Isotopic Enrichment of Boron in the Sputtering of Boron Nitride with Xenon Ions

NASA Technical Reports Server (NTRS)

Ray, P. K.; Shutthanandan, V.

1998-01-01

An experimental study is described to measure the isotopic enrichment of boron. Xenon ions from 100 eV to 1.5 keV were used to sputter a boron nitride target. An ion gun was used to generate the ion beam. The ion current density at the target surface was approximately 30 microA/sq cm. Xenon ions impinged on the target surface at 50 deg angle to the surface normal. Since boron nitride is an insulator, a flood electron gun was used in our experiments to neutralize the positive charge buildup on the target surface. The sputtered secondary ions of boron were detected by a quadrupole mass spectrometer. The spectrometer entrance aperture was located perpendicular to the ion beam direction and 10 mm away from the target surface. The secondary ion flux was observed to be enriched in the heavy isotopes at lower ion energies. The proportion of heavy isotopes in the sputtered secondary ion flux was found to decrease with increasing primary ion energy from 100 to 350 eV. Beyond 350 eV, light isotopes were sputtered preferentially. The light isotope enrichment factor was observed to reach an asymptotic value of 1.27 at 1.5 keV. This trend is similar to that of the isotopic enrichment observed earlier when copper was sputtered with xenon ions in the same energy range.

Method of separating boron isotopes

DOEpatents

Jensen, R.J.; Thorne, J.M.; Cluff, C.L.

1981-01-23

A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)-dichloroborane as the feed material. The photolysis can readily by achieved with CO/sub 2/ laser radiation and using fluences significantly below those required to dissociate BCl/sub 3/.

Method of separating boron isotopes

DOEpatents

Jensen, Reed J.; Thorne, James M.; Cluff, Coran L.; Hayes, John K.

1984-01-01

A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)dichloroborane as the feed material. The photolysis can readily be achieved with CO.sub.2 laser radiation and using fluences significantly below those required to dissociate BCl.sub.3.

Theoretical isotopic fractionation between structural boron in carbonates and aqueous boric acid and borate ion

NASA Astrophysics Data System (ADS)

Balan, Etienne; Noireaux, Johanna; Mavromatis, Vasileios; Saldi, Giuseppe D.; Montouillout, Valérie; Blanchard, Marc; Pietrucci, Fabio; Gervais, Christel; Rustad, James R.; Schott, Jacques; Gaillardet, Jérôme

2018-02-01

The 11B/10B ratio in calcite and aragonite is an important proxy of oceanic water pH. However, the physico-chemical mechanisms underpinning this approach are still poorly known. In the present study, we theoretically determine the equilibrium isotopic fractionation properties of structural boron species in calcium carbonates, BO33-, BO2(OH)2- and B(OH)4- anions substituted for carbonate groups, as well as those of B(OH)4- and B(OH)3 species in vacuum. Significant variability of equilibrium isotopic fractionation properties is observed among these structural species which is related to their contrasted coordination state, Bsbnd O bond lengths and atomic-scale environment. The isotopic composition of structural boron does not only depend on its coordination number but also on its medium range environment, i.e. farther than its first coordination shell. The isotopic fractionation between aqueous species and their counterparts in vacuum are assessed using previous investigations based on similar quantum-mechanical modeling approaches. At 300 K, the equilibrium isotope composition of structural trigonal species is 7-15‰ lighter than that of aqueous boric acid molecules, whereas substituted tetrahedral borate ions are heavier than their aqueous counterparts by 10-13‰. Although significant uncertainties are known to affect the theoretical prediction of fractionation factors between solids and solutions, the usually assumed lack of isotopic fractionation during borate incorporation in carbonates is challenged by these theoretical results. The present theoretical equilibrium fractionation factors between structural boron and aqueous species differ from those inferred from experiments which may indicate that isotopic equilibrium, unlike chemical equilibrium, was not reached in most experiments. Further research into the isotopic fractionation processes at the interface between calcium carbonates and aqueous solution as well as long duration experiments aimed at investigating the kinetics of equilibration of boron environment and isotopic composition are therefore required to refine our understanding of boron coprecipitation in carbonates and thus the theory behind the use of boron isotopes as an ocean pH proxy.

Boron Dissolved and Particulate Atmospheric Inputs to a Forest Ecosystem (Northeastern France).

PubMed

Roux, Philippe; Turpault, Marie-Pierre; Kirchen, Gil; Redon, Paul-Olivier; Lemarchand, Damien

2017-12-19

Boron concentrations and isotopic compositions of atmospheric dust and dissolved depositions were monitored over a two-year period (2012-2013) in the forest ecosystem of Montiers (Northeastern France). This time series allows the determination of the boron atmospheric inputs to this forest ecosystem and contributes to refine our understanding of the sources and processes that control the boron atmospheric cycle. Mean annual dust and dissolved boron atmospheric depositions are comparable in size (13 g·ha -1 ·yr -1 and 16 g·ha -1 ·yr -1 , respectively), which however show significant intra- and interannual variations. Boron isotopes in dust differ from dissolved inputs, with an annual mean value of +1 ‰ and +18 ‰ for, respectively. The notable high boron contents (190-390 μg·g -1 ) of the dust samples are interpreted as resulting from localized spreading of boron-rich fertilizers, thus indicating a significant local impact of regional agricultural activities. Boron isotopes in dissolved depositions show a clear seasonal trend. The absence of correlation with marine cyclic solutes contradicts a control of atmospheric boron by dissolution of seasalts. Instead, the boron data from this study are consistent with a Rayleigh-like evolution of the atmospheric gaseous boron reservoir with possible but limited anthropogenic and/or biogenic contributions.

10 CFR 50.62 - Requirements for reduction of risk from anticipated transients without scram (ATWS) events for...

Code of Federal Regulations, 2010 CFR

2010-01-01

... into the reactor pressure vessel a borated water solution at such a flow rate, level of boron concentration and boron-10 isotope enrichment, and accounting for reactor pressure vessel volume, that the... minute of 13 weight percent sodium pentaborate decahydrate solution at the natural boron-10 isotope...

10 CFR 50.62 - Requirements for reduction of risk from anticipated transients without scram (ATWS) events for...

Code of Federal Regulations, 2012 CFR

2012-01-01

... into the reactor pressure vessel a borated water solution at such a flow rate, level of boron concentration and boron-10 isotope enrichment, and accounting for reactor pressure vessel volume, that the... minute of 13 weight percent sodium pentaborate decahydrate solution at the natural boron-10 isotope...

10 CFR 50.62 - Requirements for reduction of risk from anticipated transients without scram (ATWS) events for...

Code of Federal Regulations, 2011 CFR

2011-01-01

... into the reactor pressure vessel a borated water solution at such a flow rate, level of boron concentration and boron-10 isotope enrichment, and accounting for reactor pressure vessel volume, that the... minute of 13 weight percent sodium pentaborate decahydrate solution at the natural boron-10 isotope...

10 CFR 50.62 - Requirements for reduction of risk from anticipated transients without scram (ATWS) events for...

Code of Federal Regulations, 2013 CFR

2013-01-01

... into the reactor pressure vessel a borated water solution at such a flow rate, level of boron concentration and boron-10 isotope enrichment, and accounting for reactor pressure vessel volume, that the... minute of 13 weight percent sodium pentaborate decahydrate solution at the natural boron-10 isotope...

10 CFR 50.62 - Requirements for reduction of risk from anticipated transients without scram (ATWS) events for...

Code of Federal Regulations, 2014 CFR

2014-01-01

... into the reactor pressure vessel a borated water solution at such a flow rate, level of boron concentration and boron-10 isotope enrichment, and accounting for reactor pressure vessel volume, that the... minute of 13 weight percent sodium pentaborate decahydrate solution at the natural boron-10 isotope...

Boron isotopic composition of Porites corals over the past 500 years in the South China Sea: Evaluating the potential controlling factors

NASA Astrophysics Data System (ADS)

Wang, Tzu-Hao; You, Chen-Feng; Liu, Yi; Chung, Chuan-Hsiung; Liu, Hou-Chun

2016-04-01

As the largest marginal sea in the East Asia, the South China Sea is sensitive to the environmental changes both in Asia landmass and western Pacific Ocean. Thus, the cause-consequence feedback systems between the seawater chemistry and environmental change in the South China Sea encompass various interactions and controlling factors on different spatial and temporal scales. Global and regional (e.g., continental sources, and the East Asian monsoon system) factors may have a simultaneous impact on the coral records. However, the representative meanings of coral records in the South China Sea are still poorly understood. Here we present an age-controlled coral boron isotopic (δ11B) record in the Xisha Islands, the northern South China Sea, from AD 1466 to AD 1960. We applied micro-sublimation technique and MC-ICP-MS measurement to provide a low-blank and highly precise δ11B measurement. The δ11B values of the coral specimens varied from 20.8‰ to 26.0‰ which the variation is larger than the observation in the western Pacific Ocean within the same periods. The δ11B data showed a gradual increase during AD 1466-1829 and a relatively sharp decline then until AD 1960. The anthropogenic emission of CO2 may explain the decline of coral-inferred seawater pH over the past 200 years but not for the period of AD 1466-1829. An evaluated correlation was observed between the variation of coral δ11B values and the monsoon-associated upwelling phenomenon, which implies a significant influence of the Asian monsoon system on boron geochemistry in the northern SCS. This study will provide a comprehensive discussion regarding the potential factors controlling the boron isotopic composition in the northern South China Sea over the past 500 years.

Intra-Shell boron isotope ratios in benthic foraminifera: Implications for paleo-pH reconstructions

NASA Astrophysics Data System (ADS)

Rollion-Bard, C.; Erez, J.

2009-12-01

The boron isotope composition of marine carbonates is considered to be a seawater pH proxy. Nevertheless, the use of δ11B has some limitations: 1) the knowledge of fractionation factor (α4-3) between the two boron dissolved species (boric acid and borate ion), 2) the δ11B of seawater may have varied with time and 3) the amplitude of the "vital effects" of this proxy. Using secondary ion mass spectrometry (SIMS), we looked at the internal variability in the boron isotope ratio of the shallow water, symbionts bearing foraminiferan Amphistegina lobifera. Specimens were cultured at constant temperature (24±0.1 °C) in seawater with pH ranging between 7.90 and 8.45. We performed 6 to 8 measurements of δ11B in each foraminifera. Intra-shell boron isotopes show large variability with an upper threshold value of pH ~ 9. The ranges of the skeletal calculated pH values in different cultured foraminifera, show strong correlation with the culture pH values and may thus serve as proxy for pH in the past ocean.

Boron incorporation in the foraminifer Amphistegina lessonii under a decoupled carbonate chemistry

NASA Astrophysics Data System (ADS)

Kaczmarek, K.; Langer, G.; Nehrke, G.; Horn, I.; Misra, S.; Janse, M.; Bijma, J.

2014-12-01

A number of studies have shown that the boron isotopic composition (δ11B) and the B/Ca ratio of biogenic carbonates (mostly foraminifers) can serve as proxies for two parameters of the ocean's carbonate chemistry, rendering it possible to calculate the entire carbonate system. However, the B incorporation mechanism into marine carbonates is still not fully understood and analyses of field samples show species specific and hydrographic effects on the B proxies complicating their application. Identifying the carbonate system parameter influencing boron incorporation is difficult due to the co-variation of pH, CO32-, and B(OH)4-. To shed light on the question which parameter of the carbonate system is related to the boron incorporation, we performed culture experiments with the benthic symbiont-bearing foraminifer Amphistegina lessonii using a decoupled pH-CO32- chemistry. The determination of the boron isotopic composition and B/Ca ratios was performed simultaneously by means of a new in situ technique combining optical emission spectroscopy and laser ablation MC-ICP-MS. The boron isotopic composition in the tests gets heavier with increasing pH and B/Ca increases with increasing BOH4-/HCO3- of the culture media. The latter indicates that boron uptake of A. lessonii features a competition between B(OH)4- and HCO3-. Furthermore, the simultaneous determination of B/Ca and δ11B on single specimens allows for assessing the relative variability of these parameters. Among different treatments the B/Ca shows an increasing variability with increasing boron concentration in the test whereas the variability in the isotope distribution is constant.

Coprecipitation and isotopic fractionation of boron in modern biogenic carbonates

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

Vengosh, A.; Chivas, A.R.; McCulloch, M.T.

1991-10-01

The abundances and isotopic composition of boron in modern, biogenic calcareous skeletons from the Gulf of Elat, Israel, the Great Barrier Reef, Australia, and in deep-sea sediments have been examined by negative thermal-ionization mass spectrometry. The selected species (Foraminifera, Pteropoda, corals, Gastropoda, and Pelecypoda) yield large variations in boron concentration that range from 1 ppm in gastropod shells to 80 ppm in corals. The variations of {delta}{sup 11}B may be controlled by isotopic exchange of boron species in which {sup 10}B is preferentially partitioned into the tetrahedral species, and coprecipitation of different proportions of trigonal and tetrahedral species in themore » calcium carbonates. The B content and {delta}{sup 11}B values of deep-sea sediments, Foraminifera tests, and corals are used to estimate the global oceanic sink of elemental boron by calcium carbonate deposition. As a result of enrichment of B in corals, a substantially higher biogenic sink of 6.4 {plus minus} 0.9 {times} 10{sup 10} g/yr is calculated for carbonates. This is only slightly lower than the sink for desorbable B in marine sediments (10 {times} 10{sup 10} g/yr) and approximately half that of altered oceanic crust (14 {times} 10{sup 10} g/yr). Thus, carbonates are an important sink for B in the oceans being {approximately}20% of the total sinks. The preferential incorporation of {sup 10}B into calcium carbonate results in oceanic {sup 11}B-enrichment, estimated as 1.2 {plus minus} 0.3 {times} 10{sup 12} per mil {center dot} g/yr. The boron-isotope composition of authigenic, well-preserved carbonate skeletons may provide a useful tool to record secular boron-isotope variations in seawater at various times in the geological record.« less

Separation of the isotopes of boron by chemical exchange reactions

DOEpatents

McCandless, Frank P.; Herbst, Ronald S.

1995-01-01

The isotopes of boron, .sup.10 B and .sup.11 B, are separated by means of a gas-liquid chemical exchange reaction involving the isotopic equilibrium between gaseous BF.sub.3 and a liquid BF.sub.3 . donor molecular addition complex formed between BF.sub.3 gas and a donor chosen from the group consisting of: nitromethane, acetone, methyl isobutyl ketone, or diisobutyl ketone.

Matrix Effects on Boron Containing Materials due to Laser Ablation Molecular Isotopic Spectrometry (LAMIS)

NASA Astrophysics Data System (ADS)

Brown, Staci R.; Akpovo, Charlemagne A.; Martinez, Jorge; Ford, Alan; Herbert, Kenley; Johnson, Lewis

2014-03-01

Laser Induced Breakdown Spectroscopy (LIBS) is a spectroscopic technique that is used for the qualitative and quantitative analysis of materials in the liquid, solid, or gas phase. LIBS can also be used for the detection of isotopic shifts in atomic and diatomic species via Laser-Ablation Molecular Isotopic Spectroscopy (LAMIS). However, any additional elements that are entrained into the plasma other than the element of interest, can affect the extent of ablation and quality of spectra and hence, potentially obscure or aid in the relative abundance assessment for a given element. To address the importance of matrix effects, the isotopic analysis of boron obtained from boron oxide (BO) emission originating from different boron-containing compounds, such as boron nitride (BN), boric acid (H3BO3) , and borax (Na2B4O710H2O), via LIBS has been performed here. Each of these materials has different physical properties and elemental composition in order to illustrate possible challenges for the LAMIS method. A calibration-free model similar to that for the original LAMIS work is used to determine properties of the plasma as the matrix is changed. DTRA

Separation of the isotopes of boron by chemical exchange reactions

DOEpatents

McCandless, F.P.; Herbst, R.S.

1995-05-30

The isotopes of boron, {sup 10}B and {sup 11}B, are separated by means of a gas-liquid chemical exchange reaction involving the isotopic equilibrium between gaseous BF{sub 3} and a liquid BF{sub 3} donor molecular addition complex formed between BF{sub 3} gas and a donor chosen from the group consisting of: nitromethane, acetone, methyl isobutyl ketone, or diisobutyl ketone. 1 Fig.

Coprecipitation and isotopic fractionation of boron in modern biogenic carbonates

NASA Astrophysics Data System (ADS)

Vengosh, Avner; Kolodny, Yehoshua; Starinsky, Abraham; Chivas, Allan R.; McCulloch, Malcolm T.

1991-10-01

The abundances and isotopic composition of boron in modern, biogenic calcareous skeletons from the Gulf of Elat, Israel, the Great Barrier Reef, Australia, and in deep-sea sediments have been examined by negative thermal-ionization mass spectrometry. The selected species (Foraminifera, Pteropoda, corals, Gastropoda, and Pelecypoda) yield large variations in boron concentration that range from 1 ppm in gastropod shells to 80 ppm in corals. The boron content of the biogenic skeletons is independent of mineralogical composition and is probably related to biological (vital) effects. The δ11B values of the carbonates range from 14.2 to 32.2%. (relative to NBS SRM 951) and overlap with the δ11B values of modern deep-sea carbonate sediments ( δ11B = 8.9 to 26.2%.). The variations of δ11B may be controlled by isotopic exchange of boron species in which 10B is preferentially partitioned into the tetrahedral species, and coprecipitation of different proportions of trigonal and tetrahedral species in the calcium carbonates. Carbonates with low δ11B values (~ 15%.) may indicate preferential incorporation of tetrahedral species, whereas the higher δ11B values (~30%.) may indicate (1) uptake of both boron species assuming equilibrium with seawater (2) preferential incorporation of B(OH) 4- from in situ high-pH internal fluids of organisms that are isolated from seawater. The B content and δ11B values of deep-sea sediments, Foraminifera tests, and corals are used to estimate the global oceanic sink of elemental boron by calcium carbonate deposition. As a result of enrichment of B in corals, a substantially higher biogenic sink of 6.4 ± 0.9 × 10 10 g/yr is calculated for carbonates. This is only slightly lower than the sink for desorbable B in marine sediments (10 × 10 10 g/yr) and approximately half that of altered oceanic crust (14 × 10 10 g/yr). Thus, carbonates are an important sink for B in the oceans being ~20% of the total sinks. The preferential incorporation of 10B into calcium carbonate results in oceanic 11B-enrichment, estimated as 1.2 ± 0.3 × 10 12 per mil · g/yr. The boron-isotope composition of authigenic, well-preserved carbonate skeletons may provide a useful tool to record secular boron-isotope variations in seawater at various times in the geological record. The potential use of boron-isotope geochemistry in skeletons as a tracer for palaeoenvironments is demonstrated in Ostracoda and Foraminifera from the Gulf of Carpentaria, Australia. The δ11B values of glacial-age, buried skeletons (4.0 and 4.9%., respectively) are lower than that of their modern equivalents (17.6 and 13.3%., respectively). This may reflect a "terrestrial" boron-isotope signature of the water in the gulf during the Late Quaternary when it was isolated from the ocean.

Boron Isotopes in Diatoms: a Proxy for pH?

NASA Astrophysics Data System (ADS)

Donald, H.; Foster, G. L.; Poulton, A. J.; Moore, C. M.; Swann, G. E. A.; Hendry, K. R.

2016-12-01

High latitudes are important regions to consider in terms of ocean acidification, as they are climatically sensitive regions where the greenhouse gas CO2 is exchanged between the ocean and atmosphere. In theory, an improved understanding of these regions could be achieved using the boron isotope palaeo-pH proxy, in which CaCO3-based organisms including foraminifera are traditionally measured. The Southern Ocean is of particular interest in the global carbon cycle, however, foraminifera are scarce in sediments from this region. In contrast, siliceous diatoms are a dominant group of microfossils found within sediments, but as yet, the boron isotope-pH proxy has not been extended to opal. This is the major goal of the current study. Diatoms construct their frustules from biogenic silica by polymerising Si(OH)4, and boron content of these frustules, previously investigated by LA-ICP-MS (Mejía et al. 2013), is around 5-10 ppm. Here, current solution MC-ICP-MS methods used to measure boron isotopes in calcifying organisms have been adapted and developed for use with diatom opal. Preliminary results for sediment diatoms from the onset of major Northern Hemisphere glaciation will be presented (subarctic Northwest Pacific ODP site 882), as well as results for the cultured diatom species Thalassiosira weissflogii grown at varied pCO2. In light of these results, we will speculate on the nature of boron incorporation into diatom opal and its potential as an archive for palaeo-pH reconstructions.

Investigation of Isotopically Tailored Boron in Advanced Fission and Fusion Reactor Systems.

NASA Astrophysics Data System (ADS)

Domaszek, Gerald Raymond

This research examines the use of B^ {11}, in the form of metallic boron and boron carbide, as a moderating and reflecting material. An examination of the neutronic characteristics of the B ^{11} isotope of boron has revealed that B^{11} has neutron scattering and absorption cross sections favorably comparable to those of Be^9 and C^ {12}. Preliminary analysis of the neutronics of B ^{11} were performed by conducting one dimensional transport calculations on an infinite slab of varying thickness. Beryllium is the best of the three materials in reflecting neutrons due primarily to the contribution from (n,2n) reactions. Tailored neutron energy beam transmission experiments were carried out to experimentally verify the predicted neutronic characteristics of B^{11 }. To further examine the neutron moderating and reflecting characteristics of B^{11 }, the energy dependent neutron flux was measured as a function of position in an exponential pile constructed of B_4C isotopically enriched to 98.5 percent B^{11}. After the experimental verification of the neutronic behavior of B^{11}, further design studies were conducted using metallic boron and boron carbide enriched in the B^{11 } isotope. The use of materials isotopically enriched in B^{11} as a liner in the first wall/blanket of a magnetic confinement fusion reactor demonstrated acceptable tritium regeneration in the lithium blanket. Analysis of the effect of contaminant levels of B^{10} showed that B^{10} contents of less than 1 percent in metallic boron produced negligible adverse effects on the tritium breeding. A comparison of the effectiveness of graphite and B^{11}_4C when used as moderators in a reactor fueled with natural uranium has shown that the maximum k_infty for a given fuel rod design is approximately the same for both materials. Approximately half the volume of the moderator is required when B^{11 }_4C is substituted for graphite to obtain essentially the same K_infty . An analysis of the effectiveness of various materials as reflector control elements for a compact space reactor has shown that B^{11} is neutronically superior to graphite in these applications. Metallic boron and boron carbide isotopically enriched in B^{11} have been demonstrated to be neutronically acceptable for varied applications in advanced reactor systems. B^ {11} has been shown to be superior in performance to graphite. While only somewhat inferior to beryllium as neutron multipliers, B^ {11} and B^{11} _4C have safety, supply and cost advantage over beryllium. (Abstract shortened with permission of author.).

Recycling of subducted crustal components into carbonatite melts revealed by boron isotopes

NASA Astrophysics Data System (ADS)

Hulett, Samuel R. W.; Simonetti, Antonio; Rasbury, E. Troy; Hemming, N. Gary

2016-12-01

The global boron geochemical cycle is closely linked to recycling of geologic material via subduction processes that have occurred over billions of years of Earth’s history. The origin of carbonatites, unique melts derived from carbon-rich and carbonate-rich regions of the upper mantle, has been linked to a variety of mantle-related processes, including subduction and plume-lithosphere interaction. Here we present boron isotope (δ11B) compositions for carbonatites from locations worldwide that span a wide range of emplacement ages (between ~40 and ~2,600 Ma). Hence, they provide insight into the temporal evolution of their mantle sources for ~2.6 billion years of Earth’s history. Boron isotope values are highly variable and range between -8.6‰ and +5.5‰, with all of the young (<300 Ma) carbonatites characterized by more positive δ11B values (>-4.0‰), whereas most of the older carbonatite samples record lower B isotope values. Given the δ11B value for asthenospheric mantle of -7 +/- 1‰, the B isotope compositions for young carbonatites require the involvement of an enriched (crustal) component. Recycled crustal components may be sampled by carbonatite melts associated with mantle plume activity coincident with major tectonic events, and linked to past episodes of significant subduction associated with supercontinent formation.

Raman Scattering by Crystals of Rare-Earth Hexaborides with Different Isotopes of Boron

NASA Astrophysics Data System (ADS)

Markov, Yu. F.; Gurin, V. N.; Ponkratov, K. V.

2018-04-01

Monocrystals of lanthanum hexaboride LaB6 containing both natural boron and its isotopes 10B and 11B have been produced using the solution-melt method. Polyelement hexaboride rare-earths have been grown and the corresponding ceramics have been synthesized for the first time. All these crystals have been studied by means of various techniques, generally using Raman scattering. The Raman spectra attributed to various spectral lines corresponding to nonanalyzable representations have been obtained and interpreted. Frequencies and half-widths of spectral lines have been obtained, the removal of degeneracy and the development of respective splitting of degenerate oscillations induced by defects, mainly by boron isotope inclusions, have been identified. The influence of defects on the Raman spectra has been determined.

Boron content and sources in Tertiary aquifers in the Sultanate of Oman

NASA Astrophysics Data System (ADS)

Moraetis, Daniel; Lamki, Mohamed Al; Muhammad, Dawood; Yaroubi, Saif; Batashi, Hamad Al; Pracejus, Bernhard

2017-04-01

The boron (B) content of relatively shallow groundwaters in arid areas is high due to extreme evaporation which precipitates several salts with subsequent boron accumulation originating from rocks dissolution and/or rainwater. In deeper aquifers, where there is no groundwater-surface connection, other sources of boron may affect the water quality. The present study investigates the boron origin observed in 197 wells completed within the units of Umm Er Radhuma (UeR), Rus, Dammam and Fars (from older to younger geological units) which all belong to the Tertiary units of the interior of Oman. The acquired chemical data include major ions (cations and anions), Rare Earth Elements (REE) along with B isotopes (10 and 11) and Sr isotopes (86 and 87). In addition, leaching tests were performed in selected samples to validate the release of B in distilled water. The water samples were grouped based on B concentration of less than 5 mg/l, 5 to 15 mg/l and extreme values of higher than 15 mg/l. The Fars and UeR groundwater samples showed the most extreme boron content (higher than 15 mg/l) yet the former is the shallower and younger unit and the latter is the deeper and older unit. The Fars water of high boron content (higher than 15 mg/l) shows very high content of magnesium and calcium as well as low concentration of Sr. Furthermore, the magnesium and calcium are also high in UeR, while Sr concentration is much higher in UeR compared to Fars. The UeR water with extreme boron content appears in the field of diagenetic water in a diagram of δ11BNIST951 [‰] versus 1/B, along with Sr isotopes ratio and europium (Eu) positive anomaly, while Fars waters appear in a mixing zone of marine water with infiltrated rainwater. The regression analysis of sodium and chloride showed that concentrations of boron up to 10 mg/l can be correlated to halite dissolution in infiltrated rainwater in all units. The laboratory leaching tests verified the rocks capability to release boron up to 7 mg/l with a low water/solid ratio (low porosity rocks). Thus, the lowest boron content (up to 5 mg/l) is correlated to the dissolution of minerals within the Tertiary units. Whilst the samples containing 5 to 15 mg/l of B could correspond to lower water to solid ratio aquifer and/or mixing of low and high boron waters (rainwater and diagenetic or marine water). Finally, B isotopes along the REE analysis are considered as better indices of groundwater origin compared to Sr isotopes ratio especially in the case of diagenetic water identification.

Boron isotope systematics of tourmaline formation in the Sullivan Pb-Zn-Ag deposit, British Columbia, Canada

USGS Publications Warehouse

Jiang, S.-Y.; Palmer, M.R.; Slack, J.F.; Shaw, D.R.

1999-01-01

We report here the results of 54 boron isotope analyses of tourmaline associated with the giant Sullivan Pb-Zn-Ag deposit in southeastern British Columbia, Canada. The ??11B values range from -11.1 to -2.9???, which is almost as great as the range found worldwide in tourmalines from 33 massive sulfide deposits and tourmalinites in dominantly clastic metasedimentary terranes. The major control on the overall ??11B values of the Sullivan tourmalinites is the boron source. Potential controls over the large range of the data also include: (1) differences in formation temperatures of the tourmalinites, (2) different stages of tourmaline formation, (3) variations in the proportions of dissolved boron incorporated into the tourmaline (Rayleigh fractionation), (4) seawater entrainment, and (5) post-depositional metamorphism. The boron isotope data at Sullivan are consistent with boron derivation from leaching of footwall clastic sediments. However, the great abundance of tourmaline in the Sullivan deposit suggests that the local clastic sediments were not the sole source of boron, and we argue that non-marine evaporites, buried deep below the orebody, are the most viable source of this additional boron. It is likely that some of the variation in tourmaline ??11B values reflect mixing of boron from these two sources. Comparison of the potential effects of these controls with geologic and other geochemical evidence suggests that major causes for the wide range of ??11B values measured at Sullivan are seawater entrainment and Rayleigh fractionation, although in places, post-depositional alteration and thermal metamorphism were important in determining ??11B values of some of the recrystallized tourmalinites.

Boron isotope fractionation in magma via crustal carbonate dissolution

PubMed Central

Deegan, Frances M.; Troll, Valentin R.; Whitehouse, Martin J.; Jolis, Ester M.; Freda, Carmela

2016-01-01

Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ11B values down to −41.5‰, reflecting preferential partitioning of 10B into the assimilating melt. Loss of 11B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports 11B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ11B melt values in arc magmas could flag shallow-level additions to the subduction cycle. PMID:27488228

Boron isotope fractionation in magma via crustal carbonate dissolution

NASA Astrophysics Data System (ADS)

Deegan, Frances M.; Troll, Valentin R.; Whitehouse, Martin J.; Jolis, Ester M.; Freda, Carmela

2016-08-01

Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ11B values down to -41.5‰, reflecting preferential partitioning of 10B into the assimilating melt. Loss of 11B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports 11B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ11B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

Boron isotope fractionation in magma via crustal carbonate dissolution.

PubMed

Deegan, Frances M; Troll, Valentin R; Whitehouse, Martin J; Jolis, Ester M; Freda, Carmela

2016-08-04

Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ(11)B values down to -41.5‰, reflecting preferential partitioning of (10)B into the assimilating melt. Loss of (11)B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports (11)B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ(11)B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

Low-Energy Sputtering Studies of Boron Nitride with Xenon Ions

NASA Technical Reports Server (NTRS)

Ray, P. K.; Shutthanandan, V.

1999-01-01

Sputtering of boron nitride with xenon ions was investigated using secondary ion (SIMS) and secondary neutral (SNMS) mass spectrometry. The ions generated from the ion gun were incident on the target at an angle of 50' with respect to the surface'normal. The energy of ions ranged from 100 eV to 3 keV. A flood electron gun was used to neutralize the positive charge build-up on the target surface. The intensities of sputtered neutral and charged particles, including single atoms, molecules, and clusters, were measured as a function of ion energy. Positive SIMS spectra were dominated by the two boron isotopes whereas BN- and B- were the two major constituents of the negative SIMS spectra. Nitrogen could be detected only in the SNMS spectra. The intensity-energy curves of the sputtered particles were similar in shape. The knees in P-SIMS and SNMS intensity-energy curves appear at around I keV which is significantly higher that 100 to 200 eV energy range at which knees appear in the sputtering of medium and heavy elements by ions of argon and xenon. This difference in the position of the sputter yield knee between boron nitride and heavier targets is due to the reduced ion energy differences. The isotopic composition of secondary ions of boron were measured by bombarding boron nitride with xenon ions at energies ranging from 100 eV to 1.5 keV using a quadrupole mass spectrometer. An ion gun was used to generate the ion beam. A flood electron gun was used to neutralize the positive charge buildup on the target surface. The secondary ion flux was found to be enriched in heavy isotopes at lower incident ion energies. The heavy isotope enrichment was observed to decrease with increasing primary ion energy. Beyond 350 eV, light isotopes were sputtered preferentially with the enrichment increasing to an asymptotic value of 1.27 at 1.5 keV. The trend is similar to that of the isotopic enrichment observed earlier when copper was sputtered with xenon ions in the same energy range.

Deglacial Western Equatorial Pacific pCO2 Reconstruction Using Boron Isotopes of Planktonic Foraminiferas

NASA Astrophysics Data System (ADS)

Kubota, K.; Yokoyama, Y.; Ishikawa, T.; Sagawa, T.; Ikehara, M.; Yamazaki, T.

2017-12-01

During the last deglaciation (ca. 19 - 11 ka), partial pressure of CO2 (pCO2) of the atmosphere increased by 80 μatm. Many paleoceanographers point out that the ocean had played an important role in atmospheric CO2 rise, since the ocean have 60 times larger capacity to store carbon compared to the atmosphere. However, evidence on where carbon was transferred from the ocean to the atmosphere is still lacking, hampering our understanding of global carbon cycles in glacial-interglacial timescales. Boron isotope of skeletons of marine calcifying organisms such as corals and foraminiferas can pin down where CO2 source/sink existed, because boron isotopes of marine calcium carbonates is dependent on seawater pH, from which pCO2 of the past seawater can be reconstructed. In previous studies using the boron isotope teqnique, Martinez-Boti et al. (2015, Nature) and Kubota et al. (2014, Scientific Reports) revealed that central and eastern parts of the equatorial Pacific acted as a CO2 source (i.e., CO2 emission) during the last deglaciation, suggesting the equatorial Pacific's contribution to atmospheric CO2 rise. However, some conflicting results have been confirmed in a marine sediment record from the western part of the equatorial Pacific (Palmer & Pearson, 2003, Science), making the conclusion elusive. In this presentation, we will show new results of Mg/Ca, oxygen isotope, and boron isotope measurements during the last 35 ka on two species of surface dwelling foraminiferas (Globigerinoides ruber and G. sacculifer) which was hand-picked separatedly from a well-dated marine sediment core recovered from the West Caroline Basin (KR05-15 PC01) (Yamazaki et al., 2008, GRL). From the new records, we will discuss how the equatorial Pacific behaved during the last deglaciation and how it related to the global carbon cycles.

New Isotopic Tracers for Shale Gas and Hydraulic Fracturing Fluids

EPA Pesticide Factsheets

The combined application of geochemistry, stable isotopes (δ18O, δ2H), strontium isotopes (87Sr/86Sr), boron isotopes (δ11B), and radium isotopes (228Ra/226Ra) provides a unique methodology for tracing and monitoring shale gas and fracking fluids in the environment.

Boron incorporation in the foraminifer Amphistegina lessonii under a decoupled carbonate chemistry

NASA Astrophysics Data System (ADS)

Kaczmarek, K.; Langer, G.; Nehrke, G.; Horn, I.; Misra, S.; Janse, M.; Bijma, J.

2015-03-01

A number of studies have shown that the boron isotopic composition (δ11B) and the B / Ca ratio of biogenic carbonates (mostly foraminifers) can serve as proxies for two parameters of the ocean's carbonate chemistry, rendering it possible to calculate the entire carbonate system. However, the B incorporation mechanism into marine carbonates is still not fully understood and analyses of field samples show species-specific and hydrographic effects on the B proxies complicating their application. Identifying the carbonate system parameter influencing boron incorporation is difficult due to the co-variation of pH, CO32- and B(OH)4-. To shed light on the question which parameter of the carbonate system is related to the boron incorporation, we performed culture experiments with the benthic symbiont-bearing foraminifer Amphistegina lessonii using a decoupled pH-CO32- chemistry. The determination of the δ11B and B / Ca ratios was performed simultaneously by means of a new in situ technique combining optical emission spectroscopy and laser ablation MC-ICP-MS. The boron isotopic composition in the tests gets heavier with increasing pH and B / Ca increases with increasing B(OH)4- / HCO3- of the culture media. The latter indicates that boron uptake of A. lessonii features a competition between B(OH)4- and HCO3-. Furthermore, the simultaneous determination of B / Ca and δ11B on single specimens allows for assessing the relative variability of these parameters. Among different treatments the B / Ca shows an increasing variability with increasing boron concentration in the test whereas the variability in the isotope distribution is constant.

Optical phonon modes in rhombohedral boron monosulfide under high pressure

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

Cherednichenko, Kirill A.; IMPMC, UPMC Sorbonne Universités, CNRS UMR 7590, 75005 Paris; LSPM–CNRS, Université Paris Nord, 93430 Villetaneuse

2015-05-14

Raman spectra of rhombohedral boron monosulfide (r-BS) were measured under pressures up to 34 GPa at room temperature. No pressure-induced structural phase transition was observed, while strong pressure shift of Raman bands towards higher wavenumbers has been revealed. IR spectroscopy as a complementary technique has been used in order to completely describe the phonon modes of r-BS. All experimentally observed bands have been compared with theoretically calculated ones and modes assignment has been performed. r-BS enriched by {sup 10}B isotope was synthesized, and the effect of boron isotopic substitution on Raman spectra was observed and analyzed.

The shocking development of lithium (and boron) in supernovae

NASA Technical Reports Server (NTRS)

Dearborn, David S. P.; Schramm, David N.; Steigman, Gary; Truran, James

1989-01-01

It is shown that significant amounts of Li-7 and B-11 are produced in Type 2 supernovae. The synthesis of these rare elements occurs as the supernova shock traverses the base of the hydrogen envelope burning He-3 to masses 7 and 11 via alpha capture. The yields in this process are sufficient to account for the difference in lithium abundance observed between Pop 2 and Pop 1 stars. Since lithium (and boron) would, in this manner, be created in the same stars that produce the bulk of the heavy elements, the lithium abundance even in old Pop 1 stars would be high (as observed). The B-11 production may remedy the long-standing problem of the traditional spallation scenario to account for the observed isotopic ratio of boron. Observational consequences of this mechanism are discussed, including the evolution of lithium and boron isotope ratios in the Galaxy and the possible use of the boron yields to constrain the number of blue progenitor Type 2 supernovae.

Precision and Accuracy of Analysis for Boron in ITP Samples

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

Tovo, L.L.

'Inductively Coupled Plasma Emission Spectroscopy (ICPES) has been used by the Analytical Development Section (ADS) to measure boron in catalytic tetraphenylboron decomposition studies performed by the Waste Processing Technology (WPT) section. Analysis of these samples is complicated due to the presence of high concentrations of sodium and organic compounds. Previously, we found signal suppression in samples analyzed "as received". We suspected that the suppression was due to the high organic concentration (up to 0.01 molar organic decomposition products) in the samples. When the samples were acid digested prior to analysis, the suppression was eliminated. The precision of the reported boronmore » concentration was estimated as 10 percent based on the known precision of the inorganic boron standard used for calibration and quality control check of the ICPES analysis. However, a precision better than 10 percent was needed to evaluate ITP process operating parameters. Therefore, the purpose of this work was (1) to measure, instead of estimating, the precision of the boron measurement on ITP samples and (2) to determine the optimum precision attainable with current instrumentation.'« less

Capillary electrophoresis-electrospray mass spectrometry and HR-ICP-MS for the detection and quantification of 10B-boronophenylalanine (10B-BPA) used in boron neutron capture therapy.

PubMed

Pitois, Aurélien; de las Heras, Laura Aldave; Zampolli, Antonella; Menichetti, Luca; Carlos, Ramon; Lazzerini, Guido; Cionini, Luca; Salvatori, Pietro Alberto; Betti, Maria

2006-02-01

Boron neutron capture therapy (BNCT) is a bimodal radiotherapeutic treatment based on the irradiation of neoplastic tissues with neutrons after the tissues have selectively accumulated molecules loaded with nuclides with large neutron capture cross-sections (such boron-10). Boron-10 carriers have been tested to a limited extent, and clinical trials have been conducted on sulfhydryl borane (10B-BSH) and boronophenylalanine (10B-BPA). However, precise and accurate measurements of boron-10 concentrations (0.1-100 microg/g) in specimens and samples of limited size (microg scale) are needed in order to be able to biologically characterise new compounds in predictive tissue dosimetry, toxicology and pharmacology studies as well as in clinical investigations. A new approach based on fast separation and detection of 10B-BPA performed by coupling capillary electrophoresis to electrospray mass spectrometry is reported. This method allows the quantitative analysis and characterisation of 10B-BPA in a short time with a high separation efficiency. Detection limits of 3 microM for 10B-BPA and 30 ng/mL for 10B were obtained with CE-ESI-MS. A quantification limit of 10 microM for 10B-BPA (100 ng/mL for 10B) was attained. The total boron-10 concentration was determined by high-resolution inductively coupled mass spectrometry in order to validate the method. Boron-10 isotope measurements were carried out by HR-ICP-MS at medium resolution (R=4000) due to the presence of an isobaric interference at mass 10. Good agreement was obtained between the values from CE-ESI-MS and those from HR-ICP-MS. The method has been successfully used to determine the 10B-BPA in two lines of cultured cells.

From bulk soil to intracrystalline investigation of plant-mineral interaction

NASA Astrophysics Data System (ADS)

Lemarchand, D.; Voinot, A.; Chabaux, F.; Turpault, M.

2011-12-01

Understanding the controls and feedbacks regulating the flux of matter between bio-geochemical reservoirs in forest ecosystems receives a fast growing interest for the last decades. A complex question is to understand how minerals and vegetation interact in soils to sustain life and, to a broader scope, how forest ecosystems may respond to human activity (acid rain, harvesting,...) and climate perturbations (temperature, precipitation,...). Many mineralogical and biogeochemical approaches have longtime been developed, and occasionally coupled, in order to investigate the mechanisms by which chemical elements either are exchanged between soil particles and solutions, or are transferred to plants or to deeper soil layers and finally leave the system. But the characterization of particular processes like the contribution of minor reactive minerals to plant nutrition and global fluxes or the mechanisms by which biology can modify reaction rates and balance the bioavailability of nutrients in response to environmental perturbation sometimes fails because of the lack of suitable tracers. Recent analytical and conceptual advances have opened new perspectives for the use of light "non traditional" stable isotopes. Showing a wild range of concentrations and isotopic compositions between biogeochemical reservoirs in forest ecosystem, boron has physico-chemical properties particularly relevant to the investigation of water/rock interactions even when evolving biologically-mediated reactions. In this study, we focused on the distribution of boron isotopes from intracrystalline to bulk soil scales. An overview of the boron distribution and annual fluxes in the soil-plant system clearly indicates that the vegetation cycling largely controls the mobility of boron. We also observe that the mineral and biological B pools have drastically different isotopic signature that makes the transfer of B between them very easy to follow. In particular, the podzol soil we analyzed shows a clear contribution of vegetation-recycled B to neoformed mineral phases, whereas B in minerals from the brown acidic soil rather indicates predominant mineral dissolution with little or even no B supply from the soil solution. If B isotopes thus proved their sensitivity to the soil forming conditions, a simple isotopic budget also demonstrates that the isotopic signature shown by the vegetation cannot result from fractionation during boron absorption. Analyses of B isotopes within intracrystalline phyllosilicate minerals further identify the interfoliar layers as the major source of B during plant nutrition. Additionally, weathering experiments placing phyllosilicates in contact with various alteration agents (protons, organic acid or siderophore) point to the role of the latters as likely responsible for the boron liberation from the phyllosilicate interfoliar layers. This scenario gives the phyllosilicate interfoliar layers a central function in the plant nutrition in context studied here of soils developed on granitic bedrocks. It also implies a very dynamic system in which plants and minerals can exchange matter over very short periods of time.

Basic features of boron isotope separation by SILARC method in the two-step iterative static model

NASA Astrophysics Data System (ADS)

Lyakhov, K. A.; Lee, H. J.

2013-05-01

In this paper we develop a new static model for boron isotope separation by the laser assisted retardation of condensation method (SILARC) on the basis of model proposed by Jeff Eerkens. Our model is thought to be adequate to so-called two-step iterative scheme for isotope separation. This rather simple model helps to understand combined action on boron separation by SILARC method of all important parameters and relations between them. These parameters include carrier gas, molar fraction of BCl3 molecules in carrier gas, laser pulse intensity, gas pulse duration, gas pressure and temperature in reservoir and irradiation cells, optimal irradiation cell and skimmer chamber volumes, and optimal nozzle throughput. A method for finding optimal values of these parameters based on some objective function global minimum search was suggested. It turns out that minimum of this objective function is directly related to the minimum of total energy consumed, and total setup volume. Relations between nozzle throat area, IC volume, laser intensity, number of nozzles, number of vacuum pumps, and required isotope production rate were derived. Two types of industrial scale irradiation cells are compared. The first one has one large throughput slit nozzle, while the second one has numerous small nozzles arranged in parallel arrays for better overlap with laser beam. It is shown that the last one outperforms the former one significantly. It is argued that NO2 is the best carrier gas for boron isotope separation from the point of view of energy efficiency and Ar from the point of view of setup compactness.

Thermal conduction mechanisms in isotope-disordered boron nitride and carbon nanotubes

NASA Astrophysics Data System (ADS)

Savic, Ivana; Mingo, Natalio; Stewart, Derek

2009-03-01

We present first principles studies which determine dominant effects limiting the heat conduction in isotope-disordered boron nitride and carbon nanotubes [1]. Using an ab initio atomistic Green's function approach, we demonstrate that localization cannot be observed in the thermal conductivity measurements [1], and that diffusive scattering is the dominant mechanism which reduces the thermal conductivity [2]. We also give concrete predictions of the magnitude of the isotope effect on the thermal conductivities of carbon and boron nitride single-walled nanotubes [2]. We furthermore show that intershell scattering is not the main limiting mechanism for the heat flow through multi-walled boron nitride nanotubes [1], and that heat conduction restricted to a few shells leads to the low thermal conductivities experimentally measured [1]. We consequently successfully compare the results of our calculations [3] with the experimental measurements [1]. [1] C. W. Chang, A. M. Fennimore, A. Afanasiev, D. Okawa, T. Ikuno, H. Garcia, D. Li, A. Majumdar, A. Zettl, Phys. Rev. Lett. 2006, 97, 085901. [2] I. Savic, N. Mingo, D. A. Stewart, Phys. Rev. Lett. 2008, 101, 165502. [3] I. Savic, D. A. Stewart, N. Mingo, to be published.

Crystallographic control on the boron isotope paleo-pH proxy

NASA Astrophysics Data System (ADS)

Noireaux, J.; Mavromatis, V.; Gaillardet, J.; Schott, J.; Montouillout, V.; Louvat, P.; Rollion-Bard, C.; Neuville, D. R.

2015-11-01

When using the boron isotopic composition (δ11B) of marine carbonates as a seawater pH proxy, it is assumed that only the tetrahedral borate ion is incorporated into the growing carbonate crystals and that no boron isotope fractionation occurs during uptake. However, the δ11B of the calcium carbonate from most modern foraminifera shells or corals skeletons is not the same as the δ11B of seawater borate, which depends on pH, an observation commonly attributed to vital effects. In this study, we combined previously published high-field 11B MAS NMR and new δ11B measurements on the same synthetic calcite and aragonite samples precipitated inorganically under controlled environments to avoid vital effects. Our results indicate that the main controlling factors of δ11B are the solution pH and the mineralogy of the precipitated carbonate mineral, whereas the aqueous boron concentration of the solution, CaCO3 precipitation rate and the presence or absence of growth seeds all appear to have negligible influence. In aragonite, the NMR data show that boron coordination is tetrahedral (BO4), in addition, its δ11B is equal to that of aqueous borate, thus confirming the paleo-pH hypothesis. In contrast, both trigonal BO3 and tetrahedral BO4 are present in calcite, and its δ11B values are higher than that of aqueous borate and are less sensitive to solution pH variations compared to δ11B in aragonite. These observations are interpreted in calcite as a reflection of the incorporation of decreasing amounts of boric acid with increasing pH. Moreover, the fraction of BO3 measured by NMR in calcite is higher than that inferred from δ11B which indicates a coordination change from BO4 to BO3 upon boron incorporation in the solid. Overall, this study shows that although the observed differences in δ11B between inorganic and biological aragonite are compatible with a pH increase at calcification sites, the B speciation and isotope composition of biological calcites call for a more complex mechanism of boron incorporation.

Boron isotopic constraints on the source of Hawaiian shield lavas

NASA Astrophysics Data System (ADS)

Tanaka, Ryoji; Nakamura, Eizo

2005-07-01

Boron isotopic compositions of lavas from three representative Hawaiian shield volcanoes (Kilauea, Mauna Loa, and Koolau) were analyzed by thermal ionization mass spectrometry. The boron isotopic composition of each sample was analyzed twice, once with and once without acid leaching to evaluate the effect of posteruptive boron contamination. Our acid-leaching procedure dissolved glass, olivine, secondary zeolite, and adsorbed boron; this dissolved boron was completely removed from the residue, which was comprised of plagioclase, pyroxenes, and newly formed amorphous silica. We confirmed that an appropriate acid-leaching process can eliminate adsorbed and incorporated boron contamination from all submarine samples without modifying the original 11B/ 10B ratio. On the other hand, when the sample was weathered, i.e., the olivine had an iddingsite rim, 11B/ 10B of the acid-resistant minerals are also modified, thus it is impossible to get the preeruptive 11B/ 10B value from the weathered samples. Through this elimination and evaluation procedure of posteruptive contamination, preeruptive δ 11B values for the shield lavas are -4.5 to -5.4‰ for Koolau ( N = 8), -3.6 to -4.6‰ for Kilauea ( N = 11), and -3.0 to -3.8‰ for Mauna Loa ( N = 6). Historical Kilauea lavas show a systematic temporal trend for B content and Nb/B coupled with other radiogenic isotopic ratios and trace element ratios, at constant δ 11B, indicating little or no assimilation of crustal materials in these lavas. Uncorrelated B content and δ 11B in Koolau and Mauna Loa lavas may also indicate little or no effect of crustal assimilation in these lavas. The source of KEA-component (identical to the so-called Kea end member in Hawaiian lavas) of the Hawaiian source mantle, represented by Kilauea, should be derived from lower part of subducted oceanic crust or refractory peridotite in the recycled subducted slab. The systematic trend from Kilauea to Koolau—decreasing δ 11B coupled with decreasing ɛNd as well as increasing 87Sr/ 86Sr and 206Pb/ 204Pb—is consistent with involvement of subducted sediment components in the EMK(enriched Makapuu)-component, represented by Makapuu-stage of Koolau lavas.

Electron paramagnetic resonance of deep boron in silicon carbide

NASA Astrophysics Data System (ADS)

Baranov, P. G.; Mokhov, E. N.

1996-04-01

In this article we report the first EPR observation of deep boron centres in silicon carbide. A direct identification of the boron atom involved in the defect centre, considered as deep boron, has been established by the presence of a hyperfine interaction with 0268-1242/11/4/005/img1 and 0268-1242/11/4/005/img2 nuclei in isotope-enriched 6H-SiC:B crystals. Deep boron centres were shown from EPR spectra to have axial symmetry along the hexagonal axis. A correspondence between the EPR spectra and the luminescence, ODMR and DLTS spectra of deep boron centres has been indicated. The structural model for a deep boron centre as a boron - vacancy pair is presented and the evidence for bistable behaviour of deep boron centres is discussed.

Experimental Evaluation of pH and Temperature Effects on the Adsorption of Boron onto Clay Minerals

NASA Astrophysics Data System (ADS)

Hoenisch, B.; Marone, D.; Ruprecht, J.

2017-12-01

Modeling the secular evolution of the concentration [B] and isotopic composition (δ11B) of boron in seawater is hampered by limited constraints on the relative sources (i.e. riverine input of weathering products, hydrothermal convection at mid-ocean ridges and fluids expelled from accretionary prisms) and sinks (i.e. alteration of the oceanic crust, adsorption onto clays, and co-precipitation in carbonates) of boron to and from the ocean. Clays remove approximately 28% of total boron from the ocean and quantification of this sink thus represents a major factor for reconstructing the secular evolution of seawater [B] and δ11B over the Cenozoic. However, the relative strength of the clay sink could have been much smaller in the early Cenozoic compared to today, because borate ion as the charged species is preferentially adsorbed onto detrital clays over boric acid, and because the relative abundance of borate in seawater should have been lower under the more acidic conditions of the early Cenozoic. In addition, different clay minerals tend to fractionate boron isotopes differentially, and the relative composition of clay minerals has varied in the past with the dominant climate and weathering patterns on the continents. We have conducted a range of pH (7.5-8.4) and temperature (3-32°C) experiments with four clay minerals (Kaolinite, Illite, Montmorillonite and Chlorite), to build on previously published but limited experimental data. Similar to a previous study and as expected based on the relative abundance of borate ion in seawater, boron adsorption onto these clays increases at higher pH and lower temperatures, but whereas Montmorillonite and Illite absorb similar quantities of boron, Kaolinite is most and Chlorite least efficient in this process. We are now in the process of characterizing the boron isotope fractionation associated with these adsorption experiments.

Evaluation of Ground-Water and Boron Sources by Use of Boron Stable-Isotope Ratios, Tritium, and Selected Water-Chemistry Constituents near Beverly Shores, Northwestern Indiana, 2004

USGS Publications Warehouse

Buszka, Paul M.; Fitzpatrick, John A.; Watson, Lee R.; Kay, Robert T.

2007-01-01

Concentrations of boron greater than the U.S. Environmental Protection Agency (USEPA) 900 ?g/L removal action level (RAL) standard were detected in water sampled by the USEPA in 2004 from three domestic wells near Beverly Shores, Indiana. The RAL regulates only human-affected concentrations of a constituent. A lack of well logs and screened depth information precluded identification of whether water from sampled wells, and their boron sources, were from human-affected or natural sources in the surficial aquifer, or associated with a previously defined natural, confined aquifer source of boron from the subtill or basal sand aquifers. A geochemically-based classification of the source of boron in ground water could potentially determine the similarity of boron to known sources or mixtures between known sources, or classify whether the relative age of the ground water predated the potential sources of contamination. The U.S. Geological Survey (USGS), in cooperation with the USEPA, investigated the use of a geochemical method that applied boron stable isotopes, and concentrations of boron, tritium, and other constituents to distinguish between natural and human-affected sources of boron in ground water and thereby determine if the RAL was applicable to the situation. Boron stable-isotope ratios and concentrations of boron in 17 ground-water samples and tritium concentrations in 9 ground-water samples collected in 2004 were used to identify geochemical differences between potential sources of boron in ground water near Beverly Shores, Indiana. Boron and d11B analyses for this investigation were made on unacidified samples to assure consistency of the result with unacidified analyses of d11B values from other investigations. Potential sources of boron included surficial-aquifer water affected by coal-combustion products (CCP) or domestic-wastewater, upward discharge of ground water from confined aquifers, and unaffected water from the surficial aquifer that was distant from human-affected boron sources. Boron concentrations in potential ground-water sources of boron were largest (15,700 to 24,400 ?g/L) in samples of CCP-affected surficial aquifer water from four wells at a CCP landfill and smallest (27 to 63 ?g/L) in three wells in the surficial aquifer that were distant from human-affected boron sources. Boron concentrations in water from the basal sand aquifer ranged from 656 ?g/L to 1,800 ?g/L. Boron concentrations in water from three domestic-wastewater-affected surficial aquifer wells ranged from 84 to 387 ?g/L. Among the representative ground-water samples, boron concentrations from all four samples of CCP-affected surficial aquifer water and four of five samples of water from the basal sand aquifer had concentrations greater than the RAL. A comparison of boron concentrations in acid-preserved and unacidified samples indicated that boron concentrations reported for this investigation may be from about 11 to 16 percent less than would be reported in a standard analysis of an acidified sample. The stable isotope boron-11 was most enriched in comparison to boron-10 in ground water from a confined aquifer, the basal sand aquifer (d11B, 24.6 to 34.0 per mil, five samples); it was most depleted in CCP-affected water from the surficial aquifer (d11B, 0.1 to 6.6 per mil, four samples). Domestic-wastewater-affected water from the surficial aquifer (d11B, 8.7 to 11.7 per mil, four samples) was enriched in boron-11, in comparison to individual samples of a borax detergent additive and a detergent with perborate bleach; it was intermediate in composition between basal sand aquifer water and CCP-affected water from the surficial aquifer. The similarity between a ground-water sample from the surficial aquifer and a hypothetical mixture of unaffected surficial aquifer and basal sand aquifer waters indicates the potential for long-term upward discharge of ground water into the surficial aquifer from one or more confined aquifers. Est

Experimentally determined sulfur isotope fractionation between metal and silicate and implications for planetary differentiation

NASA Astrophysics Data System (ADS)

Labidi, J.; Shahar, A.; Le Losq, C.; Hillgren, V. J.; Mysen, B. O.; Farquhar, J.

2016-02-01

The Earth's mantle displays a subchondritic 34S/32S ratio. Sulfur is a moderately siderophile element (i.e. iron-loving), and its partitioning into the Earth's core may have left such a distinctive isotope composition on the terrestrial mantle. In order to constrain the sulfur isotope fractionation occurring during core-mantle differentiation, high-pressure and temperature experiments were conducted with synthetic mixtures of metal and silicate melts. With the purpose to identify the mechanism(s) responsible for the S isotope fractionations, we performed our experiments in different capsules - namely, graphite and boron nitride capsules - and thus at different fO2, with varying major element chemistry of the silicate and metal fractions. The S isotope fractionations Δ34Smetal-silicate of equilibrated metal alloys versus silicate melts is +0.2 ± 0.1‰ in a boron-free and aluminum-poor system quenched at 1-1.5 GPa and 1650 °C. The isotope fractionation increases linearly with increasing boron and aluminum content, up to +1.4 ± 0.2‰, and is observed to be independent of the silicon abundance as well as of the fO2 over ∼3.5 log units of variations explored here. The isotope fractionations are also independent of the graphite or nitride saturation of the metal. Only the melt structural changes associated with aluminum and boron concentration in silicate melts have been observed to affect the strength of sulfur bonding. These results establish that the structure of silicate melts has a direct influence on the S2- average bonding strengths. These results can be interpreted in the context of planetary differentiation. Indeed, the structural environments of silicate evolve strongly with pressure. For example, the aluminum, iron or silicon coordination numbers increase under the effect of pressure. Consequently, based on our observations, the sulfur-bonding environment is likely to be affected. In this scheme, we tentatively hypothesize that S isotope fractionations between the silicate mantle and metallic core of terrestrial planetary bodies would depend on the average pressure at which their core-mantle differentiation occurred.

Effects of foliar boron application on seed composition, cell wall boron, and seed delta 15N and delta 13C isotopes in soybean are influenced by water stress

USDA-ARS?s Scientific Manuscript database

Although the effect of foliar boron (B) application on yield and quality is well established for crops, limited information and controversial results still exist on the effects of foliar B application on soybean seed composition (seed protein, oil, fatty acids, and sugars). The objective of this res...

Comment on “A critical evaluation of the boron isotope-pH proxy: The accuracy of ancient ocean pH estimates” by M. Pagani, D. Lemarchand, A. Spivack and J. Gaillardet

NASA Astrophysics Data System (ADS)

Hönisch, Bärbel; Hemming, N. Gary; Loose, Brice

2007-03-01

Pagani et al. [Pagani M., Lemarchand D., Spivack A., and Gaillardet J. (2005). A critical evaluation of the boron isotope-pH proxy: the accuracy of ancient ocean pH estimates. Geochim. Cosmochim. Acta69(4), 953-961] use data from previous boron isotope studies to suggest that the fractionation between boric acid and borate in seawater as well as the history of δ 11B in seawater are poorly understood, thus limiting our ability to capture realistic ocean pH with this proxy. Although we agree with the authors that the long recognized uncertainty in the secular variation of δ 11B seawater imposes a temporal limit on paleo-pH reconstructions, their evaluation of the δ 11B/pH relationship in carbonates is flawed. Potential complications from vital, temperature and dissolution effects reported in that paper are based on studies that are experimentally and/or analytically poorly constrained. Using published validation studies we will demonstrate that many of the problems outlined by Pagani et al. have already been addressed, or are based on misinterpretations of previous work. Most importantly, statistical evaluation suggests empirical data are best described by a fractionation of ˜20‰. Recent paleoreconstructions confirm that the boron isotope proxy can be used with confidence, if sample selection and analyses are done carefully.

Trace, Minor Elements, and Stable Isotopes in Montastraea faveolata as an Indicator of Stress

NASA Astrophysics Data System (ADS)

Holmes, C. W.; Buster, N. A.; Hudson, J. H.

2004-12-01

Coral cores were obtained along the fore reef from Looe Key Reef, Florida Keys, and analyzed for minor and trace elements by laser ablation ICP-MS and stable oxygen and carbon isotopes. Sample locations within the corals were chosen based on the location of annual bands as determined by x-radiographs. The LA-ICP-MS data were obtained along the corallite wall. Boron, magnesium, and phosphorous concentrations can be correlated among the corals analyzed. The highest elemental concentrations and the carbon and oxygen isotopic records in the Looe Key Montastraea faveolata were linked to times of reported bleaching. Boron, a common element in sea water, exists as two species, B(OH)3 below a pH of 8.0 and B(OH)4- above a pH of 8. Hemming and others (1998) determined that boron varied positively with 13C, both being coincident with high-density bands. They proposed that photosynthetic activity of zooxanthellae is the driving process, causing the shift in pH. During periods of stress, energy that would be used for normal coral activity (reproduction and growth) is diverted for tissue repair, food gathering, and waste removal. At extreme stress, these activities are reduced. As a result of decreased zooxanthellate activity, the chemistry at the organic-inorganic boundary may change as follows. 1. The pH rises, increasing the boron levels in the carbonate skeleton. 2. Phosphorous, expelled during normal growth activity, is retained, inhibiting the precipitation of "normal" aragonite. 3. The Mg/Ca ratio changes as calcium is being used preferentially. In the Looe Key Reef corals, boron, magnesium, and phosphorous all were elevated during times of reported bleaching. Within the same time intervals, the δ 13C, which displayed values of between -2 % and -3 % in the "normal" light-density portion of the skeleton, approached a δ 13C of 0 % in the stressed, high-density portion of the skeleton. Thus, the combination of high magnesium, boron, and phosphorous concentrations, coupled with the stable isotopic records of carbon and oxygen, correlate to stress events, such as bleaching in the Looe Key corals. These relations seem to confirm the model proposed by Hemming and others, and this chemistry may be useful in determining the record of stress events in other corals. Hemming, N.G., Guilderson, T.P. and Fairbanks, R.G., 1998, Seasonal variations in the boron isotopic composition of corals, a productivity signal?, Global Biogeochemical Cycles, v. 12, p.581-586.

Measurements of δ11B in water by use of a mass spectrometer with accelerator

NASA Astrophysics Data System (ADS)

Di Fusco, Egidio; Rubino, Mauro; Marzaioli, Fabio; Di Rienzo, Brunella; Stellato, Luisa; Ricci, Andreina; Porzio, Giuseppe; D'onofrio, Antonio; Terrasi, Filippo

2017-12-01

This study describes the tests carried out to measure the isotopic composition of Boron (B) in water samples by use of the magnetic spectrometer and accelerator of the Center for Isotopic Research on Cultural and Environmental heritage (CIRCE) of Italy. B was extracted from water samples to obtain Boric acid (B(OH)3), which was then analyzed. We quantified the precision of our experimental system and the variability introduced by the chemical extraction measuring chemically untreated and treated pure B(OH)3 samples. We found an instrumental precision around 10‰ (1σ), but, by increasing the number of replicates (>30), we obtained a standard deviation of the mean (σerr) around 3‰ or lower. We also tested whether the chemical extraction caused isotopic fractionation and found a small fractionation (ε = 5 ± 4‰) of treated samples normalized against untreated ones, compatible with zero at 2σ. In order to avoid δ11B biases, we decided to normalize unknown treated samples with treated standards. Finally, we measured δ11B of seawater and groundwater samples to test the analytical method, and obtained values of 30 ± 6‰ and -4 ± 4‰ respectively. We conclude that our experimental system is only suitable when remarkable (>10‰) δ11B differences exist among water samples, but cannot be used to measure natural differences (<10‰) unless the total uncertainty is significantly decreased.

Isotopic effects on phonon anharmonicity in layered van der Waals crystals: Isotopically pure hexagonal boron nitride

NASA Astrophysics Data System (ADS)

Cuscó, Ramon; Artús, Luis; Edgar, James H.; Liu, Song; Cassabois, Guillaume; Gil, Bernard

2018-04-01

Hexagonal boron nitride (h -BN) is a layered crystal that is attracting a great deal of attention as a promising material for nanophotonic applications. The strong optical anisotropy of this crystal is key to exploit polaritonic modes for manipulating light-matter interactions in 2D materials. h -BN has also great potential for solid-state neutron detection and neutron imaging devices, given the exceptionally high thermal neutron capture cross section of the boron-10 isotope. A good knowledge of phonons in layered crystals is essential for harnessing long-lived phonon-polariton modes for nanophotonic applications and may prove valuable for developing solid-state 10BN neutron detectors with improved device architectures and higher detection efficiencies. Although phonons in graphene and isoelectronic materials with a similar hexagonal layer structure have been studied, the effect of isotopic substitution on the phonons of such lamellar compounds has not been addressed yet. Here we present a Raman scattering study of the in-plane high-energy Raman active mode on isotopically enriched single-crystal h -BN. Phonon frequency and lifetime are measured in the 80-600-K temperature range for 10B-enriched, 11B-enriched, and natural composition high quality crystals. Their temperature dependence is explained in the light of perturbation theory calculations of the phonon self-energy. The effects of crystal anisotropy, isotopic disorder, and anharmonic phonon-decay channels are investigated in detail. The isotopic-induced changes in the phonon density of states are shown to enhance three-phonon anharmonic decay channels in 10B-enriched crystals, opening the possibility of isotope tuning of the anharmonic phonon decay processes.

Development of nanosensors in nuclear technology

NASA Astrophysics Data System (ADS)

Hassan, Thamir A. A.

2017-01-01

Selectivity, sensitivity, and stability (three S parameters) are developed as a new range of sensor this provided instruments for harsh, radioactive waste polluted environment monitoring. Isotope effect is very effective for nuclear radiation sensors preparation.in this presentation are reviewed of the development of Nanosensors in nuclear technology, such as high temperature boron and its compounds with suitable physical and chemical features as sensitive element for temperature and nuclear sensor, Boron isotopes based semiconductor nanosensors and studies of the mechanism of the removal uranium from radioactive wastewater with graphene oxide (GO).

Investigating controls on boron isotope ratios in shallow marine carbonates

NASA Astrophysics Data System (ADS)

Zhang, Shuang; Henehan, Michael J.; Hull, Pincelli M.; Reid, R. Pamela; Hardisty, Dalton S.; Hood, Ashleigh v. S.; Planavsky, Noah J.

2017-01-01

The boron isotope-pH proxy has been widely used to reconstruct past ocean pH values. In both planktic foraminifera and corals, species-specific calibrations are required in order to reconstruct absolute values of pH, due to the prevalence of so-called vital effects - physiological modification of the primary environmental signals by the calcifying organisms. Shallow marine abiotic carbonate (e.g. ooids and cements) could conceivably avoid any such calibration requirement, and therefore provide a potentially useful archive for reconstructions in deep (pre-Cenozoic) time. However, shallow marine abiotic carbonates could also be affected by local shifts in pH caused by microbial photosynthesis and respiration, something that has up to now not been fully tested. In this study, we present boron isotope measurements from shallow modern marine carbonates, from the Bahama Bank and Belize to investigate the potential of using shallow water carbonates as pH archives, and to explore the role of microbial processes in driving nominally 'abiogenic' carbonate deposition. For Bahama bank samples, our boron-based pH estimates derived from a range of carbonate types (i.e. ooids, peloids, hardground cements, carbonate mud, stromatolitic micrite and calcified filament micrite) are higher than the estimated modern mean-annual seawater pH values for this region. Furthermore, the majority (73%) of our marine carbonate-based pH estimates fall out of the range of the estimated pre-industrial seawater pH values for this region. In shallow sediment cores, we did not observe a correlation between measured pore water pH and boron-derived pH estimates, suggesting boron isotope variability is a depositional rather than early diagenetic signal. For Belize reef cements, conversely, the pH estimates are lower than likely in situ seawater pH at the time of cement formation. This study indicates the potential for complications when using shallow marine non-skeletal carbonates as marine pH archives. In addition, variability in δ11B based pH estimates provides additional support for the idea that photosynthetic CO2 uptake plays a significant role in driving carbonate precipitation in a wide range of shallow water carbonates.

Fluid sources and metallogenesis in the Blackbird Co-Cu-Au-Bi-Y-REE district, Idaho, U.S.A.: Insights from major-element and boron isotopic compositions of tourmaline

USGS Publications Warehouse

Trumbull, Robert B.; Slack, John F.; Krienitz, M.-S.; Belkin, Harvey E.; Wiedenbeck, M.

2011-01-01

Tourmaline is a widespread mineral in the Mesoproterozoic Blackbird Co–Cu–Au–Bi–Y–REE district, Idaho, where it occurs in both mineralized zones and wallrocks. We report here major-element and B-isotope compositions of tourmaline from stratabound sulfide deposits and their metasedimentary wallrocks, from mineralized and barren pipes of tourmaline breccia, from late barren quartz veins, and from Mesoproterozoic granite. The tourmalines are aluminous, intermediate in the schorl–dravite series, with Fe/(Fe + Mg) values of 0.30 to 0.85, and 10 to 50% X-site vacancies. Compositional zoning is prominent only in tourmaline from breccias and quartz veins; crystal rims are enriched in Mg, Ca and Ti, and depleted in Fe and Al relative to cores. The chemical composition of tourmaline does not correlate with the presence or absence of mineralization. The δ11B values fall into two groups. Isotopically light tourmaline (−21.7 to −7.6‰) occurs in unmineralized samples from wallrocks, late quartz veins and Mesoproterozoic granite, whereas heavy tourmaline (−6.9 to +3.2‰) is spatially associated with mineralization (stratabound and breccia-hosted), and is also found in barren breccia. At an inferred temperature of 300°C, boron in the hydrothermal fluid associated with mineralization had δ11B values of −3 to +7‰. The high end of this range indicates a marine source of the boron. A likely scenario involves leaching of boron principally from marine carbonate beds or B-bearing evaporites in Mesoproterozoic strata of the region. The δ11B values of the isotopically light tourmaline in the sulfide deposits are attributed to recrystallization during Cretaceous metamorphism, superimposed on a light boron component derived from footwall siliciclastic sediments (e.g., marine clays) during Mesoproterozoic mineralization, and possibly a minor component of light boron from a magmatic–hydrothermal fluid. The metal association of Bi–Be–Y–REE in the Blackbird ores suggests some magmatic input, but involvement of granite-derived fluids cannot be conclusively established from the present database.

Boron isotope fractionation during high-pressure dehydration of antigorite serpentinite

NASA Astrophysics Data System (ADS)

Harvey, J.; Garrido, C.; Agostini, S.; Padron Navarta, J.; López Sánchez-Vizcaíno, V.; Savov, I. P.; Marchesi, C.

2011-12-01

During subduction, antigorite-serpentinite is present in large volumes in both the downgoing slab and the overlying mantle wedge. There is strong evidence to suggest that deserpentinisation reactions are a source for several fluid mobile elements, including boron. The ultramafic rocks of Cerro del Almirez, Betic Cordillera, Spain are the only known outcrops that preserve evidence for the transition between antigorite-serpentinite and chlorite-harzburgite i.e., Almirez antigorite-serpentinite represents an early stage of prograde subduction zone metamorphism overprinting previously hydrated oceanic mantle. The stability of chlorite beyond the antigorite breakdown reaction limits the release of H2O to about 6-7 wt% (in the absence of chlorite up to 12 wt% H2O would be lost), i.e. the reaction at the antigorite-serpentinite / chlorite harzburgite front is a dehydration reaction which may fractionate boron isotopes because of the mineralogical change, because of the loss of fluid over a range of temperatures, or a combination of both. Although the behaviour of boron isotopes under closely controlled experimental conditions with a limited number of variables is reasonably well constrained, the mechanism or combination of mechanisms that fractionate 11B from 10B in natural samples can be complex and difficult to interpret, especially in samples of the sub-arc mantle wedge which is seldom accessible for direct examination. This study investigates the influence of dehydration reactions in the sub-arc region where fluid loss accompanies prograde metamorphism under well constrained pressure and temperature conditions. Initial results suggest that isotopes of boron are strongly fractionated during the dehydration of antigorite-serpentinite with marked differences in δ11B across the antigorite-serpentinite to chlorite-harzburgite isograd. Antigorite-serpentinite has a δ11B of +22.4 (± 0.9) whereas the dehydration reaction product, chlorite-harzburgite, has a δ11B ranging from +2.7 (± 0.4) to -3.5 (± 0.3). A single sample with a transitional antigorite-chlorite serpentinite lithology, taken from as near to the isograd as possible, preserves a δ11B of +3.3 (± 0.3). This suggests that a substantial proportion of fluid loss, and therefore the potential fractionation of boron isotopes, occurs early on in the prograde reaction - the largest changes in δ11B occurring between antigorite-serpentinite and the transitional lithology, while the prograde lithology preserves a narrower, yet still markedly heterogeneous range of δ11B. This suggests that dehydration of serpentinite results in a strong fractionation of boron isotopes and that the results of the dehydration reaction survive high P-T condition (650 °C, 1.7 GPa). Moreover, this may also indicate that a chlorite-hosted, B-rich reservoir with a heterogeneous δ11B can persist in the lithospheric mantle elsewhere and may modify basaltic melts with which it interacts.

A balloon measurement of the isotopic composition of galactic cosmic ray boron, carbon and nitrogen. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Zumberge, J. F.

1981-01-01

The isotopic compositions of galactic cosmic ray boron, carbon, and nitrogen were measured at energies near 300 MeV amu, using a balloon-borne instrument at an atmospheric depth of approximately 5 g/sq cm. The calibrations of the detectors comprising the instrument are described. The saturation properties of the cesium iodide scintillators used for measurement of particle energy are studied in the context of analyzing the data for mass. The achieved rms mass resolution varies from approximately 0.3 amu at boron to approximately 0.5 amu at nitrogen, consistent with a theoretical analysis of the contributing factors. Corrected for detector interactions and the effects of the residual atmosphere the results are B-10/B=0.33 (+0.17, -0.11), C-13/C=0.06 (+0.13, -0.11), and N-15/N=0.42 (+0.19, -0.17). A model of galactic propagation and solar modulation is described. Assuming a cosmic ray source composition of solar-like isotopic abundances, the model predicts abundances near Earth consistent with the measurements.

Boron isotope evidence for the involvement of non-marine evaporites in the origin of the Broken Hill ore deposits

USGS Publications Warehouse

Slack, J.F.; Palmer, M.R.; Stevens, B.P.J.

1989-01-01

IDENTIFYING the palaeogeographic setting and mode of origin of stratabound ore deposits can be difficult in high-grade metamorphic terranes, where the effects of metamorphism may obscure the nature of the protoliths. Here we report boron isotope data for tourmalines from the early Proterozoic Broken Hill block, in Australia, which hosts giant lead-zinc-silver sulphide deposits. With one exception the 11B/10B ratios are lower than those for all other tourmalines from massive sulphide deposits and tour-malinites elsewhere in the world. We propose that these low ratios reflect leaching of boron from non-marine evaporitic borates by convecting hydrothermal fluids associated with early Proterozoic continental rifting. A possible modern analogue is the Salton Sea geothermal field in California. ?? 1989 Nature Publishing Group.

Method of synthesizing enriched decaborane for use in generating boron neutron capture therapy pharmaceuticals

DOEpatents

Cowan, Robert L.; Ginosar, Daniel M.; Dunks, Gary B.

2000-01-01

A method is described for synthesizing decaborane wherein at least about 90% of the boron atoms in the decaborane are the .sup.10 B isotope, comprising the steps of: (a) reacting boric acid with a C.sub.1 to C.sub.10 alkanol to form a .sup.10 B-alkyl borate wherein at least about 90% of the boron atoms in the boric acid are the .sup.10 B isotope; (b) reducing the .sup.10 B-alkyl borate to form an alkali metal .sup.10 B-borohydride; (c) converting the alkali metal .sup.10 B-borohydride to a .sup.10 B-tetradecahydroundecaborate ion; and (d) converting the .sup.10 B-tetradecahydroundecaborate ion to .sup.10 B-decaborane. Methods of preparing tetradecahydroundecaborate ions and decaborane from alkali metal borohydrides are also described.

Study of helium embrittlement in boron doped EUROFER97 steels

NASA Astrophysics Data System (ADS)

Gaganidze, E.; Petersen, C.; Aktaa, J.

2009-04-01

To simulate helium effects in Reduced Activation Ferritic/Martensitic steels, experimental heats ADS2, ADS3 and ADS4 with the basic composition of EUROFER97 (9%Cr-WVTa) were doped with different contents of natural boron and separated 10B-isotope (0.008-0.112 wt.%) and irradiated in High Flux Reactor (HFR) Petten up to 16.3 dpa at 250-450 °C and in Bor-60 fast reactor in Dimitrovgrad up to 31.8 dpa at 332-338 °C. The embrittlement and hardening are investigated by instrumented Charpy-V tests with subsize specimens. Complete burn-up of 10B isotope under neutron irradiation in HFR Petten led to generation of 84, 432 and 5580 appm He and partial boron-to-helium transformation in Bor-60 led to generation of 9, 46, 880 appm He in ADS2, ADS3 and ADS4 heats, respectively. At low irradiation temperatures Tirr ⩽ 340 °C the boron doped steels show progressive embrittlement with increasing helium amount. Irradiation induced DBTT shift of EUROFER97 based heat doped with 1120 wppm separated 10B isotope could not be quantified due to large embrittlement found in the investigated temperature range. At Tirr ⩽ 340 °C helium induced extra embrittlement is attributed to material hardening induced by helium bubbles and described in terms of phenomenological model.

Climate and CO2 coupling in the early Cenozoic Greenhouse

NASA Astrophysics Data System (ADS)

Rae, J. W. B.; Greenop, R.; Kaminski, M.; Sexton, P. F.; Foster, G. L.; Greene, S. E.; Littley, E.; Kirtland Turner, S.; Ridgwell, A.

2017-12-01

The early Cenozoic is a time of climatic extremes: hyperthermals pepper the transition from extreme global warmth to the start of Cenozoic cooling, with these evolving climate regimes accompanied by major changes in ocean chemistry and biota. The exogenic carbon cycle, and ocean-atmospheric CO2 in particular, is thought to have played a key role in these climatic changes, but the carbon chemistry of the early Cenozoic ocean remains poorly constrained. Here we present new boron isotope data from benthic foraminifera, which can be used to constrain relative changes in ocean pH. These are coupled with modelling experiments performed with the cGenie Earth system model to provide new constraints on the carbon cycle and carbonate system of the early Cenozoic. While our benthic boron isotope data do not readily provide a record of surface ocean CO2 , they do place constraints on the whole ocean-atmosphere carbonate system, alongside changes in ocean circulation and biogeochemistry, and also have relatively robust calcite tests and small `vital effects'. During the late Paleocene ascent to peak greenhouse conditions and the middle Eocene descent towards the icehouse, our boron isotope data show close coupling with benthic δ18O, demonstrating a clear link between CO2 and climate. However within the early Eocene our boron isotope data reveal more dynamic changes in deep ocean pH, which may be linked to changes in ocean circulation. Overall, our data demonstrate the ability of CO2 to regulate the climate system across varying boundary conditions, and the influence of both the long-term carbon cycle and shorter-term ocean biogeochemical cycling on Earth's climate.

Effect of 10B isotope and vacancy defects on the phonon modes of two-dimensional hexagonal boron nitride

NASA Astrophysics Data System (ADS)

Sherajul Islam, Md.; Anindya, Khalid N.; Bhuiyan, Ashraful G.; Tanaka, Satoru; Makino, Takayuki; Hashimoto, Akihiro

2018-02-01

We report the details of the effects of the 10B isotope and those of B and N vacancies combined with the isotope on the phonon modes of two-dimensional hexagonal boron nitride (h-BN). The phonon density of states and localization problems are solved using the forced vibrational method, which is suitable for an intricate and disordered system. We observe an upward shift of Raman-active E2g-mode optical phonons (32 cm-1) for a 100% 10B isotope, which matches well with the experiment and simple harmonic oscillator model. However, a downward shift of E2g-mode phonons is observed for B or N vacancies and the combination of the isotope and vacancy-type disordered BN. Strong localized eigenmodes are found for all types of defects, and a typical localization length is on the order of ˜7 nm for naturally occurring BN samples. These results are very important for understanding the heat dissipation and electron transport properties of BN-based nanoelectronics.

Boron Isotopes in Modern and Cenozoic Scleractinian Fossil Corals

NASA Astrophysics Data System (ADS)

Gothmann, A.; Bender, M. L.; Adkins, J. F.

2016-12-01

Recent measurements of boron isotopes in modern coral support the hypothesis that coral biologically up-regulate the pH of the fluid from which they calcify to facilitate skeletal mineralization [1]. While this evidence of biological pH adjustment provides important insight into the mechanism by which coral make their skeletons, it also complicates the use of coral boron isotopes as a paleoseawater pH proxy. We measured boron isotopes in 11 modern and well preserved fossil corals using Secondary Ion Mass Spectrometry to characterize fine-scale ( 30 µm) patterns of δ11B variability. In addition to δ11B, we measured B/Ca, Mg/Ca, Sr/Ca, and Mn/Ca ratios in order to compare isotopes with element/Ca variability and monitor for diagenetic alteration. We find that in different species of modern and well preserved fossil coral, the measured range of δ11B varies from 5 to 15 ‰. Also, while corals of similar geologic age have similar average δ11B compositions, at the scale of our measurements they do not appear to share a consistent pattern of minimum δ11B, maximum δ11B, or range in δ11B. The δ11B of fossil corals increases by 7 ‰ between the Early Cenozoic and today. While the general pattern of coral δ11B change is similar to the pattern found in foraminifera-based δ11B records [e.g., 2], the magnitude of the coral change is approximately 2-3 times as large as changes inferred from foraminifera. Although it is not possible to separate the influence of changing seawater pH and changing δ11Bseawater on fossil coral boron isotope compositions, the record can be explained by a combination of lower seawater pH and lower seawater δ11B during the the Early Cenozoic. Our coral results suggest an Early Cenozoic δ11Bseawater composition that is much lower than inferred from other approaches, and similar to Early Cenozoic δ11Bseawater as inferred from brine inclusions in halite [3]. [1.] McCulloch, M.T., Trotter, J., Montagna, P., Falter, J., Dunbar, R., Freiwald, A., Forsterra, G., Lopez Correa, M., Maier, C., Ruggeberg, A., Taviani, M., 2012. Geochimica et Cosmochimica Acta 87, 21-34. [2.] Pearson, P.N., Palmer, M.R., 2000. Nature 406, 695-699. [3.] Paris, G., Gaillardet, J., Louvat, P. 2010. Geology 38, 1035-1038.

