isomerism in ligated gold clusters is revealed using electrospray ionization ion mobility spectrometry mass spectrometry. Phosphine ligated Au8 clusters are shown to adopt more “extended” type structures with increasing exchange of methyldiphenylphosphine (MePPh2) for triphenylphosphine (PPh3). These ligand-dependant structure-property relationships are critical to applications of clusters in catalysis.

Method for Continuous Monitoring of Electrospray Ion Formation

NASA Astrophysics Data System (ADS)

Metzler, Guille; Crathern, Susan; Bachmann, Lorin; Fernández-Metzler, Carmen; King, Richard

2017-10-01

A method for continuously monitoring the performance of electrospray ionization without the addition of hardware or chemistry to the system is demonstrated. In the method, which we refer to as SprayDx, cluster ions with solvent vapor natively formed by electrospray are followed throughout the collection of liquid chromatography-selected reaction monitoring data. The cluster ion extracted ion chromatograms report on the consistency of the ion formation and detection system. The data collected by the SprayDx method resemble the data collected for postcolumn infusion of analyte. The response of the cluster ions monitored reports on changes in the physical parameters of the ion source such as voltage and gas flow. SprayDx is also observed to report on ion suppression in a fashion very similar to a postcolumn infusion of analyte. We anticipate the method finding utility as a continuous readout on the performance of electrospray and other atmospheric pressure ionization processes. [Figure not available: see fulltext.

Ellipticity-dependent of multiple ionisation methyl iodide cluster using 532 nm nanosecond laser

NASA Astrophysics Data System (ADS)

Tang, Bin; Zhao, Wuduo; Wang, Weiguo; Hua, Lei; Chen, Ping; Hou, Keyong; Huang, Yunguang; Li, Haiyang

2016-03-01

The dependence of multiply charged ions on laser ellipticity in methyl iodide clusters with 532 nm nanosecond laser was measured using a time-of-flight mass spectrometer. The intensities of multiply charged ions Iq+(q = 2-4) with circularly polarised laser pulse were clearly higher than those with linearly polarised laser pulse but the intensity of single charged ions I+ was inverse. And the dependences of ions on the optical polarisation state were investigated and a flower petal and square distribution for single charged ions (I+, C+) and multiply charged ions (I2+, I3+, I4+, C2+) were observed, respectively. A theoretical calculation was also proposed to simulate the distributions of ions and theoretical results fitted well with the experimental ones. It indicated that the high multiphoton ionisation probability in the initial stage would result in the disintegration of big clusters into small ones and suppress the production of multiply charged ions.

The role of highly oxygenated molecules (HOMs) in determining the composition of ambient ions in the boreal forest

NASA Astrophysics Data System (ADS)

Bianchi, Federico; Garmash, Olga; He, Xucheng; Yan, Chao; Iyer, Siddharth; Rosendahl, Ida; Xu, Zhengning; Rissanen, Matti P.; Riva, Matthieu; Taipale, Risto; Sarnela, Nina; Petäjä, Tuukka; Worsnop, Douglas R.; Kulmala, Markku; Ehn, Mikael; Junninen, Heikki

2017-11-01

In order to investigate the negative ions in the boreal forest we have performed measurements to chemically characterise the composition of negatively charged clusters containing highly oxygenated molecules (HOMs). Additionally, we compared this information with the chemical composition of the neutral gas-phase molecules detected in the ambient atmosphere during the same period. The chemical composition of the ions was retrieved using an atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF-MS) while the gas-phase neutral molecules (mainly sulfuric acid and HOMs) were characterised using the same mass spectrometer coupled to a nitrate-based chemical ionisation unit (CI-APi-TOF). Overall, we divided the identified HOMs in two classes: HOMs containing only carbon, hydrogen and oxygen and nitrogen-containing HOMs or organonitrates (ONs). During the day, among the ions, in addition to the well-known pure sulfuric acid clusters, we found a large number of HOMs clustered with nitrate (NO3-) or bisulfate (HSO4-), with the first one being more abundant. During the night, the distribution of ions, mainly composed of HOM clustered with NO3-, was very similar to the neutral compounds that are detected in the CI-APi-TOF as adducts with the artificially introduced primary ion (NO3-). For the first time, we identified several clusters containing up to 40 carbon atoms. These ions are formed by up to four oxidised α-pinene units clustered with NO3-. While we know that dimers (16-20 carbon atoms) are probably formed by a covalent bond between two α-pinene oxidised units, it is still unclear what bonding formed larger clusters. Finally, diurnal profiles of the negative ions were consistent with the neutral compounds revealing that ONs peak during the day while HOMs are more abundant at night-time. However, during the day, a large fraction of the negative charge is taken up by the pure sulfuric acid clusters causing differences between ambient ions and neutral compounds (i.e. less available charge for HOM and ON).

Self-Assembled Gold Nano-Ripple Formation by Gas Cluster Ion Beam Bombardment.

PubMed

Tilakaratne, Buddhi P; Chen, Quark Y; Chu, Wei-Kan

2017-09-08

In this study, we used a 30 keV argon cluster ion beam bombardment to investigate the dynamic processes during nano-ripple formation on gold surfaces. Atomic force microscope analysis shows that the gold surface has maximum roughness at an incident angle of 60° from the surface normal; moreover, at this angle, and for an applied fluence of 3 × 10 16 clusters/cm², the aspect ratio of the nano-ripple pattern is in the range of ~50%. Rutherford backscattering spectrometry analysis reveals a formation of a surface gradient due to prolonged gas cluster ion bombardment, although the surface roughness remains consistent throughout the bombarded surface area. As a result, significant mass redistribution is triggered by gas cluster ion beam bombardment at room temperature. Where mass redistribution is responsible for nano-ripple formation, the surface erosion process refines the formed nano-ripple structures.

Fragmentation pathways of tungsten hexacarbonyl clusters upon electron ionization.

PubMed

Neustetter, M; Jabbour Al Maalouf, E; Limão-Vieira, P; Denifl, S

2016-08-07

Electron ionization of neat tungsten hexacarbonyl (W(CO)6) clusters has been investigated in a crossed electron-molecular beam experiment coupled with a mass spectrometer system. The molecule is used for nanofabrication processes through electron beam induced deposition and ion beam induced deposition techniques. Positive ion mass spectra of W(CO)6 clusters formed by electron ionization at 70 eV contain the ion series of the type W(CO)n (+) (0 ≤ n ≤ 6) and W2(CO)n (+) (0 ≤ n ≤ 12). In addition, a series of peaks are observed and have been assigned to WC(CO)n (+) (0 ≤ n ≤ 3) and W2C(CO)n (+) (0 ≤ n ≤ 10). A distinct change of relative fragment ion intensity can be observed for clusters compared to the single molecule. The characteristic fragmentation pattern obtained in the mass spectra can be explained by a sequential decay of the ionized organometallic, which is also supported by the study of the clusters when embedded in helium nanodroplets. In addition, appearance energies for the dissociative ionization channels for singly charged ions have been estimated from experimental ion efficiency curves.

Calculation of composition distribution of ultrafine ion-H2O-H2SO4 clusters using a modified binary ion nucleation theory

NASA Technical Reports Server (NTRS)

Singh, J. J.; Smith, A. S.; Chan, L. Y.; Yue, G. K.

1982-01-01

Thomson's ion nucleation theory was modified to include the effects of curvature dependence of the microscopic surface tension of field dependent, nonlinear, dielectric properties of the liquid; and of sulfuric acid hydrate formation in binary mixtures of water and sulfuric acid vapors. The modified theory leads to a broadening of the ion cluster spectrum, and shifts it towards larger numbers of H2O and H2SO4 molecules. Whether there is more shifting towards larger numbers of H2O or H2SO4 molecules depends on the relative humidity and relative acidity of the mixture. Usually, a broadening of the spectrum is accompanied by a lowering of the mean cluster intensity. For fixed values of relative humidity and relative acidity, a similar broadening pattern is observed when the temperature is lowered. These features of the modified theory illustrate that a trace of sulfuric acid can facilitate the formation of ultrafine, stable, prenucleation ion clusters as well as the growth of the prenucleation ion clusters towards the critical saddle point conditions, even with low values of relative humidity and relative acidity.

Recombination of electrons with NH4/+/-/NH3/n-series ions

NASA Technical Reports Server (NTRS)

Huang, C.-M.; Biondi, M. A.; Johnsen, R.

1976-01-01

The paper examines the recombination of electrons with ammonium-series cluster ions, NH4(+)-(NH3)n, for two reasons: (1) NH4(+) may be a significant ion in the lower atmospheres of the earth and the outer planets, and (2) to investigate the weak temperature dependence of the cluster ion's recombination coefficient. A microwave afterglow mass spectrometer was used to determine the recombination coefficients for the first five members of the ammonium series, (18+) through (86+), at temperatures between 200 and 410 K. The electron temperature dependence of the recombination coefficient was determined for (35+) and (52+), the n = 1 and 2 cluster ions, over the temperature range 300-3000 K.

Reprint of: Negative carbon cluster ion beams: New evidence for the special nature of C60

NASA Astrophysics Data System (ADS)

Liu, Y.; O'brien, S. C.; Zhang, Q.; Heath, J. R.; Tittel, F. K.; Curl, R. F.; Kroto, H. W.; Smalley, R. E.

2013-12-01

Cold carbon cluster negative ions are formed by supersonic expansion of a plasma created at the nozzle of a supersonic cluster beam source by an excimer laser pulse. The observed distribution of mass peaks for the Cn- ions for n > 40 demonstrates that the evidence previously given for the special stability of neutral C60 and the existence of spheroidal carbon shells cannot be an artifact of the ionization conditions.

Chemistry Within Molecular Clusters

DTIC Science & Technology

1992-06-01

reactions, and only occur within van der Waals clusters. 23 They include the generation of (C2H4F2),>4H+ ions from 1,1- difluoroethane clusters, 4 the...of fragment ions, and identification of the molecule must be made by the characteristic fragmentation pattern. The mass spectrum of 1,1- difluoroethane

Chemistry within Molecular Clusters

DTIC Science & Technology

1992-05-29

within van der Waals clusters. 23 They include the generation of (C2H4F 2),,>4H+ ions from 1,1- difluoroethane clusters, 24 the generation of (CH 3...fragment ions, and identification of the molecule must be made by the characteristic fragmentation pattern. The mass spectrum of 1,1- difluoroethane (DFE

Effect of sharp maximum in ion diffusivity for liquid xenon

NASA Astrophysics Data System (ADS)

Lankin, A. V.; Orekhov, M. A.

2016-11-01

Ion diffusion in a liquid usually could be treated as a movement of an ion cluster in a viscous media. For small ions this leads to a special feature: diffusion coefficient is either independent of the ion size or increases with it. We find a different behavior for small ions in liquid xenon. Calculation of the dependence of an ion diffusion coefficient in liquid xenon on the ion size is carried out. Classical molecular dynamics method is applied. Calculated dependence of the ion diffusion coefficient on its radius has sharp maximums at the ion radiuses 1.75 and 2 Å. Every maximum is placed between two regions with different stable ion cluster configurations. This leads to the instability of these configurations in a small region between them. Consequently ion with radius near 1.75 or 2 Å could jump from one configuration to another. This increases the speed of the diffusion. A simple qualitative model for this effect is suggested. The decomposition of the ion movement into continuous and jump diffusion shows that continuous part of the diffusion is the same as for the ion cluster in the stable region.

Charge Retention by Monodisperse Gold Clusters on Surfaces Prepared Using Soft Landing of Mass Selected Ions

NASA Astrophysics Data System (ADS)

Johnson, Grant; Priest, Thomas; Laskin, Julia

2012-02-01

Monodisperse gold clusters have been prepared on surfaces in different charge states through soft landing of mass-selected ions. Gold clusters were synthesized in methanol solution by reduction of a gold precursor with a weak reducing agent in the presence of a diphosphine capping ligand. Electrospray ionization was used to introduce the clusters into the gas-phase and mass-selection was employed to isolate a single ionic cluster species which was delivered to surfaces at well controlled kinetic energies. Using in-situ time of flight secondary ion mass spectrometry (SIMS) it is demonstrated that the cluster retains its 3+ charge state when soft landed onto the surface of a fluorinated self assembled monolayer on gold. In contrast, when deposited onto carboxylic acid terminated and conventional alkyl thiol surfaces on gold the clusters exhibit larger relative abundances of the 2+ and 1+ charge states, respectively. The kinetics of charge reduction on the surface have been investigated using in-situ Fourier Transform Ion Cyclotron Resonance SIMS. It is shown that an extremely slow interfacial charge reduction occurs on the fluorinated monolayer surface while an almost instantaneous neutralization takes place on the surface of the alkyl thiol monolayer. Our results demonstrate that the size and charge state of small gold clusters on surfaces, both of which exert a dramatic influence on their chemical and physical properties, may be tuned through soft landing of mass-selected ions onto selected substrates.

Determination of the speciation and bioavailability of samarium to Chlamydomonas reinhardtii in the presence of natural organic matter.

PubMed

Rowell, Justine-Anne; Fillion, Marc-Alexandre; Smith, Scott; Wilkinson, Kevin J

2018-06-01

As technological interest and environmental emissions of the rare earth elements increase, it is becoming more important to assess their potential environmental impact. Samarium (Sm) is a lanthanide of intermediate molar mass that is used in numerous high-technology applications including wind turbines, solar panels, and electric vehicles. The present study relates the speciation of Sm determined in the presence of natural organic matter (NOM) to its bioavailability to the unicellular green alga Chlamydomonas reinhardtii. The free ion concentration was determined using a cation exchange resin (ion exchange technique) in dynamic mode and compared with thermodynamic modeling. Short-term biouptake experiments were performed in the presence of 4 types of NOM: Suwannee River fulvic acids, Pahokee Peat fulvic acids, Suwannee River humic acids, and a Luther Marsh dissolved organic matter isolate (90-95% humic acids). It was clearly shown that even a small amount of NOM (0.5 mg C L -1 ) resulted in a significant decrease (10 times) in the Sm internalization fluxes. Furthermore, complexation with humic acids (and the corresponding reduction in Sm bioavailability) was stronger than that with fulvic acids. The results showed that the experimentally measured (free) Sm was a better predictor of Sm internalization than either the total concentrations or the free ion concentrations obtained using thermodynamic modeling. Environ Toxicol Chem 2018;37:1623-1631. © 2018 SETAC. © 2018 SETAC.

Influence of natural organic matter source on copper speciation as demonstrated by Cu binding to fish gills, by ion selective electrode, and by DGT gel sampler

USGS Publications Warehouse

Luider, C.D.; Crusius, John; Playle, R.C.; Curtis, P.J.

2004-01-01

Rainbow trout (Oncorhynchus mykiss, 2 g) were exposed to 0−5 μM total copper in ion-poor water for 3 h in the presence or absence of 10 mg C/L of qualitatively different natural organic matter (NOM) derived from water spanning a large gradient in hydrologic residence time. Accumulation of Cu by trout gills was compared to Cu speciation determined by ion selective electrode (ISE) and by diffusive gradients in thin films (DGT) gel sampler technology. The presence of NOM decreased Cu uptake by trout gills as well as Cu concentrations determined by ISE and DGT. Furthermore, the source of NOM influenced Cu binding by trout gills with high-color, allochthonous NOM decreasing Cu accumulation by the gills more than low-color autochthonous NOM. The pattern of Cu binding to the NOM measured by Cu ISE and by Cu accumulation by DGT samplers was similar to the fish gill results. A simple Cu−gill binding model required an NOM Cu-binding factor (F) that depended on NOM quality to account for observed Cu accumulation by trout gills; values of F varied by a factor of 2. Thus, NOM metal-binding quality, as well as NOM quantity, are both important when assessing the bioavailability of metals such as Cu to aquatic organisms.

The Speciation of Silver Nanoparticles in Antimicrobial Fabric Before and After Exposure to a Hypochlorite/Detergent Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Impellitteri, Christopher A.; Tolaymat, Thabet M.; Scheckel, Kirk G.

2009-07-14

Because of their antibacterial properties, silver nanoparticles are often used in consumer products. To assess environmental and/or human health risks from these nanoparticles, there is a need to identify the chemical transformations that silver nanoparticles undergo in different environments. Thus an antimicrobial sock material containing Ag nanoparticles was examined by X-ray absorption spectroscopy to identify the speciation of Ag. The material was exposed to a hypochlorite/detergent solution and subjected to agitation. An elemental Ag nanopowder was also exposed to the hypochlorite/detergent solution or to a 1 mol L{sup -1} NaCl solution. Results showed that the sock material nanoparticles consisted ofmore » elemental Ag. After exposure to the hypochlorite/detergent solution, a significant portion (more than 50%) of the sock nanoparticles were converted, in situ, to AgCl. Results from exposures to elemental Ag nanopowder suggest that an oxidation step is necessary for the elemental Ag nanoparticles to transform into AgCl as there was no evidence of AgCl formation in the presence of chloride alone. As a result, if Ag ions leach from consumer products, any chloride present may quickly scavenge the ions. In addition, the efficacy of Ag, as an antimicrobial agent in fabrics, may be limited, or even negated, after washing in solutions containing oxidizers as AgCl is much less reactive than Ag ion.« less

Biosorptive recovery of platinum from platinum group metal refining wastewaters by immobilised Saccharomyces cerevisiae.

PubMed

Mack, C L; Wilhelmi, B; Duncan, J R; Burgess, J E

2011-01-01

The process of platinum group metal (PGM) refining can be up to 99.99% efficient at best, and although it may seem small, the amount of valuable metal lost to waste streams is appreciable enough to warrant recovery. The method currently used to remove entrained metal ions from refinery wastewaters, chemical precipitation, is not effective for selective recovery of PGMs. The yeast Saccharomyces cerevisiae has been found capable of sorbing numerous precious and base metals, and is a cheap and abundant source of biomass. In this investigation, S. cerevisiae was immobilised using polyethyleneimine and glutaraldehyde to produce a suitable sorbent, capable of high platinum uptake (150-170 mg/g) at low pH (<2). The sorption mechanism was found to be a chemical reaction, which made effective desorption impossible. When applied to PGM refinery wastewater, two key wastewater characteristics limited the success of the sorption process; high inorganic ion content and complex speciation of the platinum ions. The results proved the concept principle of platinum recovery by immobilised yeast biosorption and indicated that a more detailed understanding of the platinum speciation within the wastewater is required before biosorption can be applied. Overall, the sorption of platinum by the S. cerevisiae sorbent was demonstrated to be highly effective in principle, but the complexity of the wastewater requires that pretreatment steps be taken before the successful application of this process to industrial wastewater.

Hidden Charge States in Soft-X-Ray Laser-Produced Nanoplasmas Revealed by Fluorescence Spectroscopy

NASA Astrophysics Data System (ADS)

Schroedter, L.; Müller, M.; Kickermann, A.; Przystawik, A.; Toleikis, S.; Adolph, M.; Flückiger, L.; Gorkhover, T.; Nösel, L.; Krikunova, M.; Oelze, T.; Ovcharenko, Y.; Rupp, D.; Sauppe, M.; Wolter, D.; Schorb, S.; Bostedt, C.; Möller, T.; Laarmann, T.

2014-05-01

Highly charged ions are formed in the center of composite clusters by strong free-electron laser pulses and they emit fluorescence on a femtosecond time scale before competing recombination leads to neutralization of the nanoplasma core. In contrast to mass spectrometry that detects remnants of the interaction, fluorescence in the extreme ultraviolet spectral range provides fingerprints of transient states of high energy density matter. Spectra from clusters consisting of a xenon core and a surrounding argon shell show that a small fraction of the fluorescence signal comes from multiply charged xenon ions in the cluster core. Initially, these ions are as highly charged as the ions in the outer shells of pure xenon clusters with charge states up to at least 11+.

Transmission of cluster ions through a tandem accelerator of several stripper gases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saitoh, Yuichi; Chiba, Atsuya; Narumi, Kazumasa

2009-10-15

The transmissions of carbon cluster ion beams through a tandem accelerator using several stripper gases (He, N{sub 2}, CO{sub 2}, and SF{sub 6}) with a terminal voltage of 2.5 MV were measured as a function of the gas pressure in investigating the most suitable gas for cluster ion acceleration. This resulted in it being demonstrated that the highest transmission could be obtained using the smaller size gas, i.e., helium displayed the best performance of the four gases used. In addition, the ratio of transmissions of C{sub n} with helium and nitrogen increased with increases in the n, thus revealing thatmore » helium gas should prove the most effective in larger cluster ion acceleration using the same energy.« less

Hydrogen ion speciation in the acid precipitation of the northeastern United States

Treesearch

James N. Galloway; Gene E. Likens; Eric S. Edgerton

1976-01-01

The acidity of precipitation in rural, forested areas of the northeastern United States is dominated by the strong mineral acids, sulfuric and nitric. Weak acids have a negligible effect on the measured acidity (pH) of precipitation. These conclusions are based on total acidity titrations and detailed analysis of organic and inorganic components in precipitation.

Laboratory and field based evaluation of chromatography related performance of the Monitor for Aerosols and Gases in Ambient Air (MARGA)

EPA Science Inventory

The Monitor for AeRosols and GAses in ambient air (MARGA) is an on-line ion-chromatography-based instrument designed for speciation of the inorganic gas and aerosol ammonium-nitrate-sulfate system. Previous work to characterize the performance of the MARGA has been primarily base...

Heavy metal speciation, leaching and toxicity status of a tropical rain-fed river Damodar, India.

PubMed

Pal, Divya; Maiti, Subodh Kumar

2018-03-26

Speciations of metals were assessed in a tropical rain-fed river, flowing through the highly economically important part of the India. The pattern of distribution of heavy metals (Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn) were evaluated in water and sediment along with mineralogical characterization, changes with different water quality parameters and their respective health hazard to the local population along the Damodar River basin during pre-monsoon and post-monsoon seasons. The outcome of the speciation analysis using MINTEQ indicated that free metal ions, carbonate, chloride and sulfate ions were predominantly in anionic inorganic fractions, while in cationic inorganic fractions metal loads were negligible. Metals loads were higher in sediment phase than in the aqueous phase. The estimated values of I geo in river sediment during both the seasons showed that most of the metals were found in the I geo class 0-1 which represents unpolluted to moderately polluted sediment status. The result of partition coefficient indicated the strong retention capability of Cr, Pb, Co and Mn, while Cd, Zn, Cu and Ni have resilient mobility capacity. The mineralogical analysis of sediment samples indicated that in Damodar River, quartz, kaolinite and calcite minerals were dominantly present. The hazard index values of Cd, Co and Cr were > 1 in river water, which suggested potential health risk for the children. A combination of pragmatic, computational and statistical relationship between ionic species and fractions of metals represented a strong persuasion for identifying the alikeness among the different sites of the river.

Phenytoin speciation with potentiometric and chronopotentiometric ion-selective membrane electrodes.

PubMed

Jansod, Sutida; Afshar, Majid Ghahraman; Crespo, Gastón A; Bakker, Eric

2016-05-15

We report on an electrochemical protocol based on perm-selective membranes to provide valuable information about the speciation of ionizable drugs, with phenytoin as a model example. Membranes containing varying amounts of tetradodecylammonium chloride (TDDA) were read out at zero current (potentiometry) and with applied current techniques (chronopotentiometry). Potentiometry allows one to assess the ionized form of phenytoin (pKa~8.2) that corresponds to a negatively monocharged ion. A careful optimization of the membrane components resulted in a lower limit of detection (~1.6 µM) than previous reports. Once the pH (from 9 to 10) or the concentration of albumin is varied in the sample (from 0 to 30 g L(-1)), the potentiometric signal changes abruptly as a result of reducing/increasing the ionized concentration of phenytoin. Therefore, potentiometry as a single technique is by itself not sufficient to obtain information about the concentration and speciation of the drug in the system. For this reason, a tandem configuration with chronopotentiometry as additional readout principle was used to determine the total and ionized concentration of phenytoin. In samples containing excess albumin the rate-limiting step for the chronopotentiometry readout appears to be the diffusion of ionized phenytoin preceded by comparatively rapid deprotonation and decomplexation reactions. This protocol was applied to measure phenytoin in pharmaceutical tables (100mg per tablet). This tandem approach can likely be extended to more ionizable drugs and may eventually be utilized in view of pharmacological monitoring of drugs during the delivery process. Copyright © 2015 Elsevier B.V. All rights reserved.

Raman spectroscopy of few-layer graphene prepared by C2-C6 cluster ion implantation

NASA Astrophysics Data System (ADS)

Wang, Z. S.; Zhang, R.; Zhang, Z. D.; Huang, Z. H.; Liu, C. S.; Fu, D. J.; Liu, J. R.

2013-07-01

Few-layer graphene has been prepared on 300 nm-thick Ni films by C2-C6 cluster ion implantation at 20 keV/cluster. Raman spectroscopy reveals significant influence of the number of atoms in the cluster, the implantation dose, and thermal treatment on the structure of the graphene layers. In particular, the graphene samples exhibit a sharp G peak at 1584 cm-1 and 2D peaks at 2711-2717 cm-1. The IG/I2D ratios higher than 1.70 and IG/ID ratio as high as 1.95 confirm that graphene sheets with low density of defects have been synthesized with much improved quality by ion implantation with larger clusters of C4-C6.

Chemistry of carcinogenic metals.

PubMed Central

Martell, A E

1981-01-01

The periodic distribution of known and suspected carcinogenic metal ions is described, and the chemical behavior of various types of metal ions is explained in terms of the general theory of hard and soft acids and bases. The chelate effect is elucidated, and the relatively high stability of metal chelates in very dilute solutions is discussed. The concepts employed for the chelate effect are extended to explain the high stabilities of macrocyclic and cryptate complexes. Procedures for the use of equilibrium data to determine the speciation of metal ions and complexes under varying solution conditions are described. Methods for assessing the interferences by hydrogen ion, competing metal ions, hydrolysis, and precipitation are explained, and are applied to systems containing iron(III) chelates of fourteen chelating agents designed for effective binding of the ferric ion. The donor groups available for the building up of multidentate ligands are presented, and the ways in which they may be combined to achieve high affinity and selectivity for certain types of metal ions are explained. PMID:6791915

Organic positive ions in aircraft gas-turbine engine exhaust

NASA Astrophysics Data System (ADS)

Sorokin, Andrey; Arnold, Frank

Volatile organic compounds (VOCs) represent a significant fraction of atmospheric aerosol. However the role of organic species emitted by aircraft (as a consequence of the incomplete combustion of fuel in the engine) in nucleation of new volatile particles still remains rather speculative and requires a much more detailed analysis of the underlying mechanisms. Measurements in aircraft exhaust plumes have shown the presence of both different non-methane VOCs (e.g. PartEmis project) and numerous organic cluster ions (MPIK-Heidelberg). However the link between detected organic gas-phase species and measured mass spectrum of cluster ions is uncertain. Unfortunately, up to now there are no models describing the thermodynamics of the formation of primary organic cluster ions in the exhaust of aircraft engines. The aim of this work is to present first results of such a model development. The model includes the block of thermodynamic data based on proton affinities and gas basicities of organic molecules and the block of non-equilibrium kinetics of the cluster ions evolution in the exhaust. The model predicts important features of the measured spectrum of positive ions in the exhaust behind aircraft. It is shown that positive ions emitted by aircraft engines into the atmosphere mostly consist of protonated and hydrated organic cluster ions. The developed model may be explored also in aerosol investigations of the background atmosphere as well as in the analysis of the emission of fine aerosol particles by automobiles.

The Au(n) cluster probe in secondary ion mass spectrometry: influence of the projectile size and energy on the desorption/ionization rate from biomolecular solids.

PubMed

Novikov, Alexey; Caroff, Martine; Della-Negra, Serge; Depauw, Joël; Fallavier, Mireille; Le Beyec, Yvon; Pautrat, Michèle; Schultz, J Albert; Tempez, Agnès; Woods, Amina S

2005-01-01

A Au-Si liquid metal ion source which produces Au(n) clusters over a large range of sizes was used to study the dependence of both the molecular ion desorption yield and the damage cross-section on the size (n = 1 to 400) and on the kinetic energy (E = 10 to 500 keV) of the clusters used to bombard bioorganic surfaces. Three pure peptides with molecular masses between 750 and 1200 Da were used without matrix. [M+H](+) and [M+cation](+) ion emission yields were enhanced by as much as three orders of magnitude when bombarding with Au(400) (4+) instead of monatomic Au(+), yet very little damage was induced in the samples. A 100-fold increase in the molecular ion yield was observed when the incident energy of Au(9) (+) was varied from 10 to 180 keV. Values of emission yields and damage cross-sections are presented as a function of cluster size and energy. The possibility to adjust both cluster size and energy, depending on the application, makes the analysis of biomolecules by secondary ion mass spectrometry an extremely powerful and flexible technique, particularly when combined with orthogonal time-of-flight mass spectrometry that then allows fast measurements using small primary ion beam currents. Copyright (c) 2005 John Wiley & Sons, Ltd.

Sympatric speciation revealed by genome-wide divergence in the blind mole rat Spalax.

PubMed

Li, Kexin; Hong, Wei; Jiao, Hengwu; Wang, Guo-Dong; Rodriguez, Karl A; Buffenstein, Rochelle; Zhao, Yang; Nevo, Eviatar; Zhao, Huabin

2015-09-22

Sympatric speciation (SS), i.e., speciation within a freely breeding population or in contiguous populations, was first proposed by Darwin [Darwin C (1859) On the Origins of Species by Means of Natural Selection] and is still controversial despite theoretical support [Gavrilets S (2004) Fitness Landscapes and the Origin of Species (MPB-41)] and mounting empirical evidence. Speciation of subterranean mammals generally, including the genus Spalax, was considered hitherto allopatric, whereby new species arise primarily through geographic isolation. Here we show in Spalax a case of genome-wide divergence analysis in mammals, demonstrating that SS in continuous populations, with gene flow, encompasses multiple widespread genomic adaptive complexes, associated with the sharply divergent ecologies. The two abutting soil populations of S. galili in northern Israel habituate the ancestral Senonian chalk population and abutting derivative Plio-Pleistocene basalt population. Population divergence originated ∼0.2-0.4 Mya based on both nuclear and mitochondrial genome analyses. Population structure analysis displayed two distinctly divergent clusters of chalk and basalt populations. Natural selection has acted on 300+ genes across the genome, diverging Spalax chalk and basalt soil populations. Gene ontology enrichment analysis highlights strong but differential soil population adaptive complexes: in basalt, sensory perception, musculature, metabolism, and energetics, and in chalk, nutrition and neurogenetics are outstanding. Population differentiation of chemoreceptor genes suggests intersoil population's mate and habitat choice substantiating SS. Importantly, distinctions in protein degradation may also contribute to SS. Natural selection and natural genetic engineering [Shapiro JA (2011) Evolution: A View From the 21st Century] overrule gene flow, evolving divergent ecological adaptive complexes. Sharp ecological divergences abound in nature; therefore, SS appears to be an important mode of speciation as first envisaged by Darwin [Darwin C (1859) On the Origins of Species by Means of Natural Selection].

Determination, speciation and distribution of mercury in soil in the surroundings of a former chlor-alkali plant: assessment of sequential extraction procedure and analytical technique

PubMed Central

2013-01-01

Background The paper presents the evaluation of soil contamination with total, water-available, mobile, semi-mobile and non-mobile Hg fractions in the surroundings of a former chlor-alkali plant in connection with several chemical soil characteristics. Principal Component Analysis and Cluster Analysis were used to evaluate the chemical composition variability of soil and factors influencing the fate of Hg in such areas. The sequential extraction EPA 3200-Method and the determination technique based on capacitively coupled microplasma optical emission spectrometry were checked. Results A case study was conducted in the Turda town, Romania. The results revealed a high contamination with Hg in the area of the former chlor-alkali plant and waste landfills, where soils were categorized as hazardous waste. The weight of the Hg fractions decreased in the order semi-mobile > non-mobile > mobile > water leachable. Principal Component Analysis revealed 7 factors describing chemical composition variability of soil, of which 3 attributed to Hg species. Total Hg, semi-mobile, non-mobile and mobile fractions were observed to have a strong influence, while the water leachable fraction a weak influence. The two-dimensional plot of PCs highlighted 3 groups of sites according to the Hg contamination factor. The statistical approach has shown that the Hg fate in soil is dependent on pH, content of organic matter, Ca, Fe, Mn, Cu and SO42- rather than natural components, such as aluminosilicates. Cluster analysis of soil characteristics revealed 3 clusters, one of which including Hg species. Soil contamination with Cu as sulfate and Zn as nitrate was also observed. Conclusions The approach based on speciation and statistical interpretation of data developed in this study could be useful in the investigation of other chlor-alkali contaminated areas. According to the Bland and Altman test the 3-step sequential extraction scheme is suitable for Hg speciation in soil, while the used determination method of Hg is appropriate. PMID:24252185

Fragmentation pathways of tungsten hexacarbonyl clusters upon electron ionization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neustetter, M.; Jabbour Al Maalouf, E.; Denifl, S., E-mail: Stephan.Denifl@uibk.ac.at, E-mail: plimaovieira@fct.unl.pt

2016-08-07

Electron ionization of neat tungsten hexacarbonyl (W(CO){sub 6}) clusters has been investigated in a crossed electron-molecular beam experiment coupled with a mass spectrometer system. The molecule is used for nanofabrication processes through electron beam induced deposition and ion beam induced deposition techniques. Positive ion mass spectra of W(CO){sub 6} clusters formed by electron ionization at 70 eV contain the ion series of the type W(CO){sub n}{sup +} (0 ≤ n ≤ 6) and W{sub 2}(CO){sub n}{sup +} (0 ≤ n ≤ 12). In addition, a series of peaks are observed and have been assigned to WC(CO){sub n}{sup +} (0 ≤more » n ≤ 3) and W{sub 2}C(CO){sub n}{sup +} (0 ≤ n ≤ 10). A distinct change of relative fragment ion intensity can be observed for clusters compared to the single molecule. The characteristic fragmentation pattern obtained in the mass spectra can be explained by a sequential decay of the ionized organometallic, which is also supported by the study of the clusters when embedded in helium nanodroplets. In addition, appearance energies for the dissociative ionization channels for singly charged ions have been estimated from experimental ion efficiency curves.« less

Cluster formation in precompound nuclei in the time-dependent framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schuetrumpf, B.; Nazarewicz, W.

Background: Modern applications of nuclear time-dependent density functional theory (TDDFT) are often capable of providing quantitative description of heavy ion reactions. However, the structures of precompound (preequilibrium, prefission) states produced in heavy ion reactions are difficult to assess theoretically in TDDFT as the single-particle density alone is a weak indicator of shell structure and cluster states. Purpose: We employ the time-dependent nucleon localization function (NLF) to reveal the structure of precompound states in nuclear reactions involving light and medium-mass ions. We primarily focus on spin saturated systems with N = Z . Furthermore, we study reactions with oxygen and carbonmore » ions, for which some experimental evidence for α clustering in precompound states exists. Method: We utilize the symmetry-free TDDFT approach with the Skyrme energy density functional UNEDF1 and compute the time-dependent NLFs to describe 16O + 16O, 40Ca + 16O, 40Ca + 40Ca , and 16,18O + 12C collisions at energies above the Coulomb barrier. Results: We show that NLFs reveal a variety of time-dependent modes involving cluster structures. For instance, the 16O + 16O collision results in a vibrational mode of a quasimolecular α - 12 C - 12 C- α state. For heavier ions, a variety of cluster configurations are predicted. For the collision of 16,18O + 12C, we showed that the precompound system has a tendency to form α clusters. This result supports the experimental findings that the presence of cluster structures in the projectile and target nuclei gives rise to strong entrance channel effects and enhanced α emission. Conclusion: The time-dependent nucleon localization measure is a very good indicator of cluster structures in complex precompound states formed in heavy-ion fusion reactions. Finally, the localization reveals the presence of collective vibrations involving cluster structures, which dominate the initial dynamics of the fusing system.« less

Cluster formation in precompound nuclei in the time-dependent framework

DOE PAGES

Schuetrumpf, B.; Nazarewicz, W.

2017-12-15

Background: Modern applications of nuclear time-dependent density functional theory (TDDFT) are often capable of providing quantitative description of heavy ion reactions. However, the structures of precompound (preequilibrium, prefission) states produced in heavy ion reactions are difficult to assess theoretically in TDDFT as the single-particle density alone is a weak indicator of shell structure and cluster states. Purpose: We employ the time-dependent nucleon localization function (NLF) to reveal the structure of precompound states in nuclear reactions involving light and medium-mass ions. We primarily focus on spin saturated systems with N = Z . Furthermore, we study reactions with oxygen and carbonmore » ions, for which some experimental evidence for α clustering in precompound states exists. Method: We utilize the symmetry-free TDDFT approach with the Skyrme energy density functional UNEDF1 and compute the time-dependent NLFs to describe 16O + 16O, 40Ca + 16O, 40Ca + 40Ca , and 16,18O + 12C collisions at energies above the Coulomb barrier. Results: We show that NLFs reveal a variety of time-dependent modes involving cluster structures. For instance, the 16O + 16O collision results in a vibrational mode of a quasimolecular α - 12 C - 12 C- α state. For heavier ions, a variety of cluster configurations are predicted. For the collision of 16,18O + 12C, we showed that the precompound system has a tendency to form α clusters. This result supports the experimental findings that the presence of cluster structures in the projectile and target nuclei gives rise to strong entrance channel effects and enhanced α emission. Conclusion: The time-dependent nucleon localization measure is a very good indicator of cluster structures in complex precompound states formed in heavy-ion fusion reactions. Finally, the localization reveals the presence of collective vibrations involving cluster structures, which dominate the initial dynamics of the fusing system.« less

Cluster formation in precompound nuclei in the time-dependent framework

NASA Astrophysics Data System (ADS)

Schuetrumpf, B.; Nazarewicz, W.

2017-12-01

Background: Modern applications of nuclear time-dependent density functional theory (TDDFT) are often capable of providing quantitative description of heavy ion reactions. However, the structures of precompound (preequilibrium, prefission) states produced in heavy ion reactions are difficult to assess theoretically in TDDFT as the single-particle density alone is a weak indicator of shell structure and cluster states. Purpose: We employ the time-dependent nucleon localization function (NLF) to reveal the structure of precompound states in nuclear reactions involving light and medium-mass ions. We primarily focus on spin saturated systems with N =Z . Furthermore, we study reactions with oxygen and carbon ions, for which some experimental evidence for α clustering in precompound states exists. Method: We utilize the symmetry-free TDDFT approach with the Skyrme energy density functional UNEDF1 and compute the time-dependent NLFs to describe 16O + 16O,40Ca + 16O, 40Ca + 40Ca, and O,1816 + 12C collisions at energies above the Coulomb barrier. Results: We show that NLFs reveal a variety of time-dependent modes involving cluster structures. For instance, the 16O + 16O collision results in a vibrational mode of a quasimolecular α - 12C - 12C-α state. For heavier ions, a variety of cluster configurations are predicted. For the collision of O,1816 + 12C, we showed that the precompound system has a tendency to form α clusters. This result supports the experimental findings that the presence of cluster structures in the projectile and target nuclei gives rise to strong entrance channel effects and enhanced α emission. Conclusion: The time-dependent nucleon localization measure is a very good indicator of cluster structures in complex precompound states formed in heavy-ion fusion reactions. The localization reveals the presence of collective vibrations involving cluster structures, which dominate the initial dynamics of the fusing system.

Speciation in Aqueous MgSO4 Fluid at High Pressures and Temperatures Studied by First-Principles Modeling and Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Jahn, S.; Schmidt, C.

2008-12-01

Aqueous fluids play an essential role in mass and energy transfer in the lithosphere. Their presence has also a large effect on physical properties of rocks, e.g. the electrical conductivity. Many chemical and physical properties of aqueous fluids strongly depend on the speciation, but very little is known about this fundamental parameter at high pressures and temperatures, e.g. at subduction zone conditions. Here we use a combined approach of first-principles molecular dynamics simulation and Raman spectroscopy to study the molecular structure of aqueous 2~mol/kg MgSO4 fluids up to pressures of 3~GPa and temperatures of 750~°C. MgSO4-H2O is selected as a model system for sulfate bearing subduction zone fluids. The simulations are performed using Car-Parrinello dynamics, a system size of 120 water and four MgSO4 molecules with production runs of at least 10~ps at each P and T. Raman spectra were obtained in situ using a Bassett-type hydrothermal diamond anvil cell with external heating. Both simulation and spectroscopic data show a dynamic co-existence of various associated molecular species as well as dissociated Mg2+ and SO42- in the single phase fluid. Fitting the Raman signal in the frequency range of the ν1-SO42- stretching mode yields the P-T dependence of the relative proportions of different peaks. The latter can be assigned to species based on literature data and related to the species found in the simulation. The dominant associated species found in the P-T range of interest here are Mg-SO4 ion pairs with one (monodentate) and two (bidentate) binding sites. At the highest P and T, an additional peak is identified. At low pressures and high temperature (T>230~°C), kieserite, MgSO4·H2O, nucleated in the experiment. At the same conditions the simulations show a clustering of Mg, which is interpreted as a precursor of precipitation. In conclusion, the speciation of aqueous MgSO4 fluid shows a complex behavior at high P and T that cannot be extrapolated from ambient conditions. The combination of molecular modeling and in situ spectroscopic experiments is a promising approach towards quantitative understanding of geochemical processes in subduction zones.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, H.B.; Hu, Y.J.; Bernstein, E.R.

Small methanol clusters are formed by expanding a mixture of methanol vapor seeded in helium and are detected using vacuum UV (vuv) (118 nm) single-photon ionization/linear time-of-flight mass spectrometer (TOFMS). Protonated cluster ions, (CH{sub 3}OH){sub n-1}H{sup +} (n=2-8), formed through intracluster ion-molecule reactions following ionization, essentially correlate to the neutral clusters, (CH{sub 3}OH){sub n}, in the present study using 118 nm light as the ionization source. Both experimental and Born-Haber calculational results clarify that not enough excess energy is released into protonated cluster ions to initiate further fragmentation in the time scale appropriate for linear TOFMS. Size-specific spectra for (CH{submore » 3}OH){sub n} (n=4 to 8) clusters in the OH stretch fundamental region are recorded by IR+vuv (118 nm) nonresonant ion-dip spectroscopy through the detection chain of IR multiphoton predissociation and subsequent vuv single-photon ionization. The general structures and gross features of these cluster spectra are consistent with previous theoretical calculations. The lowest-energy peak contributed to each cluster spectrum is redshifted with increasing cluster size from n=4 to 8, and limits near {approx}3220 cm{sup -1} in the heptamer and octamer. Moreover, IR+vuv nonresonant ionization detected spectroscopy is employed to study the OH stretch first overtone of the methanol monomer. The rotational temperature of the clusters is estimated to be at least 50 K based on the simulation of the monomer rotational envelope under clustering conditions.« less

Dynamic Reactive Ionization with Cluster Secondary Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Tian, Hua; Wucher, Andreas; Winograd, Nicholas

2016-02-01

Gas cluster ion beams (GCIB) have been tuned to enhance secondary ion yields by doping small gas molecules such as CH4, CO2, and O2 into an Ar cluster projectile, Arn + ( n = 1000-10,000) to form a mixed cluster. The `tailored beam' has the potential to expand the application of secondary ion mass spectrometry for two- and three-dimensional molecular specific imaging. Here, we examine the possibility of further enhancing the ionization by doping HCl into the Ar cluster. Water deposited on the target surface facilitates the dissociation of HCl. This concerted effect, occurring only at the impact site of the cluster, arises since the HCl is chemically induced to ionize to H+ and Cl- , allowing improved protonation of neutral molecular species. This hypothesis is confirmed by depth profiling through a trehalose thin film exposed to D2O vapor, resulting in ~20-fold increase in protonated molecules. The results show that it is possible to dynamically maintain optimum ionization conditions during depth profiling by proper adjustment of the water vapor pressure. H-D exchange in the trehalose molecule M was monitored upon deposition of D2O on the target surface, leading to the observation of [Mn* + H]+ or [Mn* + D]+ ions, where n = 1-8 hydrogen atoms in the trehalose molecule M have been replaced by deuterium. In general, we discuss the role of surface chemistry and dynamic reactive ionization of organic molecules in increasing the secondary ion yield.

Importance of reduced sulfur for the equilibrium chemistry and kinetics of Fe(II), Co(II) and Ni(II) supplemented to semi-continuous stirred tank biogas reactors fed with stillage.

PubMed

Shakeri Yekta, Sepehr; Lindmark, Amanda; Skyllberg, Ulf; Danielsson, Asa; Svensson, Bo H

2014-03-30

The objective of the present study was to assess major chemical reactions and chemical forms contributing to solubility and speciation of Fe(II), Co(II), and Ni(II) during anaerobic digestion of sulfur (S)-rich stillage in semi-continuous stirred tank biogas reactors (SCSTR). These metals are essential supplements for efficient and stable performance of stillage-fed SCSTR. In particular, the influence of reduced inorganic and organic S species on kinetics and thermodynamics of the metals and their partitioning between aqueous and solid phases were investigated. Solid phase S speciation was determined by use of S K-edge X-ray absorption near-edge spectroscopy. Results demonstrated that the solubility and speciation of supplemented Fe were controlled by precipitation of FeS(s) and formation of the aqueous complexes of Fe-sulfide and Fe-thiol. The relatively high solubility of Co (∼ 20% of total Co content) was attributed to the formation of compounds other than Co-sulfide and Co-thiol, presumably of microbial origin. Nickel had lower solubility than Co and its speciation was regulated by interactions with FeS(s) (e.g. co-precipitation, adsorption, and ion substitution) in addition to precipitation/dissolution of discrete NiS(s) phase and formation of aqueous Ni-sulfide complexes. Copyright © 2014 Elsevier B.V. All rights reserved.

Sudden appearance of sub-keV structured ions in the inner magnetosphere within one hour: drift simulation

NASA Astrophysics Data System (ADS)

Yamauchi, Masatoshi; Ebihara, Yusuke; Dandouras, Iannis; Nilsson, Hans

2014-05-01

Energy-latitude dispersed structured sub-keV ions in the inner magnetosphere drifts very slowly in the noon-to-afternoon sectors because the eastward corotation and the westward magnetic drift balances to each other there. However, majority of Cluster ion observation by the Cluster Ion Spectrometry (CIS) COmposition DIstribution Function (CODIF) instrument during 2001-2006 showed significant development or intensification (by more than factor of 3) within 1-2 h in that sector during the Cluster perigee traversals that quickly scans latitudinal structure at a fixed local time (Yamauchi et al., 2013). The frequent observations of significant inbound-outbound differences in the wedge-like dispersed ions by Cluster indicates either new injections or high eastward drift velocity even in the afternoon sector. To examine the former possibility, i.e., whether such sudden appearances in the dayside can be explained by the drift motion of ions that are formed during substorm-related injections, we numerically simulated two such examples, one at noon (8 September 2002) and the other in the afternoon (9 July 2001), based on the same ion drift simulation model that has successfully reproduced the ion pattern of an inbound-outbound symmetric event at 5 MLT observed by the Cluster CIS/CODIF instrument. The model uses backward phase-space mapping to a boundary at the nightside 8 Earth radii and forward numerical simulation using re-constructed distribution function at that boundary. For both examples, the ion drift model with finite duration (limited to 1-2 hours) of proton source in the nightside can explain the observed large inbound-outbound differences in the sub-keV proton population without any new sources. Ion drift motion is thus able to cause rapid changes of complicated ion populations, at remote places from the source long time after the substorm activities, although this result does not eliminate the possibility of having independent ionospheric sources. References: Yamauchi, M. et al.: Cluster observation of few-hour-scale evolution of structured plasma in the inner magnetosphere, Ann. Geophys., 31, 1569-1578, doi:10.5194/angeo-31-1569-2013, 2013.

Preparation of graphene on Cu foils by ion implantation with negative carbon clusters

NASA Astrophysics Data System (ADS)

Li, Hui; Shang, Yan-Xia; Zhang, Zao-Di; Wang, Ze-Song; Zhang, Rui; Fu, De-Jun

2015-01-01

We report on few-layer graphene synthesized on Cu foils by ion implantation using negative carbon cluster ions, followed by annealing at 950 °C in vacuum. Raman spectroscopy reveals IG/I2D values varying from 1.55 to 2.38 depending on energy and dose of the cluster ions, indicating formation of multilayer graphene. The measurements show that the samples with more graphene layers have fewer defects. This is interpreted by graphene growth seeded by the first layers formed via outward diffusion of C from the Cu foil, though nonlinear damage and smoothing effects also play a role. Cluster ion implantation overcomes the solubility limit of carbon in Cu, providing a technique for multilayer graphene synthesis. Project supported by the National Natural Science Foundation of China (Grant Nos. 11105100, 11205116, and 11375135) and the State Key Laboratory of Advanced Welding and Joining, Harbin Institute of Technology, China (Grant No. AWJ-M13-03).

Reactions and properties of clusters

NASA Astrophysics Data System (ADS)

Castleman, A. W., Jr.

1992-09-01

The elucidation from a molecular point of view of the differences and similarities in the properties and reactivity of matter in the gaseous compared to the condensed state is a subject of considerable current interest. One of the promising approaches to this problem is to utilize mass spectrometry in conjunction with laser spectroscopy and fast-flow reaction devices to investigate the changing properties, structure and reactivity of clusters as a function of the degree of solvation under well-controlled conditions. In this regard, an investigation of molecular cluster ions has provided considerable new insight into the basic mechanisms of ion reactions within a cluster, and this paper reviews some of the recent advances in cluster production, the origin of magic numbers and relationship to cluster ion stabilities, and solvation effects on reactions. There have been some notable advances in the production of large cluster ions under thermal reaction conditions, enabling a systematic study of the influence of solvation on reactions to be carried out. These and other new studies of magic numbers have traced their origin to the thermochemical stability of cluster ions. There are several classes of reaction where solvation has a notable influence on reactivity. A particularly interesting example comes from recent studies of the reactions of the hydroxyl anion with CO2 and SO2, studied as a function of the degree of hydration of OH-. Both reactions are highly exothermic, yet the differences in reactivity are dramatic. In the case of SO2, the reaction occurs at near the collision rate. By contrast, CO2 reactivity plummets dramatically for clusters having more than four water molecules. The slow rate is in accord with observations in the liquid phase.

Room-temperature bonding of epitaxial layer to carbon-cluster ion-implanted silicon wafers for CMOS image sensors

NASA Astrophysics Data System (ADS)

Koga, Yoshihiro; Kadono, Takeshi; Shigematsu, Satoshi; Hirose, Ryo; Onaka-Masada, Ayumi; Okuyama, Ryousuke; Okuda, Hidehiko; Kurita, Kazunari

2018-06-01

We propose a fabrication process for silicon wafers by combining carbon-cluster ion implantation and room-temperature bonding for advanced CMOS image sensors. These carbon-cluster ions are made of carbon and hydrogen, which can passivate process-induced defects. We demonstrated that this combination process can be used to form an epitaxial layer on a carbon-cluster ion-implanted Czochralski (CZ)-grown silicon substrate with a high dose of 1 × 1016 atoms/cm2. This implantation condition transforms the top-surface region of the CZ-grown silicon substrate into a thin amorphous layer. Thus, an epitaxial layer cannot be grown on this implanted CZ-grown silicon substrate. However, this combination process can be used to form an epitaxial layer on the amorphous layer of this implanted CZ-grown silicon substrate surface. This bonding wafer has strong gettering capability in both the wafer-bonding region and the carbon-cluster ion-implanted projection range. Furthermore, this wafer inhibits oxygen out-diffusion to the epitaxial layer from the CZ-grown silicon substrate after device fabrication. Therefore, we believe that this bonding wafer is effective in decreasing the dark current and white-spot defect density for advanced CMOS image sensors.

Copper speciation in sulfidic solutions at low sulfur activity: Further evidence for cluster complexes?

NASA Astrophysics Data System (ADS)

Thompson, Richard A.; Helz, George R.

1994-07-01

The solubility of two as0-buffering assemblages in the Cu-S system have been studied: chalcocite-djurleite (Cc-Dj) and anilite-covellite (An-Cv). Ion activity products, [Cu +]HS -] 1/2[H +] - 1/2 (25°C, I = 0) at equilibrium, derived from solubility measurements in penicillamine solutions, are 10 -17.01 ± 0.05 (Cc-Dj) and 10 -17.14 ± 0.10 (An-Cv), from which ΔG° f = -82.11 kJ/mol for Cc and -74.77 kJ/mol for An. In the An-Cv assemblage, aCu2S = 0.55 (2 σ = 0.2) vs. 1.00 in the Cc-containing assemblage. The difference in aCu2S between the two assemblages is used in a novel way to estimate stoichiometry of Cu-HS complexes. The solubility of both assemblages (0.7-0.01 M NaHS, pH 7-12.5, 25°C) can be fit with a model incorporating the same two chemical species, one containing an odd number of Cu atoms (Cu(HS) 2-3, CU 3S 4H 2-3, or a higher multimer) and the other containing an even number of Cu atoms (Cu 2S(HS) 22-, Cu 4S 4H 22-, etc.). The trimer-tetramer model fits the combined data for the two assemblages distinctly better than the monomer-dimer model, but this result is very sensitive to uncertainty in aCu2S. Along with EXAFS results, the weight of the evidence favors small cluster complexes (2-5 Cu atoms), but is inconclusive at the present level of resolution. Multimers can be rationalized because condensation of metal-centered monomers to clusters provides a means for soft acid/base elements to maintain favored coordination geometries at low ligand to metal ratios. Based on the fitting methods developed here, previous covellite solubility data from this laboratory are reinterpreted in terms of Cu 2S 2(HS) 33-, Cu 2S 3)(S 4) 2-, and Cu(S 9)S 10) 3-; the last of these could also be represented by the trimer, Cu 3(S 7) 33-, which is homologous with a known complex. With the measured equilibrium constants, the speciation of Cu in the sulfidic zone of the Black Sea is calculated. Covellite is the stable Cu-S mineral, but the sulfidic water column is vastly supersaturated with respect to it. Most of the sulfidic water column is modestly (2.5-5.5 times) supersaturated with respect to Cc, hinting that this mineral metastably controls ΣCu. The slight supersaturation suggests that Cc occurs as 10-100 nm particles.

Water cluster fragmentation probed by pickup experiments

NASA Astrophysics Data System (ADS)

Huang, Chuanfu; Kresin, Vitaly V.; Pysanenko, Andriy; Fárník, Michal

2016-09-01

Electron ionization is a common tool for the mass spectrometry of atomic and molecular clusters. Any cluster can be ionized efficiently by sufficiently energetic electrons, but concomitant fragmentation can seriously obstruct the goal of size-resolved detection. We present a new general method to assess the original neutral population of the cluster beam. Clusters undergo a sticking collision with a molecule from a crossed beam, and the velocities of neat and doped cluster ion peaks are measured and compared. By making use of longitudinal momentum conservation, one can reconstruct the sizes of the neutral precursors. Here this method is applied to H2O and D2O clusters in the detected ion size range of 3-10. It is found that water clusters do fragment significantly upon electron impact: the deduced neutral precursor size is ˜3-5 times larger than the observed cluster ions. This conclusion agrees with beam size characterization by another experimental technique: photoionization after Na-doping. Abundant post-ionization fragmentation of water clusters must therefore be an important factor in the interpretation of experimental data; interestingly, there is at present no detailed microscopic understanding of the underlying fragmentation dynamics.

Surface Modification of Silicone Rubber for Adhesion Patterning of Mesenchymal Stem Cells by Water Cluster Ion Beam

NASA Astrophysics Data System (ADS)

Sommani, Piyanuch; Ichihashi, Gaku; Ryuto, Hiromichi; Tsuji, Hiroshi; Gotoh, Yasuhito; Takaoka, Gikan H.

2011-01-01

Biocompatibility of silicone rubber sheet (SR) was improved by the water cluster ion irradiation for adhesion patterning of mesenchymal stem cells (MSCs). The water cluster ions were irradiated at acceleration voltage of 6 kV and doses of 1014-1016 ions/cm2. The effect of ion dose on changes in wettability and surface atomic bonding state was observed. Compared to the unirradiated SR, about four-time smoother surface on the irradiated one was observed. Water contact angle decreased with an increase in the ion dose up to 1×1015 ions/cm2. With an increase in ion dose, XPS showed decrease of atomic carbon due to lateral sputtering effect and increase of atomic oxygen due to surface oxidation. After 7 days in vitro culture, the complete adhesion pattern of the rat MSCs was obtained on the irradiated SR at dose of 1×1015 ions/cm2, corresponding to the low contact angle of 87°. At low dose, the partial pattern on the irradiated region was observed instead.