Determination of the geographical origin of green coffee by principal component analysis of carbon, nitrogen and boron stable isotope ratios.

PubMed

Serra, Francesca; Guillou, Claude G; Reniero, Fabiano; Ballarin, Luciano; Cantagallo, Maria I; Wieser, Michael; Iyer, Sundaram S; Héberger, Károly; Vanhaecke, Frank

2005-01-01

In this study we show that the continental origin of coffee can be inferred on the basis of coupling the isotope ratios of several elements determined in green beans. The combination of the isotopic fingerprints of carbon, nitrogen and boron, used as integrated proxies for environmental conditions and agricultural practices, allows discrimination among the three continental areas producing coffee (Africa, Asia and America). In these continents there are countries producing 'specialty coffees', highly rated on the market that are sometimes mislabeled further on along the export-sale chain or mixed with cheaper coffees produced in other regions. By means of principal component analysis we were successful in identifying the continental origin of 88% of the samples analyzed. An intra-continent discrimination has not been possible at this stage of the study, but is planned in future work. Nonetheless, the approach using stable isotope ratios seems quite promising, and future development of this research is also discussed. (c) 2005 John Wiley & Sons, Ltd.

High Resolution Glacial-interglacial Climatic Variations in the South China Sea during the Last 220,000 Years

NASA Astrophysics Data System (ADS)

Huang, K.; You, C.; Li, M.; Shieh, Y.

2002-12-01

The Asian monsoon plays an important role of both regional and global climatic variations. The South China Sea (SCS) located between Southeast Asia continent and Western Pacific Ocean is an ideal place for studying oceanographic responses and changes of monsoon system in the past. Planktonic foraminiferal shells separated from two deep sea cores, ODP Site 1144 and SCS 15B, located near the northeast continental slope and the central ocean basin respectively were used to reconstruct high-resolution climatic records during the last 220 kyrs. Average of 20 individual foraminiferal shells were hand picked and cleaned thoroughly for high precision trace element/calcium ratios (i.e., Mg/Ca, Sr/Ca, and Ba/Ca) determination using a Thermo-Fannigan Element II ICP-MS installed at NCKU. Isotopic compositions of oxygen, carbon, boron and strontium also were measured by stable isotope ratio or Triton TI thermal ionization mass spectrometer. Mg/Ca and Sr/Ca in foraminiferal shells are sensitive proxies for sea surface temperature, chemical weathering and hydrothermal activity on seafloor. The SCS foraminiferal shells Mg/Ca and Sr/Ca show negative correlation with interesting glacial-interglacial variations. The calculated Mg/Ca SSTs varied as large as 6-7 °C with the highest temperature occurred at oxygen stage 5. The Sr/Ca ratios change about 16 % (1.200-1.429 mmole/mole), possibly a result of periodic sea level changes which influencing terrigenous inputs or continental shelves weathering. On the other hand, the Ba/Ca display large variations (0.031-0.117 mmole/mole), possibly reflecting upwelling intensity or SCS bottom water chemistry. The boron isotopic compositions in planktonic foraminiferal shells are used to estimate pH in the surface ocean. Combining these proxies, high-resolution oceanic environmental records in the SCS were reconstructed for the last 220 kyrs. The results obtained from the SCS can be used to gain a better understanding of land-sea interaction in this region.

Local Atomic Arrangements and Band Structure of Boron Carbide.

PubMed

Rasim, Karsten; Ramlau, Reiner; Leithe-Jasper, Andreas; Mori, Takao; Burkhardt, Ulrich; Borrmann, Horst; Schnelle, Walter; Carbogno, Christian; Scheffler, Matthias; Grin, Yuri

2018-05-22

Boron carbide, the simple chemical combination of boron and carbon, is one of the best-known binary ceramic materials. Despite that, a coherent description of its crystal structure and physical properties resembles one of the most challenging problems in materials science. By combining ab initio computational studies, precise crystal structure determination from diffraction experiments, and state-of-the-art high-resolution transmission electron microscopy imaging, this concerted investigation reveals hitherto unknown local structure modifications together with the known structural alterations. The mixture of different local atomic arrangements within the real crystal structure reduces the electron deficiency of the pristine structure CBC+B 12 , answering the question about electron precise character of boron carbide and introducing new electronic states within the band gap, which allow a better understanding of physical properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Perspectives of the Boron Neutron Capture Therapy-Clinical Applications Research and Development in Saudi Arabia

NASA Astrophysics Data System (ADS)

Badhrees, I.; Alrumayan, F.; Mahube, F.

Boron Neutron Capture Therapy (BNCT) is a binary form of experimental radiotherapy which is based on the administration of a drug able to concentrate the isotopes in a tumor cell that later are irradiated with a neutron beam. Even though the first evidence of the success of this treatment dates back many years ago, BNCT showed successful treatment results in malignant melanoma, and Glioblastoma. In order for BNCT to be successful, a sufficient amount of Boron (10B) must be selectively delivered to the tumor cell, and then irradiated by neutrons of sufficient enough. The CS-30 cyclotron at King Faisal Specialist Hospital & Research Center is a positive-ion machine capable of accelerating protons at 26MeV, and other isotopes as well. Although the peak beam intensity from the CS-30 is low, the key to success of using it for the BNCT is by using a high average beam current at low energy. This work is aimed at testing the capability of the CS-30 Cyclotron to produce a low-energy neutron beam to be used to activate the Boron atoms injected into the tumor cell, through simulation of a compatible moderator. We are also planning to measure the overall dosimetry of the energy dose as well as that for the boron in the tumor cell.

GUM Analysis for TIMS and SIMS Isotopic Ratios in Graphite

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

Heasler, Patrick G.; Gerlach, David C.; Cliff, John B.

2007-04-01

This report describes GUM calculations for TIMS and SIMS isotopic ratio measurements of reactor graphite samples. These isotopic ratios are used to estimate reactor burn-up, and currently consist of various ratios of U, Pu, and Boron impurities in the graphite samples. The GUM calculation is a propagation of error methodology that assigns uncertainties (in the form of standard error and confidence bound) to the final estimates.

Detection of boron nitride radicals by emission spectroscopy in a laser-induced plasma

NASA Astrophysics Data System (ADS)

Dutouquet, C.; Acquaviva, S.; Hermann, J.

2001-06-01

Several vibrational bands of boron nitride radicals have been observed in a plasma produced by pulsed-laser ablation of a boron nitride target in low-pressure nitrogen or argon atmospheres. Using time- and space-resolved emission spectroscopic measurements with a high dynamic range, the most abundant isotopic species B 11N have been detected. The emission bands in the spectral range from 340 to 380 nm belong to the Δυ =-1, 0, +1 sequences of the triplet system (transition A 3Π-X 3Π). For positive identification, the molecular emission bands have been compared with synthetic spectra obtained by computer simulations. Furthermore, B 10N emission bands have been reproduced by computer simulation using molecular constants which have been deduced from the B 11N constants. Nevertheless, the presence of the lower abundant isotopic radical B 10N was not proved due the noise level which masked the low emission intensity of the B 10N band heads.

Constraints on Late Paleozoic Ocean Response to Climate Change Based on Brachiopod δ11B and 87Sr/86Sr

NASA Astrophysics Data System (ADS)

Legett, S. A.; Rasbury, T.; Grossman, E. L.; Hemming, G.

2017-12-01

In order to understand the possible effects of climate change on present day oceans, it is important to determine how marine systems responded to climate change in the past. This study uses δ11B values from well-preserved Carboniferous and Permian brachiopods as well as models to examine chemical trends in seawater and how these relate to long- and short-term climate changes. Our results show that δ11B rises rapidly going into the Carboniferous from a low of 10‰ to a high of 17‰ and remains relatively stable through the Carboniferous, despite the initiation of glaciation in the Mid Carboniferous. At the Carboniferous-Permian boundary, δ11B declines into the Early Permian before reaching a low at the Sakmarian. This decline in δ11B is coincident with the decrease in 87Sr/86Sr through this interval, which corresponds to evidence for aridity going into the Permian. We hypothesize that a reduction in silicate weathering drives an increase in atmospheric pCO2 and a subsequent lowering of ocean pH going into the Permian. This is consistent with our interpretation of the Carboniferous-Permian boundary, as a major mechanism for controlling seawater boron isotope composition is the adsorption of borate on clays, removing isotopically light boron and thus leaving seawater boron isotopically heavy. Therefore, at lower pH seawater should become isotopically lighter as this mechanism for removal is reduced. These hypotheses are supported by our initial modeling results of the B and Sr isotopic budgets of the ocean during the Late Paleozoic.

Application of major and trace elements as well as boron isotopes for tracing hydrochemical processes: the case of Trifilia coastal karst aquifer, Greece

NASA Astrophysics Data System (ADS)

Panagopoulos, G.

2009-09-01

The Trifilia karst aquifer presents a complex hydrochemical character due to the intricate geochemical processes that take place in the area. Their discernment was achieved by using the chemical analyses of major, trace elements and boron isotopes. Major ion composition indicates mixing between seawater and freshwater is occurring. Five hydrochemical zones corresponding to five respective groundwater types were distinguished, in which the chemical composition of groundwater is influenced mainly due to the different salinization grade of the aquifer. The relatively increased temperature of the aquifer indicates the presence of hydrothermal waters. Boron isotopes and trace elements indicate that the intruding seawater has been hydrothermally altered, as it is shown by the δ11B depleted signature and the increased concentrations of Li and Sr. Trace elements analyses showed that the groundwater is enriched in various metallic elements, which derive from the solid hydrocarbons (bitumens), contained in the carbonate sediments of the Tripolis zone. The concentration of these trace elements depends on the redox environment. Thus, in reductive conditions As, Mn, Co and NH4 concentrations are high, in oxidized conditions the V, Se, Mo, Tl and U concentration increases while Ni is not redox sensitive and present high concentration in both environments.

GUM Analysis for SIMS Isotopic Ratios in BEP0 Graphite Qualification Samples, Round 2

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

Gerlach, David C.; Heasler, Patrick G.; Reid, Bruce D.

2009-01-01

This report describes GUM calculations for TIMS and SIMS isotopic ratio measurements of reactor graphite samples. These isotopic ratios are used to estimate reactor burn-up, and currently consist of various ratios of U, Pu, and Boron impurities in the graphite samples. The GUM calculation is a propagation of error methodology that assigns uncertainties (in the form of standard error and confidence bound) to the final estimates.

Boron content and isotopic composition of ocean basalts: Geochemical and cosmochemical implications

NASA Astrophysics Data System (ADS)

Chaussidon, Marc; Jambon, Albert

1994-02-01

Ion microprobe determination of boron content and delta B-11 values has been performed for a set of 40 oceanic basalt glasses (N-MORB, E-MORB, BABB and OIB) whose chemical characteristics (major and trace elements and isotopic ratios) are well documented. Boron contents, determined at +/- 10% relative, range from 0.34 to 0.74 ppm in N-MORB, whereas E-MORB, BABB and OIB extend to higher concentrations (0.5-2.4 ppm). After correction for crystal fractionation, this range is reduced to 0.5-1.3 ppm. N-MORB and E-MORB also exhibit different B/K ratios, 1.0 +/- 0.3 x 10(exp -3) and 0.2 to 1.4 x 10(exp -3) respectively. This can be interpreted as resulting from the incorporation into the upper mantle of a K-rich and B-poor component (e.g., subducted oceanic crust having lost most of its initial boron). Delta B-11 values range between -7.40 +/- 2 and +0.6 +/- 2 per mill, with no significant difference between N-MORB, E-MORB, OIB or BABB. The Hawaiian samples define a strong linear correlation between boron contents, delta B-11 values, MgO and water contents and delta D values. This is interpreted as resulting from assimilation-fractionation processes which occurred within a water-rich oceanic crust, and which produced high delta B-11 values associated with high delta D values. The low level of B-11 enrichment in the upper mantle constraints the amount of boron reinjected by subduction to a maximum of about 2% of the boron present in the subducted slab. This in turn corresponds to a maximum net Boron transfer of about 3 x 10(exp 10) g/a towards the surface reservoirs. Finally, a boron content of 0.25 +/- 0.1 ppm is estimated for the bulk silicate Earth (i.e., primitive mantle), corresponding to a depletion factor relative to C1 chondrites of about 0.15 and suggesting that B was moderately volatile upon terrestrial accretion.

Reply to the comment on 'Boron content and isotopic composition of oceanic basalts: Geochemical and cosmochemical implications'

NASA Astrophysics Data System (ADS)

Chaussidon, Marc; Jambon, Albert

1994-12-01

Chen-Feng You questions some of our interpretations of the B contents and delta B-11 values of oceanic basalts. His comments can be summarized in three points: (1) He emphasizes the importance of sediments as a B carrier, which should be taken into account in any budget calculation. He suggests that our estimated amount of boron subducted into the mantle is incorrect. (2) He quotes unpublished experimental results indicating that sedimentary boron is partly leached from a hemi-pelagic sediment at moderate temperatures (T less than or = 150 C) leaving a B-depleted residue isotopically fractionated to low delta B-11 values. (3) He further argues that Boron abundance and delta B-11 values at both Hawaii and the Halmahera arc could be explained by the incorporation of such fluids (i.e., released during subduction). Although we do think that the type of experiment described by You is effectively lacking at the moment and is of great potential for the understanding of B geochemical cycle, we also think that: (1) the experiments of You are insufficient to elucidate the behavior of B during subduction; and (2) two points of our work were misunderstood. We discuss successively the three points raised by You.

Reviews and syntheses: Revisiting the boron systematics of aragonite and their application to coral calcification

NASA Astrophysics Data System (ADS)

DeCarlo, Thomas M.; Holcomb, Michael; McCulloch, Malcolm T.

2018-05-01

The isotopic and elemental systematics of boron in aragonitic coral skeletons have recently been developed as a proxy for the carbonate chemistry of the coral extracellular calcifying fluid. With knowledge of the boron isotopic fractionation in seawater and the B/Ca partition coefficient (KD) between aragonite and seawater, measurements of coral skeleton δ11B and B/Ca can potentially constrain the full carbonate system. Two sets of abiogenic aragonite precipitation experiments designed to quantify KD have recently made possible the application of this proxy system. However, while different KD formulations have been proposed, there has not yet been a comprehensive analysis that considers both experimental datasets and explores the implications for interpreting coral skeletons. Here, we evaluate four potential KD formulations: three previously presented in the literature and one newly developed. We assess how well each formulation reconstructs the known fluid carbonate chemistry from the abiogenic experiments, and we evaluate the implications for deriving the carbonate chemistry of coral calcifying fluid. Three of the KD formulations performed similarly when applied to abiogenic aragonites precipitated from seawater and to coral skeletons. Critically, we find that some uncertainty remains in understanding the mechanism of boron elemental partitioning between aragonite and seawater, and addressing this question should be a target of additional abiogenic precipitation experiments. Despite this, boron systematics can already be applied to quantify the coral calcifying fluid carbonate system, although uncertainties associated with the proxy system should be carefully considered for each application. Finally, we present a user-friendly computer code that calculates coral calcifying fluid carbonate chemistry, including propagation of uncertainties, given inputs of boron systematics measured in coral skeleton.

Effects of Boron and Graphite Uncertainty in Fuel for TREAT Simulations

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

Vaughn, Kyle; Mausolff, Zander; Gonzalez, Esteban

Advanced modeling techniques and current computational capacity make full core TREAT simulations possible, with the goal of such simulations to understand the pre-test core and minimize the number of required calibrations. But, in order to simulate TREAT with a high degree of precision the reactor materials and geometry must also be modeled with a high degree of precision. This paper examines how uncertainty in the reported values of boron and graphite have an effect on simulations of TREAT.

Accelerator-driven boron neutron capture therapy

NASA Astrophysics Data System (ADS)

Edgecock, Rob

2014-05-01

Boron Neutron Capture Therapy is a binary treatment for certain types of cancer. It works by loading the cancerous cells with a boron-10 carrying compound. This isotope has a large cross-section for thermal neutrons, the reaction producing a lithium nucleus and alpha particle that kill the cell in which they are produced. Recent studies of the boron carrier compound indicate that the uptake process works best in particularly aggressive cancers. Most studied is glioblastoma multiforme and a trial using a combination of BNCT and X-ray radiotherapy has shown an increase of nearly a factor of two in mean survival over the state of the art. However, the main technical problem with BNCT remains producing a sufficient flux of neutrons for a reasonable treatment duration in a hospital environment. This paper discusses this issue.

Molecular Medicine: Synthesis and In Vivo Detection of Agents for use in Boron Neutron Capture Therapy. Final Report

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

Kabalka, G. W.

2005-06-28

The primary objective of the project was the development of in vivo methods for the detection and evaluation of tumors in humans. The project was focused on utilizing positron emission tomography (PET) to monitor the distribution and pharamacokinetics of a current boron neutron capture therapy (BNCT) agent, p-boronophenylalanine (BPA) by labeling it with a fluorine-18, a positron emitting isotope. The PET data was then used to develop enhanced treatment planning protocols. The study also involved the synthesis of new tumor selective BNCTagents that could be labeled with radioactive nuclides for the in vivo detection of boron.

Relative Composition and Energy Spectra of Light Nuclei in Cosmic Rays: Results from AMS-01

NASA Astrophysics Data System (ADS)

Aguilar, M.; Alcaraz, J.; Allaby, J.; Alpat, B.; Ambrosi, G.; Anderhub, H.; Ao, L.; Arefiev, A.; Arruda, L.; Azzarello, P.; Basile, M.; Barao, F.; Barreira, G.; Bartoloni, A.; Battiston, R.; Becker, R.; Becker, U.; Bellagamba, L.; Béné, P.; Berdugo, J.; Berges, P.; Bertucci, B.; Biland, A.; Bindi, V.; Boella, G.; Boschini, M.; Bourquin, M.; Bruni, G.; Buénerd, M.; Burger, J. D.; Burger, W. J.; Cai, X. D.; Cannarsa, P.; Capell, M.; Casadei, D.; Casaus, J.; Castellini, G.; Cernuda, I.; Chang, Y. H.; Chen, H. F.; Chen, H. S.; Chen, Z. G.; Chernoplekov, N. A.; Chiueh, T. H.; Choi, Y. Y.; Cindolo, F.; Commichau, V.; Contin, A.; Cortina-Gil, E.; Crespo, D.; Cristinziani, M.; Dai, T. S.; dela Guia, C.; Delgado, C.; Di Falco, S.; Djambazov, L.; D'Antone, I.; Dong, Z. R.; Duranti, M.; Engelberg, J.; Eppling, F. J.; Eronen, T.; Extermann, P.; Favier, J.; Fiandrini, E.; Fisher, P. H.; Flügge, G.; Fouque, N.; Galaktionov, Y.; Gervasi, M.; Giovacchini, F.; Giusti, P.; Grandi, D.; Grimm, O.; Gu, W. Q.; Haino, S.; Hangarter, K.; Hasan, A.; Hermel, V.; Hofer, H.; Hungerford, W.; Ionica, M.; Jongmanns, M.; Karlamaa, K.; Karpinski, W.; Kenney, G.; Kim, D. H.; Kim, G. N.; Kim, K. S.; Kirn, T.; Klimentov, A.; Kossakowski, R.; Kounine, A.; Koutsenko, V.; Kraeber, M.; Laborie, G.; Laitinen, T.; Lamanna, G.; Laurenti, G.; Lebedev, A.; Lechanoine-Leluc, C.; Lee, M. W.; Lee, S. C.; Levi, G.; Lin, C. H.; Liu, H. T.; Lu, G.; Lu, Y. S.; Lübelsmeyer, K.; Luckey, D.; Lustermann, W.; Maña, C.; Margotti, A.; Mayet, F.; McNeil, R. R.; Menichelli, M.; Mihul, A.; Mujunen, A.; Oliva, A.; Palmonari, F.; Park, H. B.; Park, W. H.; Pauluzzi, M.; Pauss, F.; Pereira, R.; Perrin, E.; Pevsner, A.; Pilo, F.; Pimenta, M.; Plyaskin, V.; Pojidaev, V.; Pohl, M.; Produit, N.; Quadrani, L.; Rancoita, P. G.; Rapin, D.; Ren, D.; Ren, Z.; Ribordy, M.; Richeux, J. P.; Riihonen, E.; Ritakari, J.; Ro, S.; Roeser, U.; Sagdeev, R.; Santos, D.; Sartorelli, G.; Sbarra, C.; Schael, S.; Schultz von Dratzig, A.; Schwering, G.; Seo, E. S.; Shin, J. W.; Shoumilov, E.; Shoutko, V.; Siedenburg, T.; Siedling, R.; Son, D.; Song, T.; Spada, F. R.; Spinella, F.; Steuer, M.; Sun, G. S.; Suter, H.; Tang, X. W.; Ting, Samuel C. C.; Ting, S. M.; Tomassetti, N.; Tornikoski, M.; Torsti, J.; Trümper, J.; Ulbricht, J.; Urpo, S.; Valtonen, E.; Vandenhirtz, J.; Velikhov, E.; Verlaat, B.; Vetlitsky, I.; Vezzu, F.; Vialle, J. P.; Viertel, G.; Vité, D.; Von Gunten, H.; Waldmeier Wicki, S.; Wallraff, W.; Wang, J. Z.; Wiik, K.; Williams, C.; Wu, S. X.; Xia, P. C.; Xu, S.; Xu, Z. Z.; Yan, J. L.; Yan, L. G.; Yang, C. G.; Yang, J.; Yang, M.; Ye, S. W.; Zhang, H. Y.; Zhang, Z. P.; Zhao, D. X.; Zhou, F.; Zhou, Y.; Zhu, G. Y.; Zhu, W. Z.; Zhuang, H. L.; Zichichi, A.; Zimmermann, B.; Zuccon, P.

2010-11-01

Measurement of the chemical and isotopic composition of cosmic rays is essential for the precise understanding of their propagation in the galaxy. While the model parameters are mainly determined using the B/C ratio, the study of extended sets of ratios can provide stronger constraints on the propagation models. In this paper, the relative abundances of light-nuclei lithium, beryllium, boron, and carbon are presented. The secondary-to-primary ratios Li/C, Be/C, and B/C have been measured in the kinetic energy range 0.35-45 GeV nucleon-1. The isotopic ratio 7Li/6Li is also determined in the magnetic rigidity interval 2.5-6.3 GV. The secondary-to-secondary ratios Li/Be, Li/B, and Be/B are also reported. These measurements are based on the data collected by the Alpha Magnetic Spectrometer AMS-01 during the STS-91 space shuttle flight in 1998 June. Our experimental results are in substantial agreement with other measurements, where they exist. We describe our light-nuclei data with a diffusive-reacceleration model. A 10%-15% overproduction of Be is found in the model predictions and can be attributed to uncertainties in the production cross-section data.

ANALYTICAL METHOD FOR THE ABSORPTIOMETRIC DETERMINATION OF BORON IN SODIUM METAL

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

None

1963-01-01

Sodium metal is dissolved in water under an inert atmosphere of argon, and the resulting sodium hydroxide solution is evaporated to dryness. Rosocyanin is formed, separated from excess curcumin, and dissolved in ethanol for absorptiometric measurement. The method is applicable to sodium metal containing 0.1 to 1 ppm boron. The precision should be within plus or minus 20% (95% confidence limits) at the 0.5 ppm boron level. (auth)

Use of tracers and isotopes to evaluate vulnerability of water in domestic wells to septic waste

USGS Publications Warehouse

Verstraeten, Ingrid M.; Fetterman, G.S.; Meyer, M.J.; Bullen, T.; Sebree, S.K.

2005-01-01

In Nebraska, a large number (>200) of shallow sand-point and cased wells completed in coarse alluvial sediments along rivers and lakes still are used to obtain drinking water for human consumption, even though construction of sand-point wells for consumptive uses has been banned since 1987. The quality of water from shallow domestic wells potentially vulnerable to seepage from septic systems was evaluated by analyzing for the presence of tracers and multiple isotopes. Samples were collected from 26 sand-point and perforated, cased domestic wells and were analyzed for bacteria, coliphages, nitrogen species, nitrogen and boron isotopes, dissolved organic carbon (DOC), prescription and nonprescription drugs, or organic waste water contaminants. At least 13 of the 26 domestic well samples showed some evidence of septic system effects based on the results of several tracers including DOC, coliphages, NH4+, NO3-, N2, ?? 15N[NO3-] and boron isotopes, and antibiotics and other drugs. Sand-point wells within 30 m of a septic system and <14 m deep in a shallow, thin aquifer had the most tracers detected and the highest values, indicating the greatest vulnerability to contamination from septic waste. Copyright ?? 2005 National Ground Water Association.

Geothermal constraints on enrichment of boron and lithium in salt lakes: An example from a river-salt lake system on the northern slope of the eastern Kunlun Mountains, China

NASA Astrophysics Data System (ADS)

Tan, Hongbing; Chen, Jun; Rao, Wenbo; Zhang, Wenjie; Zhou, Huifang

2012-06-01

Some rivers on the northern slope of the eastern Kunlun Mountains in the Qaidam Basin, China, show very high concentrations of boron and lithium. Correspondingly, the salt lakes fed by these rivers show an unusual enrichment of boron and lithium, and become an important economic resource. The origin of boron and lithium has long been debated. The aim of this study is to analyze the water chemistry and hydrogen and oxygen isotopic composition of river water to understand the unusual enrichment of boron and lithium in the salt lakes of the Qaidam Basin. Oxygen and hydrogen isotope data show that the source of river water in the winter and summer originates from the Kunlun Mountain ice and snow melt water, respectively. The water chemistry shows that boron and lithium contents are high but little variable with seasons in the Nalenggele River and Wutumeiren River waters. By contrast, other rivers have much lower lithium and boron contents. Moreover, the contents of B3+ and Li+ in the river loads or bed sands show little difference amongst the rivers. This indicates that removal by adsorption or input by surface rock weathering is not the main controlling factor of the B3+ and Li+ variation in the rivers. Rivers with high B3+ and Li+ content are chemically similar to geothermal waters in the Tibetan Plateau. In addition, the source area of the Nalenggele River is located in a collision zone of the Kunlun Mountains and Altun Mountains. Large and deep faults can serve as conduits for geothermal fluids. Thus, deep geothermal waters in the source area can easily migrate to the surface and discharge as springs feeding the rivers. They are an important source of B3+ and Li+ to the rivers. The abnormally high contents of B3+ and Li+ in the Nalenggele and Wutumeiren Rivers also suggest that the geothermal source area may be a future target for boron and lithium resources.

The Boron Isotopic Composition of Elephant Dung: Inputs to the Global Boron Budget

NASA Astrophysics Data System (ADS)

Williams, L. B.; Hervig, R. L.

2011-12-01

A survey of boron in kerogen showed isotopically light δ11B values (0 to -50%) that are distinctly different from most mineral and natural water B reservoirs. Diagenesis releases this isotopically light B into pore fluids when hydrocarbons are generated, thus enriching oilfield brines in 10B. This observation suggests that borated biomolecules (BM) are primarily tetrahedral favoring 10B, whereas 11B is preferred in trigonal coordination. Plants, with optimal concentrations up to 100ppm, contribute more B than animal remains to sediment. Elephants are one of the largest herbivores on earth, consuming 200 - 250 kg of plant material/day and producing 50 kg of manure/day. They are inefficient at digestion, thus the manure contains >50% undigested plant material. Dung samples are therefore ideal for studying the δ11B of both the food input and digested output of a significant B supply to sedimentary systems. Horse and rabbit manure were studied for comparison to evaluate B isotope variations in the food supply and potential vital effects on the output. B-content and isotopic composition of dung plant material and digested fractions were measured in the solid state by secondary ion mass spectrometry. The digests were rinsed in 1.8% mannitol, a B-complexing agent, to remove surface adsorbed-B, then air dried and Au-coated for charge compensation. Results showed that the elephant diet contains 3-13 ppm B, with an average δ11B of -20 ± 0.8% (1σ), while rabbit food had 88 ppm B with a δ11B of -50 ± 1.3 %. The digested fraction of the elephant dung contains 4-10ppm B with average δ11B values of -12 ± 1.2%. In comparison, horse manure with 11-21 ppm B has a δ11B of -10.7 ± 0.5% and rabbit manure contains 2-3 ppm B with a δ11B of -8.8 ± 1%. Boron isotope compositions of these manures are indistinguishable (within error). Clearly plant material is a major contributor of isotopically light B to sediments. The herbivores studied fractionate their total B intake in favor of 11B, thus increasing the δ11B of the (solid) digested material relative to the food source. This would not affect the overall BM input to the sediment because the dung contains the undigested plants. If we assume that the average B isotopic composition of dung, ~10ppm B at -20%, represents an average BM in sediment, and that the mass of sediments (1E24 g) is comparable to the mass of seawater with an average 5ppm B at +40%, then it is clear that BM plays a major role in balancing the global B budget. Note: This research was NOT funded by taxpayer dollars. The Phoenix Zoo kindly approved the proposal to sample elephant dung for this study and their support is greatly appreciated.

Bayesian Nitrate Source Apportionment to Individual Groundwater Wells in the Central Valley by use of Nitrogen, Oxygen, and Boron Isotopic Tracers

NASA Astrophysics Data System (ADS)

Lockhart, K.; Harter, T.; Grote, M.; Young, M. B.; Eppich, G.; Deinhart, A.; Wimpenny, J.; Yin, Q. Z.

2014-12-01

Groundwater quality is a concern in alluvial aquifers underlying agricultural areas worldwide, an example of which is the San Joaquin Valley, California. Nitrate from land applied fertilizers or from animal waste can leach to groundwater and contaminate drinking water resources. Dairy manure and synthetic fertilizers are the major sources of nitrate in groundwater in the San Joaquin Valley, however, septic waste can be a major source in some areas. As in other such regions around the world, the rural population in the San Joaquin Valley relies almost exclusively on shallow domestic wells (≤150 m deep), of which many have been affected by nitrate. Consumption of water containing nitrate above the drinking water limit has been linked to major health effects including low blood oxygen in infants and certain cancers. Knowledge of the proportion of each of the three main nitrate sources (manure, synthetic fertilizer, and septic waste) contributing to individual well nitrate can aid future regulatory decisions. Nitrogen, oxygen, and boron isotopes can be used as tracers to differentiate between the three main nitrate sources. Mixing models quantify the proportional contributions of sources to a mixture by using the concentration of conservative tracers within each source as a source signature. Deterministic mixing models are common, but do not allow for variability in the tracer source concentration or overlap of tracer concentrations between sources. Bayesian statistics used in conjunction with mixing models can incorporate variability in the source signature. We developed a Bayesian mixing model on a pilot network of 32 private domestic wells in the San Joaquin Valley for which nitrate as well as nitrogen, oxygen, and boron isotopes were measured. Probability distributions for nitrogen, oxygen, and boron isotope source signatures for manure, fertilizer, and septic waste were compiled from the literature and from a previous groundwater monitoring project on several dairies in the San Joaquin Valley. Median percent contribution of nitrate to wells from fertilizer, manure, and septic waste generally match the expected source based on land use patterns, with some exceptions.

Intra-shell boron isotope ratios in the symbiont-bearing benthic foraminiferan Amphistegina lobifera: Implications for δ 11B vital effects and paleo-pH reconstructions

NASA Astrophysics Data System (ADS)

Rollion-Bard, C.; Erez, J.

2010-03-01

The boron isotope composition of marine carbonates is considered to be a seawater pH proxy. Nevertheless, the use of δ 11B has some limitations such as the knowledge of the fractionation factor ( α4-3) between boric acid and the borate ion and the amplitude of "vital effects" on this proxy that are not well constrained. Using secondary ion mass spectrometry (SIMS) we have examined the internal variability of the boron isotope ratio in the shallow water, symbionts bearing foraminiferan Amphistegina lobifera. Specimens were cultured at constant temperature (24 ± 0.1 °C) in seawater with pH ranging between 7.90 and 8.45. Intra-shell boron isotopes showed large variability with an upper limit value of ≈30‰. Our results suggest that the fractionation factor α4-3 of 0.97352 ( Klochko et al., 2006) is in better agreement with our experiments and with direct pH measurements in seawater vacuoles associated with the biomineralization process in these foraminifera. Despite the large variability of the skeletal pH values in each cultured specimen, it is possible to link the lowest calculated pH values to the experimental culture pH values while the upper pH limit is slightly below 9. This variability can be interpreted as follows: foraminifera variably increase the pH at the biomineralization site to about 9. This increase above ambient seawater pH leads to a range in δ 11B (Δ 11B) for each seawater pH. This Δ 11B is linearly correlated with the culture seawater pH with a slope of -13.1 per pH unit, and is independent of the fractionation factor α4-3, or the δ 11B sw through time. It may also be independent of the p KB (the dissociation constant of boric acid) value. Therefore, Δ 11B in foraminifera can potentially reconstruct paleo-pH of seawater.

Source of boron in the Palokas gold deposit, northern Finland: evidence from boron isotopes and major element composition of tourmaline

NASA Astrophysics Data System (ADS)

Ranta, Jukka-Pekka; Hanski, Eero; Cook, Nick; Lahaye, Yann

2017-06-01

The recently discovered Palokas gold deposit is part of the larger Rompas-Rajapalot gold-mineralized system located in the Paleoproterozoic Peräpohja Belt, northern Finland. Tourmaline is an important gangue mineral in the Palokas gold mineralization. It occurs as tourmalinite veins and as tourmaline crystals in sulfide-rich metasomatized gold-bearing rocks. In order to understand the origin of tourmaline in the gold-mineralized rocks, we have investigated the major element chemistry and boron isotope composition of tourmaline from three areas: (1) the Palokas gold mineralization, (2) a pegmatitic tourmaline granite, and (3) the evaporitic Petäjäskoski Formation. Based on textural evidence, tourmaline in gold mineralization is divided into two different types. Type 1 is located within the host rock and is cut by rock-forming anthophyllite crystals. Type 2 occurs in late veins and/or breccia zones consisting of approximately 80% tourmaline and 20% sulfides, commonly adjacent to quartz veins. All the studied tourmaline samples belong to the alkali-group tourmaline and can be classified as dravite and schorl. The δ11B values of the three localities lie in the same range, from 0 to -4‰. Tourmaline from the Au mineralization and from the Petäjäskoski Formation has similar compositional trends. Mg is the major substituent for Al; inferred low Fe3+/Fe2+ ratios and Na values (<0.8 atoms per formula unit (apfu)) of all tourmaline samples suggest that they precipitated from reduced, low-salinity fluids. Based on the similar chemical and boron isotope composition and the Re-Os age of molybdenite related to the tourmaline-sulfide-quartz veins, we propose that the tourmaline-forming process is a result of a single magmatic-hydrothermal event related to the extensive granite magmatism at around 1.79-1.77 Ga. Tourmaline was crystallized throughout the hydrothermal process, which resulted in the paragenetic variation between type 1 and type 2. The close association of tourmaline and gold suggests that the gold precipitated from the same boron-rich source as tourmaline.

Precise and accurate isotope ratio measurements by ICP-MS.

PubMed

Becker, J S; Dietze, H J

2000-09-01

The precise and accurate determination of isotope ratios by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) is important for quite different application fields (e.g. for isotope ratio measurements of stable isotopes in nature, especially for the investigation of isotope variation in nature or age dating, for determining isotope ratios of radiogenic elements in the nuclear industry, quality assurance of fuel material, for reprocessing plants, nuclear material accounting and radioactive waste control, for tracer experiments using stable isotopes or long-lived radionuclides in biological or medical studies). Thermal ionization mass spectrometry (TIMS), which used to be the dominant analytical technique for precise isotope ratio measurements, is being increasingly replaced for isotope ratio measurements by ICP-MS due to its excellent sensitivity, precision and good accuracy. Instrumental progress in ICP-MS was achieved by the introduction of the collision cell interface in order to dissociate many disturbing argon-based molecular ions, thermalize the ions and neutralize the disturbing argon ions of plasma gas (Ar+). The application of the collision cell in ICP-QMS results in a higher ion transmission, improved sensitivity and better precision of isotope ratio measurements compared to quadrupole ICP-MS without the collision cell [e.g., for 235U/238U approximately 1 (10 microg x L(-1) uranium) 0.07% relative standard deviation (RSD) vs. 0.2% RSD in short-term measurements (n = 5)]. A significant instrumental improvement for ICP-MS is the multicollector device (MC-ICP-MS) in order to obtain a better precision of isotope ratio measurements (with a precision of up to 0.002%, RSD). CE- and HPLC-ICP-MS are used for the separation of isobaric interferences of long-lived radionuclides and stable isotopes by determination of spallation nuclide abundances in an irradiated tantalum target.

Comparisons of multiple isotope systems in the aragonitic shells of cultured Arctica islandica clams

NASA Astrophysics Data System (ADS)

Liu, Y. W.; Aciego, S.; Wanamaker, A. D.

2014-12-01

Previous work using oxygen and stable carbon isotopes from Arctica islandica shells has shown that this archive can provide information on past seawater temperatures, carbon cycling and ocean circulation. However, relatively less attention has been devoted to other "non-traditional" isotope systems within this proxy archive. In this study, we report the boron (δ11B) and strontium isotopic values (87Sr/86Sr and δ88/86Sr) from A. islandicashells collected and cultured from the Gulf of Maine. The long-lived ocean quahog, A. islandica was collected and cultured in the Gulf of Maine for 8 months. Our high-resolution δ11B records from the experiment show 5-7‰ of increase through the culture, with low values from January to May and higher values after May. The 87Sr/86Sr ratios from both tank water and shell samples suggest that the shell material reflects ambient ocean chemistry without interferences from terrestrial sources. Although It has been suggested that stable Sr isotopic ratios (δ88/86Sr) in biogenic carbonates are influenced by the temperature of the precipitating fluid, our nearly identical δ88/86Sr data do not support this hypothesis despite a 15 °C temperature change during the experiment. Based on the in-situ measurements of culture seawater temperature, salinity and pH, and two commonly used fractionation factors (α3-4) for corals and forams, we predicted the range in shell δ11B values for the experiment. Our boron results are at the extreme ends of the two prediction lines suggesting the potential usage of the bivalve shells as seawater pH indicator. However, the wider range in δ11B in this experiment than the predictions based on other carbonate organisms (only 2 to 3‰) suggests that a species-specific fractionation factor may be required. Recent work from an additional constant temperature experiment (10 and 15 °C) in the Gulf of Maine will allow us to further evaluate temperature influences and potential vital effects on the shell boron isotope values.

Boron Neutron Capture Therapy - A Literature Review

PubMed Central

Nedunchezhian, Kavitaa; Thiruppathy, Manigandan; Thirugnanamurthy, Sarumathi

2016-01-01

Boron Neutron Capture Therapy (BNCT) is a radiation science which is emerging as a hopeful tool in treating cancer, by selectively concentrating boron compounds in tumour cells and then subjecting the tumour cells to epithermal neutron beam radiation. BNCT bestows upon the nuclear reaction that occurs when Boron-10, a stable isotope, is irradiated with low-energy thermal neutrons to yield α particles (Helium-4) and recoiling lithium-7 nuclei. A large number of 10 Boron (10B) atoms have to be localized on or within neoplastic cells for BNCT to be effective, and an adequate number of thermal neutrons have to be absorbed by the 10B atoms to maintain a lethal 10B (n, α) lithium-7 reaction. The most exclusive property of BNCT is that it can deposit an immense dose gradient between the tumour cells and normal cells. BNCT integrates the fundamental focusing perception of chemotherapy and the gross anatomical localization proposition of traditional radiotherapy. PMID:28209015

Isotope heat source simulator for testing of space power systems

NASA Technical Reports Server (NTRS)

Prok, G. M.; Smith, R. B.

1973-01-01

A reliable isotope heat source simulator was designed for use in a Brayton power system. This simulator is composed of an electrically heated tungsten wire which is wound around a boron nitride core and enclosed in a graphite jacket. Simulator testing was performed at the expected operating temperature of the Brayton power system. Endurance testing for 5012 hours was followed by cycling the simulator temperature. The integrity of this simulator was maintained throughout testing. Alumina beads served as a diffusion barrier to prevent interaction between the tungsten heater and boron nitride core. The simulator was designed to maintain a surface temperature of 1311 to 1366 K (1900 to 2000 F) with a power input of approximately 400 watts. The design concept and the materials used in the simulator make possible man different geometries. This flexibility increases its potential use.

New tracers identify hydraulic fracturing fluids and accidental releases from oil and gas operations.

PubMed

Warner, N R; Darrah, T H; Jackson, R B; Millot, R; Kloppmann, W; Vengosh, A

2014-11-04

Identifying the geochemical fingerprints of fluids that return to the surface after high volume hydraulic fracturing of unconventional oil and gas reservoirs has important applications for assessing hydrocarbon resource recovery, environmental impacts, and wastewater treatment and disposal. Here, we report for the first time, novel diagnostic elemental and isotopic signatures (B/Cl, Li/Cl, δ11B, and δ7Li) useful for characterizing hydraulic fracturing flowback fluids (HFFF) and distinguishing sources of HFFF in the environment. Data from 39 HFFFs and produced water samples show that B/Cl (>0.001), Li/Cl (>0.002), δ11B (25-31‰) and δ7Li (6-10‰) compositions of HFFF from the Marcellus and Fayetteville black shale formations were distinct in most cases from produced waters sampled from conventional oil and gas wells. We posit that boron isotope geochemistry can be used to quantify small fractions (∼0.1%) of HFFF in contaminated fresh water and likely be applied universally to trace HFFF in other basins. The novel environmental application of this diagnostic isotopic tool is validated by examining the composition of effluent discharge from an oil and gas brine treatment facility in Pennsylvania and an accidental spill site in West Virginia. We hypothesize that the boron and lithium are mobilized from exchangeable sites on clay minerals in the shale formations during the hydraulic fracturing process, resulting in the relative enrichment of boron and lithium in HFFF.

DEVELOPMENT OF ISOTOPICALLY ENRICHED BORON-DOPED ALUMINA DOSIMETER FOR THERMAL NEUTRONS.

PubMed

Sato, Fuminobu; Maekawa, Tatsuro; Kariba, Tomoharu; Kusaka, Sachie; Tanaka, Teruya; Murata, Isao

2017-12-01

A novel optically stimulated luminescence (OSL) detector containing isotopically enriched boron was developed for thermal neutron dosimetry. Alumina containing isotopically enriched boron (Al2O3:B) was synthesised by the sol-gel method. The Al2O3:B was annealed up to ~1800 K. For X-ray diffractometer (XRD) analysis, the diffraction pattern of the Al2O3:B had reflex peaks corresponding to α-Al2O3. The sensitivity of Al2O3:B to photons was slightly 2% of that of a commercial Al2O3:C. The Al2O3:B detector had satisfactory linearity in X-ray dose measurement. A thermal neutron field was constructed using a 241Am-Be neutron source and graphite blocks. A pair of Al2O3:10B and Al2O3:11B detectors were set in the thermal neutron field. The response of Al2O3:10B was larger than that of Al2O3:11B owing to the 10B(n,α)7Li reactions. The sensitivity of Al2O3:10B to thermal neutrons was estimated to be two orders less than the photon sensitivity. Therefore, the pair of Al2O3:10B and Al2O3:11B detectors were useful for thermal neutron dosimetry. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Towards laser spectroscopy of the proton-halo candidate boron-8

NASA Astrophysics Data System (ADS)

Maaß, Bernhard; Müller, Peter; Nörtershäuser, Wilfried; Clark, Jason; Gorges, Christian; Kaufmann, Simon; König, Kristian; Krämer, Jörg; Levand, Anthony; Orford, Rodney; Sánchez, Rodolfo; Savard, Guy; Sommer, Felix

2017-11-01

We propose to determine the nuclear charge radius of 8B by high-resolution laser spectroscopy. 8B (t 1/2 = 770 ms) is perhaps the best candidate of a nucleus exhibiting an extended proton wave-function or "one-proton-halo" in a more descriptive picture. Laser spectroscopic measurements of the isotope shift will be used to probe the change in nuclear charge radius along the three boron isotopes 8B, 10B and 11B. The change in nuclear charge radius directly correlates with the extent of the proton wave function. In-flight production and preparation of sufficient yields of 8B ions at low energies is provided by the Argonne Tandem Linac Accelerator System (ATLAS) at Argonne National Laboratory (ANL) in Chicago, IL, USA. Subsequently, the ions will be guided through a charge exchange cell for neutralization and the fluorescence signal of the atoms which interact with the resonant laser light will be detected. The charge radius can then be extracted from the measured isotope shift by employing highly accurate atomic theory calculations of this five-electron system which are carried out presently.

THE ACCURATE DETERMINATION OF MICROGRAM AMOUNTS OF BORON IN ALUMINUM AND ALUMINUM-URANIUM ALLOYS BY THE METHYL BORATE-CURCUMIN-OXALIC ACID METHOD

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

Crocker, I.H.

1958-10-01

A method was developed for the deternninntion of boron in aluminum and aluminum--uranium alloys in which the boron concentration is 30 ppm or more. Boron is separated by distillation as methyl borate from a hydrochloric acid solution of the alloy and is determined spectrophotometrically by the boric acid-- curcumin-oxalic acid color reaction. A precision of plus or minus 2% is attain able when the determination is penformed with the utmost care. The accuracy is such that no bias need be given when a calibration curve is used. (auth)

Quantitative Determination of Isotope Ratios from Experimental Isotopic Distributions

PubMed Central

Kaur, Parminder; O’Connor, Peter B.

2008-01-01

Isotope variability due to natural processes provides important information for studying a variety of complex natural phenomena from the origins of a particular sample to the traces of biochemical reaction mechanisms. These measurements require high-precision determination of isotope ratios of a particular element involved. Isotope Ratio Mass Spectrometers (IRMS) are widely employed tools for such a high-precision analysis, which have some limitations. This work aims at overcoming the limitations inherent to IRMS by estimating the elemental isotopic abundance from the experimental isotopic distribution. In particular, a computational method has been derived which allows the calculation of 13C/12C ratios from the whole isotopic distributions, given certain caveats, and these calculations are applied to several cases to demonstrate their utility. The limitations of the method in terms of the required number of ions and S/N ratio are discussed. For high-precision estimates of the isotope ratios, this method requires very precise measurement of the experimental isotopic distribution abundances, free from any artifacts introduced by noise, sample heterogeneity, or other experimental sources. PMID:17263354

Processing and characterization of boron carbide-hafnium diboride ceramics

NASA Astrophysics Data System (ADS)

Brown-Shaklee, Harlan James

Hafnium diboride based ceramics are promising candidate materials for advanced aerospace and nuclear reactor components. The effectiveness of boron carbide and carbon as HfB2 sintering additives was systematically evaluated. In the first stage of the research, boron carbide and carbon additives were found to improve the densification behavior of milled HfB2 powder in part by removing oxides at the HfB2 surface during processing. Boron carbide additives reduced the hot pressing temperature of HfB2 by 150°C compared to carbon, which reduced the hot pressing temperature by ˜50°C. Reduction of oxide impurities alone could not explain the difference in sintering enhancement, however, and other mechanisms of enhancement were evaluated. Boron carbides throughout the homogeneity range were characterized to understand other mechanisms of sintering enhancement in HfB2. Heavily faulted carbon rich and boron rich boron carbides were synthesized for addition to HfB2. The greatest enhancement to densification was observed in samples containing boron- and carbon-rich compositions whereas B6.5 C provided the least enhancement to densification. It is proposed that carbon rich and boron rich boron carbides create boron and hafnium point defects in HfB2, respectively, which facilitate densification. Evaluation of the thermal conductivity (kth) between room temperature and 2000°C suggested that the stoichiometry of the boron carbide additives did not significantly affect kth of HfB2-BxC composites. The improved sinterability and the high kth (˜110 W/m-K at 300K and ˜90 W/m-K at 1000°C ) of HfB2-BxC ceramics make them excellent candidates for isotopically enriched reactor control materials.

Deciphering the Boron Proxy Records of the Paleocene-Eocene Thermal Maximum

NASA Astrophysics Data System (ADS)

Hoenisch, B.; Haynes, L.; Harper, D. T.; Penman, D. E.; Holland, K.; Rosenthal, Y.; Zachos, J. C.

2016-12-01

Rapid surface ocean acidification at the PETM has been documented by pronounced decreases in the boron isotope and B/Ca proxies measured in surface dwelling planktic foraminifera (Babila et al., 2016; Penman et al., 2014). However, translating these geochemical signatures to past seawater carbonate chemistry is challenging due to the different-from-modern elemental and isotopic composition of seawater, in addition to the lack of constraints on vital effects in foraminifer species that are now extinct. While the pH decrease can be reasonably quantified from boron isotopes, the application of modern laboratory calibrations to translate the B/Ca signal yields unfeasible estimates, thus raising questions about how well we understand fundamental proxy systematics. Here we present a possible solution to this conundrum from laboratory culture experiments performed under simulated Paleocene seawater conditions, with lower [B] and [Mg], higher [Ca] and across a range of dissolved inorganic carbon and pH. These experiments suggest that raising DIC in addition to acidification amplifies the B/Ca decrease recorded in planktic foraminifera shells, thus providing an opportunity to deconvolve the B/Ca record into pH and DIC signals. Using the boron proxy records in ODP 1209 from Shatsky Rise in the Pacific Ocean as a case study, we will perform a series of sensitivity studies to better constrain the carbon perturbation at the PETM, and the long-term evolution of surface ocean chemistry from the Paleocene into the Eocene. Our results will be compared to LOSCAR model estimates of different carbon input scenarios at the PETM. Babila, T.L., Rosenthal, Y., Wright, J.D. and Miller, K.G. (2016) A continental shelf perspective of ocean acidification and temperature evolution during the Paleocene-Eocene Thermal Maximum. Geology 44, 275-278. Penman, D.E., Hönisch, B., Zeebe, R.E., Thomas, E. and Zachos, J.C. (2014) Rapid and sustained surface ocean acidification during the Paleocene-Eocene Thermal Maximum. Paleoceanography 29, 2014PA002621.

Boron concentration measurements by alpha spectrometry and quantitative neutron autoradiography in cells and tissues treated with different boronated formulations and administration protocols.

PubMed

Bortolussi, Silva; Ciani, Laura; Postuma, Ian; Protti, Nicoletta; Luca Reversi; Bruschi, Piero; Ferrari, Cinzia; Cansolino, Laura; Panza, Luigi; Ristori, Sandra; Altieri, Saverio

2014-06-01

The possibility to measure boron concentration with high precision in tissues that will be irradiated represents a fundamental step for a safe and effective BNCT treatment. In Pavia, two techniques have been used for this purpose, a quantitative method based on charged particles spectrometry and a boron biodistribution imaging based on neutron autoradiography. A quantitative method to determine boron concentration by neutron autoradiography has been recently set-up and calibrated for the measurement of biological samples, both solid and liquid, in the frame of the feasibility study of BNCT. This technique was calibrated and the obtained results were cross checked with those of α spectrometry, in order to validate them. The comparisons were performed using tissues taken form animals treated with different boron administration protocols. Subsequently the quantitative neutron autoradiography was employed to measure osteosarcoma cell samples treated with BPA and with new boronated formulations. © 2013 Published by Elsevier Ltd.

Ultralow-loss polaritons in isotopically pure boron nitride.

PubMed

Giles, Alexander J; Dai, Siyuan; Vurgaftman, Igor; Hoffman, Timothy; Liu, Song; Lindsay, Lucas; Ellis, Chase T; Assefa, Nathanael; Chatzakis, Ioannis; Reinecke, Thomas L; Tischler, Joseph G; Fogler, Michael M; Edgar, J H; Basov, D N; Caldwell, Joshua D

2018-02-01

Conventional optical components are limited to size scales much larger than the wavelength of light, as changes to the amplitude, phase and polarization of the electromagnetic fields are accrued gradually along an optical path. However, advances in nanophotonics have produced ultrathin, so-called 'flat' optical components that beget abrupt changes in these properties over distances significantly shorter than the free-space wavelength. Although high optical losses still plague many approaches, phonon polariton (PhP) materials have demonstrated long lifetimes for sub-diffractional modes in comparison to plasmon-polariton-based nanophotonics. We experimentally observe a threefold improvement in polariton lifetime through isotopic enrichment of hexagonal boron nitride (hBN). Commensurate increases in the polariton propagation length are demonstrated via direct imaging of polaritonic standing waves by means of infrared nano-optics. Our results provide the foundation for a materials-growth-directed approach aimed at realizing the loss control necessary for the development of PhP-based nanophotonic devices.

Ultralow-loss polaritons in isotopically pure boron nitride

NASA Astrophysics Data System (ADS)

Giles, Alexander J.; Dai, Siyuan; Vurgaftman, Igor; Hoffman, Timothy; Liu, Song; Lindsay, Lucas; Ellis, Chase T.; Assefa, Nathanael; Chatzakis, Ioannis; Reinecke, Thomas L.; Tischler, Joseph G.; Fogler, Michael M.; Edgar, J. H.; Basov, D. N.; Caldwell, Joshua D.

2018-02-01

Conventional optical components are limited to size scales much larger than the wavelength of light, as changes to the amplitude, phase and polarization of the electromagnetic fields are accrued gradually along an optical path. However, advances in nanophotonics have produced ultrathin, so-called `flat' optical components that beget abrupt changes in these properties over distances significantly shorter than the free-space wavelength. Although high optical losses still plague many approaches, phonon polariton (PhP) materials have demonstrated long lifetimes for sub-diffractional modes in comparison to plasmon-polariton-based nanophotonics. We experimentally observe a threefold improvement in polariton lifetime through isotopic enrichment of hexagonal boron nitride (hBN). Commensurate increases in the polariton propagation length are demonstrated via direct imaging of polaritonic standing waves by means of infrared nano-optics. Our results provide the foundation for a materials-growth-directed approach aimed at realizing the loss control necessary for the development of PhP-based nanophotonic devices.

System and method for high precision isotope ratio destructive analysis

DOEpatents

Bushaw, Bruce A; Anheier, Norman C; Phillips, Jon R

2013-07-02

A system and process are disclosed that provide high accuracy and high precision destructive analysis measurements for isotope ratio determination of relative isotope abundance distributions in liquids, solids, and particulate samples. The invention utilizes a collinear probe beam to interrogate a laser ablated plume. This invention provides enhanced single-shot detection sensitivity approaching the femtogram range, and isotope ratios that can be determined at approximately 1% or better precision and accuracy (relative standard deviation).

Boron contents and isotopic compositions of hog manure, selected fertilizers, and water in Minnesota

USGS Publications Warehouse

Komor, S.C.

1997-01-01

Boron-isotope (δ11B) values may be useful as surrogate tracers of contaminants and indicators of water mixing in agricultural settings. This paper characterizes the B contents and isotopic compositions of hog manure and selected fertilizers, and presents δ11B data for ground and surface water from two agricultural areas. Boron concentrations in dry hog manure averaged 61 mg/kg and in commercial fertilizers ranged from below detection limits in some brands of ammonium nitrate and urea to 382 mg/kg in magnesium sulfate. Values of δ11B of untreated hog manure ranged from 7.2 to 11.2o/oo and of N fertilizers were −2.0 to 0.7o/oo. In 22 groundwater samples from a sand-plain aquifer in east-central Minnesota, B concentrations averaged 0.04 mg/L and δ11B values ranged from 2.3 to 41.5o/oo. Groundwater beneath a hog feedlot and a cultivated field where hog manure was applied had B-isotope compositions consistent with the water containing hog-manure leachate. In a 775-km2 watershed with silty-loam soils in southcentral Minnesota: 18 samples of subsurface drainage from corn (Zea mays L.) and soybean (Glycine max L. Merr.) fields had average B concentrations of 0.06 mg/L and δ11B values of 5.3 to 15.1o/oo; 27 stream samples had average B concentrations of 0.05 mg/L and δ11B values of 1.0 to 19.0o/oo; and eight groundwater samples had average B concentrations of 0.09 mg/L and δ11B values of −0.3 to 23.0o/oo. Values of δ11B and B concentrations, when plotted against one another, define a curved mixing trend that suggests subsurface drainage and stream water contain mixtures of B from shallow and deep groundwater.

Introducing the Precision Isotope Ratio Mass Spectrometer: Novel Innovations in Multi-Collector Arrays for Isotopologues and Isotopomers in Organic Molecule Gas Analysis

NASA Astrophysics Data System (ADS)

Kasson, A.

2016-12-01

In January 2016, elementar Analysensysteme, GmbH (Germany), in conjunction with their daughter company, Isoprime Ltd. (United Kingdom) released the Precision isotope ratio mass spectrometer. The Precision is the newest light element IRMS on the market and adds some unique hardware and software functionalities to the basic core of stable isotopic research previously unseen. Although this system is designed to make the typical bulk and compound specific measurements that functioning stable isotope laboratories have been accustomed to, it has been designed to make complicated measurements of isotopologues, isotopomers and clumped isotopes much more turnkey and user friendly. Here we focus on some datasets that have been collected from three different beta test sites and highlight the functional use of the new hardware in conjunction with ionOS operating software. As part of those highlights, the improved precision, accuracy and ion optics of the Precision IRMS will be demonstrated. In addition, we intend to show that the reprocessing functions on the ionOS software package are not only beneficial to users of just the Precision IRMS, but to the entire stable isotope community as a whole.

Modeling Issues and Results for Hydrogen Isotopes in NIF Materials

NASA Astrophysics Data System (ADS)

Grossman, Arthur A.; Doerner, R. P.; Luckhardt, S. C.; Seraydarian, R.; Sze, D.; Burnham, A.

1998-11-01

The TMAP4 (G. Longhurst, et al. INEL 1992) model of hydrogen isotope transport in solid materials includes a particle diffusion calculation with Fick's Law modified for Soret Effect (Thermal Diffusion or Thermomigration), coupled to heat transport calculations which are needed because of the strong temperature dependence of diffusivity. These TMAP4 calculations applied to NIF show that high temperatures approaching the melting point and strong thermal gradients of 10^6 K/cm are reached in the first micron of wall material during the SXR pulse. These strong thermal gradients can drive hydrogen isotope migration up or down the thermal gradient depending on the sign of the heat of transport (Soret coefficient) which depends on whether the material dissolves hydrogen endothermically or exothermically. Two candidates for NIF wall material-boron carbide and stainless steel are compared. Boron carbide dissolves hydrogen exothermically so it may drive Soret migration down the thermal gradient deeper into the material, although the thermal gradient is not as large and hydrogen is not as mobile as in stainless steel. Stainless steel dissolves hydrogen endothermically, with a negative Soret coefficient which can drive hydrogen up the thermal gradient and out of the wall.

A carbon isotope challenge to the snowball Earth.

PubMed

Sansjofre, P; Ader, M; Trindade, R I F; Elie, M; Lyons, J; Cartigny, P; Nogueira, A C R

2011-10-05

The snowball Earth hypothesis postulates that the planet was entirely covered by ice for millions of years in the Neoproterozoic era, in a self-enhanced glaciation caused by the high albedo of the ice-covered planet. In a hard-snowball picture, the subsequent rapid unfreezing resulted from an ultra-greenhouse event attributed to the buildup of volcanic carbon dioxide (CO(2)) during glaciation. High partial pressures of atmospheric CO(2) (pCO2; from 20,000 to 90,000 p.p.m.v.) in the aftermath of the Marinoan glaciation (∼635 Myr ago) have been inferred from both boron and triple oxygen isotopes. These pCO2 values are 50 to 225 times higher than present-day levels. Here, we re-evaluate these estimates using paired carbon isotopic data for carbonate layers that cap Neoproterozoic glacial deposits and are considered to record post-glacial sea level rise. The new data reported here for Brazilian cap carbonates, together with previous ones for time-equivalent units, provide estimates lower than 3,200 p.p.m.v.--and possibly as low as the current value of ∼400 p.p.m.v. Our new constraint, and our re-interpretation of the boron and triple oxygen isotope data, provide a completely different picture of the late Neoproterozoic environment, with low atmospheric concentrations of carbon dioxide and oxygen that are inconsistent with a hard-snowball Earth.

Precise and traceable carbon isotope ratio measurements by multicollector ICP-MS: what next?

PubMed

Santamaria-Fernandez, Rebeca

2010-06-01

This article reviews recent developments in the use of multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) to provide high-precision carbon isotope ratio measurements. MC-ICP-MS could become an alternative method to isotope ratio mass spectrometry (IRMS) for rapid carbon isotope ratio determinations in organic compounds and characterisation and certification of isotopic reference materials. In this overview, the advantages, drawbacks and potential of the method for future applications are critically discussed. Furthermore, suggestions for future improvements in terms of precision and sensitivity are made. No doubt, this is an exciting analytical challenge and, as such, hurdles will need to be cleared.

Experimental pressure-temperature phase diagram of boron: resolving the long-standing enigma

PubMed Central

Parakhonskiy, Gleb; Dubrovinskaia, Natalia; Bykova, Elena; Wirth, Richard; Dubrovinsky, Leonid

2011-01-01

Boron, discovered as an element in 1808 and produced in pure form in 1909, has still remained the last elemental material, having stable natural isotopes, with the ground state crystal phase to be unknown. It has been a subject of long-standing controversy, if α-B or β-B is the thermodynamically stable phase at ambient pressure and temperature. In the present work this enigma has been resolved based on the α-B-to- β-B phase boundary line which we experimentally established in the pressure interval of ∼4 GPa to 8 GPa and linearly extrapolated down to ambient pressure. In a series of high pressure high temperature experiments we synthesised single crystals of the three boron phases (α-B, β-B, and γ-B) and provided evidence of higher thermodynamic stability of α-B. Our work opens a way for reproducible synthesis of α-boron, an optically transparent direct band gap semiconductor with very high hardness, thermal and chemical stability. PMID:22355614

Pb and Sr isotope measurements by inductively coupled plasma mass spectrometer: efficient time management for precision improvement

NASA Astrophysics Data System (ADS)

Monna, F.; Loizeau, J.-L.; Thomas, B. A.; Guéguen, C.; Favarger, P.-Y.

1998-08-01

One of the factors limiting the precision of inductively coupled plasma mass spectrometry is the counting statistics, which depend upon acquisition time and ion fluxes. In the present study, the precision of the isotopic measurements of Pb and Sr is examined. The time of measurement is optimally shared for each isotope, using a mathematical simulation, to provide the lowest theoretical analytical error. Different algorithms of mass bias correction are also taken into account and evaluated in term of improvement of overall precision. Several experiments allow a comparison of real conditions with theory. The present method significantly improves the precision, regardless of the instrument used. However, this benefit is more important for equipment which originally yields a precision close to that predicted by counting statistics. Additionally, the procedure is flexible enough to be easily adapted to other problems, such as isotopic dilution.

Inter-comparison of boron concentration measurements at INFN-University of Pavia (Italy) and CNEA (Argentina).

PubMed

Portu, Agustina; Postuma, Ian; Gadan, Mario Alberto; Saint Martin, Gisela; Olivera, María Silvina; Altieri, Saverio; Protti, Nicoletta; Bortolussi, Silva

2015-11-01

An inter-comparison of three boron determination techniques was carried out between laboratories from INFN-University of Pavia (Italy) and CNEA (Argentina): alpha spectrometry (alpha-spect), neutron capture radiography (NCR) and quantitative autoradiography (QTA). Samples of different nature were analysed: liquid standards, liver homogenates and tissue samples from different treatment protocols. The techniques showed a good agreement in a concentration range of interest in BNCT (1-100ppm), thus demonstrating their applicability as precise methods to quantify boron and determine its distribution in tissues. Copyright © 2015 Elsevier Ltd. All rights reserved.

Precision Measurement of the Boron to Carbon Flux Ratio in Cosmic Rays from 1.9 GV to 2.6 TV with the Alpha Magnetic Spectrometer on the International Space Station

NASA Astrophysics Data System (ADS)

Aguilar, M.; Ali Cavasonza, L.; Ambrosi, G.; Arruda, L.; Attig, N.; Aupetit, S.; Azzarello, P.; Bachlechner, A.; Barao, F.; Barrau, A.; Barrin, L.; Bartoloni, A.; Basara, L.; Başeǧmez-du Pree, S.; Battarbee, M.; Battiston, R.; Becker, U.; Behlmann, M.; Beischer, B.; Berdugo, J.; Bertucci, B.; Bindel, K. F.; Bindi, V.; Boella, G.; de Boer, W.; Bollweg, K.; Bonnivard, V.; Borgia, B.; Boschini, M. J.; Bourquin, M.; Bueno, E. F.; Burger, J.; Cadoux, F.; Cai, X. D.; Capell, M.; Caroff, S.; Casaus, J.; Castellini, G.; Cervelli, F.; Chae, M. J.; Chang, Y. H.; Chen, A. I.; Chen, G. M.; Chen, H. S.; Cheng, L.; Chou, H. Y.; Choumilov, E.; Choutko, V.; Chung, C. H.; Clark, C.; Clavero, R.; Coignet, G.; Consolandi, C.; Contin, A.; Corti, C.; Creus, W.; Crispoltoni, M.; Cui, Z.; Dai, Y. M.; Delgado, C.; Della Torre, S.; Demakov, O.; Demirköz, M. B.; Derome, L.; Di Falco, S.; Dimiccoli, F.; Díaz, C.; von Doetinchem, P.; Dong, F.; Donnini, F.; Duranti, M.; D'Urso, D.; Egorov, A.; Eline, A.; Eronen, T.; Feng, J.; Fiandrini, E.; Finch, E.; Fisher, P.; Formato, V.; Galaktionov, Y.; Gallucci, G.; García, B.; García-López, R. J.; Gargiulo, C.; Gast, H.; Gebauer, I.; Gervasi, M.; Ghelfi, A.; Giovacchini, F.; Goglov, P.; Gómez-Coral, D. M.; Gong, J.; Goy, C.; Grabski, V.; Grandi, D.; Graziani, M.; Guo, K. H.; Haino, S.; Han, K. C.; He, Z. H.; Heil, M.; Hoffman, J.; Hsieh, T. H.; Huang, H.; Huang, Z. C.; Huh, C.; Incagli, M.; Ionica, M.; Jang, W. Y.; Jinchi, H.; Kang, S. C.; Kanishev, K.; Kim, G. N.; Kim, K. S.; Kirn, Th.; Konak, C.; Kounina, O.; Kounine, A.; Koutsenko, V.; Krafczyk, M. S.; La Vacca, G.; Laudi, E.; Laurenti, G.; Lazzizzera, I.; Lebedev, A.; Lee, H. T.; Lee, S. C.; Leluc, C.; Li, H. S.; Li, J. Q.; Li, J. Q.; Li, Q.; Li, T. X.; Li, W.; Li, Y.; Li, Z. H.; Li, Z. Y.; Lim, S.; Lin, C. H.; Lipari, P.; Lippert, T.; Liu, D.; Liu, Hu; Lordello, V. D.; Lu, S. Q.; Lu, Y. S.; Luebelsmeyer, K.; Luo, F.; Luo, J. Z.; Lv, S. S.; Machate, F.; Majka, R.; Mañá, C.; Marín, J.; Martin, T.; Martínez, G.; Masi, N.; Maurin, D.; Menchaca-Rocha, A.; Meng, Q.; Mikuni, V. M.; Mo, D. C.; Morescalchi, L.; Mott, P.; Nelson, T.; Ni, J. Q.; Nikonov, N.; Nozzoli, F.; Oliva, A.; Orcinha, M.; Palmonari, F.; Palomares, C.; Paniccia, M.; Pauluzzi, M.; Pensotti, S.; Pereira, R.; Picot-Clemente, N.; Pilo, F.; Pizzolotto, C.; Plyaskin, V.; Pohl, M.; Poireau, V.; Putze, A.; Quadrani, L.; Qi, X. M.; Qin, X.; Qu, Z. Y.; Räihä, T.; Rancoita, P. G.; Rapin, D.; Ricol, J. S.; Rosier-Lees, S.; Rozhkov, A.; Rozza, D.; Sagdeev, R.; Sandweiss, J.; Saouter, P.; Schael, S.; Schmidt, S. M.; Schulz von Dratzig, A.; Schwering, G.; Seo, E. S.; Shan, B. S.; Shi, J. Y.; Siedenburg, T.; Son, D.; Song, J. W.; Sun, W. H.; Tacconi, M.; Tang, X. W.; Tang, Z. C.; Tao, L.; Tescaro, D.; Ting, Samuel C. C.; Ting, S. M.; Tomassetti, N.; Torsti, J.; Türkoǧlu, C.; Urban, T.; Vagelli, V.; Valente, E.; Vannini, C.; Valtonen, E.; Vázquez Acosta, M.; Vecchi, M.; Velasco, M.; Vialle, J. P.; Vitale, V.; Vitillo, S.; Wang, L. Q.; Wang, N. H.; Wang, Q. L.; Wang, X.; Wang, X. Q.; Wang, Z. X.; Wei, C. C.; Weng, Z. L.; Whitman, K.; Wienkenhöver, J.; Wu, H.; Wu, X.; Xia, X.; Xiong, R. Q.; Xu, W.; Yan, Q.; Yang, J.; Yang, M.; Yang, Y.; Yi, H.; Yu, Y. J.; Yu, Z. Q.; Zeissler, S.; Zhang, C.; Zhang, J.; Zhang, J. H.; Zhang, S. D.; Zhang, S. W.; Zhang, Z.; Zheng, Z. M.; Zhu, Z. Q.; Zhuang, H. L.; Zhukov, V.; Zichichi, A.; Zimmermann, N.; Zuccon, P.; AMS Collaboration

2016-12-01

Knowledge of the rigidity dependence of the boron to carbon flux ratio (B/C) is important in understanding the propagation of cosmic rays. The precise measurement of the B /C ratio from 1.9 GV to 2.6 TV, based on 2.3 million boron and 8.3 million carbon nuclei collected by AMS during the first 5 years of operation, is presented. The detailed variation with rigidity of the B /C spectral index is reported for the first time. The B /C ratio does not show any significant structures in contrast to many cosmic ray models that require such structures at high rigidities. Remarkably, above 65 GV, the B /C ratio is well described by a single power law RΔ with index Δ =-0.333 ±0.014 (fit ) ±0.005 (syst ) , in good agreement with the Kolmogorov theory of turbulence which predicts Δ =-1 /3 asymptotically.

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

Hitchcock, D.; Colon-Mercado, H.; Krentz, T.

Hydrogen isotope separation is critical to the DOE’s mission in environmental remediation and nuclear nonproliferation. Isotope separation is also a critical technology for the NNSA, and the ability to perform the separations at room temperature with a relatively small amount of power and space would be a major advancement for their respective missions. Recent work has shown that 2-D materials such as graphene and hexagonal boron nitride can act as an isotopic sieve at room temperature; efficiently separating hydrogen isotopes in water with reported separation ratios of 10:1 for hydrogen: deuterium separation for a single pass. The work performed heremore » suggests that this technique has merit, and furthermore, we are investigating optimization and scale up of the required 2-D material based membranes.« less

Subcellular SIMS imaging of isotopically labeled amino acids in cryogenically prepared cells

NASA Astrophysics Data System (ADS)

Chandra, Subhash

2004-06-01

Ion microscopy is a potentially powerful technique for localization of isotopically labeled molecules. In this study, L-arginine and phenylalanine amino acids labeled with stable isotopes 13C and 15N were localized in cultured cells with the ion microscope at 500 nm spatial resolution. Cells were exposed to the labeled amino acids and cryogenically prepared. SIMS analyses were made in fractured freeze-dried cells. A dynamic distribution was observed from labeled arginine-treated LLC-PK 1 kidney cells at mass 28 ( 13C15N) in negative secondaries, revealing cell-to-cell heterogeneity and preferential accumulation of the amino acid (or its metabolite) in the nucleus and nucleolus of some cells. The smaller nucleolus inside the nucleus was clearly resolved in SIMS images and confirmed by correlative light microscopy. The distribution of labeled phenylalanine contrasted with arginine as it was rather homogeneously distributed in T98G human glioblastoma cells. Images of 39K, 23Na and 40Ca were also recorded to confirm the reliability of sample preparation and authenticity of the observed amino acid distributions. These observations indicate that SIMS techniques can provide a valuable technology for subcellular localization of nitrogen-containing molecules in proteomics since nitrogen does not have a radionuclide tracer isotope. Amino acids labeled with stable isotopes can be used as tracers for studying their transport and metabolism in distinct subcellular compartments with SIMS. Further studies of phenylalanine uptake in human glioblastoma cells may have special significance in boron neutron capture therapy (BNCT) as a boron analogue of phenylalanine, boronophenylalanine is a clinically approved compound for the treatment of brain tumors.

Biomonitoring of boron: Development and characterization of a simple, reliable and quality controlled biomonitoring method.

PubMed

Michalke, Bernhard

2017-03-01

Boron exposure is of interest and concern from an occupational point of view. Usual daily boron intake is related to boron blood plasma concentration <1mg/L and to <3mg/L in urine, but after exposure urine concentrations are quickly elevated. Reliable boron biomonitoring, typically in urine, thus is mandatory for occupational health control institutions. This paper reports on the development of a simple, fast and reliable boron determination procedure based on inductively coupled plasma - optical emission spectrometry (ICP-OES). Major aims for this method were simplicity in sample preparation, low risk for artifacts and interferences, high precision and accuracy, possibly low costs, including lower costs for element selective detection, short total analysis time and suitability for occupational health laboratories. Precision data (serial or day-to-day) from urine and doped urine were very good: <1.5 or <2%. Accuracy was calculated from analysis of a certified reference material (ERM-CD 281), as 99% or according to recoveries of doped concentrations ranging from 102 to 109% recovery. For cross-checking ICP-OES determinations, samples were analyzed also by quadrupole ICP-qMS and by sectorfield ICP-sf-MS at low and medium resolution. Both systems confirmed ICP-OES measurements when using 11 B for quantification. Determinations based on 10 B however showed some bias, except with ICP-sf-MS at medium resolution. The observed elevated signals are discussed with respect to the known Ne ++ interference (as an impurity in Ar), which is not separated in low resolving quadrupole ICP-MS systems or ICP-sf-MS at low resolution. Copyright © 2016 Elsevier GmbH. All rights reserved.

Environmental controls on the boron and strontium isotopic composition of aragonite shell material of cultured Arctica islandica

NASA Astrophysics Data System (ADS)

Liu, Y.-W.; Aciego, S. M.; Wanamaker, A. D., Jr.

2015-06-01

Ocean acidification, the decrease in ocean pH associated with increasing atmospheric CO2, is likely to impact marine organisms, particularly those that produce carbonate skeletons or shells. Therefore, it is important to investigate how environmental factors (seawater pH, temperature and salinity) influence the chemical compositions in biogenic carbonates. In this study we report the first high-resolution strontium (87Sr / 86Sr and δ88 / 86Sr) and boron (δ11B) isotopic values in the aragonite shell of cultured Arctica islandica (A. islandica). The 87Sr / 86Sr ratios from both tank water and shell samples show ratios nearly identical to the open ocean, which suggests that the shell material reflects ambient ocean chemistry without terrestrial influence. The 84Sr-87Sr double-spike-resolved shell δ88 / 86Sr and Sr concentration data show no resolvable change throughout the culture period and reflect no theoretical kinetic mass fractionation throughout the experiment despite a temperature change of more than 15 °C. The δ11B records from the experiment show at least a 5‰ increase through the 29-week culture season (January 2010-August 2010), with low values from the beginning to week 19 and higher values thereafter. The larger range in δ11B in this experiment compared to predictions based on other carbonate organisms (2-3‰) suggests that a species-specific fractionation factor may be required. A significant correlation between the ΔpH (pHshell - pHsw) and seawater pH (pHsw) was observed (R2 = 0.35), where the pHshell is the calcification pH of the shell calculated from boron isotopic composition. This negative correlation suggests that A. islandica partly regulates the pH of the extrapallial fluid. However, this proposed mechanism only explains approximately 35% of the variance in the δ11B data. Instead, a rapid rise in δ11B of the shell material after week 19, during the summer, suggests that the boron uptake changes when a thermal threshold of > 13 °C is reached.

Ultralow-loss polaritons in isotopically pure boron nitride

DOE PAGES

Giles, Alexander J.; Dai, Siyuan; Vurgaftman, Igor; ...

2017-12-11

Conventional optical components are limited to size scales much larger than the wavelength of light, as changes to the amplitude, phase and polarization of the electromagnetic fields are accrued gradually along an optical path. However, advances in nanophotonics have produced ultrathin, so-called ‘flat’ optical components that beget abrupt changes in these properties over distances significantly shorter than the free-space wavelength. Although high optical losses still plague many approaches, phonon polariton (PhP) materials have demonstrated long lifetimes for sub-diffractional modes in comparison to plasmon-polariton-based nanophotonics. We experimentally observe a threefold improvement in polariton lifetime through isotopic enrichment of hexagonal boron nitridemore » (hBN). Commensurate increases in the polariton propagation length are demonstrated via direct imaging of polaritonic standing waves by means of infrared nano-optics. Lastly, our results provide the foundation for a materials-growth-directed approach aimed at realizing the loss control necessary for the development of PhP-based nanophotonic devices.« less

Ultralow-loss polaritons in isotopically pure boron nitride

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

Giles, Alexander J.; Dai, Siyuan; Vurgaftman, Igor

Conventional optical components are limited to size scales much larger than the wavelength of light, as changes to the amplitude, phase and polarization of the electromagnetic fields are accrued gradually along an optical path. However, advances in nanophotonics have produced ultrathin, so-called ‘flat’ optical components that beget abrupt changes in these properties over distances significantly shorter than the free-space wavelength. Although high optical losses still plague many approaches, phonon polariton (PhP) materials have demonstrated long lifetimes for sub-diffractional modes in comparison to plasmon-polariton-based nanophotonics. We experimentally observe a threefold improvement in polariton lifetime through isotopic enrichment of hexagonal boron nitridemore » (hBN). Commensurate increases in the polariton propagation length are demonstrated via direct imaging of polaritonic standing waves by means of infrared nano-optics. Lastly, our results provide the foundation for a materials-growth-directed approach aimed at realizing the loss control necessary for the development of PhP-based nanophotonic devices.« less

Fusion reactions initiated by laser-accelerated particle beams in a laser-produced plasma.

PubMed

Labaune, C; Baccou, C; Depierreux, S; Goyon, C; Loisel, G; Yahia, V; Rafelski, J

2013-01-01

The advent of high-intensity-pulsed laser technology enables the generation of extreme states of matter under conditions that are far from thermal equilibrium. This in turn could enable different approaches to generating energy from nuclear fusion. Relaxing the equilibrium requirement could widen the range of isotopes used in fusion fuels permitting cleaner and less hazardous reactions that do not produce high-energy neutrons. Here we propose and implement a means to drive fusion reactions between protons and boron-11 nuclei by colliding a laser-accelerated proton beam with a laser-generated boron plasma. We report proton-boron reaction rates that are orders of magnitude higher than those reported previously. Beyond fusion, our approach demonstrates a new means for exploring low-energy nuclear reactions such as those that occur in astrophysical plasmas and related environments.

East Europe Report, Political, Sociological and Military Affairs, No. 2151.

DTIC Science & Technology

1983-06-10

precisely. A 183-person PRON Provincial Council, elected by the congress, whose chairman will be Piotr Boron will concern itself with that. Also... Piotr Boron. He expressed the hope that thanks to the collective cooperation of all council members, PRON will achieve its goals. The professor...Znaniecki and the following who had been elected at regional conferences: Walenty Astramowicz, Marcin Blaszczak, Waldemar Brzezinski , Zenon Czarniecki, Ewa

Calcium Isotope (δ44/40Ca) Composition of Morozovella Velascoensis During the Paleocene Eocene Thermal Maximum Ocean Acidification Event

NASA Astrophysics Data System (ADS)

Kitch, G. D.; Jacobson, A. D.; Hurtgen, M.; Sageman, B. B.; Harper, D. T.; Zachos, J. C.

2017-12-01

Ocean acidification (OA) events are transient disruptions to the carbonate chemistry of seawater that involve decreases in pH, [CO32-] and carbonate mineral saturation states (Ω). Numerical modeling studies predict that the Ca isotope (δ44/40Ca) composition of primary marine carbonate should be sensitive to OA1, and recent evidence from the rock record may support this hypothesis2. Boron isotope (δ11B) data for the planktonic foraminifera Morozovella velascoensis indicate that the Paleocene-Eocene Thermal Maximum (PETM; 55 Mya) was an interval of pronounced OA3, although the Ca isotope composition of the bulk carbonate record appears to show post-burial diagenetic effects4. To further evaluate the Ca isotope proxy, we used a high-precision (2σSD=±0.04‰), double-spike (43Ca-42Ca) TIMS method5 to measure δ44/40Ca values of well-preserved M. velascoensis tests spanning the PETM. M. velascoensis tests (250-355 µm) were picked from samples recovered during ODP Leg 198, Site 1209 on Shatsky Rise in the equatorial Pacific. Five M. velascoensis tests were combined per sample, dissolved, spiked, and analyzed using a Triton TIMS. Repeat dissolutions of ten samples gave δ44/40Ca values within ±0.04‰ of the original measurements. Method and procedural blanks were negligible. δ44/40Ca values are elevated, even before the negative carbon isotope excursion (CIE) that marks the PETM. When δ11/10B values decrease during the CIE, δ44/40Ca values remain elevated, but then decrease by 0.10‰ as δ11B values return to pre-CIE levels. The apparent inverse correlation between δ44/40Ca and δ11B values suggests that Ca isotope fractionation by M. velascoensis was sensitive to OA. A decrease in pH indicated by lower δ11B values is consistent with higher δ44/40Ca values (decreased fractionation) due to elevated [Ca2+]/[CO32-] ratios and reduced W. The Ca isotope composition of pristine foraminiferal calcite may have potential for reconstructing [CO32-]. The current, preliminary dataset may indicate changes in [CO32-] prior to the CIE. 1Nielsen et al., 2012. 2Du Vivier et al., 2015. 3Penman et al., 2014. 4Griffith et al., 2015. 5Lehn et al., 2013.

Lithium isotope as a proxy for water/rock interaction between hydrothermal fluids and oceanic crust at Milos, Greece

NASA Astrophysics Data System (ADS)

Lou, U.-Lat; You, Chen-Feng; Wu, Shein-Fu; Chung, Chuan-Hsiung

2014-05-01

Hydrothermal activity at Milos in the Aegean island (Greece) is mainly located at rather shallow depth (about 5 m). It is interesting to compare these chemical compositions and the evolution processes of the hydrothermal fluids at deep sea hydrothermal vents in Mid-ocean Ridge (MOR). Lithium (Li) is a highly mobile element and its isotopic composition varies at different geological settings. Therefore, Li and its isotope could be used as an indicator for many geochemical processes. Since 6Li preferential retained in the mineral phase where 7Li is leached into fluid phase during basalt alteration, the Li isotopic fractionation between the rocks and the fluids reflect sensitively the degree of water-rock interaction. In this study, Bio-Rad AG-50W X8 cation exchange resin was used for purifying the hydrothermal fluids to separate Li from other matrix elements. The Li isotopic composition (δ7Li) was determined by Multi-collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS) with precision better than 0.2‰ (2σ, n=20). The Li concentration in the hydrothermal fluids falls between 0.02 to 10.31 mM. The δ7Li values vary from +1.9 to +29.7‰, indicating significant seawater contamination have occurred. These hydrothermal fluids fit well with seawater and brine two end-member binary mixing model. During phase separation, lithium, boron, chlorine, iodine, bromine, sodium and potassium were enriched in the brine phase. On the other hand, aluminum, sulphur and iron were enriched in the vapor phase. There is no significant isotope fractionation between the two phases. The water/rock ratio (W/R) calculated is low (about 1.5 to 1.8) for the Milos fluids, restricted seawater recharge into the oceanic crust. Moreover, the oceanic crust in the region becomes less altered since the W/R is low. The δ7Li value of the hydrothermal fluids can be used as a sensitive tool for studying water-rock interaction.

An Assessment of the Potential Use of BNNTs for Boron Neutron Capture Therapy.

PubMed

Ferreira, Tiago H; Miranda, Marcelo C; Rocha, Zildete; Leal, Alexandre S; Gomes, Dawidson A; Sousa, Edesia M B

2017-04-12

Currently, nanostructured compounds have been standing out for their optical, mechanical, and chemical features and for the possibilities of manipulation and regulation of complex biological processes. One of these compounds is boron nitride nanotubes (BNNTs), which are a nanostructured material analog to carbon nanotubes, but formed of nitrogen and boron atoms. BNNTs present high thermal stability along with high chemical inertia. Among biological applications, its biocompatibility, cellular uptake, and functionalization potential can be highlighted, in addition to its eased utilization due to its nanometric size and tumor cell internalization. When it comes to new forms of therapy, we can draw attention to boron neutron capture therapy (BNCT), an experimental radiotherapy characterized by a boron-10 isotope carrier inside the target and a thermal neutron beam focused on it. The activation of the boron-10 atom by a neutron generates a lithium atom, a gamma ray, and an alpha particle, which can be used to destroy tumor tissues. The aim of this work was to use BNNTs as a boron-10 carrier for BNCT and to demonstrate its potential. The nanomaterial was characterized through XRD, FTIR, and SEM. The WST-8 assay was performed to confirm the cell viability of BNNTs. The cells treated with BNNTs were irradiated with the neutron beam of a Triga reactor, and the apoptosis caused by the activation of the BNNTs was measured with a calcein AM/propidium iodide test. The results demonstrate that this nanomaterial is a promising candidate for cancer therapy through BNCT.

Atomic composition and electrical characteristics of epitaxial CVD diamond layers doped with boron

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

Surovegina, E. A., E-mail: suroveginaka@ipmras.ru; Demidov, E. V.; Drozdov, M. N.

2016-12-15

The results of analysis of the atomic composition, doping level, and hole mobility in epitaxial diamond layers when doped with boron are reported. The layers are produced by chemical-vapor deposition. The possibilities of uniform doping with boron to a level in the range 5 × 10{sup 17} to ~10{sup 20} at cm{sup –3} and of δ doping to the surface concentration (0.3–5) × 10{sup 13} at cm{sup –3} are shown. The conditions for precision ion etching of the structures are determined, and barrier and ohmic contacts to the layers are formed.

Waste-water characterization/hazardous-waste survey, Beale Air Force Base, California. Final report, 12-26 September 1988

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

Attebery, C.W.; Zimmer, A.T.; Hedgecock, N.S.

1989-01-01

A waste-water characterization hazardous-waste survey was conducted at Beale AFB by USAFOEHL/ECQ personnel to provide the base with sufficient information to address a State of California Notice of Violation concerning excessive discharges of boron and cyanide from the base sewage-treatment plant (STP). The results of the survey showed that the 9th RTS Precision Photo Lab along with other film-processing organizations were major contributors to the boron and cyanide discharge problems being experienced by the base STP. Maintenance organizations that utilize soaps and detergents that contain boron and cyanide also contributed to the problem.

Development of a calibration for the B isotope paleo-pH proxy in the deep sea coral Desmophyllum dianthus

NASA Astrophysics Data System (ADS)

Anagnostou, E.; Huang, K.; You, C.; Sherrell, R. M.

2011-12-01

The boron isotope ratio (δ11B) of foraminifera and coral carbonate has been proposed to record seawater pH. Here we test this pH proxy in the deep sea coral Desmophyllum dianthus (D. dianthus ). This coral species is cosmopolitan in geographic distribution and tolerates a wide temperature and depth range. Previous studies have shown that fossil D. dianthus skeletons can be dated precisely with U/Th measurements. Additionally, skeletal mass is sufficient for multiple elemental, isotopic, and radiocarbon measurements per sample making it a powerful candidate for paleoceanographic reconstructions. Ten modern corals from a depth range of 274-1470m in the Atlantic, Pacific, and Southern Oceans were analyzed using the sublimation method and multi-collector ICP-MS (Neptune), and the measured δ11B was regressed against ambient pH taken from hydrographic data sets (range pH 7.6 to 8.1). Replicate skeletal subsamples from a single coral agree within 0.35% (2SD). The array of δ11B values for these corals plots above the seawater borate δ11B vs. pH curve (Klochko et al., 2006) by an apparently constant value of 11.7 ± 1.2%, well above the range of values seen in foraminifera and surface corals. This offset is attributed to either partial incorporation of boric acid from seawater or, more likely, to physiological manipulation of the calcifying fluid to pH 8.7-9.0. The uncertainty in calculation of seawater pH from δ11B, dominated by the uncertainty in the offset value, currently limits the precision of absolute pH reconstructions to ±0.09pH units. However, the empirical calibration could be used to examine relative pH changes, thereby overcoming contributions to the uncertainty in the offset that result from the calculation of the empirical fractionation factor α and from sampling bias and variable vital effects among individuals, reducing the reconstruction error envelope. This study provides the first evidence that δ11B in D. dianthus has the potential to record ambient seawater pH.

Isotope-abundance variations and atomic weights of selected elements: 2016 (IUPAC Technical Report)

USGS Publications Warehouse

Coplen, Tyler B.; Shrestha, Yesha

2016-01-01

There are 63 chemical elements that have two or more isotopes that are used to determine their standard atomic weights. The isotopic abundances and atomic weights of these elements can vary in normal materials due to physical and chemical fractionation processes (not due to radioactive decay). These variations are well known for 12 elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, magnesium, silicon, sulfur, chlorine, bromine, and thallium), and the standard atomic weight of each of these elements is given by IUPAC as an interval with lower and upper bounds. Graphical plots of selected materials and compounds of each of these elements have been published previously. Herein and at the URL http://dx.doi.org/10.5066/F7GF0RN2, we provide isotopic abundances, isotope-delta values, and atomic weights for each of the upper and lower bounds of these materials and compounds.

Structure and Growth of Hexagonal Boron Nitride on Ir(111).

PubMed

Farwick Zum Hagen, Ferdinand H; Zimmermann, Domenik M; Silva, Caio C; Schlueter, Christoph; Atodiresei, Nicolae; Jolie, Wouter; Martínez-Galera, Antonio J; Dombrowski, Daniela; Schröder, Ulrike A; Will, Moritz; Lazić, Predrag; Caciuc, Vasile; Blügel, Stefan; Lee, Tien-Lin; Michely, Thomas; Busse, Carsten

2016-12-27

Using the X-ray standing wave method, scanning tunneling microscopy, low energy electron diffraction, and density functional theory, we precisely determine the lateral and vertical structure of hexagonal boron nitride on Ir(111). The moiré superstructure leads to a periodic arrangement of strongly chemisorbed valleys in an otherwise rather flat, weakly physisorbed plane. The best commensurate approximation of the moiré unit cell is (12 × 12) boron nitride cells resting on (11 × 11) substrate cells, which is at variance with several earlier studies. We uncover the existence of two fundamentally different mechanisms of layer formation for hexagonal boron nitride, namely, nucleation and growth as opposed to network formation without nucleation. The different pathways are linked to different distributions of rotational domains, and the latter enables selection of a single orientation only.

From Urey To The Ocean's Glacial Ph: News From The Boron-11 Paleo-acidimetry.

NASA Astrophysics Data System (ADS)

Zeebe, R. E.; Wolf-Gladrow, D. A.; Bijma, J.

Boron paleo-acidimetry is based on the stable boron isotope composition of foraminiferal shells which has been shown to be a function of seawater pH. It is cur- rently one of the most promising paleo-carbonate chemistry proxies. One important parameter of the proxy is the equilibrium fractionation between the dissolved boron species B(OH)3 and B(OH)- which was calculated to be 19 per mil at 25C by Kak- 4 ihana and Kotaka (1977), based on Urey's theory. The calculated equilibrium frac- tionation, however, depends on the vibrational frequencies of the molecules for which different values have been reported in the literature. We have recalculated the equilib- rium fractionation and find that it may be distinctly different from 19 per mil (this is the bad news). The good news is that - theoretically - the use of 11B as a paleo-pH indicator is not compromised through vital effects in planktonic foraminifera. We de- rive this conclusion by the use of a diffusion-reaction model that calculates pH profiles and 11B values in the vicinity of a foraminifer.

Precision Measurement of the Boron to Carbon Flux Ratio in Cosmic Rays from 1.9 GV to 2.6 TV with the Alpha Magnetic Spectrometer on the International Space Station.

PubMed

Aguilar, M; Ali Cavasonza, L; Ambrosi, G; Arruda, L; Attig, N; Aupetit, S; Azzarello, P; Bachlechner, A; Barao, F; Barrau, A; Barrin, L; Bartoloni, A; Basara, L; Başeğmez-du Pree, S; Battarbee, M; Battiston, R; Becker, U; Behlmann, M; Beischer, B; Berdugo, J; Bertucci, B; Bindel, K F; Bindi, V; Boella, G; de Boer, W; Bollweg, K; Bonnivard, V; Borgia, B; Boschini, M J; Bourquin, M; Bueno, E F; Burger, J; Cadoux, F; Cai, X D; Capell, M; Caroff, S; Casaus, J; Castellini, G; Cervelli, F; Chae, M J; Chang, Y H; Chen, A I; Chen, G M; Chen, H S; Cheng, L; Chou, H Y; Choumilov, E; Choutko, V; Chung, C H; Clark, C; Clavero, R; Coignet, G; Consolandi, C; Contin, A; Corti, C; Creus, W; Crispoltoni, M; Cui, Z; Dai, Y M; Delgado, C; Della Torre, S; Demakov, O; Demirköz, M B; Derome, L; Di Falco, S; Dimiccoli, F; Díaz, C; von Doetinchem, P; Dong, F; Donnini, F; Duranti, M; D'Urso, D; Egorov, A; Eline, A; Eronen, T; Feng, J; Fiandrini, E; Finch, E; Fisher, P; Formato, V; Galaktionov, Y; Gallucci, G; García, B; García-López, R J; Gargiulo, C; Gast, H; Gebauer, I; Gervasi, M; Ghelfi, A; Giovacchini, F; Goglov, P; Gómez-Coral, D M; Gong, J; Goy, C; Grabski, V; Grandi, D; Graziani, M; Guo, K H; Haino, S; Han, K C; He, Z H; Heil, M; Hoffman, J; Hsieh, T H; Huang, H; Huang, Z C; Huh, C; Incagli, M; Ionica, M; Jang, W Y; Jinchi, H; Kang, S C; Kanishev, K; Kim, G N; Kim, K S; Kirn, Th; Konak, C; Kounina, O; Kounine, A; Koutsenko, V; Krafczyk, M S; La Vacca, G; Laudi, E; Laurenti, G; Lazzizzera, I; Lebedev, A; Lee, H T; Lee, S C; Leluc, C; Li, H S; Li, J Q; Li, J Q; Li, Q; Li, T X; Li, W; Li, Y; Li, Z H; Li, Z Y; Lim, S; Lin, C H; Lipari, P; Lippert, T; Liu, D; Liu, Hu; Lordello, V D; Lu, S Q; Lu, Y S; Luebelsmeyer, K; Luo, F; Luo, J Z; Lv, S S; Machate, F; Majka, R; Mañá, C; Marín, J; Martin, T; Martínez, G; Masi, N; Maurin, D; Menchaca-Rocha, A; Meng, Q; Mikuni, V M; Mo, D C; Morescalchi, L; Mott, P; Nelson, T; Ni, J Q; Nikonov, N; Nozzoli, F; Oliva, A; Orcinha, M; Palmonari, F; Palomares, C; Paniccia, M; Pauluzzi, M; Pensotti, S; Pereira, R; Picot-Clemente, N; Pilo, F; Pizzolotto, C; Plyaskin, V; Pohl, M; Poireau, V; Putze, A; Quadrani, L; Qi, X M; Qin, X; Qu, Z Y; Räihä, T; Rancoita, P G; Rapin, D; Ricol, J S; Rosier-Lees, S; Rozhkov, A; Rozza, D; Sagdeev, R; Sandweiss, J; Saouter, P; Schael, S; Schmidt, S M; Schulz von Dratzig, A; Schwering, G; Seo, E S; Shan, B S; Shi, J Y; Siedenburg, T; Son, D; Song, J W; Sun, W H; Tacconi, M; Tang, X W; Tang, Z C; Tao, L; Tescaro, D; Ting, Samuel C C; Ting, S M; Tomassetti, N; Torsti, J; Türkoğlu, C; Urban, T; Vagelli, V; Valente, E; Vannini, C; Valtonen, E; Vázquez Acosta, M; Vecchi, M; Velasco, M; Vialle, J P; Vitale, V; Vitillo, S; Wang, L Q; Wang, N H; Wang, Q L; Wang, X; Wang, X Q; Wang, Z X; Wei, C C; Weng, Z L; Whitman, K; Wienkenhöver, J; Wu, H; Wu, X; Xia, X; Xiong, R Q; Xu, W; Yan, Q; Yang, J; Yang, M; Yang, Y; Yi, H; Yu, Y J; Yu, Z Q; Zeissler, S; Zhang, C; Zhang, J; Zhang, J H; Zhang, S D; Zhang, S W; Zhang, Z; Zheng, Z M; Zhu, Z Q; Zhuang, H L; Zhukov, V; Zichichi, A; Zimmermann, N; Zuccon, P

2016-12-02

Knowledge of the rigidity dependence of the boron to carbon flux ratio (B/C) is important in understanding the propagation of cosmic rays. The precise measurement of the B/C ratio from 1.9 GV to 2.6 TV, based on 2.3 million boron and 8.3 million carbon nuclei collected by AMS during the first 5 years of operation, is presented. The detailed variation with rigidity of the B/C spectral index is reported for the first time. The B/C ratio does not show any significant structures in contrast to many cosmic ray models that require such structures at high rigidities. Remarkably, above 65 GV, the B/C ratio is well described by a single power law R^{Δ} with index Δ=-0.333±0.014(fit)±0.005(syst), in good agreement with the Kolmogorov theory of turbulence which predicts Δ=-1/3 asymptotically.

Si-metasomatism in serpentinized peridotite: The effects of talc-alteration on strontium and boron isotopes in abyssal serpentinites from Hole 1268a, ODP Leg 209

NASA Astrophysics Data System (ADS)

Harvey, Jason; Savov, Ivan P.; Agostini, Samuele; Cliff, Robert A.; Walshaw, Richard

2014-02-01

Ultramafic rocks recovered from Hole 1268a, Ocean Drilling Program Leg 209, to the south of the 15°20‧N Fracture Zone on the Mid-Atlantic ridge have experienced a complex history of melt depletion and subsequent interaction with a series of fluids under varying temperature and pH conditions. After intense melt depletion, varying degrees of serpentinization at 100-200 °C took place, initially under seawater-like pH conditions. Subsequently, interaction with a higher temperature (300-350 °C) fluid with low (4-5) pH and low MgO/SiO2 resulted in the heterogeneous alteration of these serpentinites to talc-bearing ultramafic lithologies. The proximity of the currently active, high temperature Logatchev hydrothermal field, located on the opposite flank of the Mid-Atlantic ridge, suggests that unlike more distal localities sampled during ODP Leg 209, Hole 1268a has experienced Si-metasomatism (i.e. talc-alteration) by a Logatchev-like hydrothermal fluid. Serpentinite strontium isotope ratios were not materially shifted by interaction with the subsequent high-T fluid, despite the likelihood that this fluid had locally interacted with mid-ocean ridge gabbro. 87Sr/86Sr in the ultramafic lithologies of Hole 1268a are close to that of seawater (c.0.709) and even acid leached serpentinites retain 87Sr/86Sr in excess of 0.707, indistinguishable from Logatchev hydrothermal fluid. On the other hand, boron isotope ratios appear to have been shifted from seawater-like values in the serpentinites (δ11B = c.+40‰) to much lighter values in talc-altered serpentinites (δ11B = +9 to +20‰). This is likely a consequence of the effects of changing ambient pH and temperature during the mineralogical transition from serpentine to talc. Heterogeneous boron isotope systematics have consequences for the composition of ultramafic portions of the lithosphere returned to the convecting mantle by subduction. Inhomogeneities in δ11B, [B] and mineralogy introduce significant uncertainties in the prediction of the composition of slab fluids released during the early- to mid-stages of subduction.

Ion current as a precise measure of the loading rate of a magneto-optical trap

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

Jiang, W.; Bailey, K.; Lu, Z. -T.

2014-01-01

We have demonstrated that the ion current resulting from collisions between metastable krypton atoms in a magneto-optical trap can be used to precisely measure the trap loading rate. We measured both the ion current of the abundant isotope Kr-83 (isotopic abundance = 11%) and the single-atom counting rate of the rare isotope Kr-85 (isotopic abundance similar to 1 x 10(-11)), and found the two quantities to be proportional at a precision level of 0.9%. This work results in a significant improvement in using the magneto-optical trap as an analytical tool for noble-gas isotope ratio measurements, and will benefit both atomicmore » physics studies and applications in the earth sciences. (C) 2014 Optical Society of America« less

Boron neutron capture therapy of malignant brain tumors at the Brookhaven Medical Research Reactor

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

Joel, D.D.; Coderre, J.A.; Chanana, A.D.

1996-12-31

Boron neutron capture therapy (BNCT) is a bimodal form of radiation therapy for cancer. The first component of this treatment is the preferential localization of the stable isotope {sup 10}B in tumor cells by targeting with boronated compounds. The tumor and surrounding tissue is then irradiated with a neutron beam resulting in thermal neutron/{sup 10}B reactions ({sup 10}B(n,{alpha}){sup 7}Li) resulting in the production of localized high LET radiation from alpha and {sup 7}Li particles. These products of the neutron capture reaction are very damaging to cells, but of short range so that the majority of the ionizing energy released ismore » microscopically confined to the vicinity of the boron-containing compound. In principal it should be possible with BNCT to selectively destroy small nests or even single cancer cells located within normal tissue. It follows that the major improvements in this form of radiation therapy are going to come largely from the development of boron compounds with greater tumor selectivity, although there will certainly be advances made in neutron beam quality as well as the possible development of alternative sources of neutron beams, particularly accelerator-based epithermal neutron beams.« less

Boron-selective reactions as powerful tools for modular synthesis of diverse complex molecules.

PubMed

Xu, Liang; Zhang, Shuai; Li, Pengfei

2015-12-21

In the context of modular and rapid construction of molecular diversity and complexity for applications in organic synthesis, biomedical and materials sciences, a generally useful strategy has emerged based on boron-selective chemical transformations. In the last decade, these types of reactions have evolved from proof-of-concept to some advanced applications in the efficient preparation of complex natural products and even automated precise manufacturing on the molecular level. These advances have shown the great potential of boron-selective reactions in simplifying synthetic design and experimental operations, and should inspire new developments in related chemical and technological areas. This tutorial review will highlight the original contributions and representative advances in this emerging field.

Southern Ocean intermediate water pH information provided by modern and fossil scleraxonian deep-sea corals

NASA Astrophysics Data System (ADS)

Gutjahr, M.; Vance, D.; Foster, G. L.; Hillenbrand, C.; Kuhn, G.

2010-12-01

There is a great deal of current interest in the chemistry of the deep glacial Southern Ocean, and the degree to which it communicated with the surface ocean and atmosphere. Recent findings that include high surface water radiocarbon ages [1] and renewed upwelling during the deglacial [2], suggest a re-organisation in Southern Ocean circulation that led to the demise of a deep water mass rich in dissolved inorganic carbon (DIC), leading to its renewed equilibration with the atmosphere and the deglacial rise in atmospheric CO2. However, conclusive evidence for higher Southern Ocean deep water DIC during the glacial is scarce, largely due to the lack of suitable substrates for recording it. Boron isotopic compositions measured in deep marine organisms may help to provide records of intermediate water pH, and hence DIC changes [3]. We will present boron isotope compositions of a selection of radiocarbon-dated, calcitic, deep-sea octocorals from the Amundsen Sea sector of the Southern Ocean (˜123°W, ˜69°S, 2500 m to 1430 m water depth), with the aim of resolving deglacial intermediate water pH changes. Since boron isotopic studies have not been carried out on these types of octocorals before, we will first present the δ11B distribution within a modern sample in order to examine biological fractionation that may potentially compromise the coral δ11B (cf. [4, 5]). Contrary to previously employed scleractinia [6], the corals analysed here appear to be internally homogenous and have only slightly elevated δ11B compared to that of ambient intermediate water borate ion. Moreover, modern and early Holocene coral δ11B display fairly constant compositions, whereas deglacial coral δ11B are higher. These boron isotopic changes are accompanied by corresponding deglacial changes in the coral Nd isotopic composition (expressed in ɛNd), which has been determined on the same specimens. Together, the striking co-variation between the deep-water coral δ11B and ɛNd suggest that changes in dissolved DIC accompanied changes in Circumpolar Deep Water ɛNd, lending further support for deglacial deep ocean-atmosphere re-adjustments through elevated dissolved CO2 outgassing during a re-invigoration of Southern Ocean circulation. References [1] Skinner, L.C., et al., Science, 2010. 328 (5982): p. 1147-1151. [2] Anderson, R.F., et al., Science, 2009. 323 (5920): p. 1443-1448. [3] Yu, J.M., et al., Earth Planet. Sci. Lett., 2010. 293 (1-2): p. 114-120. [4] Hönisch, B., et al., Geochim. Cosmochim. Acta, 2004. 68 (18): p. 3675-3685. [5] Krief, S., et al., Geochim. Cosmochim. Acta, 2010. 74 (17): p. 4988-5001. [6] Allison, N., A.A. Finch, and Eimf, Geochim. Cosmochim. Acta, 2010. 74 (6): p. 1790-1800.

ICP-MS with hexapole collision cell for isotope ratio measurements of Ca, Fe, and Se.

PubMed

Boulyga, S F; Becker, J S

2001-07-01

To avoid mass interferences on analyte ions caused by argon ions and argon molecular ions via reactions with collision gases, an rf hexapole filled with helium and hydrogen has been used in inductively coupled plasma mass spectrometry (ICP-MS), and its performance has been studied. Up to tenfold improvement in sensitivity was observed for heavy elements (m > 100 u), because of better ion transmission through the hexapole ion guide. A reduction of argon ions Ar+ and the molecular ions of argon ArX+ (X = O, Ar) by up to three orders of magnitude was achieved in a hexapole collision cell of an ICP-MS ("Platform ICP", Micromass, Manchester, UK) as a result of gas-phase reactions with hydrogen when the hexapole bias (HB) was set to 0 V; at an HB of 1.6 V argon, and argon-based ions of masses 40 u, 56 u, and 80 u, were reduced by approximately four, two, and five orders of magnitude, respectively. The signal-to-noise ratio 80Se/ 40Ar2+ was improved by more than five orders of magnitude under optimized experimental conditions. Dependence of mass discrimination on collision-cell properties was studied in the mass range 10 u (boron) to 238 u (uranium). Isotopic analysis of the elements affected by mass-spectrometric interference, Ca, Fe, and Se, was performed using a Meinhard nebulizer and an ultrasonic nebulizer (USN). The measured isotope ratios were comparable with tabulated values from IUPAC. Precision of 0.26%, 0.19%, and 0.12%, respectively, and accuracy of 0.13% 0.25%, and 0.92%, respectively, was achieved for isotope ratios 44Ca/ 40Ca and 56Fe/57Fe in 10 microg L(-1) solution nebulized by means of a USN and for 78Se/80Se in 100 microg L(-1) solution nebulized by means of a Meinhard nebulizer.

Development of a Field-Deployable Methane Carbon Isotope Analyzer

NASA Astrophysics Data System (ADS)

Dong, Feng; Baer, Douglas

2010-05-01

Methane is a potent greenhouse gas, whose atmospheric surface mixing ratio has almost doubled compared with preindustrial values. Methane can be produced by biogenic processes, thermogenic processes or biomass, with different isotopic signatures. As a key molecule involved in the radiative forcing in the atmosphere, methane is thus one of the most important molecules linking the biosphere and atmosphere. Therefore precise measurements of mixing ratios and isotopic compositions will help scientists to better understand methane sources and sinks. To date, high precision isotope measurements have been exclusively performed with conventional isotope ratio mass spectrometry, which involves intensive labor and is not readily field deployable. Optical studies using infrared laser spectroscopy have also been reported to measure the isotopic ratios. However, the precision of optical-based analyses, to date, is typically unsatisfactory without pre-concentration procedures. We present characterization of the performance of a portable Methane Carbon Isotope Analyzer (MCIA), based on cavity enhanced laser absorption spectroscopy technique, that provides in-situ measurements of the carbon isotope ratio (13C/12C or del_13C) and methane mixing ratio (CH4). The sample is introduced to the analyzer directly without any requirement for pretreatment or preconcentration. A typical precision of less than 1 per mill (< 0.1%) with a 10-ppm methane sample can be achieved in a measurement time of less than 100 seconds. The MCIA can report carbon isotope ratio and concentration measurements over a very wide range of methane concentrations. Results of laboratory tests and field measurements will be presented.

Trends in Seawater Boron-based Proxies during the Late Paleocene and Early Eocene Associated with Long-term Warming

NASA Astrophysics Data System (ADS)

Harper, D. T.; Penman, D. E.; Hoenisch, B.; Zachos, J. C.

2014-12-01

Boron isotopes (δ11B) and boron/calcium ratios (B/Ca) in tests of planktic foraminifera are controlled by equilibrium reactions between boron and carbon species in seawater, and thus represent important proxies of past marine carbonate chemistry. Indeed, the recent application of these boron-based proxies to fossil shells of planktic foraminifera from cores spanning the Paleocene-Eocene Thermal Maximum (PETM; 56Ma, an abrupt global warming and ocean acidification event) reveal a decline of ~0.3 in the pH of the mixed-layer [1], an anomaly that is well within the range of estimates based on the observed shoaling of the carbonate compensation depth (CCD) [2, and references therein]. The PETM occurred superimposed on a long-term warming trend that initiated in the Late Paleocene and continued into the Early Eocene (LPEE; 53-59Ma). The magnitude of warming [3] and deepening of the CCD [4] indicate that the LPEE was driven by a rise in pCO2 nearly equivalent to that of the PETM [5]. Here we extend the PETM record of boron-based proxies at IODP Site 1209 across the LPEE, in conjunction with stable carbon and oxygen isotopes in planktic foraminifera, in order to better constrain the long-term changes in pH and carbonate chemistry that accompanied the suggested rise in atmospheric CO2. The 20kyr resolution B/Ca record shows a long-term decline of ~25% during the LPEE, as well as subtle 400kyr cycles associated with eccentricity that mirror those observed in δ13C, and thus might reflect on changes in pH. The lower resolution δ11B record exhibits little change during the Late Paleocene before decreasing step-wise to lower values following the PETM, indicating that either pH in the upper ocean did not change significantly prior to the PETM, despite warming and inferred pCO2 increase, or changes in δ11Bseawater compensated for pH driven changes. As verification of these observations at Site 1209, complementary B/Ca and δ11B records are being generated for Atlantic IODP Sites 1262 and 1263. [1] Penman et al. 2014. Paleoceanography. [2] Palike et al. 2012. Nature. [3] Zachos et al. 2001. Science. [4] Leon-Rodriguez and Dickens 2010. Palaeogeogrphy, Palaeoclimatology, and Palaeoecology. [5] Komar, Zeebe and Dickens 2013. Paleoceanography.

High Precision Isotope Analyses Using Multi-Collector SIMS: Applications to Earth and Planetary Science.

NASA Astrophysics Data System (ADS)

Kita, N. T.; Ushikubo, T.; Valley, J. W.

2008-05-01

The CAMECA IMS-1280 large radius, multicollector ion microprobe at the Wisc-SIMS National Facility is capable of high accuracy and precision for in situ analysis of isotope ratios. With improved hardware stability and software capability, high precision isotope analyses are routinely performed, typically 5 min per spot. We have developed analytical protocols for stable isotope analyses of oxygen, carbon, Mg, Si and Sulfur using multi-collector Faraday Cups (MCFC) and achieved precision of 0.1-0.2 ‰ (1SD) from a typically 10μm spot analyses. A number of isotopically homogeneous mineral standards have been prepared and calibrated in order to certify the accuracy of analyses in the same level. When spatial resolution is critical, spot size is reduced down to sub- μm for δ 18O to obtain better than 0.5‰ (1SD) precision by using electron multiplier (EM) on multi-collection system. Multi-collection EM analysis is also applied at 10 ppm level to Li isotope ratios in zircon with precision better than 2‰ (1SD). A few applications will be presented. (1) Oxygen three isotope analyses of chondrules in ordinary chondrites revealed both mass dependent and mass independent oxygen isotope fractionations among chondrules as well as within individual chondrules. The results give constraints on the process of chondrule formation and origin of isotope reservoirs in the early solar system. (2) High precision 26Al-26Mg (half life of 0.73 Ma) chronology is applied to zoned melilite and anorthite from Ca, Al-rich inclusions (CAI) in Leoville meteorite, and a well-defined internal isochron is obtained. The results indicate the Al- Mg system was remained closed within 40ky of the crystallization of melilite and anorthite in this CAI. (3) Sub- μm spot analyses of δ18O in isotopically zoned zircon from high-grade metamorphism reveals a diffusion profile of ~6‰ over 2μm, indicating slow diffusion of oxygen in zircon. This result also implies that old Archean detrital zircons (> 4Ga) might preserve their primary oxygen isotopic records, which allows us to trace the geological processes of the early earth [1]. Lithium isotope analyses of pre- 4Ga zircon from Jack Hills show high Li abundance and low δ 7Li, indicating existence of highly weathered crustal material as early as 4.3Ga. In conclusion, these new techniques allow us to study small natural variations of stable isotopes at μm-scale that permit exciting and fundamental research where samples are small, precious, or zoned. [1] Page FZ et al. (2007) Am Min 92, 1772-1775.

Laser ablation inductively coupled plasma mass spectrometry for direct isotope ratio measurements on solid samples

NASA Astrophysics Data System (ADS)

Pickhardt, Carola; Dietze, Hans-Joachim; Becker, J. Sabine

2005-04-01

Isotope ratio measurements have been increasingly used in quite different application fields, e.g., for the investigation of isotope variation in nature, in geoscience (geochemistry and geochronology), in cosmochemistry and planetary science, in environmental science, e.g., in environmental monitoring, or by the application of the isotope dilution technique for quantification purposes using stable or radioactive high-enriched isotope tracers. Due to its high sensitivity, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is today a challenging mass spectrometric technique for the direct determination of precise and accurate isotope ratios in solid samples. In comparison to laser ablation quadrupole ICP-MS (LA-ICP-QMS), laser ablation coupled to a double-focusing sector field ICP-MS (LA-ICP-SFMS) with single ion detection offers a significant improvement of sensitivity at low mass resolution, whereby isotope ratios can be measured with a precision to 0.1% relative standard deviation (R.S.D.). In LA-ICP-SFMS, many disturbing isobaric interferences of analyte and molecular ions can be separated at the required mass resolution (e.g., 40Ar16O+ and 56Fe+ for iron isotope ratio measurements). The precision on isotope ratio measurements was improved by one order of magnitude via the simultaneous detection of mass-separated ion currents of isotopes using multiple ion collectors in LA-ICP-MS (LA-MC-ICP-MS). The paper discusses the state of the art, the challenges and limits in isotope ratio measurements by LA-ICP-MS using different instrumentations at the trace and ultratrace level in different fields of application as in environmental and biological research, geochemistry and geochronology with respect to their precision and accuracy.

Mass spectrometry in Earth sciences: the precise and accurate measurement of time.

PubMed

Schaltegger, Urs; Wotzlaw, Jörn-Frederik; Ovtcharova, Maria; Chiaradia, Massimo; Spikings, Richard

2014-01-01

Precise determinations of the isotopic compositions of a variety of elements is a widely applied tool in Earth sciences. Isotope ratios are used to quantify rates of geological processes that occurred during the previous 4.5 billion years, and also at the present time. An outstanding application is geochronology, which utilizes the production of radiogenic daughter isotopes by the radioactive decay of parent isotopes. Geochronological tools, involving isotopic analysis of selected elements from smallest volumes of minerals by thermal ionization mass spectrometry, provide precise and accurate measurements of time throughout the geological history of our planet over nine orders of magnitude, from the accretion of the proto-planetary disk, to the timing of the last glaciation. This article summarizes the recent efforts of the Isotope Geochemistry, Geochronology and Thermochronology research group at the University of Geneva to advance the U-Pb geochronological tool to achieve unprecedented precision and accuracy, and presents two examples of its application to two significant open questions in Earth sciences: what are the triggers and timescales of volcanic supereruptions, and what were the causes of mass extinctions in the geological past, driven by global climatic and environmental deterioration?

Formation mechanisms of boron oxide films fabricated by large-area electron beam-induced deposition of trimethyl borate [Formation Mechanisms of Boron Oxide Fillms Fabricated by Large Area Electron Beam-Induced Deposition of Trimethyl Borate

DOE PAGES

Martin, Aiden A.; Depond, Philip J.

2018-04-24

Boron-containing materials are increasingly drawing interest for the use in electronics, optics, laser targets, neutron absorbers, and high-temperature and chemically resistant ceramics. In this article, the first investigation into the deposition of boron-based material via electron beam-induced deposition (EBID) is reported. Thin films were deposited using a novel, large-area EBID system that is shown to deposit material at rates comparable to conventional techniques such as laser-induced chemical vapor deposition. The deposition rate and stoichiometry of boron oxide fabricated by EBID using trimethyl borate (TMB) as precursor is found to be critically dependent on the substrate temperature. By comparing the depositionmore » mechanisms of TMB to the conventional, alkoxide-based precursor tetraethyl orthosilicate it is revealed that ligand chemistry does not precisely predict the pathways leading to deposition of material via EBID. Lastly, the results demonstrate the first boron-containing material deposited by the EBID process and the potential for EBID as a scalable fabrication technique that could have a transformative effect on the athermal deposition of materials.« less

Formation mechanisms of boron oxide films fabricated by large-area electron beam-induced deposition of trimethyl borate [Formation Mechanisms of Boron Oxide Fillms Fabricated by Large Area Electron Beam-Induced Deposition of Trimethyl Borate

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

Martin, Aiden A.; Depond, Philip J.

Boron-containing materials are increasingly drawing interest for the use in electronics, optics, laser targets, neutron absorbers, and high-temperature and chemically resistant ceramics. In this article, the first investigation into the deposition of boron-based material via electron beam-induced deposition (EBID) is reported. Thin films were deposited using a novel, large-area EBID system that is shown to deposit material at rates comparable to conventional techniques such as laser-induced chemical vapor deposition. The deposition rate and stoichiometry of boron oxide fabricated by EBID using trimethyl borate (TMB) as precursor is found to be critically dependent on the substrate temperature. By comparing the depositionmore » mechanisms of TMB to the conventional, alkoxide-based precursor tetraethyl orthosilicate it is revealed that ligand chemistry does not precisely predict the pathways leading to deposition of material via EBID. Lastly, the results demonstrate the first boron-containing material deposited by the EBID process and the potential for EBID as a scalable fabrication technique that could have a transformative effect on the athermal deposition of materials.« less

Accurate and precise determination of isotopic ratios by MC-ICP-MS: a review.

PubMed

Yang, Lu

2009-01-01

For many decades the accurate and precise determination of isotope ratios has remained a very strong interest to many researchers due to its important applications in earth, environmental, biological, archeological, and medical sciences. Traditionally, thermal ionization mass spectrometry (TIMS) has been the technique of choice for achieving the highest accuracy and precision. However, recent developments in multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) have brought a new dimension to this field. In addition to its simple and robust sample introduction, high sample throughput, and high mass resolution, the flat-topped peaks generated by this technique provide for accurate and precise determination of isotope ratios with precision reaching 0.001%, comparable to that achieved with TIMS. These features, in combination with the ability of the ICP source to ionize nearly all elements in the periodic table, have resulted in an increased use of MC-ICP-MS for such measurements in various sample matrices. To determine accurate and precise isotope ratios with MC-ICP-MS, utmost care must be exercised during sample preparation, optimization of the instrument, and mass bias corrections. Unfortunately, there are inconsistencies and errors evident in many MC-ICP-MS publications, including errors in mass bias correction models. This review examines "state-of-the-art" methodologies presented in the literature for achievement of precise and accurate determinations of isotope ratios by MC-ICP-MS. Some general rules for such accurate and precise measurements are suggested, and calculations of combined uncertainty of the data using a few common mass bias correction models are outlined.

Detrital, metamorphic and metasomatic tourmaline in high-pressure metasediments from Syros (Greece): intra-grain boron isotope patterns determined by secondary-ion mass spectrometry

NASA Astrophysics Data System (ADS)

Marschall, Horst R.; Altherr, Rainer; Kalt, Angelika; Ludwig, Thomas

2008-06-01

The boron isotopic composition of zoned tourmaline in two metasediments from the island of Syros, determined by secondary-ion mass spectrometry (SIMS), reflects the sedimentary and metamorphic record of the rocks. Tourmaline from a silicate-bearing marble contains small (≤20 μm) detrital cores with highly variable δ 11B values (-10.7 to +3.6‰), pointing to a heterogeneous protolith derived from multiple sources. The sedimentary B isotopic record survived the entire metamorphic cycle with peak temperatures of ˜500°C. Prograde to peak metamorphic rims are homogeneous and similar among all analysed grains ( δ 11B ≈ +0.9‰). The varying δ 11B values of detrital cores in the siliceous marble demonstrate that in situ B isotope analysis of tourmaline by SIMS is a potentially powerful tool for provenance studies not only in sediments but also in metasediments. A meta-tuffitic blueschist bears abundant tourmaline with dravitic cores of detrital or authigenic origin ( δ 11B ≈ -3.3‰), and prograde to peak metamorphic overgrowth zones (-1.6‰). Fe-rich rims, formed during influx of B-bearing fluids under retrograde conditions, show strongly increasing δ 11B values (up to +7.7‰) towards the margins of the grains. The δ 11B values of metamorphic tourmaline from Syros, formed in mixed terrigenous-marine sediments, reflect the B signal blended from these two different sources, and was probably not altered by dehydration during subduction.

Polyatomic interferences on high precision uranium isotope ratio measurements by MC-ICP-MS: Applications to environmental sampling for nuclear safeguards

DOE PAGES

Pollington, Anthony D.; Kinman, William S.; Hanson, Susan K.; ...

2015-09-04

Modern mass spectrometry and separation techniques have made measurement of major uranium isotope ratios a routine task; however accurate and precise measurement of the minor uranium isotopes remains a challenge as sample size decreases. One particular challenge is the presence of isobaric interferences and their impact on the accuracy of minor isotope 234U and 236U measurements. Furthermore, we present techniques used for routine U isotopic analysis of environmental nuclear safeguards samples and evaluate polyatomic interferences that negatively impact accuracy as well as methods to mitigate their impacts.

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

Hoegg, Edward D.; Barinaga, Charles J.; Hager, George J.

ABSTRACT In order to meet a growing need for fieldable mass spectrometer systems for precise elemental and isotopic analyses, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) has a number of very promising characteristics. One key set of attributes that await validation deals with the performance characteristics relative to isotope ratio precision and accuracy. Due to its availability and prior experience with this research team, the initial evaluation of isotope ratio (IR) performance was performed on a Thermo Scientific Exactive Orbitrap instrument. While the mass accuracy and resolution performance for orbitrap analyzers are very well documented, no detailed evaluations of themore » IR performance have been published. Efforts described here involve two variables: the inherent IR precision and accuracy delivered by the LSAPGD microplasma and the inherent IR measurement qualities of orbitrap analyzers. Important to the IR performance, the various operating parameters of the orbitrap sampling interface, HCD dissociation stage, and ion injection/data acquisition have been evaluated. The IR performance for a range of other elements, including natural, depleted, and enriched uranium isotopes was determined. In all cases the precision and accuracy are degraded when measuring low abundance (<0.1% isotope fractions). In the best case, IR precision on the order of 0.1 %RSD can be achieved, with values of 1-3 %RSD observed for low-abundance species. The results suggest that the LSAPGD is a very good candidate for field deployable MS analysis and that the high resolving powers of the orbitrap may be complemented with a here-to-fore unknown capacity to deliver high-precision isotope ratios.« less

Measurement of the D/H, 18O/16O, and 17O/16O Isotope Ratios in Water by Laser Absorption Spectroscopy at 2.73 μm

PubMed Central

Wu, Tao; Chen, Weidong; Fertein, Eric; Masselin, Pascal; Gao, Xiaoming; Zhang, Weijun; Wang, Yingjian; Koeth, Johannes; Brückner, Daniela; He, Xingdao

2014-01-01

A compact isotope ratio laser spectrometry (IRLS) instrument was developed for simultaneous measurements of the D/H, 18O/16O and 17O/16O isotope ratios in water by laser absorption spectroscopy at 2.73 μm. Special attention is paid to the spectral data processing and implementation of a Kalman adaptive filtering to improve the measurement precision. Reduction of up to 3-fold in standard deviation in isotope ratio determination was obtained by the use of a Fourier filtering to remove undulation structure from spectrum baseline. Application of Kalman filtering enables isotope ratio measurement at 1 s time intervals with a precision (<1‰) better than that obtained by conventional 30 s averaging, while maintaining a fast system response. The implementation of the filter is described in detail and its effects on the accuracy and the precision of the isotope ratio measurements are investigated. PMID:24854363

Detection of ^11B/^10B: Part II

NASA Astrophysics Data System (ADS)

Duncan, Douglas

1999-07-01

HST observations {e.g. Duncan Etal 1992; 1997} have led to new theories of how cosmic rays {CRs} rich in CNO near massive stars form the light elements Li, Be, and B {e.g. Ramaty Etal 1996, 1998}. The neutrino process in SN, which has never been experimentally verified, should also produce boron, but only ^11B, yielding a very different isotopic ratio than CR spallation. The boron isotope ratio, 11B/10B, can provide a definitive test of both these theories, but its galactic evolution is completely unknown. Our previous GHRS echelle observation of the moderately metal-poor {Fe/H=-1.0} star HD76932 placed a limit on its B isotope ratio, but not a definite value, because possible blending from an unknown spectrum line could not be ruled out {Rebull Etal 1998}. The discovery of a halo star greatly depleted in B {Primas Etal 1998b} provides a wonderful opportunity to make the result definite. By comparing two similar {Fe/H -1.6} stars, which have very different amounts of B, we can rule out or measure any blends. This should give a definite result for 11B/10B at metallcity Fe/H -1.6, an epoch when massive star SN should have dominated galactic nucleosynthesis. Furthermore, we can then use our blending knowledge to reanalyze HD76932, getting a definite result for its 11B/10B ratio as well.

A Multi-Proxy Investigation into the Biomineralization Pathways of Benthic Invertebrate Taxa

NASA Astrophysics Data System (ADS)

DeCorte, I. A.; Liu, Y. W.; Doss, W. C.; Ries, J. B.; Eagle, R.

2016-12-01

Ocean acidification is the result of surface ocean absorption of anthropogenic carbon dioxide emissions and endangers many marine organisms. Decreases in pH and a coupled reduction in CaCO3 saturation state have been shown to disrupt the process of biomineralization within many species of marine calcifiers. Recent studies, however, demonstrate that calcifying organisms respond in diverse ways to changes in pH and CaCO3 saturation state. We examine element ratios (including Sr/Ca, Mg/Ca, Li/Ca, and B/Ca) and boron isotope ratios (δ11B) in 7 macro-invertebrate species (blue crab, shrimp, coralline red algae, pencil urchin, purple urchin, temperate coral, and serpulid worm) and compare results to net calcification rates and experimental seawater carbonate system parameters. Correlations between seawater carbonate chemistry and the elemental compositions of biogenic calcite and aragonite vary widely and are highly taxon-specific, ranging from strongly correlated to no significant response—a finding that is consistent with mounting evidence that many marine calcifying organisms regulate the chemistry of the fluid at their site of calcification. A Rayleigh framework is used to interpret the elemental data. We then analyze δ11B of the same samples as a proxy for pH at their site of calcification. Preliminary results suggest that coralline red algae, shrimp, urchin, serpulid worm and temperate coral taxa elevate pH at the site of calcification relative to the organism's ambient seawater. We plan to utilize a multi-proxy approach to examine the biomineralization pathways that influence elemental and boron isotope fractionation during calcification and precipitation of biogenic aragonite and calcite. A better understanding of these biomineralization pathways will help us to predict the responses of benthic invertebrate taxa to ocean acidification, as well as provide insights into drivers of so-called vital effects on elemental and stable boron isotope fractionation within biogenic carbonates—thereby assessing the fidelity of these proxies for reconstructing paleo-environmental change within a diverse range of marine calcifiers.

Insights into Ocean Acidification During the Middle Eocene Climatic Optimum from Boron Isotopes at Southern Ocean Site 738

NASA Astrophysics Data System (ADS)

Moebius, I.; Hoenisch, B.; Friedrich, O.

2015-12-01

The Middle Eocene Climatic Optimum (MECO) is a ~650-kyr interval of global warming, with a brief ~50 ky long peak warming interval, and an abrupt termination. Deep sea and surface ocean temperature evolution across this interval are fairly well constrained, but thus far we have little understanding of the mechanisms responsible for the gradual warming and rapid recovery. Carbonate mass accumulation rates suggest a shoaling of the carbonate compensation depth, and studies on alkenones indicate increasing atmospheric CO2 levels during the MECO. This suggests an increase in surface ocean CO2, and consequently ocean acidification. However, the severity and timing of the proposed ocean acidification with respect to the onset, peak warming and the termination are currently not well resolved. The boron isotopic composition (δ11B) recorded in planktic foraminifer shells offers an opportunity to infer oceanic pH across this interval. We are working on a boron isotope reconstruction from Southern Ocean IODP site 738 and South Atlantic IODP site 1263, covering 42.0 to 38.5 Ma. These sites are characterized by good carbonate preservation and well-defined age models have been established. Additionally, ecology, nutrient content and bottom-water oxygenation have been shown to change significantly across the event towards a more eutrophic, periodically oxygen-depleted environment supporting different biological communities. We selected the planktic foraminifera species Acarinina spinuloinflata for this study because it is symbiont-bearing, suggesting a near-surface habitat and little vertical migration in the water column, and because of its abundance in the samples. δ11B data will be translated to surface ocean pH and atmospheric pCO2 will be approximated to refine knowledge about the carbon cycle during this time. Parallel analysis of two core sites will help to evaluate the tenacity of the data.

High precision isotope ratio measurements of mercury isotopes in cinnabar ores using multi-collector inductively coupled plasma mass spectrometry.

PubMed

Hintelmann, Holger; Lu, ShengYong

2003-06-01

Variations in Hg isotope ratios in cinnabar ores obtained from different countries were detected by high precision isotope ratio measurements using multi-collector inductively coupled mass spectrometry (MC-ICP-MS). Values of delta198/202Hg varied from 0.0-1.3 percent per thousand relative to a NIST SRM 1641d Hg solution. The typical external uncertainty of the delta values was 0.06 to 0.26 percent per thousand. Hg was introduced into the plasma as elemental Hg after reduction by sodium borohydride. A significant fractionation of lead isotopes was observed during the simultaneous generation of lead hydride, preventing normalization of the Hg isotope ratios using the measured 208/206Pb ratio. Hg ratios were instead corrected employing the simultaneously measured 205/203T1 ratio. Using a 10 ng ml(-1) Hg solution and 10 min of sampling, introducing 60 ng of Hg, the internal precision of the isotope ratio measurements was as low as 14 ppm. Absolute Hg ratios deviated from the representative IUPAC values by approximately 0.2% per u. This observation is explained by the inadequacy of the exponential law to correct for mass bias in MC-ICP-MS measurements. In the absence of a precisely characterized Hg isotope ratio standard, we were not able to determine unambiguously the absolute Hg ratios of the ore samples, highlighting the urgent need for certified standard materials.

High-precision measurement of (186)Os/(188)Os and (187)Os/(188)Os: isobaric oxide corrections with in-run measured oxygen isotope ratios.

PubMed

Chu, Zhu-Yin; Li, Chao-Feng; Chen, Zhi; Xu, Jun-Jie; Di, Yan-Kun; Guo, Jing-Hui

2015-09-01

We present a novel method for high precision measurement of (186)Os/(188)Os and (187)Os/(188)Os ratios, applying isobaric oxide interference correction based on in-run measurements of oxygen isotopic ratios. For this purpose, we set up a static data collection routine to measure the main Os(16)O3(-) ion beams with Faraday cups connected to conventional 10(11) amplifiers, and (192)Os(16)O2(17)O(-) and (192)Os(16)O2(18)O(-) ion beams with Faraday cups connected to 10(12) amplifiers. Because of the limited number of Faraday cups, we did not measure (184)Os(16)O3(-) and (189)Os(16)O3(-) simultaneously in-run, but the analytical setup had no significant influence on final (186)Os/(188)Os and (187)Os/(188)Os data. By analyzing UMd, DROsS, an in-house Os solution standard, and several rock reference materials, including WPR-1, WMS-1a, and Gpt-5, the in-run measured oxygen isotopic ratios were proven to present accurate Os isotopic data. However, (186)Os/(188)Os and (187)Os/(188)Os data obtained with in-run O isotopic compositions for the solution standards and rock reference materials show minimal improvement in internal and external precision, compared to the conventional oxygen correction method. We concluded that, the small variations of oxygen isotopes during OsO3(-) analytical sessions are probably not the main source of error for high precision Os isotopic analysis. Nevertheless, use of run-specific O isotopic compositions is still a better choice for Os isotopic data reduction and eliminates the requirement of extra measurements of the oxygen isotopic ratios.

Formation mechanisms of boron oxide films fabricated by large-area electron beam-induced deposition of trimethyl borate

PubMed Central

Depond, Philip J

2018-01-01

Boron-containing materials are increasingly drawing interest for the use in electronics, optics, laser targets, neutron absorbers, and high-temperature and chemically resistant ceramics. In this article, the first investigation into the deposition of boron-based material via electron beam-induced deposition (EBID) is reported. Thin films were deposited using a novel, large-area EBID system that is shown to deposit material at rates comparable to conventional techniques such as laser-induced chemical vapor deposition. The deposition rate and stoichiometry of boron oxide fabricated by EBID using trimethyl borate (TMB) as precursor is found to be critically dependent on the substrate temperature. By comparing the deposition mechanisms of TMB to the conventional, alkoxide-based precursor tetraethyl orthosilicate it is revealed that ligand chemistry does not precisely predict the pathways leading to deposition of material via EBID. The results demonstrate the first boron-containing material deposited by the EBID process and the potential for EBID as a scalable fabrication technique that could have a transformative effect on the athermal deposition of materials. PMID:29765806

Formation mechanisms of boron oxide films fabricated by large-area electron beam-induced deposition of trimethyl borate.

PubMed

Martin, Aiden A; Depond, Philip J

2018-01-01

Boron-containing materials are increasingly drawing interest for the use in electronics, optics, laser targets, neutron absorbers, and high-temperature and chemically resistant ceramics. In this article, the first investigation into the deposition of boron-based material via electron beam-induced deposition (EBID) is reported. Thin films were deposited using a novel, large-area EBID system that is shown to deposit material at rates comparable to conventional techniques such as laser-induced chemical vapor deposition. The deposition rate and stoichiometry of boron oxide fabricated by EBID using trimethyl borate (TMB) as precursor is found to be critically dependent on the substrate temperature. By comparing the deposition mechanisms of TMB to the conventional, alkoxide-based precursor tetraethyl orthosilicate it is revealed that ligand chemistry does not precisely predict the pathways leading to deposition of material via EBID. The results demonstrate the first boron-containing material deposited by the EBID process and the potential for EBID as a scalable fabrication technique that could have a transformative effect on the athermal deposition of materials.

Improvements in Boron Plate Coating Technology for Higher Efficiency Neutron Detection and Coincidence Counting Error Reduction

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

Menlove, Howard Olsen; Henzlova, Daniela

This informal report presents the measurement data and information to document the performance of the advanced Precision Data Technology, Inc. (PDT) sealed cell boron-10 plate neutron detector that makes use of the advanced coating materials and procedures. In 2015, PDT changed the boron coating materials and application procedures to significantly increase the efficiency of their basic corrugated plate detector performance. A prototype sealed cell unit was supplied to LANL for testing and comparison with prior detector cells. Also, LANL had reference detector slabs from the original neutron collar (UNCL) and the new Antech UNCL with the removable 3He tubes. Themore » comparison data is presented in this report.« less

Pharmacokinetics of Chlorin e6-Cobalt Bis(Dicarbollide) Conjugate in Balb/c Mice with Engrafted Carcinoma

PubMed Central

Volovetsky, Arthur B.; Balalaeva, Irina V.; Dudenkova, Varvara V.; Shilyagina, Natalia Yu.; Feofanov, Аlexey V.; Efremenko, Anastasija V.; Grin, Mikhail A.; Mironov, Andrey F.; Bregadze, Vladimir I.; Maslennikova, Anna V.

2017-01-01

The necessary precondition for efficient boron neutron capture therapy (BNCT) is control over the content of isotope 10B in the tumor and normal tissues. In the case of boron-containing porphyrins, the fluorescent part of molecule can be used for quantitative assessment of the boron content. Study Objective: We performed a study of the biodistribution of the chlorin e6-Cobalt bis(dicarbollide) conjugate in carcinoma-bearing Balb/c mice using ex vivo fluorescence imaging, and developed a mathematical model describing boron accumulation and release based on the obtained experimental data. Materials and Methods: The study was performed on Balb/c tumor-bearing mice (CT-26 tumor model). A solution of the chlorin e6-Cobalt bis(dicarbollide) conjugate (CCDC) was injected into the blood at a dose of 10 mg/kg of the animal’s weight. Analysis of the fluorescence signal intensity was performed at several time points by spectrofluorimetry in blood and by laser scanning microscopy in muscle, liver, and tumor tissues. The boron content in the same samples was determined by mass spectroscopy with inductively coupled plasma. Results: Analysis of a linear approximation between the fluorescence intensity and boron content in the tissues demonstrated a satisfactory value of approximation reliability with a Spearman’s rank correlation coefficient of r = 0.938, p < 0.01. The dynamics of the boron concentration change in various organs, calculated on the basis of the fluorescence intensity, enabled the development of a model describing the accumulation of the studied compound and its distribution in tissues. The obtained results reveal a high level of correspondence between the model and experimental data. PMID:29182594

Pharmacokinetics of Chlorin e₆-Cobalt Bis(Dicarbollide) Conjugate in Balb/c Mice with Engrafted Carcinoma.

PubMed

Volovetsky, Arthur B; Sukhov, Vladimir S; Balalaeva, Irina V; Dudenkova, Varvara V; Shilyagina, Natalia Yu; Feofanov, Аlexey V; Efremenko, Anastasija V; Grin, Mikhail A; Mironov, Andrey F; Sivaev, Igor B; Bregadze, Vladimir I; Maslennikova, Anna V

2017-11-28

The necessary precondition for efficient boron neutron capture therapy (BNCT) is control over the content of isotope 10 B in the tumor and normal tissues. In the case of boron-containing porphyrins, the fluorescent part of molecule can be used for quantitative assessment of the boron content. Study Objective: We performed a study of the biodistribution of the chlorin e ₆-Cobalt bis(dicarbollide) conjugate in carcinoma-bearing Balb/c mice using ex vivo fluorescence imaging, and developed a mathematical model describing boron accumulation and release based on the obtained experimental data. Materials and Methods: The study was performed on Balb/c tumor-bearing mice (CT-26 tumor model). A solution of the chlorin e ₆-Cobalt bis(dicarbollide) conjugate (CCDC) was injected into the blood at a dose of 10 mg/kg of the animal's weight. Analysis of the fluorescence signal intensity was performed at several time points by spectrofluorimetry in blood and by laser scanning microscopy in muscle, liver, and tumor tissues. The boron content in the same samples was determined by mass spectroscopy with inductively coupled plasma. Results: Analysis of a linear approximation between the fluorescence intensity and boron content in the tissues demonstrated a satisfactory value of approximation reliability with a Spearman's rank correlation coefficient of r = 0.938, p < 0.01. The dynamics of the boron concentration change in various organs, calculated on the basis of the fluorescence intensity, enabled the development of a model describing the accumulation of the studied compound and its distribution in tissues. The obtained results reveal a high level of correspondence between the model and experimental data.

Boron Isotope Evidence for Shallow Fluid Transfer Across Subduction Zones by Serpentinized Mantle

NASA Astrophysics Data System (ADS)

Scambelluri, M.; Tonarini, S.; Agostini, S.; Cannaò, E.

2012-12-01

Boron Isotope Evidence for Shallow Fluid Transfer Across Subduction Zones by Serpentinized Mantle M. Scambelluri (1), S. Tonarini (2), S. Agostini (2), E. Cannaò (1) (1) Dipartimento di Scienze della Terra, Ambiente e vita, University of Genova, Italy (2) Istituto di Geoscienze e Georisorse-CNR, Pisa, Italy In subduction zones, fluid-mediated chemical exchange between slabs and mantle dictates volatile and incompatible element cycles and influences arc magmatism. Outstanding issues concern the sources of water for arc magmas and its slab-to-mantle wedge transport. Does it occur by slab dehydration beneath arc fronts, or by hydration of fore-arc mantle and subsequent subduction of the hydrated mantle? So far, the deep slab dehydration hypothesis had strong support, but the hydrated mantle wedge idea is advancing supported by studies of fluid-mobile elements in serpentinized wedge peridotites and their subducted high-pressure (HP) equivalents. Serpentinites are volatile and fluid-mobile element reservoirs for subduction: their dehydration causes large fluid and element flux to the mantle.However, direct evidence for their key role in arc magmatism and identification of dehydration environments has been elusive and boron isotopes can trace the process. Until recently, the altered oceanic crust (AOC) was considered the 11B reservoir for arcs, which largely display positive δ11B. However, shallow slab dehydration transfers 11B to the fore-arc mantle and leaves the residual AOC very depleted in 11B below arcs. Here we present high positive δ11B of HP serpentinized peridotites from Erro Tobbio (Ligurian Alps), recording subduction metamorphism from hydration at low-grade to eclogite-facies dehydration. We show a connection among serpentinite dehydration, release of 11B-rich fluids and arc magmatism. The dataset is completed by B isotope data on other HP Alpine serpentinites from Liguria and Lanzo Massif. In general, the δ11B of these rocks is heavy (16 to + 30 permil). No significant B loss and 11B fractionation occurs with burial. Their B and 11B abundance shows that high budgets acquired during shallow hydration are transferred to HP fluids, providing the heavy-boron component requested for arcs. The B compositions of Erro-Tobbio are unexpected for slabs, deputed to loose B and 11B during dehydration: its isotopic composition can be achieved diluting in the mantle shallow subduction-fluids (30 km). The serpentinizing fluids and the fluid-transfer mechanism in Erro-Tobbio are clarified integrating B with O-H and Sr isotopes. Low δD (-102permil), high δ18O (8permil) of early serpentinites suggest low-temperature hydration by metamorphic fluids. 87Sr/86Sr (0.7044 to 0.7065) is lower than oceanic serpentinites formed from seawater. We conclude that alteration was distant from mid-ocean ridges and occurred at the slab-mantle interface or in forearc environments. We thus provide evidence for delivery of water and 11B at sub-arcs by serpentinized mantle altered by subduction-fluid infiltration atop of the slab since the early stages of burial, witnessing shallow fluid transfer across the subduction zone. Similarity of the B composition of Erro Tobbio with other Alpine serpentinized peridotites suggests that these materials might have spent much of their subduction lifetime at the plate interface, fed by B and 11Bich fluids uprising from the slab.

Boron neutron capture therapy: Moving toward targeted cancer therapy.

PubMed

Mirzaei, Hamid Reza; Sahebkar, Amirhossein; Salehi, Rasoul; Nahand, Javid Sadri; Karimi, Ehsan; Jaafari, Mahmoud Reza; Mirzaei, Hamed

2016-01-01

Boron neutron capture therapy (BNCT) occurs when a stable isotope, boton-10, is irradiated with low-energy thermal neutrons to yield stripped down helium-4 nuclei and lithium-7 nuclei. It is a binary therapy in the treatment of cancer in which a cytotoxic event is triggered when an atom placed in a cancer cell. Here, we provide an overview on the application of BNCT in cancer therapy as well as current preclinical and clinical evidence on the efficacy of BNCT in the treatment of melanoma, brain tumors, head and neck cancer, and thyroid cancer. Several studies have shown that BNCT is effective in patients who had been treated with a full dose of conventional radiotherapy, because of its selectivity. In addition, BNCT is dependent on the normal/tumor tissue ratio of boron distribution. Increasing evidence has shown that BNCT can be combined with different drug delivery systems to enhance the delivery of boron to cancer cells. The flexibility of BNCT to be used in combination with different tumor-targeting approaches has made this strategy a promising option for cancer therapy. This review aims to provide a state-of-the-art overview of the recent advances in the use of BNCT for targeted therapy of cancer.

Calcium isotope analysis by mass spectrometry.

PubMed

Boulyga, Sergei F

2010-01-01

The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. The present article discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. In Sections 2 and 3, mass spectrometric methods applied to precise stable isotope analysis and to the determination of (41)Ca are described. Section 4 contains a short summary of selected applications, and includes tracer experiments and the potential use of biological isotope fractionation in medical studies, paleoclimatic and paleoceanographic, and other terrestrial as well as extraterrestrial investigations. 2009 Wiley Periodicals, Inc.

Advances in laser ablation MC-ICPMS isotopic analysis of rock materials

NASA Astrophysics Data System (ADS)

Young, E. D.

2007-12-01

Laser ablation multiple-collector inductively coupled plasma-source mass spectrometry (LA-MC-ICPMS) is a rapid method for obtaining high-precision isotope ratio measurements in geological samples. The method has been used with success for measuring isotope ratios of numerous elements, including Pb, Hf, Mg, Si, and Fe in terrestrial and extraterrestrial samples. It fills the gap between the highest precision obtainable with acid digestion together with MC-ICPMS and thermal ionization mass spectrometry (TIMS) and the maximum spatial resolution afforded by secondary ion mass spectrometry (SIMS). Matrix effects have been shown to be negligible for Pb isotopic analysis by LA-MC-ICPMS (Simon et al., 2007). Glass standards NBS 610, 612, and 614 have Pb/matrix ratios spanning two orders of magnitude. Our sample-standard bracketing laser ablation technique gives accurate and precise 208Pb/206Pb and 207Pb/206Pb for these glasses. The accuracy is superior to that obtained when using Tl to correct for mass fractionation. Accuracy and precision (± 0.2 ‰) for Pb in feldspars is comparable to that for double-spike TIMS. Data like these have been used to distinguish distinct sources of magmas in the Long Valley silicic magma system. LA-MC-ICPMS analyses of Mg isotope ratios in calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrite meteorites have revealed a wealth of new information about the history of these objects. A byproduct of this work has been recognition of the importance of different mass fractionation laws among three isotopes of a given element. Kinetic and equilibrium processes define distinct fractionation laws. Reservoir effects can further modify these laws. The result is that the linear coefficient β that relates the logarithms of the ratios n2/n1 and n3/n1 (ni refers to the number of atoms of isotope i) of isotopes with masses m3 > m2 > m1 is not unique. Rather, it is process dependent. In the case of Mg, this coefficient ranges from 0.521 for single-step equilibrium processes to 0.510 or even lower for kinetic processes. Rayleigh fractionation involving a kinetic process with a single-step β of 0.510 produces an effective β of 0.512. Such differences in fractionation laws can be crucial for determining excesses or deficits in isotopes relative to mass fractionation. Contrary to some assertions, Si isotope ratios can be measured with high accuracy and precision using 193 nm excimer lasers with nanosecond pulse widths (Shahar and Young, 2007). Silicon isotope ratios in CAIs measured by 193 nm LA-MC-ICPMS have been combined with Mg isotope ratios to constrain the astrophysical environments in which these oldest solar system materials formed. Accuracy of the measurements was determined using gravimetric standards of various matrix compositions. The results establish that matrix effects for Si are below detection at the ± 0.2 ‰ precision of the laser ablation technique. High mass resolving power (m/Δ m ~ 9000) is necessary to obtain accurate Si isotope ratios by laser ablation. High-precision LA-MC-ICPMS measurements of 176Hf/177Hf in zircons can be obtained by normalizing to 179Hf/177Hf assuming an exponential fractionation law and no mass-dependent Hf, Lu, or Yb stable isotope fractionation. With corrections for interfering 176Lu and 176Yb precision for this method can be on the order of 0.3 epsilon (0.03 ‰). The approach has been used to infer the existence of continental crust on Earth 4.4 billion years before present (Harrison et al., 2005).

Efficacy of passive sampler collection for atmospheric NO2 isotopes under simulated environmental conditions.

PubMed

Coughlin, Justin G; Yu, Zhongjie; Elliott, Emily M

2017-07-30

Nitrogen oxides or NO x (NO x = NO + NO 2 ) play an important role in air quality, atmospheric chemistry, and climate. The isotopic compositions of anthropogenic and natural NO 2 sources are wide-ranging, and they can be used to constrain sources of ambient NO 2 and associated atmospheric deposition of nitrogen compounds. While passive sample collection of NO 2 isotopes has been used in field studies to determine NO x source influences on atmospheric deposition, this approach has not been evaluated for accuracy or precision under different environmental conditions. The efficacy of NO 2 passive sampler collection for NO 2 isotopes was evaluated under varied temperature and relative humidity (RH) conditions in a dynamic flux chamber. The precision and accuracy of the filter NO 2 collection as nitrite (NO 2 - ) for isotopic analysis were determined using a reference NO 2 gas tank and through inter-calibration with a modified EPA Method 7. The bacterial denitrifer method was used to convert 20 μM of collected NO 2 - or nitrate (NO 3 - ) into N 2 O and was carried out on an Isoprime continuous flow isotope ratio mass spectrometer. δ 15 N-NO 2 values determined from passive NO 2 collection, in conditions of 11-34 °C, 1-78% RH, have an overall accuracy and precision of ±2.1 ‰, and individual run precision of ±0.6 ‰. δ 18 O-NO 2 values obtained from passive NO 2 sampler collection, under the same conditions, have an overall precision of ± 1.3 ‰. Suitable conditions for passive sampler collection of NO 2 isotopes are in environments ranging from 11 to 34 °C and 1 to 78% RH. The passive NO 2 isotope measurement technique provides an accurate method to determine variations in atmospheric δ 15 N-NO 2 values and a precise method for determining atmospheric δ 18 O-NO 2 values. The ability to measure NO 2 isotopes over spatial gradients at the same temporal resolution provides a unique perspective on the extent and seasonality of fluctuations in atmospheric NO 2 isotopic compositions. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Spent fuel pool storage calculations using the ISOCRIT burnup credit tool

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

Kucukboyaci, Vefa; Marshall, William BJ J

2012-01-01

In order to conservatively apply burnup credit in spent fuel pool criticality safety analyses, Westinghouse has developed a software tool, ISOCRIT, for generating depletion isotopics. This tool is used to create isotopics data based on specific reactor input parameters, such as design basis assembly type; bounding power/burnup profiles; reactor specific moderator temperature profiles; pellet percent theoretical density; burnable absorbers, axial blanket regions, and bounding ppm boron concentration. ISOCRIT generates burnup dependent isotopics using PARAGON; Westinghouse's state-of-the-art and licensed lattice physics code. Generation of isotopics and passing the data to the subsequent 3D KENO calculations are performed in an automated fashion,more » thus reducing the chance for human error. Furthermore, ISOCRIT provides the means for responding to any customer request regarding re-analysis due to changed parameters (e.g., power uprate, exit temperature changes, etc.) with a quick turnaround.« less

High-precision measurement of variations in calcium isotope ratios in urine by multiple collector inductively coupled plasma mass spectrometry

USGS Publications Warehouse

Morgan, J.L.L.; Gordon, G.W.; Arrua, R.C.; Skulan, J.L.; Anbar, A.D.; Bullen, T.D.

2011-01-01

We describe a new chemical separation method to isolate Ca from other matrix elements in biological samples, developed with the long-term goal of making high-precision measurement of natural stable Ca isotope variations a clinically applicable tool to assess bone mineral balance. A new two-column procedure utilizing HBr achieves the purity required to accurately and precisely measure two Ca isotope ratios (44Ca/42Ca and 44Ca/43Ca) on a Neptune multiple collector inductively coupled plasma mass spectrometer (MC-ICPMS) in urine. Purification requirements for Sr, Ti, and K (Ca/Sr > 10000; Ca/Ti > 10000000; and Ca/K > 10) were determined by addition of these elements to Ca standards of known isotopic composition. Accuracy was determined by (1) comparing Ca isotope results for samples and standards to published data obtained using thermal ionization mass spectrometry (TIMS), (2) adding a Ca standard of known isotopic composition to a urine sample purified of Ca, and (3) analyzing mixtures of urine samples and standards in varying proportions. The accuracy and precision of δ44/42Ca measurements of purified samples containing 25 μg of Ca can be determined with typical errors less than ±0.2‰ (2σ).

The chemistry and isotopic composition of waters in the low-enthalpy geothermal system of Cimino-Vico Volcanic District, Italy

USGS Publications Warehouse

Battistel, Maria; Hurwitz, Shaul; Evans, William; Barbieri, Maurizio

2017-01-01

Geothermal energy exploration is based in part on interpretation of the chemistry, temperature, and discharge rate of thermal springs. Here we present the major element chemistry and the δD, δ18O, 87Sr/86Sr and δ11B isotopic ratio of groundwater from the low-enthalpy geothermal system near the city of Viterbo in the Cimino-Vico volcanic district of west-Central Italy. The geothermal system hosts many thermal springs and gas vents, but the resource is still unexploited. Water chemistry is controlled by mixing between low salinity,HCO3-rich fresh waters (<24.2°C) flowing in shallow volcanic rocks and SO4-rich thermal waters (25.3°C to 62.2°C) ascending from deep, high permeability Mesozoic limestones. The (equivalent) SO4/Cl (0.01–0.02), Na/Cl (2.82–5.83) and B/Cl ratios (0.02–0.38) of thermal waters differs from the ratios in other geothermal systems from Central Italy, probably implying a lack of hydraulic continuity across the region. The δ18O (−6.6‰ to −5.9‰) and δD (−40.60‰ to −36.30‰) isotopic composition of spring water suggest that the recharge area for the geothermal system is the summit region of Mount Cimino. The strontium isotope ratios (87Sr/86Sr) of thermal waters (0.70797–0.70805) are consistent with dissolution of the Mesozoic evaporite-carbonate units that constitute the reservoir, and the ratios of cold fresh waters mainly reflect shallow circulation through the volcanic cover and some minor admixture (<10%) of thermal water as well. The boron isotopic composition (δ11B) of fresh waters (−5.00 and 6.12‰) is similar to that of the volcanic cover, but the δ11B of thermal waters (−8.37‰ to −4.12‰) is a mismatch for the Mesozoic reservoir rocks and instead reflects dissolution of secondary boron minerals during fluid ascent through flysch units that overlie the reservoir. A slow and tortuous ascent enhances extraction of boron but also promotes conductive cooling, partially masking the heat present in the reservoir. Overall data from this study is consistent with previous studies that concluded that the geothermal system has a large energy potential.

[High-precision in situ analysis of the lead isotopic composition in copper using femtosecond laser ablation MC-ICP-MS and the application in ancient coins].

PubMed

Chen, Kai-Yun; Fan, Chao; Yuan, Hong-Lin; Bao, Zhi-An; Zong, Chun-Lei; Dai, Meng-Ning; Ling, Xue; Yang, Ying

2013-05-01

In the present study we set up a femtosecond laser ablation MC-ICP-MS method for lead isotopic analysis. Pb isotopic composition of fifteen copper (brass, bronze) standard samples from the National Institute of Standards Material were analyzed using the solution method (MC-ICP-MS) and laser method (fLA-MC-ICPMS) respectively, the results showed that the Pb isotopic composition in CuPb12 (GBW02137) is very homogeneous, and can be used as external reference material for Pb isotopic in situ analysis. On CuPb12 112 fLA-MC-ICPMS Pb isotope analysis, the weighted average values of the Pb isotopic ratio are in good agreement with the results analyzed by bulk solution method within 2sigma error, the internal precision RSEs of the 208 Pb/204 Pb ratio and 207 Pb/206 Pb ratio are less than 90 and 40 ppm respectively, and the external precision RSDs of them are less than 60 and 30 ppm respectively. Pb isotope of thirteen ancient bronze coins was analyzed via fLA-MC-ICPMS, the results showed that the Pb isotopic composition of ancient coins of different dynasties is significantly different, and not all the Pb isotopic compositions in the coins even from the same dynasty are in agreement with each other.

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.

Tellurium Stable Isotope Fractionation in Chondritic Meteorites

NASA Astrophysics Data System (ADS)

Fehr, M. A.; Hammond, S. J.; Parkinson, I. J.

2014-09-01

New Te double spike procedures were set up to obtain high-precision accurate Te stable isotope data. Tellurium stable isotope data for 16 chondrite falls are presented, providing evidence for significant Te stable isotope fractionation.

Preliminary Figures of Merit for Isotope Ratio Measurements: The Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Ionization Source Coupled to an Orbitrap Mass Analyzer

NASA Astrophysics Data System (ADS)

Hoegg, Edward D.; Barinaga, Charles J.; Hager, George J.; Hart, Garret L.; Koppenaal, David W.; Marcus, R. Kenneth

2016-08-01

In order to meet a growing need for fieldable mass spectrometer systems for precise elemental and isotopic analyses, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) has a number of very promising characteristics. One key set of attributes that await validation deals with the performance characteristics relative to isotope ratio precision and accuracy. Owing to its availability and prior experience with this research team, the initial evaluation of isotope ratio (IR) performance was performed on a Thermo Scientific Exactive Orbitrap instrument. While the mass accuracy and resolution performance for Orbitrap analyzers are well-documented, no detailed evaluations of the IR performance have been published. Efforts described here involve two variables: the inherent IR precision and accuracy delivered by the LS-APGD microplasma and the inherent IR measurement qualities of Orbitrap analyzers. Important to the IR performance, the various operating parameters of the Orbitrap sampling interface, high-energy collisional dissociation (HCD) stage, and ion injection/data acquisition have been evaluated. The IR performance for a range of other elements, including natural, depleted, and enriched uranium isotopes was determined. In all cases, the precision and accuracy are degraded when measuring low abundance (<0.1% isotope fractions). In the best case, IR precision on the order of 0.1% RSD can be achieved, with values of 1%-3% RSD observed for low-abundance species. The results suggest that the LS-APGD is a promising candidate for field deployable MS analysis and that the high resolving powers of the Orbitrap may be complemented with a here-to-fore unknown capacity to deliver high-precision IRs.

In vivo percutaneous absorption of boron as boric acid, borax, and disodium octaborate tetrahydrate in humans: a summary.

PubMed

Wester, R C; Hui, X; Maibach, H I; Bell, K; Schell, M J; Northington, D J; Strong, P; Culver, B D

1998-01-01

Literature from the first half of this century reports concern for toxicity from topical use of boric acid, but assessment of percutaneous absorption has been impaired by lack of analytical sensitivity. Analytical methods in this study included inductively coupled plasma-mass spectrometry, which now allows quantitation of percutaneous absorption of 10B in 10B-enriched boric acid, borax, and disodium octaborate tetrahydrate (DOT) in biological matrices. This made it possible, in the presence of comparatively large natural dietary boron intakes for the in vivo segment of this study, to quantify the boron passing through skin. Human volunteers were dosed with 10B-enriched boric acid, 5.0%, borax, 5.0%, or disodium octaborate tetrahydrate, 10% in aqueous solutions. Urinalysis, for boron and changes in boron isotope ratios, was used to measure absorption. Boric acid in vivo percutaneous absorption was 0.226 (SD = 0.125) mean percent dose, with flux and permeability constant (Kp) calculated at 0.009 microg/cm2/h and 1.9 x 10(-7) cm/h, respectively. Borax absorption was 0.210 (SD = 0.194) mean percent dose, with flux and Kp calculated at 0.009 microg/cm2/h and 1.8 x 10(-7) cm/h, respectively. DOT absorption was 0.122 (SD = 0.108) mean percent, with flux and Kp calculated at 0.01 microg/cm2/h and 1.0 x 10(-7) cm/h, respectively. Pretreatment with the potential skin irritant 2% sodium lauryl sulfate had no effect on boron skin absorption. These in vivo results show that percutaneous absorption of boron, as boric acid, borax, and disodium octaborate tetrahydrate, through intact human skin is low and is significantly less than the average daily dietary intake. This very low boron skin absorption makes it apparent that, for the borates tested, the use of gloves to prevent systemic uptake is unnecessary. These findings do not apply to abraded or otherwise damaged skin.

Measurements of Forest-Atmosphere Isotopic CO2 Exchange by Eddy Covariance

NASA Astrophysics Data System (ADS)

Wehr, R. A.; Munger, J. W.; Nelson, D. D.; McManus, J. B.; Zahniser, M. S.; Saleska, S. R.

2010-12-01

Isotopic CO2 flux measurements are a promising means for partitioning the net ecosystem exchange of CO2 into photosynthetic and respiratory components. This approach to partitioning is possible in principle because of the distinct isotopic signatures of respired and photosynthesized CO2, but has been infeasible in practice—especially in forests—because of the difficulty of measuring isotopic ratios with sufficient precision and time response for use in eddy covariance (EC) flux calculations. Recent advances in laser spectroscopic instrumentation have changed that. We report measurements of isotopic (13C and 18O) CO2 exchange made by eddy covariance at Harvard Forest between April and December, 2010. The measurements were made using a continuous-wave quantum cascade laser spectrometer (Aerodyne Research Inc.) sampling at 4 Hz and are, to our knowledge, the first EC isotopic flux measurements at a forest site. The spectrometer can measure δ13C and δ18O with internal precisions (standard deviation of 1-minute averages) of 0.03 ‰, and [CO2] with an internal precision of 15 ppb; the instrumental accuracy, calibration, and long-term stability are discussed in detail. The isotopic data are considered in relation to environmental variables (PAR, temperature, humidity, soil temperature and moisture), and a first attempt at flux partitioning using the isotopic fluxes is presented.

Automated Sample Preparation for Radiogenic and Non-Traditional Metal Isotopes: Removing an Analytical Barrier for High Sample Throughput

NASA Astrophysics Data System (ADS)

Field, M. Paul; Romaniello, Stephen; Gordon, Gwyneth W.; Anbar, Ariel D.; Herrmann, Achim; Martinez-Boti, Miguel A.; Anagnostou, Eleni; Foster, Gavin L.

2014-05-01

MC-ICP-MS has dramatically improved the analytical throughput for high-precision radiogenic and non-traditional isotope ratio measurements, compared to TIMS. The generation of large data sets, however, remains hampered by tedious manual drip chromatography required for sample purification. A new, automated chromatography system reduces the laboratory bottle neck and expands the utility of high-precision isotope analyses in applications where large data sets are required: geochemistry, forensic anthropology, nuclear forensics, medical research and food authentication. We have developed protocols to automate ion exchange purification for several isotopic systems (B, Ca, Fe, Cu, Zn, Sr, Cd, Pb and U) using the new prepFAST-MC™ (ESI, Nebraska, Omaha). The system is not only inert (all-flouropolymer flow paths), but is also very flexible and can easily facilitate different resins, samples, and reagent types. When programmed, precise and accurate user defined volumes and flow rates are implemented to automatically load samples, wash the column, condition the column and elute fractions. Unattended, the automated, low-pressure ion exchange chromatography system can process up to 60 samples overnight. Excellent reproducibility, reliability, recovery, with low blank and carry over for samples in a variety of different matrices, have been demonstrated to give accurate and precise isotopic ratios within analytical error for several isotopic systems (B, Ca, Fe, Cu, Zn, Sr, Cd, Pb and U). This illustrates the potential of the new prepFAST-MC™ (ESI, Nebraska, Omaha) as a powerful tool in radiogenic and non-traditional isotope research.

High Precision Oxygen Three Isotope Analysis of Wild-2 Particles and Anhydrous Chondritic Interplanetary Dust Particles

NASA Technical Reports Server (NTRS)

Nakashima, D.; Ushikubo, T.; Zolensky, Michael E.; Weisberg, M. K.; Joswiak, D. J.; Brownlee, D. E.; Matrajt, G.; Kita, N. T.