High current H2(+) and H3(+) beam generation by pulsed 2.45 GHz electron cyclotron resonance ion source.

PubMed

Xu, Yuan; Peng, Shixiang; Ren, Haitao; Zhao, Jie; Chen, Jia; Zhang, Ailin; Zhang, Tao; Guo, Zhiyu; Chen, Jia'er

2014-02-01

The permanent magnet 2.45 GHz electron cyclotron resonance ion source at Peking University can produce more than 100 mA hydrogen ion beam working at pulsed mode. For the increasing requirements of cluster ions (H2(+) and H3(+)) in linac and cyclotron, experimental study was carried out to further understand the hydrogen plasma processes in the ion source for the generation of cluster ions. The constituents of extracted beam have been analyzed varying with the pulsed duration from 0.3 ms to 2.0 ms (repetition frequency 100 Hz) at different operation pressure. The fraction of cluster ions dramatically increased when the pulsed duration was lower than 0.6 ms, and more than 20 mA pure H3(+) ions with fraction 43.2% and 40 mA H2(+) ions with fraction 47.7% were obtained when the operation parameters were adequate. The dependence of extracted ion fraction on microwave power was also measured at different pressure as the energy absorbed by plasma will greatly influence electron temperature and electron density then the plasma processes in the ion source. More details will be presented in this paper.

Concentrations and speciation of heavy metals in sludge from nine textile dyeing plants.

PubMed

Liang, Xin; Ning, Xun-an; Chen, Guoxin; Lin, Meiqing; Liu, Jingyong; Wang, Yujie

2013-12-01

The safe disposal of sludge from textile dyeing industry requires research on bioavailability and concentration of heavy metals. In this study, concentrations and chemical speciation of heavy metals (Cd, Cr, Cu, Ni, Zn, Pb) in sludge from nine different textile dyeing plants were examined. Some physiochemical features of sludge from textile dyeing industry were determined, and a sequential extraction procedure recommended by the Community Bureau of Reference (BCR) was used to study the metal speciation. Cluster analysis (CA) and principal component analysis (PCA) were applied to provide additional information regarding differences in sludge composition. The results showed that Zn and Cu contents were the highest, followed by Ni, Cr, Cd and Pb. The concentration of Cd and Ni in some sludge samples exceeded the standard suggested for acidic soils in China (GB18918-2002). In sludge from textile dyeing plants, Pb, Cd and Cr were principally distributed in the oxidizable and residual fraction, Cu in the oxidizable fraction, Ni in all four fractions and Zn in the acid soluble/exchangeable and reducible fractions. The pH and heat-drying method affected the fractionation of heavy metals in sludge. © 2013 Elsevier Inc. All rights reserved.

Inorganic speciation analysis of selenium by ion chromatography-inductively coupled plasma-mass spectrometry and its application to effluents from a petroleum refinery

NASA Astrophysics Data System (ADS)

Miekeley, Norbert; Pereira, Rogério C.; Casartelli, Evelton A.; Almeida, Ana C.; de F. B. Carvalho, Maria

2005-06-01

A new method for the speciation analysis of selenite (Se-IV), selenate (Se-VI), and selenocyanate (SeCN -) is described and first results are presented on the distribution of these species in wastewater samples from a Brazilian oil refinery plant. The method is based on the ion chromatographic separation of these species followed by on-line detection of 77Se, 78Se, and 82Se using quadrupole inductively coupled plasma-mass spectrometry (ICPMS). The system employed consisted of a HPLC pump equipped with a manual syringe loading injector, and an anion exchange column (Metrosep A Supp1), the latter interfaced with the ICPMS via a concentric nebulizer-cyclonic spray chamber sample introduction device. Several eluents already described in the literature for the speciation analysis of inorganic selenium were tested, permitting in most cases a good separation of Se(IV) and Se(VI), however, resulting all in very long residence times (> 30 min) and associated peak broadening for the SeCN - ion. This drawback could be effectively avoided by using as the mobile phase a solution of cyanuric acid (3 mmol L -1), modified with acetonitrile (2% v/v) and percchlorate acid (2.5 mmol L -1). Typical retention times (s) for the three analyte species were: selenite (210) < selenate (250) < selenocyanate (450). Repeatabilities in peak position were better than 1% and in peak area evaluation about 3%. Absolute limits of detection (in ng) for these species using an ELAN 5000 instrument and a 500-μL sample injection loop are 0.04, 0.05 and 0.09, respectively. No certified reference materials were available for this study, however, results on spiked wastewater samples showed acceptable recoveries (80-110%) and repeatabilities (RSD < 5%), thus validating this method for its intended purpose. Once optimized, the method was applied to wastewater samples from an oil refinery plant. In all samples until now analyzed, selenocyanate was by far the most abundant selenium species reaching concentrations of up to 90 μg L -1. Selenite was detected only in one sample and selenate could not identified in any of the samples analyzed. Total concentrations of selenium in most samples, assessed by hydride generation ICPMS and by solution nebulization inductively coupled plasma optical emission spectrometry (ICPOES), exceeded those obtained from speciation analysis, indicating the presence of other selenium species not observed by the here used methodology.

Source Apportionment Using Positive Matrix Factorization on Daily Measurements of Inorganic and Organic Speciated PM2.5

PubMed Central

Dutton, Steven J.; Vedal, Sverre; Piedrahita, Ricardo; Milford, Jana B.; Miller, Shelly L.; Hannigan, Michael P.

2012-01-01

Particulate matter less than 2.5 microns in diameter (PM2.5) has been linked with a wide range of adverse health effects. Determination of the sources of PM2.5 most responsible for these health effects could lead to improved understanding of the mechanisms of such effects and more targeted regulation. This has provided the impetus for the Denver Aerosol Sources and Health (DASH) study, a multi-year source apportionment and health effects study relying on detailed inorganic and organic PM2.5 speciation measurements. In this study, PM2.5 source apportionment is performed by coupling positive matrix factorization (PMF) with daily speciated PM2.5 measurements including inorganic ions, elemental carbon (EC) and organic carbon (OC), and organic molecular markers. A qualitative comparison is made between two models, PMF2 and ME2, commonly used for solving the PMF problem. Many previous studies have incorporated chemical mass balance (CMB) for organic molecular marker source apportionment on limited data sets, but the DASH data set is large enough to use multivariate factor analysis techniques such as PMF. Sensitivity of the PMF2 and ME2 models to the selection of speciated PM2.5 components and model input parameters was investigated in depth. A combination of diagnostics was used to select an optimum, 7-factor model using one complete year of daily data with pointwise measurement uncertainties. The factors included 1) a wintertime/methoxyphenol factor, 2) an EC/sterane factor, 3) a nitrate/polycyclic aromatic hydrocarbon (PAH) factor, 4) a summertime/selective aliphatic factor, 5) an n-alkane factor, 6) a middle oxygenated PAH/alkanoic acid factor and 7) an inorganic ion factor. These seven factors were qualitatively linked with known PM2.5 emission sources with varying degrees of confidence. Mass apportionment using the 7-factor model revealed the contribution of each factor to the mass of OC, EC, nitrate and sulfate. On an annual basis, the majority of OC and EC mass was associated with the summertime/selective aliphatic factor and the EC/sterane factor, respectively, while nitrate and sulfate mass were both dominated by the inorganic ion factor. This apportionment was found to vary substantially by season. Several of the factors identified in this study agree well with similar assessments conducted in St. Louis, MO and Pittsburgh, PA using PMF and organic molecular markers. PMID:22768005

Rumsey and Walker_AMT_2016_Figure 1.xlsx

EPA Pesticide Factsheets

Figure summarizes diurnal profiles of uncertainty in the chemical gradient and transfer velocity measurements from which fluxes are calculated. This dataset is associated with the following publication:Rumsey, I. Application of an online ion chromatography-based instrument for gradient flux measurements of speciated nitrogen and sulfur. ENVIRONMENTAL SCIENCE & TECHNOLOGY. American Chemical Society, Washington, DC, USA, 9(6): 2581-2592, (2016).

The potential of organic (electrospray- and atmospheric pressure chemical ionisation) mass spectrometric techniques coupled to liquid-phase separation for speciation analysis.

PubMed

Rosenberg, Erwin

2003-06-06

The use of mass spectrometry based on atmospheric pressure ionisation techniques (atmospheric pressure chemical ionisation, APCI, and electrospray ionisation, ESI) for speciation analysis is reviewed with emphasis on the literature published in and after 1999. This report accounts for the increasing interest that atmospheric pressure ionisation techniques, and in particular ESI, have found in the past years for qualitative and quantitative speciation analysis. In contrast to element-selective detectors, organic mass spectrometric techniques provide information on the intact metal species which can be used for the identification of unknown species (particularly with MS-MS detection) or the confirmation of the actual presence of species in a given sample. Due to the complexity of real samples, it is inevitable in all but the simplest cases to couple atmospheric pressure MS detection to a separation technique. Separation in the liquid phase (capillary electrophoresis or liquid chromatography in reversed phase, ion chromatographic or size-exclusion mode) is particularly suitable since the available techniques cover a very wide range of analyte polarities and molecular mass. Moreover, derivatisation can normally be avoided in liquid-phase separation. Particularly in complex environmental or biological samples, separation in one dimension is not sufficient for obtaining adequate resolution for all relevant species. In this case, multi-dimensional separation, based on orthogonal separation techniques, has proven successful. ESI-MS is also often used in parallel with inductively coupled plasma MS detection. This review is structured in two parts. In the first, the fundamentals of atmospheric pressure ionisation techniques are briefly reviewed. The second part of the review discusses recent applications including redox species, use of ESI-MS for structural elucidation of metal complexes, characterisation and quantification of small organometallic species with relevance to environment, health and food. Particular attention is given to the characterisation of biomolecules and metalloproteins (metallothioneins and phytochelatins) and to the investigation of the interaction of metals and biomolecules. Particularly in the latter field, ESI-MS is the ideal technique due to the softness of the ionisation process which allows to assume that the detected gas-phase ions are a true representation of the ions or ion-biomolecule complexes prevalent in solution. It is particularly this field, important to biochemistry, physiology and medical chemistry, where we can expect significant developments also in the future.

Ion-pairing reversed-phase chromatography coupled to inductively coupled plasma mass spectrometry as a tool to determine mercurial species in freshwater fish.

PubMed

Cheng, Heyong; Chen, Xiaopan; Shen, Lihuan; Wang, Yuanchao; Xu, Zigang; Liu, Jinhua

2018-01-05

Most of analytical community is focused on reversed phase high performance liquid chromatography (RP-HPLC) for mercury speciation by employing mobile phases comprising of high salts and moderate amounts of organic solvents. This study aims at rapid mercury speciation analysis by ion-pairing RP-HPLC with inductively coupled plasma mass spectrometry (ICP-MS) detection only using low salts for the sake of green analytical chemistry. Two ion-pairing HPLC methods were developed on individual usage of positively and negatively charged ion-pairing reagents (tetrabutylammonium hydroxide -TBAH and sodium dodecylbenzene sulfonate -SDBS), where sodium 3-mercapto-1-propysulfonate (MPS) and l-cysteine (Cys) were individually added in mobile phases to transform mercury species into negative and positive Hg-complexes for good resolution. Addition of phenylalanine was also utilized for rapid baseline separation in combination of short C 18 guard columns. Optimum mobile phases of 2.0mM SDBS+2.0mM Cys+1.0mM Phe (pH 3.0) and 4.0mM TBAH+2.0mM MPS+2.0mM Phe (pH 6.0) both achieved baseline separation of inorganic mercury (Hg 2+ ), methylmercury (MeHg), ethylmercury (EtHg) and phenylmercury (PhHg) on two consecutive 12.5-mm C 18 columns. The former mobile phase was selected for mercury speciation in freshwater fish because of short separation time (3.0min). Detection limits of 0.015 for Hg 2+ , 0.014 for MeHg, 0.028 for EtHg and 0.042μgL -1 for PhHg were obtained along with satisfactory precisions of peak height and area (1.0-2.8% for 5.0μgL -1 Hg-mixture standard). Good accordance of determined values of MeHg and total mercury in certified reference materials of fish tissue (GBW 10029) and tuna fish (BCR-463) with certified values as well as good recoveries (91-106%) proved good accuracy of the proposed method. An example application to freshwater fish indicated its potential in routine analysis, where MeHg was presented at 3.7-20.3μgkg -1 as the dominate species. Copyright © 2017 Elsevier B.V. All rights reserved.

Caesium sputter ion source compatible with commercial SIMS instruments

NASA Astrophysics Data System (ADS)

Belykh, S. F.; Palitsin, V. V.; Veryovkin, I. V.; Kovarsky, A. P.; Chang, R. J. H.; Adriaens, A.; Dowsett, M.; Adams, F.

2006-07-01

A simple design for a caesium sputter cluster ion source compatible with commercially available secondary ion mass spectrometers is reported. This source has been tested with the Cameca IMS 4f instrument using the cluster Si n- and Cu n- ions, and will shortly be retrofitted to the floating low energy ion gun (FLIG) of the type used on the Cameca 4500/4550 quadruple instruments. Our experiments with surface characterization and depth profiling conducted to date demonstrate improvements of analytical capabilities of the SIMS instrument due to the non-additive enhancement of secondary ion emission and shorter ion ranges of polyatomic projectiles compared to atomic ions with the same impact energy.

Selenium Speciation in the Fountain Creek Watershed (Colorado, USA) Correlates with Water Hardness, Ca and Mg Levels.

PubMed

Carsella, James S; Sánchez-Lombardo, Irma; Bonetti, Sandra J; Crans, Debbie C

2017-04-30

The environmental levels of selenium (Se) are regulated and strictly enforced by the Environmental Protection Agency (EPA) because of the toxicity that Se can exert at high levels. However, speciation plays an important role in the overall toxicity of Se, and only when speciation analysis has been conducted will a detailed understanding of the system be possible. In the following, we carried out the speciation analysis of the creek waters in three of the main tributaries-Upper Fountain Creek, Monument Creek and Lower Fountain Creek-located in the Fountain Creek Watershed (Colorado, USA). There are statistically significant differences between the Se, Ca and Mg, levels in each of the tributaries and seasonal swings in Se, Ca and Mg levels have been observed. There are also statistically significant differences between the Se levels when grouped by Pierre Shale type. These factors are considered when determining the forms of Se present and analyzing their chemistry using the reported thermodynamic relationships considering Ca 2+ , Mg 2+ , SeO₄ 2- , SeO₃ 2- and carbonates. This analysis demonstrated that the correlation between Se and water hardness can be explained in terms of formation of soluble CaSeO₄. The speciation analysis demonstrated that for the Fountain Creek waters, the Ca 2+ ion may be mainly responsible for the observed correlation with the Se level. Considering that the Mg 2+ level is also correlating linearly with the Se levels it is important to recognize that without Mg 2+ the Ca 2+ would be significantly reduced. The major role of Mg 2+ is thus to raise the Ca 2+ levels despite the equilibria with carbonate and other anions that would otherwise decrease Ca 2+ levels.

Four groups of new aromatic halogenated disinfection byproducts: effect of bromide concentration on their formation and speciation in chlorinated drinking water.

PubMed

Pan, Yang; Zhang, Xiangru

2013-02-05

Bromide is naturally present in source waters worldwide. Chlorination of drinking water can generate a variety of chlorinated and brominated disinfection byproducts (DBPs). Although substantial efforts have been made to examine the effect of bromide concentration on the formation and speciation of halogenated DBPs, almost all previous studies have focused on trihalomethanes and haloacetic acids. Given that about 50% of total organic halogen formed in chlorination remains unknown, it is still unclear how bromide concentration affects the formation and speciation of the new/unknown halogenated DBPs. In this study, chlorinated drinking water samples with different bromide concentrations were prepared, and a novel approach-precursor ion scan using ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry-was adopted for the detection and identification of polar halogenated DBPs in these water samples. With this approach, 11 new putative aromatic halogenated DBPs were identified, and they were classified into four groups: dihalo-4-hydroxybenzaldehydes, dihalo-4-hydroxybenzoic acids, dihalo-salicylic acids, and trihalo-phenols. A mechanism for the formation of the four groups of new aromatic halogenated DBPs was proposed. It was found that increasing the bromide concentration shifted the entire polar halogenated DBPs as well as the four groups of new DBPs from being less brominated to being more brominated; these new aromatic halogenated DBPs might be important intermediate DBPs formed in drinking water chlorination. Moreover, the speciation of the four groups of new DBPs was modeled: the speciation patterns of the four groups of new DBPs well matched those determined from the model equations, and the reactivity differences between HOBr and HOCl in reactions forming the four groups of new DBPs were larger than those in reactions forming trihalomethanes and haloacetic acids.

Organotin speciation in environmental matrices by automated on-line hydride generation-programmed temperature vaporization-capillary gas chromatography-mass spectrometry detection.

PubMed

Serra, H; Nogueira, J M F

2005-11-11

In the present contribution, a new automated on-line hydride generation methodology was developed for dibutyltin and tributyltin speciation at the trace level, using a programmable temperature-vaporizing inlet followed by capillary gas chromatography coupled to mass spectrometry in the selected ion-monitoring mode acquisition (PTV-GC/MS(SIM)). The methodology involves a sequence defined by two running methods, the first one configured for hydride generation with sodium tetrahydroborate as derivatising agent and the second configured for speciation purposes, using a conventional autosampler and data acquisition controlled by the instrument's software. From the method-development experiments, it had been established that injector configuration has a great effect on the speciation of the actual methodology, particularly, the initial inlet temperature (-20 degrees C; He: 150 ml/min), injection volume (2 microl) and solvent characteristics using the solvent venting mode. Under optimized conditions, a remarkable instrumental performance including very good precision (RSD < 4%), excellent linear dynamic range (up to 50 microg/ml) and limits of detection of 0.12 microg/ml and 9 ng/ml, were obtained for dibutyltin and tributyltin, respectively. The feasibility of the present methodology was validated through assays upon in-house spiked water (2 ng/ml) and a certified reference sediment matrix (Community Bureau of Reference, CRM 462, Nr. 330 dibutyltin: 68+/-12 ng/g; tributyltin: 54+/-15 ng/g on dry mass basis), using liquid-liquid extraction (LLE) and solid-phase extraction (SPE) sample enrichment and multiple injections (2 x 5 microl) for sensitivity enhancement. The methodology evidenced high reproducibility, is easy to work-up, sensitive and showed to be a suitable alternative to replace the currently dedicated analytical systems for organotin speciation in environmental matrices at the trace level.

Ionic liquids improved reversed-phase HPLC on-line coupled with ICP-MS for selenium speciation.

PubMed

Chen, Beibei; He, Man; Mao, Xiangju; Cui, Ran; Pang, Daiwen; Hu, Bin

2011-01-15

Room-temperature ionic liquids (RTILs) improved reversed-phase high performance liquid chromatography (RP-HPLC) on-line combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for selenium speciation. The different parameters affecting the retention behaviors of six target selenium species especially the effect of RTILs as mobile phase additives have been studied, it was found that the mobile phase consisting of 0.4% (v/v) 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), 0.4% (v/v) 1-butyl-2,3-dimethylimidazolium tetrafluroborate ([BMMIM]BF(4)) and 99.2% (v/v) water has effectively improved the peak profile and six target selenium species including Na(2)SeO(3) (Se(IV)), Na(2)SeO(4) (Se(VI)), L-selenocystine (SeCys(2)), D,L-selenomethionine (SeMet), Se-methylseleno-l-cysteine (MeSeCys), seleno-D,L-ethionine (SeEt) were separated in 8 min. In order to validate the accuracy of the method, a Certified Reference Material of SELM-1 yeast sample was analyzed and the results obtained were in good agreement with the certified values. The developed method was also successfully applied to the speciation of selenium in Se-enriched yeasts and clover. For fresh Se-enriched yeast cells, it was found that the spiked SeCys(2) in living yeast cells could be transformed into SeMet. Compared with other ion-pair RP-HPLC-ICP-MS approaches for selenium speciation, the proposed method possessed the advantages including ability to regulate the retention time of the target selenium species by selecting the suitable RTILs and their concentration, simplicity, rapidness and low injection volume, thus providing wide potential applications for elemental speciation in biological systems. Copyright © 2010 Elsevier B.V. All rights reserved.

Kinetic energy distribution of multiply charged ions in Coulomb explosion of Xe clusters.

PubMed

Heidenreich, Andreas; Jortner, Joshua

2011-02-21

We report on the calculations of kinetic energy distribution (KED) functions of multiply charged, high-energy ions in Coulomb explosion (CE) of an assembly of elemental Xe(n) clusters (average size (n) = 200-2171) driven by ultra-intense, near-infrared, Gaussian laser fields (peak intensities 10(15) - 4 × 10(16) W cm(-2), pulse lengths 65-230 fs). In this cluster size and pulse parameter domain, outer ionization is incomplete∕vertical, incomplete∕nonvertical, or complete∕nonvertical, with CE occurring in the presence of nanoplasma electrons. The KEDs were obtained from double averaging of single-trajectory molecular dynamics simulation ion kinetic energies. The KEDs were doubly averaged over a log-normal cluster size distribution and over the laser intensity distribution of a spatial Gaussian beam, which constitutes either a two-dimensional (2D) or a three-dimensional (3D) profile, with the 3D profile (when the cluster beam radius is larger than the Rayleigh length) usually being experimentally realized. The general features of the doubly averaged KEDs manifest the smearing out of the structure corresponding to the distribution of ion charges, a marked increase of the KEDs at very low energies due to the contribution from the persistent nanoplasma, a distortion of the KEDs and of the average energies toward lower energy values, and the appearance of long low-intensity high-energy tails caused by the admixture of contributions from large clusters by size averaging. The doubly averaged simulation results account reasonably well (within 30%) for the experimental data for the cluster-size dependence of the CE energetics and for its dependence on the laser pulse parameters, as well as for the anisotropy in the angular distribution of the energies of the Xe(q+) ions. Possible applications of this computational study include a control of the ion kinetic energies by the choice of the laser intensity profile (2D∕3D) in the laser-cluster interaction volume.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOEpatents

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

2017-01-24

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Static time-of-flight secondary ion mass spectrometry analysis of microelectronics related substrates using a polyatomic ion source

NASA Astrophysics Data System (ADS)

Ravanel, X.; Trouiller, C.; Juhel, M.; Wyon, C.; Kwakman, L. F. Tz.; Léonard, D.

2008-12-01

Recent time-of-flight secondary ion mass spectrometry studies using primary ion cluster sources such as Au n+, SF 5+, Bi n+ or C 60+ have shown the great advantages in terms of secondary ion yield enhancement and ion formation efficiency of polyatomic ion sources as compared to monoatomic ion sources like the commonly used Ga +. In this work, the effective gains provided by such a source in the static ToF-SIMS analysis of microelectronics devices were investigated. Firstly, the influence of the number of atoms in the primary cluster ion on secondary ion formation was studied for physically adsorbed di-isononyl phthalate (DNP) (plasticizer) and perfluoropolyether (PFPE). A drastic increase in secondary ion formation efficiency and a much lower detection limit were observed when using a polyatomic primary ion. Moreover, the yield of the higher mass species was much enhanced indicating a lower degree of fragmentation that can be explained by the fact that the primary ion energy is spread out more widely, or that there is a lower energy per incoming ion. Secondly, the influence of the number of Bi atoms in the Bi n primary ion on the information depth was studied using reference thermally grown silicon oxide samples. The information depth provided by a Bi n cluster was shown to be lowered when the number of atoms in the aggregate was increased.

Dual shell-like magnetic clusters containing Ni(II) and Ln(III) (Ln = La, Pr, and Nd) ions.

PubMed

Kong, Xiang-Jian; Ren, Yan-Ping; Long, La-Sheng; Zheng, Zhiping; Nichol, Gary; Huang, Rong-Bin; Zheng, Lan-Sun

2008-04-07

Dual shell-like nanoscopic magnetic clusters featuring a polynuclear nickel(II) framework encapsulating that of lanthanide ions (Ln = La, Pr, and Nd) were synthesized using Ni(NO3)(2).6H2O, Ln(NO3)(3).6H2O, and iminodiacetic acid (IDA) under hydrothermal conditions. Structurally established by crystallographic studies, these clusters are [La20Ni30(IDA)30(CO3)6(NO3)6(OH)30(H2O)12](CO3)(6).72H2O (1), [Ln20Ni21(C4H5NO4)21(OH)24(C2H2O3)6(C2O4)3(NO3)9(H2O)12](NO3)9.nH2O [C2H2O3 is the alkoxide form of glycolate; Ln = Pr (2), n = 42; Nd (3), n = 50], and {[La4Ni5Na(IDA)5(CO3)(NO3)4(OH)5(H2O)5][CO3].10H2O} infinity (4). Carbonate, oxalate, and glycolate are products of hydrothermal decomposition of IDA. Compositions of these compounds were confirmed by satisfactory elemental analyses. It has been found that the cluster structure is dependent on the identity of the lanthanide ion as well as the starting Ln/Ni/IDA ratio. The cationic cluster of 1 features a core of the Keplerate type with an outer icosidodecahedron of Ni(II) ions encaging a dodecahedral kernel of La(III). Clusters 2 and 3, distinctly different from 1, are isostructural, possessing a core of an outer shell of 21 Ni(II) ions encapsulating an inner shell of 20 Ln(III) ions. Complex 4 is a three-dimensional assembly of cluster building blocks connected by units of Na(NO3)/La(NO3)3; the structure of the building block resembles closely that of 1, with a hydrated La(III) ion internalized in the decanuclear cage being an extra feature. Magnetic studies indicated ferromagnetic interactions in 1, while overall antiferromagnetic interactions were revealed for 2 and 3. The polymeric, three-dimensional cluster network 4 displayed interesting ferrimagnetic interactions.

Equilibrium Speciation of Select Lanthanides in the Presence of Acidic Ligands in Homo- and Heterogeneous Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robinson, Troy A

2011-08-01

This dissertation explores lanthanide speciation in liquid solution systems related to separation schemes involving the acidic ligands: bis(2-ethylhexyl) phosphoric acid (HDEHP), lactate, and 8-hydroxyquinoline. Equilibrium speciation of neodymium (Nd 3+), sodium (Na+), HDEHP, water, and lactate in the TALSPEAK liquid-liquid extraction system was explored under varied Nd 3+ loading of HDEHP in the organic phase and through extraction from aqueous HCl and lactate media. System speciation was probed through vapor pressure osmometry, visible and Fourier Transform Infrared (FTIR) spectroscopy, 22Na and 13C labeled lactate radiotracer distribution measurements, Karl Fischer titrations, and equilibrium pH measurements. Distribution of Nd 3+, Na +,more » lactate, and equilibrium pH were modeled using the SXLSQI software to obtain logKNd and logKNa extraction constants under selected conditions. Results showed that high Nd 3+ loading of the HDEHP led to Nd 3+ speciation that departs from the ion exchange mechanism and includes formation of highly aggregated, polynuclear [NdLactate(DEHP) 2] x; (with x > 1). By substituting lanthanum (La 3+) for Nd 3+ in this system, NMR scoping experiments using 23Na, 31P nuclei and 13C labeled lactate were performed. Results indicated that this technique is sensitive to changes in system speciation, and that further experiments are warranted. In a homogeneous system representing the TALSPEAK aqueous phase, Lactate protonation behavior at various temperatures was characterized using a combination of potentiometric titration and modeling with the Hyperquad computer program. The temperature dependent deprotonation behavior of lactate showed little change with temperature at 2.0 M NaCl ionic strength. Cloud point extraction is a non-traditional separation technique that starts with a homogeneous phase that becomes heterogeneous by the micellization of surfactants through the increase of temperature. To better understand the behavior of europium (Eu 3+) and 8-hydroxyquinoline under cloud point extraction conditions, potentiometric and spectrophotometric titrations coupled with modeling with Hyperquad and SQUAD computer programs were performed to assess europium (Eu 3+) and 8-hydroxyquinoline speciation. Experiments in both water and a 1wt% Triton X-114/water mixed solvent were compared to understand the effect of Triton X-114 on the system speciation. Results indicated that increased solvation of 8-hydroxyquinoline by the mixed solvent lead to more stable complexes involving 8-hydroxyquinoline than in water, whereas competition between hydroxide and Triton X-114 for Eu 3+ led to lower stability hydrolysis complexes in the mixed solvent than in water. Lanthanide speciation is challenging due to the trivalent oxidation state that leads to multiple ligand complexes, including some mixed complexes. The complexity of the system demands well-designed and precise experiments that capture the nuances of the chemistry. This work increased the understanding of lanthanide speciation in the explored systems, but more work is required to produce a comprehensive understanding of the speciation involved.« less

Insight into acid-base nucleation experiments by comparison of the chemical composition of positive, negative, and neutral clusters.

PubMed

Bianchi, Federico; Praplan, Arnaud P; Sarnela, Nina; Dommen, Josef; Kürten, Andreas; Ortega, Ismael K; Schobesberger, Siegfried; Junninen, Heikki; Simon, Mario; Tröstl, Jasmin; Jokinen, Tuija; Sipilä, Mikko; Adamov, Alexey; Amorim, Antonio; Almeida, Joao; Breitenlechner, Martin; Duplissy, Jonathan; Ehrhart, Sebastian; Flagan, Richard C; Franchin, Alessandro; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Kangasluoma, Juha; Keskinen, Helmi; Kim, Jaeseok; Kirkby, Jasper; Laaksonen, Ari; Lawler, Michael J; Lehtipalo, Katrianne; Leiminger, Markus; Makhmutov, Vladimir; Mathot, Serge; Onnela, Antti; Petäjä, Tuukka; Riccobono, Francesco; Rissanen, Matti P; Rondo, Linda; Tomé, António; Virtanen, Annele; Viisanen, Yrjö; Williamson, Christina; Wimmer, Daniela; Winkler, Paul M; Ye, Penglin; Curtius, Joachim; Kulmala, Markku; Worsnop, Douglas R; Donahue, Neil M; Baltensperger, Urs

2014-12-02

We investigated the nucleation of sulfuric acid together with two bases (ammonia and dimethylamine), at the CLOUD chamber at CERN. The chemical composition of positive, negative, and neutral clusters was studied using three Atmospheric Pressure interface-Time Of Flight (APi-TOF) mass spectrometers: two were operated in positive and negative mode to detect the chamber ions, while the third was equipped with a nitrate ion chemical ionization source allowing detection of neutral clusters. Taking into account the possible fragmentation that can happen during the charging of the ions or within the first stage of the mass spectrometer, the cluster formation proceeded via essentially one-to-one acid-base addition for all of the clusters, independent of the type of the base. For the positive clusters, the charge is carried by one excess protonated base, while for the negative clusters it is carried by a deprotonated acid; the same is true for the neutral clusters after these have been ionized. During the experiments involving sulfuric acid and dimethylamine, it was possible to study the appearance time for all the clusters (positive, negative, and neutral). It appeared that, after the formation of the clusters containing three molecules of sulfuric acid, the clusters grow at a similar speed, independent of their charge. The growth rate is then probably limited by the arrival rate of sulfuric acid or cluster-cluster collision.

FTMS studies of sputtered metal cluster ions (IV): size-selective effects in the chemistry of Fe{/n +} with NH3 and Pd{/n +} with D2 or C2H4

NASA Astrophysics Data System (ADS)

Irion, M. P.; Selinger, A.; Schnabel, P.

1991-03-01

Fe{/n +} and Pd{/n +} clusters up to n=19 and n=25, respectively, are produced in an external ion source by sputtering of the respective metal foils with Xe+ primary ions at 20 keV. They are transferred to the ICR cell of a home-built Fourier transform mass spectrometer, where they are thermalized to nearly room temperature and stored for several tens of seconds. During this time, their reactions with a gas leaked in at low level are studied. Thus in the presence of ammonia, most Fe{/n +} clusters react by simply adsorbing intact NH3 molecules. Only Fe{4/+} ions show dehydrogenation/adsorption to Fe4(NH){/m +} intermediates ( m=1, 2) that in a complex scheme go on adsorbing complete NH3 units. To clarify the reaction scheme, one has to isolate each species in the ion cell, which often requires the ejection of ions very close in mass. This led to the development of a special isolation technique that avoids the use of isotopically pure metal samples. Pd{n/+} cluster ions ( n=2...9) dehydrogenate C2H4 in general to yield Pd n (C2H2)+, yet Pd{6/+} appear totally unreactive. Towards D2, Pd{7/+} ions seem inert, whereas Pd{8/+} adsorb up to two molecules.

Synthetic humic substances and their use for remediation of contaminated environments

NASA Astrophysics Data System (ADS)

Dudare, Diana; Klavins, Maris

2014-05-01

Soils are increasingly subjected to different chemical stresses, because of increasing industrialization process and other factors. Different anthropogenic compounds (organic or inorganic in nature) upon entering the soil, may not only influence its productivity potential, but may also affect the quality of groundwater and food chain. Consequently, soils of different environments contain a complex mixture of contaminants, such as oil products, metals, organic solvents, acids, bases and radionuclides. Thereby greater focus should be paid to risk assessment and evaluation of remedial techniques in order to restore the quality of the soil and groundwater. The treatment technologies presently used to remove contaminants are physical, chemical and biological technologies. Many functional groups in the structure of humic substances determine their ability to interact with metal ions forming stable complexes and influencing speciation of metal ions in the environment, as well mobility, behaviour and speciation forms in the environment. Humic substances are suggested for use in the remediation of environments contaminated with metals, owing to complex forming properties. Several efforts have been undertaken with respect to synthesize humic substances for their structural studies. At the same time the real number of methods suggested for synthesis of humic substances is highly limited and their synthesis in general has been used mostly for their structural analysis. The present study deals with development of approaches for synthesis of humic substances with increased complex forming ability in respect to metal ions. Industrially produced humic substances (TEHUM) were used for comparison and after their modification their properties were analyzed for their elemental composition; functional group content changes in spectral characteristics. Synthetic humic substances showed significant differences in the number of functional groups and in ability to interact with the metal ions, which were reflected in their complexation properties towards metal ions. FTIR spectra gave evidence of the presence of metal ions, strongly bound and protected in inner sphere complexes. Considering a large scale of production of humic substances, the obtained synthetic humic substances with modified properties are perspective and sustainable areas of use. The obtained results of this study showed that synthetic humic substances can be used for remediation of environments contaminated with heavy metal ions.

Characterization of deuterium clusters mixed with helium gas for an application in beam-target-fusion experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bang, W.; Quevedo, H. J.; Bernstein, A. C.

We measured the average deuterium cluster size within a mixture of deuterium clusters and helium gas by detecting Rayleigh scattering signals. The average cluster size from the gas mixture was comparable to that from a pure deuterium gas when the total backing pressure and temperature of the gas mixture were the same as those of the pure deuterium gas. According to these measurements, the average size of deuterium clusters depends on the total pressure and not the partial pressure of deuterium in the gas mixture. To characterize the cluster source size further, a Faraday cup was used to measure themore » average kinetic energy of the ions resulting from Coulomb explosion of deuterium clusters upon irradiation by an intense ultrashort pulse. The deuterium ions indeed acquired a similar amount of energy from the mixture target, corroborating our measurements of the average cluster size. As the addition of helium atoms did not reduce the resulting ion kinetic energies, the reported results confirm the utility of using a known cluster source for beam-target-fusion experiments by introducing a secondary target gas.« less

Characterization of deuterium clusters mixed with helium gas for an application in beam-target-fusion experiments

DOE PAGES

Bang, W.; Quevedo, H. J.; Bernstein, A. C.; ...

2014-12-10

We measured the average deuterium cluster size within a mixture of deuterium clusters and helium gas by detecting Rayleigh scattering signals. The average cluster size from the gas mixture was comparable to that from a pure deuterium gas when the total backing pressure and temperature of the gas mixture were the same as those of the pure deuterium gas. According to these measurements, the average size of deuterium clusters depends on the total pressure and not the partial pressure of deuterium in the gas mixture. To characterize the cluster source size further, a Faraday cup was used to measure themore » average kinetic energy of the ions resulting from Coulomb explosion of deuterium clusters upon irradiation by an intense ultrashort pulse. The deuterium ions indeed acquired a similar amount of energy from the mixture target, corroborating our measurements of the average cluster size. As the addition of helium atoms did not reduce the resulting ion kinetic energies, the reported results confirm the utility of using a known cluster source for beam-target-fusion experiments by introducing a secondary target gas.« less

Charging Properties of Cassiterite (alpha-SnO2) surfaces in NaCl and RbCl Ionic Media.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rosenqvist, Jorgen K; Machesky, Michael L.; Vlcek, Lukas

2009-01-01

The acid-base properties of cassiterite (alpha-SnO2) surfaces at 10-50 degrees C were studied using potentiometric titrations of powder suspensions in aqueous NaCl and RbCl media. The proton sorption isotherms exhibited common intersection points in the pH range of 4.0-4.5 under all conditions, and the magnitude of charging was similar but not identical in NaCl and RbCl. The hydrogen bonding configuration at the oxide-water interface, obtained from classical molecular dynamics (MD) simulations, was analyzed in detail, and the results were explicitly incorporated in calculations of protonation constants for the reactive surface sites using the revised MUSIC model. The calculations indicated thatmore » the terminal SnOH2 group is more acidic than the bridging Sn2OH group, with protonation constants (log KH) of 3.60 and 5.13 at 25 degrees C, respectively. This is contrary to the situation on the isostructural alpha-TiO2 (rutile), apparently because of the difference in electronegativity between Ti and Sn. MD simulations and speciation calculations indicated considerable differences in the speciation of Na+ and Rb+, despite the similarities in overall charging. Adsorbed sodium ions are almost exclusively found in bidentate surface complexes, whereas adsorbed rubidium ions form comparable numbers of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na+ between the different complexes shows a considerable dependence on the surface charge density (pH), whereas the distribution of adsorbed Rb+ is almost independent of pH. A surface complexation model (SCM) capable of accurately describing both the measured surface charge and the MD-predicted speciation of adsorbed Na+/Rb+ was formulated. According to the SCM, the deprotonated terminal group (SnOH(-0.40)) and the protonated bridging group (Sn2OH+0.36) dominate the surface speciation over the entire pH range of this study (2.7-10). The complexation of medium cations increases significantly with increasing negative surface charge, and at pH 10, roughly 40% of the terminal sites are predicted to form cation complexes, whereas anion complexation is minor throughout the studied pH range.« less

Charging properties of cassiterite (alfa-SnO2) surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rosenqvist, Jorgen K; Machesky, Michael L.; Vlcek, L.

The acid-base properties of cassiterite (alfa-SnO2) surfaces at 10 50 C were studied using potentiometric titrations of powder suspensions in aqueous NaCl and RbCl media. The proton sorption isotherms exhibited common intersection points in the pH-range 4.0 to 4.5 at all conditions and the magnitude of charging was similar but not identical in NaCl and RbCl. The hydrogen bonding configuration at the oxide-water interface, obtained from classical Molecular Dynamics (MD) simulations, was analyzed in detail and the results were explicitly incorporated in calculations of protonation constants for the reactive surface sites using the revised MUSIC model. The calculations indicated thatmore » the terminal SnOH2 group is more acidic than the bridging Sn2OH group, with protonation constants (log KH) of 3.60 and 5.13 at 25 C, respectively. This is contrary to the situation on the isostructural alfa-TiO2 (rutile), apparently due to the difference in electronegativity between Ti and Sn. MD simulations and speciation calculations indicated considerable differences in the speciation of Na+ and Rb+, despite the similarities in overall charging. Adsorbed sodium ions are almost exclusively found in bidentate surface complexes, while adsorbed rubidium ions form comparable amounts of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na+ between the different complexes shows a considerable dependence on surface charge density (pH), while the distribution of adsorbed Rb+ is almost independent of pH. A Surface Complexation Model (SCM) capable of accurately describing both the measured surface charge and the MD predicted speciation of adsorbed Na+/Rb+ was formulated. According to the SCM, the deprotonated terminal group (SnOH-0.40) and the protonated bridging group (Sn2OH+0.36) dominate the surface speciation over the entire pH-range (2.7 10), illustrating the ability of positively and negatively charged surface groups to coexist. Complexation of the medium cations increases significantly with increasing negative surface charge and at pH 10 roughly 40 percent of the terminal sites are predicted to form cation complexes, while anion complexation is minor throughout the studied pH-range.« less

ZnS Buffer Layers Grown by Modified Chemical Bath Deposition for CIGS Solar Cells

NASA Astrophysics Data System (ADS)

Lee, Dongchan; Ahn, Heejin; Shin, Hyundo; Um, Youngho

2018-03-01

ZnS thin films were prepared by the chemical bath deposition method using disodium ethylene-diaminetetraacetic acid and hexamethylenetetramine as complexing agents in acidic conditions. The film prepared using a preheated S-ion source showed full surface coverage, but some clusters were found that were generated by the cluster-by-cluster reaction mechanism. On the other hand, the film prepared without this source had a uniform, dense, and smooth surface and showed fewer clusters than the film prepared using a preheated S-ion source. The x-ray photoelectron spectroscopy spectra showed the energy core levels of Zn, O, and S components, and Zn-OH bonding decreased on the film using the preheated S-ion source. Especially, various binding energy peaks were found in the Zn 2p 3/2 spectrum by Gaussian function fitting, and no peak corresponding to Zn-OH bonding was found for the film prepared using a preheated S-ion source. Moreover, the x-ray diffraction spectrum of the ZnS thin film using a non-preheated S-ion source showed amorphous or nanoscale crystallinity, but the emission peaks indicated that the structure of the film using preheated S-ion source was zincblende.

ZnS Buffer Layers Grown by Modified Chemical Bath Deposition for CIGS Solar Cells

NASA Astrophysics Data System (ADS)

Lee, Dongchan; Ahn, Heejin; Shin, Hyundo; Um, Youngho

2018-07-01

ZnS thin films were prepared by the chemical bath deposition method using disodium ethylene-diaminetetraacetic acid and hexamethylenetetramine as complexing agents in acidic conditions. The film prepared using a preheated S-ion source showed full surface coverage, but some clusters were found that were generated by the cluster-by-cluster reaction mechanism. On the other hand, the film prepared without this source had a uniform, dense, and smooth surface and showed fewer clusters than the film prepared using a preheated S-ion source. The x-ray photoelectron spectroscopy spectra showed the energy core levels of Zn, O, and S components, and Zn-OH bonding decreased on the film using the preheated S-ion source. Especially, various binding energy peaks were found in the Zn 2 p 3/2 spectrum by Gaussian function fitting, and no peak corresponding to Zn-OH bonding was found for the film prepared using a preheated S-ion source. Moreover, the x-ray diffraction spectrum of the ZnS thin film using a non-preheated S-ion source showed amorphous or nanoscale crystallinity, but the emission peaks indicated that the structure of the film using preheated S-ion source was zincblende.

Comparison of gain degradation and deep level transient spectroscopy in pnp Si bipolar junction transistors irradiated with different ion species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aguirre, B. A.; Bielejec, E.; Fleming, R. M.

Here, we studied the effect of light ion and heavy ion irradiations on pnp Si BJTs. A mismatch in DLTS deep peak amplitude for devices with same final gain but irradiated with different ion species was observed. Also, different ions cause different gain degradation when the DLTS spectra are matched. Pre-dosed ion-irradiated samples show that ion induced ionization does not account for the differences in DLTS peak height but isochronal annealing studies suggest that light ions produce more VP defects than heavy ions to compensate for the lack of clusters that heavy ions produce. The creation of defect clusters bymore » heavy ions is evident by the higher content of E4 and V* 2 defects compared to light ions.« less

Comparison of gain degradation and deep level transient spectroscopy in pnp Si bipolar junction transistors irradiated with different ion species

DOE PAGES

Aguirre, B. A.; Bielejec, E.; Fleming, R. M.; ...

2016-12-09

Here, we studied the effect of light ion and heavy ion irradiations on pnp Si BJTs. A mismatch in DLTS deep peak amplitude for devices with same final gain but irradiated with different ion species was observed. Also, different ions cause different gain degradation when the DLTS spectra are matched. Pre-dosed ion-irradiated samples show that ion induced ionization does not account for the differences in DLTS peak height but isochronal annealing studies suggest that light ions produce more VP defects than heavy ions to compensate for the lack of clusters that heavy ions produce. The creation of defect clusters bymore » heavy ions is evident by the higher content of E4 and V* 2 defects compared to light ions.« less

Speciation of the major inorganic salts in atmospheric aerosols of Beijing, China: Measurements and comparison with model

NASA Astrophysics Data System (ADS)

Tang, Xiong; Zhang, Xiaoshan; Ci, Zhijia; Guo, Jia; Wang, Jiaqi

2016-05-01

In the winter and summer of 2013-2014, we used a sampling system, which consists of annular denuder, back-up filter and thermal desorption set-up, to measure the speciation of major inorganic salts in aerosols and the associated trace gases in Beijing. This sampling system can separate volatile ammonium salts (NH4NO3 and NH4Cl) from non-volatile ammonium salts ((NH4)2SO4), as well as the non-volatile nitrate and chloride. The measurement data was used as input of a thermodynamic equilibrium model (ISORROPIA II) to investigate the gas-aerosol equilibrium characteristics. Results show that (NH4)2SO4, NH4NO3 and NH4Cl were the major inorganic salts in aerosols and mainly existed in the fine particles. The sulfate, nitrate and chloride associated with crustal ions were also important in Beijing where mineral dust concentrations were high. About 19% of sulfate in winter and 11% of sulfate in summer were associated with crustal ions and originated from heterogeneous reactions or direct emissions. The non-volatile nitrate contributed about 33% and 15% of nitrate in winter and summer, respectively. Theoretical thermodynamic equilibrium calculations for NH4NO3 and NH4Cl suggest that the gaseous precursors were sufficient to form stable volatile ammonium salts in winter, whereas the internal mixing with sulfate and crustal species were important for the formation of volatile ammonium salts in summer. The results of the thermodynamic equilibrium model reasonably agreed with the measurements of aerosols and gases, but large discrepancy existed in predicting the speciation of inorganic ammonium salts. This indicates that the assumption on crustal species in the model was important for obtaining better understanding on gas-aerosol partitioning and improving the model prediction.

Role of isolated and clustered DNA damage and the post-irradiating repair process in the effects of heavy ion beam irradiation.

PubMed

Tokuyama, Yuka; Furusawa, Yoshiya; Ide, Hiroshi; Yasui, Akira; Terato, Hiroaki

2015-05-01

Clustered DNA damage is a specific type of DNA damage induced by ionizing radiation. Any type of ionizing radiation traverses the target DNA molecule as a beam, inducing damage along its track. Our previous study showed that clustered DNA damage yields decreased with increased linear energy transfer (LET), leading us to investigate the importance of clustered DNA damage in the biological effects of heavy ion beam radiation. In this study, we analyzed the yield of clustered base damage (comprising multiple base lesions) in cultured cells irradiated with various heavy ion beams, and investigated isolated base damage and the repair process in post-irradiation cultured cells. Chinese hamster ovary (CHO) cells were irradiated by carbon, silicon, argon and iron ion beams with LETs of 13, 55, 90 and 200 keV µm(-1), respectively. Agarose gel electrophoresis of the cells with enzymatic treatments indicated that clustered base damage yields decreased as the LET increased. The aldehyde reactive probe procedure showed that isolated base damage yields in the irradiated cells followed the same pattern. To analyze the cellular base damage process, clustered DNA damage repair was investigated using DNA repair mutant cells. DNA double-strand breaks accumulated in CHO mutant cells lacking Xrcc1 after irradiation, and the cell viability decreased. On the other hand, mouse embryonic fibroblast (Mef) cells lacking both Nth1 and Ogg1 became more resistant than the wild type Mef. Thus, clustered base damage seems to be involved in the expression of heavy ion beam biological effects via the repair process. © The Author 2015. Published by Oxford University Press on behalf of The Japan Radiation Research Society and Japanese Society for Radiation Oncology.

A meteor ablation-cluster ion atmospheric sodium theory

NASA Technical Reports Server (NTRS)

Richter, E. S.; Sechrist, C. F., Jr.

1979-01-01

Neutral and ionic forms of sodium form narrow, well-defined layers which peak in the 90-95 km altitude region at midlatitudes. A new theory for the sodium layer is presented, which is found to be in good agreement with existing atmospheric observations as well as available laboratory measurements of rate constants. The layer is believed to result naturally from a meteor ablation source over a chemical sink with vertical transport of Na(+) playing an important role in the layer shape and variation. While the neutral chemistry is believed to consist of chemical equilibrium between Na and NaO, the ion chemistry departs from earlier studies and considers a cluster ion scheme. It is possible that higher-order cluster ions of sodium play a role in the formation of aerosols, through attachment or ion-induced nucleation processes.

Inhibition of precipitation of carbonate apatite by trisodium citrate analysed in base of the formation of chemical complexes in growth solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prywer, Jolanta, E-mail: jolanta.prywer@p.lodz.pl; Olszynski, Marcin; Mielniczek-Brzóska, Ewa

2015-11-15

Effect of trisodium citrate on the precipitation of carbonate apatite is studied. The experimental series are performed in the solution of artificial urine. The investigations are related to infectious urinary stones formation as carbonate apatite is one of the main components of this kind of stones. To mimic a real infection in urinary tract the aqueous ammonia solution was added to the solution of artificial urine. The spectrophotometric results demonstrate that trisodium citrate increases induction time with respect to carbonate apatite formation and decreases the efficiency of carbonate apatite precipitation. The inhibitory effect of trisodium citrate on the precipitation ofmore » carbonate apatite is explained in base of chemical speciation analysis. Such an analysis demonstrates that the inhibitory effect is mainly related with the fact that trisodium citrate binds Ca{sup 2+} ions and causes the formation of CaCit{sup −} and Ca{sub 10}(PO{sub 4}){sub 6}CO{sub 3} complexes. Trisodium citrate binds Ca{sup 2+} ions in the range of pH from 6 to 9.5 for which carbonate apatite is favored to be formed. - Highlights: • Trisodium citrate (TC) increases induction time of carbonate apatite (CA) formation. • TC decreases the efficiency of CA precipitation. • The inhibitory effect of TC is explained in base of chemical speciation analysis. • The inhibitory effect is mainly related with the fact that TC binds Ca{sup 2+} ions. • TC binds Ca{sup 2+} ions in the range of pH from 6 to 9.5 for which CA is formed.« less

Interspecific and intraspecific gene variability in a 1-Mb region containing the highest density of NBS-LRR genes found in the melon genome.

PubMed

González, Víctor M; Aventín, Núria; Centeno, Emilio; Puigdomènech, Pere

2014-12-17

Plant NBS-LRR -resistance genes tend to be found in clusters, which have been shown to be hot spots of genome variability. In melon, half of the 81 predicted NBS-LRR genes group in nine clusters, and a 1 Mb region on linkage group V contains the highest density of R-genes and presence/absence gene polymorphisms found in the melon genome. This region is known to contain the locus of Vat, an agronomically important gene that confers resistance to aphids. However, the presence of duplications makes the sequencing and annotation of R-gene clusters difficult, usually resulting in multi-gapped sequences with higher than average errors. A 1-Mb sequence that contains the largest NBS-LRR gene cluster found in melon was improved using a strategy that combines Illumina paired-end mapping and PCR-based gap closing. Unknown sequence was decreased by 70% while about 3,000 SNPs and small indels were corrected. As a result, the annotations of 18 of a total of 23 NBS-LRR genes found in this region were modified, including additional coding sequences, amino acid changes, correction of splicing boundaries, or fussion of ORFs in common transcription units. A phylogeny analysis of the R-genes and their comparison with syntenic sequences in other cucurbits point to a pattern of local gene amplifications since the diversification of cucurbits from other families, and through speciation within the family. A candidate Vat gene is proposed based on the sequence similarity between a reported Vat gene from a Korean melon cultivar and a sequence fragment previously absent in the unrefined sequence. A sequence refinement strategy allowed substantial improvement of a 1 Mb fragment of the melon genome and the re-annotation of the largest cluster of NBS-LRR gene homologues found in melon. Analysis of the cluster revealed that resistance genes have been produced by sequence duplication in adjacent genome locations since the divergence of cucurbits from other close families, and through the process of speciation within the family a candidate Vat gene was also identified using sequence previously unavailable, which demonstrates the advantages of genome assembly refinements when analyzing complex regions such as those containing clusters of highly similar genes.

Changes in cluster magnetism and suppression of local superconductivity in amorphous FeCrB alloy irradiated by Ar+ ions

NASA Astrophysics Data System (ADS)

Okunev, V. D.; Samoilenko, Z. A.; Szymczak, H.; Szewczyk, A.; Szymczak, R.; Lewandowski, S. J.; Aleshkevych, P.; Malinowski, A.; Gierłowski, P.; Więckowski, J.; Wolny-Marszałek, M.; Jeżabek, M.; Varyukhin, V. N.; Antoshina, I. A.

2016-02-01

We show that сluster magnetism in ferromagnetic amorphous Fe67Cr18B15 alloy is related to the presence of large, D=150-250 Å, α-(Fe Cr) clusters responsible for basic changes in cluster magnetism, small, D=30-100 Å, α-(Fe, Cr) and Fe3B clusters and subcluster atomic α-(Fe, Cr, B) groupings, D=10-20 Å, in disordered intercluster medium. For initial sample and irradiated one (Φ=1.5×1018 ions/cm2) superconductivity exists in the cluster shells of metallic α-(Fe, Cr) phase where ferromagnetism of iron is counterbalanced by antiferromagnetism of chromium. At Φ=3×1018 ions/cm2, the internal stresses intensify and the process of iron and chromium phase separation, favorable for mesoscopic superconductivity, changes for inverse one promoting more homogeneous distribution of iron and chromium in the clusters as well as gigantic (twice as much) increase in density of the samples. As a result, in the cluster shells ferromagnetism is restored leading to the increase in magnetization of the sample and suppression of local superconductivity. For initial samples, the temperature dependence of resistivity ρ(T) T2 is determined by the electron scattering on quantum defects. In strongly inhomogeneous samples, after irradiation by fluence Φ=1.5×1018 ions/cm2, the transition to a dependence ρ(T) T1/2 is caused by the effects of weak localization. In more homogeneous samples, at Φ=3×1018 ions/cm2, a return to the dependence ρ(T) T2 is observed.

Influence of 400 keV carbon ion implantation on structural, optical and electrical properties of PMMA

NASA Astrophysics Data System (ADS)

Arif, Shafaq; Rafique, M. Shahid; Saleemi, Farhat; Sagheer, Riffat; Naab, Fabian; Toader, Ovidiu; Mahmood, Arshad; Rashid, Rashad; Mahmood, Mazhar

2015-09-01

Ion implantation is a useful technique to modify surface properties of polymers without altering their bulk properties. The objective of this work is to explore the 400 keV C+ ion implantation effects on PMMA at different fluences ranging from 5 × 1013 to 5 × 1015 ions/cm2. The surface topographical examination of irradiated samples has been performed using Atomic Force Microscope (AFM). The structural and chemical modifications in implanted PMMA are examined by Raman and Fourier Infrared Spectroscopy (FTIR) respectively. The effects of carbon ion implantation on optical properties of PMMA are investigated by UV-Visible spectroscopy. The modifications in electrical conductivity have been measured using a four point probe technique. AFM images reveal a decrease in surface roughness of PMMA with an increase in ion fluence from 5 × 1014 to 5 × 1015 ions/cm2. The existence of amorphization and sp2-carbon clusterization has been confirmed by Raman and FTIR spectroscopic analysis. The UV-Visible data shows a prominent red shift in absorption edge as a function of ion fluence. This shift displays a continuous reduction in optical band gap (from 3.13 to 0.66 eV) due to formation of carbon clusters. Moreover, size of carbon clusters and photoconductivity are found to increase with increasing ion fluence. The ion-induced carbonaceous clusters are believed to be responsible for an increase in electrical conductivity of PMMA from (2.14 ± 0.06) × 10-10 (Ω-cm)-1 (pristine) to (0.32 ± 0.01) × 10-5 (Ω-cm)-1 (irradiated sample).

Contact ion pair formation between hard acids and soft bases in aqueous solutions observed with 2DIR spectroscopy.

PubMed

Sun, Zheng; Zhang, Wenkai; Ji, Minbiao; Hartsock, Robert; Gaffney, Kelly J

2013-12-12

The interaction of charged species in aqueous solution has important implications for chemical, biological, and environmental processes. We have used 2DIR spectroscopy to study the equilibrium dynamics of thiocyanate chemical exchange between free ion (NCS(-)) and contact ion pair configurations (MNCS(+)), where M(2+) = Mg(2+) or Ca(2+). Detailed studies of the influence of anion concentration and anion speciation show that the chemical exchange observed with the 2DIR measurements results from NCS(-) exchanging with other anion species in the first solvation shell surrounding Mg(2+) or Ca(2+). The presence of chemical exchange in the 2DIR spectra provides an indirect, but robust, determinant of contact ion pair formation. We observe preferential contact ion pair formation between soft Lewis base anions and hard Lewis acid cations. This observation cannot be easily reconciled with Pearson's acid-base concept or Collins' Law of Matching Water Affinities. The anions that form contact ion pairs also correspond to the ions with an affinity for water and protein surfaces, so similar physical and chemical properties may control these distinct phenomena.

Neo-sex chromosomes and adaptive potential in tortricid pests

PubMed Central

Nguyen, Petr; Sýkorová, Miroslava; Šíchová, Jindra; Kůta, Václav; Dalíková, Martina; Čapková Frydrychová, Radmila; Neven, Lisa G.; Sahara, Ken; Marec, František

2013-01-01

Changes in genome architecture often have a significant effect on ecological specialization and speciation. This effect may be further enhanced by involvement of sex chromosomes playing a disproportionate role in reproductive isolation. We have physically mapped the Z chromosome of the major pome fruit pest, the codling moth, Cydia pomonella (Tortricidae), and show that it arose by fusion between an ancestral Z chromosome and an autosome corresponding to chromosome 15 in the Bombyx mori reference genome. We further show that the fusion originated in a common ancestor of the main tortricid subfamilies, Olethreutinae and Tortricinae, comprising almost 700 pest species worldwide. The Z–autosome fusion brought two major genes conferring insecticide resistance and clusters of genes involved in detoxification of plant secondary metabolites under sex-linked inheritance. We suggest that this fusion significantly increased the adaptive potential of tortricid moths and thus contributed to their radiation and subsequent speciation. PMID:23569222

On the Oxidation State of Manganese Ions in Li-Ion Battery Electrolyte Solutions.

PubMed

Banerjee, Anjan; Shilina, Yuliya; Ziv, Baruch; Ziegelbauer, Joseph M; Luski, Shalom; Aurbach, Doron; Halalay, Ion C

2017-02-08

We demonstrate herein that Mn 3+ and not Mn 2+ , as commonly accepted, is the dominant dissolved manganese cation in LiPF 6 -based electrolyte solutions of Li-ion batteries with lithium manganate spinel positive and graphite negative electrodes chemistry. The Mn 3+ fractions in solution, derived from a combined analysis of electron paramagnetic resonance and inductively coupled plasma spectroscopy data, are ∼80% for either fully discharged (3.0 V hold) or fully charged (4.2 V hold) cells, and ∼60% for galvanostatically cycled cells. These findings agree with the average oxidation state of dissolved Mn ions determined from X-ray absorption near-edge spectroscopy data, as verified through a speciation diagram analysis. We also show that the fractions of Mn 3+ in the aprotic nonaqueous electrolyte solution are constant over the duration of our experiments and that disproportionation of Mn 3+ occurs at a very slow rate.

Size-restricted proton transfer within toluene-methanol cluster ions.

PubMed

Chiang, Chi-Tung; Shores, Kevin S; Freindorf, Marek; Furlani, Thomas; DeLeon, Robert L; Garvey, James F

2008-11-20

To understand the interaction between toluene and methanol, the chemical reactivity of [(C6H5CH3)(CH3OH) n=1-7](+) cluster ions has been investigated via tandem quadrupole mass spectrometry and through calculations. Collision Induced Dissociation (CID) experiments show that the dissociated intracluster proton transfer reaction from the toluene cation to methanol clusters, forming protonated methanol clusters, only occurs for n = 2-4. For n = 5-7, CID spectra reveal that these larger clusters have to sequentially lose methanol monomers until they reach n = 4 to initiate the deprotonation of the toluene cation. Metastable decay data indicate that for n = 3 and n = 4 (CH3OH)3H(+) is the preferred fragment ion. The calculational results reveal that both the gross proton affinity of the methanol subcluster and the structure of the cluster itself play an important role in driving this proton transfer reaction. When n = 3, the cooperative effect of the methanols in the subcluster provides the most important contribution to allow the intracluster proton transfer reaction to occur with little or no energy barrier. As n >or= 4, the methanol subcluster is able to form ring structures to stabilize the cluster structures so that direct proton transfer is not a favored process. The preferred reaction product, the (CH3OH)3H(+) cluster ion, indicates that this size-restricted reaction is driven by both the proton affinity and the enhanced stability of the resulting product.

Solid state speciation of uranium and its local structure in Sr2CeO4 using photoluminescence spectroscopy.

PubMed

Sahu, M; Gupta, Santosh K; Jain, D; Saxena, M K; Kadam, R M

2018-04-15

An effort was taken to carry our speciation study of uranium ion in technologically important cerate host Sr 2 CeO 4 using time resolved photoluminescence spectroscopy. Such studies are not relevant only to nuclear industry but can give rich insight into fundamentals of 5f electron chemistry in solid state systems. In this work both undoped and varied amount of uranium doped Sr 2 CeO 4 compound is synthesized using complex polymerization method and is characterized systematically using X-ray diffraction (XRD), Raman spectroscopy, impedance spectroscopy and scanning electron microscopy (SEM). Both XRD and Raman spectroscopy confirmed the formation of pure Sr 2 CeO 4 which has tendency to decompose peritectically to SrCeO 3 and SrO at higher temperature. Uranium doping is confirmed by XRD. Uranium exhibits a rich chemistry owing to its variable oxidation state from +3 to +6. Each of them exhibits distinct luminescence properties either due to f-f transitions or ligand to metal charge transfer (LMCT). We have taken Sr 2 CeO 4 as a model host lattice to understand the photophysical characteristics of uranium ion in it. Emission spectroscopy revealed the stabilization of uranium as U (VI) in the form of UO 6 6- (octahedral uranate) in Sr 2 CeO 4 . Emission kinetics study reflects that uranate ions are not homogeneously distributed in Sr 2 CeO 4 and it has two different environments due to its stabilization at both Sr 2+ as well as Ce 4+ site. The lifetime population analysis interestingly pinpointed that majority of uranate ion resided at Ce 4+ site. The critical energy-transfer distance between the uranate ion was determined based on which the concentration quenching mechanism was attributed to electric multipolar interaction. These studies are very important in designing Sr 2 CeO 4 based optoelectronic material as well exploring it for actinides studies. Copyright © 2018 Elsevier B.V. All rights reserved.

Solid state speciation of uranium and its local structure in Sr2CeO4 using photoluminescence spectroscopy

NASA Astrophysics Data System (ADS)

Sahu, M.; Gupta, Santosh K.; Jain, D.; Saxena, M. K.; Kadam, R. M.

2018-04-01

An effort was taken to carry our speciation study of uranium ion in technologically important cerate host Sr2CeO4 using time resolved photoluminescence spectroscopy. Such studies are not relevant only to nuclear industry but can give rich insight into fundamentals of 5f electron chemistry in solid state systems. In this work both undoped and varied amount of uranium doped Sr2CeO4 compound is synthesized using complex polymerization method and is characterized systematically using X-ray diffraction (XRD), Raman spectroscopy, photoluminescence spectroscopy and scanning electron microscopy (SEM). Both XRD and Raman spectroscopy confirmed the formation of pure Sr2CeO4 which has tendency to decompose peritectically to SrCeO3 and SrO at higher temperature. Uranium doping is confirmed by XRD. Uranium exhibits a rich chemistry owing to its variable oxidation state from +3 to +6. Each of them exhibits distinct luminescence properties either due to f-f transitions or ligand to metal charge transfer (LMCT). We have taken Sr2CeO4 as a model host lattice to understand the photophysical characteristics of uranium ion in it. Emission spectroscopy revealed the stabilization of uranium as U (VI) in the form of UO66- (octahedral uranate) in Sr2CeO4. Emission kinetics study reflects that uranate ions are not homogeneously distributed in Sr2CeO4 and it has two different environments due to its stabilization at both Sr2+ as well as Ce4+ site. The lifetime population analysis interestingly pinpointed that majority of uranate ion resided at Ce4+ site. The critical energy-transfer distance between the uranate ion was determined based on which the concentration quenching mechanism was attributed to electric multipolar interaction. These studies are very important in designing Sr2CeO4 based optoelectronic material as well exploring it for actinides studies.

Speciation of arsenic in marine food (Anemonia sulcata) by liquid chromatography coupled to inductively coupled plasma mass spectrometry and organic mass spectrometry.

PubMed

Contreras-Acuña, M; García-Barrera, T; García-Sevillano, M A; Gómez-Ariza, J L

2013-03-22

Arsenic species have been investigated in Anemonia sulcata, which is frequently consumed food staple in Spain battered in wheat flour and fried with olive oil. Speciation in tissue extracts was carried out by anion/cation exchange chromatography with inductively coupled plasma mass spectrometry (HPLC-(AEC/CEC)-ICP-MS). Three methods for the extraction of arsenic species were investigated (ultrasonic bath, ultrasonic probe and focused microwave) and the optimal one was applied. Arsenic speciation was carried out in raw and cooked anemone and the dominant species are dimethylarsinic acid (DMA(V)) followed by arsenobetaine (AB), As(V), monomethylarsonic acid (MA(V)), tetramethylarsonium ion (TETRA) and trimethylarsine oxide (TMAO). In addition, arsenocholine (AsC), glyceryl phosphorylarsenocholine (GPAsC) and dimethylarsinothioic acid (DMAS) were identified by liquid chromatography coupled to triple quadrupole mass spectrometry (HPLC-MS). These results are interesting since GPAsC has been previously reported in marine organisms after experimental exposure to AsC, but not in natural samples. In addition, this paper reports for the first time the identification of DMAS in marine food. Copyright © 2013 Elsevier B.V. All rights reserved.

Simultaneous Speciation Analysis of Arsenic, Chromium, and Selenium in the Bioaccessible Fraction for Realistic Risk Assessment of Food Safety.

PubMed

Sadiq, Nausheen W; Beauchemin, Diane

2017-12-19

A simple and fast method was developed for risk assessment of As, Cr, and Se in food, which is demonstrated here using three cooked and uncooked rice samples (basmati as well as organic white and brown rice). The bioaccessible fraction was first determined through online leaching of rice minicolumns (maintained at 37 °C) sequentially with artificial saliva, gastric juice, and intestinal juice while continuously monitoring potentially toxic elements (As, Cr, and Se) by inductively coupled plasma mass spectrometry (ICPMS). Then, a new ion chromatography method with online detection by ICPMS was developed for the simultaneous speciation analysis of As, Cr, and Se in the bioaccessible fraction to determine the portion of these elements that was actually toxic. Using gradient elution, four As species [As(III), As(V), monomethylarsonic acid, and dimethylarsinic acid], two Cr species [Cr(III) and Cr(VI)], and two Se species [Se(IV) and Se(VI)] were separated within 12 min. The simultaneous speciation analysis of As, Cr, and Se revealed that the simple act of cooking can convert all of the carcinogenic Cr(VI) to the safer Cr(III).

Thallium release from acid mine drainages: Speciation in river and tap water from Valdicastello mining district (northwest Tuscany).

PubMed

Campanella, Beatrice; Casiot, Corinne; Onor, Massimo; Perotti, Martina; Petrini, Riccardo; Bramanti, Emilia

2017-08-15

In this work we present an advantageous method for the simultaneous separation and detection of Tl(I) and Tl(III) species through ion chromatography coupled with on-line inductively coupled plasma - mass spectrometry. Chromatographic separation between Tl(III) and Tl(I) was achieved in less than two minutes. The method was validated by recovery experiments on real samples, and by comparing the sum of the concentrations of individual Tl species with total thallium values obtained from continuous flow ICP-MS. The experimental procedure offers an accurate, sensitive and interference-free method for Tl speciation at trace levels in environmental samples. This allowed us to investigate the Tl speciation in acid mine drainages (AMD), surface waters and springs in a mining catchment in Valdicastello Carducci (Tuscany, Italy), where severe Tl contamination ad been evidenced previously. This study shows for the first time that Tl(III), in addition to Tl(I), is present in considerable amounts in water samples affected by acid mining outflow, raising the question of the origin of this thermodynamically unstable species. Copyright © 2017 Elsevier B.V. All rights reserved.

Specific extraction of chromium as tetrabutylammonium-chromate and spectrophotometric determination by diphenylcarbazide: speciation of chromium in effluent streams.

PubMed

Noroozifar, M; Khorasani-Motlagh, M

2003-05-01

A very specific, selective, simple, and inexpensive procedure was developed for the speciation of CrVI and CrIII. This method is based on the quantitative extraction of chromate and CrIII (previously oxidized to CrVI) as a tetrabutylammonium-chromate ion-pair in methyl isobutyl ketone (MIBK), and then back extraction and preconcentration with an acidic diphenylcarbazide (DPC) solution. Back extraction was applied to achieve further preconcentration by a final factor of 20. The CrVI-DPC complex was determined in back-extract by a spectrophotometer at 548 nm. Under these extraction conditions, most of the probable concomitant cations and anions remained in the first inorganic phase. The calibration curve was linear up to 0.14 microg L(-1) of CrVI with a detection limit of 2.22 ng L(-1). The developed procedure was found to be suitable for the determination of the CrVI and CrIII species in various natural water samples with a relative standard deviation of better than 1.6%. The method was successfully applied to the speciation of chromium in spiked natural water samples, and also samples of effluent from a leather treatment plant.

Iodine speciation in coastal and inland bathing waters and seaweeds extracts using a sequential injection standard addition flow-batch method.

PubMed

Santos, Inês C; Mesquita, Raquel B R; Bordalo, Adriano A; Rangel, António O S S

2015-02-01

The present work describes the development of a sequential injection standard addition method for iodine speciation in bathing waters and seaweeds extracts without prior sample treatment. Iodine speciation was obtained by assessing the iodide and iodate content, the two inorganic forms of iodine in waters. For the determination of iodide, an iodide ion selective electrode (ISE) was used. The indirect determination of iodate was based on the spectrophotometric determination of nitrite (Griess reaction). For the iodate measurement, a mixing chamber was employed (flow batch approach) to explore the inherent efficient mixing, essential for the indirect determination of iodate. The application of the standard addition method enabled detection limits of 0.14 µM for iodide and 0.02 µM for iodate, together with the direct introduction of the target water samples, coastal and inland bathing waters. The results obtained were in agreement with those obtained by ICP-MS and a colorimetric reference procedure. Recovery tests also confirmed the accuracy of the developed method which was effectively applied to bathing waters and seaweed extracts. Copyright © 2014 Elsevier B.V. All rights reserved.

Soil-solution speciation of Cd as affected by soil characteristics in unpolluted and polluted soils.

PubMed

Meers, Erik; Unamuno, Virginia; Vandegehuchte, Michiel; Vanbroekhoven, Karolien; Geebelen, Wouter; Samson, Roeland; Vangronsveld, Jaco; Diels, Ludo; Ruttens, Ann; Du Laing, Gijs; Tack, Filip

2005-03-01

Total metal content by itself is insufficient as a measure to indicate actual environmental risk. Understanding the mobility of heavy metals in the soil and their speciation in the soil solution is of great importance for accurately assessing environmental risks posed by these metals. In a first explorative study, the effects of general soil characteristics on Cd mobility were evaluated and expressed in the form of empirical formulations. The most important factors influencing mobility of Cd proved to be pH and total soil content. This may indicate that current legislation expressing the requirement for soil sanitation in Flanders (Belgium) as a function of total soil content, organic matter, and clay does not successfully reflect actual risks. Current legal frameworks focusing on total content, therefore, should be amended with criteria that are indicative of metal mobility and availability and are based on physicochemical soil properties. In addition, soil-solution speciation was performed using two independent software packages (Visual Minteq 2.23 and Windermere Humic Aqueous model VI [WHAM VI]). Both programs largely were in agreement in concern to Cd speciation in all 29 soils under study. Depending on soil type, free ion and the organically complexed forms were the most abundant species. Additional inorganic soluble species were sulfates and chlorides. Minor species in solution were in the form of nitrates, hydroxides, and carbonates, the relative importance of which was deemed insignificant in comparison to the four major species.

Mass spectrometric and theoretical investigation of sulfate clusters in nanoscale water droplets

NASA Astrophysics Data System (ADS)

Lemke, K.

2017-12-01

The solvation of sulfate clusters of varying size and charge in water clusters and in nanoscale water droplets has been studied using electrospray ionization (ESI) FT-MS and density functional theory (DFT) molecular simulations. ESI mass spectra of solvated [Mg(MgSO4)m]2+(H2O)n with m≤10 and up to 15 water molecules have been recorded, and ion cluster experiments have been undertaken using a custom-modified FT-ICR mass spectrometer with the ability of IRMPD for ion dissociation. We present equilibrium geometries and energies for [Mg(MgSO4)m]2+(H2O)n, water-free and solvated with up to 100 water molecules, using swarm-based optimizers and DFT level calculations. Dominant cluster species identified following ESI of dilute (1-5 mM) MgSO4 solutions include hexa- and octa-nuclear magnesium sulfate ions, water-free and with a full first shell of water molecules. The largest clusters identified are magnesium sulfate decamers, i.e. [Mg(MgSO4)10]2+(H2O)n, with n≤15. As a very first step towards understanding the distribution and intensity of ESI ion mass spectra, we have identified the global minima of [Mg(MgSO4)m]2+(H2O)n with m≤10 and n≤100, and located likely global minima of magnesium sulfate clusters in the gas phase and in nano-scale water droplets. We will present a summary of the structural and energetic trends of solvated magnesium sulfate clusters, with a particular focus on structural transitions induced by cluster growth and solvation, the occurrence of "magic" number cluster species, their energetic properties and their potential role as atmospheric aqueous species.

Desorption Induced by KEV Molecular and Cluster Projectiles.

NASA Astrophysics Data System (ADS)

Blain, Matthew Glenn

1990-01-01

A new experimental method has been developed for studying negative secondary ion (SI) emission from solid surfaces bombarded by polyatomic primary ions of 5 to 30 keV. The method is based on the time-of-flight (TOF) analysis of primary ions which are produced by either ^ {252}Cf fission fragment induced desorption or by extraction from a liquid metal ion source, and then accelerated into a field free region. The primary ions included organic monomer, dimer, and fragment ions of coronene and phenylalanine, (CsI)_ nCs ^{+} cluster ions, and Au _sp{n}{+} cluster ions. Secondary electrons, emitted from a target surface upon primary ion impact, are used to identify which primary ion has hit the surface. An event-by-event coincidence counting technique allows several secondary ion TOF spectra, correlated to several different primary ions, to be acquired simultaneously. Negative SI yields from organic (phenylalanine and dinitrostilbene), CsI, and Au surfaces have been measured for a number of different mono- and polyatomic primary ions. The results show, for example, yields ranging from 1 to 10% for phenylalanine (M-H) ^{ -}, 1 to 10% for I^{-} , and 1 to 5% for Au^{-} , with Cs_2I^ {+} and Cs_3I _sp{2}{+} clusters as projectiles. Yields for the same surfaces using Cs ^{+} primary ions are much less than 1%, indicating that SI yields are enhanced with clusters. A yield enhancement occurs when the SI yield per atom of a polyatomic projectile is greater than the SI yield of its monoatomic equivalent, at the same velocity. Thus, a (M-H) ^{-} yield increase of a factor of 50, when phenylalanine is bombarded with Cs_3I_sp{2} {+} instead of Cs^{+ }, represents a yield enhancement factor of 10. For the projectiles and samples studied, it was observed that the heavier the mass of the constituents of a projectile, the larger the enhancement effects, and that the largest yield enhancements (with CsI and Au _ n projectiles) occur for the organic target, phenylalanine. One possible explanation for the larger enhancements with organics, namely a thermal spike process, appears unlikely. Experiments with high and low melting point isomers of dinitrostilbene, bombarded with Cs _2I^{+} and Cs^{+} projectiles, showed larger Cs_2I^ {+} yield enhancements for the high melting point isomer.

Stopping and Coulomb explosion of energetic carbon clusters in a plasma irradiated by an intense laser field

NASA Astrophysics Data System (ADS)

Wang, Guiqiu; Wang, Younian

2015-09-01

The interaction of a charged particle beam with a plasma is a very important subject of relevance for many fields of physics, such as inertial confinement fusion (ICF) driven by ion or electron beams, high energy density physics, and related astrophysical problems. Recently, a promising ICF scheme has been proposed, in which the plasma target is irradiated simultaneously by intense laser and ion beams. For molecular ion or cluster, slowing down process will company the Coulomb explosion phenomenon. In this paper, we present a study of the effects of intense radiation field (RF) on the interaction of energetic carbon clusters in a plasma. The emphasis is laid on the dynamic polarization and correlation effects of the constituent ions within the cluster in order to disclose the role of the vicinage effects on the Coulomb explosion and energy deposition of the clusters in plasma. On the other hand, affecting of a strong laser field on the cluster propagating in plasma is considered, the influence of a large range of laser parameters and plasma parameters on the Coulomb explosion and stopping power are discussed. This work is supported by the National Natural Science Foundation of China (11375034), and the Fundamental Research Funds for the Central Universities of China (3132015144, 3132014337).

The initial stages of NaCl dissolution: Ion or ion pair solvation?

NASA Astrophysics Data System (ADS)

Klimes, Jiri; Michaelides, Angelos

2009-03-01

The interaction of water with rock salt (NaCl) is important in a wide variety of natural processes and human activities. A lot is known about NaCl dissolution at the macroscopic level but we do not yet have a detailed atomic scale picture of how salt crystals dissolve. Here we report an extensive series of density functional theory, forcefield and molecular dynamics studies of water clusters at flat and defective NaCl surfaces and NaCl clusters. The focus is on answering seemingly elementary questions such as how many water molecules are needed before it becomes favorable to extract an ion or a pair of ions from the crystal or the cluster. It turns out, however, that the answers to these questions are not so straightforward: below a certain number of water molecules (˜ 12) solvation of individual ions is less costly and above this number solvation of ion pairs is favored. These results reveal a hitherto unknown complexity in the NaCl dissolution process born out of a subtle interplay between water-water and water-ion interactions.

Rare-gas-cluster explosions under irradiation by intense short XUV pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoffmann, K.; Murphy, B.; Kandadai, N.

High-intensity, extreme-ultraviolet (XUV) femtosecond interactions with large rare-gas clusters of xenon and argon have been studied at a wavelength of 38 nm. Pulses of XUV radiation with nJ energy are produced by high-order harmonic conversion from a 35-fs, near-infrared, terawatt laser. Mass resolved ion spectra show charge states up to Xe{sup 8+} and Ar{sup 4+}. Kinetic-energy measurements of ions and electrons indicate that a nanoplasma is formed and a hydrodynamic cluster explosion ensues after heating by the short wavelength pulse. It appears that the observed charge states and electron temperatures are consistent with sequential, single-photon ionization and collisional ionization ofmore » ions that have had their ionization potential depressed by plasma continuum lowering in the cluster nanoplasma.« less

Cluster Ion Spectrometry (CIS) Data Archiving in the CAA

NASA Astrophysics Data System (ADS)

Dandouras, I. S.; Barthe, A.; Penou, E.; Brunato, S.; Reme, H.; Kistler, L. M.; Blagau, A.; Facsko, G.; Kronberg, E.; Laakso, H. E.

2009-12-01

The Cluster Active Archive (CAA) aims at preserving the four Cluster spacecraft data, so that they are usable in the long-term by the scientific community as well as by the instrument team PIs and Co-Is. This implies that the data are filed together with the descriptive and documentary elements making it possible to select and interpret them. The CIS (Cluster Ion Spectrometry) experiment is a comprehensive ionic plasma spectrometry package onboard the four Cluster spacecraft, capable of obtaining full three-dimensional ion distributions (about 0 to 40 keV/e) with a time resolution of one spacecraft spin (4 sec) and with mass-per-charge composition determination. The CIS package consists of two different instruments, a Hot Ion Analyser (HIA) and a time-of-flight ion Composition Distribution Function (CODIF) analyser. For the archival of the CIS data a multi-level approach has been adopted. The CAA archival includes processed raw data (Level 1 data), moments of the ion distribution functions (Level 2 data), and calibrated high-resolution data in a variety of physical units (Level 3 data). The latter are 3-D ion distribution functions and 2-D pitch-angle distributions. In addition, a software package has been developed to allow the CAA user to interactively calculate partial or total moments of the ion distributions. Instrument cross-calibration has been an important activity in preparing the data for archival. The CIS data archive includes also experiment documentation, graphical products for browsing through the data, and data caveats. In addition, data quality indexes are under preparation, to help the user. Given the complexity of an ion spectrometer, and the variety of its operational modes, each one being optimised for a different magnetospheric region or measurement objective, consultation of the data caveats by the end user will always be a necessary step in the data analysis.

Electron-induced chemistry in imidazole clusters embedded in helium nanodroplets

NASA Astrophysics Data System (ADS)

Kuhn, Martin; Raggl, Stefan; Martini, Paul; Gitzl, Norbert; Darian, Masoomeh Mahmoodi; Goulart, Marcelo; Postler, Johannes; Feketeová, Linda; Scheier, Paul

2018-02-01

Electron-induced chemistry in imidazole (IMI) clusters embedded in helium nanodroplets (with an average size of 2 × 105 He atoms) has been investigated with high-resolution time-of-flight mass spectrometry. The formation of both, negative and positive, ions was monitored as a function of the cluster size n. In both ion spectra a clear series of peaks with IMI cluster sizes up to at least 25 are observed. While the anions are formed by collisions of IMI n with He*-, the cations are formed through ionization of IMI n by He+ as the measured onset for the cation formation is observed at 24.6 eV (ionization energy of He). The most abundant series of anions are dehydrogenated anions IMI n-1(IMI-H)-, while other anion series are IMI clusters involving CN and C2H4 moieties. The formation of cations is dominated by the protonated cluster ions IMI n H+, while the intensity of parent cluster cations IMI n + is also observed preferentially for the small cluster size n. The observation of series of cluster cations [IMI n CH3]+ suggests either CH3+ cation to be solvated by n neutral IMI molecules, or the electron-induced chemistry has led to the formation of protonated methyl-imidazole solvated by ( n - 1) neutral IMI molecules.

Liquid-like cationic sub-lattice in copper selenide clusters

NASA Astrophysics Data System (ADS)

White, Sarah L.; Banerjee, Progna; Jain, Prashant K.

2017-02-01

Super-ionic solids, which exhibit ion mobilities as high as those in liquids or molten salts, have been employed as solid-state electrolytes in batteries, improved thermoelectrics and fast-ion conductors in super-capacitors and fuel cells. Fast-ion transport in many of these solids is supported by a disordered, `liquid-like' sub-lattice of cations mobile within a rigid anionic sub-lattice, often achieved at high temperatures or pressures via a phase transition. Here we show that ultrasmall clusters of copper selenide exhibit a disordered cationic sub-lattice under ambient conditions unlike larger nanocrystals, where Cu+ ions and vacancies form an ordered super-structure similar to the bulk solid. The clusters exhibit an unusual cationic sub-lattice arrangement wherein octahedral sites, which serve as bridges for cation migration, are stabilized by compressive strain. The room-temperature liquid-like nature of the Cu+ sub-lattice combined with the actively tunable plasmonic properties of the Cu2Se clusters make them suitable as fast electro-optic switches.

Ions in water: Free energies, surface effects, and geometrical constraints

NASA Astrophysics Data System (ADS)

Herce, Henry David

In this work, we present our results for ion solvation in finite and infinite water clusters. Molecular Dynamic simulations are used to connect the fundamental macroscopic quantities such as free energy, internal energy and entropy with the underlying microscopic description. Molecular dynamics studies complement experimental results and lead to a deeper insight into the solvation and diffusion of ionic species. Beyond its intrinsic interest, the ion solvation problem has practical relevance because of its role as ideal model system with which to construct and test ion-water interaction potentials. The ionic charging free energy is a very sensitive probe for the treatment of electrostatics in any given simulation setting. In this work, we present methods to compute the ionic charging free energy in systems characterized by atomic charges, and higher-order multipoles, mainly dipoles and quadrupoles. The results of these methods under periodic boundary conditions and spherical boundary conditions are then compared. For the treatment of spherical boundary conditions, we introduce a generalization of Gauss' law that links the microscopic variables to the relevant thermodynamic quantities. Ionic solvation in finite clusters is a problem relevant for many areas of chemistry and biology, such as the gas-liquid interface of tropospheric aerosol particles, or the interphase between water and proteins, membranes, etc. Careful evaluations of the free energy, internal energy and entropy are used to address controversial or unresolved issues, related to the underlying physical cause of surface solvation, and the basic assumptions that go with it. Our main conclusions are the following: (i) The main cause of surface solvation of a single ion in a water cluster is both water and ion polarization, coupled to the charge and size of the ion. Interestingly, the total energy of the ion increases near the cluster surface, while the total energy of water decreases. Also, our analysis clearly shows that the cause of surface solvation is not the size of the total water dipole (unless this is too small). (ii) The entropic contribution is the same order of magnitude as the energetic contribution, and therefore cannot be neglected for quantitative results. (iii) A pure energetic analysis can give a qualitative description of the ion position at room temperature. (iv) We have observed surface solvation of a large positive iodine-like ion in a polarizable water cluster, but not in a non-polarizable water cluster.

Solid-phase arsenic speciation in aquifer sediments: A micro-X-ray absorption spectroscopy approach for quantifying trace-level speciation

USGS Publications Warehouse

Nicholas, Sarah L.; Erickson, Melinda L.; Woodruff, Laurel G.; Knaeble, Alan R.; Marcus, Matthew A.; Lynch, Joshua K.; Toner, Brandy M.

2017-01-01

e of this research is to identify the solid-phase sources and geochemical mechanisms of release of As in aquifers of the Des Moines Lobe glacial advance. The overarching concept is that conditions present at the aquifer-aquitard interfaces promote a suite of geochemical reactions leading to mineral alteration and release of As to groundwater. A microprobe X-ray absorption spectroscopy (lXAS) approach is developed and applied to rotosonic drill core samples to identify the solid-phase speciation of As in aquifer, aquitard, and aquifer-aquitard interface sediments. This approach addresses the low solid-phase As concentrations, as well as the fine-scale physical and chemical heterogeneity of the sediments. The spectroscopy data are analyzed using novel cosine-distance and correlation-distance hierarchical clustering for Fe 1s and As 1s lXAS datasets. The solid-phase Fe and As speciation is then interpreted using sediment and well-water chemical data to propose solid-phase As reservoirs and release mechanisms. The results confirm that in two of the three locations studied, the glacial sediment forming the aquitard is the source of As to the aquifer sediments. The results are consistent with three different As release mechanisms: (1) desorption from Fe (oxyhydr)oxides, (2) reductive dissolution of Fe (oxyhydr)oxides, and (3) oxidative dissolution of Fe sulfides. The findings confirm that glacial sediments at the interface between aquifer and aquitard are geochemically active zones for As. The diversity of As release mechanisms is consistent with the geographic heterogeneity observed in the distribution of elevated-As wells.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sadeghi, Omid; Falaise, Clément; Molina, Pedro I.

The iron Keggin ion is identified as a structural building block in both magnetite and ferrihydrite, two important iron oxide phases in nature and in technology. Discrete molecular forms of the iron Keggin ion that can be both manipulated in water and chemically converted to the related metal oxides are important for understanding growth mechanisms, in particular non-classical nucleation in which cluster building units are preserved in the aggregation and condensation processes. Here we describe two iron Keggin ion structures, formulated [Bi6FeO4Fe12O12(OH)12(CF3COO)10(H2O)2]3+ and [Bi6FeO4Fe12O12(OH)12(CF3COO)12]1+. Experimental and simulated X-ray scattering studies show indefinite stability of these clusters in water from pHmore » 1-3. The tridecameric iron Keggin-ion core is protected from hydrolysis by a synergistic effect of the capping Bi3+-cations and the trifluoroacetate ligands that respectively bond to the iron and bridge to the bismuth. By introducing electrons to the aqueous solution of clusters, we achieve complete separation of bismuth from the cluster, and the iron Keggin ion rapidly converts to magnetite and/or ferrihydrite, depending on the mechanism of reduction. In this strategy, we take advantage of the easily accessible reduction potential and crystallization energy of bismuth. Reduction was executed in bulk by chemical means, by voltammetry, and by secondary effects of transmission electron microscopy imaging of solutions. Prior, we showed a less stable analogue of the iron Keggin cluster converted to ferrihydrite simply upon dissolution. The prior and currently studied clusters with a range of reactivity provide a chemical system to study molecular cluster metal oxide conversion processes in detail.« less

Electron impact ionization of size selected hydrogen clusters (H2)N: ion fragment and neutral size distributions.

PubMed

Kornilov, Oleg; Toennies, J Peter

2008-05-21

Clusters consisting of normal H2 molecules, produced in a free jet expansion, are size selected by diffraction from a transmission nanograting prior to electron impact ionization. For each neutral cluster (H2)(N) (N=2-40), the relative intensities of the ion fragments Hn+ are measured with a mass spectrometer. H3+ is found to be the most abundant fragment up to N=17. With a further increase in N, the abundances of H3+, H5+, H7+, and H9+ first increase and, after passing through a maximum, approach each other. At N=40, they are about the same and more than a factor of 2 and 3 larger than for H11+ and H13+, respectively. For a given neutral cluster size, the intensities of the ion fragments follow a Poisson distribution. The fragmentation probabilities are used to determine the neutral cluster size distribution produced in the expansion at a source temperature of 30.1 K and a source pressure of 1.50 bar. The distribution shows no clear evidence of a magic number N=13 as predicted by theory and found in experiments with pure para-H2 clusters. The ion fragment distributions are also used to extract information on the internal energy distribution of the H3+ ions produced in the reaction H2+ + H2-->H3+ +H, which is initiated upon ionization of the cluster. The internal energy is assumed to be rapidly equilibrated and to determine the number of molecules subsequently evaporated. The internal energy distribution found in this way is in good agreement with data obtained in an earlier independent merged beam scattering experiment.

Dissociation of doubly charged clusters of lithium acetate: Asymmetric fission and breakdown of the liquid drop model: Dissociation of doubly charged clusters of lithium acetate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shukla, Anil

2016-06-08

Unimolecular and collision-induced dissociation of doubly charged lithium acetate clusters, (CH3COOLi)nLi22+, demonstrated that Coulomb fission via charge separation is the dominant dissociation process with no contribution from the neutral evaporation processes for all such ions from the critical limit to larger cluster ions, although latter process have normally been observed in all earlier studies. These results are clearly in disagreement with the Rayleigh’s liquid drop model that has been used successfully to predict the critical size and explain the fragmentation behavior of multiply charged clusters.

Lithium-air batteries, method for making lithium-air batteries

DOEpatents

Vajda, Stefan; Curtiss, Larry A.; Lu, Jun; Amine, Khalil; Tyo, Eric C.

2016-11-15

The invention provides a method for generating Li.sub.2O.sub.2 or composites of it, the method uses mixing lithium ions with oxygen ions in the presence of a catalyst. The catalyst comprises a plurality of metal clusters, their alloys and mixtures, each cluster consisting of between 3 and 18 metal atoms. The invention also describes a lithium-air battery which uses a lithium metal anode, and a cathode opposing the anode. The cathode supports metal clusters, each cluster consisting of size selected clusters, taken from a range of between approximately 3 and approximately 18 metal atoms, and an electrolyte positioned between the anode and the cathode.

Living at the edge: biogeographic patterns of habitat segregation conform to speciation by niche expansion in Anopheles gambiae

PubMed Central

Costantini, Carlo; Ayala, Diego; Guelbeogo, Wamdaogo M; Pombi, Marco; Some, Corentin Y; Bassole, Imael HN; Ose, Kenji; Fotsing, Jean-Marie; Sagnon, N'Falé; Fontenille, Didier; Besansky, Nora J; Simard, Frédéric

2009-01-01

Background Ongoing lineage splitting within the African malaria mosquito Anopheles gambiae is compatible with ecological speciation, the evolution of reproductive isolation by divergent natural selection acting on two populations exploiting alternative resources. Divergence between two molecular forms (M and S) identified by fixed differences in rDNA, and characterized by marked, although incomplete, reproductive isolation is occurring in West and Central Africa. To elucidate the role that ecology and geography play in speciation, we carried out a countrywide analysis of An. gambiae M and S habitat requirements, and that of their chromosomal variants, across Burkina Faso. Results Maps of relative abundance by geostatistical interpolators produced a distinct pattern of distribution: the M-form dominated in the northernmost arid zones, the S-form in the more humid southern regions. Maps of habitat suitability, quantified by Ecological Niche Factor Analysis based on 15 eco-geographical variables revealed less contrast among forms. M was peculiar as it occurred proportionally more in habitat of marginal quality. Measures of ecological niche breadth and overlap confirmed the mismatch between the fundamental and realized patterns of habitat occupation: forms segregated more than expected from the extent of divergence of their environmental envelope – a signature of niche expansion. Classification of chromosomal arm 2R karyotypes by multilocus genetic clustering identified two clusters loosely corresponding to molecular forms, with 'mismatches' representing admixed individuals due to shared ancestral polymorphism and/or residual hybridization. In multivariate ordination space, these karyotypes plotted in habitat of more marginal quality compared to non-admixed, 'typical', karyotypes. The distribution of 'typical' karyotypes along the main eco-climatic gradient followed a consistent pattern within and between forms, indicating an adaptive role of inversions at this geographical scale. Conclusion Ecological segregation between M and S is consistent with niche expansion into marginal habitats by chromosomal inversion variants during early lineage divergence; presumably, this process is promoted by inter-karyotype competition in the higher-quality core habitat. We propose that the appearance of favourable allelic combinations in other regions of suppressed recombination (e.g. pericentromeric portions defining speciation islands in An. gambiae) fosters development of reproductive isolation to protect linkage between separate chromosomal regions. PMID:19460144

First simultaneous detection of terrestrial ionospheric molecular ions in the Earth's inner magnetosphere and at the Moon

NASA Astrophysics Data System (ADS)

Dandouras, Iannis; Poppe, Andrew R.; Fillingim, Matt O.; Kistler, Lynn M.; Mouikis, Christopher G.; Rème, Henri

2017-04-01

Heavy molecular ions escaping from a planetary atmosphere can contribute to the long-term evolution of its composition. The ARTEMIS (Acceleration, Reconnection, Turbulence, and Electrodynamics of the Moon's Interaction with the Sun) spacecraft has recently observed outflowing molecular ions at lunar distances in the terrestrial magnetotail (Poppe et al., 2016). Backward particle tracing indicated that these ions should originate from the terrestrial inner magnetosphere. Here we have examined Cluster data acquired by the CIS-CODIF (Cluster Ion Spectrometry-Composition Distribution Function) ion mass spectrometer, obtained in the terrestrial magnetosphere. An event was selected where the orbital conditions were favourable and the Cluster spacecraft were in the high-latitude inner magnetosphere a few hours before the ARTEMIS molecular ion detection. Analysis shows that the CIS-CODIF instrument detected a series of energetic ion species, including not only O+ but also a group of molecular ions around 30 amu. Given the 5-7 m/Δm mass resolution of the instrument, these could include N2+, NO+, or O2+. These ions were detected by Cluster about 14 hours before the ARTEMIS observation in the lunar environment, a time which is compatible with the transfer to lunar distances. The event was during an active period followed by a northward rotation of the IMF. Although energetic heavy molecular ions have been detected in the storm time magnetosphere in the past (e.g. Klecker et al., 1986; Christon et al., 1994), this event constitutes the first coordinated observation in the Earth's inner magnetosphere and at the Moon. Additional events of coordinated outflowing molecular ion observations are currently under analysis. Future missions, as the proposed ESCAPE mission, should investigate in detail the mechanisms of molecular ion acceleration and escape, their link to the solar and magnetospheric activity, and their role in the magnetospheric dynamics and in the long-term evolution of the atmospheric composition.

Time-of-flight secondary ion mass spectrometry studies of cluster ion analysis for semiconductors and diffusion of manganese in gallium arsenide at low temperatures

NASA Astrophysics Data System (ADS)

Goacher, Robyn Elizabeth

Secondary Ion Mass Spectrometry (SIMS) is an established method for the quantitative analysis of dopants in semiconductors. The quasi-parallel mass acquisition of Time-of-Flight SIMS, along with the development of polyatomic primary ions, have rapidly increased the use of SIMS for analysis of organic and biological specimens. However, the advantages and disadvantages of using cluster primary ions for quantitative analysis of inorganic materials are not clear. The research described in this dissertation investigates the consequences of using polyatomic primary ions for the analysis of inorganic compounds in ToF-SIMS. Furthermore, the diffusion of Mn in GaAs, which is important in Spintronic material applications such as spin injection, is also studied by quantitative ToF-SIMS depth profiling. In the first portion of this work, it was discovered that primary ion bombardment of pre-sputtered compound semiconductors GaAs and InP for the purpose of spectral analysis resulted in the formation of cluster secondary ions, as well as atomic secondary ions (Chapter 2). In particular, bombardment using a cluster primary ion such as Bi3q + or C60q+ resulted in higher yields of high-mass cluster secondary ions. These cluster secondary ions did not have bulk stoichiometry, "non-stoichiometric", in contrast to the paradigm of stoichiometric cluster ions generated from salts. This is attributed to the covalent bonding of the compound semiconductors, as well as to preferential sputtering. The utility of high-mass cluster secondary ions in depth profiling is also discussed. Relative sensitivity factors (RSFs) calculated for ion-implanted Fe and Mn samples in GaAs also exhibit differences based on whether monatomic or polyatomic primary ions are utilized (Chapter 3). These RSFs are important for the quantitative conversion of intensity to concentration. When Bi 32+ primary ions are used for analysis instead of Bi + primary ions, there is a significantly higher proportion of Mn and Fe ions present in the spectra, as referenced to the matrix species. The magnitude of this effect differs depending on the sputtering ion, Cs or C60. The use of C60cluster primary ions for depth profiling of GaAs is also investigated (Chapter 4). In particular, for quantitative depth profiling, parameters such as depth resolution, ion and sputter yields, and relative sensitivity factors are pertinent to profiling thin layered structures quantitatively and quickly. C60 sputtering is compared to Cs sputtering in all of these aspects. It is found that 10 keV C60+ is advantageous for the analysis of metals (such as Au contacts on Si) but that previously reported roughness problems prohibit successful analysis in Si. For Al delta layers and quantum wells in GaAs, C60 q+ sputtering induced very little roughness in the sample, and resulted in high ion yields and excellent signal-to-noise as compared to Cs+ sputtering. However, the depth resolution of C60 is at best equivalent to 1 keV Cs+ and does not extend into the sub 2-nm range. Furthermore, C60 sputtering results in significant carbon implantation. In the second portion of this work, quantitative ToF-SIMS depth profiling was used to evaluate the diffusion of Mn into GaAs. Samples were prepared by Molecular Beam Epitaxy in the department of Physics. Mn diffusion from MnAs was investigated first, and Mn diffusion from layered epitaxial structures of GaAs / Ga1-xMnxAs / GaAs was investigated second. Diffusion experiments were conducted by annealing portions of the samples in sealed glass ampoules at low temperatures (200-400°C). Different sputtering rates were measured for MnAs and GaAs and the measured depth profiles were corrected for these effects. RSFs measured for Mn ion-implanted standards were used to calibrate the intensity scale. For diffusion from MnAs, thin MnAs layers resulted in no measurable changes except in the surface transient. For thick MnAs layers, it was determined that substantial loss of As occurred at 400°C, resulting in severe sample roughening, which inhibited proper SIMS analysis. Results for the diffusion of Mn out of a thick buried layer of Ga1-xMnxAs show that annealing induces diffusion of Mn species from the Ga1-xMnxAs layer into the neighboring GaAs with an activation energy of 0.69+/-0.09 eV. This results in doping of the GaAs layer, which is detrimental to spin injection for Spintronics devices.

Electron-temperature dependence of dissociative recombination of electrons with CO/+/./CO/n-series ions

NASA Technical Reports Server (NTRS)

Whitaker, M.; Biondi, M. A.; Johnsen, R.

1981-01-01

The dependence on electron temperature of the coefficients for electron recombination with molecular cluster ions of the carbon monoxide series, CO(+).(CO)n, is determined. A microwave discharge lasting approximately 0.1 msec was applied in 5-20 Torr neon containing a few tenths percent CO in an afterglow mass spectrometer apparatus, and the time histories of the various afterglow ions were measured. Expressions for the dependence of the recombination coefficients of the dimer and trimer ions CO(+).CO and CO(+).(CO)2 are obtained which are found to be significantly different from those previously obtained for hydronium and ammonium series polar cluster ions, but similar to those of simple diatomic ions.

Cluster-inspired Superionic Conductors

NASA Astrophysics Data System (ADS)

Fang, Hong; Jena, Puru

Superionic conductors with desirable properties hold the key to the development of next generation of rechargeable metal-ion batteries. In this study, we report a new family of superionic conductors composed by clusters based on the antiperovskite fast-ion conductors. The new lightweight conductor shows larger electrochemical stability window and favorable thermal and mechanical properties, while maintain a high Li+-ionconductivity at room temperature and a low activation energy. We reveal the conduction mechanism of the material by identifying the relation between the orientational symmetry of the cluster rotors and the potential surface felt by the lithium ion. We also find that the mixed phase of the new conductors show further enhanced conductivity.

Indirect photometric detection of boron cluster anions electrophoretically separated in methanol.

PubMed

Vítová, Lada; Fojt, Lukáš; Vespalec, Radim

2014-04-18

3,5-Dinitrobenzoate and picrate are light absorbing anions pertinent to indirect photometric detection of boron cluster anions in buffered methanolic background electrolytes (BGEs). Tris(hydroxymethyl)aminomethane and morpholine have been used as buffering bases, which eliminated baseline steps, and minimized the baseline noise. In methanolic BGEs, mobilities of boron cluster anions depend on both ionic constituents of the BGE buffer. This dependence can be explained by ion pair interaction of detected anions with BGE cations, which are not bonded into ion pairs with the BGE anions. The former ion pair interaction decreases sensitivity of the indirect photometric detection. Copyright © 2014 Elsevier B.V. All rights reserved.

Gas cluster ion beam assisted NiPt germano-silicide formation on SiGe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ozcan, Ahmet S., E-mail: asozcan@us.ibm.com; Lavoie, Christian; Jordan-Sweet, Jean

We report the formation of very uniform and smooth Ni(Pt)Si on epitaxially grown SiGe using Si gas cluster ion beam treatment after metal-rich silicide formation. The gas cluster ion implantation process was optimized to infuse Si into the metal-rich silicide layer and lowered the NiSi nucleation temperature significantly according to in situ X-ray diffraction measurements. This novel method which leads to more uniform films can also be used to control silicide depth in ultra-shallow junctions, especially for high Ge containing devices, where silicidation is problematic as it leads to much rougher interfaces.

Radiation-induced segregation and precipitation behaviours around cascade clusters under electron irradiation.

PubMed

Sueishi, Yuichiro; Sakaguchi, Norihito; Shibayama, Tamaki; Kinoshita, Hiroshi; Takahashi, Heishichiro

2003-01-01

We have investigated the formation of cascade clusters and structural changes in them by means of electron irradiation following ion irradiation in an austenitic stainless steel. Almost all of the cascade clusters, which were introduced by the ion irradiation, grew to form interstitial-type dislocation loops or vacancy-type stacking fault tetrahedra after electron irradiation at 623 K, whereas a few of the dot-type clusters remained in the matrix. It was possible to recognize the concentration of Ni and Si by radiation-induced segregation around the dot-type clusters. After electron irradiation at 773 K, we found that some cascade clusters became precipitates (delta-Ni2Si) due to radiation-induced precipitation. This suggests that the cascade clusters could directly become precipitation sites during irradiation.

Impact of Near-Earth Plasma Sheet Dynamics on the Ring Current Composition

NASA Astrophysics Data System (ADS)

Kistler, L. M.; Mouikis, C.; Menz, A.; Spence, H. E.; Mitchell, D. G.; Gkioulidou, M.; Lanzerotti, L. J.; Skoug, R. M.; Larsen, B.; Claudepierre, S. G.; Fennell, J. F.; Blake, J. B.

2014-12-01

How the dynamics in the near-earth plasma sheet affects the heavy ion content, and therefore the ion pressure, of the ring current in Earth's magnetosphere is an outstanding question. Substorms accelerate plasma in the near-earth region and drive outflow from the aurora, and both these processes can preferentially enhance the population of heavy ions in this region. These heavy ions are then driven into the inner magnetosphere during storms. Thus understanding how the composition of the ring current changes requires simultaneous observations in the near-earth plasma sheet and in the inner magnetosphere. We use data from the CODIF instrument on Cluster and HOPE, RBSPICE, and MagEIS instruments on the Van Allen Probes to study the acceleration and transport of ions from the plasma sheet into the ring current. During the main phase of a geomagnetic storm on Aug 4-6, 2013, the Cluster spacecraft were moving inbound in the midnight central plasma sheet, while the apogees of the two Van Allen Probes were located on the duskside. The Cluster spacecraft measure the composition and spectral changes in the plasma sheet, while the Van Allen Probes measure the ions that reach the inner magnetosphere. A strong increase in 1-40 keV O+ was observed at the Cluster location during the storm main phase, and the Van Allen Probes observed both H+ and O+ being driven deep into the inner magnetosphere. By comparing the variations in phase space density (PSD) vs. magnetic moment at the Cluster and the Van Allen Probes locations, we examine how the composition changes non-adiabatically in the near-earth plasma sheet, and how those changes are propagated into the inner magnetosphere, populating the hto ion ring current.

The genetic basis of speciation in the Giliopsis lineage of Ipomopsis (Polemoniaceae)

USGS Publications Warehouse

Nakazato, Takuya; Rieseberg, Loren H.; Wood, Troy E.

2013-01-01

One of the most powerful drivers of speciation in plants is pollinator-mediated disruptive selection, which leads to the divergence of floral traits adapted to the morphology and behavior of different pollinators. Despite the widespread importance of this speciation mechanism, its genetic basis has been explored in only a few groups. Here, we characterize the genetic basis of pollinator-mediated divergence of two species in genus Ipomopsis, I. guttata and I. tenuifolia, using quantitative trait locus (QTL) analyses of floral traits and other variable phenotypes. We detected one to six QTLs per trait, with each QTL generally explaining small to modest amounts of the phenotypic variance of a backcross hybrid population. In contrast, flowering time and anthocyanin abundance (a metric of color variation) were controlled by a few QTLs of relatively large effect. QTLs were strongly clustered within linkage groups, with 26 of 37 QTLs localized to six marker-interval ‘hotspots,’ all of which harbored pleiotropic QTLs. In contrast to other studies that have examined the genetic basis of pollinator shifts, our results indicate that, in general, mutations of small to modest effect on phenotype were involved. Thus, the evolutionary transition between the distinct pollination modes of I. guttata and I. tenuifolia likely proceeded incrementally, rather than saltationally.

A multi-point perspective on the formation of polar cap arcs: kinetic modeling and observations by Cluster and TIMED

NASA Astrophysics Data System (ADS)

de Keyser, J. M.; Maggiolo, R.; Echim, M.; Simon, C.; Zhang, Y.; Trotignon, J.

2010-12-01

On April 1st, 2004 the GUVI imager onboard the TIMED spacecraft spots an isolated and elongated polar cap arc. Simultaneously, the Cluster spacecraft detects an isolated upflowing ion beam above the polar cap. Cluster observations show that the ions are accelerated upward by a quasi-stationary electric field. The field-aligned potential drop is estimated to about 600 V and the upflowing ions are accompanied by a tenuous population of isotropic protons with a temperature of about 300eV. The footprint of the magnetic field line on which the Cluster spacecraft are situated, is located just outside the GUVI field of view in the prolongation of the polar cap arc. This suggests that the upflowing ion beam and the polar cap arc may be different signatures of the same phenomenon, as suggested by a recent statistical study of polar cap ion beams using Cluster data. We use Cluster observations at high altitude as input to a quasi-stationary magnetosphere-ionosphere (MI) coupling model. Using a Knight-type current-voltage relationship and the current continuity at the topside ionosphere, the model computes the energy spectrum of precipitating electrons at ionospheric altitudes corresponding to the generator electric field observed by Cluster. The MI coupling model provides a field-aligned potential drop in agreement with Cluster observations of upflowing ions and a spatial scale of the polar cap arc consistent with the optical observations by TIMED. The energy spectrum of the precipitating electrons provided by the model is introduced as input to the Trans4 ionospheric transport code. This 1-D model, based on Boltzmann's kinetic formalism, takes into account ionospheric processes like photoionisation and electron/proton precipitation, and computes the optical and UV emissions due to precipitating electrons. The emission rates provided by the Trans4 code are then compared to the optical observations by TIMED. Data and modeling results are consistent with quasi-static acceleration of precipitating magnetospheric electrons. We also discuss possible implications of our modeling results for optical observations of polar cap arcs.

Use of ion-mobility mass spectrometry (IMS-MS) to map polyoxometalate Keplerate clusters and their supramolecular assemblies.

PubMed

Robbins, Philip J; Surman, Andrew J; Thiel, Johannes; Long, De-Liang; Cronin, Leroy

2013-03-07

We present the high-resolution (HRES-MS) and ion-mobility (IMS-MS) mass spectrometry studies of icosahedral nanoscale polyoxometalate-based {L(30)}{(Mo)Mo(5)} Keplerate clusters, and demonstrate the use of IMS-MS to resolve and map intact nanoclusters, and its potential for the discovery of new structures, in this case the first gas phase observation of 'proto-clustering' of higher order Keplerate supramolecular aggregates.

Are sympatrically speciating Midas cichlid fish special? Patterns of morphological and genetic variation in the closely related species Archocentrus centrarchus.

PubMed

Fruciano, Carmelo; Franchini, Paolo; Raffini, Francesca; Fan, Shaohua; Meyer, Axel

2016-06-01

Established empirical cases of sympatric speciation are scarce, although there is an increasing consensus that sympatric speciation might be more common than previously thought. Midas cichlid fish are one of the few substantiated cases of sympatric speciation, and they formed repeated radiations in crater lakes. In contrast, in the same environment, such radiation patterns have not been observed in other species of cichlids and other families of fish. We analyze morphological and genetic variation in a cichlid species (Archocentrus centrarchus) that co-inhabits several crater lakes with the Midas species complex. In particular, we analyze variation in body and pharyngeal jaw shape (two ecologically important traits in sympatrically divergent Midas cichlids) and relate that to genetic variation in mitochondrial control region and microsatellites. Using these four datasets, we analyze variation between and within two Nicaraguan lakes: a crater lake where multiple Midas cichlids have been described and a lake where the source population lives. We do not observe any within-lake clustering consistent across morphological traits and genetic markers, suggesting the absence of sympatric divergence in A. centrarchus. Genetic differentiation between lakes was low and morphological divergence absent. Such morphological similarity between lakes is found not only in average morphology, but also when analyzing covariation between traits and degree of morphospace occupation. A combined analysis of the mitochondrial control region in A. centrarchus and Midas cichlids suggests that a difference between lineages in the timing of crater lake colonization cannot be invoked as an explanation for the difference in their levels of diversification. In light of our results, A. centrarchus represents the ideal candidate to study the genomic differences between these two lineages that might explain why some lineages are more likely to speciate and diverge in sympatry than others.

Structural and Dynamical Properties of Alkaline Earth Metal Halides in Supercritical Water: Effect of Ion Size and Concentration.