2011-01-01

One of the most important discoveries from comet Wild-2 samples was observation of crystalline silicate particles that resemble chondrules and CAIs in carbonaceous chondrites. Previous oxygen isotope analyses of crystalline silicate terminal particles showed heterogeneous oxygen isotope ratios with delta(sup 18)O to approx. delta(sup 17)O down to -50% in the CAI-like particle Inti, a relict olivine grain in Gozen-sama, and an olivine particle. However, many Wild-2 particles as well as ferromagnesian silicates in anhydrous interplanetary dust particles (IDPs) showed Delta(sup 17)O values that cluster around -2%. In carbonaceous chondrites, chondrules seem to show two major isotope reservoirs with Delta(sup 17)O values at -5% and -2%. It was suggested that the Delta(sup 17)O = -2% is the common oxygen isotope reservoir for carbonaceous chondrite chondrules and cometary dust, from the outer asteroid belt to the Kuiper belt region. However, a larger dataset with high precision isotope analyses (+/-1-2%) is still needed to resolve the similarities or distinctions among Wild-2 particles, IDPs and chondrules in meteorites. We have made signifi-cant efforts to establish routine analyses of small particles (< or =10micronsm) at 1-2% precision using IMS-1280 at WiscSIMS laboratory. Here we report new results of high precision oxygen isotope analyses of Wild-2 particles and anhydrous chondritic IDPs, and discuss the relationship between the cometary dust and carbonaceous chondrite chondrules.

Fabrication of Subnanometer-Precision Nanopores in Hexagonal Boron Nitride

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

Gilbert, S. Matt; Dunn, Gabriel; Azizi, Amin

Here, we demonstrate the fabrication of individual nanopores in hexagonal boron nitride (h-BN) with atomically precise control of the pore shape and size. Previous methods of pore production in other 2D materials typically create pores with irregular geometry and imprecise diameters. In contrast, other studies have shown that with careful control of electron irradiation, defects in h-BN grow with pristine zig-zag edges at quantized triangular sizes, but they have failed to demonstrate production and control of isolated defects. In this work, we combine these techniques to yield a method in which we can create individual size-quantized triangular nanopores through anmore » h-BN sheet. The pores are created using the electron beam of a conventional transmission electron microscope; which can strip away multiple layers of h-BN exposing single-layer regions, introduce single vacancies, and preferentially grow vacancies only in the single-layer region. We further demonstrate how the geometry of these pores can be altered beyond triangular by changing beam conditions. Precisely size- and geometry-tuned nanopores could find application in molecular sensing, DNA sequencing, water desalination, and molecular separation.« less

Fabrication of Subnanometer-Precision Nanopores in Hexagonal Boron Nitride

DOE PAGES

Gilbert, S. Matt; Dunn, Gabriel; Azizi, Amin; ...

2017-11-08

Here, we demonstrate the fabrication of individual nanopores in hexagonal boron nitride (h-BN) with atomically precise control of the pore shape and size. Previous methods of pore production in other 2D materials typically create pores with irregular geometry and imprecise diameters. In contrast, other studies have shown that with careful control of electron irradiation, defects in h-BN grow with pristine zig-zag edges at quantized triangular sizes, but they have failed to demonstrate production and control of isolated defects. In this work, we combine these techniques to yield a method in which we can create individual size-quantized triangular nanopores through anmore » h-BN sheet. The pores are created using the electron beam of a conventional transmission electron microscope; which can strip away multiple layers of h-BN exposing single-layer regions, introduce single vacancies, and preferentially grow vacancies only in the single-layer region. We further demonstrate how the geometry of these pores can be altered beyond triangular by changing beam conditions. Precisely size- and geometry-tuned nanopores could find application in molecular sensing, DNA sequencing, water desalination, and molecular separation.« less

High precision tungsten isotope analysis using MC-ICP-MS and application for terrestrial samples

NASA Astrophysics Data System (ADS)

Suzuki, K.; Takamasa, A.

2017-12-01

Tungsten has five isotopes (M = 180, 182, 183, 184, 186), and 182W isotope is a rediogenic isotope produced by b-decay of 182Hf. Its half life is short (8.9 m.y.), and 182W isotope has been investigated to understand the early Earth geochemical evolution. Both Hf and W are highly refractory elements. As Hf is a lithophile and W is a siderophile elements, 182Hf-182W system could give constraints on metal-silicate (core-mantle) differentiation such as especially early Earth system because of its larege fractionation betwenn core-mantle and short half life. Improvement of analytical techniques of W isotope analyses leads to findings of W isotope anomaly (mostly positive) in old komatiites (2.4 - 3.8 Ga) and young volcanic rocks (12 Ma Ontong Java Plateau and 6 Ma Baffin Bay). In our study, high-precision W isotope ratio measurement with MC-ICP-MS (Thermo co. Ltd., NEPTUNE PLUS). We have measured W standard solution (SRM 3163) and obtained the isotopic compositions with an precision of ± 5ppm. However, the standard solution, which separated by cation or anion exchange resin, has systematical 183W/184W drift to -5ppm. These phenomena was also reported by Willbold et al. (2011). Therefore, we used the standard solution for correction of isotopic fractionation of samples which was processed by the same method as that of the samples. We will present the data of terrestrial samples obtained by the technique dveloped in this study.

Clarifying Atomic Weights: A 2016 Four-Figure Table of Standard and Conventional Atomic Weights

ERIC Educational Resources Information Center

Coplen, Tyler B.; Meyers, Fabienne; Holden, Norman E.

2017-01-01

To indicate that atomic weights of many elements are not constants of nature, in 2009 and 2011 the Commission on Isotopic Abundances and Atomic Weights (CIAAW) of the International Union of Pure and Applied Chemistry (IUPAC) replaced single-value standard atomic weight values with atomic weight intervals for 12 elements (hydrogen, lithium, boron,…

Characterization of the distribution of the sintering activator boron in powder metallurgical steels with SIMS.

PubMed

Krecar, Dragan; Vassileva, Vassilka; Danninger, Herbert; Hutter, Herbert

2004-06-01

Powder metallurgy is a well-established method for manufacturing ferrous precision parts. A very important step is sintering, which can be strongly enhanced by the formation of a liquid phase during the sintering process. Boron activates this process by forming such a liquid phase at about 1200 degrees C. In this work, the sintering of Fe-B was performed under the protective atmospheres of hydrogen, argon or nitrogen. Using different grain sizes of the added ferroboron leads to different formations of pores and to the formation of secondary pores. The effect of boron was investigated by means of Secondary Ion Mass Spectrometry (SIMS) supported by Scanning Electron Microscopy (SEM) and Light Microscopy (LM). To verify the influence of the process parameters on the mechanical properties, the microstructure (pore shape) was examined and impact energy measurements were performed. The concentrations of B in different samples were varied from 0.03-0.6 weight percent (wt%). Higher boron concentrations are detectable by EPMA, whereas the distributions of boron in the samples with interesting overall concentration in the low wt% range are only detectable by means of SIMS. This work shows that the distribution of boron strongly depends on its concentration and the sintering atmosphere used. At low concentration (up to 0.1 wt%) there are boride precipitations; at higher concentration there is a eutectic iron-boron grain boundary network. There is a decrease of the impact energy observed that correlates with the amount of eutectic phase.

Boron Isotopic Composition Correlates with Ultra-Structure in a - Sea Coral Lophelia Pertusa: Implications for Biomineralization and - PH

NASA Astrophysics Data System (ADS)

Blamart, D.; Rollion-Bard, C.; Meibom, A.; Cuif, J.; Juillet-Leclerc, A.; Dauphin, Y.; Douarin, M.

2007-12-01

The geochemistry (stable isotopes and trace elements) of biogenic carbonates has been widely used for more than fifty years to reconstruct past climatic variability. During this time, the studies were mainly based on bulk sampling limiting sometimes the interpretations of the geochemical data as paleoclimatic proxies. Recently, high spatial resolution sampling techniques, such as micro-mill and SIMS, have been employed in the study of C, O and B isotopic compositions and trace elements (Mg, Sr) in the skeletons of a variety of (deep-sea) coral species. These studies have documented dramatic 'vital effects' and uncovered a systematic relationship between skeletal ultra-structure and stable isotopic composition. The formation of skeleton corals follows a universal two-step growth process. At the tips of the skeletal structures, the mineralizing cell layer produces centers of calcification (COC) or, equivalently, Early Mineralization Zone (EMZ). These EMZ are subsequently overgrown by fibrous aragonite(FA) consisting of cyclically added layers. The EMZ are characterized by systematically lighter C and O isotopic compositions compared with the adjacent FA. A number of geochemical models have been proposed, in which this systematic stable isotopic difference between EMZ and FA is ascribed to a biologically induced variation in the pH of a proposed Extra-cytoplasmic Calcifying Fluid (ECF) reservoir. In these models, relatively high pH conditions during the formation of EMZ result in relatively light C and O isotopic compositions compared with FA, which form under generally lower pH conditions. A direct test of such models would be possible if the Boron isotopic composition, which is pH sensitive, of EMZ and FA could be measured. We performed ion microprobe d11B measurements for EMZ and FA in Lophelia pertusa, a deep-sea coral common in the North-East Atlantic Ocean. We observe a systematic difference in B isotopic composition between the EMZ and FA skeleton. In EMZ, the measured δ11B values are consistently low. Fibrous aragonite is characterized by systematically higher d11B values, but also display B isotopic heterogeneity associated with specific growth bands in the calyx wall. The magnitude of the observed B isotopic variations cannot be explained by changes in environmental conditions and are likely caused by biological processes involved in the biomineralization of new skeleton; i.e. 'vital' effects. The observed B isotopic variations are opposite to the predictions of geochemical models for vital effects. Our data indicate that pH variations are not responsible for the observed stable isotopic fractionations. Geochemical models therefore do not provide an adequate framework within which to understand coral skeletal formation. Without a better understanding of these processes, which require experiments, the use of B isotopic composition to reconstruct paleo-pH variations in the oceans must be considered problematic - at least as far as Lophelia pertusa is concerned.

Advances in the Metrology of Absolute Value Assignments to Isotopic Reference Materials: Consequences from the Avogadro Project

NASA Astrophysics Data System (ADS)

Vocke, Robert; Rabb, Savelas

2015-04-01

All isotope amount ratios (hereafter referred to as isotope ratios) produced and measured on any mass spectrometer are biased. This unfortunate situation results mainly from the physical processes in the source area where ions are produced. Because the ionized atoms in poly-isotopic elements have different masses, such processes are typically mass dependent and lead to what is commonly referred to as mass fractionation (for thermal ionization and electron impact sources) and mass bias (for inductively coupled plasma sources.) This biasing process produces a measured isotope ratio that is either larger or smaller than the "true" ratio in the sample. This has led to the development of numerous fractionation "laws" that seek to correct for these effects, many of which are not based on the physical processes giving rise to the biases. The search for tighter and reproducible precisions has led to two isotope ratio measurement systems that exist side-by-side. One still seeks to measure "absolute" isotope ratios while the other utilizes an artifact based measurement system called a delta-scale. The common element between these two measurement systems is the utilization of isotope reference materials (iRMs). These iRMs are used to validate a fractionation "law" in the former case and function as a scale anchor in the latter. Many value assignments of iRMs are based on "best measurements" by the original groups producing the reference material, a not entirely satisfactory approach. Other iRMs, with absolute isotope ratio values, have been produced by calibrated measurements following the Atomic Weight approach (AW) pioneered by NBS nearly 50 years ago. Unfortunately, the AW is not capable of calibrating the new generation of iRMs to sufficient precision. So how do we get iRMs with isotope ratios of sufficient precision and without bias? Such a focus is not to denigrate the extremely precise delta-scale measurements presently being made on non-traditional and tradition stable isotope systems. But even absolute isotope ratio measurements have an important role to play in delta-scale schemes. Highly precise and unbiased measurements of the artifact anchor for any scale facilitates the replacement of that scale's anchor once the initial supply of the iRM is exhausted. Absolute isotope ratio measurements of artifacts at the positive and negative extremes of a delta-scale will allow the appropriate assignment of delta-values to these normalizing iRMs, thereby minimizing any scale contractions or expansions to either side of the anchor artifact. And finally, absolute values for critical iRMs with also allow delta-scale results to be used in other scientific disciplines that employ other units of measure. Precise absolute isotope ratios of Si has been one of the consequences of the Avogadro Project (an international effort to replace the original kilogram artifact with a natural constant, the Planck constant.) We will present the results of applying such measurements to the principal iRMs for the Si isotope system (SRM 990, Big Batch and Diatomite) and its consequences for their delta-Si29 and delta-Si30 values.

Optimization Techniques for Improving the Precision of Isotopic Analysis by Thermal Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Wang, G. Q.; Xu, J. F.; Wu-Yang, S. Q.

2016-12-01

Operation of instruments and preparation of samples are also significant factors that can affect the precision of TIMS analyses, in addition to instrument hardware. We have reviewed the isotopic data of several standard materials at our TIMS lab for 5 years. It is suggested that several optimization techniques should be used in order to obtain high-precision isotopic ratio data: (1) It is important to choose a suitable filament material for isotopic measurements. We have established that W filament is likely the most efficient for ionizing Sr when selecting from W, Re, and Ta; meanwhile, Re filament can produce a higher intensity for Nd isotopes than W and Ta filament can. It is concluded that the best TIMS signals are obtained for Sr using W signal-filaments and for Nd using Re double-filaments. (2) The preparation of the activator plays a key role in the analysis of some isotopic ratios. This study indicates that choosing a suitable activator can greatly elevate the precision of 206Pb/204Pb ratios during Pb isotopic measurements. We have suggested a new scheme to make an activator by using a mixture of 10% Si-gel + 7.5% H3PO3 + 82.5% H2O (weight %). (3) It is necessary to re-set the cup configuration to avoid cup degradation when operating for a long period of time (a year or more). We propose a new cup configuration to avoid this disadvantage during Sr isotopic analyses. (4) The contamination of 187Re and 185Re after using Re-filament could be eliminated by cleaning the ion source and baking the source housing.

Molecular diffusion of stable water isotopes in polar firn as a proxy for past temperatures

NASA Astrophysics Data System (ADS)

Holme, Christian; Gkinis, Vasileios; Vinther, Bo M.

2018-03-01

Polar precipitation archived in ice caps contains information on past temperature conditions. Such information can be retrieved by measuring the water isotopic signals of δ18O and δD in ice cores. These signals have been attenuated during densification due to molecular diffusion in the firn column, where the magnitude of the diffusion is isotopologue specific and temperature dependent. By utilizing the differential diffusion signal, dual isotope measurements of δ18O and δD enable multiple temperature reconstruction techniques. This study assesses how well six different methods can be used to reconstruct past surface temperatures from the diffusion-based temperature proxies. Two of the methods are based on the single diffusion lengths of δ18O and δD , three of the methods employ the differential diffusion signal, while the last uses the ratio between the single diffusion lengths. All techniques are tested on synthetic data in order to evaluate their accuracy and precision. We perform a benchmark test to thirteen high resolution Holocene data sets from Greenland and Antarctica, which represent a broad range of mean annual surface temperatures and accumulation rates. Based on the benchmark test, we comment on the accuracy and precision of the methods. Both the benchmark test and the synthetic data test demonstrate that the most precise reconstructions are obtained when using the single isotope diffusion lengths, with precisions of approximately 1.0 °C . In the benchmark test, the single isotope diffusion lengths are also found to reconstruct consistent temperatures with a root-mean-square-deviation of 0.7 °C . The techniques employing the differential diffusion signals are more uncertain, where the most precise method has a precision of 1.9 °C . The diffusion length ratio method is the least precise with a precision of 13.7 °C . The absolute temperature estimates from this method are also shown to be highly sensitive to the choice of fractionation factor parameterization.

Isotopic Ratios of Samarium by TIMS for Nuclear Forensic Application

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

Louis Jean, James; Inglis, Jeremy David

The isotopic ratio of Nd, Sm, and Gd can provide important information regarding fissile material (nuclear devices, reactors), neutron environment, and device yield. These studies require precise measurement of Sm isotope ratios, by either TIMS or MC-ICP-MS. There has been an increasing trend to measure smaller and smaller quantities of Sm bearing samples. In nuclear forensics 10-100 ng of Sm are needed for precise measurement. To measure sub-ng Sm samples using TIMS for nuclear forensic analysis.

Isotope Analysis of Uranium by Optical Spectroscopy; ANALYSE ISOTOPIQUE DE L'URANIUM PAR SPECTROSCOPIE OPTIQUE

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

Gerstenkorn, S.

1958-06-01

Isotopic analysis of urarium is made by means of hollow cathode lamp and a Fabry-Perot photoelectric spectrometer. The line U/sup 235/, 5027 A is used. This method allows a deterraination of the isotopic concentrations in U /sup 235/ down to 0.1%. The relative precision is about 2% for amounts of U/sup 235/ over 1%. For weaker amounts this line allows relative measurements of better precision when using standard mixtures. (auth)

Uranium Measurement Improvements at the Savannah River Technology Center

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

Shick, C. Jr.

Uranium isotope ratio and isotope dilution methods by mass spectrometry are used to achieve sensitivity, precision and accuracy for various applications. This report presents recent progress made at SRTC in the analysis of minor isotopes of uranium. Comparison of routine measurements of NBL certified uranium (U005a) using the SRTC Three Stage Mass Spectrometer (3SMS) and the SRTC Single Stage Mass Spectrometer (SSMS). As expected, the three stage mass spectrometer yielded superior sensitivity, precision, and accuracy for this application.

Sputtering Erosion in Ion and Plasma Thrusters

NASA Technical Reports Server (NTRS)

Ray, Pradosh K.

1996-01-01

Low energy sputtering of molybdenum, tantalum and boron nitride with xenon ions are being studied using secondary neutral and secondary ion mass spectrometry (SNMS/SIMS). An ultrahigh vacuum chamber was used to conduct the experiment at a base pressure of 1x10(exp -9) torr. The primary ion beam is generated by an ion gun which is capable of delivering ion currents in the range of 20 to 500 nA. The ion beam can be focused to a spot size of approximately 1 mm in diameter. The mass spectrometer is positioned 10 mm from the target and 90 deg to the primary ion beam direction. SNMS and SIMS spectra were collected at various incident angles and different ion energies. For boron nitride sputtering, the target was flooded with an electron beam to neutralize the charge buildup on the surface. In the SNMS mode, sputtering of Mo and Ta can be detected at an ion energy as low as 100 eV whereas in boron nitride the same was observed up to an energy of 300 eV. However, in the positive-SIMS mode, the sputtering of Mo was observed at 10 eV incident ion energy. The SIMS spectra obtained for boron nitride clearly identifies the two isotopes of boron as well as cluster ions such as B2(sup +) and molecular ions such as BN(sup +). From the angle versus yields measurements, it was found that the maximum SNMS yield shifts towards lower incident angles at low ion energies for all three samples.

Decoupled carbonate chemistry controls on the incorporation of boron into Orbulina universa

NASA Astrophysics Data System (ADS)

Howes, Ella L.; Kaczmarek, Karina; Raitzsch, Markus; Mewes, Antje; Bijma, Nienke; Horn, Ingo; Misra, Sambuddha; Gattuso, Jean-Pierre; Bijma, Jelle

2017-01-01

In order to fully constrain paleo-carbonate systems, proxies for two out of seven parameters, plus temperature and salinity, are required. The boron isotopic composition (δ11B) of planktonic foraminifera shells is a powerful tool for reconstructing changes in past surface ocean pH. As B(OH)4- is substituted into the biogenic calcite lattice in place of CO32-, and both borate and carbonate ions are more abundant at higher pH, it was suggested early on that B / Ca ratios in biogenic calcite may serve as a proxy for [CO32-]. Although several recent studies have shown that a direct connection of B / Ca to carbonate system parameters may be masked by other environmental factors in the field, there is ample evidence for a mechanistic relationship between B / Ca and carbonate system parameters. Here, we focus on investigating the primary relationship to develop a mechanistic understanding of boron uptake. Differentiating between the effects of pH and [CO32-] is problematic, as they co-vary closely in natural systems, so the major control on boron incorporation remains unclear. To deconvolve the effects of pH and [CO32-] and to investigate their impact on the B / Ca ratio and δ11B, we conducted culture experiments with the planktonic foraminifer Orbulina universa in manipulated culture media: constant pH (8.05), but changing [CO32-] (238, 286 and 534 µmol kg-1 CO32-) and at constant [CO32-] (276 ± 19.5 µmol kg-1) and varying pH (7.7, 7.9 and 8.05). Measurements of the isotopic composition of boron and the B / Ca ratio were performed simultaneously using a femtosecond laser ablation system coupled to a MC-ICP-MS (multiple-collector inductively coupled plasma mass spectrometer). Our results show that, as expected, δ11B is controlled by pH but it is also modulated by [CO32-]. On the other hand, the B / Ca ratio is driven by [HCO3-], independently of pH. This suggests that B / Ca ratios in foraminiferal calcite can possibly be used as a second, independent, proxy for complete paleo-carbonate system reconstructions. This is discussed in light of recent literature demonstrating that the primary relationship between B / Ca and [HCO3-] can be obscured by other environmental parameters.

Search for Nucleosynthetic Cadmium Isotope Variations in Bulk Carbonaceous Chondrites

NASA Astrophysics Data System (ADS)

Toth, E. R.; Schönbächler, M.; Friebel, M.; Fehr, M. A.

2016-08-01

New high-precision Cd isotope data will be presented for bulk carbonaceous chondrites, such as Allende and Murchison. Volatile element isotope anomalies and their potential nucleosynthetic sources will be discussed.

Evaluation of UV-fs-LA-MC-ICP-MS for precise in situ copper isotopic microanalysis of cubanite.

PubMed

Ikehata, Kei; Hirata, Takafumi

2013-01-01

We evaluated the capabilities of an in situ method for measuring copper isotopes of cubanite using UV-fs-LA-MC-ICP-MS. A comparison of the UV-fs laser results with those obtained from the NIR-fs laser system shows that there is obviously an improvement in the precision (<0.10‰, 2SE) when using the UV-fs laser. In both wavelength modes, matrix-matched standards are required for reliable in situ copper isotope analysis of cubanite. This method was applied to determinations for copper isotopes of minute cubanite grains in a skarn ore. Copper isotopic ratios of cubanite grains near a weathered surface of the sample are lower than those of intact cubanite grains within the sample, suggesting that selective leaching of heavier copper isotope in primary minerals occurred during weathering.

Embrittling Components in Sintered Steels: Comparison of Phosphorus and Boron

NASA Astrophysics Data System (ADS)

Danninger, Herbert; Vassileva, Vassilka; Gierl-Mayer, Christian

2017-12-01

In ferrous powder metallurgy, both boron and phosphorus have been known to be sintering activators for a long time. However, the use has been widely different: while P is a standard additive to sintered iron and steels, boron has been frequently studied, but its use in practice is very limited. Both additives are also known to be potentially embrittling, though in a different way. In the present study the differences between the effects of both elements are shown: while P activates sintering up to a certain threshold, in part by stabilizing ferrite, in part by forming a transient liquid phase, boron is the classical additive enhancing persistent liquid phase, being virtually insoluble in the iron matrix. The consequence is that sintered steels can tolerate quite a proportion of phosphorus, depending on composition and sintering process; boron however is strongly embrittling in particular in combination with carbon, which requires establishing a precisely defined content that enhances sintering but is not yet embrittling. The fracture mode of embrittled materials is also different: while with Fe-P the classical intergranular fracture is observed, with boron a much more rugged fracture surface appears, indicating some failure through the eutectic interparticle network but mostly transgranular cleavage. If carbon is added, in both cases transgranular cleavage dominates even in the severely embrittled specimens, indicating that no more the grain boundaries and sintering necks are the weakest links in the systems.

Selected isotope ratio measurements of light metallic elements (Li, Mg, Ca, and Cu) by multiple collector ICP-MS

PubMed Central

Platzner, Thomas I.; Segal, Irina

2007-01-01

The unique capabilities of multiple collector inductively coupled mass spectrometry (MC-ICP-MS) for high precision isotope ratio measurements in light elements as Li, Mg, Ca, and Cu are reviewed in this paper. These elements have been intensively studied at the Geological Survey of Israel (GSI) and other laboratories over the past few years, and the methods used to obtain high precision isotope analyses are discussed in detail. The scientific study of isotopic fractionation of these elements is significant for achieving a better understanding of geochemical and biochemical processes in nature and the environment. PMID:17962922

Optimization and application of ICPMS with dynamic reaction cell for precise determination of 44Ca/40Ca isotope ratios.

PubMed

Boulyga, Sergei F; Klötzli, Urs; Stingeder, Gerhard; Prohaska, Thomas

2007-10-15

An inductively coupled plasma mass spectrometer with dynamic reaction cell (ICP-DRC-MS) was optimized for determining (44)Ca/(40)Ca isotope ratios in aqueous solutions with respect to (i) repeatability, (ii) robustness, and (iii) stability. Ammonia as reaction gas allowed both the removal of (40)Ar+ interference on (40)Ca+ and collisional damping of ion density fluctuations of an ion beam extracted from an ICP. The effect of laboratory conditions as well as ICP-DRC-MS parameters such a nebulizer gas flow rate, rf power, lens potential, dwell time, or DRC parameters on precision and mass bias was studied. Precision (calculated using the "unbiased" or "n - 1" method) of a single isotope ratio measurement of a 60 ng g(-1) calcium solution (analysis time of 6 min) is routinely achievable in the range of 0.03-0.05%, which corresponded to the standard error of the mean value (n = 6) of 0.012-0.020%. These experimentally observed RSDs were close to theoretical precision values given by counting statistics. Accuracy of measured isotope ratios was assessed by comparative measurements of the same samples by ICP-DRC-MS and thermal ionization mass spectrometry (TIMS) by using isotope dilution with a (43)Ca-(48)Ca double spike. The analysis time in both cases was 1 h per analysis (10 blocks, each 6 min). The delta(44)Ca values measured by TIMS and ICP-DRC-MS with double-spike calibration in two samples (Ca ICP standard solution and digested NIST 1486 bone meal) coincided within the obtained precision. Although the applied isotope dilution with (43)Ca-(48)Ca double-spike compensates for time-dependent deviations of mass bias and allows achieving accurate results, this approach makes it necessary to measure an additional isotope pair, reducing the overall analysis time per isotope or increasing the total analysis time. Further development of external calibration by using a bracketing method would allow a wider use of ICP-DRC-MS for routine calcium isotopic measurements, but it still requires particular software or hardware improvements aimed at reliable control of environmental effects, which might influence signal stability in ICP-DRC-MS and serve as potential uncertainty sources in isotope ratio measurements.

Cryptic Species and Vital Effects of Planktonic Foraminifera and the Implications for the B/Ca Carbonate System Proxy

NASA Astrophysics Data System (ADS)

Osborne, E.; Thunell, R.; Bizimis, M.; Buckley, W. P., Jr.; Sadekov, A.

2017-12-01

The concentration of boron in marine carbonates (B/Ca ratio) has been proposed to covary with seawater carbonate chemistry. However, a number of studies have evaluated the B/Ca proxy in planktonic foraminifera and found that boron incorporation may not be a straightforward process. The majority of previous research has been dedicated to tropical species that host large photosynthetic symbionts, which interfere with ambient carbonate chemistry and the incorporation of boron into the calcite lattice. This study focuses on evaluating B/Ca of subtropical and subpolar species that are asymbiontic or host small intra-shell non-dinoflagellate symbionts (Globigerina bulloides, Neogloboquadrina incompta and Neogloboquadrina dutertrei). Size-fraction replicate B/Ca measurements spanning a year-long sediment trap time-series generally indicate no size-dependent uptake of boron for these species, further supporting that symbionts influence/complicate boron incorporation/concentration. Both Neogloboquadrina species indicate strong correlation with the calcite saturation of seawater, carbonate ion concentration and pH that agree well with a recently published Pacific core-top calibration. However the relationship between G. bulloides and these variables is more complex. The presence of two cryptic species of G. bulloides (encrusted and normal) in our study region with documented offsets in stable isotopic composition also causes the unexpected differences between pooled trace element sample values and carbonate chemistry. Individual shell geochemistries determined by laser ablation ICP-MS indicate that the encrusted morphospecies have higher boron concentrations relative to the normal morphospecies. Based on these results we conclude that B/Ca ratios of non-dinoflagellate/symbiont-barren foraminifera faithfully record seawater carbonate chemistry. However inter-species and morphospecies differences may be significant and careful application of the B/Ca proxy to a single morphospecies is essential to creating meaningful data.

Thermal Properties and Phonon Spectral Characterization of Synthetic Boron Phosphide for High Thermal Conductivity Applications.

PubMed

Kang, Joon Sang; Wu, Huan; Hu, Yongjie

2017-12-13

Heat dissipation is an increasingly critical technological challenge in modern electronics and photonics as devices continue to shrink to the nanoscale. To address this challenge, high thermal conductivity materials that can efficiently dissipate heat from hot spots and improve device performance are urgently needed. Boron phosphide is a unique high thermal conductivity and refractory material with exceptional chemical inertness, hardness, and high thermal stability, which holds high promises for many practical applications. So far, however, challenges with boron phosphide synthesis and characterization have hampered the understanding of its fundamental properties and potential applications. Here, we describe a systematic thermal transport study based on a synergistic synthesis-experimental-modeling approach: we have chemically synthesized high-quality boron phosphide single crystals and measured their thermal conductivity as a record-high 460 W/mK at room temperature. Through nanoscale ballistic transport, we have, for the first time, mapped the phonon spectra of boron phosphide and experimentally measured its phonon mean free-path spectra with consideration of both natural and isotope-pure abundances. We have also measured the temperature- and size-dependent thermal conductivity and performed corresponding calculations by solving the three-dimensional and spectral-dependent phonon Boltzmann transport equation using the variance-reduced Monte Carlo method. The experimental results are in good agreement with that predicted by multiscale simulations and density functional theory, which together quantify the heat conduction through the phonon mode dependent scattering process. Our finding underscores the promise of boron phosphide as a high thermal conductivity material for a wide range of applications, including thermal management and energy regulation, and provides a detailed, microscopic-level understanding of the phonon spectra and thermal transport mechanisms of boron phosphide. The present study paves the way toward the establishment of a new framework, based on the phonon spectra-material structure relationship, for the rational design of high thermal conductivity materials and nano- to multiscale devices.

Tourmaline mineralization in the Barberton greenstone belt, South Africa: early Archean metasomatism by evaporite-derived boron.

PubMed

Byerly, G R; Palmer, M R

1991-05-01

Tourmaline-rich rocks are common in the low-grade, interior portions of the Barberton greenstone belt of South Africa, where shallow-marine sediments and underlying altered basaltic and komatiitic lavas contain up to 50% tourmaline. The presence of tourmaline-bearing rip-up clasts, intraformational tourmaline pebbles and tourmaline-coated grains indicate that boron mineralization was a low-temperature, surficial process. The association of these lithologies with stromatolites, evaporites, and shallow-water sedimentary structures and the virtual absence of tourmaline in correlative deep-water facies rocks in the greenstone belt strengthens this model. Five tourmaline-bearing lithologic groups (basalts, komatiites, evaporite-bearing sediments, stromatolitic sediments, and quartz veins) are distinguished based on field, petrographic, and geochemical criteria. Individual tourmaline crystals within these lithologies show internal chemical and textural variations that reflect continued growth through intervals of change in bulk-rock and fluid composition accompanying one or more metasomatic events. Large single-crystal variations exist in Fe/Mg, Al/Fe, and alkali-site vacancies. A wide range in tourmaline composition exists in rocks altered from similar protoliths, but tourmalines in sediments and lavas have similar compositional variations. Boron-isotope analyses of the tourmalines suggest that the boron enrichment in these rocks has a major marine evaporitic component. Sediments with gypsum pseudomorphs and lavas altered at low temperatures by shallow-level brines have the highest delta 11B values (+2.2 to -1.9%); lower delta 11B values of late quartz veins (-3.7 to -5.7%) reflect intermediate temperature, hydrothermal remobilization of evaporitic boron. The delta 11B values of tourmaline-rich stromatolitic sediments (-9.8 and -10.5%) are consistent with two-stage boron enrichment, in which earlier marine evaporitic boron was hydrothermally remobilized and vented in shallow-marine or subaerial sites, mineralizing algal stromatolites. The stromatolite-forming algae preferentially may have lived near the sites of hydrothermal discharge in Archean times.

Modern Material Analysis Instruments Add a New Dimension to Materials Characterization and Failure Analysis

NASA Technical Reports Server (NTRS)

Panda, Binayak

2009-01-01

Modern analytical tools can yield invaluable results during materials characterization and failure analysis. Scanning electron microscopes (SEMs) provide significant analytical capabilities, including angstrom-level resolution. These systems can be equipped with a silicon drift detector (SDD) for very fast yet precise analytical mapping of phases, as well as electron back-scattered diffraction (EBSD) units to map grain orientations, chambers that admit large samples, variable pressure for wet samples, and quantitative analysis software to examine phases. Advanced solid-state electronics have also improved surface and bulk analysis instruments: Secondary ion mass spectroscopy (SIMS) can quantitatively determine and map light elements such as hydrogen, lithium, and boron - with their isotopes. Its high sensitivity detects impurities at parts per billion (ppb) levels. X-ray photo-electron spectroscopy (XPS) can determine oxidation states of elements, as well as identifying polymers and measuring film thicknesses on coated composites. This technique is also known as electron spectroscopy for chemical analysis (ESCA). Scanning Auger electron spectroscopy (SAM) combines surface sensitivity, spatial lateral resolution (10 nm), and depth profiling capabilities to describe elemental compositions of near and below surface regions down to the chemical state of an atom.

Water vapor δ17O measurements using an off-axis integrated cavity output spectrometer and seasonal variation in 17O-excess of precipitation in the east-central United States

NASA Astrophysics Data System (ADS)

Tian, C.; Wang, L.; Novick, K. A.

2016-12-01

High-precision triple oxygen isotope analysis can be used to improve our understanding of multiple hydrological and meteorological processes. Recent studies focus on understanding 17O-excess variation of tropical storms, high-latitude snow and ice-core as well as spatial distribution of meteoric water (tap water). The temporal scale of 17O-excess variation in middle-latitude precipitation is needed to better understand which processes control on the 17O-excess variations. This study focused on assessing how the accuracy and precision of vapor δ17O laser spectroscopy measurements depend on vapor concentration, delta range, and averaging-time. Meanwhile, we presented 17O-excess data from two-year, event based precipitation sampling in the east-central United States. A Triple Water Vapor Isotope Analyzer (T-WVIA) was used to evaluate the accuracy and precision of δ2H, δ18O and δ17O measurements. GISP and SLAP2 from IAEA and four working standards were used to evaluate the sensitivity in the three factors. Overall, the accuracy and precision of all isotope measurements were sensitive to concentration, with higher accuracy and precision generally observed under moderate vapor concentrations (i.e., 10000-15000 ppm) for all isotopes. Precision was also sensitive to the range of delta values, though the effect was not as large when compared to the sensitivity to concentration. The precision was much less sensitive to averaging time when compared with concentration and delta range effects. The preliminary results showed that 17O-excess variation was lower in summer (23±17 per meg) than in winter (34±16 per meg), whereas spring values (30±21 per meg) was similar to fall (29±13 per meg). That means kinetic fractionation influences the isotopic composition and 17O-excess in different seasons.

Ion microprobe measurement of strontium isotopes in calcium carbonate with application to salmon otoliths

USGS Publications Warehouse

Weber, P.K.; Bacon, C.R.; Hutcheon, I.D.; Ingram, B.L.; Wooden, J.L.

2005-01-01

The ion microprobe has the capability to generate high resolution, high precision isotopic measurements, but analysis of the isotopic composition of strontium, as measured by the 87Sr/ 86Sr ratio, has been hindered by isobaric interferences. Here we report the first high precision measurements of 87Sr/ 86Sr by ion microprobe in calcium carbonate samples with moderate Sr concentrations. We use the high mass resolving power (7000 to 9000 M.R.P.) of the SHRIMP-RG ion microprobe in combination with its high transmission to reduce the number of interfering species while maintaining sufficiently high count rates for precise isotopic measurements. The isobaric interferences are characterized by peak modeling and repeated analyses of standards. We demonstrate that by sample-standard bracketing, 87Sr/86Sr ratios can be measured in inorganic and biogenic carbonates with Sr concentrations between 400 and 1500 ppm with ???2??? external precision (2??) for a single analysis, and subpermil external precision with repeated analyses. Explicit correction for isobaric interferences (peak-stripping) is found to be less accurate and precise than sample-standard bracketing. Spatial resolution is ???25 ??m laterally and 2 ??m deep for a single analysis, consuming on the order of 2 ng of material. The method is tested on otoliths from salmon to demonstrate its accuracy and utility. In these growth-banded aragonitic structures, one-week temporal resolution can be achieved. The analytical method should be applicable to other calcium carbonate samples with similar Sr concentrations. Copyright ?? 2005 Elsevier Ltd.

An international dosimetry exchange for BNCT part II: computational dosimetry normalizations.

PubMed

Riley, K J; Binns, P J; Harling, O K; Albritton, J R; Kiger, W S; Rezaei, A; Sköld, K; Seppälä, T; Savolainen, S; Auterinen, I; Marek, M; Viererbl, L; Nievaart, V A; Moss, R L

2008-12-01

The meaningful sharing and combining of clinical results from different centers in the world performing boron neutron capture therapy (BNCT) requires improved precision in dose specification between programs. To this end absorbed dose normalizations were performed for the European clinical centers at the Joint Research Centre of the European Commission, Petten (The Netherlands), Nuclear Research Institute, Rez (Czech Republic), VTT, Espoo (Finland), and Studsvik, Nyköping (Sweden). Each European group prepared a treatment plan calculation that was bench-marked against Massachusetts Institute of Technology (MIT) dosimetry performed in a large, water-filled phantom to uniformly evaluate dose specifications with an estimated precision of +/-2%-3%. These normalizations were compared with those derived from an earlier exchange between Brookhaven National Laboratory (BNL) and MIT in the USA. Neglecting the uncertainties related to biological weighting factors, large variations between calculated and measured dose are apparent that depend upon the 10B uptake in tissue. Assuming a boron concentration of 15 microg g(-1) in normal tissue, differences in the evaluated maximum dose to brain for the same nominal specification of 10 Gy(w) at the different facilities range between 7.6 and 13.2 Gy(w) in the trials using boronophenylalanine (BPA) as the boron delivery compound and between 8.9 and 11.1 Gy(w) in the two boron sulfhydryl (BSH) studies. Most notably, the value for the same specified dose of 10 Gy(w) determined at the different participating centers using BPA is significantly higher than at BNL by 32% (MIT), 43% (VTT), 49% (JRC), and 74% (Studsvik). Conversion of dose specification is now possible between all active participants and should be incorporated into future multi-center patient analyses.

A hydrogen gas-water equilibration method produces accurate and precise stable hydrogen isotope ratio measurements in nutrition studies

USDA-ARS?s Scientific Manuscript database

Stable hydrogen isotope methodology is used in nutrition studies to measure growth, breast milk intake, and energy requirement. Isotope ratio MS is the best instrumentation to measure the stable hydrogen isotope ratios in physiological fluids. Conventional methods to convert physiological fluids to ...

Boron isotope systematics during magma-carbonate interaction: an experimental study from Merapi (Indonesia) and Vesuvius (Italy)

NASA Astrophysics Data System (ADS)

Deegan, F. M.; Jolis, E. M.; Troll, V. R.; Freda, C.; Whitehouse, M.

2011-12-01

Carbonate assimilation is increasingly recognized as an important process affecting the compositional evolution of magma and its inherent ability to erupt explosively due to release of carbonate-derived CO2 [e.g., 1, 2, 3]. In order to gain insights into this process, we performed short time-scale carbonate dissolution experiments in silicate melt using natural starting materials from Merapi and Vesuvius volcanoes at magmatic pressure and temperature [2, 4]. The experiments enable us to resolve in detail the timescales, textures and chemical features of carbonate assimilation. Three compositionally distinct glass domains have been defined: i) Ca-normal glass, similar in composition to the starting material; ii) Ca-rich, contaminated glass; and iii) a diffusional glass interface between the Ca-normal and Ca-rich glass, characterized by steady interchange between SiO2 and CaO. Here we present new boron isotope data for the experimental products obtained by SIMS. The glasses show distinct and systematic variation in their δ11B (%) values. The contaminated glasses generally show extremely negative δ11B values (down to -41 %) relative to both the uncontaminated experimental glass and fresh arc volcanics (-7 to +7 % [5]). Considering that carbonates have δ11B values of +9 to +26 [6], the data cannot be explained by simple mixing processes between the end-members alone. This implies that the δ11B of the original contaminant was drastically modified before being incorporated into the melt, which can be explained by B isotope fractionation during breakdown and degassing of the carbonate. Our data represents the first B isotope analyses of experimental products of carbonate assimilation. They provide novel and well constrained insights into the behavior of boron upon degassing of carbonate. This, in turn, has implications for both i) late stage contamination and volatile addition to hazardous volcanic systems located over carbonate basement (cf. [7]) and ii) studies of mass transfer in subduction zones, where B is frequently employed as a tracer of deep crustal recycling [8]. [1] Chadwick et al. (2007) J. Petrol. 48, 1793-1812. [2] Deegan et al. (2010) J. Petrol. 51, 1027-1051. [3] Freda et al. (2010) Bull. Volcanol. 73, 241-256. [4] Jolis et al. (2011) in prep. [5] Leeman & Sisson (1996) Rev. Min. 33, 645-707. [6] Ishikawa & Nakamura (1993) Earth Planet Sci. Lett. 117, 567-580. [7] Deegan et al. (2011) Geology Today 27, 63-64. [8] Rose et al. (2001) Science 293, 281-283.

An in-depth evaluation of accuracy and precision in Hg isotopic analysis via pneumatic nebulization and cold vapor generation multi-collector ICP-mass spectrometry.

PubMed

Rua-Ibarz, Ana; Bolea-Fernandez, Eduardo; Vanhaecke, Frank

2016-01-01

Mercury (Hg) isotopic analysis via multi-collector inductively coupled plasma (ICP)-mass spectrometry (MC-ICP-MS) can provide relevant biogeochemical information by revealing sources, pathways, and sinks of this highly toxic metal. In this work, the capabilities and limitations of two different sample introduction systems, based on pneumatic nebulization (PN) and cold vapor generation (CVG), respectively, were evaluated in the context of Hg isotopic analysis via MC-ICP-MS. The effect of (i) instrument settings and acquisition parameters, (ii) concentration of analyte element (Hg), and internal standard (Tl)-used for mass discrimination correction purposes-and (iii) different mass bias correction approaches on the accuracy and precision of Hg isotope ratio results was evaluated. The extent and stability of mass bias were assessed in a long-term study (18 months, n = 250), demonstrating a precision ≤0.006% relative standard deviation (RSD). CVG-MC-ICP-MS showed an approximately 20-fold enhancement in Hg signal intensity compared with PN-MC-ICP-MS. For CVG-MC-ICP-MS, the mass bias induced by instrumental mass discrimination was accurately corrected for by using either external correction in a sample-standard bracketing approach (SSB) or double correction, consisting of the use of Tl as internal standard in a revised version of the Russell law (Baxter approach), followed by SSB. Concomitant matrix elements did not affect CVG-ICP-MS results. Neither with PN, nor with CVG, any evidence for mass-independent discrimination effects in the instrument was observed within the experimental precision obtained. CVG-MC-ICP-MS was finally used for Hg isotopic analysis of reference materials (RMs) of relevant environmental origin. The isotopic composition of Hg in RMs of marine biological origin testified of mass-independent fractionation that affected the odd-numbered Hg isotopes. While older RMs were used for validation purposes, novel Hg isotopic data are provided for the latest generations of some biological RMs.

Isotope ratios of trace elements in samples from human nutrition studies determined by TIMS and ICP-MS: precision and accuracy compared.

PubMed

Turnlund, Judith R; Keyes, William R

2002-09-01

Stable isotopes are used with increasing frequency to trace the metabolic fate of minerals in human nutrition studies. The precision of the analytical methods used must be sufficient to permit reliable measurement of low enrichments and the accuracy should permit comparisons between studies. Two methods most frequently used today are thermal ionization mass spectrometry (TIMS) and inductively coupled plasma mass spectrometry (ICP-MS). This study was conducted to compare the two methods. Multiple natural samples of copper, zinc, molybdenum, and magnesium were analyzed by both methods to compare their internal and external precision. Samples with a range of isotopic enrichments that were collected from human studies or prepared from standards were analyzed to compare their accuracy. TIMS was more precise and accurate than ICP-MS. However, the cost, ease, and speed of analysis were better for ICP-MS. Therefore, for most purposes, ICP-MS is the method of choice, but when the highest degrees of precision and accuracy are required and when enrichments are very low, TIMS is the method of choice.

Electron Energy Distribution and Transfer Phenomena in Non-Equilibrium Gases

DTIC Science & Technology

2016-09-01

and quantitative determination of species difficult. In a mass spectrometry study on boron chemistry a few decade ago, a technique of isotopic...In this FTMS study on TEB, by means of the high-mass-resolution spectrum to distinguish the isobaric ions, we have identified and quantitatively ...reproduce, release, perform, display, or disclose the work. 14. ABSTRACT During this 3-year in-house experimental research task, researchers in the

``Smoking From The Same Pipe": Developement of an 40Ar/39Ar Datting Intercalibration PIpette System (Invited)

NASA Astrophysics Data System (ADS)

Turrin, B. D.; Swisher, C. C.; Deino, A.; Hemming, S. R.; Hodges, K.; Renne, P. R.

2010-12-01

The precision and accuracy of Ar isotope ratio measurements is one of the main limiting factors in the uncertainties of an 40Ar/39Ar age. Currently, it is relatively common to measure Ar isotopic ratios to a precision of 1-2‰ or better on an intralaboratory basis. This level of analytical precision equates to a comparable level of precision (1-3‰) in the calculated age, depending on the extent of atmospheric Ar contamination, importance of nucleogenic interference corrections, and other factors. However, it has become clear that improving the precision of mass spectrometry is not the only bottleneck towards improving the accuracy and precision of 40Ar/39Ar dating in general. Rather, the most urgent issue is interlaboratory reproducibility. This became obvious in a recent EARTHTIME initiative undertaken to intercalibrate two commonly used 40Ar/39Ar standards [the Fish Canyon sanidine (FCs) and the Alder Creek sanidine (ACs)]. This effort revealed variations amongst laboratories (at the 1-2% level), an order of magnitude greater than the internal analytical precisions. To address these issues, we have proposed (to NSF) to construct two identical pipette systems loaded to identical starting pressures and with identical isotopic compositions. One pipette system will travel between participating 40Ar/39Ar labs and the second system will not travel and serve as the “Master” system to test for any fractionation or undocumented depletion of the traveling pipette system. In order to ensure delivery of uniform amounts of homogenous gas, the pipette system will be computer-controlled with preprogrammed routines and lockouts to prevent compromising the reservoirs. The pipette systems will deliver three gas samples with different isotopic ratios at two different pressures/concentrations. One pipette bulb will be of atmospheric isotopic composition, and the other two pipette bulbs will have 40Ar*/39ArK ratios corresponding to co-irradiated ACs and FCs fixed by their relative ages at ~1:23.6. A pipette system will permit the participating labs to measure gas samples with exactly the same isotopic composition(s) and similar gas volumes. Measuring the same gas controls the variables such as 1) sample heterogeneity or experimental artifacts arising from neutron dosage; 2) incomplete degassing and the possibility of isotopic fractionation of Ar; and 3) problems related to isobaric interferences from e.g. hydrocarbons or HCl. By fixing these variables, the influence of different data reduction protocols can be assessed. In addition, measuring gas samples with fixed isotopic ratios at different pressures/concentrations will also test the pressure effects on ion source and/or detector linearity.

High-precision measurement of chlorine stable isotope ratios

USGS Publications Warehouse

Long, A.; Eastoe, C.J.; Kaufmann, R.S.; Martin, J.G.; Wirt, L.; Finley, J.B.

1993-01-01

We present an analysis procedure that allows stable isotopes of chlorine to be analyzed with precision sufficient for geological and hydrological studies. The total analytical precision is ?????0.09%., and the present known range of chloride in the surface and near-surface environment is 3.5???. As Cl- is essentially nonreactive in natural aquatic environments, it is a conservative tracer and its ??37Cl is also conservative. Thus, the ??37Cl parameter is valuable for quantitative evaluation of mixing of different sources of chloride in brines and aquifers. ?? 1993.

Isotopic Analysis of Plutonium by Optical Spectroscopy; ANALYSE ISOTOPIQUE DU PLUTONIUM PAR SPECTROSCOPIE OPTIQUE

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

Artaud, J.; Chaput, M.; Gerstenkorn, S.

1961-01-01

Isotopic analyses of mixtures of plutonium-239 and -240 were carried out by means of the photoelectric spectrometer, the source being a hollow cathode cooled by liquid nitrogen. The relative precision is of the order of 2%, for samples containieg 3% of Pu/sup 240/. The study of the reproductibility of the measurements should make it possible to increase the precision; the relative precision which can be expected from the method should be 1% for mixtures containing 1% of Pu/sup 240/. (auth)

Calcium Isotope Analysis by Mass Spectrometry

NASA Astrophysics Data System (ADS)

Boulyga, S.; Richter, S.

2010-12-01

The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. This presentation discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. Additionally, the availability of Ca isotope reference materials will be discussed.

High-Precision Plutonium Isotopic Compositions Measured on Los Alamos National Laboratory’s General’s Tanks Samples: Bearing on Model Ages, Reactor Modelling, and Sources of Material. Further Discussion of Chronometry

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

Spencer, Khalil J.; Rim, Jung Ho; Porterfield, Donivan R.

2015-06-29

In this study, we re-analyzed late-1940’s, Manhattan Project era Plutonium-rich sludge samples recovered from the ''General’s Tanks'' located within the nation’s oldest Plutonium processing facility, Technical Area 21. These samples were initially characterized by lower accuracy, and lower precision mass spectrometric techniques. We report here information that was previously not discernable: the two tanks contain isotopically distinct Pu not only for the major (i.e., 240Pu, 239Pu) but trace ( 238Pu , 241Pu, 242Pu) isotopes. Revised isotopics slightly changed the calculated 241Am- 241Pu model ages and interpretations.

High-Precision Measurement of 13C/12C Isotopic Ratio Using Gas Chromatography-Combustion-Cavity Ring-Down Spectroscopy

NASA Astrophysics Data System (ADS)

Saad, N.; Kuramoto, D. S.; Haase, C.; Crosson, E.; Tan, S.; Zare, R. N.

2009-12-01

Light stable isotope analysis, and in particular, compound specific isotopic analysis (CSIA), is a valuable tool to elucidate pathways and provide a better insight into biological, ecological, and geological systems. We present here the results of compound-specific isotopic carbon analysis of short chain hydrocarbons using the world’s first combination of gas chromatography, combustion interface, and cavity ring-down spectroscopy (GC-C-CRDS). Cavity ring-down spectroscopy (CRDS) is a highly sensitive optical spectroscopy, one application of which is to measure the stable isotopic ratios in small molecules. Because it uses a highly reflective optical cavity with many kilometers effective path length, CRDS provides some of the most sensitive and precise optical absorption measurements. Most optical spectroscopy isotopic analysis measures the quantities of each isotopologue independently using their distinct ro-vibrational spectra. The most common isotopes measured with optical spectroscopy are 13C and 12C in carbon dioxide. However, the isotopes of hydrogen, oxygen, and sulfur have also been measured. Unlike isotope ratio mass spectrometry (IRMS), optical spectroscopy can distinguish among isobars, which have essentially identical m/z ratios. The combination of chemical separation, chemical conversion, and CRDS makes a nearly universal tool for isotopic analysis of mixtures. In addition, CRDS can tolerate a variety of compounds mixed with the target. For example, CRDS can measure carbon dioxide and its isotopic 13C/12C ratio in the presence of oxygen. Using the novel GC-C-CRDS system, we injected a 75-microliter mixture of approximately equal quantities of methane, ethane, and propane into a gas chromatograph using helium as carrier gas. The methane, ethane, and propane were separated in time by 100 to 200 seconds after the chromatograph. Oxygen gas was added, and the hydrocarbons were combusted in a catalytic combustor with platinum and nickel, held at 1150oC. The combusted products were combined with dry nitrogen gas to provide sufficient gas flow for the CRDS analyzer, which measured the 13C/12C isotopic ratio of the separated methane, ethane, and propane, obtaining a precision of 0.95 permil or better. The calibration accuracy was within 3 permil of the values determined using IRMS. The current CRDS-based system is less expensive, does not require highly trained personnel to operate, and is portable, compared with IRMS. We anticipate that advances in spectroscopic analysis will improve the precision and accuracy of the CRDS isotopic measurement, making it comparable with IRMS.

Community-based Approaches to Improving Accuracy, Precision, and Reproducibility in U-Pb and U-Th Geochronology

NASA Astrophysics Data System (ADS)

McLean, N. M.; Condon, D. J.; Bowring, S. A.; Schoene, B.; Dutton, A.; Rubin, K. H.

2015-12-01

The last two decades have seen a grassroots effort by the international geochronology community to "calibrate Earth history through teamwork and cooperation," both as part of the EARTHTIME initiative and though several daughter projects with similar goals. Its mission originally challenged laboratories "to produce temporal constraints with uncertainties approaching 0.1% of the radioisotopic ages," but EARTHTIME has since exceeded its charge in many ways. Both the U-Pb and Ar-Ar chronometers first considered for high-precision timescale calibration now regularly produce dates at the sub-per mil level thanks to instrumentation, laboratory, and software advances. At the same time new isotope systems, including U-Th dating of carbonates, have developed comparable precision. But the larger, inter-related scientific challenges envisioned at EARTHTIME's inception remain - for instance, precisely calibrating the global geologic timescale, estimating rates of change around major climatic perturbations, and understanding evolutionary rates through time - and increasingly require that data from multiple geochronometers be combined. To solve these problems, the next two decades of uranium-daughter geochronology will require further advances in accuracy, precision, and reproducibility. The U-Th system has much in common with U-Pb, in that both parent and daughter isotopes are solids that can easily be weighed and dissolved in acid, and have well-characterized reference materials certified for isotopic composition and/or purity. For U-Pb, improving lab-to-lab reproducibility has entailed dissolving precisely weighed U and Pb metals of known purity and isotopic composition together to make gravimetric solutions, then using these to calibrate widely distributed tracers composed of artificial U and Pb isotopes. To mimic laboratory measurements, naturally occurring U and Pb isotopes were also mixed in proportions to mimic samples of three different ages, to be run as internal standards and as measures of inter-laboratory reproducibility. The U-Th community is undertaking many of the same protocols, and has recently created publicly available gravimetric solutions, and large volumes of three age solutions for widespread distribution and inter-laboratory comparison.

Oxygen Isotope Measurements of the Reduced CV3 Chondrite Thiel Mountains 07007 Using a NanoSIMS: Implication to the Nebula Oxygen Isotope

NASA Astrophysics Data System (ADS)

Choi, B.-G.; Kim, H.; Hong, T. E.

2013-09-01

O-isotopic compositions of fine-grained CAIs in the reduced CV3 TIL 07007 using the NanoSIMS with permil-precision suggesting that O-isotopes of the nebula changed from ^16O-rich when spinel condensed to ^16O-depleted when melilite formed.

Method to make accurate concentration and isotopic measurements for small gas samples

NASA Astrophysics Data System (ADS)

Palmer, M. R.; Wahl, E.; Cunningham, K. L.

2013-12-01

Carbon isotopic ratio measurements of CO2 and CH4 provide valuable insight into carbon cycle processes. However, many of these studies, like soil gas, soil flux, and water head space experiments, provide very small gas sample volumes, too small for direct measurement by current constant-flow Cavity Ring-Down (CRDS) isotopic analyzers. Previously, we addressed this issue by developing a sample introduction module which enabled the isotopic ratio measurement of 40ml samples or smaller. However, the system, called the Small Sample Isotope Module (SSIM), does dilute the sample during the delivery with inert carrier gas which causes a ~5% reduction in concentration. The isotopic ratio measurements are not affected by this small dilution, but researchers are naturally interested accurate concentration measurements. We present the accuracy and precision of a new method of using this delivery module which we call 'double injection.' Two portions of the 40ml of the sample (20ml each) are introduced to the analyzer, the first injection of which flushes out the diluting gas and the second injection is measured. The accuracy of this new method is demonstrated by comparing the concentration and isotopic ratio measurements for a gas sampled directly and that same gas measured through the SSIM. The data show that the CO2 concentration measurements were the same within instrument precision. The isotopic ratio precision (1σ) of repeated measurements was 0.16 permil for CO2 and 1.15 permil for CH4 at ambient concentrations. This new method provides a significant enhancement in the information provided by small samples.

Uranium isotope fractionation in biogenic carbonates: biological effects

NASA Astrophysics Data System (ADS)

Chen, X.; Romaniello, S. J.; Herrmann, A. D.; Anbar, A. D.

2017-12-01

Recent laboratory experiments have demonstrated small but potentially significant isotope fractionation ( 0.10 ‰ for 238U/235U) during uranium (U) incorporation into abiotic calcite and aragonite, with heavier U isotopes preferentially enriched in the precipitates [1]. In contrast, measurements of natural biogenic carbonates to date have not been able to resolve significant U isotopic fractionation from seawater although this might be expected given a typical measurement precision of ± 0.10 ‰. Determining whether or not biogenic carbonates display U isotope fractionation similar to abiotic carbonates could have important implications for understanding the mechanisms of U incorporation into various biogenic carbonates. Furthermore, because most marine carbonates are biogenic, the extent of isotopic fractionation, if any, could have important implications for the interpretation of sedimentary carbonates record similar to effects observed for Cr and B isotopes [2, 3]. To resolve this discrepancy, we utilized a higher precision 238U/235U method which uses larger sample sizes to improve measurement precision of natural samples to ± 0.02 ‰ (2 se, N = 6) [4]. Using this method, we have surveyed 238U/235U in primary biogenic skeletal carbonates including scleractinian corals, green and red algae, and mollusks, as well as non-skeletal carbonates such as stromatolites, ooids, and carbonate sands from the Bahamas, Gulf of California, and French Polynesia. New high-precision U isotopes measurements reveal that biogenic skeletal carbonates are typically 0.02 - 0.08 ‰ heavier than modern seawater. Scleractinian corals display values closest to seawater (- 0.37 ‰), while green algae, red algae, mollusks, and echinoderms display variable but larger extents of fractionation up to 0.08 ‰. The direction and magnitude of U isotope fractionation in these biogenic precipitates are generally consistent with results from abiotic coprecipitation experiments, but may be subject to variations in U speciation and carbonate chemistry at calcification sites. [1] Chen et a., (2016), GCA, 188, 189-207. [2] Wang et a., (2016), Geobiology, 5, 51-64. [3] Pagani et al., (2005) GCA, 69, 953-961. [4] Andersen et al., (2016) CG, 420, 11-22.

A New and Improved Carbon Dioxide Isotope Analyzer for Understanding Soil-Plant-Atmosphere Interactions

NASA Astrophysics Data System (ADS)

Huang, Y. W.; Berman, E. S.; Owano, T. G.; Verfaillie, J. G.; Oikawa, P. Y.; Baldocchi, D. D.; Still, C. J.; Gardner, A.; Baer, D. S.; Rastogi, B.

2015-12-01

Stable CO2 isotopes provide information on biogeochemical processes that occur at the soil-plant-atmosphere interface. While δ13C measurement can provide information on the sources of the CO2, be it photosynthesis, natural gas combustion, other fossil fuel sources, landfills or other sources, δ18O, and δ17O are thought to be determined by the hydrological cycling of the CO2. Though researchers have called for analytical tools for CO2 isotope measurements that are reliable and field-deployable, developing such instrument remains a challenge. The carbon dioxide isotope analyzer developed by Los Gatos Research (LGR) uses LGR's patented Off-Axis ICOS (Integrated Cavity Output Spectroscopy) technology and incorporates proprietary internal thermal control for high sensitivity and optimal instrument stability. This new and improved analyzer measures CO2 concentration as well as δ13C, δ18O, and δ17O from CO2 at natural abundance (150-2500 ppm). The laboratory precision is ±200 ppb (1σ) in CO2 at 1 s, with a long-term (2 min) precision of ±20 ppb. The 1-second precision for both δ13C and δ18O is 0.7 ‰, and for δ17O is 1.8 ‰. The long-term (2 min) precision for both δ13C and δ18O is 0.08 ‰, and for δ17O is 0.18 ‰. The instrument has improved precision, stability and user interface over previous LGR CO2 isotope instruments and can be easily programmed for periodic referencing and sampling from different sources when coupled with LGR's multiport inlet unit (MIU). We have deployed two of these instruments at two different field sites, one at Twitchell Island in Sacramento County, CA to monitor the CO2 isotopic fluxes from an alfalfa field from 6/29/2015-7/13/2015, and the other at the Wind River Experimental Forest in Washington to monitor primarily the oxygen isotopes of CO2 within the canopy from 8/4/2015 through mid-November 2015. Methodology, laboratory development and testing and field performance are presented.

High-precision isotopic characterization of USGS reference materials by TIMS and MC-ICP-MS

NASA Astrophysics Data System (ADS)

Weis, Dominique; Kieffer, Bruno; Maerschalk, Claude; Barling, Jane; de Jong, Jeroen; Williams, Gwen A.; Hanano, Diane; Pretorius, Wilma; Mattielli, Nadine; Scoates, James S.; Goolaerts, Arnaud; Friedman, Richard M.; Mahoney, J. Brian

2006-08-01

The Pacific Centre for Isotopic and Geochemical Research (PCIGR) at the University of British Columbia has undertaken a systematic analysis of the isotopic (Sr, Nd, and Pb) compositions and concentrations of a broad compositional range of U.S. Geological Survey (USGS) reference materials, including basalt (BCR-1, 2; BHVO-1, 2), andesite (AGV-1, 2), rhyolite (RGM-1, 2), syenite (STM-1, 2), granodiorite (GSP-2), and granite (G-2, 3). USGS rock reference materials are geochemically well characterized, but there is neither a systematic methodology nor a database for radiogenic isotopic compositions, even for the widely used BCR-1. This investigation represents the first comprehensive, systematic analysis of the isotopic composition and concentration of USGS reference materials and provides an important database for the isotopic community. In addition, the range of equipment at the PCIGR, including a Nu Instruments Plasma MC-ICP-MS, a Thermo Finnigan Triton TIMS, and a Thermo Finnigan Element2 HR-ICP-MS, permits an assessment and comparison of the precision and accuracy of isotopic analyses determined by both the TIMS and MC-ICP-MS methods (e.g., Nd isotopic compositions). For each of the reference materials, 5 to 10 complete replicate analyses provide coherent isotopic results, all with external precision below 30 ppm (2 SD) for Sr and Nd isotopic compositions (27 and 24 ppm for TIMS and MC-ICP-MS, respectively). Our results also show that the first- and second-generation USGS reference materials have homogeneous Sr and Nd isotopic compositions. Nd isotopic compositions by MC-ICP-MS and TIMS agree to within 15 ppm for all reference materials. Interlaboratory MC-ICP-MS comparisons show excellent agreement for Pb isotopic compositions; however, the reproducibility is not as good as for Sr and Nd. A careful, sequential leaching experiment of three first- and second-generation reference materials (BCR, BHVO, AGV) indicates that the heterogeneity in Pb isotopic compositions, and concentrations, could be directly related to contamination by the steel (mortar/pestle) used to process the materials. Contamination also accounts for the high concentrations of certain other trace elements (e.g., Li, Mo, Cd, Sn, Sb, W) in various USGS reference materials.

Modified ion exchange separation for tungsten isotopic measurements from kimberlite samples using multi-collector inductively coupled plasma mass spectrometry.

PubMed

Sahoo, Yu Vin; Nakai, Shun'ichi; Ali, Arshad

2006-03-01

Tungsten isotope composition of a sample of deep-seated rock can record the influence of core-mantle interaction of the parent magma. Samples of kimberlite, which is known as a carrier of diamond, from the deep mantle might exhibit effects of core-mantle interaction. Although tungsten isotope anomaly was reported for kimberlites from South Africa, a subsequent investigation did not verify the anomaly. The magnesium-rich and calcium-rich chemical composition of kimberlite might engender difficulty during chemical separation of tungsten for isotope analyses. This paper presents a simple, one-step anion exchange technique for precise and accurate determination of tungsten isotopes in kimberlites using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Large quantities of Ca and Mg in kimberlite samples were precipitated and removed with aqueous H(2)SO(4). Highly pure fractions of tungsten for isotopic measurements were obtained following an anion exchange chromatographic procedure involving mixed acids. That procedure enabled efficient removal of high field strength elements (HFSE), such as Hf, Zr and Ti, which are small ions that carry strong charges and develop intense electrostatic fields. The tungsten yields were 85%-95%. Advantages of this system include less time and less use of reagents. Precise and accurate isotopic measurements are possible using fractions of tungsten that are obtained using this method. The accuracy and precision of these measurements were confirmed using various silicate standard rock samples, JB-2, JB-3 and AGV-1.

Precise Analysis of Gallium Isotopic Composition by MC-ICP-MS.

PubMed

Yuan, Wei; Chen, Jiu Bin; Birck, Jean-Louis; Yin, Zuo Ying; Yuan, Sheng Liu; Cai, Hong Ming; Wang, Zhong Wei; Huang, Qiang; Wang, Zhu Hong

2016-10-04

Though an isotope approach could be beneficial for better understanding the biogeochemical cycle of gallium (Ga), an analogue of the monoisotopic element aluminum (Al), the geochemistry of Ga isotopes has not been widely elaborated. We developed a two-step method for purifying Ga from geological (biological) samples for precise measurement of Ga isotope ratio using multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). Ga was thoroughly separated from other matrix elements using two chromatographic columns loaded with AG 1-X4 and Ln-spec resin, respectively. The separation method was carefully calibrated using both synthetic and natural samples and validated by assessing the extraction yield (99.8 ± 0.8%, 2SD, n = 23) and the reproducibility (2SD uncertainty better than 0.05‰, n = 116) of the measured isotopic ratio (expressed as δ 71 Ga). The validation of the whole protocol, together with instrumental analysis, was confirmed by the investigation of the matrix effect, the result of a standard addition experiment, and the comparison of Ga isotope measurement on two mass spectrometers-Nu Plasma II and Neptune Plus. Although the measurements using the sample-standard bracketing (SSB) correction method on both instruments resulted in identical δ 71 Ga values for reference materials, the modified empirical external normalization (MEEN) method gave relatively better precision compared to SSB on Neptune. Our preliminary results showed large variation of δ 71 Ga (up to 1.83‰) for 10 standards, with higher values in industrially produced materials, implying potential application of Ga isotopes.

Concomitant ion effects on isotope ratio measurements with liquid sampling – atmospheric pressure glow discharge ion source Orbitrap mass spectrometry

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

Hoegg, Edward D.; Marcus, R. Kenneth; Hager, George J.

RATIONALE: The field of highly accurate and precise isotope ratio (IR) analysis has been dominated by inductively coupled plasma and thermal ionization mass spectrometers. While these instruments are considered the gold standard for IR analysis, the International Atomic Energy Agency desires a field deployable instrument capable of accurately and precisely measuring U isotope ratios. METHODS: The proposed system interfaces the liquid sampling – atmospheric pressure glow discharge (LS-APGD) ion source with a high resolution Exactive Orbitrap mass spectrometer. With this experimental setup certified U isotope standards and unknown samples were analyzed. The accuracy and precision of the system were thenmore » determined. RESULTS: The LS-APGD /Exactive instrument measures a certified reference material of natural U (235U/238U = 0.007258) as 0.007041 with a relative standard deviation of 0.158% meeting the International Target Values for Uncertainty for the destructive analysis of U. Additionally, when three unknowns measured and compared to the results from an ICP multi collector instrument, there is no statistical difference between the two instruments.CONCLUSIONS: The LS-APGD / Orbitrap system, while still in the preliminary stages of development, offers highly accurate and precise IR analysis that suggest a paradigm shift in the world of IR analysis. Furthermore, the portability of the LS-APGD as an elemental ion source combined with the low overhead and small size of the Orbitrap suggest that the instrumentation is capable of being field deployable.With liquid sampling glow discharge-Orbitrap MS, isotope ratio and precision performance improves with rejection of concomitant ion species.« less

Organomimetic clusters: Precision in 3D

NASA Astrophysics Data System (ADS)

Majewski, Marek B.; Howarth, Ashlee J.; Farha, Omar K.

2017-04-01

Biomimetic molecules that can be easily tailored offer numerous opportunities. Now, boron-based clusters have been shown to be excellent biomimetics. The ease with which the cluster surfaces can be modified stands to change how chemists might go about preparing materials for imaging, drug delivery and other applications.

BORONATE AFFINITY ADSORPTION OF RNA: POSSIBLE ROLE OF CONFORMATIONAL CHANGES. (R825354)

EPA Science Inventory

Batch equilibrium adsorption isotherm determination is used to characterize the adsorption of mixed yeast RNA on agarose-immobilized m-aminophenylboronic acid. It is shown that the affinity-enhancing influence of divalent cations depends strongly on the precise nature of t...

The GENESIS Mission: Solar Wind Isotopic and Elemental Compositions and Their Implications

NASA Astrophysics Data System (ADS)

Wiens, R. C.; Burnett, D. S.; McKeegan, K. D.; Kallio, A. P.; Mao, P. H.; Heber, V. S.; Wieler, R.; Meshik, A.; Hohenberg, C. M.; Mabry, J. C.; Gilmour, J.; Crowther, S. A.; Reisenfeld, D. B.; Jurewicz, A.; Marty, B.; Pepin, R. O.; Barraclough, B. L.; Nordholt, J. E.; Olinger, C. T.; Steinberg, J. T.

2008-12-01

The GENESIS mission was a novel NASA experiment to collect solar wind at the Earth's L1 point for two years and return it for analysis. The capsule crashed upon re-entry in 2004, but many of the solar-wind collectors were recovered, including separate samples of coronal hole, interstream, and CME material. Laboratory analyses of these materials have allowed higher isotopic precision than possible with current in-situ detectors. To date GENESIS results have been obtained on isotopes of O, He, Ne, Ar, Kr, and Xe on the order of 1% accuracy and precision, with poorer uncertainty on Xe isotopes and significantly better uncertainties on the lighter noble gases. Elemental abundances are available for the above elements as well as Mg, Si, and Fe. When elemental abundances are compared with other in situ solar wind measurements, agreement is generally quite good. One exception is the Ne elemental abundance, which agrees with Ulysses and Apollo SWC results, but not with ACE. Neon is of particular interest because of the uncertainty in the solar Ne abundance, which has significant implications for the standard solar model. Helium isotopic results of material from the different solar wind regimes collected by GENESIS is consistent with isotopic fractionation predictions of the Coulomb drag model, suggesting that isotopic fractionation corrections need to be applied to heavier elements as well when extrapolating solar wind to solar compositions. Noble gas isotopic compositions from GENESIS are consistent with those obtained for solar wind trapped in lunar grains, but have for the first time yielded a very precise Ar isotopic result. Most interesting for cosmochemistry is a preliminary oxygen isotopic result from GENESIS which indicates a solar enrichment of ~4% in 16O relative to the planets, consistent with a photolytic self-shielding phenomenon during solar system formation. Analyses of solar wind N and C isotopes may further elucidate this phenomenon. Preliminary results from GENESIS have been reported for N, and results are still pending for C.

Can we use high precision metal isotope analysis to improve our understanding of cancer?

PubMed

Larner, Fiona

2016-01-01

High precision natural isotope analyses are widely used in geosciences to trace elemental transport pathways. The use of this analytical tool is increasing in nutritional and disease-related research. In recent months, a number of groups have shown the potential this technique has in providing new observations for various cancers when applied to trace metal metabolism. The deconvolution of isotopic signatures, however, relies on mathematical models and geochemical data, which are not representative of the system under investigation. In addition to relevant biochemical studies of protein-metal isotopic interactions, technological development both in terms of sample throughput and detection sensitivity of these elements is now needed to translate this novel approach into a mainstream analytical tool. Following this, essential background healthy population studies must be performed, alongside observational, cross-sectional disease-based studies. Only then can the sensitivity and specificity of isotopic analyses be tested alongside currently employed methods, and important questions such as the influence of cancer heterogeneity and disease stage on isotopic signatures be addressed.

High-Precision Half-Life Measurements for the Superallowed Fermi β+ Emitters 14O and 18Ne

NASA Astrophysics Data System (ADS)

Laffoley, A. T.; Andreoiu, C.; Austin, R. A. E.; Ball, G. C.; Bender, P. C.; Bidaman, H.; Bildstein, V.; Blank, B.; Bouzomita, H.; Cross, D. S.; Deng, G.; Diaz Varela, A.; Dunlop, M. R.; Dunlop, R.; Finlay, P.; Garnsworthy, A. B.; Garrett, P.; Giovinazzo, J.; Grinyer, G. F.; Grinyer, J.; Hadinia, B.; Jamieson, D. S.; Jigmeddorj, B.; Ketelhut, S.; Kisliuk, D.; Leach, K. G.; Leslie, J. R.; MacLean, A.; Miller, D.; Mills, B.; Moukaddam, M.; Radich, A. J.; Rajabali, M. M.; Rand, E. T.; Svensson, C. E.; Tardiff, E.; Thomas, J. C.; Turko, J.; Voss, P.; Unsworth, C.

High-precision half-life measurements, at the level of ±0.04%, for the superallowed Fermi emitters 14O and 18Ne have been performed at TRIUMF's Isotope Separator and Accelerator facility. Using 3 independent detector systems, a gas-proportional counter, a fast plastic scintillator, and a high-purity germanium array, a series of direct β and γ counting measurements were performed for each of the isotopes. In the case of 14O, these measurements were made to help resolve an existing discrepancy between detection methods, whereas for 18Ne the half-life precision has been improved in anticipation of forthcoming high-precision branching ratio measurements.

Mars Atmospheric Escape Recorded by H, C and O Isotope Ratios in Carbon Dioxide and Water Measured by the Sam Tunable Laser Spectrometer on the Curiosity Rover

NASA Technical Reports Server (NTRS)

Webster, C. R.; Mahaffy, P. R.; Leshin, L. A.; Atreya, S. K.; Flesch, G. J.; Stern, J.; Christensen, L. E.; Vasavada, A. R.; Owen, T.; Niles, P. B.;

Comparative performance study of different sample introduction techniques for rapid and precise selenium isotope ratio determination using multi-collector inductively coupled plasma mass spectrometry (MC-ICP/MS).

PubMed

Elwaer, Nagmeddin; Hintelmann, Holger

2007-11-01

The analytical performance of five sample introduction systems, a cross flow nebulizer spray chamber, two different solvent desolvation systems, a multi-mode sample introduction system (MSIS), and a hydride generation (LI2) system were compared for the determination of Se isotope ratio measurements using multi-collector inductively coupled plasma mass spectrometry (MC-ICP/MS). The optimal operating parameters for obtaining the highest Se signal-to-noise (S/N) ratios and isotope ratio precision for each sample introduction were determined. The hydride generation (LI2) system was identified as the most suitable sample introduction method yielding maximum sensitivity and precision for Se isotope ratio measurement. It provided five times higher S/N ratios for all Se isotopes compared to the MSIS, 20 times the S/N ratios of both desolvation units, and 100 times the S/N ratios produced by the conventional spray chamber sample introduction method. The internal precision achieved for the (78)Se/(82)Se ratio at 100 ng mL(-1) Se with the spray chamber, two desolvation, MSIS, and the LI2 systems coupled to MC-ICP/MS was 150, 125, 114, 13, and 7 ppm, respectively. Instrument mass bias factors (K) were calculated using an exponential law correction function. Among the five studied sample introduction systems the LI2 showed the lowest mass bias of -0.0265 and the desolvation system showed the largest bias with -0.0321.

High-precision Ru isotopic measurements by multi-collector ICP-MS.

PubMed

Becker, Harry; Dalpe, Claude; Walker, Richard J

2002-06-01

Ruthenium isotopic data for a pure Aldrich ruthenium nitrate solution obtained using a Nu Plasma multi collector inductively coupled plasma-mass spectrometer (MC-ICP-MS) shows excellent agreement (better than 1 epsilon unit = 1 part in 10(4)) with data obtained by other techniques for the mass range between 96 and 101 amu. External precisions are at the 0.5-1.7 epsilon level (2sigma). Higher sensitivity for MC ICP-MS compared to negative thermal ionization mass spectrometry (N-TIMS) is offset by the uncertainties introduced by relatively large mass discrimination and instabilities in the plasma source-ion extraction region that affect the long-term reproducibility. Large mass bias correction in ICP mass spectrometry demands particular attention to be paid to the choice of normalizing isotopes. Because of its position in the mass spectrum and the large mass bias correction, obtaining precise and accurate abundance data for 104Ru by MC-ICP-MS remains difficult. Internal and external mass bias correction schemes in this mass range may show similar shortcomings if the isotope of interest does not lie within the mass range covered by the masses used for normalization. Analyses of meteorite samples show that if isobaric interferences from Mo are sufficiently large (Ru/Mo < 10(4)), uncertainties on the Mo interference correction propagate through the mass bias correction and yield inaccurate results for Ru isotopic compositions. Second-order linear corrections may be used to correct for these inaccuracies, but such results are generally less precise than N-TIMS data.

Influence of magmatic volatiles on boron isotope compositions in vent fluids from the Eastern Manus Basin, Papua New Guinea

NASA Astrophysics Data System (ADS)

Wilckens, F. K.; Kasemann, S.; Bach, W.; Reeves, E. P.; Meixner, A.; Seewald, J.

2016-12-01

In this study we present boron (B), lithium (Li) and strontium (Sr) concentrations and isotopic composition of submarine hydrothermal fluids collected in 2006 and 2011 from PACMANUS, DESMOS and SuSu Knolls vent fields located in the Eastern Manus Basin [1,2]. Hydrothermal vent fluids within the Eastern Manus Basin range from high-temperature black smoker fluids to low-temperature diffuse fluids and acid-sulfate fluids. In general, the different fluid types show variable water-rock ratios during water-rock interaction and different inputs of magmatic volatiles. End-member black smoker fluids, which have in general high temperatures (mostly higher than 280°C) and pH values higher than 2 (measured at 25°C) are characterized by low δ7Li values (3.9 to 5.9‰) and 87Sr/86Sr ratios (0.704 to 0.705) similar to the values for island arc basalts. These results suggest low water-rock ratios during hydrothermal circulation. B concentrations and isotopic compositions in these fluids range from 1.0 to 2.6μM and 13 to 20‰, respectively. These data match with other vent fluids from island arc settings in the Western Pacific and plot in a B versus δ11B diagram on a two-component mixing line between seawater and island arc basalts [3]. Sr and Li isotopic composition of white smoker and acid-sulfate fluids overlap generally with the isotopic ratios for the black smoker fluids. However, in some fluids Sr isotope ratios are up to 0.709 near seawater composition suggesting higher water-rock ratios during water-rock interaction. B concentrations and isotope ratios in the white smoker and acid-sulfate fluids range from 0.6 to 2.2μM and 9 to 16‰, respectively which are lower compared with the values of black smoker fluids. In addition, these fluids do not fit on the mixing line between seawater and island arc basalt, and define another mixing trend in a B versus δ11B diagram. To explain this contradictory trend, a third mixing endmember is required that shifts B concentrations and δ11B to lower values. A possible mixing endmember is B volatized from magmatic gases. This endmember seems to be reasonable because it only influences B, whereas Li and Sr stay unaffected. [1] Reeves et al. (2011) GCA 75, 1088-1123 [2] Seewald et al. (2015) GCA 163, 178-199 [3] Yamaoka et al. (2015) CG 392, 9-18

High-Precision In Situ 87Sr/86Sr Analyses through Microsampling on Solid Samples: Applications to Earth and Life Sciences

PubMed Central

Di Salvo, Sara; Casalini, Martina; Marchionni, Sara; Adani, Teresa; Ulivi, Maurizio; Tommasini, Simone; Avanzinelli, Riccardo; Mazza, Paul P. A.; Francalanci, Lorella

2018-01-01

An analytical protocol for high-precision, in situ microscale isotopic investigations is presented here, which combines the use of a high-performing mechanical microsampling device and high-precision TIMS measurements on micro-Sr samples, allowing for excellent results both in accuracy and precision. The present paper is a detailed methodological description of the whole analytical procedure from sampling to elemental purification and Sr-isotope measurements. The method offers the potential to attain isotope data at the microscale on a wide range of solid materials with the use of minimally invasive sampling. In addition, we present three significant case studies for geological and life sciences, as examples of the various applications of microscale 87Sr/86Sr isotope ratios, concerning (i) the pre-eruptive mechanisms triggering recent eruptions at Nisyros volcano (Greece), (ii) the dynamics involved with the initial magma ascent during Eyjafjallajökull volcano's (Iceland) 2010 eruption, which are usually related to the precursory signals of the eruption, and (iii) the environmental context of a MIS 3 cave bear, Ursus spelaeus. The studied cases show the robustness of the methods, which can be also be applied in other areas, such as cultural heritage, archaeology, petrology, and forensic sciences. PMID:29850369

Mid-IR enhanced laser ablation molecular isotopic spectrometry

NASA Astrophysics Data System (ADS)

Brown, Staci; Ford, Alan; Akpovo, Codjo A.; Johnson, Lewis

2016-08-01

A double-pulsed laser-induced breakdown spectroscopy (DP-LIBS) technique utilizing wavelengths in the mid-infrared (MIR) for the second pulse, referred to as double-pulse LAMIS (DP-LAMIS), was examined for its effect on detection limits compared to single-pulse laser ablation molecular isotopic spectrometry (LAMIS). A MIR carbon dioxide (CO2) laser pulse at 10.6 μm was employed to enhance spectral emissions from nanosecond-laser-induced plasma via mid-IR reheating and in turn, improve the determination of the relative abundance of isotopes in a sample. This technique was demonstrated on a collection of 10BO and 11BO molecular spectra created from enriched boric acid (H3BO3) isotopologues in varying concentrations. Effects on the overall ability of both LAMIS and DP-LAMIS to detect the relative abundance of boron isotopes in a starting sample were considered. Least-squares fitting to theoretical models was used to deduce plasma parameters and understand reproducibility of results. Furthermore, some optimization for conditions of the enhanced emission was achieved, along with a comparison of the overall emission intensity, plasma density, and plasma temperature generated by the two techniques.