PubMed

Keshri, Sonanki; Tembe, B L

2017-11-22

Constant temperature-constant pressure molecular dynamics simulations have been performed for aqueous alkaline earth metal chloride [M 2+ -Cl - (M = Mg, Ca, Sr, and Ba)] solutions over a wide range of concentrations (0.27-5.55 m) in supercritical (SC) and ambient conditions to investigate their structural and dynamical properties. A strong influence of the salt concentration is observed on the ion-ion pair correlation functions in both ambient and SC conditions. In SC conditions, significant clustering is observed in the 0.27 m solution, whereas the reverse situation is observed at room temperature and this is also supported by the residence times of the clusters. The concentration and ion size (cation size) seem to have opposite effects on the average number of hydrogen bonds. The simulation results show that the self-diffusion coefficients of water, cations, and the chloride ion increase with increasing temperature, whereas they decrease with increasing salt concentration. The cluster size distribution shows a strong density dependence in both ambient and SC conditions. In SC conditions, cluster sizes display a near-Gaussian distribution, whereas the distribution decays monotonically in ambient conditions.

Rumsey and Walker_AMT_2016_Figure 2.xlsx

EPA Pesticide Factsheets

Figure summarizes uncertainty (error) in hourly gradient flux measurements by individual analyte. Flux uncertainty is derived from estimates of uncertainty in chemical gradients and turbulent transfer velocity.This dataset is associated with the following publication:Rumsey, I. Application of an online ion chromatography-based instrument for gradient flux measurements of speciated nitrogen and sulfur. ENVIRONMENTAL SCIENCE & TECHNOLOGY. American Chemical Society, Washington, DC, USA, 9(6): 2581-2592, (2016).

Interactions Among Chemical Speciation, Algal Accumulation, and Biogeochemical Cycling of Toxic Metals in a Major US Naval Harbor (Elizabeth River, VA)

DTIC Science & Technology

2001-09-30

Elizabeth River/Hampton Roads system and algal species grown in metal ion buff er systems: Emiliania huxleyi , Thalassiosira pseudonana, and... huxleyi -0 o ... • Elizabeth, May E ~ · + Elizabeth, July :::: 100. 6~ ~· 0 0 T. pseuclonana §_ 0 • tJ 0 8 ~ 0 0 0 <>I. galbana - 𔃺~0 0 (.) 10. s

Uranium luminescence in La2 Zr2 O7 : effect of concentration and annealing temperature.

PubMed

Mohapatra, M; Rajeswari, B; Hon, N S; Kadam, R M

2016-12-01

The speciation of a particular element in any given matrix is a prerequisite to understanding its solubility and leaching properties. In this context, speciation of uranium in lanthanum zirconate pyrochlore (La 2 Zr 2 O 7  = LZO), prepared by a low-temperature combustion route, was carried out using a simple photoluminescence lifetime technique. The LZO matrix is considered to be a potential ceramic host for fixing nuclear and actinide waste products generated during the nuclear fuel cycle. Special emphasis has been given to understanding the dynamics of the uranium species in the host as a function of annealing temperature and concentration. It was found that, in the LZO host, uranium is stabilized as the commonly encountered uranyl species (UO 2 2+ ) up to a heat treatment of 500 °C at the surface. Above 500 °C, the uranyl ion is diffused into the matrix as the more symmetric octahedral uranate species (UO 6 6- ). The uranate ions thus formed replace the six-coordinated 'Zr' atoms at regular lattice positions. Further, it was observed that concentration quenching takes place beyond 5 mol% of uranium doping. The mechanism of the quenching was found to be a multipolar interaction. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Chemical Imaging Analysis of Environmental Particles Using the Focused Ion Beam/Scanning Electron Microscopy Technique. Microanalysis Insights into Atmospheric Chemistry of Fly Ash

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Haihan; Grassian, Vicki H.; Saraf, Laxmikant V.

2012-11-08

Airborne fly ash from coal combustion may represent a source of bioavailable iron (Fe) in the open ocean. However, few studies have been made focusing on Fe speciation and distribution in coal fly ash. In this study, chemical imaging of fly ash has been performed using a dual-beam FIB/SEM (focused ion beam/scanning electron microscope) system for a better understanding of how simulated atmospheric processing modify the morphology, chemical compositions and element distributions of individual particles. A novel approach has been applied for cross-sectioning of fly ash specimen with a FIB in order to explore element distribution within the interior ofmore » individual particles. Our results indicate that simulated atmospheric processing causes disintegration of aluminosilicate glass, a dominant material in fly ash particles. Aluminosilicate-phase Fe in the inner core of fly ash particles is more easily mobilized compared with oxide-phase Fe present as surface aggregates on fly ash spheres. Fe release behavior depends strongly on Fe speciation in aerosol particles. The approach for preparation of cross-sectioned specimen described here opens new opportunities for particle microanalysis, particular with respect to inorganic refractive materials like fly ash and mineral dust.« less

Linking environmental processes to the in situ functioning of microorganisms by high-resolution secondary ion mass spectrometry (NanoSIMS) and scanning transmission X-ray microscopy (STXM).

PubMed

Behrens, Sebastian; Kappler, Andreas; Obst, Martin

2012-11-01

Environmental microbiology research increasingly focuses on the single microbial cell as the defining entity that drives environmental processes. The interactions of individual microbial cells with each other, the environment and with higher organisms shape microbial communities and control the functioning of whole ecosystems. A single-cell view of microorganisms in their natural environment requires analytical tools that measure both cell function and chemical speciation at the submicrometre scale. Here we review the technical capabilities and limitations of high-resolution secondary ion mass spectrometry (NanoSIMS) and scanning transmission (soft) X-ray microscopy (STXM) and give examples of their applications. Whereas NanoSIMS can be combined with isotope-labelling, thereby localizing the distribution of cellular activities (e.g. carbon/nitrogen fixation/turnover), STXM provides information on the location and chemical speciation of metabolites and products of redox reactions. We propose the combined use of both techniques and discuss the technical challenges of their joint application. Both techniques have the potential to enhance our understanding of cellular mechanisms and activities that contribute to microbially mediated processes, such as the biogeochemical cycling of elements, the transformation of contaminants and the precipitation of mineral phases. © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.

Simultaneous quantitation and identification of organic and inorganic selenium in diet supplements by liquid chromatography with tandem mass spectrometry.

PubMed

Zembrzuska, Joanna; Matusiewicz, Henryk; Polkowska-Motrenko, Halina; Chajduk, Ewelina

2014-01-01

A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for selenium speciation in dietary supplements. Chromatographic separation was performed on a TSK-Gel ODS-100V column using a mixture of 5mM ammonium acetate water solution and methanol as a mobile phase. Conditions chosen for this process allowed to separate all investigated chemical compounds of selenium: seleno-l-methionine, methyl-seleno-l-cysteine, l-selenocystine, methaneseleninic acid, selenite and selenate. A tandem mass spectrometer with an ion trap operating in negative or positive ion mode according to the selenium form being determined was used as a detector. Three extraction procedures: water extraction, enzymatic hydrolysis and sequential extraction were used for preparation of samples for the determination of the actual forms of selenium in diet supplements. The developed method was used for analysis of six dietary supplements containing selenium bought in a pharmacy and supermarket. Apart from speciation analysis of selenium content in supplements total selenium content was determined using instrumental neutron activation analysis (INAA). All expected forms of selenium except for selenite were determined using LC-MS/MS technique. It should be stressed that amounts of selenate were smaller than expected. Copyright © 2013 Elsevier Ltd. All rights reserved.

Influence of temperature on the molecular composition of ions and charged clusters during pure biogenic nucleation

NASA Astrophysics Data System (ADS)

Frege, Carla; Ortega, Ismael K.; Rissanen, Matti P.; Praplan, Arnaud P.; Steiner, Gerhard; Heinritzi, Martin; Ahonen, Lauri; Amorim, António; Bernhammer, Anne-Kathrin; Bianchi, Federico; Brilke, Sophia; Breitenlechner, Martin; Dada, Lubna; Dias, António; Duplissy, Jonathan; Ehrhart, Sebastian; El-Haddad, Imad; Fischer, Lukas; Fuchs, Claudia; Garmash, Olga; Gonin, Marc; Hansel, Armin; Hoyle, Christopher R.; Jokinen, Tuija; Junninen, Heikki; Kirkby, Jasper; Kürten, Andreas; Lehtipalo, Katrianne; Leiminger, Markus; Mauldin, Roy Lee; Molteni, Ugo; Nichman, Leonid; Petäjä, Tuukka; Sarnela, Nina; Schobesberger, Siegfried; Simon, Mario; Sipilä, Mikko; Stolzenburg, Dominik; Tomé, António; Vogel, Alexander L.; Wagner, Andrea C.; Wagner, Robert; Xiao, Mao; Yan, Chao; Ye, Penglin; Curtius, Joachim; Donahue, Neil M.; Flagan, Richard C.; Kulmala, Markku; Worsnop, Douglas R.; Winkler, Paul M.; Dommen, Josef; Baltensperger, Urs

2018-01-01

It was recently shown by the CERN CLOUD experiment that biogenic highly oxygenated molecules (HOMs) form particles under atmospheric conditions in the absence of sulfuric acid, where ions enhance the nucleation rate by 1-2 orders of magnitude. The biogenic HOMs were produced from ozonolysis of α-pinene at 5 °C. Here we extend this study to compare the molecular composition of positive and negative HOM clusters measured with atmospheric pressure interface time-of-flight mass spectrometers (APi-TOFs), at three different temperatures (25, 5 and -25 °C). Most negative HOM clusters include a nitrate (NO3-) ion, and the spectra are similar to those seen in the nighttime boreal forest. On the other hand, most positive HOM clusters include an ammonium (NH4+) ion, and the spectra are characterized by mass bands that differ in their molecular weight by ˜ 20 C atoms, corresponding to HOM dimers. At lower temperatures the average oxygen to carbon (O : C) ratio of the HOM clusters decreases for both polarities, reflecting an overall reduction of HOM formation with decreasing temperature. This indicates a decrease in the rate of autoxidation with temperature due to a rather high activation energy as has previously been determined by quantum chemical calculations. Furthermore, at the lowest temperature (-25 °C), the presence of C30 clusters shows that HOM monomers start to contribute to the nucleation of positive clusters. These experimental findings are supported by quantum chemical calculations of the binding energies of representative neutral and charged clusters.

Dynamics and fragmentation of van der Waals and hydrogen bonded cluster cations: (NH{sub 3}){sub n} and (NH{sub 3}BH{sub 3}){sub n} ionized at 10.51 eV

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Bing; Bernstein, Elliot R., E-mail: erb@Colostate.edu; Shin, Joong-Won

A 118 nm laser is employed as a high energy, single photon (10.51 eV/photon) source for study of the dynamics and fragmentation of the ammonia borane (NH{sub 3}BH{sub 3}) cation and its cluster ions through time of flight mass spectrometry. The behavior of ammonia ion and its cluster ions is also investigated under identical conditions in order to explicate the ammonia borane results. Charge distributions, molecular orbitals, and spin densities for (NH{sub 3}BH{sub 3}){sub n} and its cations are explored at both the second-order perturbation theory (MP2) and complete active space self-consistent field (CASSCF) theory levels. Initial dissociation mechanisms andmore » potential energy surfaces for ionized NH{sub 3}BH{sub 3}, NH{sub 3}, and their clusters are calculated at the MP2/6-311++G(d,p) level. Protonated clusters (NH{sub 3}){sub x}H{sup +} dominate ammonia cluster mass spectra: our calculations show that formation of (NH{sub 3}){sub n−1}H{sup +} and NH{sub 2} from the nascent (NH{sub 3}){sub n}{sup +} has the lowest energy barrier for the system. The only common features for the (NH{sub 3}){sub n}{sup +} and (NH{sub 3}BH{sub 3}){sub n}{sup +} mass spectra under these conditions are found to be NH{sub y}{sup +} (y = 0,…,4) at m/z = 14–18. Molecular ions with both {sup 11}B and {sup 10}B isotopes are observed, and therefore, product ions observed for the (NH{sub 3}BH{sub 3}){sub n} cluster system derive from (NH{sub 3}BH{sub 3}){sub n} clusters themselves, not from the NH{sub 3} moiety of NH{sub 3}BH{sub 3} alone. NH{sub 3}BH{sub 2}{sup +} is the most abundant ionization product in the (NH{sub 3}BH{sub 3}){sub n}{sup +} cluster spectra: calculations support that for NH{sub 3}BH{sub 3}{sup +}, an H atom is lost from the BH{sub 3} moiety with an energy barrier of 0.67 eV. For (NH{sub 3}BH{sub 3}){sub 2}{sup +} and (NH{sub 3}BH{sub 3}){sub 3}{sup +} clusters, a B{sup δ+}⋯H{sup δ−}⋯{sup δ−}H⋯{sup δ+}B bond can form in the respective cluster ions, generating a lower energy, more stable ion structure. The first step in the (NH{sub 3}BH{sub 3}){sub n}{sup +} (n = 2, 3) dissociation is the breaking of the B{sup δ+}⋯H{sup δ−}⋯{sup δ−}H⋯{sup δ+}B moiety, leading to the subsequent release of H{sub 2} from the latter cluster ion. The overall reaction mechanisms calculated are best represented and understood employing a CASSCF natural bond orbital description of the valence electron distribution for the various clusters and monomers. Comparison of the present results with those found for solid NH{sub 3}BH{sub 3} suggests that NH{sub 3}BH{sub 3} can be a good hydrogen storage material.« less

Polar cap arcs from the magnetosphere to the ionosphere: kinetic modelling and observations by Cluster and TIMED

NASA Astrophysics Data System (ADS)

Maggiolo, R.; Echim, M.; Wedlund, C. Simon; Zhang, Y.; Fontaine, D.; Lointier, G.; Trotignon, J.-G.

2012-02-01

On 1 April 2004 the GUVI imager onboard the TIMED spacecraft spots an isolated and elongated polar cap arc. About 20 min later, the Cluster satellites detect an isolated upflowing ion beam above the polar cap. Cluster observations show that the ions are accelerated upward by a quasi-stationary electric field. The field-aligned potential drop is estimated to about 700 V and the upflowing ions are accompanied by a tenuous population of isotropic protons with a temperature of about 500 eV. The magnetic footpoints of the ion outflows observed by Cluster are situated in the prolongation of the polar cap arc observed by TIMED GUVI. The upflowing ion beam and the polar cap arc may be different signatures of the same phenomenon, as suggested by a recent statistical study of polar cap ion beams using Cluster data. We use Cluster observations at high altitude as input to a quasi-stationary magnetosphere-ionosphere (MI) coupling model. Using a Knight-type current-voltage relationship and the current continuity at the topside ionosphere, the model computes the energy spectrum of precipitating electrons at the top of the ionosphere corresponding to the generator electric field observed by Cluster. The MI coupling model provides a field-aligned potential drop in agreement with Cluster observations of upflowing ions and a spatial scale of the polar cap arc consistent with the optical observations by TIMED. The computed energy spectrum of the precipitating electrons is used as input to the Trans4 ionospheric transport code. This 1-D model, based on Boltzmann's kinetic formalism, takes into account ionospheric processes such as photoionization and electron/proton precipitation, and computes the optical and UV emissions due to precipitating electrons. The emission rates provided by the Trans4 code are compared to the optical observations by TIMED. They are similar in size and intensity. Data and modelling results are consistent with the scenario of quasi-static acceleration of electrons that generate a polar cap arc as they precipitate in the ionosphere. The detailed observations of the acceleration region by Cluster and the large scale image of the polar cap arc provided by TIMED are two different features of the same phenomenon. Combined together, they bring new light on the configuration of the high-latitude magnetosphere during prolonged periods of Northward IMF. Possible implications of the modelling results for optical observations of polar cap arcs are also discussed.

Microsolvation of the potassium ion with aromatic rings: comparison between hexafluorobenzene and benzene.

PubMed

Marques, J M C; Llanio-Trujillo, J L; Albertí, M; Aguilar, A; Pirani, F

2013-08-22

We employ a recently developed methodology to study structural and energetic properties of the first solvation shells of the potassium ion in nonpolar environments due to aromatic rings, which is important to understand the selectivity of several biochemical phenomena. Our evolutionary algorithm is used in the global optimization study of clusters formed of K(+) solvated with hexafluorobenzene (HFBz) molecules. The global intermolecular interaction for these clusters has been decomposed in HFBz-HFBz and in K(+)-HFBz contributions, using a potential model based on different decompositions of the molecular polarizability of hexafluorobenzene. Putative global minimum structures of microsolvation clusters up to 21 hexafluorobenzene molecules were obtained and compared with the analogous K(+)-benzene clusters reported in our previous work (J. Phys. Chem. A 2012, 116, 4947-4956). We have found that both K(+)-(Bz)n and K(+)-(HFBz)n clusters show a strong magic number around the closure of the first solvation shell. Nonetheless, all K(+)-benzene clusters have essentially the same first solvation shell geometry with four solvent molecules around the ion, whereas the corresponding one for K(+)-(HFBz)n is completed with nine HFBz species, and its structural motif varies as n increases. This is attributed to the ion-solvent interaction that has a larger magnitude for K(+)-Bz than in the case of K(+)-HFBz. In addition, the ability of having more HFBz than Bz molecules around K(+) in the first solvation shell is intimately related to the inversion in the sign of the quadrupole moment of the two solvent species, which leads to a distinct ion-solvent geometry of approach.

Enhancement of deuterium retention in damaged tungsten by plasma-induced defect clustering

NASA Astrophysics Data System (ADS)

Jin, Younggil; Roh, Ki-Baek; Sheen, Mi-Hyang; Kim, Nam-Kyun; Song, Jaemin; Kim, Young-Woon; Kim, Gon-Ho

2017-12-01

The enhancement of deuterium retention was investigated for tungsten in the presence of both 2.8 MeV self-ion induced cascade damage and fuel hydrogen isotope plasma. Vacancy clustering in cascade damaged polycrystalline tungsten occurred due to deuterium irradiation and was observed near the grain boundary by using all-step transmission electron microscopy analysis. Analysis of the highest desorption temperature peak using thermal desorption spectroscopy supports reasonable evidence of defect clustering in the damaged polycrystalline tungsten. The defect clustering was neither observed on the damaged polycrystalline tungsten without deuterium irradiation nor on the damaged single-crystalline tungsten with deuterium irradiation. This result implies the synergetic role of deuterium and grain boundary on defect clustering. This study proposes a path for the defect transform from point defect to defect cluster, by the agglomeration between irradiated deuterium and cascade damage-induced defect. This agglomeration may induce more severe damage on the tungsten divertor at which the high fuel hydrogen ions, fast neutrons, and self-ions are irradiated simultaneously and it would increase the in-vessel tritium inventory.

Low-energy collisions of helium clusters with size-selected cobalt cluster ions

NASA Astrophysics Data System (ADS)

Odaka, Hideho; Ichihashi, Masahiko

2017-04-01

Collisions of helium clusters with size-selected cobalt cluster ions, Com+ (m ≤ 5), were studied experimentally by using a merging beam technique. The product ions, Com+Hen (cluster complexes), were mass-analyzed, and this result indicates that more than 20 helium atoms can be attached onto Com+ at the relative velocities of 103 m/s. The measured size distributions of the cluster complexes indicate that there are relatively stable complexes: Co2+Hen (n = 2, 4, 6, and 12), Co3+Hen (n = 3, 6), Co4+He4, and Co5+Hen (n = 3, 6, 8, and 10). These stabilities are explained in terms of their geometric structures. The yields of the cluster complexes were also measured as a function of the relative velocity (1 × 102-4 × 103 m/s), and this result demonstrates that the main interaction in the collision process changes with the increase of the collision energy from the electrostatic interaction, which includes the induced deformation of HeN, to the hard-sphere interaction. Supplementary material in the form of one pdf file available from the Journal web page at http://https://doi.org/10.1140/epjd/e2017-80015-0

Small-scale characterisation of irradiated nuclear materials: Part I – Microstructure

DOE PAGES

Edmondson, P. D.; London, A.; Xu, A.; ...

2014-11-26

The behaviour of nanometre-scale precipitates in oxide dispersion strengthened (ODS) ferritic alloys and tungsten-rhenium alloys for nuclear applications has been examined by atom probe tomography (APT). Low Re content tungsten alloys showed no evidence of Re clustering following self-ion irradiation whereas the 25 at.% Re resulted in cluster formation. The size and composition of clusters varied depending on the material form during irradiation (pre-sharpened needle or bulk). Lastly, these results highlight the care that must be taken in interpreting data from ion irradiated pre-sharpened needles due to the presence of free surfaces. Self-ion irradiation of the ODS ferritic alloy resultedmore » in a change in the composition of the clusters, indicating a transition from a near-stoichiometric Y 2Ti 2O 7 composition towards a Ti 2YO 5.« less

Family level phylogenies reveal modes of macroevolution in RNA viruses.

PubMed

Kitchen, Andrew; Shackelton, Laura A; Holmes, Edward C

2011-01-04

Despite advances in understanding the patterns and processes of microevolution in RNA viruses, little is known about the determinants of viral diversification at the macroevolutionary scale. In particular, the processes by which viral lineages assigned as different "species" are generated remain largely uncharacterized. To address this issue, we use a robust phylogenetic approach to analyze patterns of lineage diversification in five representative families of RNA viruses. We ask whether the process of lineage diversification primarily occurs when viruses infect new host species, either through cross-species transmission or codivergence, and which are defined here as analogous to allopatric speciation in animals, or by acquiring new niches within the same host species, analogous to sympatric speciation. By mapping probable primary host species onto family level viral phylogenies, we reveal a strong clustering among viral lineages that infect groups of closely related host species. Although this is consistent with lineage diversification within individual hosts, we argue that this pattern more likely represents strong biases in our knowledge of viral biodiversity, because we also find that better-sampled human viruses rarely cluster together. Hence, although closely related viruses tend to infect related host species, it is unlikely that they often infect the same host species, such that evolutionary constraints hinder lineage diversification within individual host species. We conclude that the colonization of new but related host species may represent the principle mode of macroevolution in RNA viruses.

Atmospheric speciated mercury concentrations on an island between China and Korea: sources and transport pathways

NASA Astrophysics Data System (ADS)

Lee, G.-S.; Kim, P.-R.; Han, Y.-J.; Holsen, T. M.; Seo, Y.-S.; Yi, S.-M.

2015-11-01

As a global pollutant, mercury (Hg) is of particular concern in East Asia where anthropogenic emissions are the largest. In this study, speciated Hg concentrations were measured in the western most island in Korea, located between China and the Korean mainland to identify the importance of local, regional and distant Hg sources. Various tools including correlations with other pollutants, conditional probability function, and back-trajectory based analysis consistently indicated that Korean sources were important for gaseous oxidized mercury (GOM) whereas, for total gaseous mercury (TGM) and particulate bound mercury (PBM), long-range and regional transport were also important. A trajectory cluster based approach considering both Hg concentration and the fraction of time each cluster was impacting the site was developed to quantify the effect of Korean sources and out-of-Korean source. This analysis suggests that Korean sources contributed approximately 55 % of the GOM and PBM while there were approximately equal contributions from Korean and out-of-Korean sources for the TGM measured at the site. The ratio of GOM / PBM decreased when the site was impacted by long-range transport, suggesting that this ratio may be a useful tool for identifying the relative significance of local sources vs. long-range transport. The secondary formation of PBM through gas-particle partitioning with GOM was found to be important at low temperatures and high relative humidity.

Atmospheric speciated mercury concentrations on an island between China and Korea: sources and transport pathways

NASA Astrophysics Data System (ADS)

Lee, Gang-San; Kim, Pyung-Rae; Han, Young-Ji; Holsen, Thomas M.; Seo, Yong-Seok; Yi, Seung-Muk

2016-03-01

As a global pollutant, mercury (Hg) is of particular concern in East Asia, where anthropogenic emissions are the largest. In this study, speciated Hg concentrations were measured on Yongheung Island, the westernmost island in Korea, located between China and the Korean mainland to identify the importance of local and regional Hg sources. Various tools including correlations with other pollutants, conditional probability function, and back-trajectory-based analysis consistently indicated that Korean sources were important for gaseous oxidized mercury (GOM) whereas, for total gaseous mercury (TGM) and particulate bound mercury (PBM), regional transport was also important. A trajectory cluster based approach, considering both Hg concentration and the fraction of time each cluster was impacting the site, was developed to quantify the effect of Korean sources and out-of-Korean sources. This analysis suggests that contributions from out-of-Korean sources were similar to Korean sources for TGM whereas Korean sources contributed slightly more to the concentration variations of GOM and PBM compared to out-of-Korean sources. The ratio of GOM/PBM decreased when the site was impacted by regional transport, suggesting that this ratio may be a useful tool for identifying the relative significance of local sources vs. regional transport. The secondary formation of PBM through gas-particle partitioning with GOM was found to be important at low temperatures and high relative humidity.

Fine-Tuning the Activity of Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Zhanyong; Peters, Aaron W.; Platero-Prats, Ana E.

Few-atom cobalt-oxide clusters, when dispersed on a Zr-based metal–organic framework (MOF) NU-1000, have previously been shown to be active for the oxidative dehydrogenation (ODH) of propane at low temperatures (< 230 °C), affording a selective and stable propene production catalyst. In our current work, a series of promoter ions with varying Lewis acidity, including Ni(II), Zn(II), Al(III), Ti(IV) and Mo(VI), are anchored as metal-oxide,hydroxide clusters to NU-1000 via SIM (solvothermal deposition within MOFs–specifically the nodes) followed by incorporation of Co(II) ions via vapor-phase AIM (atomic layer deposition (ALD) in MOFs). This process yields a series of NU-1000-supported bimetallic-oxo,hydroxo,aqua clusters. Usingmore » difference envelope density (DED) analyses, the spatial locations of the promoter ions and catalytic cobalt ions are determined. For all samples the SIM-anchored promoter ions are sited between pairs of Zr 6 nodes along the MOF c-axis (channel-aligned axis) whereas the location of the AIM-anchored cobalt ions varies depending on the identity of promoter metal ion. With Ni(II)-, Al(III)-, or Ti(IV)-containing clusters as promoters, the oxy-cobalt species are sited atop the promoter sites; with Mo(VI) they grow exclusively on the MOF nodes sites (hexa-Zr(IV)- oxo,hydroxo,aqua units); with Zn(II) they grow on both the node and promoter. The NU-1000- supported bimetallic-oxide clusters are active for propane ODH after thermal activation under O 2 to open a cobalt coordination site and to oxidize Co(II) to Co(III), as evidenced by operando Xray absorption spectroscopy at the Co K-edge. The cobalt component is exclusively responsible for the observed catalysis. In accord with the decreasing Lewis acidity of the promoter ion, catalytic activity increases in the order: Mo(VI)« less

Fine-Tuning the Activity of Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane

DOE PAGES

Li, Zhanyong; Peters, Aaron W.; Platero-Prats, Ana E.; ...

2017-10-04

Few-atom cobalt-oxide clusters, when dispersed on a Zr-based metal–organic framework (MOF) NU-1000, have previously been shown to be active for the oxidative dehydrogenation (ODH) of propane at low temperatures (< 230 °C), affording a selective and stable propene production catalyst. In our current work, a series of promoter ions with varying Lewis acidity, including Ni(II), Zn(II), Al(III), Ti(IV) and Mo(VI), are anchored as metal-oxide,hydroxide clusters to NU-1000 via SIM (solvothermal deposition within MOFs–specifically the nodes) followed by incorporation of Co(II) ions via vapor-phase AIM (atomic layer deposition (ALD) in MOFs). This process yields a series of NU-1000-supported bimetallic-oxo,hydroxo,aqua clusters. Usingmore » difference envelope density (DED) analyses, the spatial locations of the promoter ions and catalytic cobalt ions are determined. For all samples the SIM-anchored promoter ions are sited between pairs of Zr 6 nodes along the MOF c-axis (channel-aligned axis) whereas the location of the AIM-anchored cobalt ions varies depending on the identity of promoter metal ion. With Ni(II)-, Al(III)-, or Ti(IV)-containing clusters as promoters, the oxy-cobalt species are sited atop the promoter sites; with Mo(VI) they grow exclusively on the MOF nodes sites (hexa-Zr(IV)- oxo,hydroxo,aqua units); with Zn(II) they grow on both the node and promoter. The NU-1000- supported bimetallic-oxide clusters are active for propane ODH after thermal activation under O 2 to open a cobalt coordination site and to oxidize Co(II) to Co(III), as evidenced by operando Xray absorption spectroscopy at the Co K-edge. The cobalt component is exclusively responsible for the observed catalysis. In accord with the decreasing Lewis acidity of the promoter ion, catalytic activity increases in the order: Mo(VI)« less

Vacancy defect and defect cluster energetics in ion-implanted ZnO

NASA Astrophysics Data System (ADS)

Dong, Yufeng; Tuomisto, F.; Svensson, B. G.; Kuznetsov, A. Yu.; Brillson, Leonard J.

2010-02-01

We have used depth-resolved cathodoluminescence, positron annihilation, and surface photovoltage spectroscopies to determine the energy levels of Zn vacancies and vacancy clusters in bulk ZnO crystals. Doppler broadening-measured transformation of Zn vacancies to vacancy clusters with annealing shifts defect energies significantly lower in the ZnO band gap. Zn and corresponding O vacancy-related depth distributions provide a consistent explanation of depth-dependent resistivity and carrier-concentration changes induced by ion implantation.

Transfer-free synthesis of graphene-like atomically thin carbon films on SiC by ion beam mixing technique

NASA Astrophysics Data System (ADS)

Zhang, Rui; Chen, Fenghua; Wang, Jinbin; Fu, Dejun

2018-03-01

Here we demonstrate the synthesis of graphene directly on SiC substrates at 900 °C using ion beam mixing technique with energetic carbon cluster ions on Ni/SiC structures. The thickness of 7-8 nm Ni films was evaporated on the SiC substrates, followed by C cluster ion bombarding. Carbon cluster ions C4 were bombarded at 16 keV with the dosage of 4 × 1016 atoms/cm2. After thermal annealing process Ni silicides were formed, whereas C atoms either from the decomposition of the SiC substrates or the implanted contributes to the graphene synthesis by segregating and precipitating process. The limited solubility of carbon atoms in silicides, involving SiC, Ni2Si, Ni5Si2, Ni3Si, resulted in diffusion and precipitation of carbon atoms to form graphene on top of Ni and the interface of Ni/SiC. The ion beam mixing technique provides an attractive production method of a transfer-free graphene growth on SiC and be compatible with current device fabrication.

Energetic ion bombardment of Ag surfaces by C60+ and Ga+ projectiles.

PubMed

Sun, Shixin; Szakal, Christopher; Winograd, Nicholas; Wucher, Andreas

2005-10-01

The ion bombardment-induced release of particles from a metal surface is investigated using energetic fullerene cluster ions as projectiles. The total sputter yield as well as partial yields of neutral and charged monomers and clusters leaving the surface are measured and compared with corresponding data obtained with atomic projectile ions of similar impact kinetic energy. It is found that all yields are enhanced by about one order of magnitude under bombardment with the C60+ cluster projectiles compared with Ga+ ions. In contrast, the electronic excitation processes determining the secondary ion formation probability are unaffected. The kinetic energy spectra of sputtered particles exhibit characteristic differences which reflect the largely different nature of the sputtering process for both types of projectiles. In particular, it is found that under C60+ impact (1) the energy spectrum of sputtered atoms peaks at significantly lower kinetic energies than for Ga+ bombardment and (2) the velocity spectra of monomers and dimers are virtually identical, a finding which is in pronounced contrast to all published data obtained for atomic projectiles. The experimental findings are in reasonable agreement with recent molecular dynamics simulations.

Heavy-ion dominance near Cluster perigees

NASA Astrophysics Data System (ADS)

Ferradas, C. P.; Zhang, J.-C.; Kistler, L. M.; Spence, H. E.

2015-12-01

Time periods in which heavy ions dominate over H+ in the energy range of 1-40 keV were observed by the Cluster Ion Spectrometry (CIS)/COmposition DIstribution Function (CODIF) instrument onboard Cluster Spacecraft 4 at L values less than 4. The characteristic feature is a narrow flux peak at around 10 keV that extends into low L values, with He+ and/or O+ dominating. In the present work we perform a statistical study of these events and examine their temporal occurrence and spatial distribution. The observed features, both the narrow energy range and the heavy-ion dominance, can be interpreted using a model of ion drift from the plasma sheet, subject to charge exchange losses. The narrow energy range corresponds to the only energy range that has direct drift access from the plasma sheet during quiet times. The drift time to these locations from the plasma sheet is > 30 h, so that charge exchange has a significant impact on the population. We show that a simple drift/loss model can explain the dependence on L shell and MLT of these heavy-ion-dominant time periods.

Linked supramolecular building blocks for enhanced cluster formation

DOE PAGES

McLellan, Ross; Palacios, Maria A.; Beavers, Christine M.; ...

2015-01-09

Methylene-bridged calix[4]arenes have emerged as extremely versatile ligand supports in the formation of new polymetallic clusters possessing fascinating magnetic properties. Metal ion binding rules established for this building block allow one to partially rationalise the complex assembly process. The ability to covalently link calix[4]arenes at the methylene bridge provides significantly improved control over the introduction of different metal centres to resulting cluster motifs. Clusters assembled from bis-calix[4]arenes and transition metal ions or 3d-4f combinations display characteristic features of the analogous calix[4]arene supported clusters, thereby demonstrating an enhanced and rational approach towards the targeted synthesis of complex and challenging structures.

Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide

PubMed Central

Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.

2008-01-01

The division of thermodynamic solvation free energies of electrolytes into ionic constituents is conventionally accomplished by using the single-ion solvation free energy of one reference ion, conventionally the proton, to set the single-ion scales. Thus the determination of the free energy of solvation of the proton in various solvents is a fundamental issue of central importance in solution chemistry. In the present article, relative solvation free energies of ions and ion-solvent clusters in methanol, acetonitrile, and dimethyl sulfoxide (DMSO) have been determined using a combination of experimental and theoretical gas-phase free energies of formation, solution-phase reduction potentials and acid dissociation constants, and gas-phase clustering free energies. Applying the cluster pair approximation to differences between these relative solvation free energies leads to values of −263.5, −260.2, and −273.3 kcal/mol for the absolute solvation free energy of the proton in methanol, acetonitrile, and DMSO, respectively. The final absolute proton solvation free energies are used to assign absolute values for the normal hydrogen electrode potential and the solvation free energies of other single ions in the above solvents. PMID:17214493

Link between EMIC waves in a plasmaspheric plume and a detached sub-auroral proton arc with observations of Cluster and IMAGE satellites

NASA Astrophysics Data System (ADS)

Yuan, Zhigang; Deng, Xiaohua; Lin, Xi; Pang, Ye; Zhou, Meng; Décréau, P. M. E.; Trotignon, J. G.; Lucek, E.; Frey, H. U.; Wang, Jingfang

2010-04-01

In this paper, we report observations from a Cluster satellite showing that ULF wave occurred in the outer boundary of a plasmaspheric plume on September 4, 2005. The band of observed ULF waves is between the He+ ion gyrofrequency and O+ ion gyrofrequency at the equatorial plane, implying that those ULF waves can be identified as EMIC waves generated by ring current ions in the equatorial plane and strongly affected by rich cold He+ ions in plasmaspheric plumes. During the interval of observed EMIC waves, the footprint of Cluster SC3 lies in a subauroral proton arc observed by the IMAGE FUV instrument, demonstrating that the subauroral proton arc was caused by energetic ring current protons scattered into the loss cone under the Ring Current (RC)-EMIC interaction in the plasmaspheric plume. Therefore, the paper provides a direct proof that EMIC waves can be generated in the plasmaspheric plume and scatter RC ions to cause subauroral proton arcs.

Comprehensive track-structure based evaluation of DNA damage by light ions from radiotherapy-relevant energies down to stopping

PubMed Central

Friedland, W.; Schmitt, E.; Kundrát, P.; Dingfelder, M.; Baiocco, G.; Barbieri, S.; Ottolenghi, A.

2017-01-01

Track structures and resulting DNA damage in human cells have been simulated for hydrogen, helium, carbon, nitrogen, oxygen and neon ions with 0.25–256 MeV/u energy. The needed ion interaction cross sections have been scaled from those of hydrogen; Barkas scaling formula has been refined, extending its applicability down to about 10 keV/u, and validated against established stopping power data. Linear energy transfer (LET) has been scored from energy deposits in a cell nucleus; for very low-energy ions, it has been defined locally within thin slabs. The simulations show that protons and helium ions induce more DNA damage than heavier ions do at the same LET. With increasing LET, less DNA strand breaks are formed per unit dose, but due to their clustering the yields of double-strand breaks (DSB) increase, up to saturation around 300 keV/μm. Also individual DSB tend to cluster; DSB clusters peak around 500 keV/μm, while DSB multiplicities per cluster steadily increase with LET. Remarkably similar to patterns known from cell survival studies, LET-dependencies with pronounced maxima around 100–200 keV/μm occur on nanometre scale for sites that contain one or more DSB, and on micrometre scale for megabasepair-sized DNA fragments. PMID:28345622

Comparison of secondary ion intensity enhancement from polymers on silicon and silver substrates by using Au-TOF-SIMS

NASA Astrophysics Data System (ADS)

Kudo, M.; Aimoto, K.; Sunagawa, Y.; Kato, N.; Aoyagi, S.; Iida, S.; Sanada, N.

2008-12-01

The usefulness of the usage of cluster primary ion source together with an Ag substrate and detection of Ag cationized molecular ions was studied from the standpoint to realize high sensitivity TOF-SIMS analysis of organic materials. Although secondary ions from polymer thin films on a Si substrate can be detected in a higher sensitivity with Au 3+ cluster primary ion compared with Ga + ion bombardment, it was clearly observed that the secondary ion intensities from samples on an Ag substrate showed quite a different tendency from that on Si. When monoatomic primary ions, e.g., Au + and Ga +, were used for the measurement of the sample on an Ag substrate, [M+Ag] + ions (M corresponds to polyethylene glycol molecule) were detected in a high sensitivity. On the contrary, when Au 3+ was used, no intensity enhancement of [M+Ag] + ions was observed. The acceleration energy dependence of the detected secondary ions implies the different ionization mechanisms on the different substrates.

Determination and pharmacokinetic properties of arsenic speciation in Xiao-Er-Zhi-Bao-Wan by high-performance liquid chromatography with inductively coupled plasma mass spectrometry.

PubMed

Han, Xu; Luo, Jiaoyang; Zhou, Wenju; Yang, Shihai; Yang, Meihua

2016-10-01

A method of high performance liquid chromatography with a Hamilton PRP-X100 ion-exchange column (250 × 4.1 mm id, 10 μm) coupled to inductively coupled plasma mass spectrometry was employed to generate a full concentration-time profile of arsenic speciation after oral administration. The results exhibited good linearity and revealed that, in the pills, the average arsenic concentration was 10105.4 ± 380.7 mg/kg, and in the water extraction solution, the inorganic As(III) and As(V) concentrations were 220.1 ± 12.6 and 45.5 ± 2.3 mg/kg, respectively. No trace of monomethyl arsenic acid was detected in any of the plasma samples. We then successfully applied the established methodology to examine the pharmacokinetics of arsenic speciation. The resulting data revealed that, after oral administration in rats, the plasma concentration of each arsenic species reached C max shortly after initial dosing, and that the distribution and elimination of As(V) was faster than that of As(III) and dimethyl arsenic acid. Additionally, the t 1/2 values of As(V), As(III), and dimethyl arsenic acid were 3.4 ± 1.6, 14.3 ± 4.0, and 19.9 ± 1.6 h, respectively. This study provides references for the determination of arsenic speciation in mineral-containing medicines and could serve as a useful tool in measuring the true toxicity in traditional medicines that contain them. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective speciation improves efficacy and lowers toxicity of platinum anticancer and vanadium antidiabetic drugs.

PubMed

Doucette, Kaitlin A; Hassell, Kelly N; Crans, Debbie C

2016-12-01

Improving efficacy and lowering resistance to metal-based drugs can be addressed by consideration of the coordination complex speciation and key reactions important to vanadium antidiabetic drugs or platinum anticancer drugs under biological conditions. The methods of analyses vary depending on the specific metal ion chemistry. The vanadium compounds interconvert readily, whereas the reactions of the platinum compounds are much slower and thus much easier to study. However, the vanadium species are readily differentiated due to vanadium complexes differing in color. For both vanadium and platinum systems, understanding the processes as the compounds, Lipoplatin and Satraplatin, enter cells is needed to better combat the disease; there are many cellular metabolites, which may affect processing and thus the efficacy of the drugs. Examples of two formulations of platinum compounds illustrate how changing the chemistry of the platinum will result in less toxic and better tolerated drugs. The consequence of the much lower toxicity of the drug, can be readily realized because cisplatin administration requires hospital stay whereas Lipoplatin can be done in an outpatient manner. Similarly, the properties of Satraplatin allow for development of an oral drug. These forms of platinum demonstrate that the direct consequence of more selective speciation is lower side effects and cheaper administration of the anticancer agent. Therefore we urge that as the community goes forward in development of new drugs, control of speciation chemistry will be considered as one of the key strategies in the future development of anticancer drugs. Copyright © 2016 Elsevier Inc. All rights reserved.

[Effects of Low-Molecular-Weight Organic Acids on the Speciation of Pb in Purple Soil and Soil Solution].

PubMed

Liu, Jiang; Jiang, Tao; Huang, Rong; Zhang, Jin-zhong; Chen, Hong

2016-04-15

Lead (Pb) in purple soil was selected as the research target, using one-step extraction method with 0.01 mol · L⁻¹ sodium nitrate as the background electrolyte to study the release effect of citric acid (CA), tartaric acid (TA) and acetic acid (AC) with different concentrations. Sequential extraction and geochemical model (Visual Minteq v3.0) were applied to analyze and predict the speciation of Pb in soil solid phase and soil solution phase. Then the ebvironmental implications and risks of low-molecule weight organic acid (LMWOA) on soil Pb were analyzed. The results indicated that all three types of LMWOA increased the desorption capacity of Pb in purple soil, and the effect followed the descending order of CA > TA > AC. After the action of LMWOAs, the exchangeable Pb increased; the carbonate-bound Pb and Fe-Mn oxide bound Pb dropped in soil solid phase. Organic bound Pb was the main speciation in soil solution phase, accounting for 45.16%-75.05%. The following speciation of Pb in soil solution was free Pb, accounting for 22.71%-50.25%. For CA and TA treatments, free Pb ions and inorganic bound Pb in soil solution increased with increasing LMWOAs concentration, while organic bound Pb suffered a decrease in this process. An opposite trend for AC treatment was observed compared with CA and TA treatments. Overall, LMWOAs boosted the bioavailability of Pb in purple soil and had a potential risk to contaminate underground water. Among the three LMWOAs in this study, CA had the largest potential to activate soil Pb.

Clustered DNA damages induced by high and low LET radiation, including heavy ions

NASA Technical Reports Server (NTRS)

Sutherland, B. M.; Bennett, P. V.; Schenk, H.; Sidorkina, O.; Laval, J.; Trunk, J.; Monteleone, D.; Sutherland, J.; Lowenstein, D. I. (Principal Investigator)

2001-01-01

Clustered DNA damages--here defined as two or more lesions (strand breaks, oxidized purines, oxidized pyrimidines or abasic sites) within a few helical turns--have been postulated as difficult to repair accurately, and thus highly significant biological lesions. Further, attempted repair of clusters may produce double strand breaks (DSBs). However, until recently, there was no way to measure ionizing radiation-induced clustered damages, except DSB. We recently described an approach for measuring classes of clustered damages (oxidized purine clusters, oxidized pyrimidine clusters, abasic clusters, along with DSB). We showed that ionizing radiation (gamma rays and Fe ions, 1 GeV/amu) does induce such clusters in genomic DNA in solution and in human cells. These studies also showed that each damage cluster results from one radiation hit (and its track), thus indicating that they can be induced by very low doses of radiation, i.e. two independent hits are not required for cluster induction. Further, among all complex damages, double strand breaks comprise--at most-- 20%, with the other clustered damages being at least 80%.

Theoretical Study of Si(x) Ge(y)Li(z) (x=4-10, y=1-10, z=0-10) Clusters for Designing of Novel Nanostructured Materials to be Utilized as Anodes for Lithium-Ion Batteries

DTIC Science & Technology

2015-03-16

AFRL-OSR-VA-TR-2015-0088 Theoretical Study of Novel Nanostructured Materials for Lithium - Ion Batteries Mario Sanchez-Vazquez CENTRO DE INVESTIGACION...SiGeLi Clusters for Design of Novel Nanostructured Materials to Be Utilized as Anodes for Lithium - ion Batteries 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER...utilized as anodes for Lithium - ion batteries Final Report Nancy Perez-Peralta and Mario Sanchez-Vazquez Abstract In order to find out if

Sequential water molecule binding enthalpies for aqueous nanodrops containing a mono-, di- or trivalent ion and between 20 and 500 water molecules† †Electronic supplementary information (ESI) available: Detailed description of the experimental and computational modeling methods. Isolation, BIRD and UVPD sequence for [Ru(NH3)6]3+·(H2O)169–171, nanoESI spectra for 2+ and 3+ ions. Detailed description of the isotope distribution simulation program. Comparison between experimental and simulated 1+, 2+ and 3+ ion isotope distributions. Wavelength dependence of the deduced sequential binding enthalpies. Comparison of experimental UVPD binding enthalpies to the liquid drop model at different temperatures. Complete list of binding enthalpies and average number of water molecules lost upon UVPD. See DOI: 10.1039/c6sc04957e Click here for additional data file.

PubMed Central

Heiles, Sven; Cooper, Richard J.; DiTucci, Matthew J.

2017-01-01

Sequential water molecule binding enthalpies, ΔH n,n–1, are important for a detailed understanding of competitive interactions between ions, water and solute molecules, and how these interactions affect physical properties of ion-containing nanodrops that are important in aerosol chemistry. Water molecule binding enthalpies have been measured for small clusters of many different ions, but these values for ion-containing nanodrops containing more than 20 water molecules are scarce. Here, ΔH n,n–1 values are deduced from high-precision ultraviolet photodissociation (UVPD) measurements as a function of ion identity, charge state and cluster size between 20–500 water molecules and for ions with +1, +2 and +3 charges. The ΔH n,n–1 values are obtained from the number of water molecules lost upon photoexcitation at a known wavelength, and modeling of the release of energy into the translational, rotational and vibrational motions of the products. The ΔH n,n–1 values range from 36.82 to 50.21 kJ mol–1. For clusters containing more than ∼250 water molecules, the binding enthalpies are between the bulk heat of vaporization (44.8 kJ mol–1) and the sublimation enthalpy of bulk ice (51.0 kJ mol–1). These values depend on ion charge state for clusters with fewer than 150 water molecules, but there is a negligible dependence at larger size. There is a minimum in the ΔH n,n–1 values that depends on the cluster size and ion charge state, which can be attributed to the competing effects of ion solvation and surface energy. The experimental ΔH n,n–1 values can be fit to the Thomson liquid drop model (TLDM) using bulk ice parameters. By optimizing the surface tension and temperature change of the logarithmic partial pressure for the TLDM, the experimental sequential water molecule binding enthalpies can be fit with an accuracy of ±3.3 kJ mol–1 over the entire range of cluster sizes. PMID:28451364

An ion-neutral model to investigate chemical ionization mass spectrometry analysis of atmospheric molecules - application to a mixed reagent ion system for hydroperoxides and organic acids

NASA Astrophysics Data System (ADS)

Heikes, Brian G.; Treadaway, Victoria; McNeill, Ashley S.; Silwal, Indira K. C.; O'Sullivan, Daniel W.

2018-04-01

An ion-neutral chemical kinetic model is described and used to simulate the negative ion chemistry occurring within a mixed-reagent ion chemical ionization mass spectrometer (CIMS). The model objective was the establishment of a theoretical basis to understand ambient pressure (variable sample flow and reagent ion carrier gas flow rates), water vapor, ozone and oxides of nitrogen effects on ion cluster sensitivities for hydrogen peroxide (H2O2), methyl peroxide (CH3OOH), formic acid (HFo) and acetic acid (HAc). The model development started with established atmospheric ion chemistry mechanisms, thermodynamic data and reaction rate coefficients. The chemical mechanism was augmented with additional reactions and their reaction rate coefficients specific to the analytes. Some existing reaction rate coefficients were modified to enable the model to match laboratory and field campaign determinations of ion cluster sensitivities as functions of CIMS sample flow rate and ambient humidity. Relative trends in predicted and observed sensitivities are compared as instrument specific factors preclude a direct calculation of instrument sensitivity as a function of sample pressure and humidity. Predicted sensitivity trends and experimental sensitivity trends suggested the model captured the reagent ion and cluster chemistry and reproduced trends in ion cluster sensitivity with sample flow and humidity observed with a CIMS instrument developed for atmospheric peroxide measurements (PCIMSs). The model was further used to investigate the potential for isobaric compounds as interferences in the measurement of the above species. For ambient O3 mixing ratios more than 50 times those of H2O2, O3-(H2O) was predicted to be a significant isobaric interference to the measurement of H2O2 using O2-(H2O2) at m/z 66. O3 and NO give rise to species and cluster ions, CO3-(H2O) and NO3-(H2O), respectively, which interfere in the measurement of CH3OOH using O2-(CH3OOH) at m/z 80. The CO3-(H2O) interference assumed one of its O atoms was 18O and present in the cluster in proportion to its natural abundance. The model results indicated monitoring water vapor mixing ratio, m/z 78 for CO3-(H2O) and m/z 98 for isotopic CO3-(H2O)2 can be used to determine when CO3-(H2O) interference is significant. Similarly, monitoring water vapor mixing ratio, m/z 62 for NO3- and m/z 98 for NO3-(H2O)2 can be used to determine when NO3-(H2O) interference is significant.

Ion-Stockmayer clusters: Minima, classical thermodynamics, and variational ground state estimates of Li+(CH3NO2)n (n = 1-20)

NASA Astrophysics Data System (ADS)

Curotto, E.

2015-12-01

Structural optimizations, classical NVT ensemble, and variational Monte Carlo simulations of ion Stockmayer clusters parameterized to approximate the Li+(CH3NO2)n (n = 1-20) systems are performed. The Metropolis algorithm enhanced by the parallel tempering strategy is used to measure internal energies and heat capacities, and a parallel version of the genetic algorithm is employed to obtain the most important minima. The first solvation sheath is octahedral and this feature remains the dominant theme in the structure of clusters with n ≥ 6. The first "magic number" is identified using the adiabatic solvent dissociation energy, and it marks the completion of the second solvation layer for the lithium ion-nitromethane clusters. It corresponds to the n = 18 system, a solvated ion with the first sheath having octahedral symmetry, weakly bound to an eight-membered and a four-membered ring crowning a vertex of the octahedron. Variational Monte Carlo estimates of the adiabatic solvent dissociation energy reveal that quantum effects further enhance the stability of the n = 18 system relative to its neighbors.

Cluster model studies of anion and molecular specificities via electrospray ionization photoelectron spectroscopy

DOE PAGES

Wang, Xue -Bin

2017-01-06

Ion specificity, a widely observed macroscopic phenomenon in condensed phases and at interfaces, is essentially a fundamental chemical physical issue. We have been investigating such effects using cluster models in an “atom-by-atom” and “molecule-by-molecule” fashion not possible with condensed-phase methods. We use electrospray ionization (ESI) to generate molecular and ionic clusters to simulate key molecular entities involved in local binding regions, and characterize them employing negative ion photoelectron spectroscopy (NIPES). Inter- and intramolecular interactions and binding configurations are directly obtained as functions of cluster size and composition, providing insightful molecular-level description and characterization over the local active sites that playmore » crucial roles in determining solution chemistry and condensed phase phenomena. Finally, the topics covered in this article are relevant to a wide scope of research fields ranging from ion specific effects in electrolyte solutions, ion selectivity/recognition in normal functioning of life, to molecular specificity in aerosol particle formation, as well as in rational material design and synthesis.« less

Conductive tracks of 30-MeV C60 clusters in doped and undoped tetrahedral amorphous carbon

NASA Astrophysics Data System (ADS)

Krauser, J.; Gehrke, H.-G.; Hofsäss, H.; Trautmann, C.; Weidinger, A.

2013-07-01

In insulating tetrahedral amorphous carbon (ta-C), the irradiation with 30-MeV C60 cluster ions leads to the formation of well conducting tracks. While electrical currents through individual tracks produced with monoatomic projectiles (e.g. Au or U) often exhibit rather large track to track fluctuations, C60 clusters are shown to generate highly conducting tracks with very narrow current distributions. Additionally, all recorded current-voltage curves show linear characteristics. These findings are attributed to the large specific energy loss dE/dx of the 30-MeV C60 clusters. We also investigated C60 tracks in ta-C films which were slightly doped with B, N or Fe during film growth. Doping apparently increases the ion track conductivity. However, at the same time the insulating characteristics of the pristine ta-C film can be reduced. The present C60 results are compared with data from earlier experiments with monoatomic heavy ion beams. The investigations were performed by means of atomic force microscopy including temperature dependent conductivity measurements of single ion tracks.

Numerical investigation of depth profiling capabilities of helium and neon ions in ion microscopy

PubMed Central

Rzeznik, Lukasz; Wirtz, Tom

2016-01-01

The analysis of polymers by secondary ion mass spectrometry (SIMS) has been a topic of interest for many years. In recent years, the primary ion species evolved from heavy monatomic ions to cluster and massive cluster primary ions in order to preserve a maximum of organic information. The progress in less-damaging sputtering goes along with a loss in lateral resolution for 2D and 3D imaging. By contrast the development of a mass spectrometer as an add-on tool for the helium ion microscope (HIM), which uses finely focussed He+ or Ne+ beams, allows for the analysis of secondary ions and small secondary cluster ions with unprecedented lateral resolution. Irradiation induced damage and depth profiling capabilities obtained with these light rare gas species have been far less investigated than ion species used classically in SIMS. In this paper we simulated the sputtering of multi-layered polymer samples using the BCA (binary collision approximation) code SD_TRIM_SP to study preferential sputtering and atomic mixing in such samples up to a fluence of 1018 ions/cm2. Results show that helium primary ions are completely inappropriate for depth profiling applications with this kind of sample materials while results for neon are similar to argon. The latter is commonly used as primary ion species in SIMS. For the two heavier species, layers separated by 10 nm can be distinguished for impact energies of a few keV. These results are encouraging for 3D imaging applications where lateral and depth information are of importance. PMID:28144525

Structure of alcohol cluster ions in the gas phase, according to spectrometry and ab initio calculations

NASA Astrophysics Data System (ADS)

Krisilov, A. V.; Lantsuzskaya, E. V.; Levina, A. M.

2017-01-01

Reduced ion mobility and scattering cross sections are calculated from experimentally obtained spectra of the ion mobility of linear aliphatic alcohols with carbon atom numbers from 2 to 9. A linear increase in the scattering cross sections as the molecular weight grows is found. According to the results from experiments and quantum chemical calculations, alcohol cluster ions do not form a compact structure. Neither are dipole moments compensated for during dimerization, in contrast to the aldehydes and ketones described earlier. It was concluded from ab initio calculations that charge delocalization in monomeric and dimeric ions of alcohols increases the dipole moment many times over.

Method optimization and quality assurance in speciation analysis using high performance liquid chromatography with detection by inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Larsen, Erik H.

1998-02-01

Achievement of optimum selectivity, sensitivity and robustness in speciation analysis using high performance liquid chromatography (HPLC) with inductively coupled mass spectrometry (ICP-MS) detection requires that each instrumental component is selected and optimized with a view to the ideal operating characteristics of the entire hyphenated system. An isocratic HPLC system, which employs an aqueous mobile phase with organic buffer constituents, is well suited for introduction into the ICP-MS because of the stability of the detector response and high degree of analyte sensitivity attained. Anion and cation exchange HPLC systems, which meet these requirements, were used for the seperation of selenium and arsenic species in crude extracts of biological samples. Furthermore, the signal-to-noise ratios obtained for these incompletely ionized elements in the argon ICP were further enhanced by a factor of four by continously introducing carbon as methanol via the mobile phase into the ICP. Sources of error in the HPLC system (column overload), in the sample introduction system (memory by organic solvents) and in the ICP-MS (spectroscopic interferences) and their prevention are also discussed. The optimized anion and cation exchange HPLC-ICP-MS systems were used for arsenic speciation in contaminated ground water and in an in-house shrimp reference sample. For the purpose of verification, HPLC coupled with tandem mass spectrometry with electrospray ionization was additionally used for arsenic speciation in the shrimp sample. With this analytical technique the HPLC retention time in combination with mass analysis of the molecular ions and their collision-induced fragments provide almost conclusive evidence of the identity of the analyte species. The speciation methods are validated by establishing a mass balance of the analytes in each fraction of the extraction procedure, by recovery of spikes and by employing and comparing independent techniques. The urgent need for reference materials certified for elemental species is stressed.