Determination of the NPP Kr\\vsko spent fuel decay heat

NASA Astrophysics Data System (ADS)

Kromar, Marjan; Kurinčič, Bojan

2017-07-01

Nuclear fuel is designed to support fission process in a reactor core. Some of the isotopes, formed during the fission, decay and produce decay heat and radiation. Accurate knowledge of the nuclide inventory producing decay heat is important after reactor shut down, during the fuel storage and subsequent reprocessing or disposal. In this paper possibility to calculate the fuel isotopic composition and determination of the fuel decay heat with the Serpent code is investigated. Serpent is a well-known Monte Carlo code used primarily for the calculation of the neutron transport in a reactor. It has been validated for the burn-up calculations. In the calculation of the fuel decay heat different set of isotopes is important than in the neutron transport case. Comparison with the Origen code is performed to verify that the Serpent is taking into account all isotopes important to assess the fuel decay heat. After the code validation, a sensitivity study is carried out. Influence of several factors such as enrichment, fuel temperature, moderator temperature (density), soluble boron concentration, average power, burnable absorbers, and burnup is analyzed.

High-precision measurement of phenylalanine δ15N values for environmental samples: a new approach coupling high-pressure liquid chromatography purification and elemental analyzer isotope ratio mass spectrometry.

PubMed

Broek, Taylor A B; Walker, Brett D; Andreasen, Dyke H; McCarthy, Matthew D

2013-11-15

Compound-specific isotope analysis of individual amino acids (CSI-AA) is a powerful new tool for tracing nitrogen (N) source and transformation in biogeochemical cycles. Specifically, the δ(15)N value of phenylalanine (δ(15)N(Phe)) represents an increasingly used proxy for source δ(15)N signatures, with particular promise for paleoceanographic applications. However, current derivatization/gas chromatography methods require expensive and relatively uncommon instrumentation, and have relatively low precision, making many potential applications impractical. A new offline approach has been developed for high-precision δ(15)N measurements of amino acids (δ(15)N(AA)), optimized for δ(15)N(Phe) values. Amino acids (AAs) are first purified via high-pressure liquid chromatography (HPLC), using a mixed-phase column and automated fraction collection. The δ(15)N values are determined via offline elemental analyzer-isotope ratio mass spectrometry (EA-IRMS). The combined HPLC/EA-IRMS method separated most protein AAs with sufficient resolution to obtain accurate δ(15)N values, despite significant intra-peak isotopic fractionation. For δ(15)N(Phe) values, the precision was ±0.16‰ for standards, 4× better than gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS; ±0.64‰). We also compared a δ(15)N(Phe) paleo-record from a deep-sea bamboo coral from Monterey Bay, CA, USA, using our method versus GC/C/IRMS. The two methods produced equivalent δ(15)N(Phe) values within error; however, the δ(15)N(Phe) values from HPLC/EA-IRMS had approximately twice the precision of GC/C/IRMS (average stdev of 0.27‰ ± 0.14‰ vs 0.60‰ ± 0.20‰, respectively). These results demonstrate that offline HPLC represents a viable alternative to traditional GC/C/IMRS for δ(15)N(AA) measurement. HPLC/EA-IRMS is more precise and widely available, and therefore useful in applications requiring increased precision for data interpretation (e.g. δ(15)N paleoproxies). Copyright © 2013 John Wiley & Sons, Ltd.

Improved precision and accuracy in quantifying plutonium isotope ratios by RIMS

DOE PAGES

Isselhardt, B. H.; Savina, M. R.; Kucher, A.; ...

2015-09-01

Resonance ionization mass spectrometry (RIMS) holds the promise of rapid, isobar-free quantification of actinide isotope ratios in as-received materials (i.e. not chemically purified). Recent progress in achieving this potential using two Pu test materials is presented. RIMS measurements were conducted multiple times over a period of two months on two different Pu solutions deposited on metal surfaces. Measurements were bracketed with a Pu isotopic standard, and yielded absolute accuracies of the measured 240Pu/ 239Pu ratios of 0.7% and 0.58%, with precisions (95% confidence intervals) of 1.49% and 0.91%. In conclusion, the minor isotope 238Pu was also quantified despite the presencemore » of a significant quantity of 238U in the samples.« less

Outgassing of the Eastern Equatorial Pacific during the Pliocene period.

NASA Astrophysics Data System (ADS)

Guillermic, M.; Tripati, A.

2016-12-01

The transition from the warm, ice-free conditions of the early Cenozoic to present-day glacial state with ice sheets in both hemispheres has been ascribed to long- and short-term changes in atmospheric CO2. The processes causing long-term changes in atmospheric CO2 levels are of debate. One possible explanation for changes in atmospheric CO2 relates to changes in air-sea exchange due to fluctuations in ocean carbon sources and sinks, as modulated by the stratification of surface waters. While nutrient consumption in low-latitude environments and associated export of CO2 to the deep sea works to sequester CO2 in the ocean interior, the return of deep water to the surface in the high latitudes and upwelling at the equator and in the eastern portion of ocean basins releases CO2. Quantitative estimates for surface water pH and pCO2 in different regions of the ocean and identification of CO2-sources and sinks are needed to better understand the role of the ocean in driving and/or amplifying variations in the atmospheric CO2 reservoir and climate change. Here we present preliminary results of surface water pH for the early Pliocene to Holocene based on boron isotope measurements of planktic foraminifera for the Eastern Equatorial Pacific. We develop records of B/Ca, Mg/Ca ratios, boron isotopes, and oxygen isotopes measurements in foraminifera tests (Globigeneroides sacculifer, Globigeneroides ruber, Neogloboquadrina dutertrei). We reconstruct changes in ocean CO2 outgassing in the Eastern Equatorial Pacific using records from ODP Site 847 (0°N, 95°W, 3373 m water depth). These data are used to examine if there is evidence for changes in stratification and CO2 outgassing during the early Pliocene warm period and during Pliocene intensification of Northern Hemisphere glaciation.

A vibrational spectroscopic study of the borate mineral ezcurrite Na4B10O17·7H2O - Implications for the molecular structure

NASA Astrophysics Data System (ADS)

Frost, Ray L.; López, Andrés; Theiss, Frederick L.; Scholz, Ricardo; Belotti, Fernanda M.

2014-07-01

We have studied the boron containing mineral ezcurrite Na4B10O17·7H2O using electron microscopy and vibrational spectroscopy. Both tetrahedral and trigonal boron units are observed. The nominal resolution of the Raman spectrometer is of the order of 2 cm-1 and as such is sufficient enough to identify separate bands for the stretching bands of the two boron isotopes. The Raman band at 1037 cm-1 is assigned to BO stretching vibration. Raman bands at 1129, 1163, 1193 cm-1 are attributed to BO stretching vibration of the tetrahedral units. The Raman band at 947 cm-1 is attributed to the antisymmetric stretching modes of tetrahedral boron. The sharp Raman peak at 1037 cm-1 is from the 11-B component such a mode, then it should have a smaller 10-B satellite near (1.03) × (1037) = 1048 cm-1, and indeed a small peak at 1048 is observed. The broad Raman bands at 3186, 3329, 3431, 3509, 3547 and 3576 cm-1 are assigned to water stretching vibrations. Broad infrared bands at 3170, 3322, 3419, 3450, 3493, 3542, 3577 and 3597 cm-1 are also assigned to water stretching vibrations. Infrared bands at 1330, 1352, 1389, 1407, 1421 and 1457 cm-1 are assigned to the antisymmetric stretching vibrations of trigonal boron. The observation of so many bands suggests that there is considerable variation in the structure of ezcurrite. Infrared bands at 1634, 1646 and 1681 cm-1 are assigned to water bending modes. The number of water bending modes is in harmony with the number of water stretching vibrations.

Absolute measurements and certified reference material for iron isotopes using multiple-collector inductively coupled mass spectrometry.

PubMed

Zhou, Tao; Zhao, Motian; Wang, Jun; Lu, Hai

2008-01-01

Two enriched isotopes, 99.94 at.% 56Fe and 99.90 at.% 54Fe, were blended under gravimetric control to prepare ten synthetic isotope samples whose 56Fe isotope abundances ranged from 95% to 20%. For multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) measurements typical polyatomic interferences were removed by using Ar and H2 as collision gas and operating the MC-ICP-MS system in soft mode. Thus high-precision measurements of the Fe isotope abundance ratios were accomplished. Based on the measurement of the synthetic isotope abundance ratios by MC-ICP-MS, the correction factor for mass discrimination was calculated and the results were in agreement with results from IRMM014. The precision of all ten correction factors was 0.044%, indicating a good linearity of the MC-ICP-MS method for different isotope abundance ratio values. An isotopic reference material was certified under the same conditions as the instrument was calibrated. The uncertainties of ten correction factors K were calculated and the final extended uncertainties of the isotopic certified Fe reference material were 5.8363(37) at.% 54Fe, 91.7621(51) at.% 56Fe, 2.1219(23) at.% 57Fe, and 0.2797(32) at.% 58Fe.

Inadequacy, Impurity and Infidelity; Modifying the Modified Brendel Alpha-Cellulose Extraction Method for Resinous Woods in Stable Isotope Dendroclimatology

NASA Astrophysics Data System (ADS)

Brookman, T. H.; Whittaker, T. E.; King, P. L.; Horton, T. W.

2011-12-01

Stable isotope dendroclimatology is a burgeoning field in palaeoclimate science due to its unique potential to contribute (sub)annually resolved climate records, over millennial timescales, to the terrestrial palaeoclimate record. Until recently the time intensive methods precluded long-term climate reconstructions. Advances in continuous-flow mass spectrometry and isolation methods for α-cellulose (ideal for palaeoclimate studies as, unlike other wood components, it retains its initial isotopic composition) have made long-term, calendar dated palaeoclimate reconstructions a viable proposition. The Modified Brendel (mBrendel) α-cellulose extraction method is a fast, cost-effective way of preparing whole-wood samples for stable oxygen and carbon isotope analysis. However, resinous woods often yield incompletely processed α-cellulose using the standard mBrendel approach. As climate signals may be recorded by small (<1%) isotopic shifts it is important to investigate if incomplete processing affects the accuracy and precision of tree-ring isotopic records. In an effort to address this methodological issue, we investigated three highly resinous woods: kauri (Agathis australis), ponderosa pine (Pinus ponderosa) and huon pine (Lagarastrobus franklinii). Samples of each species were treated with 16 iterations of the mBrendel, varying reaction temperature, time and reagent volumes. Products were investigated using microscopic and bulk transmission Fourier Transform infrared spectroscopy (FITR) to reveal variations in the level of processing; poorly-digested fibres display a peak at 1520cm-1 suggesting residual lignin and a peak at ~1600cm-1 in some samples suggests retained resin. Despite the different levels of purity, replicate analyses of samples processed by high temperature digestion yielded consistent δ18O within and between experiments. All α-cellulose samples were 5-7% enriched compared to the whole-wood, suggesting that even incomplete processing at high temperature can provide acceptable δ18O analytical external precision. For kauri, short, lower temperature extractions produced α-cellulose with δ18O consistently ~1% lower than longer, higher temperature kauri experiments. These findings suggest that temperature and time are significant variables that influence the analytical precision of α-cellulose stable isotope analysis and that resinous hardwoods (e.g. kauri) may require longer and/or hotter digestions than softwoods. The effects of mBrendel variants on the carbon isotope ratio precision of α-cellulose extracts will also be presented. Our findings indicate that the standard mBrendel α-cellulose extraction method may not fully remove lignins and resins depending on the type of wood being analysed. Residual impurities can decrease analytical precision and accuracy. Fortunately, FTIR analysis prior to isotopic analysis is a relatively fast and cost effective way to determine α-cellulose extract purity, ultimately improving the data quality, accuracy and utility of tree-ring based stable isotopic climate records.

Precision atomic mass spectrometry with applications to fundamental constants, neutrino physics, and physical chemistry

NASA Astrophysics Data System (ADS)

Mount, Brianna J.; Redshaw, Matthew; Myers, Edmund G.

2011-07-01

We present a summary of precision atomic mass measurements of stable isotopes carried out at Florida State University. These include the alkalis 6Li, 23Na, 39,41K, 85,87Rb, 133Cs; the rare gas isotopes 84,86Kr and 129,130,132,136Xe; 17,18O, 19F, 28Si, 31P, 32S; and various isotope pairs of importance to neutrino physics, namely 74,76Se/74,76Ge, 130Xe/130Te, and 115In/115Sn. We also summarize our Penning trap measurements of the dipole moments of PH + and HCO + .

Volume Measurements of Laser-generated Pits for in Situ Geochronology Using KArLE (Potassium-Argon Laser Experiment)

NASA Technical Reports Server (NTRS)

French, R. A.; Cohen, B. A.; Miller, J. S.

2014-01-01

KArLE (Potassium-­-Argon Laser Experiment) has been developed for in situ planetary geochronology using the K - Ar (potassium-­-argon) isotope system, where material ablated by LIBS (Laser-­-Induced Breakdown Spectroscopy) is used to calculate isotope abundances. We are determining the accuracy and precision of volume measurements of these pits using stereo and laser microscope data to better understand the ablation process for isotope abundance calculations. If a characteristic volume can be determined with sufficient accuracy and precision for specific rock types, KArLE will prove to be a useful instrument for future planetary rover missions.

Isotope ratio mass spectrometry in nutrition research

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

Luke, A.H.

Many of the biochemical pathways and processes that form the foundation of modern nutrition research was elucidated using stable isotopes as physiological tracers. Since the discovery of stable isotopes, improvements and innovations in mass spectrometry and chromatography have led to greatly expanded applications. This research project was designed to evaluate gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) as a tool for isotopic tracer studies and to delineate the operational parameters for the analysis of {sup 13}C-labeled cholesterol, leucine and {alpha}-ketoisocaproate. The same isotope ratio mass spectrometer was then used as the base instrument for the ratio mass spectrometer was then usedmore » as the base instrument for the development of two additional inlet systems: a continuous-flow inlet for the analyses of {sup 13}C and {sup 18}O as CO{sub 2} and a filament inlet for on-line combustion and isotopic analysis of non-volatile organic compounds. Each of these three inlets was evaluated and their utility in nutrition research illustrated. GC/C/IRMS was used to analyze cholesterol, leucine and {alpha}-ketoisocaproate with good accuracy, precision and little isotopic memory. For all three compounds the detection limits achieved well surpassed currently used technologies. For compounds that can be well separated by GC, GC/C/IRMS is a valuable analytical tool. The continuous-flow inlet provided good accuracy and precision for measurements of {sup 13}CO{sub 2} from breath tests and {sup 18}O as CO{sub 2} from total energy expenditure tests. Most importantly, the continuous-flow inlet increased sample throughput by at least a factor of three over conventional analytical techniques. The filament inlet provided accurate and precise {sup 13}C ratio measurements of both natural abundance and enriched standards of non-volatile organic compounds of physiological interest.« less

Carbonic Anhydrase, Calcification Dynamics and Stable Isotope Vital Effects: Deep Sea Corals and Beyond

NASA Astrophysics Data System (ADS)

Chen, S.; Gagnon, A. C.; Adkins, J. F.

2017-12-01

The stable isotope compositions of biogenic carbonates have been used for paleoceanographic and paleoclimatic reconstructions for decades, and produced some of the most iconic records in the field. However, we still lack a fully mechanistic understanding of the stable isotope proxies, especially the biological overprint on the environmental signals termed "vital effects". A ubiquitous feature of stable isotope vital effects in marine calcifying organisms is a strong correlation between δ18O and δ13C in a range of values that are depleted from equilibrium. Two mechanisms have been proposed to explain this correlation, one based on kinetic isotope effects during CO2(aq)-HCO3- inter-conversion, the other based on equilibrium isotope exchange during pH dependent speciation of the dissolved inorganic carbon pool. Neither mechanism explains all the stable isotope features observed in biogenic carbonates. Here we present a fully kinetic model of biomineralization and its isotope effects using deep sea corals as a test organism. A key component of our model is the consideration of the enzyme carbonic anhydrase in catalyzing the CO2(aq)-HCO3- inter-conversion reactions in the extracellular calcifying fluid (ECF). We find that the amount of carbonic anhydrase not only modulates the carbonate chemistry of the calcifying fluid, but also helps explain the slope of the δ18O-δ13C correlation. With this model, we are not only able to fit deep sea coral data, but also explain the stable isotope vital effects of other calcifying organisms. This fully kinetic model of stable isotope vital effects and the underlying calcification dynamics may also help us better understand mechanisms of other paleoceanographic tracers in biogenic carbonates, including boron isotopes and trace metal proxies.

Arctic Ocean Cyclostratigraphy: An Alternative to Marine Oxygen Isotope curves as measures of Cryospheric and Sea-Level History

NASA Astrophysics Data System (ADS)

Cronin, T. M.; Marzen, R.; O'Regan, M.; Dwyer, G. S.

2016-12-01

The stable isotope compositions of biogenic carbonates have been used for paleoceanographic and paleoclimatic reconstructions for decades, and produced some of the most iconic records in the field. However, we still lack a fully mechanistic understanding of the stable isotope proxies, especially the biological overprint on the environmental signals termed "vital effects". A ubiquitous feature of stable isotope vital effects in marine calcifying organisms is a strong correlation between δ18O and δ13C in a range of values that are depleted from equilibrium. Two mechanisms have been proposed to explain this correlation, one based on kinetic isotope effects during CO2(aq)-HCO3- inter-conversion, the other based on equilibrium isotope exchange during pH dependent speciation of the dissolved inorganic carbon pool. Neither mechanism explains all the stable isotope features observed in biogenic carbonates. Here we present a fully kinetic model of biomineralization and its isotope effects using deep sea corals as a test organism. A key component of our model is the consideration of the enzyme carbonic anhydrase in catalyzing the CO2(aq)-HCO3- inter-conversion reactions in the extracellular calcifying fluid (ECF). We find that the amount of carbonic anhydrase not only modulates the carbonate chemistry of the calcifying fluid, but also helps explain the slope of the δ18O-δ13C correlation. With this model, we are not only able to fit deep sea coral data, but also explain the stable isotope vital effects of other calcifying organisms. This fully kinetic model of stable isotope vital effects and the underlying calcification dynamics may also help us better understand mechanisms of other paleoceanographic tracers in biogenic carbonates, including boron isotopes and trace metal proxies.

High-Precision Al-Mg Isotopic Systematics in USNM 3898 — The Benchmark "ALL" for Initial 87Sr/86Sr in the Earliest Solar System

NASA Astrophysics Data System (ADS)

MacPherson, G. J.; Defouilloy, C.; Kita, N. T.

2017-07-01

High-precision SIMS analysis of Al-Mg isotopes in USNM 3898, the CAI on which ALL is based, yields 26Al/27Al = (4.88 ± 0.14) × 10-5 in its interior vs. 26Al/27Al = (4.56 ± 0.11) × 10-5 in its outer mantle, suggesting later partial re-melting.

Mobile mapping of methane emissions and isoscapes

NASA Astrophysics Data System (ADS)

Takriti, Mounir; Ward, Sue; Wynn, Peter; Elias, Dafydd; McNamara, Niall

2017-04-01

Methane (CH4) is a potent greenhouse gas emitted from a variety of natural and anthropogenic sources. It is crucial to accurately and efficiently detect CH4 emissions and identify their sources to improve our understanding of changing emission patterns as well as to identify ways to curtail their release into the atmosphere. However, using established methods this can be challenging as well as time and resource intensive due to the temporal and spatial heterogeneity of many sources. To address this problem, we have developed a vehicle mounted mobile system that combines high precision CH4 measurements with isotopic mapping and dual isotope source characterisation. We here present details of the development and testing of a unique system for the detection and isotopic analysis of CH4 plumes built around a Picarro isotopic (13C/12C) gas analyser and a high precision Los Gatos greenhouse gas analyser. Combined with micrometeorological measurements and a mechanism for collecting discrete samples for high precision dual isotope (13C/12C, 2H/1H) analysis the system enables mapping of concentrations as well as directional and isotope based source verification. We then present findings from our mobile methane surveys around the North West of England. This area includes a variety of natural and anthropogenic methane sources within a relatively small geographical area, including livestock farming, urban and industrial gas infrastructure, landfills and waste water treatment facilities, and wetlands. We show that the system was successfully able to locate leaks from natural gas infrastructure and emissions from agricultural activities and to distinguish isotope signatures from these sources.

Boron isotopic composition of olivine-hosted melt inclusions from Gorgona komatiites, Colombia: New evidence supporting wet komatiite origin

NASA Astrophysics Data System (ADS)

Gurenko, Andrey A.; Kamenetsky, Vadim S.

2011-12-01

A fundamental question in the genesis of komatiites is whether these rocks originate from partial melting of dry and hot mantle, 400-500 °C hotter than typical sources of MORB and OIB magmas, or if they were produced by hydrous melting of the source at much lower temperatures, similar or only moderately higher than those known today. Gorgona Island, Colombia, is a unique place where Phanerozoic komatiites occur and whose origin is directly connected to the formation of the Caribbean Large Igneous Province. The genesis of Gorgona komatiites remains controversial, mostly because of the uncertain origin of volatile components which they appear to contain. These volatiles could equally result from shallow level magma contamination, melting of a "damp" mantle or fluid-induced partial melting of the source due to devolatilization of the ancient subducting plate. We have analyzed boron isotopes of olivine-hosted melt inclusions from the Gorgona komatiites. These inclusions are characterized by relatively high contents of volatile components and boron (0.2-1.0 wt.% H 2O, 0.05-0.08 wt.% S, 0.02-0.03 wt.% Cl, 0.6-2.0 μg/g B), displaying positive anomalies in the overall depleted, primitive mantle (PM) normalized trace element and REE spectra ([La/Sm] n = 0.16-0.35; [H 2O/Nb] n = 8-44; [Cl/Nb] n = 27-68; [B/Nb] n = 9-30, assuming 300 μg/g H 2O, 8 μg/g Cl and 0.1 μg/g B in PM; Kamenetsky et al., 2010. Composition and temperature of komatiite melts from Gorgona Island constrained from olivine-hosted melt inclusions. Geology 38, 1003-1006). The inclusions range in δ11B values from - 11.5 to + 15.6 ± 2.2‰ (1 SE), forming two distinct trends in a δ11B vs. B-concentration diagram. Direct assimilation of seawater, seawater-derived components, altered oceanic crust or marine sediments by ascending komatiite magma cannot readily account for the volatile contents and B isotope variations. Alternatively, injection of < 3wt.% of a 11B enriched fluid to the mantle source could be a plausible explanation for the δ11B range that also may explain the H 2O, Cl and B excess.

Recent progress in development of infrared laser based instruments for real-time ambient measurements of isotopologues of carbon dioxide, water, methane, nitrous oxide and carbon monoxide

NASA Astrophysics Data System (ADS)

Nelson, David; McManus, Barry; Shorter, Joanne; Zahniser, Mark; Ono, Shuhei

2014-05-01

The capacity for real time precise in situ measurements of isotopic ratios of a variety of trace gases at ambient concentrations continues to create new opportunities for the study of the exchanges and fluxes of gases in the environment. Aerodyne Research has made rapid progress in laser based instruments since our introduction in 2007 of the first truly field worthy instrument for real time measurements of isotopologues of carbon dioxide. We have focused on two instrument design platforms, with either one or two lasers. Absorption cells with more than 200 meters path length allow precise measurements of trace gases with low ambient concentrations. Most of our systems employ mid infrared quantum cascade lasers. However, recently available 3 micron antimonide based diode lasers are also proving useful for isotopic measurements. By substituting different lasers and detectors, we can simultaneously measure the isotopic composition of a variety of gases, including: H2O, CO2, CH4, N2O and CO. Our newest instrument for true simultaneous measurement of isotopologues of CO2 (12CO2, 13CO2, 12C18O16O) has (1 s) precision better than 0.1 per mil for both ratios. The availability of 10 Hz measurements allows measurement of isotopic fluxes via eddy correlation. The single laser instrument fits in a 19 inch rack and is only 25 cm tall. A two laser instrument is larger, but with that instrument we can also measure clumped isotopes of CO2, with 1 second precisions of: 2.3 per mil for 13C18O16O, and 6.7 per mil for 13C17O16O. The sample size for such a measurement corresponds to 0.2 micromole of pure CO2. Another variation on the two laser instrument simultaneously measures isotopologues of CO2 (12CO2, 13CO2, 12C18O16O) and H2O (H216O, H218O, HD16O). Preliminary results for water ratio precisions (in 1s) are 0.1 per mil for H218O and 0.3 per mil for HD16O, simultaneous (1 s) precisions for isotopologues of CO2 of ~0.1 per mil. Methane, nitrous oxide and carbon monoxide have such low ambient concentrations that real-time isotopologue measurements are a serious challenge. For these gases, we typically use our 200 m absorption cell. Several of these instruments have already been used for long term field measurements of isotopologues of methane, (12CH4, 13CH4), with a demonstrated (1 s) precision of 1.5 per mil. A new version of this instrument operating near 3.3 microns has recently been developed to quantify 13CH4 and CH3D simultaneously. In separate experiments at MIT, using trapped concentrated samples, we have made highly precise measurements of the abundance of the clumped isotope of methane: 13CH3D. We are also developing methods to monitor the isotopic abundance of the isotopes of CO and N2O. We have achieved a measurement precision for ambient 13CO (1 s) of 1.9 per mil. For the isotopologues of N2O (14N216O, 14N15N 16O, 15N14N 16O, 14N218O), we have demonstrated (1 s) precision at ambient levels (320 ppb) of ~3 per mil. For N2O, a quasi continuous preconcentrator has been used to give even better precisions (<0.1 per mil) and one is being developed for CO.

Isotope-abundance variations of selected elements (IUPAC technical report)

USGS Publications Warehouse

Coplen, T.B.; Böhlke, J.K.; De Bievre, P.; Ding, T.; Holden, N.E.; Hopple, J.A.; Krouse, H.R.; Lamberty, A.; Peiser, H.S.; Revesz, K.; Rieder, S.E.; Rosman, K.J.R.; Roth, E.; Taylor, P.D.P.; Vocke, R.D.; Xiao, Y.K.

2002-01-01

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic-weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic-weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope-abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope-abundance variations potentially are large enough to result in future expansion of their atomic-weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic-weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio.

A novel upgrade to Helsinki AMS: Fast switching of isotopes with electrostatic deflectors

NASA Astrophysics Data System (ADS)

Palonen, V.; Tikkanen, P.

2015-10-01

We have developed and installed electrostatic deflectors at the injection magnet entrance and exit to enable fast switching between isotopes in AMS measurements. The fast selection of the injected isotope, stable isotope current measurements, and rare isotope detection are all performed with three synchronized real-time NI-PXI computers. With the improvements, we are able to attain a precision of better than 0.2% for the 14C/13C ratio of modern samples.

Study of the {sup 10}B(p,α){sup 7}Be reaction through the indirect Trojan Horse method

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

Puglia, S. M. R., E-mail: puglia@lns.infn.it; Spitaleri, C.; Lamia, L.

2015-02-24

Boron abundances in stellar atmospheres, as well as berillium and lithium ones, can give useful hints for non-standard transport processes discrimination in stars. They can also be relevant for understanding several astrophysical processes (e.g. primordial nucleosynthesis and spallation reactions in ISM). A comprehensive study of Li Be B abundances can therefore confirm or not the presence of non-standard mixing processes in stellar envelopes. For this reason nuclear processes producing or depleting boron isotope abundance need to be studied at astrophysical energies. The {sup 10}B(p,α){sup 7}Be reaction has been studied by means of the Trojan Horse Method. The Trojan Horse Methodmore » was thus applied to the {sup 10}B(d,α{sup 7}Be)n reaction, studied at 24 MeV. The obtained results will be discussed.« less

Quantitative bioimaging of p-boronophenylalanine in thin liver tissue sections as a tool for treatment planning in boron neutron capture therapy.

PubMed

Reifschneider, Olga; Schütz, Christian L; Brochhausen, Christoph; Hampel, Gabriele; Ross, Tobias; Sperling, Michael; Karst, Uwe

2015-03-01

An analytical method using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was developed and applied to assess enrichment of 10B-containing p-boronophenylalanine-fructose (BPA-f) and its pharmacokinetic distribution in human tissues after application for boron neutron capture therapy (BNCT). High spatial resolution (50 μm) and limits of detection in the low parts-per-billion range were achieved using a Nd:YAG laser of 213 nm wavelength. External calibration by means of 10B-enriched standards based on whole blood proved to yield precise quantification results. Using this calibration method, quantification of 10B in cancerous and healthy tissue was carried out. Additionally, the distribution of 11B was investigated, providing 10B enrichment in the investigated tissues. Quantitative imaging of 10B by means of LA-ICP-MS was demonstrated as a new option to characterise the efficacy of boron compounds for BNCT.

[Determination of diborane in the air of workplace by ICP-AES].

PubMed

Ding, Chun-Guang; Zhang, Jing; Yan, Hui-Fang

2011-06-01

A sampling method was established to collect diborane in the air of workplace and an ICP-AES method was developed to determine the Boron in desorbed solution. Diborane in the air of workplace was collected by solid sorbent tube filled with oxidant impregnated activated carbon. The adsorbed diborane was desorbed into 3% H2O2 aqueous, and then the desorbed Boron was determined by ICP-AES. The sampling efficiency of this method was 99.6% with the desorption efficiency of diborane with 5.660 microg and 56.6 microg spiked were 90.9% and 99.5%, respectively. Both the intra-and inter-precision RSD were less than 8%. The standard curve of this method ranged from 0.1 to 10.0 microg/ml (Boron), and the LOD and LOQ were 0.011 mg/m3 and 0.035 mg/m3 (15L samples) respectively. The method established was suitable for diborane sampling and determination in the air of workplace.

Enhancement of thermal conductive pathway of boron nitride coated polymethylsilsesquioxane composite.

PubMed

Kim, Gyungbok; Ryu, Seung Han; Lee, Jun-Tae; Seong, Ki-Hun; Lee, Jae Eun; Yoon, Phil-Joong; Kim, Bum-Sung; Hussain, Manwar; Choa, Yong-Ho

2013-11-01

We report here in the fabrication of enhanced thermal conductive pathway nanocomposites of boron nitride (BN)-coated polymethylsilsesquioxane (PMSQ) composite beads using isopropyl alcohol (IPA) as a mixing medium. Exfoliated and size-reduced boron nitride particles were successfully coated on the PMSQ beads and explained by surface charge differences. A homogeneous dispersion and coating of BN on the PMSQ beads using IPA medium was confirmed by SEM. Each condition of the composite powder was carried into the stainless still mould and then hot pressed in an electrically heated hot press machine. Three-dimensional percolation networks and conductive pathways created by exfoliated BN were precisely formed in the nanocomposites. The thermal conductivity of nanocomposites was measured by multiplying specific gravity, specific heat, and thermal diffusivity, based upon the laser flash method. Densification of the composite resulted in better thermal properties. For an epoxy reinforced composite with 30 vol% BN and PMSQ, a thermal conductivity of nine times higher than that of pristine PMSQ was observed.

The earliest Lunar Magma Ocean differentiation recorded in Fe isotopes

NASA Astrophysics Data System (ADS)

Wang, Kun; Jacobsen, Stein B.; Sedaghatpour, Fatemeh; Chen, Heng; Korotev, Randy L.

2015-11-01

Recent high-precision isotopic measurements show that the isotopic similarity of Earth and Moon is unique among all known planetary bodies in our Solar System. These observations provide fundamental constraints on the origin of Earth-Moon system, likely a catastrophic Giant Impact event. However, in contrast to the isotopic composition of many elements (e.g., O, Mg, Si, K, Ti, Cr, and W), the Fe isotopic compositions of all lunar samples are significantly different from those of the bulk silicate Earth. Such a global Fe isotopic difference between the Moon and Earth provides an important constraint on the lunar formation - such as the amount of Fe evaporation as a result of a Giant Impact origin of the Moon. Here, we show through high-precision Fe isotopic measurements of one of the oldest lunar rocks (4.51 ± 0.10 Gyr dunite 72 415), compared with Fe isotope results of other lunar samples from the Apollo program, and lunar meteorites, that the lunar dunite is enriched in light Fe isotopes, complementing the heavy Fe isotope enrichment in other lunar samples. Thus, the earliest olivine accumulation in the Lunar Magma Ocean may have been enriched in light Fe isotopes. This new observation allows the Fe isotopic composition of the bulk silicate Moon to be identical to that of the bulk silicate Earth, by balancing light Fe in the deep Moon with heavy Fe in the shallow Moon rather than the Moon having a heavier Fe isotope composition than Earth as a result of Giant Impact vaporization.

Slow-Release Fertilizers For Plants

NASA Technical Reports Server (NTRS)

Ming, Douglas W.; Golden, D. C.

1995-01-01

Synthetic mineral provides growing plants with nutrients, including micronutrients. Dissolves slowly in moist soil or in hydroponic solution, releasing constituents. Mineral synthetic apatite into which nutrients calcium, phosphorous, iron, manganese, copper, zinc, molybdenum, chlorine, boron, and sulfur incorporated in form of various salts. Each pellet has homogeneous inorganic composition. Composition readily adjusted to meet precise needs of plant.

Laser-based measurements of δ13 C and δ2 H methane isotope signatures: precisions competitive with mass spectrometry methods

NASA Astrophysics Data System (ADS)

Yacovitch, Tara; Shorter, Joanne; Nelson, David; Herndon, Scott; Agnese, Mike; McManus, Barry; Zahniser, Mark

2017-04-01

In order to understand how and why methane (CH4 ) concentrations change over time, it is necessary to understand their sources and sinks. Stable isotope measurements of 13 CH4 :12 CH4 and CH3 D:12 CH4 ratios constrain the inventory of these sinks and sources. Current measurements often depend on Isotope Ratio Mass Spectrometry (IRMS), which requires extensive sample preparation including cryogenic separation of methane from air and subsequent conversion to either CO2 or H2 . Here, we detail improvements to a direct-absorption laser spectrometer that enable fast and precise measurements of methane isotope ratios (δ13 C and δ2 H ) of ambient air samples, without such sample preparation. The measurement system consists of a laser-based direct absorption spectrometer configured with a sample manifold for measurement of discrete samples (as opposed to flow-through measurements). Samples are trapped in the instrument using a rapid sample switching technique that compares each flask sample against a monitor tank sample. This approach reduces instrument drift and results in excellent precision. Precisions of 0.054 o/oo for δ13 C and 1.4 o/oo for δ2 H have been achieved (Allan-Werle deviations). These results are obtained in 20 minutes using 4 replicate comparisons to a monitor tank.

Separation of Platinum from Palladium and Iridium in Iron Meteorites and Accurate High-Precision Determination of Platinum Isotopes by Multi-Collector ICP-MS.

PubMed

Hunt, Alison C; Ek, Mattias; Schönbächler, Maria

2017-12-01

This study presents a new measurement procedure for the isolation of Pt from iron meteorite samples. The method also allows for the separation of Pd from the same sample aliquot. The separation entails a two-stage anion-exchange procedure. In the first stage, Pt and Pd are separated from each other and from major matrix constituents including Fe and Ni. In the second stage, Ir is reduced with ascorbic acid and eluted from the column before Pt collection. Platinum yields for the total procedure were typically 50-70%. After purification, high-precision Pt isotope determinations were performed by multi-collector ICP-MS. The precision of the new method was assessed using the IIAB iron meteorite North Chile. Replicate analyses of multiple digestions of this material yielded an intermediate precision for the measurement results of 0.73 for ε 192 Pt, 0.15 for ε 194 Pt and 0.09 for ε 196 Pt (2 standard deviations). The NIST SRM 3140 Pt solution reference material was passed through the measurement procedure and yielded an isotopic composition that is identical to the unprocessed Pt reference material. This indicates that the new technique is unbiased within the limit of the estimated uncertainties. Data for three iron meteorites support that Pt isotope variations in these samples are due to exposure to galactic cosmic rays in space.

Oxygen isotope analysis of phosphate: improved precision using TC/EA CF-IRMS.

PubMed

LaPorte, D F; Holmden, C; Patterson, W P; Prokopiuk, T; Eglington, B M

2009-06-01

Oxygen isotope values of biogenic apatite have long demonstrated considerable promise for paleothermometry potential because of the abundance of material in the fossil record and greater resistance of apatite to diagenesis compared to carbonate. Unfortunately, this promise has not been fully realized because of relatively poor precision of isotopic measurements, and exceedingly small size of some substrates for analysis. Building on previous work, we demonstrate that it is possible to improve precision of delta18O(PO4) measurements using a 'reverse-plumbed' thermal conversion elemental analyzer (TC/EA) coupled to a continuous flow isotope ratio mass spectrometer (CF-IRMS) via a helium stream [Correction made here after initial online publication]. This modification to the flow of helium through the TC/EA, and careful location of the packing of glassy carbon fragments relative to the hot spot in the reactor, leads to narrower, more symmetrically distributed CO elution peaks with diminished tailing. In addition, we describe our apatite purification chemistry that uses nitric acid and cation exchange resin. Purification chemistry is optimized for processing small samples, minimizing isotopic fractionation of PO4(-3) and permitting Ca, Sr and Nd to be eluted and purified further for the measurement of delta44Ca and 87Sr/86Sr in modern biogenic apatite and 143Nd/144Nd in fossil apatite. Our methodology yields an external precision of +/- 0.15 per thousand (1sigma) for delta18O(PO4). The uncertainty is related to the preparation of the Ag3PO4 salt, conversion to CO gas in a reversed-plumbed TC/EA, analysis of oxygen isotopes using a CF-IRMS, and uncertainty in constructing calibration lines that convert raw delta18O data to the VSMOW scale. Matrix matching of samples and standards for the purpose of calibration to the VSMOW scale was determined to be unnecessary. Our method requires only slightly modified equipment that is widely available. This fact, and the demonstrated improvement in precision, should help to make apatite paleothermometry far more accessible to paleoclimate researchers. Copyright 2009 John Wiley & Sons, Ltd.

Potential for long-term, high-frequency, high-precision methane isotope measurements to improve UK emissions estimates

NASA Astrophysics Data System (ADS)

Rennick, Chris; Bausi, Francesco; Arnold, Tim

2017-04-01

On the global scale methane (CH4) concentrations have more than doubled over the last 150 years, and the contribution to the enhanced greenhouse effect is almost half of that due to the increase in carbon dioxide (CO2) over the same period. Microbial, fossil fuel, biomass burning and landfill are dominant methane sources with differing annual variabilities; however, in the UK for example, mixing ratio measurements from a tall tower network and regional scale inversion modelling have thus far been unable to disaggregate emissions from specific source categories with any significant certainty. Measurement of the methane isotopologue ratios will provide the additional information needed for more robust sector attribution, which will be important for directing policy action Here we explore the potential for isotope ratio measurements to improve the interpretation of atmospheric mixing ratios beyond calculation of total UK emissions, and describe current analytical work at the National Physical Laboratory that will realise deployment of such measurements. We simulate isotopic variations at the four UK greenhouse gas tall tower network sites to understand where deployment of the first isotope analyser would be best situated. We calculate the levels of precision needed in both δ-13C and δ-D in order to detect particular scenarios of emissions. Spectroscopic measurement in the infrared by quantum cascade laser (QCL) absorption is a well-established technique to quantify the mixing ratios of trace species in atmospheric samples and, as has been demonstrated in 2016, if coupled to a suitable preconcentrator then high-precision measurements are possible. The current preconcentration system under development at NPL is designed to make the highest precision measurements yet of the standard isotope ratios via a new large-volume cryogenic trap design and controlled thermal desorption into a QCL spectrometer. Finally we explore the potential for the measurement of clumped isotopes at high frequency and precision. The doubly-substituted 13CH3D isotopologue is a tracer for methane formed at geological temperatures, and will provide additional information for identification of these sources.

High-precision optical measurements of 13C/12C isotope ratios in organic compounds at natural abundance

PubMed Central

Zare, Richard N.; Kuramoto, Douglas S.; Haase, Christa; Tan, Sze M.; Crosson, Eric R.; Saad, Nabil M. R.

2009-01-01

A continuous-flow cavity ring-down spectroscopy (CRDS) system integrating a chromatographic separation technique, a catalytic combustor, and an isotopic 13C/12C optical analyzer is described for the isotopic analysis of a mixture of organic compounds. A demonstration of its potential is made for the geochemically important class of short-chain hydrocarbons. The system proved to be linear over a 3-fold injection volume dynamic range with an average precision of 0.95‰ and 0.67‰ for ethane and propane, respectively. The calibrated accuracy for methane, ethane, and propane is within 3‰ of the values determined using isotope ratio mass spectrometry (IRMS), which is the current method of choice for compound-specific isotope analysis. With anticipated improvements, the low-cost, portable, and easy-to-use CRDS-based instrumental setup is poised to evolve into a credible challenge to the high-cost and complex IRMS-based technique. PMID:19564619

Sensitivity and Uncertainty Analysis of Plutonium and Cesium Isotopes in Modeling of BR3 Reactor Spent Fuel

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

Conant, Andrew; Erickson, Anna; Robel, Martin

Nuclear forensics has a broad task to characterize recovered nuclear or radiological material and interpret the results of investigation. One approach to isotopic characterization of nuclear material obtained from a reactor is to chemically separate and perform isotopic measurements on the sample and verify the results with modeling of the sample history, for example, operation of a nuclear reactor. The major actinide plutonium and fission product cesium are commonly measured signatures of the fuel history in a reactor core. This study investigates the uncertainty of the plutonium and cesium isotope ratios of a fuel rod discharged from a research pressurizedmore » water reactor when the location of the sample is not known a priori. A sensitivity analysis showed overpredicted values for the 240Pu/ 239Pu ratio toward the axial center of the rod and revealed a lower probability of the rod of interest (ROI) being on the periphery of the assembly. The uncertainty analysis found the relative errors due to only the rod position and boron concentration to be 17% to 36% and 7% to 15% for the 240Pu/ 239Pu and 137Cs/ 135Cs ratios, respectively. Lastly, this study provides a method for uncertainty quantification of isotope concentrations due to the location of the ROI. Similar analyses can be performed to verify future chemical and isotopic analyses.« less

Sensitivity and Uncertainty Analysis of Plutonium and Cesium Isotopes in Modeling of BR3 Reactor Spent Fuel

DOE PAGES

Conant, Andrew; Erickson, Anna; Robel, Martin; ...

2017-02-03

Nuclear forensics has a broad task to characterize recovered nuclear or radiological material and interpret the results of investigation. One approach to isotopic characterization of nuclear material obtained from a reactor is to chemically separate and perform isotopic measurements on the sample and verify the results with modeling of the sample history, for example, operation of a nuclear reactor. The major actinide plutonium and fission product cesium are commonly measured signatures of the fuel history in a reactor core. This study investigates the uncertainty of the plutonium and cesium isotope ratios of a fuel rod discharged from a research pressurizedmore » water reactor when the location of the sample is not known a priori. A sensitivity analysis showed overpredicted values for the 240Pu/ 239Pu ratio toward the axial center of the rod and revealed a lower probability of the rod of interest (ROI) being on the periphery of the assembly. The uncertainty analysis found the relative errors due to only the rod position and boron concentration to be 17% to 36% and 7% to 15% for the 240Pu/ 239Pu and 137Cs/ 135Cs ratios, respectively. Lastly, this study provides a method for uncertainty quantification of isotope concentrations due to the location of the ROI. Similar analyses can be performed to verify future chemical and isotopic analyses.« less

A novel procedure for Rubidium separation and its isotope measurements on geological samples by MC-ICP-MS

NASA Astrophysics Data System (ADS)

Ma, J.; Zhang, Z.; Wei, G.; Zhang, L.

2017-12-01

A method including a novel column Rb separation procedure and high-precision Rb isotope measurement in geological materials by using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) in standard-sample-bracketing (SSB) mode has been developed. Sr-Spec resin was employed, in which the distribution coefficients for Rb, K, Ba and Sr are different in nitric acid, to sequentially separate them from the matrix. The dissolved samples were loaded on the column in 3 M HNO3, the main matrix such as Al, Ca, Fe, Mg, Mn and Na were removed by rinsing with 4.5 mL HNO3, Rb and K were then sequentially eluted by 3 M HNO3 in different volumes. After that, Ba was eluted by 8 M HNO3, and Sr was finally eluted by Milli-Q water. This enable us to collect the pure Rb, K, Ba and Sr one by one with recovery close to 100% for their isotopic compositions measurement on MC-ICP-MS. We here focus on Rb isotope measurement. The measurement using MC-ICP-MS yielded an internal precision for δ87Rb of < ± 0.03‰ (2SE), and the external precision was generally better than ± 0.06‰ (2SD) based on the long-term results of the Rb standard solutions NIST SRM 984. A series of geological rock standards, were analyzed using this method, and the results indicate significant Rb isotope differences in different geologic materials. This will provide a powerful tool to investigate Rb isotope fractionation during geological processes.Based on this method, Rb isotope compositions from a basaltic weathering profile were carried out. The data show the lighter Rb (85Rb) isotope is preferentially leached from the weathering profile and remains heavy Rb isotope (87Rb) in the weathered residues during the incipient weathering stage. From the moderate to advanced weathering stage, the significant variations of Rb isotope were observed and multiple factors, such as leaching, adsorption, desorption, and precipitation, should play important role in fractionating Rb isotope.

Conditions of Mytilus edulis extracellular body fluids and shell composition in a pH-treatment experiment: Acid-base status, trace elements and δ11B

NASA Astrophysics Data System (ADS)

Heinemann, Agnes; Fietzke, Jan; Melzner, Frank; BöHm, Florian; Thomsen, JöRn; Garbe-SchöNberg, Dieter; Eisenhauer, Anton

2012-01-01

Mytilus edulis were cultured for 3 months under six different seawater pCO2 levels ranging from 380 to 4000 μatm. Specimen were taken from Kiel Fjord (Western Baltic Sea, Germany) which is a habitat with high and variable seawater pCO2 and related shifts in carbonate system speciation (e.g., low pH and low CaCO3 saturation state). Hemolymph (HL) and extrapallial fluid (EPF) samples were analyzed for pH and total dissolved inorganic carbon (CT) to calculate pCO2 and [HCO3-]. A second experiment was conducted for 2 months with three different pCO2 levels (380, 1400 and 4000 μatm). Boron isotopes (δ11B) were investigated by LA-MC-ICP-MS (Laser Ablation-Multicollector-Inductively Coupled Plasma-Mass Spectrometry) in shell portions precipitated during experimental treatment time. Additionally, elemental ratios (B/Ca, Mg/Ca and Sr/Ca) in the EPF of specimen from the second experiment were measured via ICP-OES (Inductively Coupled Plasma-Optical Emission Spectrometry). Extracellular pH was not significantly different in HL and EPF but systematically lower than ambient water pH. This is due to high extracellular pCO2 values, a prerequisite for metabolic CO2 excretion. No accumulation of extracellular [HCO3-] was measured. Elemental ratios (B/Ca, Mg/Ca and Sr/Ca) in the EPF increased slightly with pH which is in accordance with increasing growth and calcification rates at higher seawater pH values. Boron isotope ratios were highly variable between different individuals but also within single shells. This corresponds to a high individual variability in fluid B/Ca ratios and may be due to high boron concentrations in the organic parts of the shell. The mean δ11B value shows no trend with pH but appears to represent internal pH (EPF) rather than ambient water pH.

Environmental controls on the boron and strontium isotopic composition of aragonite shell material of cultured Arctica islandica

NASA Astrophysics Data System (ADS)

Liu, Y.-W.; Aciego, S. M.; Wanamaker, A. D., Jr.

2015-02-01

Ocean acidification, the decrease in ocean pH associated with increasing atmospheric CO2, is likely to impact marine organisms, particularly those that produce carbonate skeletons or shells. Therefore it is important to investigate how environmental factors (seawater pH, temperature and salinity) influence the chemical compositions in biogenic carbonates. In this study we report the first high-resolution strontium (87Sr / 86Sr and δ88 / 86Sr) and boron (δ11B) isotopic values in the aragonite shell of cultured Arctica islandica (A. islandica). The 87Sr / 86Sr ratios from both tank water and shell samples show ratios nearly identical to the open ocean, which suggests that the shell material reflects ambient ocean chemistry without terrestrial influence. The 84Sr-87Sr double spike resolved shell δ 88 / 86Sr and Sr concentration data show no resolvable change throughout the culture period and reflect no theoretical kinetic mass fractionation throughout the experiment despite a temperature change of more than 15 °C. The δ11B records from the experiment show at least a 5‰ increase through the culture season (January 2010-August 2010), with low values from beginning to week 19 and higher values hereafter. The larger range in δ11B in this experiment compared to predictions based on other carbonate organisms (2-3‰) suggests that a species-specific fractionation factor may be required. A relatively strong correlation between the Δ pH (pHshell-pHsw) and seawater pH (pHsw) was observed (R2 = 0.34), which suggests that A. islandica partly regulates the pH of the extrapallial fluid. However, this proposed mechanism only explains approximately 34% of the variance in the δ11B data. Instead, a rapid rise in δ11B after week 19 suggests that the boron uptake of the shell changes when a temperature threshold of 13 °C is reached.

Tables for determining lead, uranium, and thorium isotope ages

NASA Technical Reports Server (NTRS)

Schonfeld, E.

1974-01-01

Tables for determining lead, uranium, and thorium isotope ages are presented in the form of computer printouts. Decay constants, analytical expressions for the functions evaluated, and the precision of the calculations are briefly discussed.

High-precision lead isotopes and stripy plumes: Revisiting the Society chain in French Polynesia

NASA Astrophysics Data System (ADS)

Cordier, Carole; Chauvel, Catherine; Hémond, Christophe

2016-09-01

An increasing number of geochemical studies looked for spatial organization of the isotopic variations along Pacific volcanic island chains (e.g., Hawaii, Marquesas, Samoa and Society Islands) in order to discuss the possible zoning of the plume conduits. Here, we reexamine the occurrence of isotopic stripes in the Society archipelago in French Polynesia, using new Sr-Nd-Hf-Pb isotope ratios of sixty-six lavas from six islands (Mehetia, Moorea, Maupiti, Huahine, Raiatea, Bora-Bora). We demonstrate that the Pb isotope variability observed using literature data is an analytical artifact related to the poor control of mass fractionation during Pb measurements by conventional TIMS technique. New MC-ICP-MS Pb data demonstrate that the isotopic stripes as previously defined disappear. They rather show that individual islands cover a significant part of the entire isotopic range of the chain. We suggest, therefore, that the dominant characteristic of the Society plume is small-scale heterogeneities, evenly distributed within the plume conduit. At a global scale, we show that some ocean island chains with similar geochemical and isotopic characteristics, such as Samoa and Society Islands, define different arrays when variations of Nd with high-precision Pb isotopes are considered. We proposed that this puzzling observation might record differences in recycling age of the basalt + sediment mixture subducted into the mantle and sampled by mantle plume.

Geothermal investigation of spring and well waters of the Los Alamos Region, New Mexico

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

Goff, F.E.; Sayer, S.

1980-04-01

The chemical and isotopic characters of 20 springs and wells in the Los Alamos area were investigated for indications of geothermal potential. These waters were compared with known hot and mineral springs from adjacent Valles Caldera and San Ysidro. All waters in the Los Alamos area are composed of meteoric water. Isotopic data show that the two primary aquifers beneath the Los Alamos region have different recharge areas. Relatively high concentrations of lithium, arsenic, chlorine, boron, and fluorine in some of the Los Alamos wells suggest these waters may contain a small fraction of thermal/mineral water of deep origin. Thermalmore » water probably rises up high-angle faults associated with a graben of the Rio Grande rift now buried by the Pajarito Plateau.« less

Baseline groundwater quality from 20 domestic wells in Sullivan County, Pennsylvania, 2012

USGS Publications Warehouse

Sloto, Ronald A.

2013-01-01

Concentrations of dissolved methane ranged from less than 0.001 to 51.1 mg/L. Methane was not detected in water samples from 13 wells, and the methane concentration was less than 0.07 mg/L in samples from five wells. The highest dissolved methane concentrations were 4.1 and 51.1 mg/L, and the pH of the water from both wells was greater than 8. Water samples from these wells were analyzed for isotopes of carbon and hydrogen in the methane. The isotopic ratio values fell in the range for a thermogenic (natural gas) source. The water samples from these two wells had the highest concentrations of arsenic, boron, bromide, chloride, fluoride, lithium, molybdenum, and sodium of the 20 wells sampled.

Structural models of increasing complexity for icosahedral boron carbide with compositions throughout the single-phase region from first principles

NASA Astrophysics Data System (ADS)

Ektarawong, A.; Simak, S. I.; Alling, B.

2018-05-01

We perform first-principles calculations to investigate the phase stability of boron carbide, concentrating on the recently proposed alternative structural models composed not only of the regularly studied B11Cp (CBC) and B12(CBC), but also of B12(CBCB) and B12( B4 ). We find that a combination of the four structural motifs can result in low-energy electron precise configurations of boron carbide. Among several considered configurations within the composition range of B10.5C and B4C , we identify in addition to the regularly studied B11Cp (CBC) at the composition of B4C two low-energy configurations, resulting in a new view of the B-C convex hull. Those are [B12 (CBC)]0.67[B12(B4)] 0.33 and [B12 (CBC)]0.67[ B12 (CBCB)]0.33, corresponding to compositions of B10.5C and B6.67C , respectively. As a consequence, B12(CBC) at the composition of B6.5C , previously suggested in the literature as a stable configuration of boron carbide, is no longer part of the B -C convex hull. By inspecting the electronic density of states as well as the elastic moduli, we find that the alternative models of boron carbide can provide a reasonably good description for electronic and elastic properties of the material in comparison with the experiments, highlighting the importance of considering B12(CBCB) and B12( B4 ), together with the previously proposed B11Cp (CBC) and B12(CBC), as the crucial ingredients for modeling boron carbide with compositions throughout the single-phase region.

Liquid and gas chromatography coupled to isotope ratio mass spectrometry for the determination of 13C-valine isotopic ratios in complex biological samples.

PubMed

Godin, Jean-Philippe; Breuillé, Denis; Obled, Christiane; Papet, Isabelle; Schierbeek, Henk; Hopfgartner, Gérard; Fay, Laurent-Bernard

2008-10-01

On-line gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is commonly used to measure isotopic ratios at natural abundance as well as for tracer studies in nutritional and medical research. However, high-precision (13)C isotopic enrichment can also be measured by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Indeed, LC-IRMS can be used, as shown by the new method reported here, to obtain a baseline separation and to measure (13)C isotopic enrichment of underivatised amino acids (Asp, Thr-Ser, Glu, Pro, Gly, Ala, Cys and Val). In case of Val, at natural abundance, the SD(delta(13)C) reported with this method was found to be below 1 per thousand . Another key feature of the new LC-IRMS method reported in this paper is the comparison of the LC-IRMS approach with the conventional GC-C-IRMS determination. To perform this comparative study, isotopic enrichments were measured from underivatised Val and its N(O, S)-ethoxycarbonyl ethyl ester derivative. Between 0.0 and 1.0 molar percent excess (MPE) (delta(13)C= -12.3 to 150.8 per thousand), the calculated root-mean-square (rms) of SD was 0.38 and 0.46 per thousand and the calculated rms of accuracy was 0.023 and 0.005 MPE, respectively, for GC-C-IRMS and LC-IRMS. Both systems measured accurately low isotopic enrichments (0.002 atom percent excess (APE)) with an SD (APE) of 0.0004. To correlate the relative (delta(13)C) and absolute (atom%, APE and MPE) isotopic enrichment of Val measured by the GC-C-IRMS and LC-IRMS devices, mathematical equations showing the slope and intercept of the curves were established and validated with experimental data between 0.0 to 2.3 MPE. Finally, both GC-C-IRMS and LC-IRMS instruments were also used to assess isotopic enrichment of protein-bound (13)C-Val in tibial epiphysis in a tracer study performed in rats. Isotopic enrichments measured by LC-IRMS and GC-C-IRMS were not statistically different (p>0.05). The results of this work indicate that the LC-IRMS was successful for high-precision (13)C isotopic measurements in tracer studies giving (13)C isotopic enrichment similar to the GC-C-IRMS but without the step of GC derivatisation. Therefore, for clinical studies requiring high-precision isotopic measurement, the LC-IRMS is the method of choice to measure the isotopic ratio.

Water vapor δ(2) H, δ(18) O and δ(17) O measurements using an off-axis integrated cavity output spectrometer - sensitivity to water vapor concentration, delta value and averaging-time.

PubMed

Tian, Chao; Wang, Lixin; Novick, Kimberly A

2016-10-15

High-precision analysis of atmospheric water vapor isotope compositions, especially δ(17) O values, can be used to improve our understanding of multiple hydrological and meteorological processes (e.g., differentiate equilibrium or kinetic fractionation). This study focused on assessing, for the first time, how the accuracy and precision of vapor δ(17) O laser spectroscopy measurements depend on vapor concentration, delta range, and averaging-time. A Triple Water Vapor Isotope Analyzer (T-WVIA) was used to evaluate the accuracy and precision of δ(2) H, δ(18) O and δ(17) O measurements. The sensitivity of accuracy and precision to water vapor concentration was evaluated using two international standards (GISP and SLAP2). The sensitivity of precision to delta value was evaluated using four working standards spanning a large delta range. The sensitivity of precision to averaging-time was assessed by measuring one standard continuously for 24 hours. Overall, the accuracy and precision of the δ(2) H, δ(18) O and δ(17) O measurements were high. Across all vapor concentrations, the accuracy of δ(2) H, δ(18) O and δ(17) O observations ranged from 0.10‰ to 1.84‰, 0.08‰ to 0.86‰ and 0.06‰ to 0.62‰, respectively, and the precision ranged from 0.099‰ to 0.430‰, 0.009‰ to 0.080‰ and 0.022‰ to 0.054‰, respectively. The accuracy and precision of all isotope measurements were sensitive to concentration, with the higher accuracy and precision generally observed under moderate vapor concentrations (i.e., 10000-15000 ppm) for all isotopes. The precision was also sensitive to the range of delta values, although the effect was not as large compared with the sensitivity to concentration. The precision was much less sensitive to averaging-time than the concentration and delta range effects. The accuracy and precision performance of the T-WVIA depend on concentration but depend less on the delta value and averaging-time. The instrument can simultaneously and continuously measure δ(2) H, δ(18) O and δ(17) O values in water vapor, opening a new window to better understand ecological, hydrological and meteorological processes. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Correction algorithm for online continuous flow δ13C and δ18O carbonate and cellulose stable isotope analyses

NASA Astrophysics Data System (ADS)

Evans, M. N.; Selmer, K. J.; Breeden, B. T.; Lopatka, A. S.; Plummer, R. E.

2016-09-01

We describe an algorithm to correct for scale compression, runtime drift, and amplitude effects in carbonate and cellulose oxygen and carbon isotopic analyses made on two online continuous flow isotope ratio mass spectrometry (CF-IRMS) systems using gas chromatographic (GC) separation. We validate the algorithm by correcting measurements of samples of known isotopic composition which are not used to estimate the corrections. For carbonate δ13C (δ18O) data, median precision of validation estimates for two reference materials and two calibrated working standards is 0.05‰ (0.07‰); median bias is 0.04‰ (0.02‰) over a range of 49.2‰ (24.3‰). For α-cellulose δ13C (δ18O) data, median precision of validation estimates for one reference material and five working standards is 0.11‰ (0.27‰); median bias is 0.13‰ (-0.10‰) over a range of 16.1‰ (19.1‰). These results are within the 5th-95th percentile range of subsequent routine runtime validation exercises in which one working standard is used to calibrate the other. Analysis of the relative importance of correction steps suggests that drift and scale-compression corrections are most reliable and valuable. If validation precisions are not already small, routine cross-validated precision estimates are improved by up to 50% (80%). The results suggest that correction for systematic error may enable these particular CF-IRMS systems to produce δ13C and δ18O carbonate and cellulose isotopic analyses with higher validated precision, accuracy, and throughput than is typically reported for these systems. The correction scheme may be used in support of replication-intensive research projects in paleoclimatology and other data-intensive applications within the geosciences.

Investigation of magnesium isotope fractionation during basalt differentiation: Implications for a chondritic composition of the terrestrial mantle

USGS Publications Warehouse

Teng, F.-Z.; Wadhwa, M.; Helz, R.T.

2007-01-01

To investigate whether magnesium isotopes are fractionated during basalt differentiation, we have performed high-precision Mg isotopic analyses by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) on a set of well-characterized samples from Kilauea Iki lava lake, Hawaii, USA. Samples from the Kilauea Iki lava lake, produced by closed-system crystal-melt fractionation, range from olivine-rich cumulates to highly differentiated basalts with MgO content ranging from 2.37 to 26.87??wt.%. Our results demonstrate that although these basalts have diverse chemical compositions, mineralogies, crystallization temperatures and degrees of differentiation, their Mg isotopic compositions display no measurable variation within the limits of our external precision (average ??26Mg = - 0.36 ?? 0.10 and ??25Mg = - 0.20 ?? 0.07; uncertainties are 2SD). This indicates that Mg isotopic fractionation during crystal-melt fractionation at temperatures of ??? 1055????C is undetectable at the level of precision of the current investigation. Calculations based on our data suggest that at near-magmatic temperatures the maximum fractionation in the 26Mg/24Mg ratio between olivine and melt is 0.07???. Two additional oceanic basalts, two continental basalts (BCR-1 and BCR-2), and two primitive carbonaceous chondrites (Allende and Murchison) analyzed in this study have Mg isotopic compositions similar to the Kilauea Iki lava lake samples. In contrast to a recent report [U. Wiechert, A.N. Halliday, Non-chondritic magnesium and the origins of the inner terrestrial planets, Earth and Planetary Science Letters 256 (2007) 360-371], the results presented here suggest that the Bulk Silicate Earth has a chondritic Mg isotopic composition. ?? 2007.

Precision and long-term stability of clumped-isotope analysis of CO2 using a small-sector isotope ratio mass spectrometer.

PubMed

Yoshida, Naohiro; Vasilev, Mikhail; Ghosh, Prosenjit; Abe, Osamu; Yamada, Keita; Morimoto, Maki

2013-01-15

The ratio of the measured abundance of (13)C-(18)O bonding CO(2) to its stochastic abundance, prescribed by the δ(13)C and δ(18)O values from a carbonate mineral, is sensitive to its growth temperature. Recently, clumped-isotope thermometry, which uses this ratio, has been adopted as a new tool to elucidate paleotemperatures quantitatively. Clumped isotopes in CO(2) were measured with a small-sector isotope ratio mass spectrometer. CO(2) samples digested from several kinds of calcium carbonates by phosphoric acid at 25 °C were purified using both cryogenic and gas-chromatographic separations, and their isotopic composition (δ(13)C, δ(18)O, Δ(47), Δ(48) and Δ(49) values) were then determined using a dual-inlet Delta XP mass spectrometer. The internal precisions of the single gas Δ(47) measurements were 0.005 and 0.02‰ (1 SE) for the optimum and the routine analytical conditions, respectively, which are comparable with those obtained using a MAT 253 mass spectrometer. The long-term variations in the Δ(47) values for the in-house working standard and the heated CO(2) gases since 2007 were close to the routine, single gas uncertainty while showing seasonal-like periodicities with a decreasing trend. Unlike the MAT 253, the Delta XP did not show any significant relationship between the Δ(47) and δ(47) values. The Delta XP gave results that were approximately as precise as those of the MAT 253 for clumped-isotope analysis. The temporal stability of the Delta XP seemed to be lower, although an advantage of the Delta XP was that no dependency of δ(47) on Δ(47) was found. Copyright © 2012 John Wiley & Sons, Ltd.

High-precision Pb isotopic measurements of teeth and environmental samples from Sofia (Bulgaria): insights for regional lead sources and possible pathways to the human body

NASA Astrophysics Data System (ADS)

Kamenov, George D.

2008-08-01

High-precision Pb isotopic measurements on teeth and possible sources in a given area can provide important insights for the lead (Pb) sources and pathways in the human body. Pb isotopic analyses on soils from the area of Sofia, Bulgaria show that Pb is contributed by three end-members represented by two natural sources and leaded gasoline. Sequential leaching experiments reveal that the alumosilicate fraction of the soils is mainly controlled by natural Pb derived from two mountain massifs bordering the city. Around 1/3 to a half of the Pb in the soil leachates, however, can be explained by contamination from leaded gasoline. Contemporary teeth from Sofia residents show very similar Pb isotopic compositions to the soil leachates, also indicating that around 1/3 to a half of the Pb can be explained by derivation from leaded gasoline. The remarkable isotopic similarities between the teeth and the most labile fractions of the local soils suggest that the lead can be derived from the latter. Pb incorporation in the human body via soil-plant-human or soil-plant-animal-human chains is unlikely due to the fact that no significant farming occurs in the city area. The isotopic compositions of the local soil labile fractions can be used as approximation of the bioaccessible lead for humans. Considering all possible scenarios it appears that soil and/or soil-born dust inhalation and/or ingestion is the most probable pathway for incorporation of local soil lead in the local population. The high-precision Pb isotope data presented in this work indicate that apparently the local soil is what plays major role in the human Pb exposure.

Serpentinites and Boron Isotope Evidence for Shallow Fluid Transfer Across Subduction Zones

NASA Astrophysics Data System (ADS)

Scambelluri, M.; Tonarini, S.

2012-04-01

In subduction zones, fluid-mediated chemical exchanges between subducting plates and overlying mantle dictate volatile and incompatible element cycles in earth and influence arc magmatism. One of the outstanding issues is concerned with the sources of water for arc magmas and mechanisms for its slab-to-mantle wedge transport. Does it occur by slab dehydration at depths directly beneath arc front, or by hydration of fore-arc mantle and subsequent subduction of the hydrated mantle? Historically, the deep slab dehydration hypothesis had strong support, but it appears that the hydrated mantle wedge hypothesis is gaining ground. At the center of this hypothesis are studies of fluid-mobile element tracers in volatile-rich mantle wedge peridotites (serpentinites) and their subducted high-pressure equivalents. Serpentinites are key players in volatile and fluid-mobile element cycles in subduction zones. Their dehydration represents the main event for fluid and element flux from slabs to mantle, though direct evidence for this process and identification of dehydration environments have been elusive. Boron isotopes are known markers of fluid-assisted element transfer during subduction and can be the tracers of these processes. Until recently, the altered oceanic crust has been considered the main 11B reservoir for arc magmas, which largely display positive delta11B. However, slab dehydration below fore-arcs transfers 11B to the overlying hydrated mantle and leaves the residual mafic crust very depleted in 11B below sub-arcs. The 11B-rich composition of serpentinites candidate them as the heavy B carriers for subduction. Here we present high positive delta11B of Alpine high-pressure (HP) serpentinites recording subduction metamorphism from hydration at low gades to eclogite-facies dehydration: we show a connection among serpentinite dehydration, release of 11B-rich fluids and arc magmatism. In general, the delta11B of these rocks is heavy (16‰ to + 24‰ delta11B). No B loss and no 11B fractionation occurs in these rocks with progressive burial: their high B and 11B compositions demonstrate that initially high budgets acquired during shallow hydration are transferred and released to fluids at arc magma depths, providing the high-boron component requested for arcs. Interaction of depleted mantle-wedge with de-serpentinization fluids and/or serpentinite diapirs uprising from the slab-mantle interface thus provide an efficient self-consistent mechanism for water and B transfer to many arcs. The boron compositions documented here for Erro-Tobbio serpentinites are unexpected for slabs, deputed to loose much B and 11B during subduction dehydration. Their isotopic compositions can be achieved diluting through the mantle the subduction-fluids released during shallow dehydration (30 km) of a model slab. Moreover their delta11B is close to values measured in Syros eclogite blocks, hosted in mélanges atop of the slab and metasomatized by uprising subduction-fluids. The nature of serpentinizing fluids and the fluid-transfer mechanism in Erro-Tobbio is further clarified integrating B isotopes with O-H and Sr isotopic systems. Low deltaD (-102‰), high delta18O (8‰) of early serpentinites suggest low-temperature hydration by metamorphic fluids. 87Sr/86Sr ranges from 0.7044 to 0.7065 and is lower than oceanic serpentinites formed from seawater. Our data indicate that alteration occurred distant from mid-ocean ridges: we propose metamorphic environments like the slab-mantle interface or the fore-arc mantle fed by B- and 11B-rich slab fluids. We therefore provide field-based evidence for delivery of water and 11B at sub-arcs by serpentinites formed by subduction-fluid infiltration in mantle rocks atop of the slab since the early stages of burial, witnessing shallow fluid transfer across the subduction zone.

Concerns about Quadrupole ICP-MS Lead Isotopic Data and Interpretations in the Environment and Health Fields.

PubMed

Gulson, Brian; Kamenov, George D; Manton, William; Rabinowitz, Michael

2018-04-11

There has been a massive increase in recent years of the use of lead (Pb) isotopes in attempts to better understand sources and pathways of Pb in the environment and in man or experimental animals. Unfortunately, there have been many cases where the quality of the isotopic data, especially that obtained by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS), are questionable, resulting in questionable identification of potential sources, which, in turn, impacts study interpretation and conclusions. We present several cases where the isotopic data have compromised interpretation because of the use of only the major isotopes 208 Pb/ 206 Pb and 207 Pb/ 206 Pb, or their graphing in other combinations. We also present some examples comparing high precision data from thermal ionization (TIMS) or multi-collector plasma mass spectrometry (MC-ICP-MS) to illustrate the deficiency in the Q-ICP-MS data. In addition, we present cases where Pb isotopic ratios measured on Q-ICP-MS are virtually impossible for terrestrial samples. We also evaluate the Pb isotopic data for rat studies, which had concluded that Pb isotopic fractionation occurs between different organs and suggest that this notion of biological fractionation of Pb as an explanation for isotopic differences is not valid. Overall, the brief review of these case studies shows that Q-ICP-MS as commonly practiced is not a suitable technique for precise and accurate Pb isotopic analysis in the environment and health fields.

Concerns about Quadrupole ICP-MS Lead Isotopic Data and Interpretations in the Environment and Health Fields

PubMed Central

Gulson, Brian; Manton, William; Rabinowitz, Michael

2018-01-01

There has been a massive increase in recent years of the use of lead (Pb) isotopes in attempts to better understand sources and pathways of Pb in the environment and in man or experimental animals. Unfortunately, there have been many cases where the quality of the isotopic data, especially that obtained by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS), are questionable, resulting in questionable identification of potential sources, which, in turn, impacts study interpretation and conclusions. We present several cases where the isotopic data have compromised interpretation because of the use of only the major isotopes 208Pb/206Pb and 207Pb/206Pb, or their graphing in other combinations. We also present some examples comparing high precision data from thermal ionization (TIMS) or multi-collector plasma mass spectrometry (MC-ICP-MS) to illustrate the deficiency in the Q-ICP-MS data. In addition, we present cases where Pb isotopic ratios measured on Q-ICP-MS are virtually impossible for terrestrial samples. We also evaluate the Pb isotopic data for rat studies, which had concluded that Pb isotopic fractionation occurs between different organs and suggest that this notion of biological fractionation of Pb as an explanation for isotopic differences is not valid. Overall, the brief review of these case studies shows that Q-ICP-MS as commonly practiced is not a suitable technique for precise and accurate Pb isotopic analysis in the environment and health fields. PMID:29641487

High-precision 41K/39K measurements by MC-ICP-MS indicate terrestrial variability of δ41K

USGS Publications Warehouse

Morgan, Leah; Santiago Ramos, Danielle P.; Davidheiser-Kroll, Brett; Faithfull, John; Lloyd, Nicholas S.; Ellam, Rob M.; Higgins, John A.

2018-01-01

Potassium is a major component in continental crust, the fourth-most abundant cation in seawater, and a key element in biological processes. Until recently, difficulties with existing analytical techniques hindered our ability to identify natural isotopic variability of potassium isotopes in terrestrial materials. However, measurement precision has greatly improved and a range of K isotopic compositions has now been demonstrated in natural samples. In this study, we present a new technique for high-precision measurement of K isotopic ratios using high-resolution, cold plasma multi-collector mass spectrometry. We apply this technique to demonstrate natural variability in the ratio of 41K to 39K in a diverse group of geological and biological samples, including silicate and evaporite minerals, seawater, and plant and animal tissues. The total range in 41K/39K ratios is ca. 2.6‰, with a long-term external reproducibility of 0.17‰ (2, N=108). Seawater and seawater-derived evaporite minerals are systematically enriched in 41K compared to silicate minerals by ca. 0.6‰, a result consistent with recent findings1, 2. Although our average bulk-silicate Earth value (-0.54‰) is indistinguishable from previously published values, we find systematic δ41K variability in some high-temperature sample suites, particularly those with evidence for the presence of fluids. The δ41K values of biological samples span a range of ca. 1.2‰ between terrestrial mammals, plants, and marine organisms. Implications of terrestrial K isotope variability for the atomic weight of K and K-based geochronology are discussed. Our results indicate that high-precision measurements of stable K isotopes, made using commercially available mass spectrometers, can provide unique insights into the chemistry of potassium in geological and biological systems. 

High-precision γ -ray spectroscopy of the cardiac PET imaging isotope Rb 82 and its impact on dosimetry

DOE PAGES

Nino, M. N.; McCutchan, E. A.; Smith, S. V.; ...

2016-02-01

82Rb is a positron-emitting isotope used in cardiac positron emission tomography (PET) imaging which has been reported to deliver a significantly lower effective radiation dose than analogous imaging isotopes like 201Tl and 99mTc sestamibi. High-quality β-decay data are essential to accurately appraise the total dose received by the patients. A source of 82Sr was produced at the Brookhaven Linac Isotope Producer (BLIP), transported to Argonne National Laboratory, and studied with the Gammasphere facility. Significant revisions have been made to the level scheme of 82Kr including 12 new levels, 50 new γ-ray transitions, and the determination of many new spin assignmentsmore » through angular correlations. Lastly, these new high-quality data allow a precise reappraisal of the β-decay strength function and thus the consequent dose received by patients.« less

Calculation of boron-isotope fractionation between B(OH) 3(aq) and B(OH)4-(aq)

NASA Astrophysics Data System (ADS)

Rustad, James R.; Bylaska, Eric J.; Jackson, Virgil E.; Dixon, David A.

2010-05-01

Density functional and correlated molecular orbital calculations (MP2) are carried out on B(OH) 3· nH 2O clusters ( n = 0, 6, 32), and B(OH)4-· nH 2O ( n = 0, 8, 11, 32) to estimate the equilibrium distribution of 10B and 11B isotopes between boric acid and borate in aqueous solution. For the large 32-water clusters, multiple conformations are generated from ab initio molecular dynamics simulations to account for the effect of solvent fluctuations on the isotopic fractionation. We provide an extrapolated value of the equilibrium constant α34 for the isotope exchange reaction 10B(OH) 3(aq) + 11B(OH)4- (aq) = 11B(OH) 3(aq) + 11B(OH)4- (aq) of 1.026-1.028 near the MP2 complete basis set limit with 32 explicit waters of solvation. With some exchange-correlation functionals we find potentially important contributions from a tetrahedral neutral B(OH) 3·H 2O Lewis acid-base complex. The extrapolations presented here suggest that DFT calculations give a value for 10 3ln α34 about 15% higher than the MP2 calculations.

Separation of copper, iron, and zinc from complex aqueous solutions for isotopic measurement

USGS Publications Warehouse

Borrok, D.M.; Wanty, R.B.; Ridley, W.I.; Wolf, R.; Lamothe, P.J.; Adams, M.

2007-01-01

The measurement of Cu, Fe, and Zn isotopes in natural samples may provide valuable information about biogeochemical processes in the environment. However, the widespread application of stable Cu, Fe, and Zn isotope chemistry to natural water systems remains limited by our ability to efficiently separate these trace elements from the greater concentrations of matrix elements. In this study, we present a new method for the isolation of Cu, Fe, and Zn from complex aqueous solutions using a single anion-exchange column with hydrochloric acid media. Using this method we are able to quantitatively separate Cu, Fe, and Zn from each other and from matrix elements in a single column elution. Elution of the elements of interest, as well as all other elements, through the anion-exchange column is a function of the speciation of each element in the various concentrations of HCl. We highlight the column chemistry by comparing our observations with published studies that have investigated the speciation of Cu, Fe, and Zn in chloride solutions. The functionality of the column procedure was tested by measuring Cu, Fe, and Zn isotopes in a variety of stream water samples impacted by acid mine drainage. The accuracy and precision of Zn isotopic measurements was tested by doping Zn-free stream water with the Zn isotopic standard. The reproducibility of the entire column separation process and the overall precision of the isotopic measurements were also evaluated. The isotopic results demonstrate that the Cu, Fe, and Zn column separates from the tested stream waters are of sufficient purity to be analyzed directly using a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS), and that the measurements are fully-reproducible, accurate, and precise. Although limited in scope, these isotopic measurements reveal significant variations in ??65Cu (- 1.41 to + 0.30???), ??56Fe (- 0.56 to + 0.34???), and ??66Zn (0.31 to 0.49???) among samples collected from different abandoned mines within a single watershed. Hence, Cu, Fe, and Zn isotopic measurements may be a powerful tool for fingerprinting specific metal sources and/or examining biogeochemical reactions within fresh water systems.

Variation in the terrestrial isotopic composition and atomic weight of argon

USGS Publications Warehouse

Böhlke, John Karl

2014-01-01

The isotopic composition and atomic weight of argon (Ar) are variable in terrestrial materials. Those variations are a source of uncertainty in the assignment of standard properties for Ar, but they provide useful information in many areas of science. Variations in the stable isotopic composition and atomic weight of Ar are caused by several different processes, including (1) isotope production from other elements by radioactive decay (radiogenic isotopes) or other nuclear transformations (e.g., nucleogenic isotopes), and (2) isotopic fractionation by physical-chemical processes such as diffusion or phase equilibria. Physical-chemical processes cause correlated mass-dependent variations in the Ar isotope-amount ratios (40Ar/36Ar, 38Ar/36Ar), whereas nuclear transformation processes cause non-mass-dependent variations. While atmospheric Ar can serve as an abundant and homogeneous isotopic reference, deviations from the atmospheric isotopic ratios in other Ar occurrences limit the precision with which a standard atomic weight can be given for Ar. Published data indicate variation of Ar atomic weights in normal terrestrial materials between about 39.7931 and 39.9624. The upper bound of this interval is given by the atomic mass of 40Ar, as some samples contain almost pure radiogenic 40Ar. The lower bound is derived from analyses of pitchblende (uranium mineral) containing large amounts of nucleogenic 36Ar and 38Ar. Within this interval, measurements of different isotope ratios (40Ar/36Ar or 38Ar/36Ar) at various levels of precision are widely used for studies in geochronology, water–rock interaction, atmospheric evolution, and other fields.

In Situ measurement of Kr and Xe in the atmosphere of Mars

NASA Astrophysics Data System (ADS)

Conrad, P. G.; Malespin, C.; Franz, H. B.; Trainer, M. G.; Pepin, R. O.; Schwenzer, S. P.; Manning, H. L.; Atreya, S. K.; Wong, M. H.; Jones, J. H.; Owen, T. C.; Mahaffy, P. R.

2015-12-01

Abstract: The Sample Analysis at Mars (SAM) investigation [1] on NASA's Mars Science Laboratory mission has measured the six stable isotopes of krypton and the nine stable isotopes of xenon from the surface of Mars. Using semi-static mass spectrometry (MS) to measure the Kr, and static MS experiments (first ever on another planet) to measure the xenon, we have obtained isotopic ratios of these heavy noble gas elements with greatly improved precision over the Viking Measurements. The Viking landers detected both Kr and Xe [2] with a reported precision of ±20%, insufficient for in situ isotope measurement. Using the Viking observation of high 129Xe relative to Earth or to solar wind, Bogard & Johnson [3] and Swindle et al. [4] recognized that Shergottite meteorites may hold trapped Martian atmosphere, from which Swindle's team later reported precise noble gas isotope ratios, solidifying the theory that these meteorites were of martian origin. Our data are in very good agreement with the Swindle et al. [4] analysis, and the isotopic distributions of Kr and Xe in present day Martian atmosphere support the Pepin [5] model of massive hydrodynamic escape of the martian atmosphere early after formation. References: [1] Mahaffy, Paul R., et al. Space Science Revs 170.1-4 (2012): 401-478. [2] Owen, T., et al. Science 194.4271 (1976): 1293-1295. [3] Bogard, D. D. & Johnson, P. (1983) Science, 221: 651-654. [4] Swindle, T. D., M. W. Caffee, and C. M. Hohenberg. Geochim et Cosmochim Acta 50.6 (1986): 1001-1015. [5] Pepin, Robert O. Icarus 111.2 (1994): 289-304.

High precision calcium isotope analysis using 42Ca-48Ca double-spike TIMS technique

NASA Astrophysics Data System (ADS)

Feng, L.; Zhou, L.; Gao, S.; Tong, S. Y.; Zhou, M. L.

2014-12-01

Double spike techniques are widely used for determining calcium isotopic compositions of natural samples. The most important factor controlling precision of the double spike technique is the choice of appropriate spike isotope pair, the composition of double spikes and the ratio of spike to sample（CSp/CN）. We propose an optimal 42Ca-48Ca double spike protocol which yields the best internal precision for calcium isotopic composition determinations among all kinds of spike pairs and various spike compositions and ratios of spike to sample, as predicted by linear error propagation method. It is suggested to use spike composition of 42Ca/(42Ca+48Ca) = 0.44 mol/mol and CSp/(CN+ CSp)= 0.12mol/mol because it takes both advantages of the largest mass dispersion between 42Ca and 48Ca (14%) and lowest spike cost. Spiked samples were purified by pass through homemade micro-column filled with Ca special resin. K, Ti and other interference elements were completely separated, while 100% calcium was recovered with negligible blank. Data collection includes integration time, idle time, focus and peakcenter frequency, which were all carefully designed for the highest internal precision and lowest analysis time. All beams were automatically measured in a sequence by Triton TIMS so as to eliminate difference of analytical conditions between samples and standards, and also to increase the analytical throughputs. The typical internal precision of 100 duty cycles for one beam is 0.012‒0.015 ‰ (2δSEM), which agrees well with the predicted internal precision of 0.0124 ‰ (2δSEM). Our methods improve internal precisions by a factor of 2‒10 compared to previous methods of determination of calcium isotopic compositions by double spike TIMS. We analyzed NIST SRM 915a, NIST SRM 915b and Pacific Seawater as well as interspersed geological samples during two months. The obtained average δ44/40Ca (all relative to NIST SRM 915a) is 0.02 ± 0.02 ‰ (n=28), 0.72±0.04 ‰ (n=10) and 1.93±0.03 ‰ (n=21) for NIST SRM 915a, NIST SRM 915b and Pacific Seawater, respectively. The long-term reproducibility is 0.10‰ (2 δSD), which is comparable to the best external precision of 0.04 ‰ (2 δSD) of previous methods, but our sample throughputs are doubled with significant reduction in amount of spike used for single samples.