Ion-Size-Dependent Formation of Mixed Titanium/Lanthanide Oxo Clusters.

PubMed

Artner, Christine; Kronister, Stefan; Czakler, Matthias; Schubert, Ulrich

2014-11-01

The mixed-metal oxo clusters LnTi 4 O 3 (O i Pr) 2 (OMc) 11 (Ln = La, Ce; OMc = methacrylate), Ln 2 Ti 6 O 6 (OMc) 18 (HO i Pr) (Ln = La, Ce, Nd, Sm) and Ln 2 Ti 4 O 4 (OMc) 14 (HOMc) 2 (Ln = Sm, Eu, Gd, Ho) have been synthesized from titanium isopropoxide, the corresponding lanthanide acetate and methacrylic acid. The type of cluster obtained strongly depends on the size of the lanthanide ion.

Atmospheric ions, boreal forests and impacts on climate

NASA Astrophysics Data System (ADS)

Manninen, H. E.; Nieminen, T.; Franchin, A.; Järvinen, E.; Kontkanen, J.; Hirsikko, A.; Hõrrak, U.; Mirme, A.; Tammet, H.; Kerminen, V.-M.; Petäjä, T.; Kulmala, M.

2012-04-01

Aerosol particles play an important role in the Earth's atmosphere and in the climate system: They scatter and absorb solar radiation, facilitate chemical processes, and serve as seeds for cloud formation. The aerosol particles have direct cooling and warming effects on climate (IPCC, 2007). Secondary new particle formation (NPF) is a globally important source of aerosol particles (Kulmala and Kerminen, 2008). Currently, the mechanisms of particle formation and the vapors participating in this process are, however, not truly understood. Several formation and growth mechanisms have been proposed for the very first steps of the process: homogeneous, heterogeneous, ion-induced and kinetic nucleation and activation type cluster growth. Small ions are part of the atmospheric aerosol spectrum, and in atmospheric sciences study of ion-aerosol interactions is essential. Small ions are small molecular clusters carrying a net electric charge. They are produced by ionisation of molecules in the air. Typically the small ion concentrations vary in the range of 100-2000 cm-3 in both polarities (Hirsikko et al., 2011). Ion-induced NPF is limited by the ion production rate, which typically is around 10 ion pairs cm-3s-1 in the boundary layer over the ground. The ion production rate has strong spatial and temporal dependence. The ionisation mechanisms change with altitude: radon and gamma radiation from the ground and galactic cosmic rays dominate close to the Earth's surface, while higher in the free troposphere cosmic rays become the main driving factor. In order to fully explain atmospheric NPF and subsequent growth, we need to measure directly the very initial steps of the formation processes. Air ion spectrometers measure the mobility distributions of charged aerosol particles in the mobility diameter range of 0.8-42 nm (Mirme et al., 2007; Tammet et al., 2011). Neutral cluster and air ion spectrometers measure additionally the mobility distribution of neutral particles larger than 2 nm in diameter by charging the aerosol sample with unipolar corona chargers (Manninen et al., 2009). According to earlier studies, the atmospheric nucleation and cluster activation take place at the mobility diameter range of 1.5-2 nm. Therefore, the ion spectrometers allow direct measurements at exactly the size where atmospheric nucleation takes place. The results indicate that the ion-induced nucleation contributes ~1-30% to the NPF events in most atmospheric conditions (Manninen et al., 2010). In other words, neutral particle formation seems to dominate over ion-mediated mechanisms, at least in the boreal forest conditions. Acknowledgements. This research was supported by the Academy of Finland Center of Excellence program (project number 1118615). Hirsikko, A. et al.: Atmospheric ions and nucleation: a review of observations, Atmos. Chem. Phys., 11, 767-798, 2011. IPCC, Climate Change 2007: The Physical Science Basis, Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, Cambridge University Press, Cambridge, UK and New York, NY, USA, 996 pp, 2007. Kulmala, M., and Kerminen, V.-M.: On the growth of atmospheric nanoparticles, Atmos. Res., 90, 132-150, 2008. Manninen, H.E. et al.: Long-term field measurements of charged and neutral clusters using Neutral cluster and Air Ion Spectrometer (NAIS). Boreal Env. Res. 14, 591-605, 2009. Manninen, H.E. et al., EUCAARI ion spectrometer measurements at 12 European sites - analysis of new particle formation events, Atmos. Chem. Phys., 10, 7907-7927, 2010. Mirme, A. et al.: A Wide-range multi-channel Air Ion Spectrometer, Boreal Environ. Res., 12, 247-264, 2007. Tammet, H.: Symmetric inclined grid mobility analyzer for the measurement of charged clusters and fine nanoparticles in atmospheric air. Aerosol Science and Technology, 45, 468 - 479, 2011.

Secondary ionisations in a wall-less ion-counting nanodosimeter: quantitative analysis and the effect on the comparison of measured and simulated track structure parameters in nanometric volumes

NASA Astrophysics Data System (ADS)

Hilgers, Gerhard; Bug, Marion U.; Gargioni, Elisabetta; Rabus, Hans

2015-10-01

The object of investigation in nanodosimetry is the physical characteristics of the microscopic structure of ionising particle tracks, i.e. the sequence of the interaction types and interaction sites of a primary particle and all its secondaries, which reflects the stochastic nature of the radiation interaction. In view of the upcoming radiation therapy with protons and carbon ions, the ionisation structure of the ion track is of particular interest. Owing to limitations in current detector technology, the only way to determine the ionisation cluster size distribution in a DNA segment is to simulate the particle track structure in condensed matter. This is done using dedicated computer programs based on Monte Carlo procedures simulating the interaction of the primary ions with the target. Hence, there is a need to benchmark these computer codes using suitable experimental data. Ionisation cluster size distributions produced in the nanodosimeter's sensitive volume by monoenergetic protons and alpha particles (with energies between 0.1 MeV and 20 MeV) were measured at the PTB ion accelerator facilities. C3H8 and N2 were alternately used as the working gas. The measured data were compared with the simulation results obtained with the PTB Monte-Carlo code PTra [B. Grosswendt, Radiat. Environ. Biophys. 41, 103 (2002); M.U. Bug, E. Gargioni, H. Nettelbeck, W.Y. Baek, G. Hilgers, A.B. Rosenfeld, H. Rabus, Phys. Rev. E 88, 043308 (2013)]. Measured and simulated characteristics of the particle track structure are generally in good agreement for protons over the entire energy range investigated. For alpha particles with energies higher than the Bragg peak energy, a good agreement can also be seen, whereas for energies lower than the Bragg peak energy differences of as much as 25% occur. Significant deviations are only observed for large ionisation cluster sizes. These deviations can be explained by a background consisting of secondary ions. These ions are produced in the region downstream of the extraction aperture by electrons with a kinetic energy of about 2.5 keV, which are themselves released by ions of the "primary" ionisation cluster hitting an electrode in the ion transport system. Including this background of secondary ions in the simulated cluster size distributions leads to a significantly better agreement between measured and simulated data, especially for large ionisation clusters.

Speciation and preservation of CrVI and CrIII in finished drinking water matrices using collision cell ion chromatography-inductively coupled plasma-mass spectrometry

EPA Science Inventory

The polyatomic background at the major isotope of Cr was evaluated as a function of collision cell gas flow rate using three different mobile phases. The stability of CrVI was evaluated as a function of solution pH using an enriched 53CrVI. The recovery was ≥ 95% at pH 7.8 but...

Elemental speciation for chromium in chromium picolinate products

NASA Astrophysics Data System (ADS)

Ding, Hong; Olson, Lisa K.; Caruso, Joseph A.

1996-12-01

Chromium picolinate products have been examined for different forms of chromium, using chromatographic separation and inductively coupled plasma mass spectrometric detection. The brands we evaluated contained no detectable amount of elemental chromium(VI), the toxic form. Since chromium picolinate might have other chromium forms as impurities, different products may contain different forms of chromium species. Compared with ion-exchange, reversed-phase chromatography showed excellent chromium recovery based on the amount stated on the product label.

UV-light-driven prebiotic synthesis of iron-sulfur clusters

NASA Astrophysics Data System (ADS)

Bonfio, Claudia; Valer, Luca; Scintilla, Simone; Shah, Sachin; Evans, David J.; Jin, Lin; Szostak, Jack W.; Sasselov, Dimitar D.; Sutherland, John D.; Mansy, Sheref S.

2017-12-01

Iron-sulfur clusters are ancient cofactors that play a fundamental role in metabolism and may have impacted the prebiotic chemistry that led to life. However, it is unclear whether iron-sulfur clusters could have been synthesized on prebiotic Earth. Dissolved iron on early Earth was predominantly in the reduced ferrous state, but ferrous ions alone cannot form polynuclear iron-sulfur clusters. Similarly, free sulfide may not have been readily available. Here we show that UV light drives the synthesis of [2Fe-2S] and [4Fe-4S] clusters through the photooxidation of ferrous ions and the photolysis of organic thiols. Iron-sulfur clusters coordinate to and are stabilized by a wide range of cysteine-containing peptides and the assembly of iron-sulfur cluster-peptide complexes can take place within model protocells in a process that parallels extant pathways. Our experiments suggest that iron-sulfur clusters may have formed easily on early Earth, facilitating the emergence of an iron-sulfur-cluster-dependent metabolism.

What is the minimum number of water molecules required to dissolve a potassium chloride molecule?

PubMed

Sen, Anik; Ganguly, Bishwajit

2010-12-01

This work answers an unsolved question that consists of determining the least number of water molecules necessary to separate a potassium chloride molecule. The answer based on accurate quantum chemical calculations suggests that tetramers are the smallest clusters necessary to dissociate KCl molecules. The study was made with Møller-Plesset second-order perturbation theory modified with the cluster theory having single, double, and perturbative triple excitations. With this extensive study, the dissociation of KCl molecule in different water clusters was evaluated. The calculated results show that four water molecules stabilize a solvent separated K(+)/Cl(-) ion-pair in prismatic structure and with six water molecules further dissociation was observed. Attenuated total reflection infrared spectroscopy of KCl dissolved in water establishes that clusters are made of closely bound ions with a mean of five water molecules per ion-pair [K(+)(H(2)O)(5)Cl(-)]. (Max and Chapados, Appl Spectrosc 1999, 53, 1601; Max and Chapados, J Chem Phys 2001, 115, 2664.) The calculated results tend to support that five water molecules leads toward the formation of contact ion-pair. The structures, energies, and infrared spectra of KCl molecules in different water clusters are also discussed. © 2010 Wiley Periodicals, Inc.

Charging Properties of Cassiterite (alpha-SnO2) Surfaces in NaCl and RbCl Ionic Media.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rosenqvist, Jorgen K; Machesky, Michael L.; Vlcek, Lukas

2009-01-01

The acid-base properties of cassiterite ({alpha}-SnO{sub 2}) surfaces at 10-50 C were studied using potentiometric titrations of powder suspensions in aqueous NaCl and RbCl media. The proton sorption isotherms exhibited common intersection points in the pH range of 4.0-4.5 under all conditions, and the magnitude of charging was similar but not identical in NaCl and RbCl. The hydrogen bonding configuration at the oxide-water interface, obtained from classical molecular dynamics (MD) simulations, was analyzed in detail, and the results were explicitly incorporated in calculations of protonation constants for the reactive surface sites using the revised MUSIC model. The calculations indicated thatmore » the terminal SnOH{sub 2} group is more acidic than the bridging Sn{sub 2}OH group, with protonation constants (log K{sub H}) of 3.60 and 5.13 at 25 C, respectively. This is contrary to the situation on the isostructural {alpha}-TiO{sub 2} (rutile), apparently because of the difference in electronegativity between Ti and Sn. MD simulations and speciation calculations indicated considerable differences in the speciation of Na{sup +} and Rb{sup +}, despite the similarities in overall charging. Adsorbed sodium ions are almost exclusively found in bidentate surface complexes, whereas adsorbed rubidium ions form comparable numbers of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na{sup +} between the different complexes shows a considerable dependence on the surface charge density (pH), whereas the distribution of adsorbed Rb{sup +} is almost independent of pH. A surface complexation model (SCM) capable of accurately describing both the measured surface charge and the MD-predicted speciation of adsorbed Na{sup +}/Rb{sup +} was formulated. According to the SCM, the deprotonated terminal group (SnOH{sup -0.40}) and the protonated bridging group (Sn{sub 2}OH{sup +0.36}) dominate the surface speciation over the entire pH range of this study (2.7-10). The complexation of medium cations increases significantly with increasing negative surface charge, and at pH 10, roughly 40% of the terminal sites are predicted to form cation complexes, whereas anion complexation is minor throughout the studied pH range.« less

Ligand exchange in ionic systems and its effect on silver nucleation and growth.

PubMed

Abbott, Andrew P; Azam, Muhammad; Frisch, Gero; Hartley, Jennifer; Ryder, Karl S; Saleem, Saima

2013-10-28

The electrodeposition of metals from ionic solutions is intrinsically linked to the reactivity of the solute ions. When metal salts dissolve, the exchange of the anion with the molecular and ionic components from solution affects the speciation and therefore the characteristics of metal reduction. This study investigates the nucleation mechanism, deposition kinetics, metal speciation and diffusion coefficients of silver salts dissolved in Deep Eutectic Solvents. The electrochemical reduction of AgCl, AgNO3 and Ag2O is studied in 1 : 2 choline chloride : ethylene glycol and 1 : 2 choline chloride : urea. Cyclic voltammetry is used to evaluate electrochemical kinetics. Detailed analysis of chronoamperometric data shows that silver deposits form via multiple 3D nucleation with mass transport controlled hemispherical growth. The nucleation mechanism was found to be potential dependent, varying from progressive to instantaneous as the reduction potential becomes more cathodic. Diffusion coefficients are determined using three different methods. Trends are rationalised in terms of solvent viscosity and silver speciation analysis with EXAFS. The morphology of electroreduced silver is investigated with scanning electron microscopy and shows that deposits from the urea based liquid form more dense morphologies than those from the ethylene glycol based liquid.

Impact of ozonation on naphthenic acids speciation and toxicity of oil sands process-affected water to Vibrio fischeri and mammalian immune system.

PubMed

Wang, Nan; Chelme-Ayala, Pamela; Perez-Estrada, Leonidas; Garcia-Garcia, Erick; Pun, Jonathan; Martin, Jonathan W; Belosevic, Miodrag; Gamal El-Din, Mohamed

2013-06-18

Oil sands process-affected water (OSPW) is the water contained in tailings impoundment structures in oil sands operations. There are concerns about the environmental impacts of the release of OSPW because of its toxicity. In this study, ozonation followed by biodegradation was used to remediate OSPW. The impacts of the ozone process evolution on the naphthenic acids (NAs) speciation and acute toxicity were evaluated. Ion-mobility spectrometry (IMS) was used to preliminarily separate isomeric and homologous species. The results showed limited effects of the ozone reactor size on the treatment performance in terms of contaminant removal. In terms of NAs speciation, high reactivity of NAs with higher number of carbons and rings was only observed in a region of high reactivity (i.e., utilized ozone dose lower than 50 mg/L). It was also found that nearly 0.5 mg/L total NAs was oxidized per mg/L of utilized ozone dose, at utilized ozone doses lower than 50 mg/L. IMS showed that ozonation was able to degrade NAs, oxidized NAs, and sulfur/nitrogenated NAs. Complete removal of toxicity toward Vibrio fischeri was achieved after ozonation followed by 28-day biodegradation period. In vitro and in vivo assays indicated that ozonation reduced the OSPW toxicity to mice.

Uranium(IV) adsorption by natural organic matter in anoxic sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bone, Sharon E.; Dynes, James J.; Cliff, John

2017-01-09

Uranium is an important fuel source and a global environmental contaminant. It accumulates in the tetravalent state, U(IV), in anoxic sediments, including ore deposits, marine basins, and contaminated aquifers. However, very little is known about the speciation of U(IV) in low temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO 2) in anoxic sediments; yet studies now show that UO 2 is not often dominant in these environments. However, a model of U(IV) speciation under environmentally relevant conditions has not yetmore » been developed. Here we show that complexes of U(IV) adsorb on organic carbon and organic carbon-coated clays in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that the U(IV) product depended on the reduction pathway, our results demonstrate that UO 2 formation can be inhibited simply by decreasing the U:solid ratio. Thus, it is the number and type of surface ligands that controls U(IV) speciation subsequent to U(VI) reduction. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider retention of U(IV) ions within the local sediment environment.« less

Antimony leaching and chemical species analyses in an industrial solid waste: Surface and bulk speciation using ToF-SIMS and XANES.

PubMed

Kappen, P; Ferrando-Miguel, G; Reichman, S M; Innes, L; Welter, E; Pigram, P J

2017-05-05

The surface chemistry and bulk chemical speciation of solid industrial wastes containing 8wt-% antimony (Sb) were investigated using synchrotron X-ray Absorption Near Edge Structure (XANES) and Time-of-Flight Ion Secondary Mass Spectrometry (ToF-SIMS). Leaching experiments were conducted in order to better understand the behavior of Sb in waste streams and to inform regulatory management of antimony-containing wastes. The experiments also demonstrate how a combination of XANES and ToF-SIMS adds value to the field of waste investigations. Leaching treatments (acid and base) were performed at a synchrotron over 24h time periods. Surface analyses of the wastes before leaching showed the presence of Sb associated with S and O. Bulk analyses revealed Sb to be present, primarily, as trivalent sulfide species. Both acid and base leaching did not change the antimony speciation on the solid. Leaching transferred about 1% of the total Sb into solution where Sb was found to be present as Sb(V). XANES data showed similarities between leachate and FeSbO 4 . During base leaching, the Sb content in solution gradually increased over time, and potential desorption mechanisms are discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Selective speciation and determination of inorganic arsenic in water, food and biological samples.

PubMed

Tuzen, Mustafa; Saygi, Kadriye Ozlem; Karaman, Isa; Soylak, Mustafa

2010-01-01

A procedure for the speciation of arsenic(III) and arsenic(V) in natural water samples has been established in the presented work. Arsenic(III) ions were quantitatively recovered on Alternaria solani coated Diaion HP-2MG resin at pH 7, while the recoveries of arsenic(V) was below 10%. Arsenic(V) in the mixing solution containing As(III) and As(V) was reduced by using KI and L(+) ascorbic acid solution, then the procedure was applied to determination of total arsenic. Arsenic(V) was calculated as the difference between the total arsenic content and As(III) content. The determination of arsenic was performed by using hydride generation atomic absorption spectrometry. The influences of some alkali, earth alkali and transition metals on the biosorption of arsenic(III) were investigated. The preconcentration factor was 35. The detection limits for As(III) (N=20, k=3) was found as 11 ng L(-1). The relative standard deviation and relative error of the determinations were found to be lower than 7% and 4%, respectively. The accuracy of the method was confirmed with certified reference materials. The method was successively applied for the determination and speciation of inorganic arsenic in water, food and biological samples. Copyright 2009 Elsevier Ltd. All rights reserved.

Comparison of the SAWNUC model with CLOUD measurements of sulphuric acid-water nucleation.

PubMed

Ehrhart, Sebastian; Ickes, Luisa; Almeida, Joao; Amorim, Antonio; Barmet, Peter; Bianchi, Federico; Dommen, Josef; Dunne, Eimear M; Duplissy, Jonathan; Franchin, Alessandro; Kangasluoma, Juha; Kirkby, Jasper; Kürten, Andreas; Kupc, Agnieszka; Lehtipalo, Katrianne; Nieminen, Tuomo; Riccobono, Francesco; Rondo, Linda; Schobesberger, Siegfried; Steiner, Gerhard; Tomé, António; Wimmer, Daniela; Baltensperger, Urs; Wagner, Paul E; Curtius, Joachim

2016-10-27

Binary nucleation of sulphuric acid-water particles is expected to be an important process in the free troposphere at low temperatures. SAWNUC (Sulphuric Acid Water Nucleation) is a model of binary nucleation that is based on laboratory measurements of the binding energies of sulphuric acid and water in charged and neutral clusters. Predictions of SAWNUC are compared for the first time comprehensively with experimental binary nucleation data from the CLOUD chamber at European Organization for Nuclear Research. The experimental measurements span a temperature range of 208-292 K, sulphuric acid concentrations from 1·10 6 to 1·10 9  cm -3 , and distinguish between ion-induced and neutral nucleation. Good agreement, within a factor of 5, is found between the experimental and modeled formation rates for ion-induced nucleation at 278 K and below and for neutral nucleation at 208 and 223 K. Differences at warm temperatures are attributed to ammonia contamination which was indicated by the presence of ammonia-sulphuric acid clusters, detected by an Atmospheric Pressure Interface Time of Flight (APi-TOF) mass spectrometer. APi-TOF measurements of the sulphuric acid ion cluster distributions ( (H2SO4)i·HSO4- with i = 0, 1, ..., 10) show qualitative agreement with the SAWNUC ion cluster distributions. Remaining differences between the measured and modeled distributions are most likely due to fragmentation in the APi-TOF. The CLOUD results are in good agreement with previously measured cluster binding energies and show the SAWNUC model to be a good representation of ion-induced and neutral binary nucleation of sulphuric acid-water clusters in the middle and upper troposphere.

Multiheteromacrocycles that Complex Metal Ions. Ninth Progress Report (includes results of last three years), 1 May 1980 -- 30 April 1983

DOE R&D Accomplishments Database

Cram, D. J.

1982-09-15

The overall objective of this research is to design, synthesize, and evaluate cyclic and polycyclic host organic compounds for the abilities to complex and lipophilize guest metal ions, their complexes, and their clusters. Host organic compounds consist of strategically placed solvating, coordinating, and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions, or by metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; numbers of binding sites; characters of binding sites; and valences. The hope is to synthesize new classes of compounds useful in the separation of metal ions, their complexes, and their clusters.

Quasichemical analysis of the cluster-pair approximation for the thermodynamics of proton hydration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pollard, Travis; Beck, Thomas L.; Department of Physics, University of Cincinnati, Cincinnati, Ohio 45221

2014-06-14

A theoretical analysis of the cluster-pair approximation (CPA) is presented based on the quasichemical theory of solutions. The sought single-ion hydration free energy of the proton includes an interfacial potential contribution by definition. It is shown, however, that the CPA involves an extra-thermodynamic assumption that does not guarantee uniform convergence to a bulk free energy value with increasing cluster size. A numerical test of the CPA is performed using the classical polarizable AMOEBA force field and supporting quantum chemical calculations. The enthalpy and free energy differences are computed for the kosmotropic Na{sup +}/F{sup −} ion pair in water clusters ofmore » size n = 5, 25, 105. Additional calculations are performed for the chaotropic Rb{sup +}/I{sup −} ion pair. A small shift in the proton hydration free energy and a larger shift in the hydration enthalpy, relative to the CPA values, are predicted based on the n = 105 simulations. The shifts arise from a combination of sequential hydration and interfacial potential effects. The AMOEBA and quantum chemical results suggest an electrochemical surface potential of water in the range −0.4 to −0.5 V. The physical content of single-ion free energies and implications for ion-water force field development are also discussed.« less

Incipient sympatric speciation in Midas cichlid fish from the youngest and one of the smallest crater lakes in Nicaragua due to differential use of the benthic and limnetic habitats?

PubMed

Kautt, Andreas F; Machado-Schiaffino, Gonzalo; Torres-Dowdall, Julian; Meyer, Axel

2016-08-01

Understanding how speciation can occur without geographic isolation remains a central objective in evolutionary biology. Generally, some form of disruptive selection and assortative mating are necessary for sympatric speciation to occur. Disruptive selection can arise from intraspecific competition for resources. If this competition leads to the differential use of habitats and variation in relevant traits is genetically determined, then assortative mating can be an automatic consequence (i.e., habitat isolation). In this study, we caught Midas cichlid fish from the limnetic (middle of the lake) and benthic (shore) habitats of Crater Lake Asososca Managua to test whether some of the necessary conditions for sympatric speciation due to intraspecific competition and habitat isolation are given. Lake As. Managua is very small (<900 m in diameter), extremely young (maximally 1245 years of age), and completely isolated. It is inhabited by, probably, only a single endemic species of Midas cichlids, Amphilophus tolteca. We found that fish from the limnetic habitat were more elongated than fish collected from the benthic habitat, as would be predicted from ecomorphological considerations. Stable isotope analyses confirmed that the former also exhibit a more limnetic lifestyle than the latter. Furthermore, split-brood design experiments in the laboratory suggest that phenotypic plasticity is unlikely to explain much of the observed differences in body elongation that we observed in the field. Yet, neutral markers (microsatellites) did not reveal any genetic clustering in the population. Interestingly, demographic inferences based on RAD-seq data suggest that the apparent lack of genetic differentiation at neutral markers could simply be due to a lack of time, as intraspecific competition may only have begun a few hundred generations ago.

Effects of molecular weight and cationization agent on the sensitivity of Bi cluster secondary ion mass spectrometry.

PubMed

Fujii, Makiko; Shishido, Rie; Satoh, Takaya; Suzuki, Shigeru; Matsuo, Jiro

2016-07-30

Bi cluster secondary ion mass spectrometry (SIMS) is one of the most promising tools for precise analysis of synthetic polymers. However, the sensitivity in the high-mass region is still insufficient compared with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). Accordingly, the effects of metal assistance (cationization agents) were investigated in this study. To investigate the effects caused by varying the ionization agent, three different polyethylene glycol (PEG) samples were prepared, one with an Ag-deposited film, and two others mixed with Ag and Na, respectively. The measurements were performed by using a commercial Bi cluster SIMS and MALDI-TOFMS systems. The mass spectrum obtained with MALDI-TOFMS was used as a reference molecular weight distribution to evaluate the effects of molecular weight and primary ion species (Bi + , Bi 3 + , Bi 3 2 + ) on the sensitivity of Bi cluster SIMS. The intensity of each secondary ion was the highest in Bi 3 2 + irradiation, and the lowest in Bi + irradiation. Regarding the cationization agents, the secondary ion yield was the highest for the sample mixed with Ag, while the degree of decay of sensitivity along with the increase in molecular weight was the smallest for the sample mixed with Na. It was suggested that the cationization mechanism consists of pre-formed ionization and gas-phase ionization processes. The sensitivity of Bi cluster SIMS decreases to approximately one-fiftieth in every 1000 u. These results might help in understanding the mechanism of cationization and further enhancement of secondary ion yields of polymers. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

The sensitivity of benzene cluster cation chemical ionization mass spectrometry to select biogenic terpenes

NASA Astrophysics Data System (ADS)

Lavi, Avi; Vermeuel, Michael P.; Novak, Gordon A.; Bertram, Timothy H.

2018-06-01

Benzene cluster cations are a sensitive and selective reagent ion for chemical ionization of select biogenic volatile organic compounds. We have previously reported the sensitivity of a field deployable chemical ionization time-of-flight mass spectrometer (CI-ToFMS), using benzene cluster cation ion chemistry, for detection of dimethyl sulfide, isoprene and α-pinene. Here, we present laboratory measurements of the sensitivity of the same instrument to a series of terpenes, including isoprene, α-pinene, β-pinene, D-limonene, ocimene, β-myrcene, farnesene, α-humulene, β-caryophyllene, and isolongifolene at atmospherically relevant mixing ratios (< 100 pptv). In addition, we determine the dependence of CI-ToFMS sensitivity on the reagent ion neutral delivery concentration and water vapor concentration. We show that isoprene is primarily detected as an adduct (C5H8 ṡ C6H6+) with a sensitivity ranging between 4 and 10 ncps ppt-1, which depends strongly on the reagent ion precursor concentration, de-clustering voltages, and specific humidity (SH). Monoterpenes are detected primarily as the molecular ion (C10H16+) with an average sensitivity, across the five measured compounds, of 14 ± 3 ncps ppt-1 for SH between 7 and 14 g kg-1, typical of the boreal forest during summer. Sesquiterpenes are detected primarily as the molecular ion (C15H24+) with an average sensitivity, across the four measured compounds, of 9.6 ± 2.3 ncps ppt-1, that is also independent of specific humidity. Comparable sensitivities across broad classes of terpenes (e.g., monoterpenes and sesquiterpenes), coupled to the limited dependence on specific humidity, suggest that benzene cluster cation CI-ToFMS is suitable for field studies of biosphere-atmosphere interactions.

The new ClusterTrap setup

NASA Astrophysics Data System (ADS)

Martinez, F.; Marx, G.; Schweikhard, L.; Vass, A.; Ziegler, F.

2011-07-01

ClusterTrap has been designed to investigate properties of atomic clusters in the gas phase with particular emphasis on the dependence on the cluster size and charge state. The combination of cluster source, Penning trap and time-of-flight mass spectrometry allows a variety of experimental schemes including collision-induced dissociation, photo-dissociation, further ionization by electron impact, and electron attachment. Due to the storage capability of the trap extended-delay reaction experiments can be performed. Several recent modifications have resulted in an improved setup. In particular, an electrostatic quadrupole deflector allows the coupling of several sources or detectors to the Penning trap. Furthermore, a linear radio-frequency quadrupole trap has been added for accumulation and ion bunching and by switching the potential of a drift tube the kinetic energy of the cluster ions can be adjusted on their way towards or from the Penning trap. Recently, experiments on multiply negatively charged clusters have been resumed.

Properties of Prussian blue materials manifested in molecular complexes: observation of cyanide linkage isomerism and spin-crossover behavior in pentanuclear cyanide clusters.

PubMed

Shatruk, Mikhail; Dragulescu-Andrasi, Alina; Chambers, Kristen E; Stoian, Sebastian A; Bominaar, Emile L; Achim, Catalina; Dunbar, Kim R

2007-05-16

Pentanuclear, cyanide-bridged clusters [M(tmphen)2]3[M'(CN)6]2 (M/M' = Zn/Cr (1), Zn/Fe (2), Fe/Fe (3), Fe/Co (4), and Fe/Cr (5); tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline) were prepared by combining [M'III(CN)6]3- anions with mononuclear complexes of MII ions with two capping tmphen ligands. The clusters consist of a trigonal bipyramidal (TBP) core with three MII ions in the equatorial positions and two M'III ions in the axial positions. Compounds 1-4 are isostructural and crystallize in the monoclinic space group P21/c. Complex 5 crystallizes in the enantiomorphic space group P3221. The magnetic properties of compounds 1 and 2 reflect the contributions of the individual [CrIII(CN)6]3- and [FeIII(CN)6]3- ions. The FeII ions in compounds 3 and 4 exhibit a gradual, temperature-induced spin transition between high spin (HS) and low spin (LS), as determined by the combination of Mössbauer spectroscopy, magnetic measurements, and single-crystal X-ray studies. The investigation of compound 5 by these methods and by IR spectroscopy indicates that cyanide linkage isomerism occurs during cluster formation. The magnetic behavior of 5 is determined by weak ferromagnetic coupling between the axial CrIII centers mediated by the equatorial diamagnetic FeII ions. Mössbauer spectra collected in the presence of a high applied field have allowed, for the first time, the direct experimental observation of uncompensated spin density at diamagnetic metal ions that bridge paramagnetic metal ions.

Buffer Gas Modifiers Effect Resolution in Ion Mobility Spectrometry through Selective Ion-Molecule Clustering Reactions

PubMed Central

Fernández-Maestre, Roberto; Wu, Ching; Hill, Herbert H.

2013-01-01

RATIONALE When polar molecules (modifiers) are introduced into the buffer gas of an ion mobility spectrometer, most ion mobilities decrease due to the formation of ion-modifier clusters. METHODS We used ethyl lactate, nitrobenzene, 2-butanol, and tetrahydrofuran-2-carbonitrile as buffer gas modifiers and electrospray ionization ion mobility spectrometry (IMS) coupled to quadrupole mass spectrometry. Ethyl lactate, nitrobenzene, and tetrahydrofuran-2-carbonitrile had not been tested as buffer gas modifiers and 2-butanol had not been used with basic amino acids. RESULTS The ion mobilities of several diamines (arginine, histidine, lysine, and atenolol) were not affected or only slightly reduced when these modifiers were introduced into the buffer gas (3.4% average reduction in an analyte's mobility for the three modifiers). Intramolecular bridges caused limited change in the ion mobilities of diamines when modifiers were added to the buffer gas; these bridges hindered the attachment of modifier molecules to the positive charge of ions and delocalized the charge, which deterred clustering. There was also a tendency towards large changes in ion mobility when the mass of the analyte decreased; ethanolamine, the smallest compound tested, had the largest reduction in ion mobility with the introduction of modifiers into the buffer gas (61%). These differences in mobilities, together with the lack of shift in bridge-forming ions, were used to separate ions that overlapped in IMS, such as isoleucine and lysine, and arginine and phenylalanine, and made possible the prediction of separation or not of overlapping ions. CONCLUSIONS The introduction of modifiers into the buffer gas in IMS can selectively alter the mobilities of analytes to aid in compound identification and/or enable the separation of overlapping analyte peaks. PMID:22956312

Arsenate reductase from Thermus thermophilus conjugated to polyethylene glycol-stabilized gold nanospheres allow trace sensing and speciation of arsenic ions.

PubMed

Politi, Jane; Spadavecchia, Jolanda; Fiorentino, Gabriella; Antonucci, Immacolata; De Stefano, Luca

2016-10-01

Water sources pollution by arsenic ions is a serious environmental problem all around the world. Arsenate reductase enzyme (TtArsC) from Thermus thermophilus extremophile bacterium, naturally binds arsenic ions, As(V) and As (III), in aqueous solutions. In this research, TtArsC enzyme adsorption onto hybrid polyethylene glycol-stabilized gold nanoparticles (AuNPs) was studied at different pH values as an innovative nanobiosystem for metal concentration monitoring. Characterizations were performed by UV/Vis and circular dichroism spectroscopies, TEM images and in terms of surface charge changes. The molecular interaction between arsenic ions and the TtArsC-AuNPs nanobiosystem was also monitored at all pH values considered by UV/Vis spectroscopy. Tests performed revealed high sensitivities and limits of detection equal to 10 ± 3 M -12 and 7.7 ± 0.3 M -12 for As(III) and As(V), respectively. © 2016 The Author(s).

Evaluation of biomolecular distributions in rat brain tissues by means of ToF-SIMS using a continuous beam of Ar clusters.

PubMed

Nakano, Shusuke; Yokoyama, Yuta; Aoyagi, Satoka; Himi, Naoyuki; Fletcher, John S; Lockyer, Nicholas P; Henderson, Alex; Vickerman, John C

2016-06-08

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) provides detailed chemical structure information and high spatial resolution images. Therefore, ToF-SIMS is useful for studying biological phenomena such as ischemia. In this study, in order to evaluate cerebral microinfarction, the distribution of biomolecules generated by ischemia was measured with ToF-SIMS. ToF-SIMS data sets were analyzed by means of multivariate analysis for interpreting complex samples containing unknown information and to obtain biomolecular mapping indicated by fragment ions from the target biomolecules. Using conventional ToF-SIMS (primary ion source: Bi cluster ion), it is difficult to detect secondary ions beyond approximately 1000 u. Moreover, the intensity of secondary ions related to biomolecules is not always high enough for imaging because of low concentration even if the masses are lower than 1000 u. However, for the observation of biomolecular distributions in tissues, it is important to detect low amounts of biological molecules from a particular area of tissue. Rat brain tissue samples were measured with ToF-SIMS (J105, Ionoptika, Ltd., Chandlers Ford, UK), using a continuous beam of Ar clusters as a primary ion source. ToF-SIMS with Ar clusters efficiently detects secondary ions related to biomolecules and larger molecules. Molecules detected by ToF-SIMS were examined by analyzing ToF-SIMS data using multivariate analysis. Microspheres (45 μm diameter) were injected into the rat unilateral internal carotid artery (MS rat) to cause cerebral microinfarction. The rat brain was sliced and then measured with ToF-SIMS. The brain samples of a normal rat and the MS rat were examined to find specific secondary ions related to important biomolecules, and then the difference between them was investigated. Finally, specific secondary ions were found around vessels incorporating microspheres in the MS rat. The results suggest that important biomolecules related to cerebral microinfarction can be detected by ToF-SIMS.

Observation of novel photochemistry in the multiphoton ionization of Mo(CO) sub 6 van der Waals clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peifer, W.R.; Garvey, J.F.

1989-07-27

van der Waals clusters of Mo(CO){sub 6} generated in the free-jet expansion of a pulsed beam of seeded helium are subjected to multiphoton ionization and the product ions analyzed by quadrupole mass spectrometry. Oxomolybdenum and dioxomolybdenum ions are observed to be produced with high efficiency. This behavior is in striking contrast to that of metal carbonyl monomers and covalently bound cluster carbonyls, which under complete ligand loss prior to ionization. The observed photochemistry is ascribed to reactions between a photoproduced molybdenum atom and the ligands of neighboring Mo(CO){sub 6} solvent molecules within the van der Waals cluster.

Ions in motor vehicle exhaust and their dispersion near busy roads

NASA Astrophysics Data System (ADS)

Jayaratne, E. R.; Ling, X.; Morawska, L.

2010-09-01

Measurements in the exhaust plume of a petrol-driven motor car showed that molecular cluster ions of both signs were present in approximately equal amounts. The emission rate increased sharply with engine speed while the charge symmetry remained unchanged. Measurements at the kerbside of nine motorways and five city roads showed that the mean total cluster ion concentration near city roads (603 cm -3) was about one-half of that near motorways (1211 cm -3) and about twice as high as that in the urban background (269 cm -3). Both positive and negative ion concentrations near a motorway showed a significant linear increase with traffic density ( R2 = 0.3 at p < 0.05) and correlated well with each other in real time ( R2 = 0.87 at p < 0.01). Heavy duty diesel vehicles comprised the main source of ions near busy roads. Measurements were conducted as a function of downwind distance from two motorways carrying around 120-150 vehicles per minute. Total traffic-related cluster ion concentrations decreased rapidly with distance, falling by one-half from the closest approach of 2 m to 5 m of the kerb. Measured concentrations decreased to background at about 15 m from the kerb when the wind speed was 1.3 m s -1, this distance being greater at higher wind speed. The number and net charge concentrations of aerosol particles were also measured. Unlike particles that were carried downwind to distances of a few hundred metres, cluster ions emitted by motor vehicles were not present at more than a few tens of metres from the road.

Smoothing metallic glasses without introducing crystallization by gas cluster ion beam

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shao, Lin; Chen, Di; Myers, Michael

2013-03-11

We show that 30 keV Ar cluster ion bombardment of Ni{sub 52.5}Nb{sub 10}Zr{sub 15}Ti{sub 15}Pt{sub 7.5} metallic glass (MG) can remove surface mountain-like features and reduce the root mean square surface roughness from 12 nm to 0.7 nm. X-ray diffraction analysis reveals no crystallization after cluster ion irradiation. Molecular dynamics simulations show that, although damage cascades lead to local melting, the subsequent quenching rate is a few orders of magnitude higher than the critical cooling rate for MG formation, thus the melted zone retains its amorphous nature down to room temperature. These findings can be applied to obtain ultra-smooth MGsmore » without introducing crystallization.« less

Formation of multiply charged ions from large molecules using massive-cluster impact.

PubMed

Mahoney, J F; Cornett, D S; Lee, T D

1994-05-01

Massive-cluster impact is demonstrated to be an effective ionization technique for the mass analysis of proteins as large as 17 kDa. The design of the cluster source permits coupling to both magnetic-sector and quadrupole mass spectrometers. Mass spectra are characterized by the almost total absence of chemical background and a predominance of multiply charged ions formed from 100% glycerol matrix. The number of charge states produced by the technique is observed to range from +3 to +9 for chicken egg lysozyme (14,310 Da). The lower m/z values provided by higher charge states increase the effective mass range of analyses performed with conventional ionization by fast-atom bombardment or liquid secondary ion mass spectrometry.

A framework to spatially cluster air pollution monitoring sites in US based on the PM2.5 composition

PubMed Central

Austin, Elena; Coull, Brent A.; Zanobetti, Antonella; Koutrakis, Petros

2013-01-01

Background Heterogeneity in the response to PM2.5 is hypothesized to be related to differences in particle composition across monitoring sites which reflect differences in source types as well as climatic and topographic conditions impacting different geographic locations. Identifying spatial patterns in particle composition is a multivariate problem that requires novel methodologies. Objectives Use cluster analysis methods to identify spatial patterns in PM2.5 composition. Verify that the resulting clusters are distinct and informative. Methods 109 monitoring sites with 75% reported speciation data during the period 2003–2008 were selected. These sites were categorized based on their average PM2.5 composition over the study period using k-means cluster analysis. The obtained clusters were validated and characterized based on their physico-chemical characteristics, geographic locations, emissions profiles, population density and proximity to major emission sources. Results Overall 31 clusters were identified. These include 21 clusters with 2 or more sites which were further grouped into 4 main types using hierarchical clustering. The resulting groupings are chemically meaningful and represent broad differences in emissions. The remaining clusters, encompassing single sites, were characterized based on their particle composition and geographic location. Conclusions The framework presented here provides a novel tool which can be used to identify and further classify sites based on their PM2.5 composition. The solution presented is fairly robust and yielded groupings that were meaningful in the context of air-pollution research. PMID:23850585

Speciation of copper diffused in a bi-porous molecular sieve

NASA Astrophysics Data System (ADS)

Huang, C.-H.; Paul Wang, H.; Wei, Y.-L.; Chang, J.-E.

2010-07-01

To better understand diffusion of copper in the micro- and mesopores, speciation of copper in a bi-porous molecular sieve (BPMS) possessing inter-connecting 3-D micropores (0.50-0.55 nm) and 2-D mesopores (4.1 nm) has been studied by X-ray absorption near edge structure (XANES) spectroscopy. It is found that about 77% (16% of CuO nanoparticles and 61% of CuO clusters) and 23% (CuO ads) of copper can be diffused into the meso- and micropores, respectively, in the BPMS. At least two diffusion steps in the BPMS may be involved: (i) free diffusion of copper in the mesopores and (ii) diffusion-controlled copper migrating into the micropores of the BPMS. The XANES data also indicate that diffusion rate of copper in the BPMS (4.68×10 -5 g/s) is greater than that in the ZSM-5 (1.11×10 -6 g/s) or MCM-41 (1.17×10 -5 g/s).

Reversible Electrochemical Lithium-Ion Insertion into the Rhenium Cluster Chalcogenide-Halide Re6Se8Cl2.

PubMed

Bruck, Andrea M; Yin, Jiefu; Tong, Xiao; Takeuchi, Esther S; Takeuchi, Kenneth J; Szczepura, Lisa F; Marschilok, Amy C

2018-05-07

The cluster-based material Re 6 Se 8 Cl 2 is a two-dimensional ternary material with cluster-cluster bonding across the a and b axes capable of multiple electron transfer accompanied by ion insertion across the c axis. The Li/Re 6 Se 8 Cl 2 system showed reversible electron transfer from 1 to 3 electron equivalents (ee) at high current densities (88 mA/g). Upon cycling to 4 ee, there was evidence of capacity degradation over 50 cycles associated with the formation of an organic solid-electrolyte interface (between 1.45 and 1 V vs Li/Li + ). This investigation highlights the ability of cluster-based materials with two-dimensional cluster bonding to be used in applications such as energy storage, showing structural stability and high rate capability.

Measuring free metal ion concentrations in situ in natural waters using the Donnan Membrane Technique.

PubMed

Kalis, Erwin J J; Weng, Liping; Dousma, Freerk; Temminghoff, Erwin J M; Van Riemsdijk, Willem H

2006-02-01

Metal toxicity is not related to the total but rather to the free or labile metal ion concentration. One of the techniques that can be used to measure several free metal ion concentrations simultaneously is the Donnan Membrane Technique (DMT) in combination with the inductively coupled plasma-mass spectrometer (ICP-MS). However, free metal ion concentrations in natural waters are commonly below the detection limit of ICP-MS. We decreased the detection limit by making use of a ligand, and we developed a field DMT cell that can be applied in situ in natural waters. A kinetic approach can be used to calculate free metal ion concentrations when the equilibrium time becomes too large. The field DMT measured in situ in natural waters a free metal ion concentration ranging from 0.015% (Cu) to 13% (Zn) of a total metal concentration ranging from 0.06 nM (Cd) to 237 nM (Zn). The free metal ion concentrations were difficult to predict using an equilibrium speciation model, probably due to the uncertainty in the nature of the dissolved organic matter or the presence of other reactive colloids. It is shown that DMT can follow changes in the free metal ion concentration on times scales less than a day under certain conditions.

Total arsenic determination and speciation in infant food products by ion chromatography-inductively coupled plasma-mass spectrometry.

PubMed

Vela, Nohora P; Heitkemper, Douglas T

2004-01-01

Health risk associated with dietary arsenic intake may be different for infants and adults. Seafood is the main contributor to arsenic intake for adults while terrestrial-based food is the primary source for infants. Processed infant food products such as rice-based cereals, mixed rice/formula cereals, milk-based infant formula, applesauce and puree of peaches, pears, carrots, sweet potatoes, green beans, and squash were evaluated for total and speciated arsenic content. Arsenic concentrations found in rice-based cereals (63-320 ng/g dry weight) were similar to those reported for raw rice. Results for the analysis of powdered infant formula by inductively coupled plasma-mass spectrometry (ICP-MS) indicated a narrow and low arsenic concentration range (12 to 17 ng/g). Arsenic content in puree infant food products, including rice cereals, fruits, and vegetables, varies from <1 to 24 ng/g wet weight. Sample treatment with trifluoroacetic acid at 100 degrees C were an efficient and mild method for extraction of arsenic species present in different food matrixes as compared to alternative methods that included sonication and accelerated solvent extraction. Extraction recoveries from 94 to 128% were obtained when the summation of species was compared to total arsenic. The ion chromatography (IC)-ICP-MS method selected for arsenic speciation allowed for the quantitative determination of inorganic arsenic [As(III) + As(V)], dimethylarsinic acid (DMA), and methylarsonic acid (MMA). Inorganic arsenic and DMA are the main species found in rice-based and mixed rice/formula cereals, although traces of MMA were also detected. Inorganic arsenic was present in freeze-dried sweet potatoes, carrots, green beans, and peaches. MMA and DMA were not detected in these samples. Arsenic species in squash, pears, and applesauce were not detected above the method detection limit [5 ng/g dry weight for As(III), MMA, and DMA and 10 ng/g dry weight for As(V)].

Liquid chromatography-mass spectrometry (LC-MS): a powerful combination for selenium speciation in garlic (Allium sativum).

PubMed

Dumont, Emmie; Ogra, Yasumitsu; Vanhaecke, Frank; Suzuki, Kazuo T; Cornelis, Rita

2006-03-01

Liquid chromatography (LC) hyphenated with both elemental and molecular mass spectrometry has been used for Se speciation in Se-enriched garlic. Different species were separated by ion-pair liquid chromatography-inductively coupled plasma mass spectrometry (LC-ICP-MS) after hot-water extraction. They were identified by on-line reversed-phase liquid chromatography-electrospray ionization tandem mass spectrometry (RPLC-ESI-MS-MS). Se-methionine and Se-methylselenocysteine were determined by monitoring their product ions. Another compound, gamma-glutamyl-Se-methylselenocysteine, shown to be the most abundant form of Se in the garlic, was determined without any additional sample pre-treatment after extraction and without the need for a synthesized standard. Product ions for this dipeptide were detected by LC-ESI-MS-MS for three isotopes of Se-78 Se, 80Se: and 82Se. The method was extended to the species extracted during in-vitro gastrointestinal digestion. Because both Se-methylselenocysteine and gamma-glutamyl-Se-methylselenocysteine have anticarcinogenic properties, their extractability and stability during human digestion are very important. Garlic was also treated with saliva, to enable detection and analysis of species extracted during mastication. Detailed information on the extractability of selenium species by both simulated gastric and intestinal fluid are given, and variation of the distribution of Se among the different species with time is discussed. Although the main species in garlic is the dipeptide gamma-glutamyl-Se-methylselenocysteine, Se-methylselenocysteine is the main compound present in the extracts after treatment with gastrointestinal fluids. Two more, so far unknown compounds were observed in the chromatogram. The extracted species and their transformations were analysed by combining LC-ICP-MS and LC-ESI-MS-MS. In both the simulated gastric and intestinal digests, Se-methionine, Se-methylselenocysteine, and gamma-glutamyl-Se-methylselenocysteine could be determined by LC-ESI-MS-MS by measuring their typical product ions.

Water-Chemistry and On-Site Sulfur-Speciation Data for Selected Springs in Yellowstone National Park, Wyoming, 1996-1998

USGS Publications Warehouse

Ball, James W.; Nordstrom, D. Kirk; McCleskey, R. Blaine; Schoonen, Martin A.A.; Xu, Yong

2001-01-01

Fifty-eight water analyses are reported for samples collected from 19 hot springs and their overflow drainages and one ambient-temperature acid stream in Yellowstone National Park (YNP) during 1996-98. These water samples were collected and analyzed as part of research investigations on microbially mediated sulfur oxidation in stream waters and sulfur redox speciation in hot springs in YNP and chemical changes in overflow drainages that affect major ions, redox species, and trace elements. The research on sulfur redox speciation in hot springs is a collaboration with the State University of New York at Stony Brook, Northern Arizona University, and the U.S. Geological Survey (USGS). One ambient-temperature acidic stream system, Alluvium Creek and its tributaries in Brimstone Basin, was studied in detail. Analyses were performed adjacent to the sampling site, in an on-site mobile laboratory truck, or later in a USGS laboratory, depending on stability and preservability of the constituent. Water temperature, specific conductance, pH, Eh, dissolved oxygen (D.O.), and dissolved H2S were determined on-site at the time of sampling. Alkalinity and F were determined within a few days of sample collection by titration and by ion-selective electrode, respectively. Concentrations of S2O3 and SxO6 were determined as soon as possible (minutes to hours later) by ion chromatography (IC). Concentrations of Cl, SO4, and Br were determined by IC within a few days of sample collection. Concentrations of Fe(II) and Fe(total) were determined by ultraviolet/visible spectrophotometry within a few days of sample collection. Densities were determined later in the USGS laboratory. Concentrations of Li, Na, and K were determined by flame atomic absorption (Li) and emission (Na, K) spectrometry. Concentrations of Al, As(total), B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe(total), Mg, Mn, Ni, Pb, Si, Sr, V, and Zn were determined by inductively-coupled plasma optical emission spectrometry. Trace concentrations of Cd, Se, As(total), Ni, and Pb were determined by Zeeman-corrected graphite-furnace atomic-absorption spectrometry. Trace concentrations of As(total) and As(III) were determined by hydride generation using a flow-injection analysis system.

The Effect of Composition of Different Ecotoxicological Test Media on Free and Bioavailable Copper from CuSO4 and CuO Nanoparticles: Comparative Evidence from a Cu-Selective Electrode and a Cu-Biosensor

PubMed Central

Käkinen, Aleksandr; Bondarenko, Olesja; Ivask, Angela; Kahru, Anne

2011-01-01

The analysis of (bio)available copper in complex environmental settings, including biological test media, is a challenging task. In this study, we demonstrated the potential of a recombinant Pseudomonas fluorescens-based biosensor for bioavailability analysis of CuSO4 and CuO nanoparticles (nano-CuO) in seventeen different ecotoxicological and microbiologial test media. In parallel, free Cu in these test media was analysed using Cu-ion selective electrode (Cu-ISE). In the case of CuSO4, both free and bioavailable Cu decreased greatly with increasing concentration of organics and phosphates in the tested media. A good correlation between free and bioavailable Cu was observed (r = 0.854, p < 0.01) indicating that the free Cu content in biological test media may be a reasonably good predictor for the toxicity of CuSO4. As a proof, it was demonstrated that when eleven EC50 values for CuSO4 from different organisms in different test media were normalized for the free Cu in these media, the difference in these EC50 values was decreased from 4 to 1.8 orders of magnitude. Thus, toxicity of CuSO4 to these organisms was attributed to the properties of the test media rather than to inherent differences in sensitivity between the test organisms. Differently from CuSO4, the amount of free and bioavailable Cu in nano-CuO spiked media was not significantly correlated with the concentration of organics in the test media. Thus, the speciation of nano-CuO in toxicological test systems was not only determined by the complexation of Cu ions but also by differential dissolution of nano-CuO in different test conditions leading to a new speciation equilibrium. In addition, a substantial fraction of nano-CuO that was not detectable by Cu-ISE (i.e., not present as free Cu-ions) was bioavailable to Cu-biosensor bacteria. Thus, in environmental hazard analysis of (nano) particulate materials, biosensor analysis may be more informative than other analytical techniques. Our results demonstrate that bacterial Cu-biosensors either in combination with other analytical/speciation techniques or on their own, may serve as a rapid (eco)toxicological screening method. PMID:22346655

How do air ions reflect variations in ionising radiation in the lower atmosphere in a boreal forest?

NASA Astrophysics Data System (ADS)

Chen, Xuemeng; Kerminen, Veli-Matti; Paatero, Jussi; Paasonen, Pauli; Manninen, Hanna E.; Nieminen, Tuomo; Petäjä, Tuukka; Kulmala, Markku

2016-11-01

Most of the ion production in the atmosphere is attributed to ionising radiation. In the lower atmosphere, ionising radiation consists mainly of the decay emissions of radon and its progeny, gamma radiation of the terrestrial origin as well as photons and elementary particles of cosmic radiation. These types of radiation produce ion pairs via the ionisation of nitrogen and oxygen as well as trace species in the atmosphere, the rate of which is defined as the ionising capacity. Larger air ions are produced out of the initial charge carriers by processes such as clustering or attachment to pre-existing aerosol particles. This study aimed (1) to identify the key factors responsible for the variability in ionising radiation and in the observed air ion concentrations, (2) to reveal the linkage between them and (3) to provide an in-depth analysis into the effects of ionising radiation on air ion formation, based on measurement data collected during 2003-2006 from a boreal forest site in southern Finland. In general, gamma radiation dominated the ion production in the lower atmosphere. Variations in the ionising capacity came from mixing layer dynamics, soil type and moisture content, meteorological conditions, long-distance transportation, snow cover attenuation and precipitation. Slightly similar diurnal patterns to variations in the ionising capacity were observed in air ion concentrations of the cluster size (0.8-1.7 nm in mobility diameters). However, features observed in the 0.8-1 nm ion concentration were in good connection to variations of the ionising capacity. Further, by carefully constraining perturbing variables, a strong dependency of the cluster ion concentration on the ionising capacity was identified, proving the functionality of ionising radiation in air ion production in the lower atmosphere. This relationship, however, was only clearly observed on new particle formation (NPF) days, possibly indicating that charges after being born underwent different processes on NPF days and non-event days and also that the transformation of newly formed charges to cluster ions occurred in a shorter timescale on NPF days than on non-event days.

Thiol surface complexation on growing CdS clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swayambunathan, V.; Hayes, D.; Schmidt, K.H.

1990-05-09

The growth of small CdS colloidal particles has been initiated by pulse radiolytic release of sulfide from thiol (3-mercapto-1,2-propanediol, RSH) in the presence of Cd{sup 2+} ions. The kinetics and stoichiometry of the ensuring reactions were followed by conductivity, absorption spectroscopy, and light-scattering techniques. The final CdS product has been identified by electron diffraction. The formation of Cd-thiolate complexes at the surface of the particles is indicated by conductivity and by energy dispersive analysis of X-ray (EDAX) results. The rate of formation of CdS clusters is strongly pH dependent due to the pH effect on the stability of Dd{sup 2+}/HS{supmore » {minus}} complexes. At low pHs (4.0-5.3) the growth mechanism is proposed to be primarily a cluster-molecule process. At this pH range Cd{sup 2+} ions at the CdS particle surface complex with thiolate ions stronger than in the bulk of the solution. The size control of the particles by thiols is proposed to result from a competition of thiolate ions with HS{sup {minus}} ions for cadmium ions at the surface of the growing particles.« less

Formation of positive cluster ions Li(n) Br (n = 2-7) and ionization energies studied by thermal ionization mass spectrometry.

PubMed

Veličković, S R; Đustebek, J B; Veljković, F M; Veljković, M V

2012-05-01

Clusters of the type Li(n)X (X = halides) can be considered as potential building blocks of cluster-assembly materials. In this work, Li(n)Br (n = 2-7) clusters were obtained by a thermal ionization source of modified design and selected by a magnetic sector mass spectrometer. Positive ions of the Li(n)Br (n = 4-7) cluster were detected for the first time. The order of ion intensities was Li(2)Br(+) > Li(4)Br(+) > Li(5)Br(+) > Li(6)Br(+) > Li(3)Br(+). The ionization energies (IEs) were measured and found to be 3.95 ± 0.20 eV for Li(2)Br, 3.92 ± 0.20 eV for Li(3)Br, 3.93 ± 0.20 eV for Li(4)Br, 4.08 ± 0.20 eV for Li(5)Br, 4.14 ± 0.20 eV for Li(6)Br and 4.19 ± 0.20 eV for Li(7)Br. All of these clusters have a much lower ionization potential than that of the lithium atom, so they belong to the superalkali class. The IEs of Li(n)Br (n = 2-4) are slightly lower than those in the corresponding small Li(n) or Li(n)H clusters, whereas the IEs of Li(n)Br are very similar to those of Li(n) or Li(n)H for n = 5 and 6. The thermal ionization source of modified design is an important means for simultaneously obtaining and measuring the IEs of Li(n)Br (n = 2-7) clusters (because their ions are hermodynamically stable with respect to the loss of lithium atoms in the gas phase) and increasingly contributes toward the development of clusters for practical applications. Copyright © 2012 John Wiley & Sons, Ltd.

The Measurement of Sulfur Oxidation Products and Their Role in Homogeneous Nucleation

NASA Technical Reports Server (NTRS)

Eisele, F. L.

1999-01-01

An improved version of a transverse ion source was developed which uses selected ion chemical ionization mass spectrometry techniques inside of a particle nucleation flow tube. These new techniques are very unique, in that the chemical ionization is done inside of the flow tube rather than by having to remove the compounds and clusters of interest which are lost on first contact,with any surfaces. The transverse source is also unique because it allows the ion reaction time to be varied over more than an order of magnitude, which in turn makes possible the separation of ion induced cluster growth from the charging of preexisting molecular clusters. As a result of combining these unique capabilities, the first ever measurements of prenucleation molecular clusters were performed. These clusters are the intermediate stage of growth in the gas-to-particle conversion process. This new technique provides a means of observing clusters containing 2, 3, 4, ... and up to about 8 sulfuric acid molecules, where the critical cluster size under these measurement conditions was about 4 or 5. Thus, the nucleation process can now be directly observed and even growth beyond the critical cluster size can be investigated. The details of this investigation are discussed in a recently submitted paper, which is included as Appendix A. Measurements of the diffusion coefficient of sulfuric acid and sulfuric acid clustered with a water molecule have also been performed. The measurements are also discussed in more detail in another recently submitted paper which is included as Appendix B. The empirical results discussed in both of these papers provide a critical test of present nucleation theories. They also provide new hope for resolving many of the huge discrepancies between field observation and model prediction of particle nucleation. The second part of the research conducted under this project was directed towards the development of new chemical ionization techniques for measuring sulfur oxidation products.

Spectroscopic and computational studies of ionic clusters as models of solvation and atmospheric reactions

NASA Astrophysics Data System (ADS)

Kuwata, Keith T.

Ionic clusters are useful as model systems for the study of fundamental processes in solution and in the atmosphere. Their structure and reactivity can be studied in detail using vibrational predissociation spectroscopy, in conjunction with high level ab initio calculations. This thesis presents the applications of infrared spectroscopy and computation to a variety of gas-phase cluster systems. A crucial component of the process of stratospheric ozone depletion is the action of polar stratospheric clouds (PSCs) to convert the reservoir species HCl and chlorine nitrate (ClONO2) to photochemically labile compounds. Quantum chemistry was used to explore one possible mechanism by which this activation is effected: Cl- + ClONO2 /to Cl2 + NO3- eqno(1)Correlated ab initio calculations predicted that the direct reaction of chloride ion with ClONO2 is facile, which was confirmed in an experimental kinetics study. In the reaction a weakly bound intermediate Cl2-NO3- is formed, with ~70% of the charge localized on the nitrate moiety. This enables the Cl2-NO3- cluster to be well solvated even in bulk solution, allowing (1) to be facile on PSCs. Quantum chemistry was also applied to the hydration of nitrosonium ion (NO+), an important process in the ionosphere. The calculations, in conjunction with an infrared spectroscopy experiment, revealed the structure of the gas-phase clusters NO+(H2O)n. The large degree of covalent interaction between NO+ and the lone pairs of the H2O ligands is contrasted with the weak electrostatic bonding between iodide ion and H2O. Finally, the competition between ion solvation and solvent self-association is explored for the gas-phase clusters Cl/-(H2O)n and Cl-(NH3)n. For the case of water, vibrational predissociation spectroscopy reveals less hydrogen bonding among H2O ligands than predicted by ab initio calculations. Nevertheless, for n /ge 5, cluster structure is dominated by water-water interactions, with Cl- only partially solvated by the water cluster. Preliminary infrared spectra and computations on Cl- (NH3)n indicate that NH3 preferentially binds to Cl- ion instead of forming inter-solvent networks.

Ultrasound-assisted analyte extraction for the determination of sulfate and elemental sulfur in zinc sulfide by different liquid chromatography techniques.

PubMed

Dash, K; Thangavel, S; Krishnamurthy, N V; Rao, S V; Karunasagar, D; Arunachalam, J

2005-04-01

The speciation and determination of sulfate (SO4(2-)) and elemental sulfur (S degree) in zinc sulfide (ZnS) using ion-chromatography (IC) and reversed-phase liquid chromatography (RPLC) respectively is described. Three sample pretreatment approaches were employed with the aim of determining sulfate: (i) conventional water extraction of the analyte; (ii) solid-liquid aqueous extraction with an ultrasonic probe; and (iii) elimination of the zinc sulfide matrix via ion-exchange dissolution (IED). The separation of sulfate was carried out by an anion-exchange column (IonPac AS17), followed by suppressed conductivity detection. Elemental sulfur was extracted ultrasonically from the acid treated sample solution into chloroform and separated on a reversed phase HPLC column equipped with a diode array detector (DAD) at 264 nm. The achievable solid detection limits for sulfate and sulfur were 35 and 10 microg g(-1) respectively.

Low-pressure barrier discharge ion source using air as a carrier gas and its application to the analysis of drugs and explosives.

PubMed

Usmanov, Dilshadbek T; Yu, Zhan; Chen, Lee Chuin; Hiraoka, Kenzo; Yamabe, Shinichi

2016-02-01

In this work, a low-pressure air dielectric-barrier discharge (DBD) ion source using a capillary with the inner diameter of 0.115 and 12 mm long applicable to miniaturized mass spectrometers was developed. The analytes, trinitrotoluene (TNT), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), 1,3,5,7-tetranitroperhydro-1,3,5,7-tetrazocine (HMX), pentaerythritol tetranitrate (PETN), nitroglycerine (NG), hexamethylene triperoxide diamine (HMTD), caffeine, cocaine and morphine, introduced through the capillary, were ionized by a low-pressure air DBD. The ion source pressures were changed by using various sizes of the ion sampling orifice. The signal intensities of those analytes showed marked pressure dependence. TNT was detected with higher sensitivity at lower pressure but vice versa for other analytes. For all analytes, a marked signal enhancement was observed when a grounded cylindrical mesh electrode was installed in the DBD ion source. Among nine analytes, RDX, HMX, NG and PETN could be detected as cluster ions [analyte + NO3 ](-) even at low pressure and high temperature up to 180 °C. The detection indicates that these cluster ions are stable enough to survive under present experimental conditions. The unexpectedly high stabilities of these cluster ions were verified by density functional theory calculation. Copyright © 2016 John Wiley & Sons, Ltd.

ION INJECTION AT QUASI-PARALLEL SHOCKS SEEN BY THE CLUSTER SPACECRAFT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johlander, A.; Vaivads, A.; Khotyaintsev, Yu. V.

2016-01-20

Collisionless shocks in space plasma are known to be capable of accelerating ions to very high energies through diffusive shock acceleration (DSA). This process requires an injection of suprathermal ions, but the mechanisms producing such a suprathermal ion seed population are still not fully understood. We study acceleration of solar wind ions resulting from reflection off short large-amplitude magnetic structures (SLAMSs) in the quasi-parallel bow shock of Earth using in situ data from the four Cluster spacecraft. Nearly specularly reflected solar wind ions are observed just upstream of a SLAMS. The reflected ions are undergoing shock drift acceleration (SDA) andmore » obtain energies higher than the solar wind energy upstream of the SLAMS. Our test particle simulations show that solar wind ions with lower energy are more likely to be reflected off the SLAMS, while high-energy ions pass through the SLAMS, which is consistent with the observations. The process of SDA at SLAMSs can provide an effective way of accelerating solar wind ions to suprathermal energies. Therefore, this could be a mechanism of ion injection into DSA in astrophysical plasmas.« less

Cryogenically cooled octupole ion trap for spectroscopy of biomolecular ions.

PubMed

Boyarkin, Oleg V; Kopysov, Vladimir

2014-03-01

We present here the design of a linear octupole ion trap, suitable for collisional cryogenic cooling and spectroscopy of large ions. The performance of this trap has been assessed using ultraviolet (UV) photofragmentation spectroscopy of protonated dipeptides. At the trap temperature of 6.1 K, the vibrational temperature of the ions reaches 9.1 K, although their estimated translational temperature is ~150 K. This observation suggests that, despite the significant translational heating by radio-frequency electrical field, vibrational cooling of heavy ions in the octupole is at least as efficient as in the 22-pole ion traps previously used in our laboratory. In contrast to the 22-pole traps, excellent radial confinement of ions in the octupole makes it convenient for laser spectroscopy and boosts the dissociation yield of the stored ions to 30%. Overlap of the entire ion cloud by the laser beam in the octupole also allows for efficient UV depletion spectroscopy of ion-He clusters. The measured electronic spectra of the dipeptides and the clusters differ drastically, complicating a use of UV tagging spectroscopy for structural determination of large species.

The mutual influence of speciation and combination of Cu and Pb on the photodegradation of dimethyl o-phthalate.

PubMed

Jiang, Xinshu; Wang, Zhe; Zhang, Yiyue; Wang, Fei; Zhu, Mijia; Yao, Jun

2016-12-01

Specific industrial application of dimethyl o-phthalate (DMP) in ore flotation has led to DMP-heavy metals combined pollution, which causes the abiotic degradation of DMP in the environment more complex. This study focused on the effect of Cu and Pb on photodegradation of DMP. The major mechanism of inhibiting effect of Cu and Pb on degradation of DMP involved their speciation and combination. It was found that the Cu (5 mg/L, I = 95.4%) and Pb (5 mg/L, I = 100%) could inhibit the photodegradation of DMP. The main species that inhibit the DMP degradation were Cu(OH) + and Pb(OH) + , respectively. The intensity of the UV-Vis absorbance of DMP was obviously related to the concentration of Cu 2+ (R 2  = 0.8655) or Pb 2+ (R 2  = 0.9019) ions. Fluorescence quenching effect of Cu 2+ (R 2  > 0.9946), Pb 2+ (R 2  > 0.6879) on DMP is strongly correlated with the concentration of ions. And the equilibrium membrane dialysis experiment has also verified the combination of DMP and Cu, Pb. These results are useful to understand the effect mechanism of metal species on the photodegradation of organic chemicals. Copyright © 2016 Elsevier Ltd. All rights reserved.

Solid surface photochemistry of montmorillonite: mechanisms for the arsenite oxidation under UV-A irradiation.

PubMed

Yuan, Yanan; Wang, Yajie; Ding, Wei; Li, Jinjun; Wu, Feng

2016-01-01

Transformation of inorganic arsenic species has drawn great concern in recent decades because of worldwide and speciation-dependent pollution and the hazards that they pose to the environment and to human health. As(III) photooxidation in aquatic systems has received much attention, but little is known about photochemical transformation of arsenic species on top soil. As(III) photooxidation on natural montmorillonite under UV-A radiation was investigated by using a moisture- and temperature-controlled photochemical chamber with two black-light lamps. Initial As(III) concentration, pH, layer thickness, humic acid (HA) concentration, the presence of additional iron ions, and the contribution of reactive oxygen species (ROS) were examined. The results show that pH values of the clay layers greatly influenced As(III) photooxidation on montmorillonite. As(III) photooxidation followed the Langmuir-Hinshelwood model. HA and additional iron ions greatly promoted photooxidation, but excess Fe(II) competed with As(III) for oxidation by ROS. Scavenging experiments revealed that natural montmorillonite induced the conversion of As(III) to As(V) by generating ROS (mainly HO(•) and HO2(•)/O2(•-)) and that HO(•) radical was the predominant oxidant in this system. Our work demonstrates that photooxidation on the surface of natural clay minerals in top soil can be important to As(III) transformation. This allows understanding and predicting the speciation and behavior of arsenic on the soil surface.

Speciation in Metal Toxicity and Metal-Based Therapeutics

PubMed Central

Templeton, Douglas M.

2015-01-01

Metallic elements, ions and compounds produce varying degrees of toxicity in organisms with which they come into contact. Metal speciation is critical to understanding these adverse effects; the adjectives “heavy” and “toxic” are not helpful in describing the biological properties of individual elements, but detailed chemical structures are. As a broad generalization, the metallic form of an element is inert, and the ionic salts are the species that show more significant bioavailability. Yet the salts and other chelates of a metal ion can give rise to quite different toxicities, as exemplified by a range of carcinogenic potential for various nickel species. Another important distinction comes when a metallic element is organified, increasing its lipophilicity and hence its ability to penetrate the blood brain barrier, as is seen, for example, with organic mercury and tin species. Some metallic elements, such as gold and platinum, are themselves useful therapeutic agents in some forms, while other species of the same element can be toxic, thus focusing attention on species interconversions in evaluating metal-based drugs. The therapeutic use of metal-chelating agents introduces new species of the target metal in vivo, and this can affect not only its desired detoxification, but also introduce a potential for further mechanisms of toxicity. Examples of therapeutic iron chelator species are discussed in this context, as well as the more recent aspects of development of chelation therapy for uranium exposure. PMID:29056656

A cluster ion chemistry for the mesospheric sodium layer

NASA Technical Reports Server (NTRS)

Richter, E. S.; Sechrist, C. F., Jr.

1979-01-01

A cluster ion chemistry for sodium is developed which relates the Na(+) profile to the Na profile using reactions involving Na(+).N2, Na(+).CO2, and Na(+).H2O. Removal of sodium from the mesosphere is accomplished by the formation of higher order clusters of the form Na(+).(H2O)n which presumably precipitate to the lower atmosphere. This sink is most effective in the 80-85 km altitude range. The chemical equilibrium model is applied to experimental observations of the Na and Na(+) layers.

Polar cap ion beams during periods of northward IMF: Cluster statistical results

NASA Astrophysics Data System (ADS)

Maggiolo, R.; Echim, M.; de Keyser, J.; Fontaine, D.; Jacquey, C.; Dandouras, I.

2011-05-01

Above the polar caps and during prolonged periods of northward IMF, the Cluster satellites detect upward accelerated ion beams with energies up to a few keV. They are associated with converging electric field structures indicating that the acceleration is caused by a quasi-static field-aligned electric field that can extend to altitudes higher than 7 RE (Maggiolo et al., 2006; Teste et al., 2007). Using the AMDA science analysis service provided by the Centre de Données de la Physique des Plasmas, we have been able to extract about 200 events of accelerated upgoing ion beams above the polar caps from the Cluster database. Most of these observations are taken at altitudes lower than 7 RE and in the Northern Hemisphere. We investigate the statistical properties of these ion beams. We analyze their geometry, the properties of the plasma populations and of the electric field inside and around the beams, as well as their dependence on solar wind and IMF conditions. We show that ~40 % of the ion beams are collocated with a relatively hot and isotropic plasma population. The density and temperature of the isotropic population are highly variable but suggest that this plasma originates from the plasma sheet. The ion beam properties do not change significantly when the isotropic, hot background population is present. Furthermore, during one single polar cap crossing by Cluster it is possible to detect upgoing ion beams both with and without an accompanying isotropic component. The analysis of the variation of the IMF BZ component prior to the detection of the beams indicates that the delay between a northward/southward turning of IMF and the appearance/disappearance of the beams is respectively ~2 h and 20 min. The observed electrodynamic characteristics of high altitude polar cap ion beams suggest that they are closely connected to polar cap auroral arcs. We discuss the implications of these Cluster observations above the polar cap on the magnetospheric dynamics and configuration during prolonged periods of northward IMF.

Transport of Light Ions in Matter

NASA Technical Reports Server (NTRS)

Wilson, J. W.; Cucinotta, F. A.; Tai, H.; Shinn, J. L.; Chun, S. Y.; Tripathi, R. K.; Sihver, L.

1998-01-01

A recent set of light ion experiments are analyzed using the Green's function method of solving the Boltzmann equation for ions of high charge and energy (the GRNTRN transport code) and the NUCFRG2 fragmentation database generator code. Although the NUCFRG2 code reasonably represents the fragmentation of heavy ions, the effects of light ion fragmentation requires a more detailed nuclear model including shell structure and short range correlations appearing as tightly bound clusters in the light ion nucleus. The most recent NTJCFRG2 code is augmented with a quasielastic alpha knockout model and semiempirical adjustments (up to 30 percent in charge removal) in the fragmentation process allowing reasonable agreement with the experiments to be obtained. A final resolution of the appropriate cross sections must await the full development of a coupled channel reaction model in which shell structure and clustering can be accurately evaluated.

Irradiation-induced Ag nanocluster nucleation in silicate glasses: Analogy with photography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Espiau de Lamaestre, R.; Fontainebleau Research Center, Corning SA, 77210 Avon; Bea, H.

2007-11-15

The synthesis of Ag nanoclusters in soda lime silicate glasses and silica was studied by optical absorption and electron spin resonance experiments under both low (gamma ray) and high (MeV ion) deposited energy density irradiation conditions. Both types of irradiation create electrons and holes whose density and thermal evolution--notably via their interaction with defects--are shown to determine the clustering and growth rates of Ag nanocrystals. We thus establish the influence of redox interactions of defects and silver (poly)ions. The mechanisms are similar to the latent image formation in photography: Irradiation-induced photoelectrons are trapped within the glass matrix, notably on dissolvedmore » noble metal ions and defects, which are thus neutralized (reverse oxidation reactions are also shown to exist). Annealing promotes metal atom diffusion, which, in turn, leads to cluster nuclei formation. The cluster density depends not only on the irradiation fluence but also--and primarily--on the density of deposited energy and the redox properties of the glass. Ion irradiation (i.e., large deposited energy density) is far more effective in cluster formation, despite its lower neutralization efficiency (from Ag{sup +} to Ag{sup 0}) as compared to gamma photon irradiation.« less

Ion-Stockmayer clusters: Minima, classical thermodynamics, and variational ground state estimates of Li{sup +}(CH{sub 3}NO{sub 2}){sub n} (n = 1–20)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Curotto, E., E-mail: curotto@arcadia.edu

2015-12-07

Structural optimizations, classical NVT ensemble, and variational Monte Carlo simulations of ion Stockmayer clusters parameterized to approximate the Li{sup +}(CH{sub 3}NO{sub 2}){sub n} (n = 1–20) systems are performed. The Metropolis algorithm enhanced by the parallel tempering strategy is used to measure internal energies and heat capacities, and a parallel version of the genetic algorithm is employed to obtain the most important minima. The first solvation sheath is octahedral and this feature remains the dominant theme in the structure of clusters with n ≥ 6. The first “magic number” is identified using the adiabatic solvent dissociation energy, and it marksmore » the completion of the second solvation layer for the lithium ion-nitromethane clusters. It corresponds to the n = 18 system, a solvated ion with the first sheath having octahedral symmetry, weakly bound to an eight-membered and a four-membered ring crowning a vertex of the octahedron. Variational Monte Carlo estimates of the adiabatic solvent dissociation energy reveal that quantum effects further enhance the stability of the n = 18 system relative to its neighbors.« less

Optimization of the neutron yield in fusion plasmas produced by Coulomb explosions of deuterium clusters irradiated by a petawatt laser.

PubMed

Bang, W; Dyer, G; Quevedo, H J; Bernstein, A C; Gaul, E; Donovan, M; Ditmire, T

2013-02-01

The kinetic energy of hot (multi-keV) ions from the laser-driven Coulomb explosion of deuterium clusters and the resulting fusion yield in plasmas formed from these exploding clusters has been investigated under a variety of conditions using the Texas Petawatt laser. An optimum laser intensity was found for producing neutrons in these cluster fusion plasmas with corresponding average ion energies of 14 keV. The substantial volume (1-10 mm(3)) of the laser-cluster interaction produced by the petawatt peak power laser pulse led to a fusion yield of 1.6×10(7) neutrons in a single shot with a 120 J, 170 fs laser pulse. Possible effects of prepulses are discussed.

Isotopologue Distributions of Peptide Product Ions by Tandem Mass Spectrometry: Quantitation of Low Levels of Deuterium Incorporation1

PubMed Central

Wang, Benlian; Sun, Gang; Anderson, David R.; Jia, Minghong; Previs, Stephen; Anderson, Vernon E.

2007-01-01

Protonated molecular peptide ions and their product ions generated by tandem mass spectrometry appear as isotopologue clusters due to the natural isotopic variations of carbon, hydrogen, nitrogen, oxygen and sulfur. Quantitation of the isotopic composition of peptides can be employed in experiments involving isotope effects, isotope exchange, isotopic labeling by chemical reactions, and studies of metabolism by stable isotope incorporation. Both ion trap and quadrupole-time of flight mass spectrometry are shown to be capable of determining the isotopic composition of peptide product ions obtained by tandem mass spectrometry with both precision and accuracy. Tandem mass spectra obtained in profile-mode of clusters of isotopologue ions are fit by non-linear least squares to a series of Gaussian peaks (described in the accompanying manuscript) which quantify the Mn/M0 values which define the isotopologue distribution (ID). To determine the isotopic composition of product ions from their ID, a new algorithm that predicts the Mn/M0 ratios is developed which obviates the need to determine the intensity of all of the ions of an ID. Consequently a precise and accurate determination of the isotopic composition a product ion may be obtained from only the initial values of the ID, however the entire isotopologue cluster must be isolated prior to fragmentation. Following optimization of the molecular ion isolation width, fragmentation energy and detector sensitivity, the presence of isotopic excess (2H, 13C, 15N, 18O) is readily determined within 1%. The ability to determine the isotopic composition of sequential product ions permits the isotopic composition of individual amino acid residues in the precursor ion to be determined. PMID:17559791

Chromium(III)-imprinted silica gel for speciation analysis of chromium in environmental water samples with ICP-MS detection.

PubMed

Zhang, Nan; Suleiman, Jibrin Sabo; He, Man; Hu, Bin

2008-04-15

A new chromium(III)-imprinted 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTS)-functionalized silica gel sorbent was synthesized by a surface imprinting technique and was employed as a selective solid-phase extraction material for speciation analysis of chromium in environmental water samples prior to its determination by inductively coupled plasma mass spectrometry (ICP-MS). The prepared Cr(III)-imprinted silica gel shows the selectivity coefficient of more than 700 for Cr(III) in the presence of Mn(II). The static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Cr(III) were 30.5 mg g(-1) and 13.4 mg g(-1). It was also found that Cr(VI) could be adsorbed at low pH by the prepared imprinted silica gel, and this finding makes it feasible to enrich and determine Cr(VI) at low pH without adding reducing reagents. The imprinted silica gel sorbent offered a fast kinetics for the adsorption and desorption of both chromium species. Under the optimized conditions, the detection limits of 4.43 pg mL(-1) and 8.30 pg mL(-1) with the relative standard deviations (R.S.D.s) of 4.44% and 4.41% (C=0.5 ng mL(-1), n=7) for Cr(III) and Cr(VI) were obtained, respectively. The proposed method was successfully applied to the speciation of trace chromium in environmental water samples. To validate the proposed method, two certified reference materials were analyzed and the determined values were in a good agreement with the certified values. The developed method is rapid, selective, sensitive and applicable for the speciation of trace chromium in environmental water samples.

Ion-neutral Clustering of Bile Acids in Electrospray Ionization Across UPLC Flow Regimes

NASA Astrophysics Data System (ADS)

Brophy, Patrick; Broeckling, Corey D.; Murphy, James; Prenni, Jessica E.

2018-02-01

Bile acid authentic standards were used as model compounds to quantitatively evaluate complex in-source phenomenon on a UPLC-ESI-TOF-MS operated in the negative mode. Three different diameter columns and a ceramic-based microfluidic separation device were utilized, allowing for detailed descriptions of bile acid behavior across a wide range of flow regimes and instantaneous concentrations. A custom processing algorithm based on correlation analysis was developed to group together all ion signals arising from a single compound; these grouped signals produce verified compound spectra for each bile acid at each on-column mass loading. Significant adduction was observed for all bile acids investigated under all flow regimes and across a wide range of bile acid concentrations. The distribution of bile acid containing clusters was found to depend on the specific bile acid species, solvent flow rate, and bile acid concentration. Relative abundancies of each cluster changed non-linearly with concentration. It was found that summing all MS level (low collisional energy) ions and ion-neutral adducts arising from a single compound improves linearity across the concentration range (0.125-5 ng on column) and increases the sensitivity of MS level quantification. The behavior of each cluster roughly follows simple equilibrium processes consistent with our understanding of electrospray ionization mechanisms and ion transport processes occurring in atmospheric pressure interfaces. [Figure not available: see fulltext.

Clustering and Filtering Tandem Mass Spectra Acquired in Data-Independent Mode

NASA Astrophysics Data System (ADS)

Pak, Huisong; Nikitin, Frederic; Gluck, Florent; Lisacek, Frederique; Scherl, Alexander; Muller, Markus

2013-12-01

Data-independent mass spectrometry activates all ion species isolated within a given mass-to-charge window ( m/z) regardless of their abundance. This acquisition strategy overcomes the traditional data-dependent ion selection boosting data reproducibility and sensitivity. However, several tandem mass (MS/MS) spectra of the same precursor ion are acquired during chromatographic elution resulting in large data redundancy. Also, the significant number of chimeric spectra and the absence of accurate precursor ion masses hamper peptide identification. Here, we describe an algorithm to preprocess data-independent MS/MS spectra by filtering out noise peaks and clustering the spectra according to both the chromatographic elution profiles and the spectral similarity. In addition, we developed an approach to estimate the m/z value of precursor ions from clustered MS/MS spectra in order to improve database search performance. Data acquired using a small 3 m/z units precursor mass window and multiple injections to cover a m/z range of 400-1400 was processed with our algorithm. It showed an improvement in the number of both peptide and protein identifications by 8 % while reducing the number of submitted spectra by 18 % and the number of peaks by 55 %. We conclude that our clustering method is a valid approach for data analysis of these data-independent fragmentation spectra. The software including the source code is available for the scientific community.

Silicon decorated cone shaped carbon nanotube clusters for lithium ion battery anodes.

PubMed

Wang, Wei; Ruiz, Isaac; Ahmed, Kazi; Bay, Hamed Hosseini; George, Aaron S; Wang, Johnny; Butler, John; Ozkan, Mihrimah; Ozkan, Cengiz S

2014-08-27

In this work, we report the synthesis of an three-dimensional (3D) cone-shape CNT clusters (CCC) via chemical vapor deposition (CVD) with subsequent inductively coupled plasma (ICP) treatment. An innovative silicon decorated cone-shape CNT clusters (SCCC) is prepared by simply depositing amorphous silicon onto CCC via magnetron sputtering. The seamless connection between silicon decorated CNT cones and graphene facilitates the charge transfer in the system and suggests a binder-free technique of preparing lithium ion battery (LIB) anodes. Lithium ion batteries based on this novel 3D SCCC architecture demonstrates high reversible capacity of 1954 mAh g(-1) and excellent cycling stability (>1200 mAh g(-1) capacity with ≈ 100% coulombic efficiency after 230 cycles). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impact of nucleation of carbonaceous clusters on structural, electrical and optical properties of Cr+-implanted PMMA

NASA Astrophysics Data System (ADS)

Arif, Shafaq; Rafique, M. Shahid; Saleemi, Farhat; Naab, Fabian; Toader, Ovidiu; Mahmood, Arshad; Aziz, Uzma

2016-09-01

Specimens of polymethylmethacrylate (PMMA) have been implanted with 400 keV Cr+ ions at different ion fluences ranging from 5 × 1013 to 5 × 1015 ions/cm2. The possible chemical reactions involved in the nucleation of conjugated carbonaceous clusters in implanted PMMA are discussed. Furthermore, impact of formation of carbonaceous clusters on structural, optical, electrical and morphological properties of implanted PMMA has been examined. The structural modifications in implanted PMMA are observed by Raman spectroscopy. The variation in optical band gap and Urbach energy is measured using UV-visible spectroscopic analysis. The effects of Cr+ ion implantation on electrical and morphological properties are investigated by four-probe apparatus and atomic force microscopy, respectively. The Raman spectroscopic analysis confirmed the formation of carbonaceous clusters with the transformation of implanted layer of PMMA into amorphous carbon. Simultaneously, the optical band gap of implanted PMMA has reduced from 3.13 to 0.85 eV. The increase in Urbach energy favors the decline in band gap together with the structural modification in implanted PMMA. As a result of Cr+ ion implantation, the electrical conductivity of PMMA has improved from 2.14 ± 0.06 × 10-10 S/cm (pristine) to 7.20 ± 0.36 × 10-6 S/cm. The AFM images revealed a decrease in surface roughness with an increment in ion fluence up to 5 × 1014 ions/cm2. The modification in the electrical, optical and structural properties makes the PMMA a promising candidate for its future utilization, as a semiconducting and optically active material, in various fields like plastic electronics and optoelectronic devices.

Soft Landing of Mass-Selected Gold Clusters: Influence of Ion and Ligand on Charge Retention and Reactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Grant E.; Laskin, Julia

Herein, we employ a combination of reduction synthesis in solution, soft landing of mass-selected precursor and product ions, and in situ time-of-flight secondary ion mass spectrometry (TOF-SIMS) to examine the influence of ion and the length of diphosphine ligands on the charge retention and reactivity of ligated gold clusters deposited onto self-assembled monolayer surfaces (SAMs). Product ions (Au10L42+, (10,4)2+, L = 1,3-bis(diphenyl-phosphino)propane, DPPP) were prepared through in-source collision induced dissociation (CID) and precursor ions [(8,4)2+, L = 1,6-bis(diphenylphosphino)hexane, DPPH] were synthesized in solution for comparison to (11,5)3+ precursor ions ligated with DPPP investigated previously (ACS Nano 2012, 6, 573 andmore » J. Phys. Chem. C. 2012, 116, 24977). Similar to (11,5)3+ precursor ions, the (10,4)2+ product ions are shown to retain charge on 1H,1H,2H,2H-perfluorodecanethiol monolayers (FSAMs). Additional abundant peaks at higher m/z indicative of reactivity are observed in the TOF-SIMS spectrum of (10,4)2+ product ions that are not seen for (11,5)3+ precursor ions. The abundance of (10,4)2+ on 16-mercaptohexadecanoic acid (COOH-SAMs) is demonstrated to be lower than on FSAMs, consistent with partial reduction of charge. The (10,4)2+ product ion on 1-dodecanethiol (HSAMs) exhibits peaks similar to those seen on the COOH-SAM. On the HSAM, higher m/z peaks indicative of reactivity are observed similar to those on the FSAM. The (8,4)2+ DPPH precursor ions are shown to retain charge on FSAMs similar to (11,5)3+ precursor ions prepared with DPPP. An additional peak corresponding to attachment of one gold atom to (8,4)2+ is observed at higher m/z for DPPH-ligated clusters. On the COOH-SAM, (8,4)2+ is less abundant than on the FSAM consistent with partial neutralization. The results indicate that although retention of charge by product ions generated by CID is similar to precursor ions their reactivity during analysis with SIMS is different resulting in the formation of peaks corresponding to reaction products. The length of the ligand exerts only a minor influence on the charge retention and reactivity of gold clusters. Based on the observed reactivity of (10,4)2+ it is anticipated that in-source CID will be increasingly applied for the preparation of a distribution of product ions, including undercoordinated and reactive species, for soft landing onto surfaces.« less

Cryogenically cooled octupole ion trap for spectroscopy of biomolecular ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boyarkin, Oleg V., E-mail: oleg.boiarkin@epfl.ch; Kopysov, Vladimir

2014-03-15

We present here the design of a linear octupole ion trap, suitable for collisional cryogenic cooling and spectroscopy of large ions. The performance of this trap has been assessed using ultraviolet (UV) photofragmentation spectroscopy of protonated dipeptides. At the trap temperature of 6.1 K, the vibrational temperature of the ions reaches 9.1 K, although their estimated translational temperature is ∼150 K. This observation suggests that, despite the significant translational heating by radio-frequency electrical field, vibrational cooling of heavy ions in the octupole is at least as efficient as in the 22-pole ion traps previously used in our laboratory. In contrastmore » to the 22-pole traps, excellent radial confinement of ions in the octupole makes it convenient for laser spectroscopy and boosts the dissociation yield of the stored ions to 30%. Overlap of the entire ion cloud by the laser beam in the octupole also allows for efficient UV depletion spectroscopy of ion–He clusters. The measured electronic spectra of the dipeptides and the clusters differ drastically, complicating a use of UV tagging spectroscopy for structural determination of large species.« less

Electron and nuclear dynamics of molecular clusters in ultraintense laser fields. IV. Coulomb explosion of molecular heteroclusters

NASA Astrophysics Data System (ADS)

Last, Isidore; Jortner, Joshua

2004-11-01

In this paper we present a theoretical and computational study of the temporal dynamics and energetics of Coulomb explosion of (CD4)n and (CH4)n (n=55-4213) molecular heteroclusters in ultraintense (I=1016-1019W cm-2) laser fields, addressing the manifestation of electron dynamics, together with nuclear energetic and kinematic effects on the heterocluster Coulomb instability. The manifestations of the coupling between electron and nuclear dynamics were explored by molecular dynamics simulations for these heteroclusters coupled to Gaussian laser fields (pulse width τ=25 fs), elucidating outer ionization dynamics, nanoplasma screening effects (being significant for I⩽1017 W cm-2), and the attainment of cluster vertical ionization (CVI) (at I=1017 W cm-2 for cluster radius R0⩽31 Å). Nuclear kinematic effects on heterocluster Coulomb explosion are governed by the kinematic parameter η=qCmA/qAmC for (CA4)n clusters (A=H,D), where qj and mj (j=A,C) are the ionic charges and masses. Nonuniform heterocluster Coulomb explosion (η>1) manifests an overrun effect of the light ions relative to the heavy ions, exhibiting the expansion of two spatially separated subclusters, with the light ions forming the outer subcluster at the outer edge of the spatial distribution. Important features of the energetics of heterocluster Coulomb explosion originate from energetic triggering effects of the driving of the light ions by the heavy ions (C4+ for I=1017-1018W cm-2 and C6+ for I=1019 W cm-2), as well as for kinematic effects. Based on the CVI assumption, scaling laws for the cluster size (radius R0) dependence of the energetics of uniform Coulomb explosion of heteroclusters (η=1) were derived, with the size dependence of the average (Ej,av) and maximal (Ej,M) ion energies being Ej,av=aR02 and Ej,M=(5a/3)R02, as well as for the ion energy distributions P(Ej)∝Ej1/2; Ej⩽Ej,M. These results for uniform Coulomb explosion serve as benchmark reference data for the assessment of the effects of nonuniform explosion, where the CVI scaling law for the energetics still holds, with deviations of the a coefficient, which increase with increasing η. Kinematic effects (for η>1) result in an isotope effect, predicting the enhancement (by 9%-11%) of EH,av for Coulomb explosion of (C4+H4+)η (η=3) relative to ED,av for Coulomb explosion of (C4+D4+)η (η=1.5), with the isotope effect being determined by the ratio of the kinematic parameters for the pair of Coulomb exploding clusters. Kinematic effects for nonuniform explosion also result in a narrow isotope dependent energy distribution (of width ΔE) of the light ions (with ΔE/EH,av≃0.3 and ΔE/ED,av≃0.4), with the distribution peaking at the high energy edge, in marked contrast with the uniform explosion case. Features of laser-heterocluster interactions were inferred from the analyses of the intensity dependent boundary radii (R0)I and the corresponding average D+ ion energies (ED,av)I, which provide a measure for optimization of the cluster size at intensity I for the neutron yield from dd nuclear fusion driven by Coulomb explosion (NFDCE) of these heteroclusters. We infer on the advantage of deuterium containing heteronuclear clusters, e.g., (CD4)n in comparison to homonuclear clusters, e.g., (D2)n/2, for dd NFDCE, where the highly charged heavy ions (e.g., C4+ or C6+) serve as energetic and kinematic triggers driving the D+ ions to a high (10-200 keV) energy domain.

ALICE HLT Cluster operation during ALICE Run 2

NASA Astrophysics Data System (ADS)

Lehrbach, J.; Krzewicki, M.; Rohr, D.; Engel, H.; Gomez Ramirez, A.; Lindenstruth, V.; Berzano, D.; ALICE Collaboration

2017-10-01

ALICE (A Large Ion Collider Experiment) is one of the four major detectors located at the LHC at CERN, focusing on the study of heavy-ion collisions. The ALICE High Level Trigger (HLT) is a compute cluster which reconstructs the events and compresses the data in real-time. The data compression by the HLT is a vital part of data taking especially during the heavy-ion runs in order to be able to store the data which implies that reliability of the whole cluster is an important matter. To guarantee a consistent state among all compute nodes of the HLT cluster we have automatized the operation as much as possible. For automatic deployment of the nodes we use Foreman with locally mirrored repositories and for configuration management of the nodes we use Puppet. Important parameters like temperatures, network traffic, CPU load etc. of the nodes are monitored with Zabbix. During periods without beam the HLT cluster is used for tests and as one of the WLCG Grid sites to compute offline jobs in order to maximize the usage of our cluster. To prevent interference with normal HLT operations we separate the virtual machines running the Grid jobs from the normal HLT operation via virtual networks (VLANs). In this paper we give an overview of the ALICE HLT operation in 2016.

Model of large volumetric capacitance in graphene supercapacitors based on ion clustering

NASA Astrophysics Data System (ADS)

Skinner, Brian; Fogler, M. M.; Shklovskii, B. I.

2011-12-01

Electric double-layer supercapacitors (SCs) are promising devices for high-power energy storage based on the reversible absorption of ions into porous conducting electrodes. Graphene is a particularly good candidate for the electrode material in SCs due to its high conductivity and large surface area. In this paper, we consider SC electrodes made from a stack of graphene sheets with randomly inserted spacer molecules. We show that the large volumetric capacitances C≳100F/cm3 observed experimentally can be understood as a result of collective intercalation of ions into the graphene stack and the accompanying nonlinear screening by graphene electrons that renormalizes the charge of the ion clusters.

A model of large volumetric capacitance in graphene supercapacitors based on ion clustering

NASA Astrophysics Data System (ADS)

Skinner, Brian; Fogler, Michael; Shklovskii, Boris

2012-02-01

Electric double layer supercapacitors are promising devices for high-power energy storage based on the reversible absorption of ions into porous, conducting electrodes. Graphene is a particularly good candidate for the electrode material in supercapacitors due to its high conductivity and large surface area. In this paper we consider supercapacitor electrodes made from a stack of graphene sheets with randomly-inserted ``spacer" molecules. We show that the large volumetric capacitances C > 100 F/cm^3 observed experimentally can be understood as a result of collective intercalation of ions into the graphene stack and the accompanying nonlinear screening by graphene electrons that renormalizes the charge of the ion clusters.

The structure of clusters of galaxies

NASA Astrophysics Data System (ADS)

Fox, David Charles

When infalling gas is accreted onto a cluster of galaxies, its kinetic energy is converted to thermal energy in a shock, heating the ions. Using a self-similar spherical model, we calculate the collisional heating of the electrons by the ions, and predict the electron and ion temperature profiles. While there are significant differences between the two, they occur at radii larger than currently observable, and too large to explain observed X-ray temperature declines in clusters. Numerical simulations by Navarro, Frenk, & White (1996) predict a universal dark matter density profile. We calculate the expected number of multiply-imaged background galaxies in the Hubble Deep Field due to foreground groups and clusters with this profile. Such groups are up to 1000 times less efficient at lensing than the standard singular isothermal spheres. However, with either profile, the expected number of galaxies lensed by groups in the Hubble Deep Field is at most one, consistent with the lack of clearly identified group lenses. X-ray and Sunyaev-Zel'dovich (SZ) effect observations can be combined to determine the distance to clusters of galaxies, provided the clusters are spherical. When applied to an aspherical cluster, this method gives an incorrect distance. We demonstrate a method for inferring the three-dimensional shape of a cluster and its correct distance from X-ray, SZ effect, and weak gravitational lensing observations, under the assumption of hydrostatic equilibrium. We apply this method to simple, analytic models of clusters, and to a numerically simulated cluster. Using artificial observations based on current X-ray and SZ effect instruments, we recover the true distance without detectable bias and with uncertainties of 4 percent.

Core Ion Structures and Solvation Effects in Gas Phase [Sn(CO_{2})_{n}]^{-} Clusters

NASA Astrophysics Data System (ADS)

Thompson, Michael C.; Weber, J. Mathias

2017-06-01

We report infrared photodissociation spectra of [Sn(CO_{2})_{n}] (n=2-6) clusters. We explore core ion geometries through quantum chemical calculations and assign our experimental spectra through comparison with calculated vibrational frequencies. We discuss our results in the context of heterogeneous catalytic reduction of CO_{2}, and compare our results with previous work on other post-transition metal species.

Major signal suppression from metal ion clusters in SFC/ESI-MS - Cause and effects.

PubMed

Haglind, Alfred; Hedeland, Mikael; Arvidsson, Torbjörn; Pettersson, Curt E

2018-05-01

The widening application area of SFC-MS with polar analytes and water-containing samples facilitates the use of quick and simple sample preparation techniques such as "dilute and shoot" and protein precipitation. This has also introduced new polar interfering components such as alkali metal ions naturally abundant in e.g. blood plasma and urine, which have shown to be retained using screening conditions in SFC/ESI-TOF-MS and causing areas of major ion suppression. Analytes co-eluting with these clusters will have a decreased signal intensity, which might have a major effect on both quantification and identification. When investigating the composition of the alkali metal clusters using accurate mass and isotopic pattern, it could be concluded that they were previously not described in the literature. Using NaCl and KCl standards and different chromatographic conditions, varying e.g. column and modifier, the clusters proved to be formed from the alkali metal ions in combination with the alcohol modifier and make-up solvent. Their compositions were [(XOCH 3 ) n  + X] + , [(XOH) n  + X] + , [(X 2 CO 3 ) n  + X] + and [(XOOCOCH 3 ) n  + X] + for X = Na + or K + in ESI+. In ESI-, the clusters depended more on modifier, with [(XCl) n  + Cl] - and [(XOCH 3 ) n  + OCH 3 ] - mainly formed in pure methanol and [(XOOCH) n  + OOCH] - when 20 mM NH 4 Fa was added. To prevent the formation of the clusters by avoiding methanol as modifier might be difficult, as this is a widely used modifier providing good solubility when analyzing polar compounds in SFC. A sample preparation with e.g. LLE would remove the alkali ions, however also introducing a time consuming and discriminating step into the method. Since the alkali metal ions were retained and affected by chromatographic adjustments as e.g. mobile phase modifications, a way to avoid them could therefore be chromatographic tuning, when analyzing samples containing them. Copyright © 2018 Elsevier B.V. All rights reserved.

Specific modification of polysulfone with cluster bombardment with assistance of Ar ion irradiation

NASA Astrophysics Data System (ADS)

Xu, Guochun; Hibino, Y.; Awazu, K.; Tanihara, M.; Imanishi, Y.

2000-02-01

Objective: To develop a rapid method for the modification of polysulfone with ammonium sulfamate with the assistance of Ar ion irradiation with a multi-source cluster deposition apparatus. These surfaces mimicking the structure of heparin, a bioactive molecule, have a high anti-thrombosis property. Experimental Design: Polysulfone film, setting on a turning holder, was irradiated by Ar ions during bombardment with ammonium sulfamate clusters. The Ar ion source serves for the activation of a polymer surface and a cluster ion source supplies ammonium sulfamate molecules to react with the activated surface. After thorough washing with de-ionized sterile water, the modified surfaces were evaluated in terms of the contact angle of water, elemental composition, and binding state on electron spectroscopy for chemical analysis and platelet adhesion with platelet rich plasma. Results: The modification of polysulfone decreased the contact angle of water on surfaces from 82.6 ° down to 34.5 °. Ammonium, amine, sulfate, and thiophene combinations were formed on the modified surfaces. The adhesion numbers of the platelet were decreased to one tenth compared to the original surface. The same process was also applied to other polymers such as polyethylene, polypropylene, and polystyrene and similar outcomes were also observed. Conclusion: The primary studies showed successful modification of polysulfone with ammonium sulfamate with the assistance of Ar ion irradiation. Since the same concept can also be applied to other materials with various substrates, combined with the features of no solvent and no topographic changes, this method might be developed into a promising way for modification of polymeric materials.

Statistical study of ionospheric ion beams observed by CLUSTER above the polar caps

NASA Astrophysics Data System (ADS)

Maggiolo, R.; Echim, M.; Fontaine, D.; Teste, A. F.; Jacquey, C.

2009-12-01

Above the polar caps and during prolonged periods of Northward IMF, the Cluster spacecraft detect accelerated ion beams with energies up to a few keV. They are associated with downward precipitating electrons and converging electric field structures indicating that the acceleration is caused by a quasi-static field aligned electric field that can extend to altitudes up to 5 RE (Maggiolo et al. 2006, Teste et al. 2007). Using the AMDA science analysis service provided by the Centre de Données de la Physique des Plasmas (CDPP, http://cdpp.cesr.fr), we have been able to extract from the Cluster ion detectors dataset the time periods when Cluster encounters polar cap local ion beams. 6 years of data have been mined with this tool. Almost 200 events have been found giving new insight on these structures. After a description of the method used for the automatic detection of the beams, we will discuss their statistical properties. We analyze their relation to solar wind and IMF. In particular, we estimate the delay between a Northward/Southward turning of the IMF and the appearance/disappearance of these beams. The characteristics of the particles detected inside these structures as well as their size, orientation and location are also presented. We show that these ion beams are located on magnetic field lines mapping close to the high latitude magnetopause and in the central part of the lobes and that 40 % of them are detected together with hot isotropic ions. These results will be discussed in term of magnetotail configuration during prolonged periods of Northward IMF.

Thermally Cross-Linked Anion Exchange Membranes from Solvent Processable Isoprene Containing Ionomers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsai, Tsung-Han; Ertem, S. Piril; Maes, Ashley M.

2015-01-28

Random copolymers of isoprene and 4-vinylbenzyl chloride (VBCl) with varying compositions were synthesized via nitroxide-mediated polymerization. Subsequent quaternization afforded solvent processable and cross-linkable ionomers with a wide range of ion exchange capacities (IECs). Solution cast membranes were thermally cross-linked to form anion exchange membranes. Cross-linking was achieved by taking advantage of the unsaturations on the polyisoprene backbone, without added cross-linkers. A strong correlation was found between water uptake and ion conductivity of the membranes: conductivities of the membranes with IECs beyond a critical value were found to be constant related to their high water absorption. Environmentally controlled small-angle X-ray scatteringmore » experiments revealed a correlation between the average distance between ionic clusters and the ion conductivity, indicating that a well-connected network of ion clusters is necessary for efficient ion conduction and high ion conductivity.« less

Ce, Ti modified MCM-48 mesoporous photocatalysts: Effect of the synthesis route on support and metal ion properties

NASA Astrophysics Data System (ADS)

Mureseanu, Mihaela; Filip, Mihaela; Somacescu, Simona; Baran, Adriana; Carja, Gabriela; Parvulescu, Viorica

2018-06-01

New Ti-MCM-48 and CeTi-MCM-48 photocatalysts were obtained by impregnation of the MCM-48 silica support synthesized by a hydrothermal process with aqueous solution of Ti and Ce precursors. The immobilization of metal cations presented a low effect on the porosity, morphology and structure of MCM-48 mesoporous silica support as was evidenced by N2 adsorption-desorption, X-ray diffraction, SEM and TEM electron microscopy. EDAX analysis and X-ray photoelectron microscopy (XPS) indicated that titanium cations were present on the mesoporous silica surface only as Ti4+ species and the effect of ceria on titanium speciation was different, compared to the CeTi-MCM-48 sample, previously obtained by direct synthesis. The photocatalytic properties of mono- and bimetallic catalysts were evaluated in degradation of phenol from water and correlated with the active metallic species concentration, distribution, speciation and their interaction with the support or each other. An advanced oxidation mechanism for phenol degradation by radical species was proposed.

Modeling the binding of fulvic acid by goethite: the speciation of adsorbed FA molecules

NASA Astrophysics Data System (ADS)

Filius, Jeroen D.; Meeussen, Johannes C. L.; Lumsdon, David G.; Hiemstra, Tjisse; van Riemsdijk, Willem H.

2003-04-01

Under natural conditions, the adsorption of ions at the solid-water interface may be strongly influenced by the adsorption of organic matter. In this paper, we describe the adsorption of fulvic acid (FA) by metal(hydr)oxide surfaces with a heterogeneous surface complexation model, the ligand and charge distribution (LCD) model. The model is a self-consistent combination of the nonideal competitive adsorption (NICA) equation and the CD-MUSIC model. The LCD model can describe simultaneously the concentration, pH, and salt dependency of the adsorption with a minimum of only three adjustable parameters. Furthermore, the model predicts the coadsorption of protons accurately for an extended range of conditions. Surface speciation calculations show that almost all hydroxyl groups of the adsorbed FA molecules are involved in outer sphere complexation reactions. The carboxylic groups of the adsorbed FA molecule form inner and outer sphere complexes. Furthermore, part of the carboxylate groups remain noncoordinated and deprotonated.

Evaluation of factors that affect diesel exhaust toxicity. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Norbeck, J.M.; Smith, M.R.; Arey, J.

1998-07-01

The scope of this project was to obtain a preliminary assessment of the potential impact of the fuel formulation on the speciation and toxic components of diesel exhaust. The test bed was a Cummins L10 engine operating over the heavy-duty transient test cycle using three diesel fuels: a pre-1993 diesel fuel, a low aromatic diesel fuel, and an alternative formulation diesel fuel. The sampling/analysis plan included: determination of the criteria pollutant emission rates (THC, CO, NOx, and PM); determination of PM(10) and PM(2.5) emission rates; collection and analysis of particulate samples for elemental, inorganic ion and elemental/organic carbon analyses; collectionmore » of bas samples for VOC speciation analyses; collection of 2,4-dinitrophenylhydrazine (DNPH) cartridges for determination of oxygenates; collection of nitrosomorpholine with Thermosorb N cartridges; collection of semi-volatiles on PF/XAD and particulate samples for PAH, nitro-PAH, and mutagenicity studies; and collection and analysis of dioxins for the pre-1993 and alternative formulation diesel fuels.« less

Mass spectrometry detection and imaging of inorganic and organic explosive device signatures using desorption electro-flow focusing ionization.

PubMed

Forbes, Thomas P; Sisco, Edward

2014-08-05

We demonstrate the coupling of desorption electro-flow focusing ionization (DEFFI) with in-source collision induced dissociation (CID) for the mass spectrometric (MS) detection and imaging of explosive device components, including both inorganic and organic explosives and energetic materials. We utilize in-source CID to enhance ion collisions with atmospheric gas, thereby reducing adducts and minimizing organic contaminants. Optimization of the MS signal response as a function of in-source CID potential demonstrated contrasting trends for the detection of inorganic and organic explosive device components. DEFFI-MS and in-source CID enabled isotopic and molecular speciation of inorganic components, providing further physicochemical information. The developed system facilitated the direct detection and chemical mapping of trace analytes collected with Nomex swabs and spatially resolved distributions within artificial fingerprints from forensic lift tape. The results presented here provide the forensic and security sectors a powerful tool for the detection, chemical imaging, and inorganic speciation of explosives device signatures.

Study of Electron Ionization and Fragmentation of Non-hydrated and Hydrated Tetrahydrofuran Clusters

NASA Astrophysics Data System (ADS)

Neustetter, Michael; Mahmoodi-Darian, Masoomeh; Denifl, Stephan

2017-05-01

Mass spectroscopic investigations on tetrahydrofuran (THF, C4H8O), a common model molecule of the DNA-backbone, have been carried out. We irradiated isolated THF and (hydrated) THF clusters with low energy electrons (electron energy 70 eV) in order to study electron ionization and ionic fragmentation. For elucidation of fragmentation pathways, deuterated TDF (C4D8O) was investigated as well. One major observation is that the cluster environment shows overall a protective behavior on THF. However, also new fragmentation channels open in the cluster. In this context, we were able to solve a discrepancy in the literature about the fragment ion peak at mass 55 u in the electron ionization mass spectrum of THF. We ascribe this ion yield to the fragmentation of ionized THF clusters.

Supercritical fluid chromatography coupled with in-source atmospheric pressure ionization hydrogen/deuterium exchange mass spectrometry for compound speciation.

PubMed

Cho, Yunju; Choi, Man-Ho; Kim, Byungjoo; Kim, Sunghwan

2016-04-29

An experimental setup for the speciation of compounds by hydrogen/deuterium exchange (HDX) with atmospheric pressure ionization while performing chromatographic separation is presented. The proposed experimental setup combines the high performance supercritical fluid chromatography (SFC) system that can be readily used as an inlet for mass spectrometry (MS) and atmospheric pressure photo ionization (APPI) or atmospheric pressure chemical ionization (APCI) HDX. This combination overcomes the limitation of an approach using conventional liquid chromatography (LC) by minimizing the amount of deuterium solvents used for separation. In the SFC separation, supercritical CO2 was used as a major component of the mobile phase, and methanol was used as a minor co-solvent. By using deuterated methanol (CH3OD), AP HDX was achieved during SFC separation. To prove the concept, thirty one nitrogen- and/or oxygen-containing standard compounds were analyzed by SFC-AP HDX MS. The compounds were successfully speciated from the obtained SFC-MS spectra. The exchange ions were observed with as low as 1% of CH3OD in the mobile phase, and separation could be performed within approximately 20min using approximately 0.24 mL of CH3OD. The results showed that SFC separation and APPI/APCI HDX could be successfully performed using the suggested method. Copyright © 2016 Elsevier B.V. All rights reserved.

Speciation analysis of aluminium in plant parts of Betula pendula and in soil.

PubMed

Zioła-Frankowska, Anetta; Frankowski, Marcin

2018-03-01

The research presents the first results of aluminium speciation analysis in aqueous extracts of individual plant parts of Betula pendula and soil samples, using High Performance Ion Chromatography with Diode Array Detection (HPIC-DAD). The applied method allowed us to carry out a full speciation analysis of aluminium in the form of predominant aluminium-fluoride complexes: AlF (x=2,3,4) (3-x) (first analytical signal), AlF 2+ (second analytical signal) and Al 3+ (third analytical signal) in samples of lateral roots, tap roots, twigs, stem, leaf and soil collected under roots of B. pendula. Concentrations of aluminium and its complexes were determined for two types of environment characterised by different degree of human impact: contaminated site of the Chemical Plant in Luboń and protected area of the Wielkopolski National Park. For all the analysed samples of B. pendula and soil, AlF (x=2,3,4) (3-x) had the largest contribution, followed by Al 3+ and AlF 2+ . Significant differences in concentration and contribution of Al-F complexes and Al 3+ form, depending on the place of sampling (different anthropogenic pressure) and plant part of B. pendula were observed. Based on the obtained results, it was found that transport of aluminium is "blocked" by lateral roots, and is closely related to Al content of soil. Copyright © 2017. Published by Elsevier B.V.