Tracing wastewater effluents in surface and groundwaters: a couple approach with organic/inorganic tracers and isotopes

NASA Astrophysics Data System (ADS)

Petelet-Giraud, Emmanuelle; Baran, Nicole; Soulier, Coralie

2017-04-01

In the context of land use change, the origins of contamination of water resources are often multiple, including for a single chemical element or molecule. For instance, excess of nitrates in both surface and groundwater can originate from agricultural practices and wastewater effluents. The discrimination of the origins and vectors of contamination in the environment is both an environmental and societal issue in order to define an integrated water resources management at the catchment or water body scale by implementing appropriate measures to effectively struggle against pollution. The objective of this study is to define a methodology for the identification of a "domestic wastewater" contamination within surface waters and groundwater. An ideal tracer should be conservative, persistent in the different water compartments, present in quantity above the detection limit and originate from a single type of pollution source. There is, however, no ideal tracer in the strict sense. Indeed, even chloride which is present in quantity in wastewater, and which behaves conservatively in the environment, is not an univocal tracer of wastewater, as it may come from atmospheric inputs, from the dissolution of evaporitic rocks, from the salting of roads or from fertilizers. To overcome this limitation, in this study, we propose a multi-tracer approach (chemical and isotopic) to identify and validate the relevance of foreseen tracers. Among the relevant tracers of wastewater, the following may be used for their intrinsic or combined discriminant power: 1) organic effluent tracers: nitrogen contents and isotopic ratios of nitrogen and oxygen of nitrates; 2) tracer of detergents: boron contents and boron isotopes; 3) pharmaceuticals tracers: e.g. carbamazepine, ibuprofen, paracetamol, gadolinium anomaly; 4) life-style tracers: e.g. caffeine. The originality of the study relies on small capacities wastewater treatment plants without tertiary treatment process. Results on a catchment impacted both by diffuse agricultural pollution and punctual wastewater inputs are presented. Investigations concern wastewater effluents resulting from different type of treatment plants, surface and groundwater. Potential combination of suitable tracers is discussed.

"Sequential” Boron Neutron Capture Therapy (BNCT): A Novel Approach to BNCT for the Treatment of Oral Cancer in the Hamster Cheek Pouch Model

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

Ana J. Molinari; Andrea Monti Hughes; Elisa M. Heber

2011-04-01

Boron Neutron Capture Therapy (BNCT) is a binary treatment modality that involves the selective accumulation of 10B carriers in tumors followed by irradiation with a thermal or epithermal neutron beam. The minor abundance stable isotope of boron, 10B, interacts with low energy (thermal) neutrons to produce high linear energy transfer (LET) a-particles and 7Li ions. These disintegration products are known to have a high relative biological effectiveness (RBE). Their short range (<10 {micro}m) would limit the damage to cells containing 10B (1,2). Thus, BNCT would target tumor tissue selectively, sparing normal tissue. Clinical trials of BNCT for the treatment ofmore » glioblastoma multiforme and/or melanoma and, more recently, head and neck tumors and liver metastases, using boronophenylalanine (BPA) or sodium mercaptoundecahydrododecaborane (BSH) as the 10B carriers, have been performed or are underway in Argentina, Japan, the US and Europe (e.g. 3-8). To date, the clinical results have shown a potential, albeit inconclusive, therapeutic advantage for this technique. Contributory translational studies have been carried out employing a variety of experimental models based on the implantation of tumor cells in normal tissue (e.g. 5).« less

Application of environmental groundwater tracers at the Sulphur Bank Mercury Mine, California, USA

USGS Publications Warehouse

Engle, M.A.; Goff, F.; Jewett, D.G.; Reller, G.J.; Bauman, J.B.

2008-01-01

Boron, chloride, sulfate, ??D, ??18O, and 3H concentrations in surface water and groundwater samples from the Sulphur Bank Mercury Mine (SBMM), California, USA were used to examine geochemical processes and provide constraints on evaporation and groundwater flow. SBMM is an abandoned sulfur and mercury mine with an underlying hydrothermal system, adjacent to Clear Lake, California. Results for non-3H tracers (i.e., boron, chloride, sulfate, ??D, and ??18O) identify contributions from six water types at SBMM. Processes including evaporation, mixing, hydrothermal water input and possible isotopic exchange with hydrothermal gases are also discerned. Tritium data indicate that hydrothermal waters and other deep groundwaters are likely pre-bomb (before ???1952) in age while most other waters were recharged after ???1990. A boron-based steady-state reservoir model of the Herman Impoundment pit lake indicates that 71-79% of its input is from meteoric water with the remainder from hydrothermal contributions. Results for groundwater samples from six shallow wells over a 6-month period for ??D and ??18O suggests that water from Herman Impoundment is diluted another 3% to more than 40% by infiltrating meteoric water, as it leaves the site. Results for this investigation show that environmental tracers are an effective tool to understand the SBMM hydrogeologic regime. ?? Springer-Verlag 2007.

Proton Radii of 4,6,8He Isotopes from High-Precision Nucleon-Nucleon Interactions

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

Caurier, E; Navratil, P

2005-11-16

Recently, precision laser spectroscopy on {sup 6}He atoms determined accurately the isotope shift between {sup 4}He and {sup 6}He and, consequently, the charge radius of {sup 6}He. A similar experiment for {sup 8}He is under way. We have performed large-scale ab initio calculations for {sup 4,6,8}He isotopes using high-precision nucleon-nucleon (NN) interactions within the no-core shell model (NCSM) approach. With the CD-Bonn 2000 NN potential we found point-proton root-mean-square (rms) radii of {sup 4}He and {sup 6}He 1.45(1) fm and 1.89(4), respectively, in agreement with experiment and predict the {sup 8}He point proton rms radius to be 1.88(6) fm. Atmore » the same time, our calculations show that the recently developed nonlocal INOY NN potential gives binding energies closer to experiment, but underestimates the charge radii.« less

Metal stable isotopes in low-temperature systems: A primer

USGS Publications Warehouse

Bullen, T.D.; Eisenhauer, A.

2009-01-01

Recent advances in mass spectrometry have allowed isotope scientists to precisely determine stable isotope variations in the metallic elements. Biologically infl uenced and truly inorganic isotope fractionation processes have been demonstrated over the mass range of metals. This Elements issue provides an overview of the application of metal stable isotopes to low-temperature systems, which extend across the borders of several science disciplines: geology, hydrology, biology, environmental science, and biomedicine. Information on instrumentation, fractionation processes, data-reporting terminology, and reference materials presented here will help the reader to better understand this rapidly evolving field.

Si Isotopes in Enstatite Chondrites: Implications to Accretion and Differentiation Event of the Earth

NASA Astrophysics Data System (ADS)

Sikdar, J.; Rai, V. K.

2018-05-01

The abstract summarizes the recent results on high precision Si isotope analyses in various micro milled components of Enstatite chondrites with implications towards the accretion and primary differentiation event of the Earth.

Measurement of plutonium isotope ratios in nuclear fuel samples by HPLC-MC-ICP-MS

NASA Astrophysics Data System (ADS)

Günther-Leopold, I.; Waldis, J. Kobler; Wernli, B.; Kopajtic, Z.

2005-04-01

Radioactive isotopes are traditionally quantified by means of radioactivity counting techniques ([alpha], [beta], [gamma]). However, these methods often require extensive matrix separation and sample purification before the identification of specific isotopes and their relative abundance is possible as it is necessary in the frame of post-irradiation examinations on nuclear fuel samples. The technique of multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is attracting much attention because it permits the precise measurement of the isotope compositions for a wide range of elements combined with excellent limits of detection due to high ionization efficiencies. The present paper describes one of the first applications of an online high-performance liquid chromatographic separation system coupled to a MC-ICP-MS in order to overcome isobaric interferences for the determination of the plutonium isotope composition and concentrations in irradiated nuclear fuels. The described chromatographic separation is sufficient to prevent any isobaric interference between 238Pu present at trace concentrations and 238U present as the main component of the fuel samples. The external reproducibility of the uncorrected plutonium isotope ratios was determined to be between 0.04 and 0.2% (2 s) resulting in a precision in the [per mille sign] range for the isotopic vectors of the irradiated fuel samples.

Measurement of isotope ratios on transient signals by MC-ICP-MS.

PubMed

Günther-Leopold, Ines; Wernli, Beat; Kopajtic, Zlatko; Günther, Detlef

2004-01-01

Precise and accurate isotope ratio measurements are an important task in many applications such as isotope-dilution mass spectrometry, bioavailability studies, or the determination of isotope variations in geological or nuclear samples. The technique of MC-ICP-MS has attracted much attention because it permits the precise measurement of isotope compositions for a wide range of elements combined with excellent detection limits due to high ionisation efficiencies. However, the results are based mainly on measurements using continuous sample introduction. In the present study the determination of isotope ratios on various transient signals with a time duration of 30 to 60 s has been achieved by coupling high-performance liquid chromatography to a multicollector inductively coupled plasma mass spectrometer. In order to investigate the origin of ratio drifts across the transient signals for this hyphenated technique, measurements with the same standard solutions were also carried out using a flow-injection device for sample introduction. As a result of this application it could be concluded that the main source of the bias in the measured isotope ratios is within the ICP-MS instead of fractionation effects on the chromatographic column material. Preliminary studies on short transient signals of gaseous samples (dry plasma) showed a reverse fractionation effect compared with wet plasma conditions (flow injection and HPLC).

Carbon kinetic isotope effect in the oxidation of methane by the hydroxyl radical

NASA Technical Reports Server (NTRS)

Cantrell, Christopher A.; Shetter, Richard E.; Mcdaniel, Anthony H.; Calvert, Jack G.; Davidson, James A.

1990-01-01

The reaction of the hydroxyl radical (HO) with the stable carbon isotopes of methane has been studied as a function of temperature from 273 to 353 K. The measued ratio of the rate coefficients for reaction with (C-12)H4 relative to (C-13)H4 (k12/k13) was 1.0054 (+ or - 0.0009 at the 95 percent confidence interval), independent of temperature within the precision of the measurement, over the range studied. The precision of the present value is much improved over that of previous studies, and this result provides important constraints on the current understanding of the cycling of methane through the atmosphere through the use of carbon isotope measurements.

SHRIMP-SI Multiple Sulfur Isotope Analysis of Sulfides from Brazilian Deposits: Analytical Capability to Resolve Single Grain Textural Complexities and Distinct Sulfur Sources

NASA Astrophysics Data System (ADS)

Ireland, T. R.; Teles, G. D. S.; Chemale, F., Jr.; Avila, J.

2016-12-01

The Archean atmosphere is thought to be several times more reducing than the present day atmosphere, and the occurrence of Mass Independent Fractionation of Sulfur isotopes (MIF-S) in sulfides of sedimentary and volcanogenic rocks older than 2.45 Ga reinforces it. The most accepted mechanism to generate MIF-S requires photochemical reactions with volcanogenic SO2 in an anoxic atmosphere (O2 levels <10-5 PAL). The identification of MIF-S, noted as Δ33S and Δ36S, requires precise measurements of less abundant 33S and 36S isotopes, which were first attained by bulk isotope analyses. However, in-situ analysis has become essential, as many of ancient sulfide samples have suffered post-depositional processes, and their primary isotopic signature from the atmosphere are now overprinted by mass-dependent fractionation processes. High-precision and resolution in situ measurements of 32S, 33S, 34S and 36S in sulfides can be achieved by SHRIMP-SI, which allows isotopic determinations with internal errors better than 0.05‰ for Δ33S and 0.2‰ for Δ36S (2SE), and reproducibility about 0.1‰ for Δ33S and better than 0.5‰ for Δ36S (2SD). Examples of the SHRIMP-SI capability are provided by multiple sulfur isotope analysis of samples from Brazil, the Au-(U) and pyrite deposits of Jacobina Basin and the massive sulfide deposits of the 3.3 Ga Mundo Novo Greenstone Belt. The level of precision and spatial resolution achievable with SHRIMP-SI allowed the isotopic distinction between sedimentary and post-depositional pyrites in Jacobina Basin, as well as the identification of different sulfur sources in the Mundo Novo Greenstone Belt VMS deposits.

Effects of Simple Leaching of Crushed and Powdered Materials on High-precision Pb Isotope Analyses

NASA Astrophysics Data System (ADS)

Todd, E.; Stracke, A.

2013-12-01

We present new results of simple leaching experiments on the Pb isotope composition of USGS standard reference material powders and on ocean island basalt whole rock splits and powders. Rock samples were leached with 6N HCl in two steps, first hot and then in an ultrasonic bath, and washed with ultrapure H2O before conventional sample digestion and chromatographic purification of Pb. Pb isotope analyses were determined with Tl-doped MC-ICP-MS. Intra- and inter-session analytical reproducibility of repeated analyses of both synthetic Pb solutions and Pb from single digests of chemically processed natural samples were generally < 100 ppm (2 S.D.). The comparison of leached and unleached samples shows that leaching reliably removes variable amounts of different contaminants for different starting materials. For repeated digests of a single sample, the leached samples reproduce better than the unleached ones, showing that leaching effectively removes heterogeneously distributed extraneous Pb. However, the reproducibility of repeated digests of variably contaminated natural samples is up to an order of magnitude worse than the analytical reproducibility of ca. 100 ppm. More complex leaching methods (e.g., Nobre Silva et al., 2009) yield Pb isotope ratios within error of and with similar reproducibility to our method, showing that the simple leaching method is reliable. The remaining Pb isotope heterogeneity of natural samples, which typically exceeds 100 ppm, is thus attributed to inherent isotopic sample heterogeneity. Tl-doped MC-ICP-MS Pb ratio determination is therefore a sufficiently precise method for Pb isotope analyses in natural rocks. More precise Pb double- or triple-spike methods (e.g., Galer, 1999; Thirlwall, 2000), may exploit their full potential only in cases where natural isotopic sample heterogeneity is demonstrably negligible. References: Galer, S., 1999, Chem. Geol. 157, 255-274. Nobre Silva, et al. 2009, Geochemistry Geophysics Geosystems 10, Q08012. Thirlwall, M.F., 2000, Chem. Geol. 163, 299-322.

Unraveling Vital Effects: Photosynthesis of Symbiotic Algae in Foraminifera Hosts

NASA Astrophysics Data System (ADS)

Fish, C.; Phelps, S. R.; Goes, J. I.; Hoenisch, B.

2015-12-01

B/Ca and boron isotope proxies recorded in the calcium carbonate shells of planktic foraminifera are sensitive to seawater acidity. We seek to understand how the biology of the organism affects the geochemical signals, as planktic foraminifera shells differ in their chemical composition from inorganic calcite and also between foraminifer species. These differences are most likely related to physiological processes like respiration, calcification, and photosynthesis in symbiont-bearing foraminifera. The modifications of geochemical signals by these biological parameters are termed vital effects. Our study is based on the hypothesis that the B/Ca and δ11B offsets observed in planktic foraminifer shells are primarily due to the photosynthetic activity of their symbionts, which may elevate the microenvironmental pH to different degrees in different foraminifer species. Using fast repetition rate fluorometry, chlorophyll α analyses and symbiont counts, we investigated the symbiont-photosynthetic activity associated with three foraminifera species - Globigerinoides ruber, G. sacculifer, and Orbulina universa. Boron proxy systematics in these species suggest that photosynthetic activity should be greater in G. ruber compared to G. sacculifer and O. universa, but this is not confirmed by our study. While symbiont photosynthesis undoubtedly explains microenvironmental pH-elevation and boron proxy systematics in symbiont-bearing compared to symbiont-barren foraminifer species, additional processes must be responsible for the boron geochemical offsets between symbiont-bearing species. Respiration of the symbiont-host association and the calcification process are most likely candidates that require further analysis. Our study highlights the potential danger of misinterpreting geochemical signals in biological organisms when the biology of the organism in question is not entirely understood.

Boron desorption and fractionation in Subduction Zone Fore Arcs: Implications for the sources and transport of deep fluids

NASA Astrophysics Data System (ADS)

Saffer, Demian M.; Kopf, Achim J.

2016-12-01

At many subduction zones, pore water geochemical anomalies at seafloor seeps and in shallow boreholes indicate fluid flow and chemical transport from depths of several kilometers. Identifying the source regions for these fluids is essential toward quantifying flow pathways and volatile fluxes through fore arcs, and in understanding their connection to the loci of excess pore pressure at depth. Here we develop a model to track the coupled effects of boron desorption, smectite dehydration, and progressive consolidation within sediment at the top of the subducting slab, where such deep fluid signals likely originate. Our analysis demonstrates that the relative timing of heating and consolidation is a dominant control on pore water composition. For cold slabs, pore water freshening is maximized because dehydration releases bound water into low porosity sediment, whereas boron concentrations and isotopic signatures are modest because desorption is strongly sensitive to temperature and is only partially complete. For warmer slabs, freshening is smaller, because dehydration occurs earlier and into larger porosities, but the boron signatures are larger. The former scenario is typical of nonaccretionary margins where insulating sediment on the subducting plate is commonly thin. This result provides a quantitative explanation for the global observation that signatures of deeply sourced fluids are generally strongest at nonaccretionary margins. Application of our multitracer approach to the Costa Rica, N. Japan, N. Barbados, and Mediterranean Ridge subduction zones illustrates that desorption and dehydration are viable explanations for observed geochemical signals, and suggest updip fluid migration from these source regions over tens of km.

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

A precise few-nucleon size difference by isotope shift measurements of helium

NASA Astrophysics Data System (ADS)

Rezaeian, Nima Hassan

We perform high precision measurements of an isotope shift between the two stable isotopes of helium. We use laser excitation of the 23 S1 -- 23P0 transition at 1083 .... in a metastable beam of 3He and 4He atoms. A newly developed tunable laser frequency selector along with our previous electro-optic frequency modulation technique provides extremely reliable, adaptable, and precise frequency and intensity control. The intensity control contributes negligibly to overall experimental uncertainty by selecting (t selection < 50 ) and stabilizing the intensity of the required sideband and eliminating (˜10-5) the unwanted frequencies generated during the modulation of 1083 nm laser carrier frequency. The selection technique uses a MEMS based fiber switch (tswitch ≈ 10 ms) and several temperature stabilized narrow band (˜3 GHz) fiber gratings. A fiber based optical circulator and an inline fiber amplifier provide the desired isolation and the net gain for the selected frequency. Also rapid (˜2 sec.) alternating measurements of the 23 S1 -- 23P0 interval for both species of helium is achieved with a custom fiber laser for simultaneous optical pumping. A servo-controlled retro-reflected laser beam eliminates residual Doppler effects during the isotope shift measurement. An improved detection design and software control makes negligible subtle potential biases in the data collection. With these advances, combined with new internal and external consistency checks, we are able to obtain results consistent with the best previous measurements, but with substantially improved precision. Our measurement of the 23S 1 -- 23P0 isotope shift between 3He and 4He is 31 097 535.2 (5)kHz. The most recent theoretic calculation combined with this measuremen. yields a new determination for nuclear size differences between 3He and 4He: Deltarc = 0.292 6 (1)exp (8)th(52)expfm, with a precision of less than a part in 104 coming from the experimental uncertainty (first parenthesis), and a part in 10 3 coming from theory. This value is consistent with electron scattering measurement, but a factor of 10 more precise. It is inconsistent (4 sigma) with a recent isotope shift measurement on another helium transition (2 1S0 -- 23 S1). Comparisons with ongoing muonic helium measurements may provide clues to the origin of what is currently called the proton puzzle: electronic and muonic measurements of the proton size do not agree. In the future, the experimental improvements described here can be used for higher precision tests of atomic theory and quantum electrodynamics, as well as an important atomic physics source of the fine structure constant.

Highly Siderophile Elements, 187Re-187 Os and 182Hf-182W Isotopic Systematics of Early Solar System Materials: Constraining the Early Evolution of Chondritic and Achondritic Parent Bodies

NASA Astrophysics Data System (ADS)

Archer, Gregory J.

Highly siderophile element (HSE) abundances and 187Re- 187Os isotopic systematics for H chondrites and ungrouped achondrites, as well as 182Hf-182W isotopic systematics of H and CR chondrites are reported. Achondrite fractions with higher HSE abundances show little disturbance of 187Re-187Os isotopic systematics. By contrast, isotopic systematics for lower abundance fractions are consistent with minor Re mobilization. For magnetically separated H chondrite fractions, the magnitudes of disturbance for the 187Re-187Os isotopic system follow the trend coarse-metal isotopic system follow the trend coarse-metal

Non-Chondritic Ni Isotope Composition of the Bulk Silicate Earth

NASA Astrophysics Data System (ADS)

Klaver, M.; Elliott, T.

2018-05-01

We present high-precision Ni isotope data of chondritic meteorites and carefully selected mantle peridotites. These data show that the Bulk Silicate Earth is ca. 90 ppm lighter than chondritic meteorites, possibly as the result of core formation.

Research in cosmic and gamma ray astrophysics

NASA Technical Reports Server (NTRS)

Stone, Edward C.; Mewaldt, Richard A.; Prince, Thomas A.

1992-01-01

Discussed here is research in cosmic ray and gamma ray astrophysics at the Space Radiation Laboratory (SRL) of the California Institute of Technology. The primary activities discussed involve the development of new instrumentation and techniques for future space flight. In many cases these instrumentation developments were tested in balloon flight instruments designed to conduct new investigations in cosmic ray and gamma ray astrophysics. The results of these investigations are briefly summarized. Specific topics include a quantitative investigation of the solar modulation of cosmic ray protons and helium nuclei, a study of cosmic ray positron and electron spectra in interplanetary and interstellar space, the solar modulation of cosmic rays, an investigation of techniques for the measurement and interpretation of cosmic ray isotopic abundances, and a balloon measurement of the isotopic composition of galactic cosmic ray boron, carbon, and nitrogen.

Characterizing sources and natural attenuation of nitrate contamination in the Baix Ter aquifer system (NE Spain) using a multi-isotope approach.

PubMed

Puig, Roger; Soler, Albert; Widory, David; Mas-Pla, Josep; Domènech, Cristina; Otero, Neus

2017-02-15

Nitrate pollution is a widespread issue affecting global water resources with significant economic and health effects. Knowledge of both the corresponding pollution sources and of processes naturally attenuating them is thus of crucial importance in assessing water management policies and the impact of anthropogenic activities. In this study, an approach combining hydrodynamic, hydrochemical and multi-isotope systematics (8 isotopes) is used to characterize the sources of nitrate pollution and potential natural attenuation processes in a polluted basin of NE Spain. δ 2 H and δ 18 O isotopes were used to further characterize the sources of recharge of the aquifers. Results show that NO 3 - is not homogeneously distributed and presents a large range of concentrations, from no NO 3 - to up to 480mgL -1 . δ 15 N and δ 18 O of dissolved NO 3 - identified manure as the main source of nitrate, although sewage and mineral fertilizers can also be isotopically detected using boron isotopes (δ 11 B) and δ 34 S and δ 18 O of dissolved sulphate, respectively. The multi-isotope approach proved that natural denitrification is occurring, especially in near-river environments or in areas hydrologically related to fault zones. δ 34 S and δ 18 O indicated that denitrification is not driven by pyrite oxidation but rather by the oxidation of organic matter. This could not be confirmed by the study of δ 13 C HCO3 that was buffered by the entanglement of other processes and sources. Copyright © 2016 Elsevier B.V. All rights reserved.

Chemical and boron isotopic composition of tourmaline from the Mariinsky emerald deposit, Central Urals, Russia

NASA Astrophysics Data System (ADS)

Baksheev, Ivan A.; Trumbull, Robert B.; Popov, Mikhail P.; Erokhin, Yuri V.; Kudryavtseva, Olesya E.; Yapaskurt, Vasily O.; Khiller, Vera V.; Vovna, Galina M.; Kiselev, Vladimir I.

2018-04-01

Tourmaline is abundant at the Mariinsky schist-hosted emerald deposit in the Central Urals, Russia, both in emerald-bearing phlogopite veins (type 1) and later, emerald-free pockets, lenses, and veinlets cutting the phlogopite veins (type 2). The Ca content in tourmaline is influenced by the host rocks (ultramafic and mafic rocks), associated minerals, and minerals crystallized before tourmaline (amphibole, fluorite, margarite). The Na concentration in tourmaline depends on the presence or absence of paragonite, and the association with micas also strongly influences the contents of Li, Zn, Ni, and Co in tourmaline. Type 1 tourmalines associated with phlogopite are relatively depleted in these elements, whereas type 2 tourmalines associated with margarite or paragonite are enriched. Some differences in isomorphic substitutions along with the trace element composition (Zn, V, Sr, Co, REE) may have value in exploration of emerald-bearing and emerald-free veins in schist-hosted emerald deposits. The δ11B values in tourmaline of all types fall in a narrow total range from -11.3 to -8.4‰. These values, combined with a mineralization temperature of 420-360 °C, yield an estimated δ11B fluid composition of -7.4 to -6.8‰ suggesting a mixed source of boron, likely dominated from the granitic rocks surrounding the emerald belt. The narrow range of B-isotope compositions in tourmaline from throughout the Mariinsky deposit suggests a well-mixed hydrothermal system.

Elastic and mechanical softening in boron-doped diamond

PubMed Central

Liu, Xiaobing; Chang, Yun-Yuan; Tkachev, Sergey N.; Bina, Craig R.; Jacobsen, Steven D.

2017-01-01

Alternative approaches to evaluating the hardness and elastic properties of materials exhibiting physical properties comparable to pure diamond have recently become necessary. The classic linear relationship between shear modulus (G) and Vickers hardness (HV), along with more recent non-linear formulations based on Pugh’s modulus extending into the superhard region (HV > 40 GPa) have guided synthesis and identification of novel superabrasives. These schemes rely on accurately quantifying HV of diamond-like materials approaching or potentially exceeding the hardness of the diamond indenter, leading to debate about methodology and the very definition of hardness. Elasticity measurements on such materials are equally challenging. Here we used a high-precision, GHz-ultrasonic interferometer in conjunction with a newly developed optical contact micrometer and 3D optical microscopy of indentations to evaluate elasticity-hardness relations in the ultrahard range (HV > 80 GPa) by examining single-crystal boron-doped diamond (BDD) with boron contents ranging from 50–3000 ppm. We observe a drastic elastic-mechanical softening in highly doped BDD relative to the trends observed for superhard materials, providing insight into elasticity-hardness relations for ultrahard materials. PMID:28233808

Light scattering and random lasing in aqueous suspensions of hexagonal boron nitride nanoflakes

NASA Astrophysics Data System (ADS)

O'Brien, S. A.; Harvey, A.; Griffin, A.; Donnelly, T.; Mulcahy, D.; Coleman, J. N.; Donegan, J. F.; McCloskey, D.

2017-11-01

Liquid phase exfoliation allows large scale production of 2D materials in solution. The particles are highly anisotropic and strongly scatter light. While spherical particles can be accurately and precisely described by a single parameter—the radius, 2D nanoflakes, however, cannot be so easily described. We investigate light scattering in aqueous solutions of 2D hexagonal boron nitride nanoflakes in the single and multiple scattering regimes. In the single scattering regime, the anisotropic 2D materials show a much stronger depolarization of light when compared to spherical particles of similar size. In the multiple scattering regime, the scattering as a function of optical path for hexagonal boron nitride nanoflakes of a given lateral length was found to be qualitatively equivalent to scattering from spheres with the same diameter. We also report the presence of random lasing in high concentration suspensions of aqueous h-BN mixed with Rhodamine B dye. The h-BN works as a scattering agent and Rhodamine B as a gain medium for the process. We observed random lasing at 587 nm with a threshold energy of 0.8 mJ.

Light scattering and random lasing in aqueous suspensions of hexagonal boron nitride nanoflakes.

PubMed

O'Brien, S A; Harvey, A; Griffin, A; Donnelly, T; Mulcahy, D; Coleman, J N; Donegan, J F; McCloskey, D

2017-11-24

Liquid phase exfoliation allows large scale production of 2D materials in solution. The particles are highly anisotropic and strongly scatter light. While spherical particles can be accurately and precisely described by a single parameter-the radius, 2D nanoflakes, however, cannot be so easily described. We investigate light scattering in aqueous solutions of 2D hexagonal boron nitride nanoflakes in the single and multiple scattering regimes. In the single scattering regime, the anisotropic 2D materials show a much stronger depolarization of light when compared to spherical particles of similar size. In the multiple scattering regime, the scattering as a function of optical path for hexagonal boron nitride nanoflakes of a given lateral length was found to be qualitatively equivalent to scattering from spheres with the same diameter. We also report the presence of random lasing in high concentration suspensions of aqueous h-BN mixed with Rhodamine B dye. The h-BN works as a scattering agent and Rhodamine B as a gain medium for the process. We observed random lasing at 587 nm with a threshold energy of 0.8 mJ.

Feasibility of BNCT radiobiological experiments at the HYTHOR facility

NASA Astrophysics Data System (ADS)

Esposito, J.; Ceballos, C.; Soncin, M.; Fabris, C.; Friso, E.; Moro, D.; Colautti, P.; Jori, G.; Rosi, G.; Nava, E.

2008-06-01

HYTHOR (HYbrid Thermal spectrum sHifter tapirO Reactor) is a new thermal-neutron irradiation facility, which was installed and became operative in mid 2005 at the TAPIRO (TAratura PIla Rapida potenza 0) fast reactor, in the Casaccia research centre (near Rome) of ENEA (Ente per le Nuove tecnologie Energia ed Ambiente). The facility has been designed for in vivo radiobiological studies. In HYTHOR irradiation cavity, 1-6 mice can be simultaneously irradiated to study skin melanoma treatments with the BNCT (boron neutron capture therapy). The therapeutic effects of HYTHOR radiation field on mouse melanoma has been studied as a preliminary investigation before studying the tumour local control due to boron neutron capture effect after boronated molecule injection. The method to properly irradiate small animals has been precisely defined. Results show that HYTHOR radiation field is by itself effective in reducing the tumour-growth rate. This finding has to be taken into account in studying the effectiveness of new 10B carriers. A method to properly measure the reduction of the tumour-growth rate is reported and discussed.

Elastic and mechanical softening in boron-doped diamond

NASA Astrophysics Data System (ADS)

Liu, Xiaobing; Chang, Yun-Yuan; Tkachev, Sergey N.; Bina, Craig R.; Jacobsen, Steven D.

2017-02-01

Alternative approaches to evaluating the hardness and elastic properties of materials exhibiting physical properties comparable to pure diamond have recently become necessary. The classic linear relationship between shear modulus (G) and Vickers hardness (HV), along with more recent non-linear formulations based on Pugh’s modulus extending into the superhard region (HV > 40 GPa) have guided synthesis and identification of novel superabrasives. These schemes rely on accurately quantifying HV of diamond-like materials approaching or potentially exceeding the hardness of the diamond indenter, leading to debate about methodology and the very definition of hardness. Elasticity measurements on such materials are equally challenging. Here we used a high-precision, GHz-ultrasonic interferometer in conjunction with a newly developed optical contact micrometer and 3D optical microscopy of indentations to evaluate elasticity-hardness relations in the ultrahard range (HV > 80 GPa) by examining single-crystal boron-doped diamond (BDD) with boron contents ranging from 50-3000 ppm. We observe a drastic elastic-mechanical softening in highly doped BDD relative to the trends observed for superhard materials, providing insight into elasticity-hardness relations for ultrahard materials.

Potassium Stable Isotopic Compositions Measured by High-Resolution MC-ICP-MS

NASA Technical Reports Server (NTRS)

Morgan, Leah E.; Lloyd, Nicholas S.; Ellam, Robert M.; Simon, Justin I.

2012-01-01

Potassium isotopic (K-41/K-39) compositions are notoriously difficult to measure. TIMS measurements are hindered by variable fractionation patterns throughout individual runs and too few isotopes to apply an internal spike method for instrumental mass fractionation corrections. Internal fractionation corrections via the K-40/K-39 ratio can provide precise values but assume identical K-40/K-39 ratios (e.g. 0.05% (1sigma) in [1]); this is appropriate in some cases (e.g. identifying excess K-41) but not others (e.g., determining mass fractionation effects and metrologically traceable isotopic abundances). SIMS analyses have yielded measurements with 0.25% precisions (1sigma) [2]. ICP-MS analyses are significantly affected by interferences from molecular species such as Ar-38H(+) and Ar-40H(+) and instrument mass bias. Single collector ICP-MS instruments in "cold plasma" mode have yielded uncertainties as low as 2% (1sigma, e.g. [3]). Although these precisions may be acceptable for some concentration determinations, they do not resolve isotopic variation in terrestrial materials. Here we present data from a series of measurements made on the Thermo Scientific NEPTUNE Plus multi-collector ICP-MS that demonstrate the ability to make K-41/K-39 ratio measurements with 0.07% precisions (1sigma). These data, collected on NIST K standards, indicate the potential for MC-ICP-MS measurements to look for K isotopic variations at the sub-permil level. The NEPTUNE Plus can sufficiently resolve 39K and 41K from the interfering 38ArH+ and 40ArH+ peaks in wet cold plasma and high-resolution mode. Measurements were made on small but flat, interference-free, plateaus (ca. 50 ppm by mass width for K-41). Although ICP-MS does not yield accurate K-41/K-39 values due to significant instrumental mass fractionation (ca. 6%), this bias can be sufficiently stable over the time required for several measurements so that relative K-41/K-39 values can be precisely determined via sample-standard bracketing. As cold plasma conditions can amplify matrix effects, experiments were conducted to test the matrix tolerance of measurements; the use of clean, matrix-matched samples and standards is critical. Limitations of the cold-plasma high-resolution MC-ICP-MS methodology with respect to matrix tolerance are discussed and compared with the limitations of TIMS methodologies.

Mass spectrometric measurements of the isotopic anatomies of molecules (Invited)

NASA Astrophysics Data System (ADS)

Eiler, J. M.; Krumwiede, D.; Schlueter, H.

2013-12-01

Site-specific and multiple isotopic substitutions in molecular structures potentially provide an extraordinarily rich set of constraints on their sources, conditions of formation, reaction and transport histories, and perhaps other issues. Examples include carbonate ';clumped isotope' thermometry, clumped isotope measurements of CO2, O2, and, recently, methane, ethane and N2O; site-specific 15N measurements in N2O and 13C and D analyses of fatty acids, sugars, cellulose, food products, and, recently, n-alkanes. Extension of the principles behind these tools to the very large number of isotopologues of complex molecules could potentially lead to new uses of isotope chemistry, similar to proteomics, metabolomics and genomics in their complexity and depth of detail (';isotomics'?). Several technologies are potentially useful for this field, including ';SNIF-NMR', gas source mass spectrometry and IR absorption spectroscopy. However, all well established methods have restrictive limits in the sizes of samples, types of analyzes, and the sorts of isotopologues that can be measured with useful precision. We will present an overview of several emerging instruments and techniques of high-resolution gas source mass spectrometry that may enable study of a large proportion of the isotopologues of a wide range of volatile and semi-volatile compounds, including many organics, with precisions and sample sizes suitable for a range of applications. A variety of isotopologues can be measured by combining information from the Thermo 253 Ultra (a new high resolution, multi-collector gas source mass spectrometer) and the Thermo DFS (a very high resolution single collector, but used here on a novel mode to achieve ~per mil precision ratio measurements), sometimes supplemented by conventional bulk isotopic measurements. It is possible to design methods in which no one of these sources of data meaningfully constrain abundances of specific isotopologues, but their combination fully and precisely constrains a large number. We have assembled a suite of instruments (including the prototype of the Ultra, and a modified version of the DFS that is capable of dual inlet analyses) that make it logistically straightforward to perform such multi-instrument analyses. Examples will be presented documenting the accuracy of these techniques for systems that are independently well known (e.g., isotopologues of methane), and the precision and internal consistency of results for larger, more complex molecules (e.g., a suite of singly and doubly substituted isotopologues of hexane and other moderate-molecular-weight organics).

Spectroscopic Measurement of LEAD-204 Isotope Shift and LEAD-205 Nuclear Spin.

NASA Astrophysics Data System (ADS)

Schonberger, Peter

The isotope shift of ('204)Pb and the nuclear spin of 1.4 x 10('7)-y ('205)Pb was determined from a high -resolution optical measurement of the 6p('2) ('3)P(,o) -6p7s('3)P(,1)('o) 283.3-nm resonance line. The value of the shift, relative to ('208)Pb is -140.2(8) x 10('-3)cm(' -1), the negative sign indicating a shift to lower wave numbers. The precision is 3-4 times greater than that of previous measurements. The spin of ('205)Pb l = 5/2 was obtained from the measurement of the relative intensities of its three hyperfine components. This method of absorption spectroscopy determination of ground state nuclear spin is applicable to any stable or longlived isotope. High resolution optical absorption spectra were obtained with a 25.4cm diffraction grating in a 9.1m focal length Czerny-Turner spectrometer. A signal-averaging scanning technique was used to record the spectra. Increased precision in the isotope shift measurement was attained by using separated isotope samples of ('204)Pb and ('207)Pb. A controlled amount of the later was incorporated in the absorption cell to provide internal calibration by its 6p7s ('3)P(,1)('o) hfs separation. Absorption spectra were recorded for several optical thicknesses of the absorber. A single spin value of increased precision was derived from the entire set of combined data.

Delta13C and delta18O isotopic composition of CaCO3 measured by continuous flow isotope ratio mass spectrometry: statistical evaluation and verification by application to Devils Hole core DH-11 calcite.

PubMed

Révész, Kinga M; Landwehr, Jurate M

2002-01-01

A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400 +/- 20 micro g) of calcium carbonate. This new method streamlines the classical phosphoric acid/calcium carbonate (H(3)PO(4)/CaCO(3)) reaction method by making use of a recently available Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. Conditions for which the H(3)PO(4)/CaCO(3) reaction produced reproducible and accurate results with minimal error had to be determined. When the acid/carbonate reaction temperature was kept at 26 degrees C and the reaction time was between 24 and 54 h, the precision of the carbon and oxygen isotope ratios for pooled samples from three reference standard materials was

Optimal design of isotope labeling experiments.

PubMed

Yang, Hong; Mandy, Dominic E; Libourel, Igor G L

2014-01-01

Stable isotope labeling experiments (ILE) constitute a powerful methodology for estimating metabolic fluxes. An optimal label design for such an experiment is necessary to maximize the precision with which fluxes can be determined. But often, precision gained in the determination of one flux comes at the expense of the precision of other fluxes, and an appropriate label design therefore foremost depends on the question the investigator wants to address. One could liken ILE to shadows that metabolism casts on products. Optimal label design is the placement of the lamp; creating clear shadows for some parts of metabolism and obscuring others.An optimal isotope label design is influenced by: (1) the network structure; (2) the true flux values; (3) the available label measurements; and, (4) commercially available substrates. The first two aspects are dictated by nature and constrain any optimal design. The second two aspects are suitable design parameters. To create an optimal label design, an explicit optimization criterion needs to be formulated. This usually is a property of the flux covariance matrix, which can be augmented by weighting label substrate cost. An optimal design is found by using such a criterion as an objective function for an optimizer. This chapter uses a simple elementary metabolite units (EMU) representation of the TCA cycle to illustrate the process of experimental design of isotope labeled substrates.

DoE optimization of a mercury isotope ratio determination method for environmental studies.

PubMed

Berni, Alex; Baschieri, Carlo; Covelli, Stefano; Emili, Andrea; Marchetti, Andrea; Manzini, Daniela; Berto, Daniela; Rampazzo, Federico

2016-05-15

By using the experimental design (DoE) technique, we optimized an analytical method for the determination of mercury isotope ratios by means of cold-vapor multicollector ICP-MS (CV-MC-ICP-MS) to provide absolute Hg isotopic ratio measurements with a suitable internal precision. By running 32 experiments, the influence of mercury and thallium internal standard concentrations, total measuring time and sample flow rate was evaluated. Method was optimized varying Hg concentration between 2 and 20 ng g(-1). The model finds out some correlations within the parameters affect the measurements precision and predicts suitable sample measurement precisions for Hg concentrations from 5 ng g(-1) Hg upwards. The method was successfully applied to samples of Manila clams (Ruditapes philippinarum) coming from the Marano and Grado lagoon (NE Italy), a coastal environment affected by long term mercury contamination mainly due to mining activity. Results show different extents of both mass dependent fractionation (MDF) and mass independent fractionation (MIF) phenomena in clams according to their size and sampling sites in the lagoon. The method is fit for determinations on real samples, allowing for the use of Hg isotopic ratios to study mercury biogeochemical cycles in complex ecosystems. Copyright © 2016 Elsevier B.V. All rights reserved.

Potassium isotopic evidence for a high-energy giant impact origin of the Moon.

PubMed

Wang, Kun; Jacobsen, Stein B

2016-10-27

The Earth-Moon system has unique chemical and isotopic signatures compared with other planetary bodies; any successful model for the origin of this system therefore has to satisfy these chemical and isotopic constraints. The Moon is substantially depleted in volatile elements such as potassium compared with the Earth and the bulk solar composition, and it has long been thought to be the result of a catastrophic Moon-forming giant impact event. Volatile-element-depleted bodies such as the Moon were expected to be enriched in heavy potassium isotopes during the loss of volatiles; however such enrichment was never found. Here we report new high-precision potassium isotope data for the Earth, the Moon and chondritic meteorites. We found that the lunar rocks are significantly (>2σ) enriched in the heavy isotopes of potassium compared to the Earth and chondrites (by around 0.4 parts per thousand). The enrichment of the heavy isotope of potassium in lunar rocks compared with those of the Earth and chondrites can be best explained as the result of the incomplete condensation of a bulk silicate Earth vapour at an ambient pressure that is higher than 10 bar. We used these coupled constraints of the chemical loss and isotopic fractionation of K to compare two recent dynamic models that were used to explain the identical non-mass-dependent isotope composition of the Earth and the Moon. Our K isotope result is inconsistent with the low-energy disk equilibration model, but supports the high-energy, high-angular-momentum giant impact model for the origin of the Moon. High-precision potassium isotope data can also be used as a 'palaeo-barometer' to reveal the physical conditions during the Moon-forming event.

Boron Isotopic Composition of Metasomatized Mantle Xenoliths from the Western Rift, East Africa

NASA Astrophysics Data System (ADS)

Hudgins, T.; Nelson, W. R.

2017-12-01

The Western Branch of the East African Rift System is known to have a thick lithosphere and sparse, alkaline volcanism associated with a metasomatized mantle source. Recent work investigating the relationship between Western Branch metasomatized mantle xenoliths and associated lavas has suggested that these metasomes are a significant factor in the evolution of the rift. Hydrous/carbonated fluids or silicate melts are potent metasomatic agents, however gaining insight into the source of a metasomatic agent proves challenging. Here we investigate the potential metasomatic fluid sources using B isotope analysis of mineral separates from Western Branch xenoliths. Preliminary SIMS analyses of phlogopite from Katwe Kikorongo and Bufumbira have and average B isotopic composition of -28.2‰ ± 5.1 and -16.4‰ ± 3.6, respectively. These values are are dissimilar to MORB (-7.5‰ ± 0.7; Marschall and Monteleone, 2015), primitive mantle (-10‰ ± 2; Chaussidon and Marty, 1995), and bulk continental crust (-9.1‰ ± 2.4; Marschall et al., 2017) and display significant heterogeneity across a relatively short ( 150km) portion of the Western Branch. Though displaying large variability, these B isotopic compositions are indicative of a metasomatic agent with a more negative B isotopic composition than MORB, PM, or BCC. These results are consistent with fluids that released from a subducting slab and may be related to 700 Ma Pan-African subduction.

Testing isotopic labeling with [¹³C₆]glucose as a method of advanced glycation sites identification.

PubMed

Kielmas, Martyna; Kijewska, Monika; Stefanowicz, Piotr; Szewczuk, Zbigniew

2012-12-01

The Maillard reaction occurring between reducing sugars and reactive amino groups of biomolecules leads to the formation of a heterogeneous mixture of compounds: early, intermediate, and advanced glycation end products (AGEs). These compounds could be markers of certain diseases and of the premature aging process. Detection of Amadori products can be performed by various methods, including MS/MS techniques and affinity chromatography on immobilized boronic acid. However, the diversity of the structures of AGEs makes detection of these compounds more difficult. The aim of this study was to test a new method of AGE identification based on isotope (13)C labeling. The model protein (hen egg lysozyme) was modified with an equimolar mixture of [(12)C(6)]glucose and [(13)C(6)]glucose and then subjected to reduction of the disulfide bridges followed by tryptic hydrolysis. The digest obtained was analyzed by LC-MS. The glycation products were identified on the basis of characteristic isotopic patterns resulting from the use of isotopically labeled glucose. This method allowed identification of 38 early Maillard reaction products and five different structures of the end glycation products. This isotopic labeling technique combined with LC-MS is a sensitive method for identification of advanced glycation end products even if their chemical structure is unknown. Copyright © 2012 Elsevier Inc. All rights reserved.

Boron isotopes in brachiopods during the end-Permian mass extinction: constraints on pH evolution and seawater chemistry

NASA Astrophysics Data System (ADS)

Jurikova, Hana; Gutjahr, Marcus; Liebetrau, Volker; Brand, Uwe; Posenato, Renato; Garbelli, Claudio; Angiolini, Lucia; Eisenhauer, Anton

2017-04-01

The global biogeochemical cycling of carbon is fundamental for life on Earth with the ocean playing a key role as the largest and dynamically evolving CO2 reservoir. The boron isotope composition (commonly expressed in δ11B) of marine calcium carbonate is considered to be one of the most reliable paleo-pH proxies, potentially enabling us to reconstruct past ocean pH changes and understand carbon cycle perturbations along Earth's geological record (e.g. Foster et al., 2008; Clarkson et al., 2015). Brachiopods present an advantageous and largely underutilised archive for Phanerozoic carbon cycle reconstructions considering their high abundance in the geological record and its origin dating back to the early Cambrian. Moreover, their shell made of low-magnesium calcite makes these marine calcifiers more resistant to post-depositional diagenetic alteration of primary chemical signals. We have investigated the δ11B using MC-ICP-MS (Neptune Plus) and B/Ca and other elemental ratios (Mg/Ca, Sr/Ca, Al/Ca, Li/Ca, Ba/Ca, Na/Ca and Fe/Ca) using ICP-MS-Quadrupole (Agilent 7500cx) from the same specimens in pristine brachiopod shells from two sections from northern Italy during the Late Permian. These sections cover the δ13C excursion in excess of ˜4 ‰ (Brand et al., 2012) and are associated with major climate and environmental perturbations that lead to the mass extinction event at the Permian-Triassic boundary. Particular emphasis will be placed on the implications of our new paleo-pH estimates on the seawater chemistry during the Late Permian. Brand, U., Posenato, R., Came, R., Affek, H., Angiolini, L., Azmy, K. and Farabegoli, E.: The end-Permian mass extinction: A rapid volcanic CO2 and CH4-climatic catastrophe, Chemical Geology 323, 121-144, doi:10.1016/j.chemgeo.2012.06.015, 2012. Clarkson, M.O., Kasemann, S.A., Wood, R.A., Lenton, T.M., Daines, S.J., Richoz, S., Ohnemueller, F., Meixner, A., Poulton, S.W. and Tipper, E.T.: Ocean acidification and the Permo-Triassic mass extinction. Science 348, 229-232, doi: 10.1126/science.aaa0193, 2015. Foster, G.L.: Seawater pH, pCO2 and [CO32-] variations in the Caribbean Sea over the last 130 kyr: A boron isotope and B/Ca study of planktic foraminifera. Earth and Planetary Science Letters 271, 254-266. doi:10.1016/j.epsl.2008.04.015, 2008.

Advances in Multicollector ICPMS for precise and accurate isotope ratio measurements of Uranium isotopes

NASA Astrophysics Data System (ADS)

Bouman, C.; Lloyd, N. S.; Schwieters, J.

2011-12-01

The accurate and precise determination of uranium isotopes is challenging, because of the large dynamic range posed by the U isotope abundances and the limited available sample material. Various mass spectrometric techniques are used for the measurement of U isotopes, where TIMS is the most accepted and accurate one. Multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) can offer higher productivity compared to TIMS, but is traditionally limited by low efficiency of sample utilisation. This contribution will discuss progress in MC-ICPMS for detecting 234U, 235U, 236U and 238U in various uranium reference materials from IRMM and NBL. The Thermo Scientific NEPTUNE Plus with Jet Interface offers a modified dry plasma ICP interface using a large interface pump combined with a special set of sample and skimmer cones giving ultimate sensitivity for all elements across the mass range. For uranium, an ion yield of > 3 % was reported previously [1]. The NEPTUNE Plus also offers Multi Ion Counting using discrete dynode electron multipliers as well as two high abundance-sensitivity filters to discriminate against peak tailing effects on 234U and 236U originating from the major uranium beams. These improvements in sensitivity and dynamic range allow accurate measurements of 234U, 235U and 236U abundances on very small samples and at low concentration. In our approach, minor U isotopes 234U and 236U were detected on ion counters with high abundance sensitivity filters, whereas 235U and 238U were detected on Faraday Cups using a high gain current amplifier (10e12 Ohm) for 235U. Precisions and accuracies for 234U and 236U were down to ~1%. For 235U, subpermil levels were reached.

Matrix effects of calcium on high-precision sulfur isotope measurement by multiple-collector inductively coupled plasma mass spectrometry.

PubMed

Liu, Chenhui; Bian, Xiao-Peng; Yang, Tao; Lin, An-Jun; Jiang, Shao-Yong

2016-05-01

Multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has been successfully applied in the rapid and high-precision measurement for sulfur isotope ratios in recent years. During the measurement, the presence of matrix elements would affect the instrumental mass bias for sulfur and these matrix-induced effects have aroused a lot of researchers' interest. However, these studies have placed more weight on highlighting the necessity for their proposed correction protocols (e.g., chemical purification and matrix-matching) while less attention on the key property of the matrix element gives rise to the matrix effects. In this study, four groups of sulfate solutions, which have different concentrations of sulfur (0.05-0.60mM) but a constant sequence of atomic calcium/sulfur ratios (0.1-50), are investigated under wet (solution) and dry (desolvation) plasma conditions to make a detailed evaluation on the matrix effects from calcium on sulfur isotope measurement. Based on a series of comparative analyses, we indicated that, the matrix effects of calcium on both measured sulfur isotope ratios and detected (32)S signal intensities are dependent mainly on the absolute calcium concentration rather than its relative concentration ratio to sulfur (i.e., atomic calcium/sulfur ratio). Also, for the same group of samples, the matrix effects of calcium under dry plasma condition are much more significant than that of wet plasma. This research affords the opportunity to realize direct and relatively precise sulfur isotope measurement for evaporite gypsum, and further provides some suggestions with regard to sulfur isotope analytical protocols for sedimentary pore water. Copyright © 2016 Elsevier B.V. All rights reserved.

Light Isotopes and Trace Organics Analysis of Mars Samples with Mass Spectrometry

NASA Technical Reports Server (NTRS)

Mahaffy, P.; Niemann, Hasso (Technical Monitor)

2001-01-01

Precision measurement of light isotopes in Mars surface minerals and comparison of this isotopic composition with atmospheric gas and other, well-mixed reservoirs such as surface dust are necessary to understand the history of atmospheric evolution from a possibly warmer and wetter Martian surface to the present state. Atmospheric sources and sinks that set these ratios are volcanism, solar wind sputtering, photochemical processes, and weathering. Measurement of a range of trace organic species with a particular focus on species such as amino acids that are the building blocks of terrestrial life are likewise important to address the questions of prebiotic and present or past biological activity on Mars. The workshop topics "isotopic mineralogy" and "biology and pre-biotic chemistry" will be addressed from the point of view of the capabilities and limitations of insitu mass spectrometry (MS) techniques such as thermally evolved gas analysis (TEGA) and gas chromatography (GC) surface experiments using MS, in both cases, as a final chemical and isotopic composition detector. Insitu experiments using straightforward adaptations of existing space proven hardware can provide a substantial improvement in the precision and accuracy of our present knowledge of isotopic composition both in molecular and atomic species in the atmosphere and those chemically bound in rocks and soils. Likewise, detection of trace organic species with greatly improved sensitivity from the Viking GCMS experiment is possible using gas enrichment techniques. The limits to precision and accuracy of presently feasible insitu techniques compared to laboratory analysis of returned samples will be explored. The insitu techniques are sufficiently powerful that they can provide a high fidelity method of screening samples obtained from a diverse set of surface locations such as the subsurface or the interior of rocks for selection of those that are the most interesting for return to Earth.

An accelerator-based Boron Neutron Capture Therapy (BNCT) facility based on the 7Li(p,n)7Be

NASA Astrophysics Data System (ADS)

Musacchio González, Elizabeth; Martín Hernández, Guido

2017-09-01

BNCT (Boron Neutron Capture Therapy) is a therapeutic modality used to irradiate tumors cells previously loaded with the stable isotope 10B, with thermal or epithermal neutrons. This technique is capable of delivering a high dose to the tumor cells while the healthy surrounding tissue receive a much lower dose depending on the 10B biodistribution. In this study, therapeutic gain and tumor dose per target power, as parameters to evaluate the treatment quality, were calculated. The common neutron-producing reaction 7Li(p,n)7Be for accelerator-based BNCT, having a reaction threshold of 1880.4 keV, was considered as the primary source of neutrons. Energies near the reaction threshold for deep-seated brain tumors were employed. These calculations were performed with the Monte Carlo N-Particle (MCNP) code. A simple but effective beam shaping assembly (BSA) was calculated producing a high therapeutic gain compared to previously proposed facilities with the same nuclear reaction.

Development of high through-put Sr isotope analysis for monitoring reservoir integrity for CO{sub 2} storage.

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

Wall, Andy; Jain, Jinesh; Stewart, Brian

2012-01-01

Recent innovations in multi-collector ICP-mass spectrometry (MC-ICP-MS) have allowed for rapid and precise measurements of isotope ratios in geological samples. Naturally occurring Sr isotopes has the potential for use in Monitoring, Verification, and Accounting (MVA) associated with geologic CO2 storage. Sr isotopes can be useful for: Sensitive tracking of brine migration; Determining seal rock leakage; Studying fluid/rock reactions. We have optimized separation chemistry procedures that will allow operators to prepare samples for Sr isotope analysis off site using rapid, low cost methods.

Lead isotopes in iron and manganese oxide coatings and their use as an exploration guide for concealed mineralization

USGS Publications Warehouse

Gulson, B.L.; Church, S.E.; Mizon, K.J.; Meier, A.L.

1992-01-01

Lead isotopes from Fe and Mn oxides that coat stream pebbles from around the Mount Emmons porphyry molybdenum deposit in Colorado were studied to assess the feasibility of using Pb isotopes to detect concealed mineral deposits. The Fe/Mn oxide coatings were analyzed to determine their elemental concentrations using ICP-AES. The Pb isotope compositions of solutions from a selected suite of samples were measured, using both thermal ionization and ICP mass spectrometry, to compare results determined by the two analytical methods. Heavy mineral concentrates from the same sites were also analyzed to compare the Pb isotope compositions of the Fe/Mn coatings with those found in panned concentrates. The Fe/Mn and 206Pb/204Pb ratios of the oxide coatings are related to the lithology of the host rocks; Fe/Mn oxide coatings on pebbles of black shale have higher Fe/Mn values than do the coatings on either sandstone or igneous rocks. The shale host rocks have a more radiogenic signature (e.g. higher 206Pb/ 204Pb) than the sandstone or igneous host rocks. The Pb isotope data from sandstone and igneous hosts can detect concealed mineralized rock on both a regional and local scale, even though there are contributions from: (1) metals from the main-stage molybdenite ore deposit; (2) metals from the phyllic alteration zone which has a more radiogenic Pb isotope signature reflecting hydrothermal leaching of Pb from the Mancos Shale; (3) Pb-rich base metal veins with a highly variable Pb isotope signature; and (4) sedimentary country rocks which have a more radiogenic Pb isotope signature. An investigation of within-stream variation shows that the Pb isotope signature of the molybdenite ore zone is retained in the Fe/Mn oxide coatings and is not camouflaged by contributions from Pb-rich base-metal veins that crop out upstream. In another traverse, the Pb isotope data from Fe/Mn oxide coatings reflect a complex mixing of Pb from the molybdenite ore zone and its hornfels margin, Pb-rich base-metal veins, and sedimentary country rocks. Stream-sediment anomalies detected using oxalic acid leaches can be evaluated using Pb isotope analysesof selected geochemical anomalies. Such an evaluation procedure, given regional target Pb isotope signatures for concealed mineralization, can greatly reduce the cost of exploration for undiscovered ore deposits concealed beneath barren overburden. Lead isotope measurements on aliquots of the same solutions showed that ICP-MS determinations are of low precision and vary non-systematically when compared with the Pb isotope values of the higher precision thermal ionization method. These variations and lower precision of the ICP-MS measurements are attributed to matrix effects. ?? 1992.

Moving Beyond Boron: The Emergence of New Linkage Chemistries in Covalent Organic Frameworks

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

DeBlase, Catherine R.; Dichtel, William R.

Since their discovery in 2005, covalent organic frameworks (COFs) have attracted interest as potential materials for gas storage, catalysis, energy storage, and other applications because of their ability to periodically and reliably organize designed functionality into high surface area materials. Most of the first examples relied on boron-containing linkages, which suffer from hydrolytic and oxidative instability that limit their utility. In this Perspective, we describe the trend toward more robust linkages by highlighting the design, synthesis, and properties of several recent examples. Finally, the continued development of new COF chemistries, along with improved understanding of their formation and control ofmore » their final form, will provide a means to harness their molecularly precise solidstate structures for useful purposes.« less

Moving Beyond Boron: The Emergence of New Linkage Chemistries in Covalent Organic Frameworks

DOE PAGES

DeBlase, Catherine R.; Dichtel, William R.

2016-06-21

Since their discovery in 2005, covalent organic frameworks (COFs) have attracted interest as potential materials for gas storage, catalysis, energy storage, and other applications because of their ability to periodically and reliably organize designed functionality into high surface area materials. Most of the first examples relied on boron-containing linkages, which suffer from hydrolytic and oxidative instability that limit their utility. In this Perspective, we describe the trend toward more robust linkages by highlighting the design, synthesis, and properties of several recent examples. Finally, the continued development of new COF chemistries, along with improved understanding of their formation and control ofmore » their final form, will provide a means to harness their molecularly precise solidstate structures for useful purposes.« less

Multi-walled boron nitride nanotubes as self-excited launchers.

PubMed

Li, Yifan; Zhou, Yi; Wu, Yan; Huang, Chengchi; Wang, Long; Zhou, Xuyan; Zhao, Zhenyang; Li, Hui

2017-07-27

A self-excited launcher consisting of multi-walled boron nitride nanotubes (BNNTs) has been investigated using molecular dynamics simulation. The results show that, after a period of high frequency oscillation, the innermost BNNT can be spontaneously ejected along its central axis at a relatively fast speed. The launching is caused by the energy transfer between the nanotubes and without absorbing energy from the external environment. Most self-excited launchers could launch their innermost nanotube, although an inappropriate structure of the nanotubes contributes to a blocked or failed launch. In addition, a launch angle corrector and a nanotube receiver associated with a self-excited launcher are also manufactured to precisely control the launch angle and distance of the BNNTs. This study provides the possibility to fabricate and design self-excited launchers using multi-walled nanotubes.

Determination of boron in produced water using the carminic acid assay.

PubMed

Floquet, Cedric F A; Sieben, Vincent J; MacKay, Bruce A; Mostowfi, Farshid

2016-04-01

Using the carminic acid assay, we determined the concentration of boron in oilfield waters. We investigated the effect of high concentrations of salts and dissolved metals on the assay performance. The influence of temperature, development time, reagent concentration, and water volume was studied. Ten produced and flowback water samples of different origins were measured, and the method was successfully validated against ICP-MS measurements. In water-stressed regions, produced water is a potential source of fresh water for irrigation, industrial applications, or consumption. Therefore, boron concentration must be determined and controlled to match the envisaged waste water reuse. Fast, precise, and onsite measurements are needed to minimize errors introduced by sample transportation to laboratories. We found that the optimum conditions for our application were a 5:1 mixing volume ratio (reagent to sample), a 1 g L(-1) carminic acid concentration in 99.99% sulfuric acid, and a 30 min reaction time at ambient temperature (20 °C to 23 °C). Absorption values were best measured at 610 nm and 630 nm and baseline corrected at 865 nm. Under these conditions, the sensitivity of the assay to boron was maximized while its cross-sensitivity to dissolved titanium, iron, barium and zirconium was minimized, alleviating the need for masking agents and extraction methods. Copyright © 2015 Elsevier B.V. All rights reserved.

Nitrate source indicators in ground water of the Scimitar Subdivision, Peters Creek area, Anchorage, Alaska

USGS Publications Warehouse

Wang, Bronwen; Strelakos, Pat M.; Jokela, Brett

2000-01-01

A combination of aqueous chemistry, isotopic measurement, and in situ tracers were used to study the possible nitrate sources, the factors contributing to the spatial distribution of nitrate, and possible septic system influence in the ground water in the Scimitar Subdivision, Municipality of Anchorage, Alaska. Two water types were distinguished on the basis of the major ion chemistry: (1) a calcium sodium carbonate water, which was associated with isotopically heavier boron and with chlorofluorocarbons (CFC's) that were in the range expected from equilibration with the atmosphere (group A water) and (2) a calcium magnesium carbonate water, which was associated with elevated nitrate, chloride, and magnesium concentrations, generally isotopically lighter boron, and CFC's concentrations that were generally in excess of that expected from equilibration with the atmosphere (group B water). Water from wells in group B had nitrate concentrations that were greater than 3 milligrams per liter, whereas those in group A had nitrate concentrations of 0.2 milligram per liter or less. Nitrate does not appear to be undergoing extensive transformation in the ground-water system and behaves as a conservative ion. The major ion chemistry trends and the presence of CFC's in excess of an atmospheric source for group B wells are consistent with waste-water influences. The spatial distribution of the nitrate among wells is likely due to the magnitude of this influence on any given well. Using an expanded data set composed of 16 wells sampled only for nitrate concentration, a significant difference in the static water level relative to bedrock was found. Well water samples with less than 1 milligram per liter nitrate had static water levels within the bedrock, whereas those samples with greater than 1 milligram per liter nitrate had static water levels near or above the top of the bedrock. This observation would be consistent with a conceptual model of a low-nitrate fractured bedrock aquifer that receives slow recharge from an overlying nitrate-enriched surficial aquifer.

Measurement of δ18O, δ17O, and 17O-excess in Water by Off-Axis Integrated Cavity Output Spectroscopy and Isotope Ratio Mass Spectrometry

PubMed Central

Berman, Elena S.F.; Levin, Naomi E.; Landais, Amaelle; Li, Shuning; Owano, Thomas

2013-01-01

Stable isotopes of water have long been used to improve understanding of the hydrological cycle, catchment hydrology, and polar climate. Recently, there has been increasing interest in measurement and use of the less-abundant 17O isotope in addition to 2H and 18O. Off-axis integrated cavity output spectroscopy (OA-ICOS) is demonstrated for accurate and precise measurements δ18O, δ17O, and 17O-excess in liquid water. OA-ICOS involves no sample conversion and has a small footprint, allowing measurements to be made by researchers collecting the samples. Repeated (514) high-throughput measurements of the international isotopic reference water standard GISP demonstrate the precision and accuracy of OA-ICOS: δ18OVSMOW-SLAP =−24.74 ± 0.07 ‰ (1σ) and δ17OVSMOW-SLAP = −13.12 ± 0.05 ‰ (1σ). For comparison, the IAEA value for δ18OVSMOW-SLAP is −24.76 ± 0.09 ‰ (1σ) and an average of previously reported values for δ17OVSMOW-SLAP is −13.12 ± 0.06 ‰ (1σ). Multiple (26) high-precision measurements of GISP provide a 17O-excessVSMOW-SLAP of 23 ± 10 per meg (1σ); an average of previously reported values for 17O-excessVSMOW-SLAP is 22 ± 11 per meg (1σ). For all these OA-ICOS measurements, precision can be further enhanced by additional averaging. OA-ICOS measurements were compared with two independent isotope ratio mass spectrometry (IRMS) laboratories and shown to have comparable accuracy and precision as the current fluorination-IRMS techniques in δ18O, δ17O, and 17O-excess. The ability to measure accurately δ18O, δ17O, and 17O-excess in liquid water inexpensively and without sample conversion is expected to increase vastly the application of δ17O and 17O-excess measurements for scientific understanding of the water cycle, atmospheric convection, and climate modeling among others. PMID:24032448

Tungsten isotopes in bulk meteorites and their inclusions—Implications for processing of presolar components in the solar protoplanetary disk

PubMed Central

Holst, J. C.; Paton, C.; Wielandt, D.; Bizzarro, M.

2016-01-01

We present high precision, low- and high-resolution tungsten isotope measurements of iron meteorites Cape York (IIIAB), Rhine Villa (IIIE), Bendego (IC), and the IVB iron meteorites Tlacotepec, Skookum, and Weaver Mountains, as well as CI chondrite Ivuna, a CV3 chondrite refractory inclusion (CAI BE), and terrestrial standards. Our high precision tungsten isotope data show that the distribution of the rare p-process nuclide 180W is homogeneous among chondrites, iron meteorites, and the refractory inclusion. One exception to this pattern is the IVB iron meteorite group, which displays variable excesses relative to the terrestrial standard, possibly related to decay of rare 184Os. Such anomalies are not the result of analytical artifacts and cannot be caused by sampling of a protoplanetary disk characterized by p-process isotope heterogeneity. In contrast, we find that 183W is variable due to a nucleosynthetic s-process deficit/r-process excess among chondrites and iron meteorites. This variability supports the widespread nucleosynthetic s/r-process heterogeneity in the protoplanetary disk inferred from other isotope systems and we show that W and Ni isotope variability is correlated. Correlated isotope heterogeneity for elements of distinct nucleosynthetic origin (183W and 58Ni) is best explained by thermal processing in the protoplanetary disk during which thermally labile carrier phases are unmixed by vaporization thereby imparting isotope anomalies on the residual processed reservoir. PMID:27445452

The influence of room temperature on Mg isotope measurements by MC-ICP-MS.

PubMed

Zhang, Xing-Chao; Zhang, An-Yu; Zhang, Zhao-Feng; Huang, Fang; Yu, Hui-Min

2018-03-24

We observed that the accuracy and precision of magnesium (Mg) isotope analyses could be affected if the room temperature oscillated during measurements. To achieve high quality Mg isotopic data, it is critical to evaluate how the unstable room temperature affects Mg isotope measurements by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We measured the Mg isotopes for the reference material DSM-3 using MC-ICP-MS under oscillating room temperatures in spring. For a comparison, we also measured the Mg isotopes under stable room temperatures, which was achieved by the installation of an improved temperature control system in the laboratory. The δ 26 Mg values measured under oscillating room temperatures have a larger deviation (δ 26 Mg from -0.09 to 0.08‰, with average δ 26 Mg = 0.00 ± 0.08 ‰) than those measured under a stable room temperature (δ 26 Mg from -0.03 to 0.03‰, with average δ 26 Mg = 0.00 ± 0.02 ‰) using the same MC-ICP-MS system. The room temperature variation can influence the stability of MC-ICP-MS. Therefore, it is critical to keep the room temperature stable to acquire high precise and accurate isotopic data when using MC-ICP-MS, especially when using the sample-standard bracketing (SSB) correction method. This article is protected by copyright. All rights reserved.

Fractionation of uranium isotopes in minerals screened by gamma spectrometry.

NASA Astrophysics Data System (ADS)

Geiger, Jeffrey L.; Baldwin, Austin M.; Blatchley, Charles C.

2008-03-01

At least two groups have reported finding shifts in the ratio of U-235/U-238 for sandstone, black shale, and other sedimentary samples using precision ICP-MS. These shifts were tentatively attributed to a recently predicted isotope effect based on nuclear volume that causes fractionation for U^IV-U^VI transitions. However, fractionation of high Z elements may be less likely an explanation than U-235 depletion induced by galactic cosmic ray neutrons. Isotope depletion in marine sediments could therefore be an indicator of changes in cosmic ray flux due to nearby supernovae, gamma-ray bursts, or longer term changes during the 62 million year cycle of the Sun above and below the galactic plane. We report using a less precise approach than ICP-MS, but one which can quickly screen samples to look for anomalies in isotope ratios, namely HPGe gamma ray spectrometry. Various levels of depletion were measured for uranium rich minerals, including brannerite, carnotite, and pitchblende, as well as coal and limestone samples.

Improvements on high-precision measurement of bromine isotope ratios by multicollector inductively coupled plasma mass spectrometry.

PubMed

Wei, Hai-Zhen; Jiang, Shao-Yong; Zhu, Zhi-Yong; Yang, Tao; Yang, Jing-Hong; Yan, Xiong; Wu, He-Pin; Yang, Tang-Li

2015-10-01

A new, feasible procedure for high-precision bromine isotope analysis using multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is described. With a combination of HR mass resolution mode and accurate optimization of the Zoom Optics parameters (Focus Quad: -1.30; Zoom Quad: 0.00), the challenging problem of the isobaric interferences ((40)Ar(38)ArH(+) and (40)Ar(40)ArH(+)) in the measurement of bromine isotopes ((79)Br(+), (81)Br(+)) has been effectively solved. The external reproducibility of the measured (81)Br/(79)Br ratios in the selected standard reference materials ranged from ±0.03‰ to ±0.14‰, which is superior to or equivalent to the best results from previous contributions. The effect of counter cations on the Br(+) signal intensity and the instrumental-induced mass bias was evaluated as the loss of HBr aerosol in nebulizer and potential diffusive isotope fractionations. Copyright © 2015 Elsevier B.V. All rights reserved.

A Reassessment of the Precision of Carbonate Clumped Isotope Measurements: Implications for Calibrations and Paleoclimate Reconstructions

NASA Astrophysics Data System (ADS)

Fernandez, Alvaro; Müller, Inigo A.; Rodríguez-Sanz, Laura; van Dijk, Joep; Looser, Nathan; Bernasconi, Stefano M.

2017-12-01

Carbonate clumped isotopes offer a potentially transformational tool to interpret Earth's history, but the proxy is still limited by poor interlaboratory reproducibility. Here, we focus on the uncertainties that result from the analysis of only a few replicate measurements to understand the extent to which unconstrained errors affect calibration relationships and paleoclimate reconstructions. We find that highly precise data can be routinely obtained with multiple replicate analyses, but this is not always done in many laboratories. For instance, using published estimates of external reproducibilities we find that typical clumped isotope measurements (three replicate analyses) have margins of error at the 95% confidence level (CL) that are too large for many applications. These errors, however, can be systematically reduced with more replicate measurements. Second, using a Monte Carlo-type simulation we demonstrate that the degree of disagreement on published calibration slopes is about what we should expect considering the precision of Δ47 data, the number of samples and replicate analyses, and the temperature range covered in published calibrations. Finally, we show that the way errors are typically reported in clumped isotope data can be problematic and lead to the impression that data are more precise than warranted. We recommend that uncertainties in Δ47 data should no longer be reported as the standard error of a few replicate measurements. Instead, uncertainties should be reported as margins of error at a specified confidence level (e.g., 68% or 95% CL). These error bars are a more realistic indication of the reliability of a measurement.

Chemical separation and mass spectrometry of Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial materials using thermal ionization mass spectrometry.

PubMed

Yamakawa, Akane; Yamashita, Katsuyuki; Makishima, Akio; Nakamura, Eizo

2009-12-01

A sequential chemical separation technique for Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial silicate rocks was developed for precise and accurate determination of elemental concentration by the isotope dilution method (ID). The technique uses a combination of cation-anion exchange chromatography and Eichrom nickel specific resin. The method was tested using a variety of matrixes including bulk meteorite (Allende), terrestrial peridotite (JP-1), and basalt (JB-1b). Concentrations of each element was determined by thermal ionization mass spectrometry (TIMS) using W filaments and a Si-B-Al type activator for Cr, Fe, Ni, and Zn and a Re filament and silicic acid-H3PO4 activator for Cu. The method can be used to precisely determine the concentrations of these elements in very small silicate samples, including meteorites, geochemical reference samples, and mineral standards for microprobe analysis. Furthermore, the Cr mass spectrometry procedure developed in this study can be extended to determine the isotopic ratios of 53Cr/52Cr and 54Cr/52Cr with precision of approximately 0.05epsilon and approximately 0.10epsilon (1epsilon = 0.01%), respectively, enabling cosmochemical applications such as high precision Mn-Cr chronology and investigation of nucleosynthetic isotopic anomalies in meteorites.

Discrimination of the Cigarettes Geographical Origin by DRC-ICP-MS Measurements of Pb Isotope Compositions

NASA Astrophysics Data System (ADS)

Guo, W.; Hu, S.; Jin, L.

2014-12-01

Trace Pb are taken up with the same isotopic ratios as is present in the source soil, and the isotopic composition of Pb could used to reflect these sources and provide powerful indicators of the geographic origin of agriculture products derived from vegetative matter. We developed a simple and high throughput method, which based on DRC-ICP-MS for determination of Pb isotope ratios for discriminating the geographic origin of cigarettes. After acid digestion procedure, the cigarette digested solutions were directly analyzed by ICP-QMS with a DRC pressurized by the non-reactive gas Ne. In the DRC, Ne molecules collision with Pb ions and improves Pb isotope ratios precision 3-fold, which may be due to the collisional dampling smoothes out the ion beam fluctuations. Under the optimum DRC rejection parameter Q (RPq = 0.45), the main matrix components (K, Na, Ca, Mg, Al, Fe etc.) originating from cigarettes were filtered out. Mass discrimination of 208Pb/206Pb ratio in Ne DRC mode increased 0.3% compared to the standard mode, the mass bias due to the in-cell Ne gas collision can be accurately corrected by NIST 981 Pb isotope standard. This method was verified by a tobacco reference material CTV-OTL-2. Results of 208Pb/206Pb and 207Pb/206Pb were 2.0848 ± 0.0028 (2δ) and 0.8452 ± 0.0011 (2δ) for CTA-VTL-2, which were agreed with the literature values (208Pb/206Pb = 2.0884 ± 0.0090 and 207Pb/206Pb = 0.8442 ± 0.0032). The precision of Pb isotope ratios (208Pb/206Pb and 207Pb/206Pb) for the cigarette samples are ranged from 0.01 to 0.08% (N = 5). It has sufficient precision to discriminate 91 different brand cigarettes originated from four different geographic regions (Shown in Fig).

An optical method for carbon dioxide isotopes and mole fractions in small gas samples: tracing microbial respiration from soil, litter, and lignin.

Treesearch

Steven J. Hall; Wenjuan Huang; Kenneth Hammel

2017-01-01

RATIONALE: Carbon dioxide isotope (Δ13C value) measurements enable quantification of the sources of soil microbial respiration, thus informing ecosystem C dynamics. Tunable diode lasers (TDLs) can precisely measure CO2 isotopes at low cost and high throughput, but are seldom used for small samples (≤5 mL). We developed a...

Defining Uncertainty and Error in Planktic Foraminiferal Oxygen Isotope Measurements

NASA Astrophysics Data System (ADS)

Fraass, A. J.; Lowery, C.

2016-12-01

Foraminifera are the backbone of paleoceanography, and planktic foraminifera are one of the leading tools for reconstructing water column structure. Currently, there are unconstrained variables when dealing with the reproducibility of oxygen isotope measurements. This study presents the first results from a simple model of foraminiferal calcification (Foraminiferal Isotope Reproducibility Model; FIRM), designed to estimate the precision and accuracy of oxygen isotope measurements. FIRM produces synthetic isotope data using parameters including location, depth habitat, season, number of individuals included in measurement, diagenesis, misidentification, size variation, and vital effects. Reproducibility is then tested using Monte Carlo simulations. The results from a series of experiments show that reproducibility is largely controlled by the number of individuals in each measurement, but also strongly a function of local oceanography if the number of individuals is held constant. Parameters like diagenesis or misidentification have an impact on both the precision and the accuracy of the data. Currently FIRM is a tool to estimate isotopic error values best employed in the Holocene. It is also a tool to explore the impact of myriad factors on the fidelity of paleoceanographic records. FIRM was constructed in the open-source computing environment R and is freely available via GitHub. We invite modification and expansion, and have planned inclusions for benthic foram reproducibility and stratigraphic uncertainty.

Dual Si and O Isotope Measurement of Lunar Samples Using IRMS

NASA Astrophysics Data System (ADS)

Banerjee, N.; Hill, P. J. A.; Osinski, G. R.

2016-12-01

The use of isotopic systems and their associated theoretical models have become an increasingly sophisticated tool for investigating the origin of planetary bodies in the solar system. It was originally hypothesized that evidence for the impact origin of Moon would manifest itself as an isotopic heterogeneity between lunar and terrestrial samples; however, most isotope systems show no difference between the bulk Earth and Moon. The stable isotopes of both silicon (Si) and oxygen (O) have been essential in further understanding planetary processes including core formation. Historically the analysis of the Si and O isotope ratios in terrestrial and extraterrestrial material has primarily been measured independent of each other through three main techniques: isotope ratio mass spectrometry (IRMS), secondary ion mass spectrometry (SIMS), and multi-collector inductively coupled plasma mass-spectrometry (MC-ICPMS). Each technique has its own strength and weakness in regards to resolution and precision; however, one of the main limiting factors in all three of these techniques rests on the requirement of multiple aliquots. As most literature focuses on the measurement of oxygen or silicon isotopes, this unique line allows for the precise analysis of Si and O isotopes from the same aliquot of bulk sample, which cannot be done with SIMS or ICP-MS analysis. To deal with this problem a unique laser line system has been developed in the Laboratory for Stable Isotope Science at Western University, Canada, that simultaneously extracts SiF4 and O2 from the same 1-2 mg aliquot. We present the application of analyzing both isotopic systems from the sample aliquot to Apollo, meteoritic, and terrestrial samples and its implication for the formation of the Moon. Preliminary results from this line suggest that although the O isotopes ratios are consistent with a homogenous Moon-Earth system, a difference is observed in Si isotopes between Apollo and terrestrial samples compared to previous studies.

Chromatographic speciation of Cr(III)-species, inter-species equilibrium isotope fractionation and improved chemical purification strategies for high-precision isotope analysis.

PubMed

Larsen, K K; Wielandt, D; Schiller, M; Bizzarro, M

2016-04-22

Chromatographic purification of chromium (Cr), which is required for high-precision isotope analysis, is complicated by the presence of multiple Cr-species with different effective charges in the acid digested sample aliquots. The differing ion exchange selectivity and sluggish reaction rates of these species can result in incomplete Cr recovery during chromatographic purification. Because of large mass-dependent inter-species isotope fractionation, incomplete recovery can affect the accuracy of high-precision Cr isotope analysis. Here, we demonstrate widely differing cation distribution coefficients of Cr(III)-species (Cr(3+), CrCl(2+) and CrCl2(+)) with equilibrium mass-dependent isotope fractionation spanning a range of ∼1‰/amu and consistent with theory. The heaviest isotopes partition into Cr(3+), intermediates in CrCl(2+) and the lightest in CrCl2(+)/CrCl3°. Thus, for a typical reported loss of ∼25% Cr (in the form of Cr(3+)) through chromatographic purification, this translates into 185 ppm/amu offset in the stable Cr isotope ratio of the residual sample. Depending on the validity of the mass-bias correction during isotope analysis, this further results in artificial mass-independent effects in the mass-bias corrected (53)Cr/(52)Cr (μ(53)Cr* of 5.2 ppm) and (54)Cr/(52)Cr (μ(54)Cr* of 13.5 ppm) components used to infer chronometric and nucleosynthetic information in meteorites. To mitigate these fractionation effects, we developed strategic chemical sample pre-treatment procedures that ensure high and reproducible Cr recovery. This is achieved either through 1) effective promotion of Cr(3+) by >5 days exposure to HNO3H2O2 solutions at room temperature, resulting in >∼98% Cr recovery for most types of sample matrices tested using a cationic chromatographic retention strategy, or 2) formation of Cr(III)-Cl complexes through exposure to concentrated HCl at high temperature (>120 °C) for several hours, resulting in >97.5% Cr recovery using a chromatographic elution strategy that takes advantage of the slow reaction kinetics of de-chlorination of Cr in dilute HCl at room temperature. These procedures significantly improve cation chromatographic purification of Cr over previous methods and allow for high-purity Cr isotope analysis with a total recovery of >95%. Copyright © 2016 Elsevier B.V. All rights reserved.

Chromatographic speciation of Cr(III)-species, inter-species equilibrium isotope fractionation and improved chemical purification strategies for high-precision isotope analysis

PubMed Central

Larsen, K.K.; Wielandt, D.; Schiller, M.; Bizzarro, M.

2016-01-01

Chromatographic purification of chromium (Cr), which is required for high-precision isotope analysis, is complicated by the presence of multiple Cr-species with different effective charges in the acid digested sample aliquots. The differing ion exchange selectivity and sluggish reaction rates of these species can result in incomplete Cr recovery during chromatographic purification. Because of large mass-dependent inter-species isotope fractionation, incomplete recovery can affect the accuracy of high-precision Cr isotope analysis. Here, we demonstrate widely differing cation distribution coefficients of Cr(III)-species (Cr3+, CrCl2+ and CrCl2+) with equilibrium mass-dependent isotope fractionation spanning a range of ~1‰/amu and consistent with theory. The heaviest isotopes partition into Cr3+, intermediates in CrCl2+ and the lightest in CrCl2+/CrCl3°. Thus, for a typical reported loss of ~25% Cr (in the form of Cr3+) through chromatographic purification, this translates into 185 ppm/amu offset in the stable Cr isotope ratio of the residual sample. Depending on the validity of the mass-bias correction during isotope analysis, this further results in artificial mass-independent effects in the mass-bias corrected 53Cr/52Cr (μ53 Cr* of 5.2 ppm) and 54Cr/52Cr (μ54Cr* of 13.5 ppm) components used to infer chronometric and nucleosynthetic information in meteorites. To mitigate these fractionation effects, we developed strategic chemical sample pre-treatment procedures that ensure high and reproducible Cr recovery. This is achieved either through 1) effective promotion of Cr3+ by >5 days exposure to HNO3 —H2O2 solutions at room temperature, resulting in >~98% Cr recovery for most types of sample matrices tested using a cationic chromatographic retention strategy, or 2) formation of Cr(III)-Cl complexes through exposure to concentrated HCl at high temperature (>120 °C) for several hours, resulting in >97.5% Cr recovery using a chromatographic elution strategy that takes advantage of the slow reaction kinetics of de-chlorination of Cr in dilute HCl at room temperature. These procedures significantly improve cation chromatographic purification of Cr over previous methods and allow for high-purity Cr isotope analysis with a total recovery of >95%. PMID:27036208

High Throughput Strontium Isotope Method for Monitoring Fluid Flow Related to Geological CO2 Storage

NASA Astrophysics Data System (ADS)

Capo, R. C.; Wall, A. J.; Stewart, B. W.; Phan, T. T.; Jain, J. C.; Hakala, J. A.; Guthrie, G. D.