Determination of an organic-acid analog of DOC for use in copper toxicity studies on salmonids

DOE Office of Scientific and Technical Information (OSTI.GOV)

MacRae, R.K.; Meyer, J.S.; Hansen, J.A.

1995-12-31

Concentrations of dissolved copper in streams draining mine sites often exceed concentrations shown to cause acute and chronic mortality in salmonids. However, toxicity and impaired behaviors may be modified by dissolved organic carbon (DOC) and other inorganic components present in the site water. The effects of DOC on copper speciation, and thus bioavailability and toxicity, were determined by titrating stream waters with copper, using a cupric ion-specific electrode to detect free copper concentrations. Effects of various competing cations (e.g., Ca{sup +2}, Co{sup +2}) on copper-DOC binding were also evaluated. Titration results were evaluated using Scatchard and non-linear regression analyses tomore » quantify the strength and capacity of copper-DOC binding. Inorganic speciation was determined using the geochemical model MINEQL{sup +}. Results of these titrations indicated the presence of two or three distinct copper binding components in site water DOC. Three commercially available organic acids where then chosen to mimic the binding characteristics of natural DOC. This DOC-analog was used successfully in fish toxicity studies to evaluate the influence of DOC on copper bioavailability. Geochemical models were developed to predict copper speciation in both laboratory test waters and site waters, for any typical combination of water chemistry parameters (pH, alkalinity, [DOC], etc.). A combined interpretation of fish toxicity and modeling results indicate that some DOC-bound copper was bioavailable.« less

Prediction of the bioavailability of potentially toxic elements in freshwaters. Comparison between speciation models and passive samplers.

PubMed

Sierra, Jordi; Roig, Neus; Giménez Papiol, Gemma; Pérez-Gallego, Elena; Schuhmacher, Marta

2017-12-15

The aim of this work is to predict the bioavailability of the Potentially Toxic Elements (PTEs) Cd, Pb, Hg, Ni, Cu, Zn, As, Cr and Se in 6 sites within the Ebro River basin. In situ Diffusive gradient in thin-films (DGTs) and classical sampling have been used and compared. The potentially bioavailable fractions of each PTE was estimated by modelling their chemical speciation using three programs (WHAM 7.0, Visual MINTEQ 3.1 and Bio-met), following the suggestions published in recent European regulations. Results of the equilibrium-based models WHAM 7.0 and Visual MINTEQ 3.1 indicate that As, Cd, Ni, Se and Zn, predominate as free metals ions or forming inorganic soluble complexes. Copper, Pb and Hg bioavailability is conditioned by their affinity to dissolved humic substances. According to Visual MINTEQ 3.1, Cr is subjected to redox reactions, being Cr (VI) present (at low concentrations) in the studied rivers. According to Bio-met model, the bioavailability of Cu and Zn is highly influenced by soluble organic matter and water hardness, respectively. For most PTEs, the bioavailability estimated by deploying DGTs in river waters tends to be slightly lower than the estimation obtained with speciation models, since in real conditions more environmental factors take place comparing to the finite number of parameters considered in models. Copyright © 2017 Elsevier B.V. All rights reserved.

New Insight in Copper-Ion Binding to Human Islet Amyloid: The Contribution of Metal-Complex Speciation To Reveal the Polypeptide Toxicity.

PubMed

Magrì, Antonio; La Mendola, Diego; Nicoletti, Vincenzo Giuseppe; Pappalardo, Giuseppe; Rizzarelli, Enrico

2016-09-05

Type-2 diabetes (T2D) is considered to be a potential threat on a global level. Recently, T2D has been listed as a misfolding disease, such as Alzheimer's and Parkinson's diseases. Human islet amyloid polypeptide (hIAPP) is a molecule cosecreted in pancreatic β cells and represents the main constituent of an aggregated amyloid found in individuals affected by T2D. The trace-element serum level is significantly influenced during the development of diabetes. In particular, the dys-homeostasis of Cu(2+) ions may adversely affect the course of the disease. Conflicting results have been reported on the protective role played by complex species formed by Cu(2+) ions with hIAPP or its peptide fragments in vitro. The histidine (His) residue at position 18 represents the main binding site for the metal ion, but contrasting results have been reported on other residues involved in metal-ion coordination, in particular those toward the N or C terminus. Sequences that encompass regions 17-29 and 14-22 were used to discriminate between the two models of the hIAPP coordination mode. Due to poor solubility in water, poly(ethylene glycol) (PEG) derivatives were synthesized. A peptide fragment that encompasses the 17-29 region of rat amylin (rIAPP) in which the arginine residue at position 18 was substituted by a histidine residue was also obtained to assess that the PEG moiety does not alter the peptide secondary structure. The complex species formed by Cu(2+) ions with Ac-PEG-hIAPP(17-29)-NH2 , Ac-rIAPP(17-29)R18H-NH2 , and Ac-PEG-hIAPP(14-22)-NH2 were studied by using potentiometric titrations coupled with spectroscopic methods (UV/Vis, circular dichroism, and EPR). The combined thermodynamic and spectroscopic approach allowed us to demonstrate that hIAPP is able to bind Cu(2+) ions starting from the His18 imidazole nitrogen atom toward the N-terminus domain. The stability constants of copper(II) complexes with Ac-PEG-hIAPP(14-22)-NH2 were used to simulate the different experimental conditions under which aggregate formation and oxidative stress of hIAPP has been reported. Speciation unveils: 1) the protective role played by increased amounts of Cu(2+) ions on the hIAPP fibrillary aggregation, 2) the effect of adventitious trace amounts of Cu(2+) ions present in phosphate-buffered saline (PBS), and 3) a reducing fluorogenic probe on H2 O2 production attributed to the polypeptide alone. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Collision-Induced Dissociation Study of Strong Hydrogen-Bonded Cluster Ions Y−(HF)n (Y=F, O2) Using Atmospheric Pressure Corona Discharge Ionization Mass Spectrometry Combined with a HF Generator

PubMed Central

Sakamoto, Kenya; Sekimoto, Kanako; Takayama, Mitsuo

2017-01-01

Hydrogen fluoride (HF) was produced by a homemade HF generator in order to investigate the properties of strong hydrogen-bonded clusters such as (HF)n. The HF molecules were ionized in the form of complex ions associated with the negative core ions Y− produced by atmospheric pressure corona discharge ionization (APCDI). The use of APCDI in combination with the homemade HF generator led to the formation of negative-ion HF clusters Y−(HF)n (Y=F, O2), where larger clusters with n≥4 were not detected. The mechanisms for the formation of the HF, F−(HF)n, and O2−(HF)n species were discussed from the standpoints of the HF generator and APCDI MS. By performing energy-resolved collision-induced dissociation (CID) experiments on the cluster ions F−(HF)n (n=1–3), the energies for the loss of HF from F−(HF)3, F−(HF)2, and F−(HF) were evaluated to be 1 eV or lower, 1 eV or higher, and 2 eV, respectively, on the basis of their center-of-mass energy (ECM). These ECM values were consistent with the values of 0.995, 1.308, and 2.048 eV, respectively, obtained by ab initio calculations. The stability of [O2(HF)n]− (n=1–4) was discussed on the basis of the bond lengths of O2H–F−(HF)n and O2−H–F(HF)n obtained by ab initio calculations. The calculations indicated that [O2(HF)4]− separated into O2H and F−(HF)3. PMID:28966900

Collision-Induced Dissociation Study of Strong Hydrogen-Bonded Cluster Ions Y-(HF) n (Y=F, O2) Using Atmospheric Pressure Corona Discharge Ionization Mass Spectrometry Combined with a HF Generator.

PubMed

Sakamoto, Kenya; Sekimoto, Kanako; Takayama, Mitsuo

2017-01-01

Hydrogen fluoride (HF) was produced by a homemade HF generator in order to investigate the properties of strong hydrogen-bonded clusters such as (HF) n . The HF molecules were ionized in the form of complex ions associated with the negative core ions Y - produced by atmospheric pressure corona discharge ionization (APCDI). The use of APCDI in combination with the homemade HF generator led to the formation of negative-ion HF clusters Y - (HF) n (Y=F, O 2 ), where larger clusters with n ≥4 were not detected. The mechanisms for the formation of the HF, F - (HF) n , and O 2 - (HF) n species were discussed from the standpoints of the HF generator and APCDI MS. By performing energy-resolved collision-induced dissociation (CID) experiments on the cluster ions F - (HF) n ( n =1-3), the energies for the loss of HF from F - (HF) 3 , F - (HF) 2 , and F - (HF) were evaluated to be 1 eV or lower, 1 eV or higher, and 2 eV, respectively, on the basis of their center-of-mass energy ( E CM ). These E CM values were consistent with the values of 0.995, 1.308, and 2.048 eV, respectively, obtained by ab initio calculations. The stability of [O 2 (HF) n ] - ( n =1-4) was discussed on the basis of the bond lengths of O 2 H-F - (HF) n and O 2 - H-F(HF) n obtained by ab initio calculations. The calculations indicated that [O 2 (HF) 4 ] - separated into O 2 H and F - (HF) 3 .

Absolute single-ion solvation free energy scale in methanol determined by the lithium cluster-continuum approach.

PubMed

Pliego, Josefredo R; Miguel, Elizabeth L M

2013-05-02

Absolute solvation free energy of the lithium cation in methanol was calculated by the cluster-continuum quasichemical theory of solvation. Clusters with up to five methanol molecules were investigated using X3LYP, MP2, and MP4 methods with DZVP, 6-311+G(2df,2p), TZVPP+diff, and QZVPP+diff basis sets and including the cluster solvation through the PCM and SMD continuum models. Our calculations have determined a value of -118.1 kcal mol(-1) for the solvation free energy of the lithium, in close agreement with a value of -116.6 kcal mol(-1) consistent with the TATB assumption. Using data of solvation and transfer free energy of a pair of ions, electrode potentials and pKa, we have obtained the solvation free energy of 25 ions in methanol. Our analysis leads to a value of -253.6 kcal mol(-1) for the solvation free energy of the proton, which can be compared with the value of -263.5 kcal mol(-1) obtained by Kelly et al. using the cluster pair approximation. Considering that this difference is due to the methanol surface potential, we have estimated that it corresponds to -0.429 V.

Melatonin Protects Human Cells from Clustered DNA Damages, Killing and Acquisition of Soft Agar Growth Induced by X-rays or 970 MeV/n Fe ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, B.; Sutherland, B.; Bennett, P. V.

We tested the ability of melatonin (N-acetyl-5 methoxytryptamine), a highly effective radical scavenger and human hormone, to protect DNA in solution and in human cells against induction of complex DNA clusters and biological damage induced by low or high linear energy transfer radiation (100 kVp X-rays, 970 MeV/nucleon Fe ions). Plasmid DNA in solution was treated with increasing concentrations of melatonin (0.0-3.5 mM) and were irradiated with X-rays. Human cells (28SC monocytes) were also irradiated with X-rays and Fe ions with and without 2 mM melatonin. Agarose plugs containing genomic DNA were subjected to Contour Clamped Homogeneous Electrophoretic Field (CHEF)more » followed by imaging and clustered DNA damages were measured by using Number Average length analysis. Transformation experiments on human primary fibroblast cells using soft agar colony assay were carried out which were irradiated with Fe ions with or without 2 mM melatonin. In plasmid DNA in solution, melatonin reduced the induction of single- and double-strand breaks. Pretreatment of human 28SC cells for 24 h before irradiation with 2 mM melatonin reduced the level of X-ray induced double-strand breaks by {approx}50%, of abasic clustered damages about 40%, and of Fe ion-induced double-strand breaks (41% reduction) and abasic clusters (34% reduction). It decreased transformation to soft agar growth of human primary cells by a factor of 10, but reduced killing by Fe ions only by 20-40%. Melatonin's effective reduction of radiation-induced critical DNA damages, cell killing, and striking decrease of transformation suggest that it is an excellent candidate as a countermeasure against radiation exposure, including radiation exposure to astronaut crews in space travel.« less

Sixteenth International Conference on the physics of electronic and atomic collisions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dalgarno, A.; Freund, R.S.; Lubell, M.S.

1989-01-01

This report contains abstracts of papers on the following topics: photons, electron-atom collisions; electron-molecule collisions; electron-ion collisions; collisions involving exotic species; ion- atom collisions, ion-molecule or atom-molecule collisions; atom-atom collisions; ion-ion collisions; collisions involving rydberg atoms; field assisted collisions; collisions involving clusters and collisions involving condensed matter.

Generation of gas-phase ions from charged clusters: an important ionization step causing suppression of matrix and analyte ions in matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Lou, Xianwen; van Dongen, Joost L J; Milroy, Lech-Gustav; Meijer, E W

2016-12-30

Ionization in matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is a very complicated process. It has been reported that quaternary ammonium salts show extremely strong matrix and analyte suppression effects which cannot satisfactorily be explained by charge transfer reactions. Further investigation of the reasons causing these effects can be useful to improve our understanding of the MALDI process. The dried-droplet and modified thin-layer methods were used as sample preparation methods. In the dried-droplet method, analytes were co-crystallized with matrix, whereas in the modified thin-layer method analytes were deposited on the surface of matrix crystals. Model compounds, tetrabutylammonium iodide ([N(Bu) 4 ]I), cesium iodide (CsI), trihexylamine (THA) and polyethylene glycol 600 (PEG 600), were selected as the test analytes given their ability to generate exclusively pre-formed ions, protonated ions and metal ion adducts respectively in MALDI. The strong matrix suppression effect (MSE) observed using the dried-droplet method might disappear using the modified thin-layer method, which suggests that the incorporation of analytes in matrix crystals contributes to the MSE. By depositing analytes on the matrix surface instead of incorporating in the matrix crystals, the competition for evaporation/ionization from charged matrix/analyte clusters could be weakened resulting in reduced MSE. Further supporting evidence for this inference was found by studying the analyte suppression effect using the same two sample deposition methods. By comparing differences between the mass spectra obtained via the two sample preparation methods, we present evidence suggesting that the generation of gas-phase ions from charged matrix/analyte clusters may induce significant suppression of matrix and analyte ions. The results suggest that the generation of gas-phase ions from charged matrix/analyte clusters is an important ionization step in MALDI-MS. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Finding the patterns in complex specimens by improving the acquisition and analysis of x-ray spectromicroscopy data

NASA Astrophysics Data System (ADS)

Lerotic, Mirna

Soft x-ray spectromicroscopy provides spectral data on the chemical speciation of light elements at sub-100 nanometer spatial resolution. The high resolution imaging places a strong demand on the microscope stability and on the reproducibility of the scanned image field, and the volume of data necessitates the need for improved data analysis methods. This dissertation concerns two developments in extending the capability of soft x-ray transmission microscopes to carry out studies of chemical speciation at high spatial resolution. One development involves an improvement in x-ray microscope instrumentation: a new Stony Brook scanning transmission x-ray microscope which incorporates laser interferometer feedback in scanning stage positions. The interferometer is used to control the position between the sample and focusing optics, and thus improve the stability of the system. A second development concerns new analysis methods for the study of chemical speciation of complex specimens, such as those in biological and environmental science studies. When all chemical species in a specimen are known and separately characterized, existing approaches can be used to measure the concentration of each component at each pixel. In other cases (such as often occur in biology or environmental science), where the specimen may be too complicated or provide at least some unknown spectral signatures, other approaches must be used. We describe here an approach that uses principal component analysis (similar to factor analysis) to orthogonalize and noise-filter spectromicroscopy data. We then use cluster analysis (a form of unsupervised pattern matching) to classify pixels according to spectral similarity, to extract representative, cluster-averaged spectra with good signal-to-noise ratio, and to obtain gradations of concentration of these representative spectra at each pixel. The method is illustrated with a simulated data set of organic compounds, and a mixture of lutetium in hematite used to understand colloidal transport properties of radionuclides. Also, we describe here an extension of that work employing an angle distance measure; this measure provides better classification based on spectral signatures alone in specimens with significant thickness variations. The method is illustrated using simulated data, and also to examine sporulation in the bacterium Clostridium sp.

Chemistry within Molecular van der Waals Clusters

DTIC Science & Technology

1990-07-18

and Discussion 1) Stabilizing an Unstable Reagent within a Cluster a) 1, 1- Difluoroethane Clusters 2) Providing New Chemical Pathways a) Ammonia...1- difluoroethane clusters 24, the generation of (CH3 OCH 3 )nH3 O+ & (CH3 OCH 3 )nCH3 OH2 + ions from dimethyl ether dusters25 ,26, the generation of...Stabilizing an Unstable Reagent within a Cluster a) 1.1- Difluoroethane Clusters 24 The dominant reactive process which occurs within the majority of cluster

Proceedings of the Cooling, Condensation, and Storage of Hydrogen Cluster Ions Workshop Held in Menlo Park, California on 8-9 January 1987.

DTIC Science & Technology

1987-12-01

a kind of race track .13 ".is " . oo 0,.& :,- .., V~e v C4 si Fig. 4. Sketch of cylinder rf-type trap for k - 2. Experimental examples of higher order...1983. 31 S 52. Hiraoka, K. and P. Kebarle, "A Determination of the Stabilities of H5*, H7 + , Hg. and H11 + from Measurement of the Gas Phase Ion...73 H. Michels and J. Montgomery -- Electronic Structure and Stability of Small Cation and Anion Hydrogen Cluster Ions

Molecular dynamics simulations of the electrical double layer on smectite surfaces contacting concentrated mixed electrolyte (NaCl-CaCl2) solutions.

PubMed

Bourg, Ian C; Sposito, Garrison

2011-08-15

We report new molecular dynamics results elucidating the structure of the electrical double layer (EDL) on smectite surfaces contacting mixed NaCl-CaCl(2) electrolyte solutions in the range of concentrations relevant to pore waters in geologic repositories for CO(2) or high-level radioactive waste (0.34-1.83 mol(c) dm(-3)). Our results confirm the existence of three distinct ion adsorption planes (0-, β-, and d-planes), often assumed in EDL models, but with two important qualifications: (1) the location of the β- and d-planes are independent of ionic strength or ion type and (2) "indifferent electrolyte" ions can occupy all three planes. Charge inversion occurred in the diffuse ion swarm because of the affinity of the clay surface for CaCl(+) ion pairs. Therefore, at concentrations ≥0.34 mol(c) dm(-3), properties arising from long-range electrostatics at interfaces (electrophoresis, electro-osmosis, co-ion exclusion, colloidal aggregation) will not be correctly predicted by most EDL models. Co-ion exclusion, typically neglected by surface speciation models, balanced a large part of the clay mineral structural charge in the more concentrated solutions. Water molecules and ions diffused relatively rapidly even in the first statistical water monolayer, contradicting reports of rigid "ice-like" structures for water on clay mineral surfaces. Published by Elsevier Inc.

Bibliography of NRL Publications--1988

DTIC Science & Technology

1990-10-31

2749-2752 Free-Electron Laser , by Schuetz. L.S., Ott, E., and Antonsen, T.M., Physics of Fluids Exact but Computationally Intensive Predictions 0 31...Chemistry. 92:1200-1203, 1988 pp. 212-225 Reactions of Carbon Cluster Ions with Small Picosecond and Nanosecond Laser Photolyses of Hydrocarbons, by...Temperature Superconductors, by Ramnaker, The Study of Cluster Ions by Combined D.E., Turner. N.H.. and Hutson, F.L. ,* Physical Laser /Mass Spectrometry

Multimodal Estimation of Distribution Algorithms.

PubMed

Yang, Qiang; Chen, Wei-Neng; Li, Yun; Chen, C L Philip; Xu, Xiang-Min; Zhang, Jun

2016-02-15

Taking the advantage of estimation of distribution algorithms (EDAs) in preserving high diversity, this paper proposes a multimodal EDA. Integrated with clustering strategies for crowding and speciation, two versions of this algorithm are developed, which operate at the niche level. Then these two algorithms are equipped with three distinctive techniques: 1) a dynamic cluster sizing strategy; 2) an alternative utilization of Gaussian and Cauchy distributions to generate offspring; and 3) an adaptive local search. The dynamic cluster sizing affords a potential balance between exploration and exploitation and reduces the sensitivity to the cluster size in the niching methods. Taking advantages of Gaussian and Cauchy distributions, we generate the offspring at the niche level through alternatively using these two distributions. Such utilization can also potentially offer a balance between exploration and exploitation. Further, solution accuracy is enhanced through a new local search scheme probabilistically conducted around seeds of niches with probabilities determined self-adaptively according to fitness values of these seeds. Extensive experiments conducted on 20 benchmark multimodal problems confirm that both algorithms can achieve competitive performance compared with several state-of-the-art multimodal algorithms, which is supported by nonparametric tests. Especially, the proposed algorithms are very promising for complex problems with many local optima.

Understanding the evolution of luminescent gold quantum clusters in protein templates.

PubMed

Chaudhari, Kamalesh; Xavier, Paulrajpillai Lourdu; Pradeep, Thalappil

2011-11-22

We show that the time-dependent biomineralization of Au(3+) by native lactoferrin (NLf) and bovine serum albumin (BSA) resulting in near-infrared (NIR) luminescent gold quantum clusters (QCs) occurs through a protein-bound Au(1+) intermediate and subsequent emergence of free protein. The evolution was probed by diverse tools, principally, using matrix-assisted laser desorption ionization mass spectrometry (MALDI MS), X-ray photoelectron spectroscopy (XPS), and photoluminescence spectroscopy (PL). The importance of alkaline pH in the formation of clusters was probed. At neutral pH, a Au(1+)-protein complex was formed (starting from Au(3+)) with the binding of 13-14 gold atoms per protein. When the pH was increased above 12, these bound gold ions were further reduced to Au(0) and nucleation and growth of cluster commenced, which was corroborated by the beginning of emission; at this point, the number of gold atoms per protein was ~25, suggesting the formation of Au(25). During the cluster evolution, at certain time intervals, for specific molar ratios of gold and protein, occurrence of free protein was noticed in the mass spectra, suggesting a mixture of products and gold ion redistribution. By providing gold ions at specific time of the reaction, monodispersed clusters with enhanced luminescence could be obtained, and the available quantity of free protein could be utilized efficiently. Monodispersed clusters would be useful in obtaining single crystals of protein-protected noble metal quantum clusters where homogeneity of the system is of primary concern. © 2011 American Chemical Society

Speciation of arsenic in different types of nuts by ion chromatography-inductively coupled plasma mass spectrometry.

PubMed

Kannamkumarath, Sasi S; Wróbel, Kazimierz; Wróbel, Katarzyna; Caruso, Joseph A

2004-03-24

In this work the quantitative determination and analytical speciation of arsenic were undertaken in different types of nuts, randomly purchased from local markets. The hardness of the whole nuts and high lipid content made the preparation of this material difficult for analysis. The lack of sample homogeneity caused irreproducible results. To improve the precision of analysis, arsenic was determined separately in nut oil and in the defatted sample. The lipids were extracted from the ground sample with the two portions of a mixture of chloroform and methanol (2:1). The defatted material was dried and ground again, yielding a fine powder. The nut oil was obtained by combining the two organic extracts and by evaporating the solvents. The two nut fractions were microwave digested, and total arsenic was determined by inductively coupled plasma mass spectrometry (ICP-MS). The results obtained for oils from different types of nuts showed element concentration in the range 2.9-16.9 ng g(-)(1). Lower levels of arsenic were found in defatted material (<0.1 ng g(-)(1) with the exception of Brazil nuts purchased with and without shells, 3.0 and 2.8 ng g(-)(1) respectively). For speciation analysis of arsenic in nut oils, elemental species were extracted from 2 g of oil with 12 mL of chloroform/methanol (2:1) and 8 mL of deionized water. The aqueous layer, containing polar arsenic species, was evaporated and the residue dissolved and analyzed by ion chromatography-ICP-MS. The anion exchange chromatography enabled separation of As(III), dimethylarsinic acid (DMAs(V)), monomethylarsonic acid (MMAs(V)), and As(V) within 8 min. Several types of nuts were analyzed, including walnuts, Brazil nuts, almonds, cashews, pine nuts, peanuts, pistachio nuts, and sunflower seeds. The recovery for the speciation procedure was in the range 72.7-90.6%. The primary species found in the oil extracts were As(III) and As(V). The arsenic concentration levels in these two species were 0.7-12.7 and 0.5-4.3 ng g(-)(1), respectively. The contribution of As in DMAs(V) ranged from 0.1 +/- 0.1 ng g(-)(1) in walnuts to 1.3 +/- 0.3 ng g(-)(1) in pine nuts. MMAs(V) was not detected in almonds, peanuts, pine nuts, sunflower seeds, or walnuts, and the highest concentration was found in pistachio nuts (0.5 +/- 0.2 ng g(-)(1)).

Analysis of plasmaspheric plumes: CLUSTER and IMAGE observations and numerical simulations

NASA Technical Reports Server (NTRS)

Darouzet, Fabien; DeKeyser, Johan; Decreau, Pierrette; Gallagher, Dennis; Pierrard, Viviane; Lemaire, Joseph; Dandouras, Iannis; Matsui, Hiroshi; Dunlop, Malcolm; Andre, Mats

2005-01-01

Plasmaspheric plumes have been routinely observed by CLUSTER and IMAGE. The CLUSTER mission provides high time resolution four-point measurements of the plasmasphere near perigee. Total electron density profiles can be derived from the plasma frequency and/or from the spacecraft potential (note that the electron spectrometer is usually not operating inside the plasmasphere); ion velocity is also measured onboard these satellites (but ion density is not reliable because of instrumental limitations). The EUV imager onboard the IMAGE spacecraft provides global images of the plasmasphere with a spatial resolution of 0.1 RE every 10 minutes; such images acquired near apogee from high above the pole show the geometry of plasmaspheric plumes, their evolution and motion. We present coordinated observations for 3 plume events and compare CLUSTER in-situ data (panel A) with global images of the plasmasphere obtained from IMAGE (panel B), and with numerical simulations for the formation of plumes based on a model that includes the interchange instability mechanism (panel C). In particular, we study the geometry and the orientation of plasmaspheric plumes by using a four-point analysis method, the spatial gradient. We also compare several aspects of their motion as determined by different methods: (i) inner and outer plume boundary velocity calculated from time delays of this boundary observed by the wave experiment WHISPER on the four spacecraft, (ii) ion velocity derived from the ion spectrometer CIS onboard CLUSTER, (iii) drift velocity measured by the electron drift instrument ED1 onboard CLUSTER and (iv) global velocity determined from successive EUV images. These different techniques consistently indicate that plasmaspheric plumes rotate around the Earth, with their foot fully co-rotating, but with their tip rotating slower and moving farther out.

Preparation of Ion Exchange Films for Solid-Phase Spectrophotometry and Solid-Phase Fluorometry

NASA Technical Reports Server (NTRS)

Hill, Carol M.; Street, Kenneth W.; Tanner, Stephen P.; Philipp, Warren H.

2000-01-01

Atomic spectroscopy has dominated the field of trace inorganic analysis because of its high sensitivity and selectivity. The advantages gained by the atomic spectroscopies come with the disadvantage of expensive and often complicated instrumentation. Solid-phase spectroscopy, in which the analyte is preconcentrated on a solid medium followed by conventional spectrophotometry or fluorometry, requires less expensive instrumentation and has considerable sensitivity and selectivity. The sensitivity gains come from preconcentration and the use of chromophore (or fluorophore) developers and the selectivity is achieved by use of ion exchange conditions that favor the analyte in combination with speciative chromophores. Little work has been done to optimize the ion exchange medium (IEM) associated with these techniques. In this report we present a method for making ion exchange polymer films, which considerably simplify the solid-phase spectroscopic techniques. The polymer consists of formaldehyde-crosslinked polyvinyl alcohol with polyacrylic acid entrapped therein. The films are a carboxylate weak cation exchanger in the calcium form. They are mechanically sturdy and optically transparent in the ultraviolet and visible portion of the spectrum, which makes them suitable for spectrophotometry and fluorometry.

AFLP markers provide insights into the evolutionary relationships and diversification of New Caledonian Araucaria species (Araucariaceae).

PubMed

Gaudeul, Myriam; Rouhan, Germinal; Gardner, Martin F; Hollingsworth, Peter M

2012-01-01

Despite its small size, New Caledonia is characterized by a very diverse flora and striking environmental gradients, which make it an ideal setting to study species diversification. Thirteen of the 19 Araucaria species are endemic to the territory and form a monophyletic group, but patterns and processes that lead to such a high species richness are largely unexplored. We used 142 polymorphic AFLP markers and performed analyses based on Bayesian clustering algorithms, genetic distances, and cladistics on 71 samples representing all New Caledonian Araucaria species. We examined correlations between the inferred evolutionary relationships and shared morphological, ecological, or geographic parameters among species, to investigate evolutionary processes that may have driven speciation. We showed that genetic divergence among the present New Caledonian Araucaria species is low, suggesting recent diversification rather than pre-existence on Gondwana. We identified three genetic groups that included small-leaved, large-leaved, and coastal species, but detected no association with soil preference, ecological habitat, or rainfall. The observed patterns suggested that speciation events resulted from both differential adaptation and vicariance. Last, we hypothesize that speciation is ongoing and/or there are cryptic species in some genetically (sometimes also morphologically) divergent populations. Further data are required to provide better resolution and understanding of the diversification of New Caledonian Araucaria species. Nevertheless, our study allowed insights into their evolutionary relationships and provides a framework for future investigations on the evolution of this emblematic group of plants in one of the world's biodiversity hotspots.

Ion energy distributions and densities in the plume of Enceladus

NASA Astrophysics Data System (ADS)

Sakai, Shotaro; Cravens, Thomas E.; Omidi, Nojan; Perry, Mark E.; Waite, J. Hunter

2016-10-01

Enceladus has a dynamic plume that is emitting gas, including water vapor, and dust. The gas is ionized by solar EUV radiation, charge exchange, and electron impact and extends throughout the inner magnetosphere of Saturn. The charge exchange collisions alter the plasma composition. Ice grains (dust) escape from the vicinity of Enceladus and form the E ring, including a portion that is negatively charged by the local plasma. The inner magnetosphere within 10 RS (Saturn radii) contains a complex mixture of plasma, neutral gas, and dust that links back to Enceladus. In this paper we investigate the energy distributions, ion species and densities of water group ions in the plume of Enceladus using test particle and Monte Carlo methods that include collisional processes such as charge exchange and ion-neutral chemical reactions. Ion observations from the Cassini Ion and Neutral Mass Spectrometer (INMS) for E07 are presented for the first time. We use the modeling results to interpret observations made by the Cassini Plasma Spectrometer (CAPS) and the INMS. The low energy ions, as observed by CAPS, appear to be affected by a vertical electric field (EZ=-10 μV/m) in the plume. The EZ field may be associated with the charged dust and/or the pressure gradient of plasma. The model results, along with the results of earlier models, show that H3O+ ions created by chemistry are predominant in the plume, which agrees with INMS and CAPS data, but the INMS count rate in the plume for the model is several times greater than the data, which we do not fully understand. This composition and the total ion count found in the plume agree with INMS and CAPS data. On the other hand, the Cassini Langmuir Probe measured a maximum plume ion density more than 30,000 cm-3, which is far larger than the maximum ion density from our model, 900 cm-3. The model results also demonstrate that most of the ions in the plume are from the external magnetospheric flow and are not generated by local ionization. The origin of the ions in the plume was investigated using two different velocity models. Most ions were created by the interaction with background magnetospheric plasma and by photoionization. INMS and CAPS also detected water cluster ions. We will interpret these observations as a result of ion collisions with neutral water clusters, (H2O)n, originating in the tiger stripe vents as suggested by Tokar et al. (2009). We also estimated the process of generating cluster ions based on the INMS observations. We suggest that the most likely source is reaction of H3O+ with neutral water clusters or dimers such as (H2O)2 formed in the plume vents.

Effect of dose and size on defect engineering in carbon cluster implanted silicon wafers

NASA Astrophysics Data System (ADS)

Okuyama, Ryosuke; Masada, Ayumi; Shigematsu, Satoshi; Kadono, Takeshi; Hirose, Ryo; Koga, Yoshihiro; Okuda, Hidehiko; Kurita, Kazunari

2018-01-01

Carbon-cluster-ion-implanted defects were investigated by high-resolution cross-sectional transmission electron microscopy toward achieving high-performance CMOS image sensors. We revealed that implantation damage formation in the silicon wafer bulk significantly differs between carbon-cluster and monomer ions after implantation. After epitaxial growth, small and large defects were observed in the implanted region of carbon clusters. The electron diffraction pattern of both small and large defects exhibits that from bulk crystalline silicon in the implanted region. On the one hand, we assumed that the silicon carbide structure was not formed in the implanted region, and small defects formed because of the complex of carbon and interstitial silicon. On the other hand, large defects were hypothesized to originate from the recrystallization of the amorphous layer formed by high-dose carbon-cluster implantation. These defects are considered to contribute to the powerful gettering capability required for high-performance CMOS image sensors.

Ion mobility studies of PdC{sub n}{sup +} clusters: Where are the fullerenes?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shelimov, K.B.; Jarrold, M.F.

1995-12-14

Gas-phase ion mobility measurements have been used to study the structures and isomerization of PdC{sub n}{sup +} (n = 10-60) clusters. Non-fullerene isomers of PdC{sub n}{sup +} clusters are similar to those of C{sub n}{sup +} and MC{sub n}{sup +} (M = La and Nb) clusters, and include metal-containing mono- and bicyclic rings and graphite sheets. Neither endohedral nor nonendohedral PdC{sub n} {sup +} fullerene isomers are detected. When collisionally heated, PdC{sub n}{sup +} clusters efficiently convert into fullerenes, but the exothermicity of this process results in the loss of the Pd atom and the formation of a pure carbonmore » cluster cation. PdC{sub n}{sup +} bicyclic rings with an odd number of carbon atoms efficiently isomerize into monocyclic rings, while no evidence is found for this isomerization process for bicyclic rings with an even number of carbon atoms. 18 refs., 4 figs.« less

Collision-induced dissociation of protonated water clusters

NASA Astrophysics Data System (ADS)

Berthias, F.; Buridon, V.; Abdoul-Carime, H.; Farizon, B.; Farizon, M.; Dinh, P. M.; Reinhard, P.-G.; Suraud, E.; Märk, T. D.

2014-06-01

Collision-induced dissociation (CID) has been studied for protonated water clusters H+(H2O)n, with n = 2-8, colliding with argon atoms at a laboratory energy of 8 keV. The experimental data have been taken with an apparatus (Device for Irradiation of Molecular Clusters, `Dispositif d'Irradiation d'Agrégats Moléculaire,' DIAM) that has been recently constructed at the Institut de Physique Nucléaire de Lyon. It includes an event-by-event mass spectrometry detection technique, COINTOF (correlated ion and neutral fragment time of flight). The latter device allows, for each collision event, to detect and identify in a correlated manner all produced neutral and charged fragments. For all the studied cluster ions, it has allowed us to identify branching ratios for the loss of i = 1 to i = n water molecules, leading to fragment ions ranging from H+(H2O)i=n-1 all the way down to the production of protons. Using a corresponding calibration technique we determine total charged fragment production cross sections for incident protonated water clusters H+(H2O)n, with n = 2-7. Observed trends for branching ratios and cross sections, and a comparison with earlier data on measured attenuation cross sections for water clusters colliding with other noble gases (He and Xe), give insight into the underlying dissociation mechanisms.

SPECIATE 4.3: Addendum to SPECIATE 4.2--Speciation database development documentation

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Among the many uses of speciation data, these source profiles are used to: (1) create speciated emissions inve...

SPECIATE 4.0: SPECIATION DATABASE DEVELOPMENT DOCUMENTATION--FINAL REPORT

EPA Science Inventory

SPECIATE is the U.S. EPA's repository of total organic compounds (TOC) and particulate matter (PM) speciation profiles of air pollution sources. This report documents how EPA developed the SPECIATE 4.0 database that replaces the prior version, SPECIATE 3.2. SPECIATE 4.0 includes ...

Optimization and application of atmospheric pressure chemical and photoionization hydrogen-deuterium exchange mass spectrometry for speciation of oxygen-containing compounds.

PubMed

Acter, Thamina; Kim, Donghwi; Ahmed, Arif; Jin, Jang Mi; Yim, Un Hyuk; Shim, Won Joon; Kim, Young Hwan; Kim, Sunghwan

2016-05-01

This paper presents a detailed investigation of the feasibility of optimized positive and negative atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) and atmospheric pressure photoionization (APPI) MS coupled to hydrogen-deuterium exchange (HDX) for structural assignment of diverse oxygen-containing compounds. The important parameters for optimization of HDX MS were characterized. The optimized techniques employed in the positive and negative modes showed satisfactory HDX product ions for the model compounds when dichloromethane and toluene were employed as a co-solvent in APCI- and APPI-HDX, respectively. The evaluation of the mass spectra obtained from 38 oxygen-containing compounds demonstrated that the extent of the HDX of the ions was structure-dependent. The combination of information provided by different ionization techniques could be used for better speciation of oxygen-containing compounds. For example, (+) APPI-HDX is sensitive to compounds with alcohol, ketone, or aldehyde substituents, while (-) APPI-HDX is sensitive to compounds with carboxylic functional groups. In addition, the compounds with alcohol can be distinguished from other compounds by the presence of exchanged peaks. The combined information was applied to study chemical compositions of degraded oils. The HDX pattern, double bond equivalent (DBE) distribution, and previously reported oxidation products were combined to predict structures of the compounds produced from oxidation of oil. Overall, this study shows that APCI- and APPI-HDX MS are useful experimental techniques that can be applied for the structural analysis of oxygen-containing compounds.

Complexation of Cd, Ni, and Zn by DOC in polluted groundwater: A comparison of approaches using resin exchange, aquifer material sorption, and computer speciation models (WHAM and MINTEQA2)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Christensen, J.B.; Christensen, T.H.

1999-11-01

Complexation of cadmium (Cd), nickel (Ni), and zinc (Zn) by dissolved organic carbon (DOC) in leachate-polluted groundwater was measured using a resin equilibrium method and an aquifer material sorption technique. The first method is commonly used in complexation studies, while the second method better represents aquifer conditions. The two approaches gave similar results. Metal-DOC complexation was measured over a range of DOC concentrations using the resin equilibrium method, and the results were compared to simulations made by two speciation models containing default databases on metal-DOC complexes (WHAM and MINTEQA2). The WHAM model gave reasonable estimates of Cd and Ni complexationmore » by DOC for both leachate-polluted groundwater samples. The estimated effect of complexation differed less than 50% from the experimental values corresponding to a deviation on the activity of the free metal ion of a factor of 2.5. The effect of DOC complexation for Zn was largely overestimated by the WHAM model, and it was found that using a binding constant of 1.7 instead of the default value of 1.3 would improve the fit between the simulations and experimental data. The MINTEQA2 model gave reasonable predictions of the complexation of Cd and Zn by DOC, whereas deviations in the estimated activity of the free Ni{sup 2+} ion as compared to experimental results are up to a factor of 5.« less

Assessment of the hazard posed by metal forms in water and sediments.

PubMed

Wojtkowska, Małgorzata; Bogacki, Jan; Witeska, Anna

2016-05-01

This study aimed to describe the prevalence heavy metals (Zn, Cu, Pb, and Cd) forms in the ecosystem of the Utrata river in order to determine the mobile forms and bioavailability of metals. To extract the dissolved forms of metals in the water of the Utrata PHREEQC2 geochemical speciation model was used. The river waters show a high percentage of mobile and eco-toxic forms of Zn, Cu and Pb. The percentage of carbonate forms for all the studied metals was low (<1%). The content of carbonates in the water and the prevailing physical and chemical conditions (pH, hardness, alkalinity) reduce the share of toxic metal forms, which precipitate as hardly soluble carbonate salts of Zn, Cu, Cd and Pb. Cu in the water in 90% of cases appeared in the form of hydroxyl compounds. To identify the forms of metal occurrence in the sediments Tessier's sequential extraction was used, allowing to assay bound metals in five fractions (ion exchange, carbonate, adsorption, organic, residual), whose nature and bioavailability varies in aquatic environments. The study has shown a large share of metals in labile and bioavailable forms. The speciation analysis revealed an absolute dominance of the organic fraction in the binding of Cu and Pb. Potent affinity for this fraction was also exhibited by Cd. The rations of exchangeable Zn and Cu forms in the sediments were similar. Both these metals had the lowest share in the most mobile ion exchange fraction. Copyright © 2016. Published by Elsevier B.V.

Investigation of defect clusters in ion-irradiated Ni and NiCo using diffuse X-ray scattering and electron microscopy

DOE PAGES

Olsen, Raina J.; Jin, Ke; Lu, Chenyang; ...

2015-11-23

The nature of defect clusters in Ni and Nimore » $$_{50}$$Co$$_{50}$$ (NiCo) irradiated at room temperature with 2–16 MeV Ni ions is studied using asymptotic diffuse X-ray scattering and transmission electron microscopy (TEM). Analysis of the scattering data provides separate size distributions for vacancy and interstitial type defect clusters, showing that both types of defect clusters have a smaller size and higher density in NiCo than in Ni. Diffuse scattering results show good quantitative agreement with TEM results for cluster sizes greater than 4 nm diameter, but find that the majority of vacancy clusters are under 2 nm in NiCo, which, if not detected, would lead to the conclusion that defect density was actually lower in the alloy. Interstitial dislocation loops and stacking fault tetrahedra are identified by TEM. Lastly comparison of diffuse scattering lineshapes to those calculated for dislocation loops and SFTs indicates that most of the vacancy clusters are SFTs.« less

Group IIB-VIA semiconductor oxide cluster ions

NASA Astrophysics Data System (ADS)

Jayasekharan, Thankan

2018-05-01

Metal oxide cluster ions, MnOm± (M = Zn, Cd) and HgnOm- of various stoichiometry have been generated from solid IIB-VIA semiconductor oxides targets, (ZnO(s), CdO(s), and HgO(s)) by using pulse laser desorption ionization time of flight mass spectrometry with a laser of λ = 355 nm. Analysis of mass spectral data indicates the formation of stoichiometric cluster ions viz., (ZnO)n=1-30+ and (CdO)n=1-40+ along with -O bound anions, (ZnO)n=1-30O-, (CdO)n=1-40O- and (HgO)n=1-36O- from their respective solids. Further, metal oxoanions such as ZnOn=2,3-, CdOn=2,3,6-, and HgOn=2,3,6,7- have also been noted signifying the higher coordination ability of both Cd and Hg with O/O2/O3 species.

IR photodissociation spectroscopy of (OCS){sub n}{sup +} and (OCS){sub n}{sup −} cluster ions: Similarity and dissimilarity in the structure of CO{sub 2}, OCS, and CS{sub 2} cluster ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Inokuchi, Yoshiya, E-mail: y-inokuchi@hiroshima-u.ac.jp; Ebata, Takayuki

2015-06-07

Infrared photodissociation (IRPD) spectra of (OCS){sub n}{sup +} and (OCS){sub n}{sup −} (n = 2–6) cluster ions are measured in the 1000–2300 cm{sup −1} region; these clusters show strong CO stretching vibrations in this region. For (OCS){sub 2}{sup +} and (OCS){sub 2}{sup −}, we utilize the messenger technique by attaching an Ar atom to measure their IR spectra. The IRPD spectrum of (OCS){sub 2}{sup +}Ar shows two bands at 2095 and 2120 cm{sup −1}. On the basis of quantum chemical calculations, these bands are assigned to a C{sub 2} isomer of (OCS){sub 2}{sup +}, in which an intermolecular semi-covalent bondmore » is formed between the sulfur ends of the two OCS components by the charge resonance interaction, and the positive charge is delocalized over the dimer. The (OCS){sub n}{sup +} (n = 3–6) cluster ions show a few bands assignable to “solvent” OCS molecules in the 2000–2080 cm{sup −1} region, in addition to the bands due to the (OCS){sub 2}{sup +} ion core at ∼2090 and ∼2120 cm{sup −1}, suggesting that the dimer ion core is kept in (OCS){sub 3–6}{sup +}. For the (OCS){sub n}{sup −} cluster anions, the IRPD spectra indicate the coexistence of a few isomers with an OCS{sup −} or (OCS){sub 2}{sup −} anion core over the cluster range of n = 2–6. The (OCS){sub 2}{sup −}Ar anion displays two strong bands at 1674 and 1994 cm{sup −1}. These bands can be assigned to a C{sub s} isomer with an OCS{sup −} anion core. For the n = 2–4 anions, this OCS{sup −} anion core form is dominant. In addition to the bands of the OCS{sup −} core isomer, we found another band at ∼1740 cm{sup −1}, which can be assigned to isomers having an (OCS){sub 2}{sup −} ion core; this dimer core has C{sub 2} symmetry and {sup 2}A electronic state. The IRPD spectra of the n = 3–6 anions show two IR bands at ∼1660 and ∼2020 cm{sup −1}. The intensity of the latter component relative to that of the former one becomes stronger and stronger with increasing the size from n = 2 to 4, which corresponds to the increase of “solvent” OCS molecules attached to the OCS{sup −} ion core, but it suddenly decreases at n = 5 and 6. These IR spectral features of the n = 5 and 6 anions are ascribed to the formation of another (OCS){sub 2}{sup −} ion core having C{sub 2v} symmetry with {sup 2}B{sub 2} electronic state.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

The following are reported: theoretical calculations (configuration interaction, relativistic effective core potentials, polyatomics, CASSCF); proposed theoretical studies (clusters of Cu, Ag, Au, Ni, Pt, Pd, Rh, Ir, Os, Ru; transition metal cluster ions; transition metal carbide clusters; bimetallic mixed transition metal clusters); reactivity studies on transition metal clusters (reactivity with H{sub 2}, C{sub 2}H{sub 4}, hydrocarbons; NO and CO chemisorption on surfaces). Computer facilities and codes to be used, are described. 192 refs, 13 figs.

Beam power-dependent laser-induced fluorescence radiation quenching of silver-ion-exchanged glasses

NASA Astrophysics Data System (ADS)

Nahal, Arashmid; Khalesifard, Hamid Reza M.

2007-04-01

In this article, results of an investigation about the modification of silver ions embedded in a glass matrix under the action of a CW high-power Ar + laser beam, by means of laser-induced fluorescence, is reported. It is known [A. Nahal, H.R.M. Khalesifard, J. Mostafavi-Amjad, Appl. Phys. B 79 (2004) 513-518] that, as a result of the interaction of the laser beam with the sample, the embedded silver ions reduce to neutral ones and silver clusters are formed. We observed that the fluorescence radiation of the central part of the interaction area, on the sample, diminishes simultaneously with the formation of the neutral clusters. Further increase in the exposure time or the power of the beam results in reappearance of the fluorescence radiation, in the central part of the interaction area. We found that, during and after the interaction the spectrum of the fluorescence radiation changes. This makes it possible to study the laser-induced changes in the embedded silver ions and clusters, in real-time.

ToF-SIMS observation for evaluating the interaction between amyloid β and lipid membranes.

PubMed

Aoyagi, Satoka; Shimanouchi, Toshinori; Kawashima, Tomoko; Iwai, Hideo

2015-04-01

The adsorption behaviour of amyloid beta (Aβ), thought to be a key peptide for understanding Alzheimer's disease, was investigated by means of time-of-flight secondary ion mass spectrometry (ToF-SIMS). Aβ aggregates depending on the lipid membrane condition though it has not been fully understood yet. In this study, Aβ samples on different lipid membranes, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), were observed with ToF-SIMS and the complex ToF-SIMS data of the Aβ samples was interpreted using data analysis techniques such as principal component analysis (PCA), gentle-SIMS (G-SIMS) and g-ogram. DOPC and DMPC are liquid crystal at room temperature, while DPPC is gel at room temperature. As primary ion beams, Bi3(+) and Ar cluster ion beams were used and the effect of an Ar cluster ion for evaluating biomolecules was also studied. The secondary ion images of the peptide fragment ions indicated by G-SIMS and g-ogram were consistent with the PCA results. It is suggested that Aβ is adsorbed homogeneously on the liquid-crystalline-phase lipid membranes, while it aggregates along the lipid on the gel-phase lipid membrane. Moreover, in the results using the Ar cluster, the influence of contamination was reduced.

Target Plate Material Influence on Fullerene-C60 Laser Desorption/Ionization Efficiency

NASA Astrophysics Data System (ADS)

Zeegers, Guido P.; Günthardt, Barbara F.; Zenobi, Renato

2016-04-01

Systematic laser desorption/ionization (LDI) experiments of fullerene-C60 on a wide range of target plate materials were conducted to gain insight into the initial ion formation in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. The positive and negative ion signal intensities of precursor, fragment, and cluster ions were monitored, varying both the laser fluence (0-3.53 Jcm-2) and the ion extraction delay time (0-950 ns). The resulting species-specific ion signal intensities are an indication for the ionization mechanisms that contribute to LDI and the time frames in which they operate, providing insight in the (MA)LDI primary ionization. An increasing electrical resistivity of the target plate material increases the fullerene-C60 precursor and fragment anion signal intensity. Inconel 625 and Ti90/Al6/V4, both highly electrically resistive, provide the highest anion signal intensities, exceeding the cation signal intensity by a factor ~1.4 for the latter. We present a mechanism based on transient electrical field strength reduction to explain this trend. Fullerene-C60 cluster anion formation is negligible, which could be due to the high extraction potential. Cluster cations, however, are readily formed, although for high laser fluences, the preferred channel is formation of precursor and fragment cations. Ion signal intensity depends greatly on the choice of substrate material, and careful substrate selection could, therefore, allow for more sensitive (MA)LDI measurements.

Genomic Species Are Ecological Species as Revealed by Comparative Genomics in Agrobacterium tumefaciens

PubMed Central

Lassalle, Florent; Campillo, Tony; Vial, Ludovic; Baude, Jessica; Costechareyre, Denis; Chapulliot, David; Shams, Malek; Abrouk, Danis; Lavire, Céline; Oger-Desfeux, Christine; Hommais, Florence; Guéguen, Laurent; Daubin, Vincent; Muller, Daniel; Nesme, Xavier

2011-01-01

The definition of bacterial species is based on genomic similarities, giving rise to the operational concept of genomic species, but the reasons of the occurrence of differentiated genomic species remain largely unknown. We used the Agrobacterium tumefaciens species complex and particularly the genomic species presently called genomovar G8, which includes the sequenced strain C58, to test the hypothesis of genomic species having specific ecological adaptations possibly involved in the speciation process. We analyzed the gene repertoire specific to G8 to identify potential adaptive genes. By hybridizing 25 strains of A. tumefaciens on DNA microarrays spanning the C58 genome, we highlighted the presence and absence of genes homologous to C58 in the taxon. We found 196 genes specific to genomovar G8 that were mostly clustered into seven genomic islands on the C58 genome—one on the circular chromosome and six on the linear chromosome—suggesting higher plasticity and a major adaptive role of the latter. Clusters encoded putative functional units, four of which had been verified experimentally. The combination of G8-specific functions defines a hypothetical species primary niche for G8 related to commensal interaction with a host plant. This supports that the G8 ancestor was able to exploit a new ecological niche, maybe initiating ecological isolation and thus speciation. Searching genomic data for synapomorphic traits is a powerful way to describe bacterial species. This procedure allowed us to find such phenotypic traits specific to genomovar G8 and thus propose a Latin binomial, Agrobacterium fabrum, for this bona fide genomic species. PMID:21795751

Plant adaptive radiation mediated by polyploid plasticity in transcriptomes.

PubMed

Shimizu-Inatsugi, Rie; Terada, Aika; Hirose, Kyosuke; Kudoh, Hiroshi; Sese, Jun; Shimizu, Kentaro K

2017-01-01

The habitats of polyploid species are generally distinct from their parental species. Stebbins described polyploids as 'general purpose genotypes', which can tolerate a wide range of environmental conditions. However, little is known about its molecular basis because of the complexity of polyploid genomes. We hypothesized that allopolyploid species might utilize the expression patterns of both parents depending on environments (polyploid plasticity hypothesis). We focused on hydrological niche segregation along fine-scale soil moisture and waterlogging gradients. Two diploid species, Cardamine amara and Cardamine hirsuta, grew best in submerged and unsubmerged conditions, respectively, consistent with their natural habitats. Interestingly, the allotetraploid Cardamine flexuosa derived from them grew similarly in fluctuating as well as submerged and unsubmerged conditions, consistent with its wide environmental tolerance. A similar pattern was found in another species trio: allotetraploid Cardamine scutata and its parents. Using the close relatedness of Cardamine and Arabidopsis, we quantified genomewide expression patterns following dry and wet treatments using an Arabidopsis microarray. Hierarchical clustering analysis revealed that the expression pattern of C. flexuosa clustered with C. hirsuta in the dry condition and with C. amara in the wet condition, supporting our hypothesis. Furthermore, the induction levels of most genes in the allopolyploid were lower than in a specialist diploid species. This reflects a disadvantage of being allopolyploid arising from fixed heterozygosity. We propose that recurrent allopolyploid speciation along soil moisture and waterlogging gradients confers niche differentiation and reproductive isolation simultaneously and serves as a model for studying the molecular basis of ecological speciation and adaptive radiation. © 2016 The Authors. Molecular Ecology Published by John Wiley & Sons Ltd.

Role of Anions Associated with the Formation and Properties of Silver Clusters.

PubMed

Wang, Quan-Ming; Lin, Yu-Mei; Liu, Kuan-Guan

2015-06-16

Metal clusters have been very attractive due to their aesthetic structures and fascinating properties. Different from nanoparticles, each cluster of a macroscopic sample has a well-defined structure with identical composition, size, and shape. As the disadvantages of polydispersity are ruled out, informative structure-property relationships of metal clusters can be established. The formation of a high-nuclearity metal cluster involves the organization of metal ions into a complex entity in an ordered way. To achieve controllable preparation of metal clusters, it is helpful to introduce a directing agent in the formation process of a cluster. To this end, anion templates have been used to direct the formation of high nuclearity clusters. In this Account, the role of anions played in the formation of a variety of silver clusters has been reviewed. Silver ions are positively charged, so anionic species could be utilized to control the formation of silver clusters on the basis of electrostatic interactions, and the size and shape of the resulted clusters can be dictated by the templating anions. In addition, since the anion is an integral component in the silver clusters described, the physical properties of the clusters can be modulated by functional anions. The templating effects of simple inorganic anions and polyoxometales are shown in silver alkynyl clusters and silver thiolate clusters. Intercluster compounds are also described regarding the importance of anions in determining the packing of the ion pairs and making contribution to electron communications between the positive and negative counterparts. The role of the anions is threefold: (a) an anion is advantageous in stabilizing a cluster via balancing local positive charges of the metal cations; (b) an anion template could help control the size and shape of a cluster product; (c) an anion can be a key factor in influencing the function of a cluster through bringing in its intrinsic properties. Properties including electron communication, luminescent thermochromism, single-molecule magnet, and intercluster charge transfer associated with anion-directed silver clusters have been discussed. We intend to attract chemists' attention to the role that anions could play in determining the structures and properties of metal complexes, especially clusters. We hope that this Account will stimulate more efforts in exploiting new role of anions in various metal cluster systems. Anions can do much more than counterions for charge balance, and they should be considered in the design and synthesis of cluster-based functional materials.

How Does Boiling in the Earth's Crust Influence Metal Speciation and Transport?

NASA Astrophysics Data System (ADS)

Kam, K.; Lemke, K.

2014-12-01

The presence of large quantities of precious metals, such as gold and copper, near the Earth's surface (upper crust) is commonly attributed to transport in aqueous solution and precipitation upon variations in temperature and pressure. As a consequence, gold exploration is closely linked to solution chemistry, i.e. hydrothermal processes involving aqueous fluids with densities of around unity. However, as crustal fluids buoyantly ascend, boiling produces a coexisting low-density aqueous liquid with fundamentally different physical and chemical properties, and a, most importantly, a high affinity for coinage metals (Heinrich et al., Econ Geol., 1992, 87, 1566). From recent experimental studies of Au (Hurtig and Williams-Jones, 2014, Geochim. Cosmochim. Acta,, 127, 304), we know that metal speciation in this low-density phase differs fundamentally from that observed in bulk solution, clearly, with important implications for Au, and metal speciation in general, transport and ore concentrations processes (these processes would also be operable in industrial geothermal plants given the quite special solvent properties of steam). In brief, this study focuses on the speciation of select metal halides in bulk solution as well as in water vapor, and is driven by our need to understand the solvent properties of around 2.0x109 cubic kilometers of free water (or 2,500 times as much water as stored in all lakes and rivers) present in the Earth's crust. The scope of this study has particular applications in the geothermal and oil industries, as both deal with high temperature low-density aqueous fluids. Understanding how metal halide species behave upon boiling can also provide insight into how metals, such as copper and silver, coat turbine equipment and steam piping in geothermal plants, ultimately rendering these components inoperable. This study will also provide preliminary results from mass spectrometric experiments of transition metal halides, and will be augmented with results from molecular simulations of metal halides that are aimed at characterizing the nature (i.e. relativistic structures and energies) of metal clusters in water vapor.