2012-12-01

Natural isotope tracers, such as strontium (Sr), can be a unique and powerful component of a monitoring strategy at a CO2 storage site, facilitating both the quantification of reaction progress for fluid-rock interactions and the tracking of brine migration caused by CO2 injection. Several challenges must be overcome, however, to enable the routine use of isotopic tracers, including the ability to rapidly analyze numerous aqueous samples with potentially complex chemical compositions. In a field situation, it might be necessary to analyze tens of samples over a short period of time to identify subsurface reactions and respond to unexpected fluid movement in the host formation. These conditions require streamlined Sr separation chemistry for samples ranging from pristine groundwaters to those containing high total dissolved solids, followed by rapid measurement of isotope ratios with high analytical precision. We have optimized Sr separation chemistry and MC-ICP-MS methods to provide rapid and precise measurements of isotope ratios in geologic, hydrologic, and environmental samples. These improvements will allow an operator to independently prepare samples for Sr isotope analysis off-site using fast, low cost chemical separation procedures and commercially available components. Existing vacuum-assisted Sr separation procedures were modified by using inexpensive disposable parts to eliminate cross contamination. Experimental results indicate that the modified columns provide excellent separation of Sr from chemically complex samples and that Sr can be effectively isolated from problematic matrix elements (e.g., Ca, Ba, K) associated with oilfield brines and formation waters. The separation procedure is designed for high sample throughput in which batches of 24 samples can be processed in approximately 2 hours, and are ready for Sr isotope measurements by MC-ICP-MS immediately after collection from the columns. Precise Sr isotope results can be achieved by MC-ICP-MS with a throughput of 4 to 5 samples per hour. Our mean measured value of NIST Sr isotope standard SRM 987 is 0.710265 ± 0.000014 (2σ, n = 94). A range of brines and CO2-rich fluids analyzed by this method yielded results within the analytical uncertainty of 87Sr/86Sr ratios previously determined by standard column separation and thermal ionization mass spectrometry. This method provides a fast and effective way to use Sr isotopes for monitoring purposes related to geological CO2 storage.

Precise measurement of Fe isotopes in marine samples by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS).

PubMed

de Jong, Jeroen; Schoemann, Véronique; Tison, Jean-Louis; Becquevort, Sylvie; Masson, Florence; Lannuzel, Delphine; Petit, Jérôme; Chou, Lei; Weis, Dominique; Mattielli, Nadine

2007-04-18

A novel analytical technique for isotopic analysis of dissolved and particulate iron (Fe) from various marine environments is presented in this paper. It combines coprecipitation of dissolved Fe (DFe) samples with Mg(OH)(2), and acid digestion of particulate Fe (PFe) samples with double pass chromatographic separation. Isotopic data were obtained using a Nu Plasma MC-ICP-MS in dry plasma mode, applying a combination of standard-sample bracketing and external normalization by Cu doping. Argon interferences were determined prior to each analysis and automatically subtracted during analysis. Sample size can be varied between 200 and 600 ng of Fe per measurement and total procedural blanks are better than 10 ng of Fe. Typical external precision of replicate analyses (1S.D.) is +/-0.07 per thousand on delta(56)Fe and +/-0.09 per thousand on delta(57)Fe while typical internal precision of a measurement (1S.E.) is +/-0.03 per thousand on delta(56)Fe and +/-0.04 per thousand on delta(57)Fe. Accuracy and precision were assured by the analysis of reference material IRMM-014, an in-house pure Fe standard, an in-house rock standard, as well as by inter-laboratory comparison using a hematite standard from ETH (Zürich). The lowest amount of Fe (200 ng) at which a reliable isotopic measurement could still be performed corresponds to a DFe or PFe concentration of approximately 2 nmol L(-1) for a 2 L sample size. To show the versatility of the method, results are presented from contrasting environments characterized by a wide range of Fe concentrations as well as varying salt content: the Scheldt estuary, the North Sea, and Antarctic pack ice. The range of DFe and PFe concentrations encountered in this investigation falls between 2 and 2000 nmol L(-1) Fe. The distinct isotopic compositions detected in these environments cover the whole range reported in previous studies of natural Fe isotopic fractionation in the marine environment, i.e. delta(56)Fe varies between -3.5 per thousand and +1.5 per thousand. The largest fractionations were observed in environments characterized by redox changes and/or strong Fe cycling. This demonstrates the potential use of Fe isotopes as a tool to trace marine biogeochemical processes involving Fe.

Comprehensive Pb-Sr-Nd-Hf isotopic, trace element, and mineralogical characterization of mafic to ultramafic rock reference materials

NASA Astrophysics Data System (ADS)

Fourny, Anaïs.; Weis, Dominique; Scoates, James S.

2016-03-01

Controlling the accuracy and precision of geochemical analyses requires the use of characterized reference materials with matrices similar to those of the unknown samples being analyzed. We report a comprehensive Pb-Sr-Nd-Hf isotopic and trace element concentration data set, combined with quantitative phase analysis by XRD Rietveld refinement, for a wide range of mafic to ultramafic rock reference materials analyzed at the Pacific Centre for Isotopic and Geochemical Research, University of British Columbia. The samples include a pyroxenite (NIM-P), five basalts (BHVO-2, BIR-1a, JB-3, BE-N, GSR-3), a diabase (W-2), a dolerite (DNC-1), a norite (NIM-N), and an anorthosite (AN-G); results from a leucogabbro (Stillwater) are also reported. Individual isotopic ratios determined by MC-ICP-MS and TIMS, and multielement analyses by HR-ICP-MS are reported with 4-12 complete analytical duplicates for each sample. The basaltic reference materials have coherent Sr and Nd isotopic ratios with external precision below 50 ppm (2SD) and below 100 ppm for Hf isotopes (except BIR-1a). For Pb isotopic reproducibility, several of the basalts (JB-3, BHVO-2) require acid leaching prior to dissolution. The plutonic reference materials also have coherent Sr and Nd isotopic ratios (<50 ppm), however, obtaining good reproducibility for Pb and Hf isotopic ratios is more challenging for NIM-P, NIM-N, and AN-G due to a variety of factors, including postcrystallization Pb mobility and the presence of accessory zircon. Collectively, these results form a comprehensive new database that can be used by the geochemical community for evaluating the radiogenic isotope and trace element compositions of volcanic and plutonic mafic-ultramafic rocks.

High-precision 87Sr/86Sr analyses in wines and their use as a geological fingerprint for tracing geographic provenance.

PubMed

Marchionni, Sara; Braschi, Eleonora; Tommasini, Simone; Bollati, Andrea; Cifelli, Francesca; Mulinacci, Nadia; Mattei, Massimo; Conticelli, Sandro

2013-07-17

The radiogenic isotopic compositions of inorganic heavy elements such as Sr, Nd, and Pb of the food chain may constitute a reliable geographic fingerprint, their isotopic ratios being inherited by the geological substratum of the territory of production. The Sr isotope composition of geomaterials (i.e., rocks and soils) is largely variable, and it depends upon the age of the rocks and their nature (e.g., genesis, composition). In this study we developed a high-precision analytical procedure for determining Sr isotopes in wines at comparable uncertainty levels of geological data. With the aim of verifying the possibility of using Sr isotope in wine as a reliable tracer for geographic provenance, we performed Sr isotope analyses of 45 bottled wines from four different geographical localities of the Italian peninsula. Their Sr isotope composition has been compared with that of rocks from the substrata (i.e., rocks) of their vineyards. In addition wines from the same winemaker but different vintage years have been analyzed to verify the constancy with time of the (87)Sr/(86)Sr. Sr isotope compositions have been determined by solid source thermal ionization mass spectrometry following purification of Sr in a clean laboratory. (87)Sr/(86)Sr of the analyzed wines is correlated with the isotopic values of the geological substratum of the vineyards, showing little or no variation within the same vineyard and among different vintages. Large (87)Sr/(86)Sr variation is observed among wines from the different geographical areas, reinforcing the link with the geological substratum of the production territory. This makes Sr isotopes a robust geochemical tool for tracing the geographic authenticity and provenance of wine.

Isotope dependence of the Zeeman effect in lithium-like calcium

PubMed Central

Köhler, Florian; Blaum, Klaus; Block, Michael; Chenmarev, Stanislav; Eliseev, Sergey; Glazov, Dmitry A.; Goncharov, Mikhail; Hou, Jiamin; Kracke, Anke; Nesterenko, Dmitri A.; Novikov, Yuri N.; Quint, Wolfgang; Minaya Ramirez, Enrique; Shabaev, Vladimir M.; Sturm, Sven; Volotka, Andrey V.; Werth, Günter

2016-01-01

The magnetic moment μ of a bound electron, generally expressed by the g-factor μ=−g μB s ħ−1 with μB the Bohr magneton and s the electron's spin, can be calculated by bound-state quantum electrodynamics (BS-QED) to very high precision. The recent ultra-precise experiment on hydrogen-like silicon determined this value to eleven significant digits, and thus allowed to rigorously probe the validity of BS-QED. Yet, the investigation of one of the most interesting contribution to the g-factor, the relativistic interaction between electron and nucleus, is limited by our knowledge of BS-QED effects. By comparing the g-factors of two isotopes, it is possible to cancel most of these contributions and sensitively probe nuclear effects. Here, we present calculations and experiments on the isotope dependence of the Zeeman effect in lithium-like calcium ions. The good agreement between the theoretical predicted recoil contribution and the high-precision g-factor measurements paves the way for a new generation of BS-QED tests. PMID:26776466

METHOD OF PREPARING RADIOACTIVE CESIUM SOURCES

DOEpatents

Quinby, T.C.

1963-12-17

A method of preparing a cesium-containing radiation source with physical and chemical properties suitable for high-level use is presented. Finely divided silica is suspended in a solution containing cesium, normally the fission-product isotope cesium 137. Sodium tetraphenyl boron is then added to quantitatively precipitate the cesium. The cesium-containing precipitate is converted to borosilicate glass by heating to the melting point and cooling. Up to 60 weight percent cesium, with a resulting source activity of up to 21 curies per gram, is incorporated in the glass. (AEC)

Solar neutrino production of technetium-97 and technetium-98.

PubMed

Cowan, G A; Haxton, W C

1982-04-02

It may be possible to determine the boron-8 solar neutrino flux, averaged over the past several million years, from the concentration of technetium-98 in molybdenite. The mass spectrometry of this system is greatly simplified by the absence of stable technetium isotopes, and the presence of the fission product technetium-99 provides a monitor of uiranium-induced backgrounds. This geochemical experiment could provide the first test of nonstandard solar models that suggest a relation between the chlorine-37 solar neutrino puzzle and the recent ice age.

Isotopic Abundances as Tracers of the Processes of Lunar Formation

NASA Astrophysics Data System (ADS)

Pahlevan, K.

2011-12-01

Ever since Apollo, isotopic abundances have been used as tracers to study lunar formation, in particular, to study the sources of the lunar material. In the last decade, however, a number of isotopic similarities have been observed between the lunar samples and the Earth's mantle such that these two reservoirs are now known to be indistinguishable from one another to high precision for a variety of isotopic tracers. This occurs against the backdrop of a Solar System that exhibits widespread heterogeneity with respect to these tracers, a situation that strongly argues that the source of the lunar material is the silicate Earth. To reconcile this observation with the fact that the Moon is thought to result from the collision of two isotopically distinct planetary bodies, a scenario has emerged in which the material from the Moon-forming impactor and the proto-Earth are homogenized in the aftermath of the giant impact. This takes place via turbulent mixing in the time after the giant impact but before lunar accretion while the Earth-Moon system exists in the form of a continuous, high-temperature fluid. Importantly, this high-temperature phase of the evolution occurs in the presence of at least two phases (liquid + vapor) making possible chemical and isotopic fractionation. While equilibrium isotopic fractionation tends to zero at high temperatures, and the post giant impact environment experiences some of the highest temperatures encountered in the Earth sciences, there are several factors that nevertheless make equilibrium isotope effects important probes of this early evolution. (1) Because the vaporization of silicates involves decomposition reactions, the bonding environment for elements in the liquid is often very different from that in the vapor. This difference makes the magnitude of isotopic fractionation intrinsically large, even at the relevant temperatures. (2) Since the isotopic composition of a silicate liquid and co-existing vapor are distinctly different, if the Moon preferentially forms from the liquid or vapor relative to the Earth, mass-dependent isotopic differences at the planetary scale may arise. The large density contrast between liquid and vapor makes phase separation possible. (3) The precision with which planetary isotopic compositions can be determined has increased such that measurements are sensitive to even small degrees of high-temperature phase separation. Using thermodynamic models of silicate liquids to determine the partial vaporization behavior of the major elements, we will present calculations of isotopic fractionation due to liquid-vapor separation for the elements iron, magnesium, silicon, and oxygen. Improvements in analytical precision have largely settled the question of the source of the lunar material - the Earth's mantle - and isotopic measurements are now beginning to yield insight into the high-temperatures processes operating during lunar formation.

Photochemical isotope separation

DOEpatents

Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Greiner, Norman R.; Boyer, Keith

1987-01-01

A process for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium.

Laser isotope separation

DOEpatents

Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Boyer, Keith; Greiner, Norman R.

1988-01-01

A process and apparatus for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photolysis, photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photolysis, photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium.

Isotope separation by laser means

DOEpatents

Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Greiner, Norman R.; Boyer, Keith

1982-06-15

A process for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium.

Instability of seawater pH in the South China Sea during the mid-late Holocene: Evidence from boron isotopic composition of corals

USGS Publications Warehouse

Liu, Yajing; Liu, W.; Peng, Z.; Xiao, Y.; Wei, G.; Sun, W.; He, J.; Liu, Gaisheng; Chou, C.-L.

2009-01-01

We used positive thermal ionization mass spectrometry (PTIMS) to generate high precision ??11B records in Porites corals of the mid-late Holocene from the South China Sea (SCS). The ??11B values of the Holocene corals vary significantly, ranging from 22.2??? to 25.5???. The paleo-pH records of the SCS, reconstructed from the ??11B data, were not stable as previously thought but show a gradual increase from the Holocene thermal optimal and a sharp decrease to modern values. The latter is likely caused by the large amount of anthropogenic CO2 emissions since the Industrial Revolution but variations of atmospheric pCO2 cannot explain the pH change of the SCS before the Industrial Revolution. We suggest that variations of monsoon intensity during the mid-late Holocene may have driven the sea surface pH increase from the mid to late Holocene. Results of this study indicate that the impact of anthropogenic atmospheric CO2 emissions may have reversed the natural pH trend in the SCS since the mid-Holocene. Such ocean pH records in the current interglacial period can help us better understand the physical and biological controls on ocean pH and possibly predict the long-term impact of climate change on future ocean acidification. ?? 2008 Elsevier Ltd. All rights reserved.

Instability of seawater pH in the South China Sea during the mid-late Holocene: Evidence from boron isotopic composition of corals

NASA Astrophysics Data System (ADS)

Liu, Yi; Liu, Weiguo; Peng, Zicheng; Xiao, Yingkai; Wei, Gangjian; Sun, Weidong; He, Jianfeng; Liu, Guijian; Chou, Chen-Lin

2009-03-01

We used positive thermal ionization mass spectrometry (PTIMS) to generate high precision δ 11B records in Porites corals of the mid-late Holocene from the South China Sea (SCS). The δ 11B values of the Holocene corals vary significantly, ranging from 22.2‰ to 25.5‰. The paleo-pH records of the SCS, reconstructed from the δ 11B data, were not stable as previously thought but show a gradual increase from the Holocene thermal optimal and a sharp decrease to modern values. The latter is likely caused by the large amount of anthropogenic CO 2 emissions since the Industrial Revolution but variations of atmospheric pCO 2 cannot explain the pH change of the SCS before the Industrial Revolution. We suggest that variations of monsoon intensity during the mid-late Holocene may have driven the sea surface pH increase from the mid to late Holocene. Results of this study indicate that the impact of anthropogenic atmospheric CO 2 emissions may have reversed the natural pH trend in the SCS since the mid-Holocene. Such ocean pH records in the current interglacial period can help us better understand the physical and biological controls on ocean pH and possibly predict the long-term impact of climate change on future ocean acidification.

High Precision Low-blank Lithium Isotope Ratios in Forams.

NASA Astrophysics Data System (ADS)

Misra, S.; Froelich, P. N.

2007-12-01

We present a high precision (±1‰, 2σ) low blank (<500 fg/ml) method for Li isotope measurements of forams using <2 ng of Li by single collector Quad ICP-MS (Agilent 7500cs). The Li isotope ratio of seawater (δ7Li) recorded in planktonic forams has the potential to constrain the evolution of seawater chemistry and elucidate the factors driving variations of oceanic mass balances linked to the continental and sea floor/hydrothermal silica cycles. In addition a δ7Li record of seawater will complement other long-term recorders of seawater chemistry such as Sr, Os and S isotopes. Li isotope measurements of forams are limited by several factors: low Li concentrations in forams (1-2 ppm), instrument-induced fractionation and mass bias effects, matrix effects, high Li blanks and incomplete recovery of Li during column separation. Modest concentrations of alkali and alkaline earth elements in the matrix result in variable mass bias in measured Li isotope ratios. Even worse, Li strongly fractionates during chromatographic clean-up to remove Na+, Ca2+ and Mg2+, from +100‰ in the leading edge to - 100‰ in the trailing edge of elution peaks (Urey 1938). Consequently, miniscule incomplete recoveries of Li during chromatographic separations can result in large unrecognized isotope fractionation of eluents. Large mass-dependent fractionation caused by a difference of 17% in mass between 6Li and 7Li, makes Li a powerful tracer of geochemical processes, but also promotes large and difficult-to-fix isotope fractionations during laboratory chemical processing. Matrix effects of Na & Ca and of column chromatography on Li isotope ratios were investigated using artificial Li solutions representative of foram compositions (matrix matching). Li/Ca and Li/Na ratios in cleaned forams are 10 μmol/mol and 3 mmol/mol respectively. An ICP-MS tolerance limit of 20 ppb for Na and 20 μM for Ca was established, much higher tolerances than by TIMS. A single step chromatographic method to quantitatively separate Li from matrix elements using both small volume resin (3.4 meq/2ml AG50W-X8) and acid (6 ml of 0.5N HCl) was developed. Our low blank (<0.5 pg/ml) and high yield (>99.99%) column method minimizes errors in measured Li isotope ratios associated with incomplete column recovery and presence of matrix elements. High sensitivity and precision achieved with a 7500cs using cold plasma (600W), soft extraction and peak jumping coupled with very low sample to blank ratios enables high precision (±1‰, 2σ) statistically significant Li isotope measurements using very small mass of Li (0.8 ng). The development of this technique makes possible good quality Li isotope measurements from samples that are mass limited for Li, i.e., reasonable number of picked forams. This will enable us to test interferences regarding chemical cleaning and species effects in planktonic forams along the road toward creating a δ7Li record of seawater for the Cenozoic.

Diagnosis and assessment of skeletal related disease using calcium 41

DOEpatents

Hillegonds, Darren J [Oakland, CA; Vogel, John S [San Jose, CA; Fitzgerald, Robert L [Encinitas, CA; Deftos, Leonard J [Del Mar, CA; Herold, David [Del Mar, CA; Burton, Douglas W [San Diego, CA

2012-05-15

A method of determining calcium metabolism in a patient comprises the steps of administering radioactive calcium isotope .sup.41Ca to the patient, allowing a period of time to elapse sufficient for dissemination and reaction of the radioactive calcium isotope .sup.41Ca by the patient, obtaining a sample of the radioactive calcium isotope .sup.41Ca from the patient, isolating the calcium content of the sample in a form suitable for precise measurement of isotopic calcium concentrations, and measuring the calcium content to determine parameters of calcium metabolism in the patient.

Diagnosis and assessment of skeletal related disease using calcium 41

DOEpatents

Hillegonds, Darren J.; Vogel, John S.; Fitzgerald, Robert L.; Deftos, Leonard J.; Herold, David; Burton, Douglas W.

2013-03-05

A method of determining calcium metabolism in a patient comprises the steps of administering radioactive calcium isotope .sup.41Ca to the patient, allowing a period of time to elapse sufficient for dissemination and reaction of the radioactive calcium isotope .sup.41Ca by the patient, obtaining a sample of the radioactive calcium isotope .sup.41Ca from the patient, isolating the calcium content of the sample in a form suitable for precise measurement of isotopic calcium concentrations, and measuring the calcium content to determine parameters of calcium metabolism in the patient.

Relevance of the Nuclear Quantum Effects on the Proton/Deuteron Transmission through Hexagonal Boron Nitride and Graphene Monolayers

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

Ekanayake, Niranji; Huang, Jingsong; Jakowski, Jacek

According to recent experiments, atomically thin hexagonal boron nitride and graphene are permeable to protons and deuterons (and not to other atomic species), and the experimental estimates of the activation energy are lower than the theoretical values by about 0.5 eV for the isolated proton-membrane transfer model. Our analysis of the electronic potential energy surfaces along the normal to the transmission direction, obtained using correlated electronic structure methods, suggests that the aqueous environment is essential to stabilize the proton { as opposed to the hydrogenatom { transmission. Therefore, the process is examined within a molecular model of H 2O {more » H(D) + { material { H 2O. Exact quantum-mechanical scattering calculations are performed to assess the relevance of the nuclear quantum eects, such as tunneling factors and the kinetic isotope eect (KIE). Deuteration is found to aect the thermal reaction rate constants (KIE of 3-4 for hexagonal boron nitride and 20-30 for the graphene) and to eectively lower the barriers to the proton transfer by 0.2 and 0.4 eV for the two membranes, respectively. This lowering eect is reduced for the deuteron by approximately a factor of three. A more comprehensive description of the proton transmission is likely to require an extended explicit aqueous environment.« less

Relevance of the Nuclear Quantum Effects on the Proton/Deuteron Transmission through Hexagonal Boron Nitride and Graphene Monolayers

DOE PAGES

Ekanayake, Niranji; Huang, Jingsong; Jakowski, Jacek; ...

2017-10-02

According to recent experiments, atomically thin hexagonal boron nitride and graphene are permeable to protons and deuterons (and not to other atomic species), and the experimental estimates of the activation energy are lower than the theoretical values by about 0.5 eV for the isolated proton-membrane transfer model. Our analysis of the electronic potential energy surfaces along the normal to the transmission direction, obtained using correlated electronic structure methods, suggests that the aqueous environment is essential to stabilize the proton { as opposed to the hydrogenatom { transmission. Therefore, the process is examined within a molecular model of H 2O {more » H(D) + { material { H 2O. Exact quantum-mechanical scattering calculations are performed to assess the relevance of the nuclear quantum eects, such as tunneling factors and the kinetic isotope eect (KIE). Deuteration is found to aect the thermal reaction rate constants (KIE of 3-4 for hexagonal boron nitride and 20-30 for the graphene) and to eectively lower the barriers to the proton transfer by 0.2 and 0.4 eV for the two membranes, respectively. This lowering eect is reduced for the deuteron by approximately a factor of three. A more comprehensive description of the proton transmission is likely to require an extended explicit aqueous environment.« less

Hydrology and water quality in the Green River and surrounding agricultural areas near Green River in Emery and Grand Counties, Utah, 2004-05

USGS Publications Warehouse

Gerner, S.J.; Spangler, L.E.; Kimball, B.A.; Wilberg, D.E.; Naftz, D.L.

2006-01-01

Water from the Colorado River and its tributaries is used for municipal and industrial purposes by about 27 million people and irrigates nearly 4 million acres of land in the Western United States. Water users in the Upper Colorado River Basin consume water from the Colorado River and its tributaries, reducing the amount of water in the river. In addition, application of water to agricultural land within the basin in excess of crop needs can increase the transport of dissolved solids to the river. As a result, dissolved-solids concentrations in the Colorado River have increased, affecting downstream water users. During 2004-05, the U.S. Geological Survey, in cooperation with the Natural Resources Conservation Service, investigated the occurrence and distribution of dissolved solids in water from the agricultural areas near Green River, Utah, and in the adjacent reach of the Green River, a principle tributary of the Colorado River.The flow-weighted concentration of dissolved solids diverted from the Green River for irrigation during 2004 and 2005 was 357 milligrams per liter and the mean concentration of water collected from seeps and drains where water was returning to the river during low-flow conditions was 4,170 milligrams per liter. The dissolved-solids concentration in water from the shallow part of the ground-water system ranged from 687 to 55,900 milligrams per liter.Measurable amounts of dissolved solids discharging to the Green River are present almost exclusively along the river banks or near the mouths of dry washes that bisect the agricultural areas. The median dissolved-solids load in discharge from the 17 drains and seeps visited during the study was 0.35 ton per day. Seasonal estimates of the dissolved-solids load discharging from the study area ranged from 2,800 tons in the winter to 6,400 tons in the spring. The estimate of dissolved solids discharging from the study area annually is 15,700 tons.Water samples collected from selected sites within the Green River agricultural areas were analyzed for naturally occurring isotopes of strontium and boron, which can be useful for differentiating dissolved-solids sources. Substantial variations in the delta strontium-87 and delta boron-11 values among the sites were measured. Canal and river samples had relatively low concentrations of strontium and the most positive (heavier) isotopic ratios, while drains and seeps had a wide range of strontium concentrations and isotopic ratios that generally were less positive (lighter). Further study of the variation in strontium and boron concentrations and isotope ratios may provide a means to distinguish end members and discern processes affecting dissolved solids within the Green River study area; however, the results from isotope data collected during this study are inconclusive.Flow and seepage losses were estimated for the three main canals in the study area for May 2 to October 4 in any given year. This period coincides with the frost-free period in the Green River area. Estimated diversion from the Green River into the Thayn, East Side, and Green River Canals is 6,600, 6,070, and 19,900 acre-feet, respectively. The estimated seepage loss to ground water from the Thayn, East Side, and Green River Canals during the same period is 1,550, 1,460, and 4,710 acre-feet, respectively.

Precision mass measurements of neutron-rich Co isotopes beyond N =40

NASA Astrophysics Data System (ADS)

Izzo, C.; Bollen, G.; Brodeur, M.; Eibach, M.; Gulyuz, K.; Holt, J. D.; Kelly, J. M.; Redshaw, M.; Ringle, R.; Sandler, R.; Schwarz, S.; Stroberg, S. R.; Sumithrarachchi, C. S.; Valverde, A. A.; Villari, A. C. C.

2018-01-01

The region near Z =28 and N =40 is a subject of great interest for nuclear structure studies due to spectroscopic signatures in 68Ni suggesting a subshell closure at N =40 . Trends in nuclear masses and their derivatives provide a complementary approach to shell structure investigations via separation energies. Penning trap mass spectrometry has provided precise measurements for a number of nuclei in this region; however, a complete picture of the mass surfaces has so far been limited by the large uncertainty remaining for nuclei with N >40 along the iron (Z =26 ) and cobalt (Z =27 ) chains because these species are not available from traditional isotope separator online rare isotope facilities. The Low-Energy Beam and Ion Trap Facility at the National Superconducting Cyclotron Laboratory is the first and only Penning trap mass spectrometer coupled to a fragmentation facility and therefore presents the unique opportunity to perform precise mass measurements of these elusive isotopes. Here we present the first Penning trap measurements of Co,6968, carried out at this facility. Some ambiguity remains as to whether the measured values are ground-state or isomeric-state masses. A detailed discussion is presented to evaluate this question and to motivate future work. In addition, we perform ab initio calculations of ground-state and two-neutron separation energies of cobalt isotopes with the valence-space in-medium similarity renormalization group approach based on a particular set of two- and three-nucleon forces that predict saturation in infinite matter. We discuss the importance of these measurements and calculations for understanding the evolution of nuclear structure near 68Ni.

Recent Developments in MC-ICP-MS for Uranium Isotopic Determination from Small Samples.

NASA Astrophysics Data System (ADS)

Field, P.; Lloyd, N. S.

2016-12-01

V002: Advances in approaches and instruments for isotope studies Session ID#: 12653 Recent Developments in MC-ICP-MS for Uranium Isotopic Determination from small samples.M. Paul Field 1 & Nicholas S. Lloyd. 1 Elemental Scientific Inc., Omaha, Nebraska, USA. field@icpms.com 2 Thermo Fisher Scientific, Hanna-Kunath-Str. 11, 28199 Bremen, Germany. nicholas.lloyd@thermofisher.com Uranium isotope ratio determination for nuclear, nuclear safeguards and for environmental applications can be challenging due to, 1) the large isotopic differences between samples and 2) low abundance of 234U and 236U. For some applications the total uranium quantities can be limited, or it is desirable to run at lower concentrations for radiological protection. Recent developments in inlet systems and detector technologies allow small samples to be analyzed at higher precisions using MC-ICP-MS. Here we evaluate the combination of Elemental Scientific apex omega desolvation system and microFAST-MC dual loop-loading flow-injection system with the Thermo Scientific NEPTUNE Plus MC-ICP-MS. The inlet systems allow for the automated syringe loading and injecting handling of small sample volumes with efficient desolvation to minimize the hydride interference on 236U. The highest ICP ion sampling efficiency is realized using the Thermo Scientific Jet Interface. Thermo Scientific 1013 ohm amplifier technology allows small ion beams to be measured at higher precision, offering the highest signal/noise ratio with a linear and stable response that covers a wide dynamic range (ca. 1 kcps - 30 Mcps). For nanogram quantities of low enriched and depleted uranium standards the 235U was measured with 1013 ohm amplifier technology. The minor isotopes (234U and 236U) were measured by SEM ion counters with RPQ lens filters, which offer the lowest detection limits. For sample amounts ca. 20 ng the minor isotopes can be moved onto 1013 ohm amplifiers and the 235U onto standard 1011 ohm amplifier. To illustrate the application a set of solutions from environmental particles [1] were analyzed, the use of precise three isotope ratio plots allows for source attribution with increased confidence. [1] Lloyd et al. 2009, J. Anal. At. Spectrom., 24(6), 752-758.

High Precision Iron Isotope Compositions in Components From the Allende CV3 Meteorite by MC-ICP-MS

NASA Astrophysics Data System (ADS)

Mullane, E.; Russell, S. S.; Weiss, D.; Mason, T. F.; Gounelle, M.

2001-12-01

Four chondrules and one matrix sample of Allende were examined for Fe-isotope frac-tionation, using multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). Iron is the most volatile major constituent of chondrules and a recent study [1] suggested that solar system Fe was initially isotopically homogeneous. Thus, any isotopic variation is likely due to mass fractionation during nebular process-ing. The chondrule samples were split. One portion was subject to a standard acid dis-solution whilst the other was polished, ena-bling textural and compositional characteri-zation. Fe, Cu and Zn are separated from the remaining matrix elements [2], removing potential interfering ions from the solution. 100 % elemental recovery (within error) is achieved, ensuring that chromatographic fractionation does not occur [2]. Hydrogen is bled into the collision cell, minimising Ar polyatomic species interferences. Typical precisions of 0.1‰ (2σ ) for 54Fe/56Fe ratios are achieved for 75 replicates. Instrumental mass bias is assessed using (1) sample-standard brack-eting and (2) doping with Cu. A variation of 0.8‰ /amu is observed, which is approximately 18 times the analyti-cal uncertainty at the 2σ level. Our high precision data show that: (1) Allende chondrules and matrix exhibit clear isotopic variation in iron. (2) δ 54Fe val-ues appear to be correlated to the bulk FeO content, with the more iron rich samples enriched in the lighter 54Fe isotope. (3) δ 54Fe values appear to be unre-lated to texture, and consequently to the temperature of chondrule formation. Bulk Fe-content may be a proxy for the amount of volatilisation experienced, and volatilisation of Fe in chondrule precursor material has resulted in a residue of the heavier Fe isotopes. Chondrules are known to have often experienced several heating events, and their texture primarily reflects the nature of the last event. Thus, the lack of correlation between the δ 54Fe value and chondrule texture suggests that Fe-isotope composi-tion was derived from chondrule precursor material. [1] Zhu et al. (2001) Nature 412, p.311 [2] Mullane et al. (2001) LPS XXXII, No.1545.

Light elements burning reaction rates at stellar temperatures as deduced by the Trojan Horse measurements

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

Lamia, L.; Spitaleri, C.; La Cognata, M.

2015-02-24

Experimental nuclear astrophysics aims at determining the reaction rates for astrophysically relevant reactions at their Gamow energies. For charged-particle induced reactions, the access to these energies is usually hindered, in direct measurements, by the presence of the Coulomb barrier between the interacting particles or by electron screening effects, which make hard the determination of the bare-nucleus S(E)-factor of interest for astrophysical codes. The use of the Trojan Horse Method (THM) appears as one of the most suitable tools for investigating nuclear processes of interest for astrophysics. Here, in view of the recent TH measurements, the main destruction channels for deuteriummore » ({sup 2}H), for the two lithium {sup 6,7}Li isotopes, for the {sup 9}Be and the one for the two boron {sup 10,11}B isotopes will be discussed.« less

Geologic map showing springs rich in carbon dioxide or or chloride in California

USGS Publications Warehouse

Barnes, Ivan; Irwin, William P.; Gibson, H.A.

1975-01-01

Carbon dioxide- and chloride-rich springs occur in all geologic provinces in California, but are most abundant in the Coast Ranges and the Great Valley. The carbon-dioxide-rich springs issue mainly from Franciscan terrane; they also are rich in boron and are of the metamorphic type (White, 1957). Based on isotopic data, either the carbon dioxide or the water, or both, may be of metamorphic origin. Because of high magnesium values, the water of many of the carbon-dioxide-rich springs is thought to have passed through serpentinite. The chloride-rich waters are most common in rocks of the Great Valley sequence. Nearly all are more dilute than present-day sea water. The similarity in isotopic compositions of the metamorphic carbon-dioxide-rich water and the chloride-rich water may indicate a similar extent of water-rock interaction.

AMS with light nuclei at small accelerators

NASA Astrophysics Data System (ADS)

Stan-Sion, C.; Enachescu, M.

2017-06-01

AMS applications with lighter nuclei are presented. It will be shown how Carbon-14, Boron-10, Beryllium-10, and Tritium-3 can be used to provide valuable information in forensic science, environmental physics, nuclear pollution, in material science and for diagnose of the plasma confinement in fusion reactors. Small accelerators are reliable, efficient and possess the highest ion beam transmissions that confer high precision in measurements.

Application of isotope dilution inductively coupled plasma mass spectrometry to the analysis of marine sediments

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

McLaren, J.W.; Beauchemin, D.; Berman, S.S.

1987-02-15

Isotope dilution inductively coupled plasma mass spectrometry (ICP-MS) has been applied to the determination of 11 trace elements (Cr, Ni, Zn, Sr, Mo, Cd, Sn, Sb, Tl, Pb, and U) in the marine sediment reference materials MESS-1 and BCSS-1. Accuracy and, especially, precision are better than those that can be easily achieved by other ICP-MS calibration strategies, as long as isotopic equilibration is achieved and the isotopes used for the ratio measurement are free of isobaric interferences by molecular species. The measurement of the isotope ratios on unspiked samples provides a sensitive diagnostic of such interferences.

Stabile Chlorine Isotope Study of Martian Shergottites and Nakhlites; Whole Rock and Acid Leachates and Residues

NASA Technical Reports Server (NTRS)

Nakamura, N.; Nyquist, L. E.; Reese, Y.; Shih, C-Y; Fujitani, T.; Okano, O.

2011-01-01

We have established a precise analytical technique for stable chlorine isotope measurements of tiny planetary materials by TIMS (Thermal Ionization Mass Spectrometry) [1], for which the results are basically consistent with the IRMS tech-nique (gas source mass spectrometry) [2,3,4]. We present here results for Martian shergottites and nakhlites; whole rocks, HNO3-leachates and residues, and discuss the chlorine isotope evolution of planetary Mars.

Frontiers of QC Laser spectroscopy for high precision isotope ratio analysis of greenhouse gases

NASA Astrophysics Data System (ADS)

Emmenegger, Lukas; Mohn, Joachim; Harris, Eliza; Eyer, Simon; Ibraim, Erkan; Tuzson, Béla

2016-04-01

An important milestone for laser spectroscopy was achieved when isotope ratios of greenhouse gases were reported at precision levels that allow addressing research questions in environmental sciences. Real-time data with high temporal resolution at moderate cost and instrument size make the optical approach highly attractive, complementary to the well-established isotope-ratio mass-spectrometry (IRMS) method. Especially appealing, in comparison to IRMS, is the inherent specificity to structural isomers having the same molecular mass. Direct absorption in the MIR in single or dual QCL configuration has proven highly reliable for the sta-ble isotopes of CO2, N2O and CH4. The longest time series of real-time measurements is currently available for δ13C and δ18O in CO2 at the high-alpine station Jung-fraujoch. At this well-equipped site, QCL based direct absorption spectroscopy (QCLAS) measurements are ongoing since 2008 1,2. Applications of QCLAS for N2O and CH4 stable isotopes are considerably more challenging because of the lower atmospheric mixing ratios, especially for the less abundant species, such as N218O and CH3D. For high precision (< 0.1 ‰) measurements in ambient air, QCLAS may be combined with a fully automated preconcentration unit yielding an up to 500 times concentration increase and the capability to separate the target gas from spectral interferants by se-quential desorption 3. Here, we review our recent developments on high precision isotope ratio analysis of greenhouse gases, with special focus on the isotopic species of N2O and CH4. Furthermore, we show environ-mental applications illustrating the highly valuable information that isotope ratios of atmospheric trace gases can carry. For example, the intramolecular distribution of 15N in N2O gives important information on the geochemical cycle of N2O4-6, while the analysis of δ13C and δ D in CH4 may be applied to disentangle microbial, fossil and landfill sources 7. 1 Sturm, P., Tuzson, B., Henne, S. & Emmenegger, L. Tracking isotopic signatures of CO2 at the high altitude site Jungfraujoch with laser spectroscopy: Analytical improvements and representative re-sults. Atmospheric Measurement Techniques 6, 1659-1671 (2013). 2 Tuzson, B. et al. Continuous isotopic composition measurements of tropospheric CO2 at Jungfraujoch (3580 m a.s.l.), Switzerland: real-time observation of regional pollution events. Atmospheric Chemistry and Physics 11, 1685-1696 (2011). 3 Mohn, J. et al. A liquid nitrogen-free preconcentration unit for measurements of ambient N2O isotopomers by QCLAS. Atmospheric Measurement Techniques 3, 609-618 (2010). 4 Wolf, B. et al. First on-line isotopic characterization of N2O above intensively managed grassland. Biogeosciences 12, 2517-1960 (2015). 5 Harris, E. et al. Nitrous oxide and methane emissions and nitrous oxide isotopic composition from waste incineration in Switzerland. Waste Management 35, 135-140 (2015). 6 Harris, E. et al. Isotopic evidence for nitrous oxide production pathways in a partial nitritation-anammox reactor. Water Research 83, 258-270 (2015). 7 Eyer, S. et al. Real-time analysis of δ13C- and δ D-CH4 in ambient air with laser spectroscopy: method development and first intercomparison results. Atmos. Meas. Tech. Discuss. 8, 8925-8970 (2015).

New methods for measuring atmospheric heavy noble gas isotope and elemental ratios in ice core samples.

PubMed

Bereiter, Bernhard; Kawamura, Kenji; Severinghaus, Jeffrey P

2018-05-30

The global ocean constitutes the largest heat buffer in the global climate system, but little is known about its past changes. The isotopic and elemental ratios of heavy noble gases (krypton and xenon), together with argon and nitrogen in trapped air from ice cores, can be used to reconstruct past mean ocean temperatures (MOTs). Here we introduce two successively developed methods to measure these parameters with a sufficient precision to provide new constraints on past changes in MOT. The air from an 800-g ice sample - containing roughly 80 mL STP air - is extracted and processed to be analyzed on two independent dual-inlet isotope ratio mass spectrometers. The primary isotope ratios (δ 15 N, δ 40 Ar and δ 86 Kr values) are obtained with precisions in the range of 1 per meg (0.001‰) per mass unit. The three elemental ratio values δKr/N 2 , δXe/N 2 and δXe/Kr are obtained using sequential (non-simultaneous) peak-jumping, reaching precisions in the range of 0.1-0.3‰. The latest version of the method achieves a 30% to 50% better precision on the elemental ratios and a twofold better sample throughput than the previous one. The method development uncovered an unexpected source of artefactual gas fractionation in a closed system that is caused by adiabatic cooling and warming of gases (termed adiabatic fractionation) - a potential source of measurement artifacts in other methods. The precisions of the three elemental ratios δKr/N 2 , δXe/N 2 and δXe/Kr - which all contain the same MOT information - suggest smaller uncertainties for reconstructed MOTs (±0.3-0.1°C) than previous studies have attained. Due to different sensitivities of the noble gases to changes in MOT, δXe/N 2 provides the best constraints on the MOT under the given precisions followed by δXe/Kr, and δKr/N 2 ; however, using all of them helps to detect methodological artifacts and issues with ice quality. Copyright © 2018 John Wiley & Sons, Ltd.

Microwave digestion preparation and ICP determination of boron in human plasma

NASA Technical Reports Server (NTRS)

Ferrando, A. A.; Green, N. R.; Barnes, K. W.; Woodward, B.

1993-01-01

A microwave digestion procedure, followed by Inductively Coupled Argon Plasma Spectroscopy, is described for the determination of boron (B) in human plasma. The National Institute of Standards and Technology (NIST) currently does not certify the concentration of B in any substance. The NIST citrus leaves 1572 (CL) Standard Reference Material (SRM) and wheat flour 1567a (WF) were chosen to determine the efficacy of digestion. CL and WF values compare favorably to those obtained from an open-vessel, wet digestion followed by ICP, and by neutron activation and mass spectrometric measurements. Plasma samples were oxidized by doubled-distilled ultrapure HNO3 in 120 mL PFA Teflon vessels. An MDS-81D microwave digestion procedure allows for rapid and relatively precise determination of B in human plasma, while limiting handling hazards and sources of contamination.

Macroscopic self-reorientation of interacting two-dimensional crystals

PubMed Central

Woods, C. R.; Withers, F.; Zhu, M. J.; Cao, Y.; Yu, G.; Kozikov, A.; Ben Shalom, M.; Morozov, S. V.; van Wijk, M. M.; Fasolino, A.; Katsnelson, M. I.; Watanabe, K.; Taniguchi, T.; Geim, A. K.; Mishchenko, A.; Novoselov, K. S.

2016-01-01

Microelectromechanical systems, which can be moved or rotated with nanometre precision, already find applications in such fields as radio-frequency electronics, micro-attenuators, sensors and many others. Especially interesting are those which allow fine control over the motion on the atomic scale because of self-alignment mechanisms and forces acting on the atomic level. Such machines can produce well-controlled movements as a reaction to small changes of the external parameters. Here we demonstrate that, for the system of graphene on hexagonal boron nitride, the interplay between the van der Waals and elastic energies results in graphene mechanically self-rotating towards the hexagonal boron nitride crystallographic directions. Such rotation is macroscopic (for graphene flakes of tens of micrometres the tangential movement can be on hundreds of nanometres) and can be used for reproducible manufacturing of aligned van der Waals heterostructures. PMID:26960435

Coupled Nd-142, Nd-143 and Hf-176 Isotopic Data from 3.6-3.9 Ga Rocks: New Constraints on the Timing of Early Terrestrial Chemical Reservoirs

NASA Technical Reports Server (NTRS)

Bennett, Vickie C.; Brandon, alan D.; Hiess, Joe; Nutman, Allen P.

2007-01-01

Increasingly precise data from a range of isotopic decay schemes, including now extinct parent isotopes, from samples of the Earth, Mars, Moon and meteorites are rapidly revising our views of early planetary differentiation. Recognising Nd-142 isotopic variations in terrestrial rocks (which can only arise from events occurring during the lifetime of now extinct Sm-146 [t(sub 1/2)=103 myr]) has been an on-going quest starting with Harper and Jacobsen. The significance of Nd-142 variations is that they unequivocally reflect early silicate differentiation processes operating in the first 500 myr of Earth history, the key time period between accretion and the beginning of the rock record. The recent establishment of the existence of Nd-142 variations in ancient Earth materials has opened a new range of questions including, how widespread is the evidence of early differentiation, how do Nd-142 compositions vary with time, rock type and geographic setting, and, combined with other types of isotopic and geochemical data, what can Nd-142 isotopic variations reveal about the timing and mechanisms of early terrestrial differentiation? To explore these questions we are determining high precision Nd-142, Nd-143 and Hf-176 isotopic compositions from the oldest well preserved (3.63- 3.87 Ga), rock suites from the extensive early Archean terranes of southwest Greenland and western Australia.

A comparison of lead-isotope measurements on exploration-type samples using inductively coupled plasma and thermal ionization mass spectrometry

USGS Publications Warehouse

Gulson, B.L.; Meier, A.L.; Church, S.E.; Mizon, K.J.

1989-01-01

Thermal ionization mass spectrometry (TI-MS) has long been the method of choice for Pb-isotope determinations. More recently, however, inductively coupled plasma mass spectrometry (ICP-MS) has been used to determine Pb-isotope ratios for mineral exploration. The ICP-MS technique, although not as precise as TI-MS, may promote a wider application of Ph-isotope ratio methods because it allows individual isotopes to be determined more rapidly, generally without need for chemical separation (e.g., Smith et al., 1984; Hinners et al., 1987). To demonstrate the utility of the ICP-MS method, we have conducted a series of Pb-isotope measurements on several suites of samples using both TI-MS and ICP-MS. ?? 1989.

Laser isotope separation

DOEpatents

Robinson, C.P.; Reed, J.J.; Cotter, T.P.; Boyer, K.; Greiner, N.R.

1975-11-26

A process and apparatus for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light is described. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photolysis, photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photolysis, photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium.

Photochemical isotope separation

DOEpatents

Robinson, C.P.; Jensen, R.J.; Cotter, T.P.; Greiner, N.R.; Boyer, K.

1987-04-28

A process is described for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium. 8 figs.

Detailed study of water quality, bottom sediment, and biota associated with irrigation drainage in the Salton Sea area, California, 1988-90

USGS Publications Warehouse

Setmire, J.G.; Schroeder, R.A.; Densmore, J.N.; Goodbred, S.O.; Audet, D.J.; Radke, W.R.

1993-01-01

Results of a detailed study by the National Irrigation Water-Quality Program (NIWQP), U.S. Department of the Interior, indicate that factors controlling contaminant concentrations in subsurface irrigation drainwater in the Imperial Valley are soil characteristics, hydrology, and agricultural practices. Higher contaminant concentrations commonly were associated with clayey soils, which retard the movement of irrigation water and thus increase the degree of evaporative concentration. Regression of hydrogen- and oxygen-isotope ratios in samples collected from sumps yields a linear drainwater evaporation line that extrapolates through the isotopic composition of Colorado River water, thus demonstrating that Colorado River water is the sole source of subsurface drainwater in the Imperial Valley. Ratios of selenium to chloride indicate that selenium present in subsurface drainwater throughout the Imperial Valley originates from the Colorado River. The selenium load discharged to the Salton Sea from the Alamo River, the largest contributor, is about 6.5 tons/yr. Biological sampling and analysis showed that drainwater contaminants, including selenium, boron, and DDE, are accumulating in tissues of migratory and resident birds that use food sources in the Imperial Valley and the Salton Sea. Selenium concentration in fish-eating birds, shorebirds, and the endangered Yuma clapper rail were at levels that could affect reproduction. Boron concentrations in migratory waterfowl and resident shorebirds were at levels that potentially could cause reduced growth in young. As a result of DDE contamination of food sources, waterfowl and fish-eating birds in the Imperial Valley may be experiencing reproductive impairment.

Very high precision and accuracy analysis of triple isotopic ratios of water. A critical instrumentation comparison study.

NASA Astrophysics Data System (ADS)

Gkinis, Vasileios; Holme, Christian; Morris, Valerie; Thayer, Abigail Grace; Vaughn, Bruce; Kjaer, Helle Astrid; Vallelonga, Paul; Simonsen, Marius; Jensen, Camilla Marie; Svensson, Anders; Maffrezzoli, Niccolo; Vinther, Bo; Dallmayr, Remi

2017-04-01

We present a performance comparison study between two state of the art Cavity Ring Down Spectrometers (Picarro L2310-i, L2140-i). The comparison took place during the Continuous Flow Analysis (CFA) campaign for the measurement of the Renland ice core, over a period of three months. Instant and complete vaporisation of the ice core melt stream, as well as of in-house water reference materials is achieved by accurate control of microflows of liquid into a homemade calibration system by following simple principles of the Hagen-Poiseuille law. Both instruments share the same vaporisation unit in a configuration that minimises sample preparation discrepancies between the two analyses. We describe our SMOW-SLAP calibration and measurement protocols for such a CFA application and present quality control metrics acquired during the full period of the campaign on a daily basis. The results indicate an unprecedented performance for all 3 isotopic ratios (δ2H, δ17O, δ18O ) in terms of precision, accuracy and resolution. We also comment on the precision and accuracy of the second order excess parameters of HD16O and H217O over H218O (Dxs, Δ17O ). To our knowledge these are the first reported CFA measurements at this level of precision and accuracy for all three isotopic ratios. Differences on the performance of the two instruments are carefully assessed during the measurement and reported here. Our quality control protocols extend to the area of low water mixing ratios, a regime in which often atmospheric vapour measurements take place and Cavity Ring Down Analysers show a poorer performance due to the lower signal to noise ratios. We address such issues and propose calibration protocols from which water vapour isotopic analyses can benefit from.

High‐precision determination of lithium and magnesium isotopes utilising single column separation and multi‐collector inductively coupled plasma mass spectrometry

PubMed Central

Misra, Sambuddha; Lloyd, Nicholas; Elderfield, Henry; Bickle, Mike J.

2017-01-01

Rationale Li and Mg isotopes are increasingly used as a combined tool within the geosciences. However, established methods require separate sample purification protocols utilising several column separation procedures. This study presents a single‐step cation‐exchange method for quantitative separation of trace levels of Li and Mg from multiple sample matrices. Methods The column method utilises the macro‐porous AGMP‐50 resin and a high‐aspect ratio column, allowing quantitative separation of Li and Mg from natural waters, sediments, rocks and carbonate matrices following the same elution protocol. High‐precision isotope determination was conducted by multi‐collector inductively coupled plasma mass spectrometry (MC‐ICPMS) on the Thermo Scientific™ NEPTUNE Plus™ fitted with 1013 Ω amplifiers which allow accurate and precise measurements at ion beams ≤0.51 V. Results Sub‐nanogram Li samples (0.3–0.5 ng) were regularly separated (yielding Mg masses of 1–70 μg) using the presented column method. The total sample consumption during isotopic analysis is <0.5 ng Li and <115 ng Mg with long‐term external 2σ precisions of ±0.39‰ for δ7Li and ±0.07‰ for δ26Mg. The results for geological reference standards and seawater analysed by our method are in excellent agreement with published values despite the order of magnitude lower sample consumption. Conclusions The possibility of eluting small sample masses and the low analytical sample consumption make this method ideal for samples of limited mass or low Li concentration, such as foraminifera, mineral separates or dilute river waters. PMID:29078008

δ13C and δ18O isotopic composition of CaCO3 measured by continuous flow isotope ratio mass spectrometry: statistical evaluation and verification by application to Devils Hole core DH-11 calcite

USGS Publications Warehouse

Revesz, Kinga M.; Landwehr, Jurate M.

2002-01-01

A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400 ± 20 µg) of calcium carbonate. This new method streamlines the classical phosphoric acid/calcium carbonate (H3PO4/CaCO3) reaction method by making use of a recently available Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. Conditions for which the H3PO4/CaCO3 reaction produced reproducible and accurate results with minimal error had to be determined. When the acid/carbonate reaction temperature was kept at 26 °C and the reaction time was between 24 and 54 h, the precision of the carbon and oxygen isotope ratios for pooled samples from three reference standard materials was ≤0.1 and ≤0.2 per mill or ‰, respectively, although later analysis showed that materials from one specific standard required reaction time between 34 and 54 h for δ18O to achieve this level of precision. Aliquot screening methods were shown to further minimize the total error. The accuracy and precision of the new method were analyzed and confirmed by statistical analysis. The utility of the method was verified by analyzing calcite from Devils Hole, Nevada, for which isotope-ratio values had previously been obtained by the classical method. Devils Hole core DH-11 recently had been re-cut and re-sampled, and isotope-ratio values were obtained using the new method. The results were comparable with those obtained by the classical method with correlation = +0.96 for both isotope ratios. The consistency of the isotopic results is such that an alignment offset could be identified in the re-sampled core material, and two cutting errors that occurred during re-sampling then were confirmed independently. This result indicates that the new method is a viable alternative to the classical reaction method. In particular, the new method requires less sample material permitting finer resolution and allows automation of some processes resulting in considerable time savings. 

How strange was the Strangelove Ocean? New insights from Boron Isotopes.

NASA Astrophysics Data System (ADS)

Henehan, M. J.; Ridgwell, A.; Thomas, E.; Zhang, S.; Planavsky, N.; Alegret, L.; Schmidt, D. N.; Rae, J. W. B.; Foster, G. L.; Huber, B. T.; Hull, P. M.

2016-12-01

The idea of the `Strangelove Ocean'1 has captured the imagination of palaeoceanographers (and the public) since it was posited to explain the collapse or reverse in surface-deep ocean δ13C gradients after the Cretaceous-Palaeogene (K-Pg) boundary1. It describes a post-extinction ocean where primary productivity was drastically reduced, eliminating the surface-to-deep carbon isotope gradient produced by the biological pump. Survival of benthic foraminifera across the K-Pg (suggesting a persistent supply of organic matter to the deep) is difficult to reconcile with this ideae.g. 2. Geochemical proxies also suggest that severe export productivity reductions were at most regional3. This mismatch between patterns in δ13C and other indicators has thus been interpreted as a signal of changing vital effects in post-extinction pelagic calcifiers, toward lighter δ13C e.g. 2. However, it may be that vital effects in earliest Palaeocene foraminiferal survivors can account for only part of the convergence in δ13C between surface and deep ocean.4 In addition, analysis of carbonate preservation after the K-Pg boundary indicates large-scale carbonate system/ocean pH shifts at this time5, which could have produced secular changes in carbon isotope signals. Here we present new paired benthic and planktic boron isotope measurements that allow us to examine surface to deep ocean pH gradients (which in today's ocean are driven largely by biological activity) across the K-Pg boundary interval and into the early Palaeocene. We then couple these to model simulations to untangle the carbon cycle drivers, both physical and biological, that could have caused these changes in ocean pH gradients. We discuss implications for our understanding of this important interval in Earth history, with reference to the mechanisms of Earth system recovery following mass extinction. References:1. Hsü, K. J. & McKenzie, J. A., 1985. AGU Geophysical Monograph Series 32. doi:10.1029/GM032p0487 2. Alegret, L., et al., 2012. PNAS 109, 728-732. doi:10.1073/pnas.1110601109 3. Hull, P.M. & Norris, R.D., 2011. Paleoceanography 26, PA3205. doi:10.1029/2010PA002082 4. Birch, H.S., et al., 2016. Geology 44, 287-290. doi:10.1130/G37581.1 5. Henehan et al., 2016. Phil. Trans. Roy. Soc. B. 371, 20150510. doi:10.1098/rstb.2015.0510

FOREWORD: Focus on Superconductivity in Semiconductors Focus on Superconductivity in Semiconductors

NASA Astrophysics Data System (ADS)

Takano, Yoshihiko

2008-12-01

Since the discovery of superconductivity in diamond, much attention has been given to the issue of superconductivity in semiconductors. Because diamond has a large band gap of 5.5 eV, it is called a wide-gap semiconductor. Upon heavy boron doping over 3×1020 cm-3, diamond becomes metallic and demonstrates superconductivity at temperatures below 11.4 K. This discovery implies that a semiconductor can become a superconductor upon carrier doping. Recently, superconductivity was also discovered in boron-doped silicon and SiC semiconductors. The number of superconducting semiconductors has increased. In 2008 an Fe-based superconductor was discovered in a research project on carrier doping in a LaCuSeO wide-gap semiconductor. This discovery enhanced research activities in the field of superconductivity, where many scientists place particular importance on superconductivity in semiconductors. This focus issue features a variety of topics on superconductivity in semiconductors selected from the 2nd International Workshop on Superconductivity in Diamond and Related Materials (IWSDRM2008), which was held at the National Institute for Materials Science (NIMS), Tsukuba, Japan in July 2008. The 1st workshop was held in 2005 and was published as a special issue in Science and Technology of Advanced Materials (STAM) in 2006 (Takano 2006 Sci. Technol. Adv. Mater. 7 S1). The selection of papers describe many important experimental and theoretical studies on superconductivity in semiconductors. Topics on boron-doped diamond include isotope effects (Ekimov et al) and the detailed structure of boron sites, and the relation between superconductivity and disorder induced by boron doping. Regarding other semiconductors, the superconducting properties of silicon and SiC (Kriener et al, Muranaka et al and Yanase et al) are discussed, and In2O3 (Makise et al) is presented as a new superconducting semiconductor. Iron-based superconductors are presented as a new series of high-TC superconductors (Tamegai et al), and the mechanism of superconductivity is discussed. Last but not least, a novel highest-density phase of boron is produced and characterized (Zarechnaya et al). We hope that this focus issue will help readers to understand the frontiers of superconductivity in semiconductors and assist in the application of new devices using a combination of superconductivity and semiconductivity.

Empirical calibration of the clinopyroxene-garnet magnesium isotope geothermometer and implications

NASA Astrophysics Data System (ADS)

Li, Wang-Ye; Teng, Fang-Zhen; Xiao, Yilin; Gu, Hai-Ou; Zha, Xiang-Ping; Huang, Jian

2016-07-01

The large equilibrium Mg isotope fractionation between clinopyroxene and garnet observed in eclogites makes it a potential high-precision geothermometer, but calibration of this thermometer by natural samples is still limited. Here, we report Mg isotopic compositions of eclogite whole rocks as well as Mg and O isotopic compositions of clinopyroxene and garnet separates from 16 eclogites that formed at different temperatures from the Dabie orogen, China. The whole-rock δ26Mg values vary from -1.20 to +0.10 ‰. Among them, 11 samples display limited δ26Mg variations from -0.36 to -0.17 ‰, similar to those of their protoliths. The mineral separates exhibit very different δ26Mg values, from -0.39 to +0.39 ‰ for clinopyroxenes and from -1.94 to -0.81 ‰ for garnets. The clinopyroxene-garnet Mg isotope fractionation (Δ26Mgclinopyroxene-garnet = δ26Mgclinopyroxene-δ26Mggarnet) varies from 1.05 to 2.15 ‰. The clinopyroxene-garnet O isotope fractionation (Δ18Oclinopyroxene-garnet = δ18Oclinopyroxene-δ18Ogarnet) varies from -1.01 to +0.98 ‰. Equilibrium Mg isotope fractionation between clinopyroxene and garnet in the investigated samples is selected based on both the δ26Mgclinopyroxene versus δ26Mggarnet plot and the state of O isotope equilibrium between clinopyroxene and garnet. The equilibrium Δ26Mgclinopyroxene-garnet and corresponding temperature data obtained in this study, together with those available so far in literatures for natural eclogites, are used to calibrate the clinopyroxene-garnet Mg isotope thermometer. This yields a function of Δ26Mgclinopyroxene-garnet = (0.99 ± 0.06) × 106/ T 2, where T is temperature in Kelvin. The refined function not only provides the best empirically calibrated clinopyroxene-garnet Mg isotope thermometer for precise constraints of temperatures of clinopyroxene- and garnet-bearing rocks, but also has potential applications in high-temperature Mg isotope geochemistry.

The Osmium Isotopic Composition of Tagish Lake and Other Chondrites, Implications for Late Terrestrial Planetary Accretion

NASA Technical Reports Server (NTRS)

Brandon, A. D.

2003-01-01

The goals of this investigation are twofold. First, obtain high-precision Os isotope measurements of Tagish Lake and other chondrites by TIMS. Second, measure Re, Os, Pt, and other HSE concentrations by isotope dilution using TIMS and ICPMS. These measurements will determine whether this meteorite does in fact represent C-chondrite material with timeintegrated elevated Re/Os and Pt/Os with the implications to late accretion material characteristics.

Statistical clumped isotope signatures

PubMed Central

Röckmann, T.; Popa, M. E.; Krol, M. C.; Hofmann, M. E. G.

2016-01-01

High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of a molecule, which is the conventional reference. When multiple indistinguishable atoms of the same element are present in a molecule, this reference is calculated from the bulk (≈average) isotopic composition of the involved atoms. We show here that this referencing convention leads to apparent negative clumped isotope anomalies (anti-clumping) when the indistinguishable atoms originate from isotopically different populations. Such statistical clumped isotope anomalies must occur in any system where two or more indistinguishable atoms of the same element, but with different isotopic composition, combine in a molecule. The size of the anti-clumping signal is closely related to the difference of the initial isotope ratios of the indistinguishable atoms that have combined. Therefore, a measured statistical clumped isotope anomaly, relative to an expected (e.g. thermodynamical) clumped isotope composition, may allow assessment of the heterogeneity of the isotopic pools of atoms that are the substrate for formation of molecules. PMID:27535168

RAPID AND PRECISE METHOD FOR MEASURING STABLE CARBON ISOTOPE RATIOS OF DISSOLVED INORGANIC CARBON

EPA Science Inventory

We describe a method for rapid preparation, concentration and stable isotopic analysis of dissolved inorganic carbon (d13C-DIC). Liberation of CO2 was accomplished by placing 100 ?l phosphoric acid and 0.9 ml water in an evacuated 1.7-ml gas chromatography (GC) injection vial. Fo...

Continuous flow stable isotope methods for study of δ13C fractionation during halomethane production and degradation

USGS Publications Warehouse

Kalin, Robert M.; Hamilton, John T.G.; Harper, David B.; Miller, Laurence G.; Lamb, Clare; Kennedy, James T.; Downey, Angela; McCauley, Sean; Goldstein, Allen H.

2001-01-01

Gas chromatography/mass spectrometry/isotope ratio mass spectrometry (GC/MS/IRMS) methods for δ13C measurement of the halomethanes CH3Cl, CH3Br, CH3I and methanethiol (CH3SH) during studies of their biological production, biological degradation, and abiotic reactions are presented. Optimisation of gas chromatographic parameters allowed the identification and quantification of CO2, O2, CH3Cl, CH3Br, CH3I and CH3SH from a single sample, and also the concurrent measurement of δ13C for each of the halomethanes and methanethiol. Precision of δ13C measurements for halomethane standards decreased (±0.3, ±0.5 and ±1.3‰) with increasing mass (CH3Cl, CH3Br, CH3I, respectively). Given that carbon isotope effects during biological production, biological degradation and some chemical (abiotic) reactions can be as much as 100‰, stable isotope analysis offers a precise method to study the global sources and sinks of these halogenated compounds that are of considerable importance to our understanding of stratospheric ozone destruction. 

Acquisition and processing of data for isotope-ratio-monitoring mass spectrometry

NASA Technical Reports Server (NTRS)

Ricci, M. P.; Merritt, D. A.; Freeman, K. H.; Hayes, J. M.

1994-01-01

Methods are described for continuous monitoring of signals required for precise analyses of 13C, 18O, and 15N in gas streams containing varying quantities of CO2 and N2. The quantitative resolution (i.e. maximum performance in the absence of random errors) of these methods is adequate for determination of isotope ratios with an uncertainty of one part in 10(5); the precision actually obtained is often better than one part in 10(4). This report describes data-processing operations including definition of beginning and ending points of chromatographic peaks and quantitation of background levels, allowance for effects of chromatographic separation of isotopically substituted species, integration of signals related to specific masses, correction for effects of mass discrimination, recognition of drifts in mass spectrometer performance, and calculation of isotopic delta values. Characteristics of a system allowing off-line revision of parameters used in data reduction are described and an algorithm for identification of background levels in complex chromatograms is outlined. Effects of imperfect chromatographic resolution are demonstrated and discussed and an approach to deconvolution of signals from coeluting substances described.

AMS Observations of Light Cosmic Ray Isotopes and Implications for their Production in the Galaxy

NASA Astrophysics Data System (ADS)

Tomassetti, Nicola

2012-08-01

Observations of light isotopes in cosmic rays provide information on their origin and propagation in the Galaxy. Using the data collected by AMS-01 in the STS-91 space mission, we report our final results on the isotopic composition of hydrogen and helium between 200 MeV and 1.4 GeV per nucleon. These measurements are in good agreement with the previous data and set new standards of precision. We discuss the role of isotopic composition data in modeling the cosmic ray production, acceleration and diffusive transport in the Galaxy.

In situ sulfur isotopes (δ(34)S and δ(33)S) analyses in sulfides and elemental sulfur using high sensitivity cones combined with the addition of nitrogen by laser ablation MC-ICP-MS.

PubMed

Fu, Jiali; Hu, Zhaochu; Zhang, Wen; Yang, Lu; Liu, Yongsheng; Li, Ming; Zong, Keqing; Gao, Shan; Hu, Shenghong

2016-03-10

The sulfur isotope is an important geochemical tracer in diverse fields of geosciences. In this study, the effects of three different cone combinations with the addition of N2 on the performance of in situ S isotope analyses were investigated in detail. The signal intensities of S isotopes were improved by a factor of 2.3 and 3.6 using the X skimmer cone combined with the standard sample cone or the Jet sample cone, respectively, compared with the standard arrangement (H skimmer cone combined with the standard sample cone). This signal enhancement is important for the improvement of the precision and accuracy of in situ S isotope analysis at high spatial resolution. Different cone combinations have a significant effect on the mass bias and mass bias stability for S isotopes. Poor precisions of S isotope ratios were obtained using the Jet and X cones combination at their corresponding optimum makeup gas flow when using Ar plasma only. The addition of 4-8 ml min(-1) nitrogen to the central gas flow in laser ablation MC-ICP-MS was found to significantly enlarge the mass bias stability zone at their corresponding optimum makeup gas flow in these three different cone combinations. The polyatomic interferences of OO, SH, OOH were also significantly reduced, and the interference free plateaus of sulfur isotopes became broader and flatter in the nitrogen mode (N2 = 4 ml min(-1)). However, the signal intensity of S was not increased by the addition of nitrogen in this study. The laser fluence and ablation mode had significant effects on sulfur isotope fractionation during the analysis of sulfides and elemental sulfur by laser ablation MC-ICP-MS. The matrix effect among different sulfides and elemental sulfur was observed, but could be significantly reduced by line scan ablation in preference to single spot ablation under the optimized fluence. It is recommended that the d90 values of the particles in pressed powder pellets for accurate and precise S isotope analysis should be less than 10 μm. Under the selected optimized analytical conditions, excellent agreements between the determined values and the reference values were achieved for the IAEA-S series standard reference materials and a set of six well-characterized, isotopic homogeneous sulfide standards (PPP-1, MoS2, MASS-1, P-GBW07267, P-GBW07268, P-GBW07270), validating the capability of the developed method for providing high-quality in situ S isotope data in sulfides and elemental sulfur. Copyright © 2016. Published by Elsevier B.V.

The Mn-53-Cr-53 System in CAIs: An Update

NASA Technical Reports Server (NTRS)

Papanastassiou, D. A.; Wasserburg, G. J.; Bogdanovski, O.

2005-01-01

High precision techniques have been developed for the measurement of Cr isotopes on the Triton mass spectrometer, at JPL. It is clear that multiple Faraday cup, simultaneous ion collection may reduce the uncertainty of isotope ratios relative to single Faraday cup ion collection, by the elimination of uncertainties from ion beam instabilities (since ion beam intensities for single cup collection are interpolated in time to calculate isotope ratios), and due to a greatly increased data collection duty cycle, for simultaneous ion collection. Efforts to measure Cr by simultaneous ion collection have not been successful in the past. Determinations on Cr-50-54Cr, by simultaneous ion collection on the Finnigan/ MAT 262 instrument at Caltech, resulted in large variations in extrinsic precision, for normal Cr, of up to 1% in Cr-53/Cr-52 (data corrected for mass fractionation, using Cr-50/Cr-52).

A new method for stable lead isotope extraction from seawater.

PubMed

Zurbrick, Cheryl M; Gallon, Céline; Flegal, A Russell

2013-10-24

A new technique for stable lead (Pb) isotope extraction from seawater is established using Toyopearl AF-Chelate 650M(®) resin (Tosoh Bioscience LLC). This new method is advantageous because it is semi-automated and relatively fast; in addition it introduces a relatively low blank by minimizing the volume of chemicals used in the extraction. Subsequent analyses by HR ICP-MS have a good relative external precision (2σ) of 3.5‰ for (206)Pb/(207)Pb, while analyses by MC-ICP-MS have a better relative external precision of 0.6‰. However, Pb sample concentrations limit MC-ICP-MS analyses to (206)Pb, (207)Pb, and (208)Pb. The method was validated by processing the common Pb isotope reference material NIST SRM-981 and several GEOTRACES intercalibration samples, followed by analyses by HR ICP-MS, all of which showed good agreement with previously reported values. Copyright © 2013 Elsevier B.V. All rights reserved.

An Experimental Approach to Controllably Vary Protein Oxidation While Minimizing Electrode Adsorption for Boron-Doped Diamond Electrochemical Surface Mapping Applications

PubMed Central

McClintock, Carlee S; Hettich, Robert L.

2012-01-01

Oxidative protein surface mapping has become a powerful approach for measuring the solvent accessibility of folded protein structures. A variety of techniques exist for generating the key reagent – hydroxyl radicals – for these measurements; however, these approaches range significantly in their complexity and expense of operation. This research expands upon earlier work to enhance the controllability of boron-doped diamond (BDD) electrochemistry as an easily accessible tool for producing hydroxyl radicals in order to oxidize a range of intact proteins. Efforts to modulate oxidation level while minimizing the adsorption of protein to the electrode involved the use of relatively high flow rates to reduce protein residence time inside the electrochemical flow chamber. Additionally, a different cell activation approach using variable voltage to supply a controlled current allowed us to precisely tune the extent of oxidation in a protein-dependent manner. In order to gain perspective on the level of protein adsorption onto the electrode surface, studies were conducted to monitor protein concentration during electrolysis and gauge changes in the electrode surface between cell activation events. This report demonstrates the successful use of BDD electrochemistry for greater precision in generating a target number of oxidation events upon intact proteins. PMID:23210708

Isotopic Analysis and Evolved Gases

NASA Technical Reports Server (NTRS)

Swindle, Timothy D.; Boynton, William V.; Chutjian, Ara; Hoffman, John H.; Jordan, Jim L.; Kargel, Jeffrey S.; McEntire, Richard W.; Nyquist, Larry

1996-01-01

Precise measurements of the chemical, elemental, and isotopic composition of planetary surface material and gases, and observed variations in these compositions, can contribute significantly to our knowledge of the source(s), ages, and evolution of solar system materials. The analyses discussed in this paper are mostly made by mass spectrometers or some other type of mass analyzer, and address three broad areas of interest: (1) atmospheric composition - isotopic, elemental, and molecular, (2) gases evolved from solids, and (3) solids. Current isotopic data on nine elements, mostly from in situ analysis, but also from meteorites and telescopic observations are summarized. Potential instruments for isotopic analysis of lunar, Martian, Venusian, Mercury, and Pluto surfaces, along with asteroid, cometary and icy satellites, surfaces are discussed.

Optimal tracers for parallel labeling experiments and 13C metabolic flux analysis: A new precision and synergy scoring system.

PubMed

Crown, Scott B; Long, Christopher P; Antoniewicz, Maciek R

2016-11-01

13 C-Metabolic flux analysis ( 13 C-MFA) is a widely used approach in metabolic engineering for quantifying intracellular metabolic fluxes. The precision of fluxes determined by 13 C-MFA depends largely on the choice of isotopic tracers and the specific set of labeling measurements. A recent advance in the field is the use of parallel labeling experiments for improved flux precision and accuracy. However, as of today, no systemic methods exist for identifying optimal tracers for parallel labeling experiments. In this contribution, we have addressed this problem by introducing a new scoring system and evaluating thousands of different isotopic tracer schemes. Based on this extensive analysis we have identified optimal tracers for 13 C-MFA. The best single tracers were doubly 13 C-labeled glucose tracers, including [1,6- 13 C]glucose, [5,6- 13 C]glucose and [1,2- 13 C]glucose, which consistently produced the highest flux precision independent of the metabolic flux map (here, 100 random flux maps were evaluated). Moreover, we demonstrate that pure glucose tracers perform better overall than mixtures of glucose tracers. For parallel labeling experiments the optimal isotopic tracers were [1,6- 13 C]glucose and [1,2- 13 C]glucose. Combined analysis of [1,6- 13 C]glucose and [1,2- 13 C]glucose labeling data improved the flux precision score by nearly 20-fold compared to widely use tracer mixture 80% [1- 13 C]glucose +20% [U- 13 C]glucose. Copyright © 2016 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

Ion microscopy with resonant ionization mass spectrometry : time-of-flight depth profiling with improved isotopic precision.

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

Pellin, M. J.; Veryovkin, I. V.; Levine, J.

2010-01-01

There are four generally mutually exclusive requirements that plague many mass spectrometric measurements of trace constituents: (1) the small size (limited by the depth probed) of many interesting materials requires high useful yields to simply detect some trace elements, (2) the low concentrations of interesting elements require efficient discrimination from isobaric interferences, (3) it is often necessary to measure the depth distribution of elements with high surface and low bulk contributions, and (4) many applications require precise isotopic analysis. Resonant ionization mass spectrometry has made dramatic progress in addressing these difficulties over the past five years.

An improved CeO2 method for high-precision measurements of 17O/16O ratios for atmospheric carbon dioxide.

PubMed

Mahata, Sasadhar; Bhattacharya, Sourandra K; Wang, Chung-Ho; Liang, Mao-Chang

2012-09-15

The oxygen isotopic composition of carbon dioxide originating at the Earth's surface is modified in the stratosphere by interaction with ozone which has anomalous oxygen isotope ratio (Δ(17)O = 1000 * ln(1 + δ(17)O/1000) - 0.522 * 1000 * ln (1 + δ(18)O/1000) >0). The inherited anomaly provides a powerful tracer for studying biogeochemical cycles involving CO(2). However, the existing methods are either too imprecise or have difficulty in determining the small Δ(17)O variations found in the tropospheric CO(2). In this study an earlier published CeO(2) and CO(2) exchange method has been modified and improved for measuring the Δ(17)O values of atmospheric carbon dioxide with high precision. The CO(2) fraction from air samples was separated by cryogenic means and purified using gas chromatography. This CO(2) was first analyzed in an isotope ratio mass spectrometer, then artificially equilibrated with hot CeO(2) to alter its oxygen isotopes mass-dependently and re-analyzed. From these data the (17)O/(16)O and (18)O/(16)O ratios were calculated and the Δ(17)O value was determined. The validity of the method was established in several tests by using artificially prepared CO(2) with zero and non-zero Δ(17)O values. The published value of the CO(2)-H(2) O equilibrium slope was also reproduced. The CO(2)-CeO(2) equilibration method has been improved to measure the oxygen isotope anomaly (Δ(17)O value) of atmospheric CO(2) with an analytical precision of ±0.12‰ (2σ). Copyright © 2012 John Wiley & Sons, Ltd.

Fully automatic and precise data analysis developed for time-of-flight mass spectrometry.

PubMed

Meyer, Stefan; Riedo, Andreas; Neuland, Maike B; Tulej, Marek; Wurz, Peter

2017-09-01

Scientific objectives of current and future space missions are focused on the investigation of the origin and evolution of the solar system with the particular emphasis on habitability and signatures of past and present life. For in situ measurements of the chemical composition of solid samples on planetary surfaces, the neutral atmospheric gas and the thermal plasma of planetary atmospheres, the application of mass spectrometers making use of time-of-flight mass analysers is a technique widely used. However, such investigations imply measurements with good statistics and, thus, a large amount of data to be analysed. Therefore, faster and especially robust automated data analysis with enhanced accuracy is required. In this contribution, an automatic data analysis software, which allows fast and precise quantitative data analysis of time-of-flight mass spectrometric data, is presented and discussed in detail. A crucial part of this software is a robust and fast peak finding algorithm with a consecutive numerical integration method allowing precise data analysis. We tested our analysis software with data from different time-of-flight mass spectrometers and different measurement campaigns thereof. The quantitative analysis of isotopes, using automatic data analysis, yields results with an accuracy of isotope ratios up to 100 ppm for a signal-to-noise ratio (SNR) of 10 4 . We show that the accuracy of isotope ratios is in fact proportional to SNR -1 . Furthermore, we observe that the accuracy of isotope ratios is inversely proportional to the mass resolution. Additionally, we show that the accuracy of isotope ratios is depending on the sample width T s by T s 0.5 . Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Evaluating the provenance of Permian-Triassic and Palaeocene-Eocene ash beds by high precision U-Pb and Lu-Hf isotopic analyses of zircons: linking local sedimentary records to global events

NASA Astrophysics Data System (ADS)

Eivind Augland, Lars; Jones, Morgan; Planke, Sverre; Svensen, Henrik; Tegner, Christian

2016-04-01

Zircons are a powerful tool in geochronology and isotope geochemistry, as their affinity for U and Hf in the crystal structure and the low initial Pb and Lu allow for precise and accurate dating by U-Pb ID-TIMS and precise and accurate determination of initial Hf isotopic composition by solution MC-ICP-MS analysis. The U-Pb analyses provide accurate chronostratigraphic controls on the sedimentary successions and absolute age frames for the biotic evolution across geological boundaries. Moreover, the analyses of Lu-Hf by solution MC-ICP-MS after Hf-purification column chemistry provide a powerful and robust fingerprinting tool to test the provenance of individual ash beds. Here we focus on ash beds from Permian-Triassic and Palaeocene successions in Svalbard and from the Palaeocene-Eocene Thermal Maximum (PETM) in Fur, Denmark. Used in combination with whole rock geochemistry from the ash layers and the available geochemical and isotopic data from potential source volcanoes, these data are used to evaluate the provenance of the Permian-Triassic and Palaeocene ashes preserved in Svalbard and PETM ashes in Denmark. If explosive eruptions from volcanic centres such as the Siberian Traps and the North Atlantic Igneous Province (NAIP) can be traced to distal basins as ash layers, they provide robust tests of hypotheses of global synchronicity of environmental changes and biotic crises. In addition, the potential correlation of ash layers with source volcanoes will aid in constraining the extent of explosive volcanism in the respective volcanic centres. The new integrated data sets will also contribute to establish new reference sections for the study of these boundary events when combined with stable isotope data and biostratigraphy.

High-Precision (MC-ICPMS) Isotope Ratio Analysis Reveals Contrasting Sources of Elevated Blood Lead Levels of an Adult with Retained Bullet Fragments, and of His Child, in Milwaukee, Wisconsin.

PubMed

Smith, Kate E; Shafer, Martin M; Weiss, Debora; Anderson, Henry A; Gorski, Patrick R

2017-05-01

Exposure to the neurotoxic element lead (Pb) continues to be a major human health concern, particularly for children in US urban settings, and the need for robust tools for assessment of exposure sources has never been greater. The latest generation of multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) instrumentation offers the capability of using Pb isotopic signatures as a tool for environmental source tracking in public health. We present a case where MC-ICPMS was applied to isotopically resolve Pb sources in human clinical samples. An adult male and his child residing in Milwaukee, Wisconsin, presented to care in August 2015 with elevated blood lead levels (BLLs) (>200 μg/dL for the adult and 10 μg/dL for the child). The adult subject is a gunshot victim who had multiple bullet fragments embedded in soft tissue of his thigh for approximately 10 years. This study compared the high-precision isotopic fingerprints (<1 ‰ 2σ external precision) of Pb in the adult's and child's whole blood (WB) to the following possible Pb sources: a surgically extracted bullet fragment, household paint samples and tap water, and a Pb water-distribution pipe removed from servicing a house in the same neighborhood. Pb in the bullet and adult WB were nearly isotopically indistinguishable (matching within 0.05-0.56 ‰), indicating that bullet fragments embedded in soft tissue could be the cause of both acute and chronic elevated blood Pb levels. Among other sources investigated, no single source dominated the child's exposure profile as reflected in the elevated BLL.

DeuteRater: a tool for quantifying peptide isotope precision and kinetic proteomics.

PubMed

Naylor, Bradley C; Porter, Michael T; Wilson, Elise; Herring, Adam; Lofthouse, Spencer; Hannemann, Austin; Piccolo, Stephen R; Rockwood, Alan L; Price, John C

2017-05-15

Using mass spectrometry to measure the concentration and turnover of the individual proteins in a proteome, enables the calculation of individual synthesis and degradation rates for each protein. Software to analyze concentration is readily available, but software to analyze turnover is lacking. Data analysis workflows typically don't access the full breadth of information about instrument precision and accuracy that is present in each peptide isotopic envelope measurement. This method utilizes both isotope distribution and changes in neutromer spacing, which benefits the analysis of both concentration and turnover. We have developed a data analysis tool, DeuteRater, to measure protein turnover from metabolic D 2 O labeling. DeuteRater uses theoretical predictions for label-dependent change in isotope abundance and inter-peak (neutromer) spacing within the isotope envelope to calculate protein turnover rate. We have also used these metrics to evaluate the accuracy and precision of peptide measurements and thereby determined the optimal data acquisition parameters of different instruments, as well as the effect of data processing steps. We show that these combined measurements can be used to remove noise and increase confidence in the protein turnover measurement for each protein. Source code and ReadMe for Python 2 and 3 versions of DeuteRater are available at https://github.com/JC-Price/DeuteRater . Data is at https://chorusproject.org/pages/index.html project number 1147. Critical Intermediate calculation files provided as Tables S3 and S4. Software has only been tested on Windows machines. jcprice@chem.byu.edu. Supplementary data are available at Bioinformatics online. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com

A New Pb Isotope Perspective on Oceanic Basalts: Reading Between the Lines

NASA Astrophysics Data System (ADS)

Galer, S. J.; Abouchami, W.; Eisele, J.; Haase, K.; Moller, H.; Regelous, M.; Hofmann, A. W.