Solid-phase arsenic speciation in aquifer sediments: A micro-X-ray absorption spectroscopy approach for quantifying trace-level speciation

DOE PAGES

Nicholas, Sarah L.; Erickson, Melinda L.; Woodruff, Laurel G.; ...

2017-05-19

Arsenic (As) is a geogenic contaminant affecting groundwater in geologically diverse systems globally. Arsenic release from aquifer sediments to groundwater is favored when biogeochemical conditions, especially oxidation-reduction (redox) potential, in aquifers fluctuate. The specific objective of this research is to identify the solid-phase sources and geochemical mechanisms of release of As in aquifers of the Des Moines Lobe glacial advance. The overarching concept is that conditions present at the aquifer-aquitard interfaces promote a suite of geochemical reactions leading to mineral alteration and release of As to groundwater. A microprobe X-ray absorption spectroscopy (μXAS) approach is developed and applied to rotosonicmore » drill core samples to identify the solid-phase speciation of As in aquifer, aquitard, and aquifer-aquitard interface sediments. This approach addresses the low solid-phase As concentrations, as well as the fine-scale physical and chemical heterogeneity of the sediments. The spectroscopy data are analyzed using novel cosine-distance and correlation-distance hierarchical clustering for Fe 1s and As 1s μXAS datasets. The solid-phase Fe and As speciation is then interpreted using sediment and well-water chemical data to propose solid-phase As reservoirs and release mechanisms. The results confirm that in two of the three locations studied, the glacial sediment forming the aquitard is the source of As to the aquifer sediments. The results are consistent with three different As release mechanisms: (1) desorption from Fe (oxyhydr)oxides, (2) reductive dissolution of Fe (oxyhydr)oxides, and (3) oxidative dissolution of Fe sulfides. The findings confirm that glacial sediments at the interface between aquifer and aquitard are geochemically active zones for As. The diversity of As release mechanisms is consistent with the geographic heterogeneity seen in the distribution of elevated-As wells.« less

Solid-phase arsenic speciation in aquifer sediments: A micro-X-ray absorption spectroscopy approach for quantifying trace-level speciation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nicholas, Sarah L.; Erickson, Melinda L.; Woodruff, Laurel G.

Arsenic (As) is a geogenic contaminant affecting groundwater in geologically diverse systems globally. Arsenic release from aquifer sediments to groundwater is favored when biogeochemical conditions, especially oxidation-reduction (redox) potential, in aquifers fluctuate. The specific objective of this research is to identify the solid-phase sources and geochemical mechanisms of release of As in aquifers of the Des Moines Lobe glacial advance. The overarching concept is that conditions present at the aquifer-aquitard interfaces promote a suite of geochemical reactions leading to mineral alteration and release of As to groundwater. A microprobe X-ray absorption spectroscopy (μXAS) approach is developed and applied to rotosonicmore » drill core samples to identify the solid-phase speciation of As in aquifer, aquitard, and aquifer-aquitard interface sediments. This approach addresses the low solid-phase As concentrations, as well as the fine-scale physical and chemical heterogeneity of the sediments. The spectroscopy data are analyzed using novel cosine-distance and correlation-distance hierarchical clustering for Fe 1s and As 1s μXAS datasets. The solid-phase Fe and As speciation is then interpreted using sediment and well-water chemical data to propose solid-phase As reservoirs and release mechanisms. The results confirm that in two of the three locations studied, the glacial sediment forming the aquitard is the source of As to the aquifer sediments. The results are consistent with three different As release mechanisms: (1) desorption from Fe (oxyhydr)oxides, (2) reductive dissolution of Fe (oxyhydr)oxides, and (3) oxidative dissolution of Fe sulfides. The findings confirm that glacial sediments at the interface between aquifer and aquitard are geochemically active zones for As. The diversity of As release mechanisms is consistent with the geographic heterogeneity seen in the distribution of elevated-As wells.« less

Evidence for radical anion formation during liquid secondary ion mass spectrometry analysis of oligonucleotides and synthetic oligomeric analogues: a deconvolution algorithm for molecular ion region clusters.

PubMed

Laramée, J A; Arbogast, B; Deinzer, M L

1989-10-01

It is shown that one-electron reduction is a common process that occurs in negative ion liquid secondary ion mass spectrometry (LSIMS) of oligonucleotides and synthetic oligonucleosides and that this process is in competition with proton loss. Deconvolution of the molecular anion cluster reveals contributions from (M-2H).-, (M-H)-, M.-, and (M + H)-. A model based on these ionic species gives excellent agreement with the experimental data. A correlation between the concentration of species arising via one-electron reduction [M.- and (M + H)-] and the electron affinity of the matrix has been demonstrated. The relative intensity of M.- is mass-dependent; this is rationalized on the basis of base-stacking. Base sequence ion formation is theorized to arise from M.- radical anion among other possible pathways.

Recombination of ions of a dense ion plasma in a fluorine atmosphere

NASA Astrophysics Data System (ADS)

Lankin, A. V.

2016-08-01

A new effect leading to the slowing of recombination in a weakly nonideal ion plasma is considered. The solvation of ions is included in the explanation of the results from studying a gas discharge afterglow in a fluorine atmosphere. It is shown that recombination in such a system is slowed in comparison to the standard relationships for ideal plasma. The formation and composition of cluster ions in such a medium are considered. The relationship between the variation in the kinetics of recombination and the course of the process according to a complicated mechanism with the intermediate formation of metastable cluster pairs is established. A quantitative model is built and a formula allowing us to describe the recombination rate over a wide range of parameters of the medium is obtained. It is shown that the proposed model is in good agreement with the experimental data.

User's guide to PHREEQC, a computer program for speciation, reaction-path, advective-transport, and inverse geochemical calculations

USGS Publications Warehouse

Parkhurst, D.L.

1995-01-01

PHREEQC is a computer program written in the C pwgranuning language that is designed to perform a wide variety of aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations, (2) reaction-path and advective-transport calculations involving specified irreversible reactions, mixing of solutions, mineral and gas equilibria surface-complex-ation reactions, and ion-exchange reactions, and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for composition differences between waters, within specified compositional uncertainties. PHREEQC is derived from the Fortran program PHREEQE, but it has been completely rewritten in C with the addition many new capabilities. New features include the capabilities to use redox couples to distribute redox elements among their valence states in speciation calculations; to model ion-exchange and surface-compiexation reactions; to model reactions with a fixed-pressure, multicomponent gas phase (that is, a gas bubble); to calculate the mass of water in the aqueous phase during reaction and transport calculations; to keep track of the moles of minerals present in the solid phases and determine antomaticaHy the thermodynamically stable phase assemblage; to simulate advective transport in combination with PHREEQC's reaction-modeling capability; and to make inverse modeling calculations that allow for uncertainties in the analytical data. The user interface is improved through the use of a simplified approach to redox reactions, which includes explicit mole-balance equations for hydrogen and oxygen; the use of a revised input that is modular and completely free format; and the use of mineral names and standard chemical symbolism rather than index numbers. The use of (2 eliminates nearly all limitations on army sizes, including numbers of elements, aqueous species, solutions, phases, and lengths of character strings. A new equation solver that optimizes a set of equalities subject to both equality and inequality constraints is used to determine the thermodynamically stable set of phases in equilibrium with a solution. A more complete Newton-Raphson formulation, master-species switching, and scaling of the algebraic equations reduce the number of failures of the nunmrical method in PHREEQC relative to PHREEQE. This report presents the equations that are the basis for chemical equilibrium and inverse-modeling calculations in PHREEQC, describes the input for the program, and presents twelve examples that demonstrate most of the program's capabilities.

Determination of adsorbable organic halogens in surface water samples by combustion-microcoulometry versus combustion-ion chromatography titration.

PubMed

Kinani, Aziz; Sa Lhi, Hacène; Bouchonnet, Stéphane; Kinani, Said

2018-03-02

Adsorbable Organic Halogen (AOX) is an analytical parameter of considerable interest since it allows to evaluate the amount of organohalogen disinfection by-products (OXBPs) present in a water sample. Halogen speciation of AOX into adsorbable organic chlorine, bromine and iodine, respectively AOCl, AOBr and AOI, is extremely important since it has been shown that iodinated and brominated organic by-products tend to be more toxic than their chlorinated analogues. Chemical speciation of AOX can be performed by combustion-ion chromatography (C-IC). In the present work, the effectiveness of the nitrate wash according to ISO 9562 standard method protocol to eliminate halide ions interferences was firstly examined. False positive AOX values were observed when chloride concentration exceeded 100 ppm. The improvements made to the washing protocol have eliminated chloride interference for concentrations up to 1000 ppm. A C-IC method for chemical speciation of AOX into AOCl, AOBr, and AOI has been developed and validated. The most important analytical parameters were investigated. The following optimal conditions were established: an aqueous solution containing 2.4 mM sodium bicarbonate/2.0 mM sodium carbonate, and 2% acetone (v/v) as mobile phase, 2 mL of aqueous sodium thiosulfate (500 ppm) as absorption solution, 0.2 mL min -1 as water inlet flow rate for hydropyrolysis, and 10 min as post-combustion time. The method was validated according to NF T90-210 standard method. Calibration curves fitted through a quadratic equation show coefficients of determination (r 2 ) greater than 0.9998, and RSD less than 5%. The LOQs were 0.9, 4.3, and 5.7 μg L -1 Cl for AOCl, AOBr, and AOI, respectively. The accuracy, in terms of relative error, was within a ± 10% interval. The applicability of the validated method was demonstrated by the analysis of twenty four water samples from three rivers in France. The measurements reveals AOX amounts above 10 μg L -1 Cl in all untreated samples, suggesting the presence of organohalogen compounds in the sampled rivers. On weight concentration basis, AOCl accounted for 77-100% of AOX in the treated water samples. A good agreement between the conventional AOX method and the developed C-IC method was found. Copyright © 2018 Elsevier B.V. All rights reserved.

Imaging Mass Spectrometry on the Nanoscale with Cluster Ion Beams

PubMed Central

2015-01-01

Imaging with cluster secondary ion mass spectrometry (SIMS) is reaching a mature level of development. Using a variety of molecular ion projectiles to stimulate desorption, 3-dimensional imaging with the selectivity of mass spectrometry can now be achieved with submicrometer spatial resolution and <10 nm depth resolution. In this Perspective, stock is taken regarding what it will require to routinely achieve these remarkable properties. Issues include the chemical nature of the projectile, topography formation, differential erosion rates, and perhaps most importantly, ionization efficiency. Shortcomings of existing instrumentation are also noted. Speculation about how to successfully resolve these issues is a key part of the discussion. PMID:25458665

Cluster observations of band-limited Pc 1 waves associated with streaming H+ and O+ ions in the high-altitude plasma mantle

NASA Astrophysics Data System (ADS)

Engebretson, M. J.; Kahlstorf, C. R. G.; Murr, D. L.; Posch, J. L.; Keiling, A.; Lavraud, B.; Rème, H.; Lessard, M. R.; Kim, E.-H.; Johnson, J. R.; Dombeck, J.; Grison, B.; Robert, P.; Glassmeier, K.-H.; Décréau, P. M. E.

2012-10-01

Bursts of band-limited Pc 1 waves (0.2 to ˜1.0 Hz) with normalized frequency f/fH+ ˜ 0.5 have been observed by the Cluster spacecraft during many passes through the high-latitude plasma mantle. These transverse, left-hand polarized waves are associated with regions of H+ and O+ ions streaming away from Earth along magnetic field lines at the same velocity (˜140 km/s). Waves were observed only when H+ fluxes increased by factors of 10-1000 and energies of both ion species increased by factors of up to 10. We present two satellite-ground conjunctions to demonstrate the high latitude localization of these waves and their ability to reach the polar ionosphere and two extended examples of waves and associated ion distribution functions near the southern dusk flank magnetopause. We also present the results of a search for all such events during Cluster's 2002 and 2003 passages through the magnetotail, with orbital precession covering dawn to dusk on Earth's night side (June through December). A total of 46 events (band-limited Pc 1-2 waves accompanied by a sustained population of streaming H+ and O+ ions, separated by at least 12 min) were observed on 29 days. The waves were generally associated with intervals of southward IMF Bz and/or large IMF By (times of active cusp reconnection), and often but not always occurred during the main phase or early recovery phase of magnetic storms. Analysis of selected events shows that the waves are associated with large H+ temperature anisotropy, and that the waves propagate opposite to the direction of the streaming ions. A wave instability analysis using the WHAMP code confirms that the generation of these waves, via the ion cyclotron instability, is basically consistent with known physics. Their extended region of wave growth is likely, however, to reach tailward significantly beyond the Cluster orbit.

Control of Chemical Effects in the Separation Process of a Differential Mobility / Mass Spectrometer System

PubMed Central

Schneider, Bradley B.; Coy, Stephen L.; Krylov, Evgeny V.; Nazarov, Erkinjon G.

2013-01-01

Differential mobility spectrometry (DMS) separates ions on the basis of the difference in their migration rates under high versus low electric fields. Several models describing the physical nature of this field mobility dependence have been proposed but emerging as a dominant effect is the clusterization model sometimes referred to as the dynamic cluster-decluster model. DMS resolution and peak capacity is strongly influenced by the addition of modifiers which results in the formation and dissociation of clusters. This process increases selectivity due to the unique chemical interactions that occur between an ion and neutral gas phase molecules. It is thus imperative to bring the parameters influencing the chemical interactions under control and find ways to exploit them in order to improve the analytical utility of the device. In this paper we describe three important areas that need consideration in order to stabilize and capitalize on the chemical processes that dominate a DMS separation. The first involves means of controlling the dynamic equilibrium of the clustering reactions with high concentrations of specific reagents. The second area involves a means to deal with the unwanted heterogeneous cluster ion populations emitted from the electrospray ionization process that degrade resolution and sensitivity. The third involves fine control of parameters that affect the fundamental collision processes, temperature and pressure. PMID:20065515

Structural insights into the light-driven auto-assembly process of the water-oxidizing Mn 4CaO 5-cluster in photosystem II

DOE PAGES

Zhang, Miao; Bommer, Martin; Chatterjee, Ruchira; ...

2017-07-18

In plants, algae and cyanobacteria, Photosystem II (PSII) catalyzes the light-driven splitting of water at a protein-bound Mn 4CaO 5-cluster, the water-oxidizing complex (WOC). In the photosynthetic organisms, the light-driven formation of the WOC from dissolved metal ions is a key process because it is essential in both initial activation and continuous repair of PSII. Structural information is required for understanding of this chaperone-free metal-cluster assembly. For the first time, we obtained a structure of PSII from Thermosynechococcus elongatus without the Mn 4CaO 5-cluster. Surprisingly, cluster-removal leaves the positions of all coordinating amino acid residues and most nearby water moleculesmore » largely unaffected, resulting in a pre-organized ligand shell for kinetically competent and error-free photo-assembly of the Mn 4CaO 5-cluster. First experiments initiating (i) partial disassembly and (ii) partial re-assembly after complete depletion of the Mn4CaO5-cluster agree with a specific bi-manganese cluster, likely a di-µ-oxo bridged pair of Mn(III) ions, as an assembly intermediate.« less

Structural insights into the light-driven auto-assembly process of the water-oxidizing Mn4CaO5-cluster in photosystem II.

PubMed

Zhang, Miao; Bommer, Martin; Chatterjee, Ruchira; Hussein, Rana; Yano, Junko; Dau, Holger; Kern, Jan; Dobbek, Holger; Zouni, Athina

2017-07-18

In plants, algae and cyanobacteria, Photosystem II (PSII) catalyzes the light-driven splitting of water at a protein-bound Mn 4 CaO 5 -cluster, the water-oxidizing complex (WOC). In the photosynthetic organisms, the light-driven formation of the WOC from dissolved metal ions is a key process because it is essential in both initial activation and continuous repair of PSII. Structural information is required for understanding of this chaperone-free metal-cluster assembly. For the first time, we obtained a structure of PSII from Thermosynechococcus elongatus without the Mn 4 CaO 5 -cluster. Surprisingly, cluster-removal leaves the positions of all coordinating amino acid residues and most nearby water molecules largely unaffected, resulting in a pre-organized ligand shell for kinetically competent and error-free photo-assembly of the Mn 4 CaO 5 -cluster. First experiments initiating (i) partial disassembly and (ii) partial re-assembly after complete depletion of the Mn 4 CaO 5 -cluster agree with a specific bi-manganese cluster, likely a di-µ-oxo bridged pair of Mn(III) ions, as an assembly intermediate.

Plasma flow around and charge distribution of a dust cluster in a rf discharge

NASA Astrophysics Data System (ADS)

Schleede, J.; Lewerentz, L.; Bronold, F. X.; Schneider, R.; Fehske, H.

2018-04-01

We employ a particle-in-cell Monte Carlo collision/particle-particle particle-mesh simulation to study the plasma flow around and the charge distribution of a three-dimensional dust cluster in the sheath of a low-pressure rf argon discharge. The geometry of the cluster and its position in the sheath are fixed to the experimental values, prohibiting a mechanical response of the cluster. Electrically, however, the cluster and the plasma environment, mimicking also the experimental situation, are coupled self-consistently. We find a broad distribution of the charges collected by the grains. The ion flux shows on the scale of the Debye length strong focusing and shadowing inside and outside the cluster due to the attraction of the ions to the negatively charged grains, whereas the electron flux is characterized on this scale only by a weak spatial modulation of its magnitude depending on the rf phase. On the scale of the individual dust potentials, however, the electron flux deviates in the vicinity of the cluster strongly from the laminar flow associated with the plasma sheath. It develops convection patterns to compensate for the depletion of electrons inside the dust cluster.

Effect of Temperature on the Protonation of the TALSPEAK Ligands: Lactic and Diethylenetrinitropentaacetic Acids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tian, Guoxin; Rao, Linfeng

2009-10-20

The protonation reactions of two ligands that play important roles in the TALSPEAK process for the separation of trivalent actinides from lanthanides, lactic acid and diethylenetrinitropentaacetic acid (DTPA), have been studied at variable temperatures. The protonation constants at 10-70 C were determined by titration potentiometry and the protonation enthalpies were determined at 25 C by titration microcalorimetry. The protonation constants remain essentially unchanged (25-70 C) within the experimental uncertainties, indicating that the effect of temperature on the protonation of lactate is insignificant. In contrast, the protonation constants of DTPA (log {beta}H's) generally decrease as the temperature is increased. Results frommore » this study indicate that the effect of temperature on the protonation of DTPA could alter the speciation of metal ions (actinides and lanthanides) in the TALSPEAK system, since lower values of log{beta}H at higher temperatures suggest that the hydrogen ions would compete less strongly with the metal ions for the complexation of DTPA at higher temperatures.« less

Water network-mediated, electron-induced proton transfer in [C5H5N ṡ (H2O)n]- clusters

NASA Astrophysics Data System (ADS)

DeBlase, Andrew F.; Wolke, Conrad T.; Weddle, Gary H.; Archer, Kaye A.; Jordan, Kenneth D.; Kelly, John T.; Tschumper, Gregory S.; Hammer, Nathan I.; Johnson, Mark A.

2015-10-01

The role of proton-assisted charge accommodation in electron capture by a heterocyclic electron scavenger is investigated through theoretical analysis of the vibrational spectra of cold, gas phase [Py ṡ (H2O)n=3-5]- clusters. These radical anions are formed when an excess electron is attached to water clusters containing a single pyridine (Py) molecule in a supersonic jet ion source. Under these conditions, the cluster ion distribution starts promptly at n = 3, and the photoelectron spectra, combined with vibrational predissociation spectra of the Ar-tagged anions, establish that for n > 3, these species are best described as hydrated hydroxide ions with the neutral pyridinium radical, PyH(0), occupying one of the primary solvation sites of the OH-. The n = 3 cluster appears to be a special case where charge localization on Py and hydroxide is nearly isoenergetic, and the nature of this species is explored with ab initio molecular dynamics calculations of the trajectories that start from metastable arrangements of the anion based on a diffuse, essentially dipole-bound electron. These calculations indicate that the reaction proceeds via a relatively slow rearrangement of the water network to create a favorable hydration configuration around the water molecule that eventually donates a proton to the Py nitrogen atom to yield the product hydroxide ion. The correlation between the degree of excess charge localization and the evolving shape of the water network revealed by this approach thus provides a microscopic picture of the "solvent coordinate" at the heart of a prototypical proton-coupled electron transfer reaction.

Atom probe tomography of the evolution of the nanostructure of oxide dispersion strengthened steels under ion irradiation

NASA Astrophysics Data System (ADS)

Orlov, N. N.; Rogozhkin, S. V.; Bogachev, A. A.; Korchuganova, O. A.; Nikitin, A. A.; Zaluzhnyi, A. G.; Kozodaev, M. A.; Kulevoy, T. V.; Kuibeda, R. P.; Fedin, P. A.; Chalykh, B. B.; Lindau, R.; Hoffmann, Ya.; Möslang, A.; Vladimirov, P.

2017-09-01

The atom probe tomography of the nanostructure evolution in ODS1 Eurofer, ODS 13.5Cr, and ODS 13.5Cr-0.3Ti steels under heavy ion irradiation at 300 and 573 K is performed. The samples were irradiated by 5.6 MeV Fe2+ ions and 4.8 MeV Ti2+ ions to a fluence of 1015 cm-2. It is shown that the number of nanoclusters increases by a factor of 2-3 after irradiation. The chemical composition of the clusters in the steels changes after irradiation at 300 K, whereas the chemical composition of the clusters in the 13.5Cr-0.3Ti ODS steel remains the same after irradiation at 573 K.

Electron and nuclear dynamics of molecular clusters in ultraintense laser fields. IV. Coulomb explosion of molecular heteroclusters.

PubMed

Last, Isidore; Jortner, Joshua

2004-11-01

In this paper we present a theoretical and computational study of the temporal dynamics and energetics of Coulomb explosion of (CD4)(n) and (CH4)(n) (n=55-4213) molecular heteroclusters in ultraintense (I=10(16)-10(19) W cm(-2)) laser fields, addressing the manifestation of electron dynamics, together with nuclear energetic and kinematic effects on the heterocluster Coulomb instability. The manifestations of the coupling between electron and nuclear dynamics were explored by molecular dynamics simulations for these heteroclusters coupled to Gaussian laser fields (pulse width tau=25 fs), elucidating outer ionization dynamics, nanoplasma screening effects (being significant for I< or =10(17) W cm(-2)), and the attainment of cluster vertical ionization (CVI) (at I=10(17) W cm(-2) for cluster radius R(0)< or =31 A). Nuclear kinematic effects on heterocluster Coulomb explosion are governed by the kinematic parameter eta=q(C)m(A)/q(A)m(C) for (CA(4))(n) clusters (A=H,D), where q(j) and m(j) (j=A,C) are the ionic charges and masses. Nonuniform heterocluster Coulomb explosion (eta >1) manifests an overrun effect of the light ions relative to the heavy ions, exhibiting the expansion of two spatially separated subclusters, with the light ions forming the outer subcluster at the outer edge of the spatial distribution. Important features of the energetics of heterocluster Coulomb explosion originate from energetic triggering effects of the driving of the light ions by the heavy ions (C(4+) for I=10(17)-10(18) W cm(-2) and C(6+) for I=10(19) W cm(-2)), as well as for kinematic effects. Based on the CVI assumption, scaling laws for the cluster size (radius R(0)) dependence of the energetics of uniform Coulomb explosion of heteroclusters (eta=1) were derived, with the size dependence of the average (E(j,av)) and maximal (E(j,M)) ion energies being E(j,av)=aR(0) (2) and E(j,M)=(5a/3)R(0) (2), as well as for the ion energy distributions P(E(j)) proportional to E(j) (1/2); E(j)< or =E(j,M). These results for uniform Coulomb explosion serve as benchmark reference data for the assessment of the effects of nonuniform explosion, where the CVI scaling law for the energetics still holds, with deviations of the a coefficient, which increase with increasing eta. Kinematic effects (for eta>1) result in an isotope effect, predicting the enhancement (by 9%-11%) of E(H,av) for Coulomb explosion of (C(4+)H(4) (+))(eta) (eta=3) relative to E(D,av) for Coulomb explosion of (C(4+)D(4) (+))(eta) (eta=1.5), with the isotope effect being determined by the ratio of the kinematic parameters for the pair of Coulomb exploding clusters. Kinematic effects for nonuniform explosion also result in a narrow isotope dependent energy distribution (of width DeltaE) of the light ions (with DeltaE/E(H,av) approximately 0.3 and DeltaE/E(D,av) approximately 0.4), with the distribution peaking at the high energy edge, in marked contrast with the uniform explosion case. Features of laser-heterocluster interactions were inferred from the analyses of the intensity dependent boundary radii (R(0))(I) and the corresponding average D+ ion energies (E(D,av))(I), which provide a measure for optimization of the cluster size at intensity I for the neutron yield from dd nuclear fusion driven by Coulomb explosion (NFDCE) of these heteroclusters. We infer on the advantage of deuterium containing heteronuclear clusters, e.g., (CD4)(n) in comparison to homonuclear clusters, e.g., (D2)(n/2), for dd NFDCE, where the highly charged heavy ions (e.g., C4+ or C6+) serve as energetic and kinematic triggers driving the D+ ions to a high (10-200 keV) energy domain. (c) 2004 American Institute of Physics.

SPECIATE and using the Speciation Tool to prepare VOC and PM chemical speciation profiles for air quality modeling

EPA Science Inventory

This product provides training to air pollution inventory and modeling professionals to understand the US EPA's SPECIATE database base and Speciation Tool and their use to develop speciated emission inventories.

SPECIATE's VOC and PM Speciation Profiles and Their use to Prepare for Air quality Modeling (2017 EIC)

EPA Pesticide Factsheets

This training provides general concepts on chemical speciation, the SPECIATE database and browser, and how to use the Speciation Tool to create model ready speciation inputs for a photochemical air quality model.

SPECIATE 4.2: speciation Database Development Documentation

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Among the many uses of speciation data, these source profiles are used to: (1) create speciated emissions inve...

Multivalent Cation-Bridged PI(4,5)P2 Clusters Form at Very Low Concentrations.

PubMed

Wen, Yi; Vogt, Volker M; Feigenson, Gerald W

2018-06-05

Phosphatidylinositol 4,5-bisphosphate (PI(4,5)P 2 or PIP2), is a key component of the inner leaflet of the plasma membrane in eukaryotic cells. In model membranes, PIP2 has been reported to form clusters, but whether these locally different conditions could give rise to distinct pools of unclustered and clustered PIP2 is unclear. By use of both fluorescence self-quenching and Förster resonance energy transfer assays, we have discovered that PIP2 self-associates at remarkably low concentrations starting below 0.05 mol% of total lipids. Formation of these clusters was dependent on physiological divalent metal ions, such as Ca 2+ , Mg 2+ , Zn 2+ , or trivalent ions Fe 3+ and Al 3+ . Formation of PIP2 clusters was also headgroup-specific, being largely independent of the type of acyl chain. The similarly labeled phospholipids phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, and phosphatidylinositol exhibited no such clustering. However, six phosphoinositide species coclustered with PIP2. The degree of PIP2 cation clustering was significantly influenced by the composition of the surrounding lipids, with cholesterol and phosphatidylinositol enhancing this behavior. We propose that PIP2 cation-bridged cluster formation, which might be similar to micelle formation, can be used as a physical model for what could be distinct pools of PIP2 in biological membranes. To our knowledge, this study provides the first evidence of PIP2 forming clusters at such low concentrations. The property of PIP2 to form such clusters at such extremely low concentrations in model membranes reveals, to our knowledge, a new behavior of PIP2 proposed to occur in cells, in which local multivalent metal ions, lipid compositions, and various binding proteins could greatly influence PIP2 properties. In turn, these different pools of PIP2 could further regulate cellular events. Copyright © 2018 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Influence of the environment on the [4Fe-4S]2+ to [2Fe-2S]2+ cluster switch in the transcriptional regulator FNR.

PubMed

Crack, Jason C; Gaskell, Alisa A; Green, Jeffrey; Cheesman, Myles R; Le Brun, Nick E; Thomson, Andrew J

2008-02-06

In Escherichia coli, the switch between aerobic and anaerobic metabolism is primarily controlled by the fumarate and nitrate reduction transcriptional regulator FNR. In the absence of O2, FNR binds a [4Fe-4S]2+ cluster, generating a transcriptionally active dimeric form. Exposure to O2 results in the conversion of the cluster to a [2Fe-2S]2+ form, leading to dissociation of the protein into transcriptionally inactive monomers. The [4Fe-4S]2+ to [2Fe-2S]2+ cluster conversion proceeds in two steps. Step 1 involves the one-electron oxidation of the cluster, resulting in the release of Fe2+, generating a [3Fe-4S]1+ cluster intermediate, and a superoxide ion. In step 2, the cluster intermediate spontaneously rearranges to form the [2Fe-2S]2+ cluster, with the release of a Fe3+ ion and two sulfide ions. Here, we demonstrate that, in both native and reconstituted [4Fe-4S] FNR, the reaction environment and, in particular, the presence of Fe2+ and/or Fe3+ chelators can influence significantly the cluster conversion reaction. We demonstrate that while the rate of step 1 is largely insensitive to chelators, that of step 2 is significantly enhanced by both Fe2+ and Fe3+ chelators. We show that, for reactions in Fe3+-coordinating phosphate buffer, step 2 is enhanced to the extent that step 1 becomes the rate determining step and the [3Fe-4S]1+ intermediate is no longer detectable. Furthermore, Fe3+ released during this step is susceptible to reduction in the presence of Fe2+ chelators. This work, which may have significance for the in vivo FNR cluster conversion reaction in the cell cytoplasm, provides an explanation for apparently contradictory results reported from different laboratories.

Revisit the landscape of protonated water clusters H+(H2O)n with n = 10-17: An ab initio global search.

PubMed

Shi, Ruili; Li, Keyao; Su, Yan; Tang, Lingli; Huang, Xiaoming; Sai, Linwei; Zhao, Jijun

2018-05-07

Using a genetic algorithm incorporated with density functional theory, we explore the ground state structures of protonated water clusters H + (H 2 O) n with n = 10-17. Then we re-optimize the isomers at B97-D/aug-cc-pVDZ level of theory. The extra proton connects with a H 2 O molecule to form a H 3 O + ion in all H + (H 2 O) 10-17 clusters. The lowest-energy structures adopt a monocage form at n = 10-16 and core-shell structure at n = 17 based on the MP2/aug-cc-pVTZ//B97-D/aug-cc-pVDZ+ZPE single-point-energy calculation. Using second-order vibrational perturbation theory, we further calculate the infrared spectra with anharmonic correction for the ground state structures of H + (H 2 O) 10-17 clusters at the PBE0/aug-cc-pVDZ level. The anharmonic correction to the spectra is crucial since it reproduces the experimental results quite well. The extra proton weakens the O-H bond strength in the H 3 O + ion since the Wiberg bond order of the O-H bond in the H 3 O + ion is smaller than that in H 2 O molecules, which causes a red shift of the O-H stretching mode in the H 3 O + ion.

Revisit the landscape of protonated water clusters H+(H2O)n with n = 10-17: An ab initio global search

NASA Astrophysics Data System (ADS)

Shi, Ruili; Li, Keyao; Su, Yan; Tang, Lingli; Huang, Xiaoming; Sai, Linwei; Zhao, Jijun

2018-05-01

Using a genetic algorithm incorporated with density functional theory, we explore the ground state structures of protonated water clusters H+(H2O)n with n = 10-17. Then we re-optimize the isomers at B97-D/aug-cc-pVDZ level of theory. The extra proton connects with a H2O molecule to form a H3O+ ion in all H+(H2O)10-17 clusters. The lowest-energy structures adopt a monocage form at n = 10-16 and core-shell structure at n = 17 based on the MP2/aug-cc-pVTZ//B97-D/aug-cc-pVDZ+ZPE single-point-energy calculation. Using second-order vibrational perturbation theory, we further calculate the infrared spectra with anharmonic correction for the ground state structures of H+(H2O)10-17 clusters at the PBE0/aug-cc-pVDZ level. The anharmonic correction to the spectra is crucial since it reproduces the experimental results quite well. The extra proton weakens the O-H bond strength in the H3O+ ion since the Wiberg bond order of the O-H bond in the H3O+ ion is smaller than that in H2O molecules, which causes a red shift of the O-H stretching mode in the H3O+ ion.

Clusters and holes: Exchange networks in hematite-ilmenite solid solutions

NASA Astrophysics Data System (ADS)

Fabian, K.; McEnroe, S. A.; Robinson, P.

2009-04-01

Holes and clusters of exchange networks dominate the low-temperature, metastable phase diagram of the system (1 - x)Fe2O3 xF eTiO3 (Ilmx ). By our measurements we have probed and extended the phase diagram of Ishikawa et al. (1985) in the light of magnetic influences of the random exchange links, which originate either by replacing random pairs of Fe2+ and Ti4+ ions in the ordered ilmenite lattice by two Fe3+ions (ordered Ilmx phase), or by randomly replacing two Fe3+ ions in the hematite lattice by a pair of Fe2+ and Ti4+ ions (disordered Ilmx phase). Now a large dataset is available from these measurements, and we propose several new ideas to interpret the sometimes unexpected results. By refining a method of Ishikawa (1967), we analyze the PM' region of the phase diagram in terms of a mean field theory of interacting clusters. This allows to determine cluster sizes and interaction field distribution by inverting hysteresis measurements of Ilm92 and Ilm97. To understand the relation between ordered and disordered phases we design a mean field theory to determine Neel and Curie temperatures of both. An especially interesting finding is that the experimentally observed intersection of PM-PM' crossover with the AF phase boundary close to Ilm97 can be explained by analyzing average exchange interaction strengths.

Diffusion dynamics of the Li+ ion on a model surface of amorphous carbon: a direct molecular orbital dynamics study.

PubMed

Tachikawa, Hiroto; Shimizu, Akira

2005-07-14

Diffusion processes of the Li+ ion on a model surface of amorphous carbon (Li+C96H24 system) have been investigated by means of the direct molecular orbital (MO) dynamics method at the semiempirical AM1 level. The total energy and energy gradient on the full-dimensional AM1 potential energy surface were calculated at each time step in the dynamics calculation. The optimized structure, where Li+ is located in the center of the cluster, was used as the initial structure at time zero. The dynamics calculation was carried out in the temperature range 100-1000 K. The calculations showed that the Li+ ion vibrates around the equilibrium point below 200 K, while the Li+ ion moves on the surface above 250 K. At intermediate temperatures (300 K < T < 400 K), the ion moves on the surface and falls in the edge regions of the cluster. At higher temperatures (600 K < T), the Li+ ion transfers freely on the surface and edge regions. The diffusion pathway of the Li+ ion was discussed on the basis of theoretical results.

A new turn-on fluorimetric method for the rapid speciation of Cr(III)/Cr(VI) species in tea samples with rhodamine-based fluorescent reagent

NASA Astrophysics Data System (ADS)

Özyol, Esra; Saçmacı, Şerife; Saçmacı, Mustafa; Ülgen, Ahmet

2018-02-01

A new fluorimetric method with rhodamine-based fluorescent agent was developed for the rapid speciation of Cr(III)/Cr(VI) in tea, soil and water samples. The system, which utilizes a fluorescent reagent, was used for the first time after synthesis/characterization of 3‧,6‧-bis(diethylamino)-2-{[(1E)-(2,4-dimethoxyphenyl)methylene] amino}spiro[isoindole-1,9‧-xanthen]-3(2H)-one (BDAS). The reagent responds instantaneously at room temperature in a 1:1 stoichiometric manner to the amount of Cr(III). The selectivity of this system for Cr(III) over other metal ions is remarkably high, and its sensitivity is below 0.01 mg L- 1 in aqueous solutions which enables a simplification without any pretreatment of the real sample. The method has a wide linear range of 0.1-10 mg L- 1 and a detection limit of 0.15 μg L- 1 for Cr(III) while the relative standard deviation was 0.1% for 0.1 mg L- 1 Cr(III) concentration. The results of detection and recovery experiments for Cr(III) in tea, soil and water were satisfactory, indicating that the method has better feasibility and application potential in the routine determination and speciation of Cr(III)/Cr(VI). The results of analysis of the certified reference material (INCT-TL-1 tea sample and CWW-TM-D waste water) are in good agreement with the certified value.

Rumsey and Walker_AMT_2016_Table 2.xlsx

EPA Pesticide Factsheets

Table summarizes instrument precision assessed by collocating the two sample boxes. Precision is quantified as the standard deviation of the residuals of an orthogonal least squares regression of concentrations from the two sample boxes. This allows for an estimation of gradient precision and ultimately gradient and flux detection limits. This dataset is associated with the following publication:Rumsey, I. Application of an online ion chromatography-based instrument for gradient flux measurements of speciated nitrogen and sulfur. ENVIRONMENTAL SCIENCE & TECHNOLOGY. American Chemical Society, Washington, DC, USA, 9(6): 2581-2592, (2016).

Speciation of Trace Di- and Triorganotins in Water by Ion Exchange HPLC-GFAA.

DTIC Science & Technology

1980-08-05

Equation 2 are available (38,40) in the form, pKa = pKo C0 4 for all of the R groups examined on organotins in this paper. The new Hammett - type QSAR o...specified by Equation 1. barring influences of competing neutral ligands (such an methanol in the solvent). Thus K presumes either an "inert" neutral or an...different anionic groups in order to test the validity of Equation I with the SCX column and its relevance to Scheme 1. Fertinent daia are summarized in

Selected AB4 2−/− (A = C, Si, Ge; B = Al, Ga, In) ions: a battle between covalency and aromaticity, and prediction of square planar Si in SiIn4 2−/−†

PubMed Central

Alexandrova, Anastassia N.; Nayhouse, Michael J.; Huynh, Mioy T.; Kuo, Jonathan L.; Melkonian, Arek V.; Chavez, Gerardo; Hernando, Nina M.; Kowal, Matthew D.; Liu, Chi-Ping

2012-01-01

CAl4 2−/− (D4h, 1A1g) is a cluster ion that has been established to be planar, aromatic, and contain a tetracoordinate planar C atom. Valence isoelectronic substitution of C with Si and Ge in this cluster leads to a radical change of structure toward distorted pentagonal species. We find that this structural change goes together with the cluster acquiring partial covalency of bonding between Si/Ge and Al4, facilitated by hybridization of the atomic orbitals (AOs). Counter intuitively, for the AAl4 2−/− (A = C, Si, Ge) clusters, hybridization in the dopant atom is strengthened from C, to Si, and to Ge, even though typically AOs are more likely to hybridize if they are closer in energy (i.e. in earlier elements in the Periodic Table). The trend is explained by the better overlap of the hybrids of the heavier dopants with the orbitals of Al4. From the thus understood trend, it is inferred that covalency in such clusters can be switched off, by varying the relative sizes of the AOs of the main element and the dopant. Using this mechanism, we then successfully killed covalency in Si, and predicted a new aromatic cluster ion containing a tetracoordinate square planar Si, SiIn4 2−/−. PMID:22868353

Understanding ligand effects in gold clusters using mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Grant E.; Laskin, Julia

This review summarizes recent research on the influence of phosphine ligands on the size, stability, and reactivity of gold clusters synthesized in solution. Sub-nanometer clusters exhibit size- and composition-dependent properties that are unique from those of larger nanoparticles. The highly tunable properties of clusters and their high surface-to-volume ratio make them promising candidates for a variety of technological applications. However, because “each-atom-counts” toward defining cluster properties it is critically important to develop robust synthesis methods to efficiently prepare clusters of predetermined size. For decades phosphines have been known to direct the size-selected synthesis of gold clusters. Despite the preparation ofmore » numerous species it is still not understood how different functional groups at phosphine centers affect the size and properties of gold clusters. Using electrospray ionization mass spectrometry (ESI-MS) it is possible to characterize the effect of ligand substitution on the distribution of clusters formed in solution at defined reaction conditions. In addition, ligand exchange reactions on preformed clusters may be monitored using ESI-MS. Collision induced dissociation (CID) may also be employed to obtain qualitative insight into the fragmentation of mixed ligand clusters and the relative binding energies of differently substituted phosphines. Quantitative ligand binding energies and cluster stability may be determined employing surface induced dissociation (SID) in a custom-built Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS). Rice-Ramsperger-Kassel-Marcus (RRKM) based modeling of the SID data allows dissociation energies and entropy values to be extracted that may be compared with the results of high-level theoretical calculations. The charge reduction and reactivity of atomically precise gold clusters, including partially ligated species generated in the gas-phase by in source CID, on well-defined surfaces may be explored using ion soft landing (SL) in a custom-built instrument combined with in situ time of flight secondary ion mass spectrometry (TOF-SIMS). Jointly, this multipronged experimental approach allows characterization of the full spectrum of relevant phenomena including cluster synthesis, ligand exchange, thermochemistry, surface immobilization, and reactivity. The fundamental insights obtained from this work will facilitate the directed synthesis of gold clusters with predetermined size and properties for specific applications.« less

Design and utilization of a top hat analyzer for Hall thruster plume diagnostics

NASA Astrophysics Data System (ADS)

Victor, Allen Leoraj

Electric propulsion offers new capabilities for ambitious space missions of the future. However, coating, uneven heating, and the charging of spacecraft components have impeded the integration of Hall thrusters for space missions and encouraged plume diagnostics of the thruster plasma environment. Plume diagnostics are also important for the inference of thruster performance through plume properties downstream of the engine. While the top hat analyzer has been available for low-density space plasma diagnostics for over twenty years, the use of this instrument for plasma thruster plume diagnostics has been nonexistent. This thesis describes the development of a new diagnostics tool, the Top Hat Electric Propulsion Plume Analyzer (TOPAZ), which provides unprecedented insight into the physical mechanisms that govern the performance of Hall thrusters. Novel measurements conducted by TOPAZ on the BHT-600 Hall thruster cluster yielded interesting and undocumented phenomena in the far-field plume. SIMION, a commercial ion optics program, was used to design TOPAZ and estimate the energy and angular resolutions as well as the instrument's sensitivity and plate-voltage relationships. TOPAZ was experimentally characterized through an ion beam facility operating on air, xenon, and krypton gases. Measurements on the BHT-600 cluster indicated lower-energy ions emanated from positions closer to the cathode while higher-energy ions were measured from along the discharge channel centerlines. Low-energy ions were also measured from behind the cathodes only during cluster operation. Charge-exchange and ionization outside the primary acceleration region are believed to be the cause of the variance in the energy distributions. Cross pollination of the cathode plume with the opposite thruster is argued to create low-energy ions which emanate from behind the cathode. Time-of-flight measurements through TOPAZ allowed for charge-state and species fraction discriminations as functions of emanation points from the cluster. Multiply-charged ions (˜5%) were measured from regions near the discharge channels and only for plume angles less than 20 degrees. Calculations of the axial and radial velocity distributions for the first three charge-states downstream of the cluster centerline revealed a symmetric triple-peak structure in the radial velocity distributions and a double-peak profile in the axial velocity distribution of the first charge-state of xenon.

Accelerator-based chemical and elemental analysis of atmospheric aerosols

NASA Astrophysics Data System (ADS)

Mentes, Besim

Aerosol particles have always been present in the atmosphere, arising from natural sources. But it was not until recently when emissions from anthropogenic (man made) sources began to dominate, that atmospheric aerosols came into focus and the aerosol science in the environmental perspective started to grow. These sources emit or produce particles with different elemental and chemical compositions, as well as different sizes of the individual aerosols. The effects of increased pollution of the atmosphere are many, and have different time scales. One of the effects known today is acid rain, which causes problems for vegetation. Pollution is also a direct human health risk, in many cities where traffic driven by combustion engines is forbidden at certain times when the meteorological conditions are unfavourable. Aerosols play an important role in the climate, and may have both direct and indirect effect which cause cooling of the planet surface, in contrast to the so-called greenhouse gases. During this work a technique for chemical and elemental analysis of atmospheric aerosols and an elemental analysis methodology for upper tropospheric aerosols have been developed. The elemental analysis is performed by the ion beam analysis (IBA) techniques, PIXE (elements heavier than Al). PESA (C, N and O), cPESA (H) and pNRA (Mg and Na). The chemical speciation of atmospheric aerosols is obtained by ion beam thermography (IBT). During thermography the sample temperature is stepwise increased and the IBA techniques are used to continuously monitor the elemental concentration. A thermogram is obtained for each element. The vaporisation of the compounds in the sample appears as a concentration decrease in the thermograms at characteristic vaporisation temperatures (CVTs). Different aspects of IBT have been examined in Paper I to IV. The features of IBT are: almost total elemental speciation of the aerosol mass, chemical speciation of the inorganic compounds, carbon content obtained as volatile and non-volatile fractions, analysis of acidic aerosols is possible, aerosols can be size-fractionated using a cascade impactor as collection device, total analysis time for a sample is around 45 min, the sample mass load is from around 1 to 30 μg/cm2. An intercomparison of IBT and ion chromatography (IC) when a DMPS system was used as a reference instrument has been performed (Paper IV). Ions of K, Na, SO4, NO3 and NH4 were determined and quantified by both IBT and IC. The intercomparison showed that the procedure used in IBT does not suffer from any selective losses, especially not from the NO3 and NH4 compounds, which exhibit an appreciable interaction with the gas phase as NH3 and HNO3. An impactor-based aerosol sampler for upper tropospheric conditions has been developed (Paper V). Despite the low aerosol concentration at that altitude the sulphur concentration can be measured, with a detection limit of 1 ng/m 3 for one hour sampling by optimising parameters in the use of PIXE analysis.

New Cs sputter ion source with polyatomic ion beams for secondary ion mass spectrometry applications

NASA Astrophysics Data System (ADS)

Belykh, S. F.; Palitsin, V. V.; Veryovkin, I. V.; Kovarsky, A. P.; Chang, R. J. H.; Adriaens, A.; Dowsett, M. G.; Adams, F.

2007-08-01

A simple design for a cesium sputter ion source compatible with vacuum and ion-optical systems as well as with electronics of the commercially available Cameca IMS-4f instrument is reported. This ion source has been tested with the cluster primary ions of Sin- and Cun-. Our experiments with surface characterization and depth profiling conducted to date demonstrate improvements of the analytical capabilities of the secondary ion mass spectrometry instrument due to the nonadditive enhancement of secondary ion emission and shorter ion ranges of polyatomic projectiles compared to atomic ones with the same impact energy.

Synthesis efficiency of heavy carbon clusters from ETFE ablated by different numbers of laser pulse in vacuum

NASA Astrophysics Data System (ADS)

Shibagaki, K.; Takada, N.; Sasaki, K.; Kadota, K.

2002-09-01

We have carried out mass spectral analysis of positive ions produced by laser ablation of a copolymer of ethylene and tetrafluoroethylene (ETFE: [CH 2CH 2CF 2CF 2] n) in vacuum using time-of-flight mass spectrometry (TOF-MS). The surfaces of the ETFE targets irradiated by different numbers of laser pulse were analyzed by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Heavy carbon cluster ions C n+ with n≥30 were observed in the mass spectra. The fractional abundance of heavy clusters in the mass spectrum decreased with the number of laser pulse. On the other hand, carbon became rich in the atomic composition of the laser-irradiated surface, and the eroded area on the surface increased with the number of laser pulse. From these results, it is suggested that the carbon-rich material surface results in the less efficient production of heavy carbon clusters. In addition, it is also suggested that clustering reactions in eroded craters do not contribute to the synthesis of heavy clusters.

Theoretical and Experimental Insights into the Dissociation of 2-Hydroxyethylhydrazinium Nitrate Clusters Formed via Electrospray.

PubMed

Patrick, Amanda L; Vogelhuber, Kristen M; Prince, Benjamin D; Annesley, Christopher J

2018-03-01

Ionic liquids are used for myriad applications, including as catalysts, solvents, and propellants. Specifically, 2-hydroxyethylhydrazinium nitrate (HEHN) has been developed as a chemical propellant for space applications. The gas-phase behavior of HEHN ions and clusters is important in understanding its potential as an electrospray thruster propellant. Here, the unimolecular dissociation pathways of two clusters are experimentally observed, and theoretical modeling of hydrogen bonding and dissociation pathways is used to help rationalize those observations. The cation/deprotonated cation cluster [HEH 2 - H] + , which is observed from electrospray ionization, is calculated to be considerably more stable than the complementary cation/protonated anion adduct, [HEH + HNO 3 ] + , which is not observed experimentally. Upon collisional activation, a larger cluster [(HEHN) 2 HEH] + undergoes dissociation via loss of nitric acid at lower collision energies, as predicted theoretically. At higher collision energies, additional primary and secondary loss pathways open, including deprotonated cation loss, ion-pair loss, and double-nitric-acid loss. Taken together, these experimental and theoretical results contribute to a foundational understanding of the dissociation of protic ionic liquid clusters in the gas phase.

Negative ion productions in high velocity collision between small carbon clusters and Helium atom target

NASA Astrophysics Data System (ADS)

M, Chabot; K, Béroff; T, Pino; G, Féraud; N, Dothi; Padellec A, Le; G, Martinet; S, Bouneau; Y, Carpentier

2012-11-01

We measured absolute double capture cross section of Cn+ ions (n=1,5) colliding, at 2.3 and 2.6 a.u velocities, with an Helium target atom and the branching ratios of fragmentation of the so formed electronically excited anions Cn-*. We also measured absolute cross section for the electronic attachment on neutral Cn clusters colliding at same velocities with He atom. This is to our knowledge the first measurement of neutral-neutral charge exchange in high velocity collision.

Magnetic solid-phase extraction combined with graphite furnace atomic absorption spectrometry for speciation of Cr(III) and Cr(VI) in environmental waters.

PubMed

Jiang, Hong-mei; Yang, Ting; Wang, Yan-hong; Lian, Hong-zhen; Hu, Xin

2013-11-15

A new approach of magnetic solid phase extraction (MSPE) coupled with graphite furnace atomic absorption spectrometry (GFAAS) has been developed for the speciation of Cr(III) and Cr(VI) using zincon-immobilized silica-coated magnetic Fe3O4 nanoparticles (Zincon-Si-MNPs) as the MSPE absorbent. Cr(III) was quantitatively reserved on the absorbent at pH 9.1 while total Cr was reserved at pH 6.5. The absorbed Cr species were eluted by using 2 mol/L HCl and detected by GFAAS. The concentration of Cr(VI) could be calculated by subtracting Cr(III) from total Cr. All the parameters affecting the separation and extraction efficiency of Cr species such as pH, extraction time, concentration and volume of eluent, sample volume and influence of co-existing ions were systematically examined and the optimized conditions were established accordingly. The detection limit (LOD) of the method was 0.016 and 0.011 ng mL(-1) for Cr(III) and Cr(VI), respectively, with the enrichment factor of 100 and 150. The precisions of this method (Relative standard deviation, RSD, n=7) for Cr(III) and Cr(VI) at 0.1 ng mL(-1) were 6.0% and 6.2%, respectively. In order to validate the proposed method, a certified reference material of environmental water was analyzed, and the result of Cr speciation was in good agreement with the certified value. This MSPE-GFAAS method has been successfully applied for the speciation of Cr(III) and Cr(VI) in lake and tap waters with the recoveries of 88-109% for the spiked samples. Moreover, the MSPE separation mechanism of Cr(III) and Cr(VI) based on their adsorption-desorption on Zincon-Si-MNPs has been explained through various spectroscopic characterization. © 2013 Elsevier B.V. All rights reserved.

Imaging Mass Spectrometry on the Nanoscale with Cluster Ion Beams

DOE PAGES

Winograd, Nicholas

2014-12-02

Imaging with cluster secondary ion mass spectrometry (SIMS) is reaching a mature level of development. When, using a variety of molecular ion projectiles to stimulate desorption, 3-dimensional imaging with the selectivity of mass spectrometry can now be achieved with submicrometer spatial resolution and <10 nm depth resolution. In this Perspective, stock is taken regarding what it will require to routinely achieve these remarkable properties. Some issues include the chemical nature of the projectile, topography formation, differential erosion rates, and perhaps most importantly, ionization efficiency. Shortcomings of existing instrumentation are also noted. One key part of this discussion involves speculation onmore » how best to resolve these issues.« less

Imaging Mass Spectrometry on the Nanoscale with Cluster Ion Beams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Winograd, Nicholas

Imaging with cluster secondary ion mass spectrometry (SIMS) is reaching a mature level of development. When, using a variety of molecular ion projectiles to stimulate desorption, 3-dimensional imaging with the selectivity of mass spectrometry can now be achieved with submicrometer spatial resolution and <10 nm depth resolution. In this Perspective, stock is taken regarding what it will require to routinely achieve these remarkable properties. Some issues include the chemical nature of the projectile, topography formation, differential erosion rates, and perhaps most importantly, ionization efficiency. Shortcomings of existing instrumentation are also noted. One key part of this discussion involves speculation onmore » how best to resolve these issues.« less

An improved experimental scheme for simultaneous measurement of high-resolution zero electron kinetic energy (ZEKE) photoelectron and threshold photoion (MATI) spectra

NASA Astrophysics Data System (ADS)

Michels, François; Mazzoni, Federico; Becucci, Maurizio; Müller-Dethlefs, Klaus

2017-10-01

An improved detection scheme is presented for threshold ionization spectroscopy with simultaneous recording of the Zero Electron Kinetic Energy (ZEKE) and Mass Analysed Threshold Ionisation (MATI) signals. The objective is to obtain accurate dissociation energies for larger molecular clusters by simultaneously detecting the fragment and parent ion MATI signals with identical transmission. The scheme preserves an optimal ZEKE spectral resolution together with excellent separation of the spontaneous ion and MATI signals in the time-of-flight mass spectrum. The resulting improvement in sensitivity will allow for the determination of dissociation energies in clusters with substantial mass difference between parent and daughter ions.

Electron-Temperature Dependence of the Recombination of NH4(+)((NH3)(sub n) Ions with Electrons

NASA Technical Reports Server (NTRS)

Skrzypkowski, M. P.; Johnson, R.

1997-01-01

The two-body recombination of NH4(+)(NH3)(sub 2,3) cluster-ions with electrons has been studied in an afterglow experiment in which the electron temperature T, was elevated by radio-frequency heating from 300 K up to 900 K. The recombination coefficients for the n = 2 and n = 3 cluster ions were found to be equal, alpha(sub 2, sup(2)) = alpha(sub 3, sup(2)) = (4.8 +/- 0.5) x 10(exp - 6)cu cm/s, and to vary with electron temperature as T(sub c, sup -0.65) rather than to be nearly temperature-independent as had been inferred from measurements in microwave-heated plasmas.

Formation and emission mechanisms of Ag nanoclusters in the Ar matrix assembly cluster source

NASA Astrophysics Data System (ADS)

Zhao, Junlei; Cao, Lu; Palmer, Richard E.; Nordlund, Kai; Djurabekova, Flyura

2017-11-01

In this paper, we study the mechanisms of growth of Ag nanoclusters in a solid Ar matrix and the emission of these nanoclusters from the matrix by a combination of experimental and theoretical methods. The molecular dynamics simulations show that the cluster growth mechanism can be described as "thermal spike-enhanced clustering" in multiple sequential ion impact events. We further show that experimentally observed large sputtered metal clusters cannot be formed by direct sputtering of Ag mixed in the Ar. Instead, we describe the mechanism of emission of the metal nanocluster that, at first, is formed in the cryogenic matrix due to multiple ion impacts, and then is emitted as a result of the simultaneous effects of interface boiling and spring force. We also develop an analytical model describing this size-dependent cluster emission. The model bridges the atomistic simulations and experimental time and length scales, and allows increasing the controllability of fast generation of nanoclusters in experiments with a high production rate.