2001-12-01

Recent high-precision Pb isotope analyses ( ~100 ppm) obtained using double and triple spikes demonstrate that much of the scatter in previous, conventionally obtained data is analytical in origin. Here we pool together all the currently available high-precision Pb isotope data on oceanic basalts to provide a new "sharpened up" picture of the gross Pb isotope heterogeneity in the mantle. These Pb isotope data are from MORB glasses from the East Pacific Rise (EPR) and South Atlantic (26° S, Ascension), seven Hawaiian volcanoes, Pitcairn, Rurutu, the Azores (all MPI data), Mangaia (Woodhead, 1996), and St. Helena and Iceland (Thirlwall, 2000), totalling around 250 samples. The high-precision data for a given location do not form the "clouds" in Pb-Pb isotope space seen in conventional literature data. Rather, each data set forms tight linear arrays in both Pb isotope spaces. More surprising, though, is that the samples lying on a given array cover a limited geographic extent: (1) In the case of the EPR, six distinct arrays are found, each of which is confined to a particular range in latitude along the ridge, corresponding to length-scales of ~100 to 5000 km. The same is true of MORB samples from the South Atlantic (2) Distinct arrays are resolved for individual volcanoes along the Hawaiian chain, indicating that the heterogeneities within the Hawaiian plume are tapped in a long-lived and highly systematic fashion. It is also quite clear that these data are not readily interpretable in terms of mixing between notional end-member "components" in the mantle. For example, the EM1 "component" present in Pitcairn is quite clearly different in Pb isotope space from that sampled by Koolau. Similarly, the HIMU "component" present in the Austral-Cook chain is distinct in the islands Mangaia and Rurutu, and is not the same as that found in St. Helena. In all of these cases it is impossible to find common crossing points of the arrays in both Pb isotope spaces. Moreover, none of the arrays "point" towards any of the putative end-member "mantle components." If such common end-members do exist in the mantle, almost perfect premixing between them would be required to form viable intermediate end-members to each of the arrays observed. Overall, these new Pb isotope data pose the questions: (1) What is the significance of the linear arrays and why are there so many of them?, and (2) how can such heterogeneities survive intact in the convecting mantle over long periods of time?

Precise ruthenium fission product isotopic analysis using dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS)

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

Brown, Christopher F.; Dresel, P. Evan; Geiszler, Keith N.

2006-05-09

99Tc is a subsurface contaminant of interest at numerous federal, industrial, and international facilities. However, as a mono-isotopic fission product, 99Tc lacks the ability to be used as a signature to differentiate between the different waste disposal pathways that could have contributed to subsurface contamination at these facilities. Ruthenium fission-product isotopes are attractive analogues for the characterization of 99Tc sources because of their direct similarity to technetium with regard to subsurface mobility, and their large fission yields and low natural background concentrations. We developed an inductively coupled plasma mass spectrometry (ICP-MS) method capable of measuring ruthenium isotopes in groundwater samplesmore » and extracts of vadose zone sediments. Samples were analyzed directly on a Perkin Elmer ELAN DRC II ICP-MS after a single pass through a 1-ml bed volume of Dowex AG 50W-X8 100-200 mesh cation exchange resin. Precise ruthenium isotopic ratio measurements were achieved using a low-flow Meinhard-type nebulizer and long sample acquisition times (150,000 ms). Relative standard deviations of triplicate replicates were maintained at less than 0.5% when the total ruthenium solution concentration was 0.1 ng/ml or higher. Further work was performed to minimize the impact caused by mass interferences using the dynamic reaction cell (DRC) with O2 as the reaction gas. The aqueous concentrations of 96Mo and 96Zr were reduced by more than 99.7% in the reaction cell prior to injection of the sample into the mass analyzer quadrupole. The DRC was used in combination with stable-mass correction to quantitatively analyze samples containing up to 2-orders of magnitude more zirconium and molybdenum than ruthenium. The analytical approach documented herein provides an efficient and cost-effective way to precisely measure ruthenium isotopes and quantitate total ruthenium (natural vs. fission-product) in aqueous matrixes.« less

Mass spectrometry of long-lived radionuclides

NASA Astrophysics Data System (ADS)

Becker, Johanna Sabine

2003-10-01

The capability of determining element concentrations at the trace and ultratrace level and isotope ratios is a main feature of inorganic mass spectrometry. The precise and accurate determination of isotope ratios of long-lived natural and artificial radionuclides is required, e.g. for their environmental monitoring and health control, for studying radionuclide migration, for age dating, for determining isotope ratios of radiogenic elements in the nuclear industry, for quality assurance and determination of the burn-up of fuel material in a nuclear power plant, for reprocessing plants, nuclear material accounting and radioactive waste control. Inorganic mass spectrometry, especially inductively coupled plasma mass spectrometry (ICP-MS) as the most important inorganic mass spectrometric technique today, possesses excellent sensitivity, precision and good accuracy for isotope ratio measurements and practically no restriction with respect to the ionization potential of the element investigated—therefore, thermal ionization mass spectrometry (TIMS), which has been used as the dominant analytical technique for precise isotope ratio measurements of long-lived radionuclides for many decades, is being replaced increasingly by ICP-MS. In the last few years instrumental progress in improving figures of merit for the determination of isotope ratio measurements of long-lived radionuclides in ICP-MS has been achieved by the application of a multiple ion collector device (MC-ICP-MS) and the introduction of the collision cell interface in order to dissociate disturbing argon-based molecular ions, to reduce the kinetic energy of ions and neutralize the disturbing noble gas ions (e.g. of 129Xe + for the determination of 129I). The review describes the state of the art and the progress of different inorganic mass spectrometric techniques such as ICP-MS, laser ablation ICP-MS vs. TIMS, glow discharge mass spectrometry, secondary ion mass spectrometry, resonance ionization mass spectrometry and accelerator mass spectrometry for the determination of long-lived radionuclides in quite different materials.

Precise determination of triple Sr isotopes (δ⁸⁷Sr and δ⁸⁸Sr) using MC-ICP-MS.

PubMed

Liu, Hou-Chun; You, Chen-Feng; Huang, Kuo-Fang; Chung, Chuan-Hsiung

2012-01-15

The non-traditional stable strontium (Sr) isotopes have received increasing attention recently as new geochemical tracers for studying Sr isotopic fractionation and source identification. This has been attributed to the advancement in multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), allows to determine precisely and simultaneously of the triple Sr isotopes. In this study, we applied a modified empirical external normalization (EEN) MC-ICPMS procedure for mass bias correction in Sr isotopic measurement using (92)Zr/(90)Zr. High-purity Zr Standard was spiked into sample solutions and the degree of fractionation was calculated off-line using an exponential law. The long-term external reproducibility for NIST SRM 987 δ(87)Sr and δ(88)Sr was better than 0.040‰ and 0.018‰ (2SD), respectively. The IAPSO standard seawater was used as a secondary standard to validate the analytical protocol and the absolute ratios measured were 0.709161±0.000018 for (87)Sr/(86)Sr, 0.177±0.021‰ for δ(87)Sr, and 0.370±0.026‰ for δ(88)Sr (2SD, n=7). These values are in good agreement with the literature data analyzed by thermal ionization mass spectrometry (TIMS) double spike technique. Rock standards, BHVO-2, BCR-2 and AGV-2 were also analyzed to validate the robustness of the methodology and showed identical results with literature data. Compared to previous (91)Zr/(90)Zr correction, we obtained improved results based on (92)Zr/(90)Zr, probably due to similar mass difference between (92)Zr/(90)Zr and measured Sr isotopes. The new analytical protocol presented in this study not only improves the analytical precision but also increases sample efficiency by omitting the use of the standard-sample bracketing (SSB) procedure. Copyright © 2011 Elsevier B.V. All rights reserved.

Comparison of gas chromatography/isotope ratio mass spectrometry and liquid chromatography/isotope ratio mass spectrometry for carbon stable-isotope analysis of carbohydrates.

PubMed

Moerdijk-Poortvliet, Tanja C W; Schierbeek, Henk; Houtekamer, Marco; van Engeland, Tom; Derrien, Delphine; Stal, Lucas J; Boschker, Henricus T S

2015-07-15

We compared gas chromatography/isotope ratio mass spectrometry (GC/IRMS) and liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) for the measurement of δ(13)C values in carbohydrates. Contrary to GC/IRMS, no derivatisation is needed for LC/IRMS analysis of carbohydrates. Hence, although LC/IRMS is expected to be more accurate and precise, no direct comparison has been reported. GC/IRMS with the aldonitrile penta-acetate (ANPA) derivatisation method was compared with LC/IRMS without derivatisation. A large number of glucose standards and a variety of natural samples were analysed for five neutral carbohydrates at natural abundance as well as at (13)C-enriched levels. Gas chromatography/chemical ionisation mass spectrometry (GC/CIMS) was applied to check for incomplete derivatisation of the carbohydrate, which would impair the accuracy of the GC/IRMS method. The LC/IRMS technique provided excellent precision (±0.08‰ and ±3.1‰ at natural abundance and enrichment levels, respectively) for the glucose standards and this technique proved to be superior to GC/IRMS (±0.62‰ and ±19.8‰ at natural abundance and enrichment levels, respectively). For GC/IRMS measurements the derivatisation correction and the conversion of carbohydrates into CO2 had a considerable effect on the measured δ(13)C values. However, we did not find any significant differences in the accuracy of the two techniques over the full range of natural δ(13)C abundances and (13)C-labelled glucose. The difference in the performance of GC/IRMS and LC/IRMS diminished when the δ(13)C values were measured in natural samples, because the chromatographic performance and background correction became critical factors, particularly for LC/IRMS. The derivatisation of carbohydrates for the GC/IRMS method was complete. Although both LC/IRMS and GC/IRMS are reliable techniques for compound-specific stable carbon isotope analysis of carbohydrates (provided that derivatisation is complete and the calibration requirements are met), LC/IRMS is the technique of choice. The reasons for this are the improved precision, simpler sample preparation, and straightforward isotopic calibration. Copyright © 2015 John Wiley & Sons, Ltd.

Stratigraphic implications of trace element and strontium-isotope analyses of Kimmeridgian shell calcite from the Lower Saxony Basin, Germany

NASA Astrophysics Data System (ADS)

Zuo, Fanfan; Heimhofer, Ulrich; Huck, Stefan; Erbacher, Jochen; Bodin, Stephane

2017-04-01

Stratigraphic uncertainties due to the lack of open marine marker fossils (e.g. ammonites) hamper the precise age assignment and stratigraphic correlation of Kimmeridgian strata found in the Lower Saxony Basin of Northern Germany. Correlation of these deposits with the Jurassic standard ammonite zonation is still difficult, since the existing ostracod biostratigraphy is facies-controlled and of only limited stratigraphic precision. In this study, a chemostratigraphic approach has been chosen and biogenic shell material produced by brachiopods, oysters and lithiotids is evaluated for its reliability to act as proxy of the original Jurassic seawater strontium isotope composition. Low-Mg calcite shells have been collected from three stratigraphic sections accessible in open-cast quarries located in the Lower Saxony Basin of Northern Germany. In order to identify diagenetically altered shell calcite, trace element and stable isotope analysis of 227 calcite samples (oysters=101; brachiopods=60; Trichites=52) has been carried out. The geochemical results reveal that (1) concentration of different trace elements varies between the different groups of shell-forming organisms, which may be related to vital effects and (2) high strontium contents, low Mn and Fe contents and the lack of correlation between these elements indicate near-pristine calcite shells, and therefore shells are supposed to record the ambient sea water composition during the Late Jurassic. Strontium-isotope (87Sr/86Sr) analysis of diagenetically screened samples indicates an Early Kimmeridgian age of the studied deposits, which is in accordance with ostracod biostratigraphic data. An increasing trend in 87Sr/86Sr with stratigraphic height fits well with the global strontium-isotope curve. Besides, similar 87Sr/86Sr ratios derived from different organisms from a single stratigraphic level highlight the suitability of the shells for strontium-isotope stratigraphy. Despite the shallow-marine character of the studied deposits, no evidence for significant riverine influence on the strontium-isotope signature is observed. The new chemostratigraphic data will provide a more precise age assignment for Kimmeridgian strata in the Lower Saxony Basin and thus enable the establishment of a solid integrated stratigraphic scheme that can be used for correlation on both regional and global scale.

Handbook of Isotopes in the Cosmos

NASA Astrophysics Data System (ADS)

Clayton, Donald

2007-08-01

List of illustrations; Preface; Introduction; 1. Hydrogen (H); 2. Helium (He); 3. Lithium (Li); 4. Beryllium (Be); 5. Boron (B); 6. Carbon (C); 7. Nitrogen (N); 8. Oxygen (O); 9. Fluorine (F); 10. Neon (Ne); 11. Sodium (Na); 12. Magnesium (Mg); 13. Aluminium (Al); 14. Silicon (Si); 15. Phosphorous (P); 16. Sulphur (S); 17. Chlorine (Cl); 18. Argon (Ar); 19. Potassium (K); 20. Calcium (Ca); 21. Scandium (Sc); 22. Titanium (Ti); 23. Vanadium (V); 24. Chromium (Cr); 25. Manganese (Mn); 26. Iron (Fe); 27. Cobalt (Co); 28. Nickel (Ni); 29. Copper (Cu); 30. Zinc (Zn); 31. Gallium (Ga); Glossary.

Handbook of Isotopes in the Cosmos

NASA Astrophysics Data System (ADS)

Clayton, Donald

2003-09-01

List of illustrations; Preface; Introduction; 1. Hydrogen (H); 2. Helium (He); 3. Lithium (Li); 4. Beryllium (Be); 5. Boron (B); 6. Carbon (C); 7. Nitrogen (N); 8. Oxygen (O); 9. Fluorine (F); 10. Neon (Ne); 11. Sodium (Na); 12. Magnesium (Mg); 13. Aluminium (Al); 14. Silicon (Si); 15. Phosphorous (P); 16. Sulphur (S); 17. Chlorine (Cl); 18. Argon (Ar); 19. Potassium (K); 20. Calcium (Ca); 21. Scandium (Sc); 22. Titanium (Ti); 23. Vanadium (V); 24. Chromium (Cr); 25. Manganese (Mn); 26. Iron (Fe); 27. Cobalt (Co); 28. Nickel (Ni); 29. Copper (Cu); 30. Zinc (Zn); 31. Gallium (Ga); Glossary.

Standard line slopes as a measure of a relative matrix effect in quantitative HPLC-MS bioanalysis.

PubMed

Matuszewski, B K

2006-01-18

A simple experimental approach for studying and identifying the relative matrix effect (for example "plasma-to-plasma" and/or "urine-to-urine") in quantitative analyses by HPLC-MS/MS is described. Using as a database a large number of examples of methods developed in recent years in our laboratories, the relationship between the precision of standard line slopes constructed in five different lots of a biofluid (for example plasma) and the reliability of determination of concentration of an analyte in a particular plasma lot (or subject) was examined. In addition, the precision of standard line slopes was compared when stable isotope-labeled analytes versus analogs were used as internal standards (IS). Also, in some cases, a direct comparison of standard line slopes was made when different HPLC-MS interfaces (APCI versus ESI) were used for the assay of the same compound, using the same IS and the same sample preparation and chromatographic separation conditions. In selected cases, the precision of standard line slopes in five different lots of a biofluid was compared with precision values determined five times in a single lot. The results of these studies indicated that the variability of standard line slopes in different lots of a biofluid [precision of standard line slopes expressed as coefficient of variation, CV (%)] may serve as a good indicator of a relative matrix effect and, it is suggested, this precision value should not exceed 3-4% for the method to be considered reliable and free from the relative matrix effect liability. Based on the results presented, in order to assess the relative matrix effect in bioanalytical methods, it is recommended to perform assay precision and accuracy determination in five different lots of a biofluid, instead of repeat (n=5) analysis in the same, single biofluid lot, calculate standard line slopes and precision of these slopes, and to use <3-4% slope precision value as a guide for method applicability to support clinical studies. It was also demonstrated that when stable isotope-labeled analytes were used as internal standards, the precision of standard line slopes in five different lots of a biofluid was

Legacy of contaminant N sources to the NO3- signature in rivers: a combined isotopic (δ15N-NO3-, δ18O-NO3-, δ11B) and microbiological investigation

NASA Astrophysics Data System (ADS)

Briand, Cyrielle; Sebilo, Mathieu; Louvat, Pascale; Chesnot, Thierry; Vaury, Véronique; Schneider, Maude; Plagnes, Valérie

2017-02-01

Nitrate content of surface waters results from complex mixing of multiple sources, whose signatures can be modified through N reactions occurring within the different compartments of the whole catchment. Despite this complexity, the determination of nitrate origin is the first and crucial step for water resource preservation. Here, for the first time, we combined at the catchment scale stable isotopic tracers (δ15N and δ18O of nitrate and δ11B) and fecal indicators to trace nitrate sources and pathways to the stream. We tested this approach on two rivers in an agricultural region of SW France. Boron isotopic ratios evidenced inflow from anthropogenic waters, microbiological markers revealed organic contaminations from both human and animal wastes. Nitrate δ15N and δ18O traced inputs from the surface leaching during high flow events and from the subsurface drainage in base flow regime. They also showed that denitrification occurred within the soils before reaching the rivers. Furthermore, this study highlighted the determinant role of the soil compartment in nitrate formation and recycling with important spatial heterogeneity and temporal variability.

Self-Diffusion in Amorphous Silicon by Local Bond Rearrangements

NASA Astrophysics Data System (ADS)

Kirschbaum, J.; Teuber, T.; Donner, A.; Radek, M.; Bougeard, D.; Böttger, R.; Hansen, J. Lundsgaard; Larsen, A. Nylandsted; Posselt, M.; Bracht, H.

2018-06-01

Experiments on self-diffusion in amorphous silicon (Si) were performed at temperatures between 460 to 600 ° C . The amorphous structure was prepared by Si ion implantation of single crystalline Si isotope multilayers epitaxially grown on a silicon-on-insulator wafer. The Si isotope profiles before and after annealing were determined by means of secondary ion mass spectrometry. Isothermal diffusion experiments reveal that structural relaxation does not cause any significant intermixing of the isotope interfaces whereas self-diffusion is significant before the structure recrystallizes. The temperature dependence of self-diffusion is described by an Arrhenius law with an activation enthalpy Q =(2.70 ±0.11 ) eV and preexponential factor D0=(5.5-3.7+11.1)×10-2 cm2 s-1 . Remarkably, Q equals the activation enthalpy of hydrogen diffusion in amorphous Si, the migration of bond defects determining boron diffusion, and the activation enthalpy of solid phase epitaxial recrystallization reported in the literature. This close agreement provides strong evidence that self-diffusion is mediated by local bond rearrangements rather than by the migration of extended defects as suggested by Strauß et al. (Phys. Rev. Lett. 116, 025901 (2016), 10.1103/PhysRevLett.116.025901).

A Method to Determine 18O Kinetic Isotope Effects in the Hydrolysis of Nucleotide Triphosphates

PubMed Central

Du, Xinlin; Ferguson, Kurt; Sprang, Stephen R.

2007-01-01

A method to determine 18O kinetic isotope effects (KIE) in the hydrolysis of GTP is described that is generally applicable to reactions involving other nucleotide triphosphates. Internal competition, wherein the substrate of the reaction is a mixture of 18O-labeled and unlabeled nucleotides, is employed and the change in relative abundance of the two species in the course of the reaction is used to calculate KIE. The nucleotide labeled with 18O at sites of mechanistic interest also contains 13C at all carbon positions, while the 16O-nucleotide is depleted of 13C. The relative abundance of the labeled and unlabeled substrates or products is reflected in the carbon isotope ratio (13C/12C) in GTP or GDP, which is determined by use of a liquid chromatography-coupled isotope ratio mass spectrometer (LC-coupled IRMS). The LC is coupled to the IRMS by an Isolink™ interface (ThermoFinnigan). Carbon isotope ratios can be determined with accuracy and precision greater than 0.04%, and are consistent over an order of magnitude in sample amount. KIE values for Ras/NF1333-catalyzed hydrolysis of [β18O3,13C]GTP were determined by change in the isotope ratio of GTP or GDP or the ratio of the isotope ratio of GDP to that of GTP. KIE values computed in the three ways agree within 0.1%, although the method using the ratio of isotope ratios of GDP and GTP gives superior precision (< 0.1%). A single KIE measurement can be conducted in 25 minutes with less than 5 μg nucleotide reaction product. PMID:17963711

Evaluation strategies for isotope ratio measurements of single particles by LA-MC-ICPMS.

PubMed

Kappel, S; Boulyga, S F; Dorta, L; Günther, D; Hattendorf, B; Koffler, D; Laaha, G; Leisch, F; Prohaska, T

2013-03-01

Data evaluation is a crucial step when it comes to the determination of accurate and precise isotope ratios computed from transient signals measured by multi-collector-inductively coupled plasma mass spectrometry (MC-ICPMS) coupled to, for example, laser ablation (LA). In the present study, the applicability of different data evaluation strategies (i.e. 'point-by-point', 'integration' and 'linear regression slope' method) for the computation of (235)U/(238)U isotope ratios measured in single particles by LA-MC-ICPMS was investigated. The analyzed uranium oxide particles (i.e. 9073-01-B, CRM U010 and NUSIMEP-7 test samples), having sizes down to the sub-micrometre range, are certified with respect to their (235)U/(238)U isotopic signature, which enabled evaluation of the applied strategies with respect to precision and accuracy. The different strategies were also compared with respect to their expanded uncertainties. Even though the 'point-by-point' method proved to be superior, the other methods are advantageous, as they take weighted signal intensities into account. For the first time, the use of a 'finite mixture model' is presented for the determination of an unknown number of different U isotopic compositions of single particles present on the same planchet. The model uses an algorithm that determines the number of isotopic signatures by attributing individual data points to computed clusters. The (235)U/(238)U isotope ratios are then determined by means of the slopes of linear regressions estimated for each cluster. The model was successfully applied for the accurate determination of different (235)U/(238)U isotope ratios of particles deposited on the NUSIMEP-7 test samples.

Online Compound-Specific δ13C and δD Determinations Using Laser Spectroscopy

NASA Astrophysics Data System (ADS)

Saad, N.; Hoffnagle, J.

2012-04-01

A unique laser spectroscopic approach for making online high-precision compound-specific isotope analysis (CSIA) of both δ13C and δD of the CO2 and H2O organic combustion products is described. The system consists of a gas chromatograph (GC) for the separation of an organic mixture coupled to a novel micro-fabricated microreactor (MFMR) for the complete combustion of each organic compound into CO2 and H2O and the precise measurements of δ13C in the CO2 gas and δ2H in the H2O vapor from the well established infrared spectrum of both gases, using an isotopic CO2 Cavity Ring-Down Spectroscopy (CRDS) analyzer and an isotopic H2O vapor CRDS analyzer, respectively. Light hydrocarbons are used as our test compounds in this study. The analyses of CH4, C2H6 and C3H8 for δ13C and δ2H values resulted in precisions of SD(δ13C)<1‰ and SD(δ2H)<2‰, respectively. These results were further compared to the gold standard method using Dual Inlet IRMS (DI-IRMS) and showed excellent agreements in isotopic measurements. The preliminary results presented here pave the way for a single CRDS analyzer-based system that simultaneously measures δ13C and δD, is field-deployable, less costly and necessitates less operator expertise than IRMS-based systems.

Determination of U isotope ratios in sediments using ICP-QMS after sample cleanup with anion-exchange and extraction chromatography.

PubMed

Zheng, Jian; Yamada, Masatoshi

2006-01-15

The determination of uranium is important for environmental radioactivity monitoring, which investigates the releases of uranium from nuclear facilities and of naturally occurring radioactive materials by the coal, oil, natural gas, mineral, ore refining and phosphate fertilizer industries, and it is also important for studies on the biogeochemical behavior of uranium in the environment. In this paper, we describe a quadrupole ICP-MS (ICP-QMS)-based analytical procedure for the accurate determination of U isotope ratios ((235)U/(238)U atom ratio and (234)U/(238)U activity ratio) in sediment samples. A two-stage sample cleanup using anion-exchange and TEVA extraction chromatography was employed in order to obtain accurate and precise (234)U/(238)U activity ratios. The factors that affect the accuracy and precision of U isotope ratio analysis, such as detector dead time, abundance sensitivity, dwell time and mass bias were carefully evaluated and corrected. With natural U, a precision lower than 0.5% R.S.D. for (235)U/(238)U atom ratio and lower than 2.0% R.S.D. for (234)U/(238)U activity ratio was obtained with less than 90 ng uranium. The developed analytical method was validated using an ocean sediment reference material and applied to an investigation into the uranium isotopic compositions in a sediment core in a brackish lake in the vicinity of U-related nuclear facilities in Japan.

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS for isotope analysis of long-lived radionuclides

NASA Astrophysics Data System (ADS)

Becker, J. Sabine

2005-04-01

For a few years now inductively coupled plasma mass spectrometry has been increasingly used for precise and accurate determination of isotope ratios of long-lived radionuclides at the trace and ultratrace level due to its excellent sensitivity, good precision and accuracy. At present, ICP-MS and also laser ablation ICP-MS are applied as powerful analytical techniques in different fields such as the characterization of nuclear materials, recycled and by-products (e.g., spent nuclear fuel or depleted uranium ammunitions), radioactive waste control, in environmental monitoring and in bioassay measurements, in health control, in geochemistry and geochronology. Especially double-focusing sector field ICP mass spectrometers with single ion detector or with multiple ion collector device have been used for the precise determination of long-lived radionuclides isotope ratios at very low concentration levels. Progress has been achieved by the combination of ultrasensitive mass spectrometric techniques with effective separation and enrichment procedures in order to improve detection limits or by the introduction of the collision cell in ICP-MS for reducing disturbing interfering ions (e.g., of 129Xe+ for the determination of 129I). This review describes the state of the art and the progress of ICP-MS and laser ablation ICP-MS for isotope ratio measurements of long-lived radionuclides in different sample types, especially in the main application fields of characterization of nuclear and radioactive waste material, environmental research and health controls.

PALOMA : an isotope analyzer using static mass spectrometry, coupled with cryogenic and chemical trapping, for the MSL mission to Mars

NASA Astrophysics Data System (ADS)

Chassefiere, E.; Jambon, A.; Berthelier, J.-J.; Goulpeau, G.; Leblanc, F.; Montmessin, F.; Sarda, P.; Agrinier, P.; Fouchet, T.; Waite, H.

The technique of GCMS analysis has to be completed by static mass spectrometry for precise in-situ measurements of the isotopic composition of planetary atmospheres (noble gases, stable isotopes), and volatile outgassed products from solid sample pyrolysis. Static mass spectrometry, coupled with gas separation by cryo-separation and gettering, is commonly used in the laboratory to study volatiles extracted from terrestrial and meteoritic samples. Such an instrument (PALOMA) is presently developed in our laboratories, and it will be coupled with a Pyr-GCMS analyzer (MACE), built by a US consortium of science laboratories and industrials (University of Michigan, Southwest Research Institute, JPL, Ball Aerospace). The MACE/PALOMA experiment will be proposed on the NASA Mars Science Laboratory mission, planned to be launched in 2009. The scientific objectives of PALOMA, coupled with MACE, may be listed as follows : (i) search for isotopic signatures of past life in atmosphere, rock, dust and ice samples, with emphasis on carbon, nitrogen and hydrogen; (ii) accurately measure isotopic composition of atmospheric noble gases, and stable isotopes, in order to better constrain past escape, surface interaction, outgassing history and climate evolution; (iii) precisely measure diurnal/ seasonal variations of isotopic ratios of H2O, CO2, and N2, for improving our understanding of present and past climate, and of the role of water cycle. Main measurement objectives are : (i) C, H, O, N isotopic composition in both organic evolved samples (provided by MACE pyrolysis system) and atmosphere with high accuracy (a few per mil at 1-s level); (ii) noble gas (He, Ne, Ar, Kr, Xe) and stable (C, H, O, N) isotope composition in atmosphere with high accuracy (a few per mil at 1-s level); (iii) molecular and isotopic composition of inorganic evolved samples (salts, hydrates, nitrates, {ldots}), including ices; (iv) diurnal and seasonal monitoring of D/H in water vapor, and water ice.

Effect of Neutron Absorbers Mixed in or Coating the Fuel of a 1-MWt Lithium-Cooled Space Reactor

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

Amiri, Benjamin W.; Los Alamos National Laboratory, Los Alamos, NM 87545; Poston, David I.

2005-02-06

The goal of this study was to determine the effect of various neutron poisons (boron, dysprosium, erbium, and gadolinium) on a 1-MWt, lithium-cooled liquid-metal reactor. The isotopes were considered to be in-fuel poisons, as well as poisons coating the fuel. One way to quantify the effectiveness of a poison in meeting accident-condition requirements is by defining the safety margin as the difference between keff at the beginning of life and keff during the accident scenarios. The isotope that showed the most potential in increasing the safety margin for the wet-sand/water case was 157Gd. The safety margin was 10%-20% greater usingmore » 157Gd as an in-fuel poison as opposed to a coating, depending on the poison quantity. However, the most limiting condition (i.e., the accident scenario with the highest keff, thus the lowest safety margin) is when the reactor is submerged in wet sand. None of the isotopes considered significantly affected the safety margin for the dry-sand case. However, the poison isotopes considered may have applicability for meeting the wet-sand/water keff requirements or as burnable poisons in a moderated system. The views expressed in this document are those of the author and do not necessarily reflect agreement by the government.« less

Determination of 13C isotopic enrichment of valine and threonine by GC-C-IRMS after formation of the N(O,S)-ethoxycarbonyl ethyl ester derivatives of the amino acids.

PubMed

Godin, Jean-Philippe; Faure, Magali; Breuille, Denis; Hopfgartner, Gérard; Fay, Laurent-Bernard

2007-06-01

We describe a new method of assessing, in a single run, (13)C isotopic enrichment of both Val and Thr by gas chromatography-combustion-isotope-ratio mass spectrometry (GC-C-IRMS). This method characterised by a rapid one-step derivatisation procedure performed at room temperature to form the N(O,S)-ethoxycarbonyl ethyl ester derivatives, and a polar column for GC. The suitability of this method for Val and Thr in in-vivo samples (mucosal hydrolysate) was demonstrated by studying protein metabolism with two tracers ((13)C-valine or (13)C-threonine). The intra-day and inter-day repeatability were both assessed either with standards or with in-vivo samples at natural abundance and at low (13)C isotopic enrichment. For inter-day repeatability CVs were between 0.8 and 1.5% at natural abundance and lower than 5.5% at 0.112 and 0.190 atom% enrichment for Val and Thr, respectively. Overall isotopic precision was studied for eleven standard amino acid derivatives (those of Val, Ala, Leu, Iso, Gly, Pro, Asp, Thr, Ser, Met, and Phe) and was assessed at 0.32 per thousand. The (13)C isotopic measurement was then extended to the other amino acids (Ala, Val, Leu, Iso, Gly, Pro, Thr, and Phe) at natural abundance for in-vivo samples. The isotopic precision was better than 0.002 atom% per amino acid (for n = 4 rats). This analytical method was finally applied to an animal study to measure Thr utilization in protein synthesis.

Sm-Nd isotopic compositions of LREE minerals for use as reference materials for in situ analysis by LA-MC-ICPMS

NASA Astrophysics Data System (ADS)

Fisher, C. M.; McFarlane, C. R.; Sylvester, P.; Hanchar, J. M.; Lam, R.; Schmitz, M. D.

2009-12-01

Recent work has demonstrated the possibility of obtaining both accurate and precise in situ Sm-Nd isotopic data in light rare earth enriched (LREE) accessory minerals including apatite, titanite, and monazite, using laser ablation-multicollector-inductively coupled plasma mass spectrometry (LA-MC-ICPMS). A distinct advantage of using LA-MC-ICPMS is that Sm-Nd isotopic data from these minerals can be determined in sub-grain domains potentially avoiding problems of isotopic mixing from inherited or xenocrystic components and allowing both valuable tracer isotope and geochronologic data to be obtained. However, a number of analytical obstacles complicate accurate Sm-Nd determination by LA-MC-ICPMS including mass bias corrections, the 144Sm isobaric interference on 144Nd, and potential offset (ca. 20-40 ppm) from thermal ionization mass spectrometry (TIMS) determination of similar materials. Thus, in order to verify Sm-Nd isotopic determination from unknowns, matrix-matched quality control standards (i.e., reference materials) must be developed to test the data handling protocol. This talk will present new Sm-Nd isotopic data determined by both TIMS as well as LA-MC-ICPMS of a number of natural potential reference minerals including Durango apatite, Fish Canyon titanite, Daibosatsu allanite, Trebilcock monazite, as well as a monazite from the Doi Inthanon core complex in northern Thailand. Our preliminary LA-MC-ICPMS results demonstrate that Durango apatite, Fish Canyon titanite, and Thailand monazite show both inter- and intra-grain homogeneity at current levels of precision (ca. 0.3-0.5 ɛNd) and close agreement with our TIMS data.

Natural variations in the rhenium isotopic composition of meteorites

NASA Astrophysics Data System (ADS)

Liu, R.; Hu, L.; Humayun, M.

2017-03-01

Rhenium is an important element with which to test hypotheses of isotope variation. Historically, it has been difficult to precisely correct the instrumental mass bias in thermal ionization mass spectrometry. We used W as an internal standard to correct mass bias on the MC-ICP-MS, and obtained the first precise δ187Re values ( ±0.02‰, 2SE) for iron meteorites and chondritic metal. Relative to metal from H chondrites, IVB irons are systematically higher in δ187Re by 0.14 ‰. δ187Re for other irons are similar to H chondritic metal, although some individual samples show significant isotope fractionation. Since 185Re has a high neutron capture cross section, the effect of galactic cosmic-ray (GCR) irradiation on δ187Re was examined using correlations with Pt isotopes. The pre-GCR irradiation δ187Re for IVB irons is lower, but the difference in δ187Re between IVB irons and other meteoritic metal remains. Nuclear volume-dependent fractionation for Re is about the right magnitude near the melting point of iron, but because of the refractory and compatible character of Re, a compelling explanation in terms of mass-dependent fractionation is elusive. The magnitude of a nucleosynthetic s-process deficit for Re estimated from Mo and Ru isotopes is essentially unresolvable. Since thermal processing reduced nucleosynthetic effects in Pd, it is conceivable that Re isotopic variations larger than those in Mo and Ru may be present in IVBs since Re is more refractory than Mo and Ru. Thus, the Re isotopic difference between IVBs and other irons or chondritic metal remains unexplained.

Osmium isotopic homogeneity in the CK carbonaceous chondrites

NASA Astrophysics Data System (ADS)

Goderis, Steven; Brandon, Alan D.; Mayer, Bernhard; Humayun, Munir

2017-11-01

Variable proportions of isotopically diverse presolar components are known to account for nucleosynthetic isotopic anomalies for a variety of elements (e.g., Ca, Ti, Cr, Ni, Sr, Zr, Mo, Ru, Pd, Ba, Nd, and Sm) in both bulk chondrites and achondrites. However, although large Os isotopic anomalies have been measured in acid leachates and residues of unequilibrated chondrites, bulk chondrites of various groups, iron meteorites, and pallasites exhibit Os isotopic compositions that are indistinguishable from terrestrial or bulk solar isotopic abundances. Since the magnitude of nucleosynthetic anomalies is typically largest in the carbonaceous chondrites, this study reports high-precision Os isotopic compositions and highly siderophile element (HSE) concentrations for ten CK chondrites. The isotope dilution concentration data for HSE and high-precision Os isotope ratios were determined on the same digestion aliquots, to precisely correct for radiogenic contributions to 186Os and 187Os. While acid leached bulk unequilibrated carbonaceous chondrites show deficits of s-process Os components to the same extent as revealed by unequilibrated enstatite, ordinary, and Rumuruti chondrites, equilibrated bulk CK chondrites exhibit no resolvable Os isotopic anomalies. These observations support the idea that acid-resistant, carbon-rich presolar grains, such as silicon carbide (SiC) or graphite, are major carriers for nucleosynthetic isotopic anomalies of Os. The destruction of these presolar grains, which are omnipresent in unequilibrated meteorites, must have occurred during aqueous alteration and thermal metamorphism, early in the CK chondrite parent body history. The dispersal of CK chondrites along the IIIAB iron meteorite isochron on a 187Os/188Os versus 187Re/188Os diagram, with Re/Os ratios from 0.032 to 0.083, in combination with the observed redistribution of other HSE (e.g., Pt, Pd), highlights the influence of parent body processes, overprinted by effects of recent terrestrial alteration. Under the oxidizing conditions prevalent on the CK parent body, evident from high abundances of magnetite and limited Fe-Ni metal in CK chondrites, these parent body processes made all isotopically anomalous Os, originally hosted in reduced presolar grains, accessible. The absence of Os isotopic anomalies in ordinary, enstatite, and now also carbonaceous chondrites, implies that the carriers of s- and r-process Os must have been effectively homogenized across the region of chondrite formation, and possibly even the entire solar protoplanetary nebula, as suggested by the Os isotopic compositions of iron meteorites and non-anomalous ureilites. Except for a limited number of ureilites, the relative proportions of presolar s- and r-process carriers of Os (and other elements such as W) in chondrites, and most other planetary bodies, must have remained constant during all subsequent nebular and planetary processes, which appears not to have been the case for other siderophile elements, including Mo, Ru, and Pd. The existence of Mo, Ru, Pd and other siderophile element isotopic anomalies thus appears to be in part controlled by the chemical properties of these elements (e.g., volatility), their host phase(s) (e.g., SiC, graphite, metal, sulfides), and the nature of the nebular or planetary processes experienced in the early solar system.

Concentration comparison of selected constituents between groundwater samples collected within the Missouri River alluvial aquifer using purge and pump and grab-sampling methods, near the city of Independence, Missouri, 2013

USGS Publications Warehouse

Krempa, Heather M.

2015-10-29

Relative percent differences between methods were greater than 10 percent for most analyzed trace elements. Barium, cobalt, manganese, and boron had concentrations that were significantly different between sampling methods. Barium, molybdenum, boron, and uranium method concentrations indicate a close association between pump and grab samples based on bivariate plots and simple linear regressions. Grab sample concentrations were generally larger than pump concentrations for these elements and may be because of using a larger pore sized filter for grab samples. Analysis of zinc blank samples suggests zinc contamination in filtered grab samples. Variations of analyzed trace elements between pump and grab samples could reduce the ability to monitor temporal changes and potential groundwater contamination threats. The degree of precision necessary for monitoring potential groundwater threats and application objectives need to be considered when determining acceptable variation amounts.

Borate minerals and origin of the RNA world.

PubMed

Grew, Edward S; Bada, Jeffrey L; Hazen, Robert M

2011-08-01

The RNA World is generally thought to have been an important link between purely prebiotic (>3.7 Ga) chemistry and modern DNA/protein biochemistry. One concern about the RNA World hypothesis is the geochemical stability of ribose, the sugar moiety of RNA. Prebiotic stabilization of ribose by solutions associated with borate minerals, notably colemanite, ulexite, and kernite, has been proposed as one resolution to this difficulty. However, a critical unresolved issue is whether borate minerals existed in sufficient quantities on the primitive Earth, especially in the period when prebiotic synthesis processes leading to RNA took place. Although the oldest reported colemanite and ulexite are 330 Ma, and the oldest reported kernite, 19 Ma, boron isotope data and geologic context are consistent with an evaporitic borate precursor to 2400-2100 Ma borate deposits in the Liaoning and Jilin Provinces, China, as well as to tourmaline-group minerals at 3300-3450 Ma in the Barberton belt, South Africa. The oldest boron minerals for which the age of crystallization could be determined are the metamorphic tourmaline species schorl and dravite in the Isua complex (metamorphism between ca. 3650 and ca. 3600 Ma). Whether borates such as colemanite, ulexite and kernite were present in the Hadean (>4000 Ma) at the critical juncture when prebiotic molecules such as ribose required stabilization depends on whether a granitic continental crust had yet differentiated, because in its absence we see no means for boron to be sufficiently concentrated for borates to be precipitated.

SU-F-I-56: High-Precision Gamma-Ray Analysis of Medical Isotopes

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

Chopra, N; Chillery, T; Chowdhury, P

2016-06-15

Purpose: Advanced, time-resolved, Compton-suppressed gamma-ray spectroscopy with germanium detectors is implemented for assaying medical isotopes to study the radioactive decay process leading to a more accurate appraisal of the received dose and treatment planning. Lowell’s Array for Radiological Assay (LARA), a detector array that is comprised of six Compton-suppressed high-purity germanium detectors, is currently under development at UMass-Lowell which combines Compton-suppression and time-and-angle correlations to allow for highly efficient and highly sensitive measurements. Methods: Two isotopes produced Brookhaven Linac Isotope Producer (BLIP) were investigated. {sup 82}Sr which is the parent isotope for producing {sup 82}Rb is often used in cardiacmore » PET. {sup 82}Sr gamma-ray spectrum is dominated by the 511keV photons from positron annihilation which prevent precise measurement of co-produced contaminant isotopes. A second project was to investigate the production of platinum isotopes. Natural platinum was bombarded with protons from 53MeV to 200MeV. The resulting spectrum was complicated due to the large number of stable platinum isotopes in the target, the variety of open reaction channels (p,xn), (p,pxn), (p,axn). Results: By using face-to-face NaI(Tl) counters 90-degrees to the Compton-suppressed germaniums to detect the 511keV photons, a much cleaner and more sensitive measurement of {sup 85}Sr and other contaminants was obtained. For the platinum target, we identified the production of {sup 188–189–191–195}Pt, {sup 191–192–193–194–195–196}Au and {sup 186–188–189–190–192–194–189–190–192–194}Ir. For example, at the lower energies (53 and 65MeV), we measured {sup 191}Pt production cross-sections of 144mb and 157mb. Considerable care was needed in following the process of dissolving and diluting the samples to get consistent results. The new LARA array will help us better ascertain the absolute efficiency of the counting system and more reliable production cross-sections. Conclusion: Modern HPGe spectroscopic techniques provide enhanced sensitivity, promising precise quantification of the quality of radioisotopes used in medical physics. Using new decay information may have non-trivial impact on treatment planning and dose-assessment.« less

Quantification of spatial and seasonal variations in the proportional contribution of nitrate sources using a multi-isotope approach and Bayesian isotope mixing model.

PubMed

Meghdadi, Aminreza; Javar, Narmin

2018-04-01

Spatial and seasonal variations in nitrate contamination are a globally concern. While numerous studies have used δ 15 N-NO 3 and δ 18 O-NO 3 to elucidate the dominant sources of nitrate in groundwater, this approach has significant limitations due to the overlap of nitrate isotopic ranges and the occurrence of nitrate isotopic fractionation. This study quantitatively assessed the spatial and seasonal variations in the proportional contributions of nitrate sources from different land uses in the Tarom watershed in North-West Iran. To achieve this aim, orthogonal projection of the hydrochemical and isotopic dataset of the principal component analysis (PCA) as well as correlation coefficient matrix (Corr-PCA) were evaluated to reduce the dimensionality of the inter-correlated dataset. Next, a nitrate isotopic biplot accompanied with a Bayesian isotope mixing model (SIAR) were applied to specify the spatial and seasonal trends in the proportional contribution of three dominant sources of nitrate (fertilizers, animal manure and residential waste) in the watershed. Finally, in order to provide a sensitive framework for nitrate source appointment and overcome the associated limitations of dual nitrate isotope application, the integration of boron isotope (δ 11 B) and strontium isotopic ratio ( 87 Sr/ 86 Sr) was introduced. The results revealed that the mean contribution of residential sewage increased (17%-27.5%), while the mean contribution of fertilizers decreased (28.3%-19%), from late spring to early autumn. Also, fertilizer was the highest contributor (42.1% ± 3.2) during late spring, especially in regions with more than 75% agricultural land. Meanwhile, the mean contribution of sewage was highest in early autumn (32.1% ± 2.8) in the areas with more than 20% residential land. These results were confirmed by coupled application of δ 11 B and 87 Sr/ 86 Sr. This study provides a useful insight for environmental managers to verify groundwater pollution contributors and to better apply remedial solutions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Limitations of the isotopic composition of nitrates as a tracer of their origin

NASA Astrophysics Data System (ADS)

Kloppmann, Wolfram; Mayer, Bernhard; Otero, Neus; Sebilo, Mathieu; Gooddy, Daren; Lapworth, Dan; Surridge, Ben; Petelet Giraud, Emmanuelle; Flehoc, Christine; Baran, Nicole

2017-04-01

Nitrogen and oxygen isotopes are traditionally considered and frequently used as tracers of nitrate sources in watersheds used for drinking water production. The enrichment of synthetic nitrate-containing fertilizers in 18O due to the contribution of atmospheric oxygen in the production process confers a specific isotopic fingerprint to mineral fertilizers. In spite of the still widespread use on nitrate-containing synthetic fertilizers, their characteristic N and O isotope signatures are rarely unambiguously observed in nitrate-contaminated groundwater. We postulate, in line with Mengis et al. (2001), that fertilizer-derived nitrate is not directly and rapidly transferred to groundwater but rather retained in the soil-plant system as organic N and then mineralized and re-oxidized (termed the mineralization-immobilization turnover, MIT) thereby re-setting the oxygen isotope composition of nitrate and also changing its N isotope ratios. We show examples from watersheds on diverse alluvial/clastic and carbonate aquifers in eastern and northern France where, in spite of the use of mineral fertilizers, evidenced also through other isotopic tracers (boron isotopes), both N and O-isotope ratios are very homogeneous and compatible with nitrification of ammonium where 2/3 of oxygen is derived from soil water and 1/3 from atmospheric O2. These field data are corroborated by lysimeter data from Canada. Even if in areas where ammonium is derived from chemical fertilizers, N values still tend to be lower than in areas where ammonium is derived from manure/sewage, this is clearly a limitation to the dual isotope method (N, O) for nitrate source identification, but has important implications for the nitrogen mobility and residence time in soils amended with synthetic fertilizers (Sebilo et al., 2013). Mengis M., Walther U., Bernasconi S. M., Wehrli B. (2001) Limitations of Using δ18O for the Source Identification of Nitrate in Agricultural Soils. Environmental Science & Technology, 35, 1840-1844. Sebilo M., Mayer B., Nicolardot B., Pinay G., Mariotti A. (2013) Long-term fate of nitrate fertilizer in agricultural soils. Proceedings of the National Academy of Sciences of the United States of America, 110, 18185-18189.

Precise determination of the lutetium isotopic composition in rocks and minerals using multicollector ICPMS.

PubMed

Wimpenny, Josh B; Amelin, Yuri; Yin, Qing-Zhu

2013-12-03

Evidence of (176)Hf excess in select meteorites older than 4556Ma was suggested to be caused by excitation of long-lived natural radionuclide (176)Lu to its short-lived isomer (176m)Lu, due to an irradiation event during accretion in the early solar system. A result of this process would be a deficit in (176)Lu in irradiated samples by between 1‰ and 7‰. Previous measurements of the Lu isotope ratio in rock samples have not been of sufficient precision to resolve such a phenomenon. We present a new analytical technique designed to measure the (176)Lu/(175)Lu isotope ratio in rock samples to a precision of ~0.1‰ using a multicollector inductively coupled mass spectrometer (MC-ICPMS). To account for mass bias we normalized all unknowns to Ames Lu. To correct for any drift and instability associated with mass bias, all standards and samples are doped with W metal and normalized to the nominal W isotopic composition. Any instability in the mass bias is then corrected by characterizing the relationship between the fractionation factor of Lu and W, which is calculated at the start of every analytical session. After correction for isobaric interferences, in particular (176)Yb, we were able to measure (176)Lu/(175)Lu ratios in samples to a precision of ~0.1‰. However, these terrestrial standards were fractionated from Ames Lu by an average of 1.22 ± 0.09‰. This offset in (176)Lu/(175)Lu is probably caused by isotopic fractionation of Lu during industrial processing of the Ames Lu standard. To allow more straightforward data comparison we propose the use of NIST3130a as a bracketing standard in future studies. Relative to NIST3130a, the terrestrial standards have a final weighted mean δ(176)Lu value of 0.11 ± 0.09‰. All samples have uncertainties of better than 0.11‰; hence, our technique is fully capable of resolving any differences in δ(176)Lu of greater than 1‰.

Age and isotopic relationships among the angrites Lewis Cliff 86010 and Angra dos Reis

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

Lugmair, G.W.; Galer, S.J.G.

1992-04-01

Results of a wide-ranging isotopic investigation of the unique Antarctican angrite LEW-86010 (LEW) are presented, together with a reassessment of the type angrite Angra dos Reis (ADOR). The principal objectives of this study are to obtain precise radiometric ages, initial Sr isotopic compositions, and to search for the erstwhile presence of the short-lived nuclei {sup 146}Sm and {sup 26}Al via their daughter products. The isotopic compositions of Sm, U, Ca, and Ti were also measured. This allows a detailed appraisal to be made of the relations between, and the genealogy of, these two angrites.

Nd and Sm isotopic composition of spent nuclear fuels from three material test reactors

DOE PAGES

Sharp, Nicholas; Ticknor, Brian W.; Bronikowski, Michael; ...

2016-11-17

Rare earth elements such as neodymium and samarium are ideal for probing the neutron environment that spent nuclear fuels are exposed to in nuclear reactors. The large number of stable isotopes can provide distinct isotopic signatures for differentiating the source material for nuclear forensic investigations. The rare-earth elements were isolated from the high activity fuel matrix via ion exchange chromatography in a shielded cell. The individual elements were then separated using cation exchange chromatography. In conclusion, the neodymium and samarium aliquots were analyzed via MC–ICP–MS, resulting in isotopic compositions with a precision of 0.01–0.3%.

Nd and Sm isotopic composition of spent nuclear fuels from three material test reactors

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

Sharp, Nicholas; Ticknor, Brian W.; Bronikowski, Michael

Rare earth elements such as neodymium and samarium are ideal for probing the neutron environment that spent nuclear fuels are exposed to in nuclear reactors. The large number of stable isotopes can provide distinct isotopic signatures for differentiating the source material for nuclear forensic investigations. The rare-earth elements were isolated from the high activity fuel matrix via ion exchange chromatography in a shielded cell. The individual elements were then separated using cation exchange chromatography. In conclusion, the neodymium and samarium aliquots were analyzed via MC–ICP–MS, resulting in isotopic compositions with a precision of 0.01–0.3%.

Laboratory Instruments Available to Support Space Station Researchers at Marshall Space Flight Center

NASA Technical Reports Server (NTRS)

Panda, Binayak; Gorti, Sridhar

2013-01-01

A number of research instruments are available at NASA's Marshall Space Flight Center (MSFC) to support ISS researchers and their investigations. These modern analytical tools yield valuable and sometimes new informative resulting from sample characterization. Instruments include modern scanning electron microscopes equipped with field emission guns providing analytical capabilities that include angstron-level image resolution of dry, wet and biological samples. These microscopes are also equipped with silicon drift X-ray detectors (SDD) for fast yet precise analytical mapping of phases, as well as electron back-scattered diffraction (EBSD) units to map grain orientations in crystalline alloys. Sample chambers admit large samples, provide variable pressures for wet samples, and quantitative analysis software to determine phase relations. Advances in solid-state electronics have also facilitated improvements for surface chemical analysis that are successfully employed to analyze metallic materials and alloys, ceramics, slags, and organic polymers. Another analytical capability at MSFC is a mganetic sector Secondary Ion Mass Spectroscopy (SIMS) that quantitatively determines and maps light elements such as hydrogen, lithium, and boron along with their isotopes, identifies and quantifies very low level impurities even at parts per billion (ppb) levels. Still other methods available at MSFC include X-ray photo-electron spectroscopy (XPS) that can determine oxidation states of elements as well as identify polymers and measure film thicknesses on coated materials, Scanning Auger electron spectroscopy (SAM) which combines surface sensitivity, spatial lateral resolution (approximately 20 nm), and depth profiling capabilities to describe elemental compositions in near surface regions and even the chemical state of analyzed atoms. Conventional Transmission Electron Microscope (TEM) for observing internal microstructures at very high magnifications and the Electron Probe Micro-analyzer (EPMA) for very precise microanalysis are available as needed by the researcher. Space Station researchers are invited to work with MSFC in analyzing their samples using these techniques.

Possible Nuclear Safeguards Applications: Workshop on Next-Generation Laser Compton Gamma Source

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

Durham, J. Matthew

2016-11-17

These are a set of slides for the development of a next-generation photon source white paper. The following topics are covered in these slides: Nuclear Safeguards; The Nuclear Fuel Cycle; Precise isotopic determination via NRF; UF 6 Enrichment Assay; and Non-Destructive Assay of Spent Nuclear Fuel. In summary: A way to non-destructively measure precise isotopics of ~kg and larger samples has multiple uses in nuclear safeguards; Ideally this is a compact, fieldable device that can be used by international inspectors. Must be rugged and reliable; A next-generation source can be used as a testing ground for these techniques as technologymore » develops.« less

Determination of fatty acid methyl esters derived from algae Scenedesmus dimorphus biomass by GC-MS with one-step esterification of free fatty acids and transesterification of glycerolipids.

PubMed

Avula, Satya Girish Chandra; Belovich, Joanne M; Xu, Yan

2017-05-01

Algae can synthesize, accumulate and store large amounts of lipids in its cells, which holds immense potential as a renewable source of biodiesel. In this work, we have developed and validated a GC-MS method for quantitation of fatty acids and glycerolipids in forms of fatty acid methyl esters derived from algae biomass. Algae Scenedesmus dimorphus dry mass was pulverized by mortar and pestle, then extracted by the modified Folch method and fractionated into free fatty acids and glycerolipids on aminopropyl solid-phase extraction cartridges. Fatty acid methyl esters were produced by an optimized one-step esterification of fatty acids and transesterification of glycerolipids with boron trichloride/methanol. The matrix effect, recoveries and stability of fatty acids and glycerolipids in algal matrix were first evaluated by spiking stable isotopes of pentadecanoic-2,2-d 2 acid and glyceryl tri(hexadecanoate-2,2-d 2 ) as surrogate analytes and tridecanoic-2,2-d 2 acid as internal standard into algal matrix prior to sample extraction. Later, the method was validated in terms of lower limits of quantitation, linear calibration ranges, intra- and inter-assay precision and accuracy using tridecanoic-2,2-d 2 acid as internal standard. The method developed has been applied to the quantitation of fatty acid methyl esters from free fatty acid and glycerolipid fractions of algae Scenedesmus dimorphus. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Plume mapping and isotopic characterisation of anthropogenic methane sources

NASA Astrophysics Data System (ADS)

Zazzeri, G.; Lowry, D.; Fisher, R. E.; France, J. L.; Lanoisellé, M.; Nisbet, E. G.

2015-06-01

Methane stable isotope analysis, coupled with mole fraction measurement, has been used to link isotopic signature to methane emissions from landfill sites, coal mines and gas leaks in the United Kingdom. A mobile Picarro G2301 CRDS (Cavity Ring-Down Spectroscopy) analyser was installed on a vehicle, together with an anemometer and GPS receiver, to measure atmospheric methane mole fractions and their relative location while driving at speeds up to 80 kph. In targeted areas, when the methane plume was intercepted, air samples were collected in Tedlar bags, for δ13C-CH4 isotopic analysis by CF-GC-IRMS (Continuous Flow Gas Chromatography-Isotope Ratio Mass Spectrometry). This method provides high precision isotopic values, determining δ13C-CH4 to ±0.05 per mil. The bulk signature of the methane plume into the atmosphere from the whole source area was obtained by Keeling plot analysis, and a δ13C-CH4 signature, with the relative uncertainty, allocated to each methane source investigated. Both landfill and natural gas emissions in SE England have tightly constrained isotopic signatures. The averaged δ13C-CH4 for landfill sites is -58 ± 3‰. The δ13C-CH4 signature for gas leaks is also fairly constant around -36 ± 2‰, a value characteristic of homogenised North Sea supply. In contrast, signatures for coal mines in N. England and Wales fall in a range of -51.2 ± 0.3‰ to -30.9 ± 1.4‰, but can be tightly constrained by region. The study demonstrates that CRDS-based mobile methane measurement coupled with off-line high precision isotopic analysis of plume samples is an efficient way of characterising methane sources. It shows that isotopic measurements allow type identification, and possible location of previously unknown methane sources. In modelling studies this measurement provides an independent constraint to determine the contributions of different sources to the regional methane budget and in the verification of inventory source distribution.

Precise dating of Dansgaard-Oeschger climate oscillations in western Europe from stalagmite data.

PubMed

Genty, D; Blamart, D; Ouahdi, R; Gilmour, M; Baker, A; Jouzel, J; Van-Exter, Sandra

2003-02-20

The signature of Dansgaard-Oeschger events--millennial-scale abrupt climate oscillations during the last glacial period--is well established in ice cores and marine records. But the effects of such events in continental settings are not as clear, and their absolute chronology is uncertain beyond the limit of (14)C dating and annual layer counting for marine records and ice cores, respectively. Here we present carbon and oxygen isotope records from a stalagmite collected in southwest France which have been precisely dated using 234U/230Th ratios. We find rapid climate oscillations coincident with the established Dansgaard-Oeschger events between 83,000 and 32,000 years ago in both isotope records. The oxygen isotope signature is similar to a record from Soreq cave, Israel, and deep-sea records, indicating the large spatial scale of the climate oscillations. The signal in the carbon isotopes gives evidence of drastic and rapid vegetation changes in western Europe, an important site in human cultural evolution. We also find evidence for a long phase of extremely cold climate in southwest France between 61.2 +/- 0.6 and 67.4 +/- 0.9 kyr ago.

Dynamic response of laser ablative shock waves from coated and uncoated amorphous Boron nanoparticles

NASA Astrophysics Data System (ADS)

Paturi, Prem Kiran; Chelikani, Leela; Pinnoju, Venkateshwarlu; Verma, Pankaj; Singh, Raja V.; Acrhem Collaboration; Hemrl Collaboration

2015-06-01

Nanoparticles (NP) improve the performance of solid rocket motors with increased burning rate and lower ignition threshold owing to their larger surface area. We present spatio-temporal evolution of laser ablative shock waves (LASWs) from compacted amorphous Boron (B) and Lithium Fluoride coated Boron (LiF-B) of 70-110nm sizes that were compacted to form pellets. Thickness of the LiF coating is 5.5 +/- 1 nm in LiF-B. Laser pulses from second harmonic of Nd:YAG laser (532 nm, 7 ns) are used to generate LASWs expanding in ambient air. The precise time of energy release from the pellets under extreme ablative pressures is studied using shadowgraphy with a temporal resolution of 1.5 ns. Different nature of the shock front (SF) following Sedov-Taylor theory, before and after detachment, indicated two specific time dependent stages of energy release. From the position of SF, velocity behind the SF, similar to that of exhaust velocity is measured. Specific impulse of 241 +/- 5 and 201 +/- 4 sec for LiF-B and B, respectively, at a delay of 0.8 μs from shock inducing laser pulse makes them potential candidates for laser based micro thruster applications. The work is supported by Defence Research and Developement Organization, India through Grants-in-Aid Program.

A glucose-sensitive block glycopolymer hydrogel based on dynamic boronic ester bonds for insulin delivery.

PubMed

Cai, Baoqi; Luo, Yanping; Guo, Qianqian; Zhang, Xinge; Wu, Zhongming

2017-06-05

Hydrogels are good candidates to satisfy many needs for functional and tunable biomaterials. How to precisely control the gel structure and functions is crucial for the construction of sophisticated soft biomaterials comprising the hydrogels, which facilitates the impact of the surrounding environment on a unique biological function occurring. Here, glucose-responsive hydrogels comprised of 3-acrylamidophenyl boronic acid copolymerized with 2-lactobionamidoethyl methacrylate (p(APBA-b-LAMA)) were synthesized, and further evaluated as carriers for insulin delivery. The formation of (p(APBA-b-LAMA)) hydrogel was based on dynamic covalent bond using the association of boronic acid with diols. P(APBA-b-LAMA) hydrogel with the typical porous structure showed a rapid increase in equilibrium of swelling, which was up to 1856% after incubation with aqueous solution. Using insulin as a model protein therapeutic, p(APBA-b-LAMA) hydrogel exhibited high drug loading capability up to 15.6%, and also displayed glucose-dependent insulin release under physiological conditions. Additionally, the viability of NIH3T3 cells was more than 90% after treated with p(APBA-b-LAMA) hydrogel, indicating that the hydrogel had no cytotoxicity. Consequently, the novel p(APBA-b-LAMA) hydrogel has a practical application for diabetes treatment. Copyright © 2017. Published by Elsevier Ltd.

A Procedure to Determine the Coordinated Chromium and Calcium Isotopic Composition of Astromaterials Including the Chelyabinsk Meteorite

NASA Technical Reports Server (NTRS)

Tappa, M. J.; Mills, R. D.; Ware, B.; Simon, J. I.

2014-01-01

The isotopic compositions of elements are often used to characterize nucelosynthetic contributions in early Solar System objects. Coordinated multiple middle-mass elements with differing volatilities may provide information regarding the location of condensation of early Solar System solids. Here we detail new procedures that we have developed to make high-precision multi-isotope measurements of chromium and calcium using thermal ionization mass spectrometry, and characterize a suite of chondritic and terrestrial material including two fragments of the Chelyabinsk LL-chondrite.

Differential Effects of Ocean Acidification on Coral Calcification: Insights from Geochemistry.

NASA Astrophysics Data System (ADS)

Holcomb, M.; Decarlo, T. M.; Venn, A.; Tambutte, E.; Gaetani, G. A.; Tambutte, S.; Allemand, D.; McCulloch, M. T.

2014-12-01

Although ocean acidification is expected to negatively impact calcifying animals due to the formation of CaCO3 becoming less favorable, experimental evidence is mixed. Corals have received considerable attention in this regard; laboratory culture experiments show there to be a wide array of calcification responses to acidification. Here we will show how relationships for the incorporation of various trace elements and boron isotopes into synthetic aragonite can be used to reconstruct carbonate chemistry at the site of calcification. In turn the chemistry at the site of calcification can be determined under different ocean acidification scenarios and differences in the chemistry at the site of calcification linked to different calcification responses to acidification. Importantly we will show that the pH of the calcifying fluid alone is insufficient to estimate calcification responses, thus a multi-proxy approach using multiple trace elements and isotopes is required to understand how the site of calcification is affected by ocean acidification.

Precision mass measurements of some isotopes of tungsten and mercury for an adjustment to the mass table in the region A = 184 to A = 204

NASA Astrophysics Data System (ADS)

Barillari, Domenico K.

This thesis concerns the precise re-measurement of mass values in the region of the mercury isotopes, such that important discrepancies in the high-mass end of the mass table could be resolved. Scope and contents. Four mass spectroscopic doublets involving a comparison between 201Hg, 199Hg and 183W (and using a chlorocarbon reference) are reported from measurements made with the upgraded Manitoba 11 deflection instrument. The measurements address the problem of a mass table mis-adjustment in the region of the valley of β-stability between the tungsten group and the noble metals. The results, forming a well-closed loop of mass differences, support the earlier results of Kozier [Ko(1977)] regarding the (stable) mercury isotope masses and confirm an approximate 20 μu discrepancy in the mass adjustment of Audi et al [Au(1993)]. A local least- square re-adjustment conducted using these and existing mass table data suggests that the error originates with mass differences pertaining to one or more other nuclide pairs, perhaps 193Ir-192Ir. The work on upgrading the precision voltage supply and potentiometry system of the Manitoba II instrument is also reported, as is a new assessment on the data processing method. (Abstract shortened by UMI.)

Comparison of Total Evaporation (TE) and Direct Total Evaporation (DTE) methods in TIMS by using NBL CRMs

NASA Astrophysics Data System (ADS)

Hasözbek, Altug; Mathew, Kattathu; Wegener, Michael

2013-04-01

The total evaporation (TE) is a well-established analytical method for safeguards measurement of uranium and plutonium isotope-amount ratios using the thermal ionization mass spectrometry (TIMS). High accuracy and precision isotopic measurements find many applications in nuclear safeguards, for e.g. assay measurements using isotope dilution mass spectrometry. To achieve high accuracy and precision in TIMS measurements, mass dependent fractionation effects are minimized by either the measurement technique or changes in the hardware components that are used to control sample heating and evaporation process. At NBL, direct total evaporation (DTE) method on the modified MAT261 instrument, uses the data system to read the ion signal intensity and its difference from a pre-determined target intensity, is used to control the incremental step at which the evaporation filament is heated. The feedback and control is achieved by proprietary hardware from SPECTROMAT that uses an analog regulator in the filament power supply with direct feedback of the detector intensity. Compared to traditional TE method on this instrument, DTE provides better precision (relative standard deviation, expressed as a percent) and accuracy (relative difference, expressed as a percent) of 0.05 to 0.08 % for low enriched and high enriched NBL uranium certified reference materials.

Evaluation of laser ablation double-focusing SC-ICPMS for “common” lead isotopic measurements in silicate glasses and mineral

USGS Publications Warehouse

Pietruszka, Aaron J.; Neymark, Leonid

2017-01-01

An analytical method for the in situ measurement of “common” Pb isotope ratios in silicate glasses and minerals using a 193-nm excimer laser ablation (LA) system with a double-focusing single-collector (SC)-ICPMS is presented and evaluated as a possible alternative to multiple-collector (MC)-ICPMS. This LA-SC-ICPMS technique employs fast-scanning ion deflectors to sequentially place a series of flat-topped isotope peaks into a single ion-counting detector at a fixed accelerating voltage and magnetic field strength. Reference materials (including NIST, MPI-DING, and USGS glasses) are used to identify two analytical artifacts on the Pb isotope ratios (expressed here as heavier/lighter isotopes) when corrected for mass bias relative to NIST SRM610. The first artifact is characterized by anomalously low Pb isotope ratios (~0.1%/AMU) when SRM610 is analyzed in raster mode as an unknown at small spot sizes (<25 µm), which may indicate that (1) SRM610 is isotopically heterogeneous on a small length scale and/or (2) there is a non-spectral matrix effect on the Pb isotope ratios related to differences in spot size. The second artifact is characterized by anomalously high Pb isotope ratios (<0.1%/AMU) for NIST SRM612 (in raster mode) and some Fe-rich glass reference materials (BCR-2G, GOR132-G, and T1-G). These offsets are thought to be caused by one or more non-spectral matrix effects related to differences in the ablation behavior, composition, or physical properties of these reference materials compared to the bracketing SRM610 standard. The precision (±2SD) of our LA-SC-ICPMS Pb isotopic measurements is similar to (207Pb/206Pb and 208Pb/206Pb, or 20XPb/206Pb) or better than (206Pb/204Pb,207Pb/204Pb, and 208Pb/204Pb, or 20XPb/204Pb) a series of published studies that used a different type of SC-ICPMS and obtained a factor of ~3-4 higher sensitivity for Pb. An increase in the sensitivity of our LA-SC-ICPMS would likely improve the precision of the 20XPb/206Pb and 20XPb/204Pb ratios for low-Pb materials (<5 ppm), possibly making the technique broadly similar to LA-MC-ICPMS (particularly compared to methods that rely upon at least one ion-counting detector). Further improvement in the precision of the 20XPb/206Pb and 20XPb/204Pb ratios for high-Pb materials (>5 ppm) by LA-SC-ICPMS is unlikely, and in this case, LA-MC-ICPMS remains the preferable analytical technique.

Multiplexed MRM-Based Protein Quantitation Using Two Different Stable Isotope-Labeled Peptide Isotopologues for Calibration.

PubMed

LeBlanc, André; Michaud, Sarah A; Percy, Andrew J; Hardie, Darryl B; Yang, Juncong; Sinclair, Nicholas J; Proudfoot, Jillaine I; Pistawka, Adam; Smith, Derek S; Borchers, Christoph H

2017-07-07

When quantifying endogenous plasma proteins for fundamental and biomedical research - as well as for clinical applications - precise, reproducible, and robust assays are required. Targeted detection of peptides in a bottom-up strategy is the most common and precise mass spectrometry-based quantitation approach when combined with the use of stable isotope-labeled peptides. However, when measuring protein in plasma, the unknown endogenous levels prevent the implementation of the best calibration strategies, since no blank matrix is available. Consequently, several alternative calibration strategies are employed by different laboratories. In this study, these methods were compared to a new approach using two different stable isotope-labeled standard (SIS) peptide isotopologues for each endogenous peptide to be quantified, enabling an external calibration curve as well as the quality control samples to be prepared in pooled human plasma without interference from endogenous peptides. This strategy improves the analytical performance of the assay and enables the accuracy of the assay to be monitored, which can also facilitate method development and validation.

Progress at the TITAN-EBIT

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

Klawitter, R.; Alanssari, M.; Frekers, D.

2015-01-09

Precision mass measurements of short-lived isotopes provide insight into a wide array of physics, including nuclear structure, nucleosynthesis, and tests of the Standard Model. The precision of Penning trap mass spectrometry (PTMS) measurements is limited by the lifetime of the isotopes of interest, but scales proportionally with their charge state q, making highly charged ions attractive for mass measurements of nuclides far from stability. TITAN, TRIUMF's Ion Trap(s) for Atomic and Nuclear science, is currently the only setup in the world coupling an EBIT to a rare isotope facility for the purpose of PTMS. Charge breeding ions for Penning trapmore » mass spectrometry, however, entails specific set of challenges. To make use of its potential, efficiencies have to be high, breeding times have to be short and the ion energy spread has to be small. An overview of the TITAN facility and charge-breeding program is given, current and future developments are highlighted and some selected results are presented.« less

Inter- and intraindividual correlations of background abundances of (2)H, (18)O and (17)O in human urine and implications for DLW measurements.

PubMed

Berman, E S F; Melanson, E L; Swibas, T; Snaith, S P; Speakman, J R

2015-10-01

The method of choice for measuring total energy expenditure in free-living individuals is the doubly labeled water (DLW) method. This experiment examined the behavior of natural background isotope abundance fluctuations within and between individuals over time to assess possible methods of accounting for variations in the background isotope abundances to potentially improve the precision of the DLW measurement. In this work, we measured natural background variations in (2)H, (18)O and (17)O in water from urine samples collected from 40 human subjects who resided in the same geographical area. Each subject provided a urine sample for 30 consecutive days. Isotopic abundances in the samples were measured using Off-Axis Integrated Cavity Output Spectroscopy. Autocorrelation analyses demonstrated that the background isotopes in a given individual were not temporally correlated over the time scales of typical DLW studies. Using samples obtained from different individuals on the same calendar day, cross-correlation analyses demonstrated that the background variations of different individuals were not correlated in time. However, the measured ratios of the three isotopes (2)H, (18)O and (17)O were highly correlated (R(2)=0.89-0.96). Although neither specific timing of DLW water studies nor intraindividual comparisons were found to be avenues for reducing the impact of background isotope abundance fluctuations on DLW studies, strong inter-isotope correlations within an individual confirm that use of a dosing ratio of 8‰:1‰ (0.6 p.p.m.: p.p.m.) optimizes DLW precision. Theoretical implications for the possible use of (17)O measurements within a DLW study require further study.

Calibrating NIST SRM 683 as A New International Reference Standard for Zn Isotopes

NASA Astrophysics Data System (ADS)

Yang, Y.; Zhang, X.; Yu, H.; Huang, F.

2017-12-01

Zinc isotopes have been widely applied in the cosmochemical, geochemical, and environmental studies (Moynier et al. 2017). Obtaining precise Zn isotopic data for inter-laboratory comparison is a prerequisite to these applications. Currently, the JMC3-0749L is the primary reference standard for Zn isotopes (Albarède 2004), but it is not commercially available now. Thus, it is necessary to calibrate a new international primary reference standard for Zn isotopic analysis. Chen et al. (2016) showed that NIST SRM 683 (a pure Zn metal nugget of 140 grams) has a δ66ZnJMC of 0.12‰, which is falling within the range of natural Zn isotopic compositions, and it may a good candidate for the next generation of international reference standard (Chen et al. 2016). In order to further examine whether NIST SRM 683 has a homogeneous Zn isotopic composition, we measured more NIST SRM 683 by double-spike methods using MC-ICPMS (Conway et al. 2013). The metal nuggets of NIST SRM 683 were intensively sampled by micro-drilling. Zinc isotope analyses for two nuggets show that they have δ66Zn of 0.14 ± 0.02‰ (2SD, N = 32) and 0.13 ± 0.02‰ (2SD, N = 33), respectively. These values are similar to those of two Zn metal nuggets (0.11 ± 0.02‰ vs. 0.12 ± 0.02‰) reported previously by Chen et al. (2016). We fully dissolved one nugget, producing pure Zn solution with identical Zn isotopic composition with the drilling samples. All results strongly support that NIST SRM 683 is homogeneous in Zn isotopic compositions which could be an ideal candidate for the next reference for Zn isotopes. Tests on more metal nuggets will be performed in a few months for further confirming the Zn isotope compositions and homogeneity. Reference: Albarède et al., 2004. 'The stable isotope geochemistry of copper and zinc', Reviews in Mineralogy and Geochemistry, 55: 409-27. Chen et al., 2016. 'Zinc Isotopic Compositions of NIST SRM 683 and Whole-Rock Reference Materials', Geostandards and Geoanalytical Research, 40: 417-32. Conway et al., 2013. 'A new method for precise determination of iron, zinc and cadmium stable isotope ratios in seawater by double-spike mass spectrometry', Analytica chimica acta, 793: 44-52. Moynier et al., 2017. 'The isotope geochemistry of zinc and copper', Reviews in Mineralogy and Geochemistry, 82: 543-600.

Improved accuracy and precision in δ15 NAIR measurements of explosives, urea, and inorganic nitrates by elemental analyzer/isotope ratio mass spectrometry using thermal decomposition.

PubMed

Lott, Michael J; Howa, John D; Chesson, Lesley A; Ehleringer, James R

2015-08-15

Elemental analyzer systems generate N(2) and CO(2) for elemental composition and isotope ratio measurements. As quantitative conversion of nitrogen in some materials (i.e., nitrate salts and nitro-organic compounds) is difficult, this study tests a recently published method - thermal decomposition without the addition of O(2) - for the analysis of these materials. Elemental analyzer/isotope ratio mass spectrometry (EA/IRMS) was used to compare the traditional combustion method (CM) and the thermal decomposition method (TDM), where additional O(2) is eliminated from the reaction. The comparisons used organic and inorganic materials with oxidized and/or reduced nitrogen and included ureas, nitrate salts, ammonium sulfate, nitro esters, and nitramines. Previous TDM applications were limited to nitrate salts and ammonium sulfate. The measurement precision and accuracy were compared to determine the effectiveness of converting materials containing different fractions of oxidized nitrogen into N(2). The δ(13) C(VPDB) values were not meaningfully different when measured via CM or TDM, allowing for the analysis of multiple elements in one sample. For materials containing oxidized nitrogen, (15) N measurements made using thermal decomposition were more precise than those made using combustion. The precision was similar between the methods for materials containing reduced nitrogen. The %N values were closer to theoretical when measured by TDM than by CM. The δ(15) N(AIR) values of purchased nitrate salts and ureas were nearer to the known values when analyzed using thermal decomposition than using combustion. The thermal decomposition method addresses insufficient recovery of nitrogen during elemental analysis in a variety of organic and inorganic materials. Its implementation requires relatively few changes to the elemental analyzer. Using TDM, it is possible to directly calibrate certain organic materials to international nitrate isotope reference materials without off-line preparation. Copyright © 2015 John Wiley & Sons, Ltd.

Determination of 238u/235u, 236u/238u and uranium concentration in urine using sf-icp-ms and mc-icp-ms: an interlaboratory comparison.

PubMed

Parrish, Randall R; Thirlwall, Matthew F; Pickford, Chris; Horstwood, Matthew; Gerdes, Axel; Anderson, James; Coggon, David

2006-02-01

Accidental exposure to depleted or enriched uranium may occur in a variety of circumstances. There is a need to quantify such exposure, with the possibility that the testing may post-date exposure by months or years. Therefore, it is important to develop a very sensitive test to measure precisely the isotopic composition of uranium in urine at low levels of concentration. The results of an interlaboratory comparison using sector field (SF)-inductively coupled plasma-mass spectrometry (ICP-MS) and multiple collector (MC)-ICP-MS for the measurement of uranium concentration and U/U and U/U isotopic ratios of human urine samples are presented. Three urine samples were verified to contain uranium at 1-5 ng L and shown to have natural uranium isotopic composition. Portions of these urine batches were doped with depleted uranium (DU) containing small quantities of U, and the solutions were split into 100 mL and 400 mL aliquots that were subsequently measured blind by three laboratories. All methods investigated were able to measure accurately U/U with precisions of approximately 0.5% to approximately 4%, but only selected MC-ICP-MS methods were capable of consistently analyzing U/U to reasonable precision at the approximately 20 fg L level of U abundance. Isotope dilution using a U tracer demonstrates the ability to measure concentrations to better than +/-4% with the MC-ICP-MS method, though sample heterogeneity in urine samples was shown to be problematic in some cases. MC-ICP-MS outperformed SF-ICP-MS methods, as was expected. The MC-ICP-MS methodology described is capable of measuring to approximately 1% precision the U/U of any sample of human urine over the entire range of uranium abundance down to <1 ng L, and detecting very small amounts of DU contained therein.

13C metabolic flux analysis: optimal design of isotopic labeling experiments.

PubMed

Antoniewicz, Maciek R

2013-12-01

Measuring fluxes by 13C metabolic flux analysis (13C-MFA) has become a key activity in chemical and pharmaceutical biotechnology. Optimal design of isotopic labeling experiments is of central importance to 13C-MFA as it determines the precision with which fluxes can be estimated. Traditional methods for selecting isotopic tracers and labeling measurements did not fully utilize the power of 13C-MFA. Recently, new approaches were developed for optimal design of isotopic labeling experiments based on parallel labeling experiments and algorithms for rational selection of tracers. In addition, advanced isotopic labeling measurements were developed based on tandem mass spectrometry. Combined, these approaches can dramatically improve the quality of 13C-MFA results with important applications in metabolic engineering and biotechnology. Copyright © 2013 Elsevier Ltd. All rights reserved.

Isotope shifts in francium isotopes Fr 206 - 213 and Fr 221

DOE PAGES

Collister, R.; Gwinner, G.; Tandecki, M.; ...

2014-11-07

We present the isotope shifts of the 7s 1/2 to 7p 1/2 transition for francium isotopes ²⁰⁶⁻²¹³Fr with reference to ²²¹Fr collected from two experimental periods. The shifts are measured on a sample of atoms prepared within a magneto-optical trap by a fast sweep of radio-frequency sidebands applied to a carrier laser. King plot analysis, which includes literature values for 7s 1/2 to 7p 3/2 isotope shifts, provides a field shift constant ratio of 1.0520(10) and a difference between the specific mass shift constants of 170(100) GHz amu between the D₁ and D₂ transitions, of sufficient precision to differentiate betweenmore » ab initio calculations.« less

Prediction, Detection, and Validation of Isotope Clusters in Mass Spectrometry Data

PubMed Central

Treutler, Hendrik; Neumann, Steffen

2016-01-01

Mass spectrometry is a key analytical platform for metabolomics. The precise quantification and identification of small molecules is a prerequisite for elucidating the metabolism and the detection, validation, and evaluation of isotope clusters in LC-MS data is important for this task. Here, we present an approach for the improved detection of isotope clusters using chemical prior knowledge and the validation of detected isotope clusters depending on the substance mass using database statistics. We find remarkable improvements regarding the number of detected isotope clusters and are able to predict the correct molecular formula in the top three ranks in 92% of the cases. We make our methodology freely available as part of the Bioconductor packages xcms version 1.50.0 and CAMERA version 1.30.0. PMID:27775610

Martian carbon dioxide: Clues from isotopes in SNC meteorites

NASA Technical Reports Server (NTRS)

Karlsson, H. R.; Clayton, R. N.; Mayeda, T. K.; Jull, A. J. T.; Gibson, E. K., Jr.

1993-01-01

Attempts to unravel the origin and evolution of the atmosphere and hydrosphere on Mars from isotopic data have been hampered by the impreciseness of the measurements made by the Viking Lander and by Earth-based telescopes. The SNC meteorites which are possibly pieces of the Martian surface offer a unique opportunity to obtain more precise estimates of the planet's volatile inventory and isotopic composition. Recently, we reported results on oxygen isotopes of water extracted by pyrolysis from samples of Shergotty, Zagami, Nakhla, Chassigny, Lafayette, and EETA-79001. Now we describe complementary results on the stable isotopic composition of carbon dioxide extracted simultaneously from those same samples. We will also report on C-14 abundances obtained by accelerator mass spectrometry (AMS) for some of these CO2 samples.

Identification of an Extremely 180-Rich Presolar Silicate Grain in Acfer 094

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Messenger, S.

2009-01-01

Presolar silicate grains have been abundantly identified since their first discovery less than a decade ago [1,2,3]. The O isotopic compositions of both silicate and oxide stardust indicate the vast majority (>90%) condensed around Orich asymptotic giant branch (AGB) stars. Though both presolar phases have average sizes of 300 nm, grains larger than 1 m are extremely uncommon for presolar silicates. Thus, while numerous isotopic systems have been measured in presolar oxide grains [4], very few isotopic analyses for presolar silicates exist outside of O and Si [2,5]. And still, these measurements suffer from isotopic dilution with surrounding matrix material [6]. We conduct a search for presolar silicates in the primitive carbonaceous chondrite Acfer 094 and in some cases obtain high spatial resolution, high precision isotopic ratios.

2H NMR and 13C-IRMS analyses of acetic acid from vinegar, 18O-IRMS analysis of water in vinegar: international collaborative study report.

PubMed

Thomas, Freddy; Jamin, Eric

2009-09-01

An international collaborative study of isotopic methods applied to control the authenticity of vinegar was organized in order to support the recognition of these procedures as official methods. The determination of the 2H/1H ratio of the methyl site of acetic acid by SNIF-NMR (site-specific natural isotopic fractionation-nuclear magnetic resonance) and the determination of the 13C/12C ratio, by IRMS (isotope ratio mass spectrometry) provide complementary information to characterize the botanical origin of acetic acid and to detect adulterations of vinegar using synthetic acetic acid. Both methods use the same initial steps to recover pure acetic acid from vinegar. In the case of wine vinegar, the determination of the 18O/16O ratio of water by IRMS allows to differentiate wine vinegar from vinegars made from dried grapes. The same set of vinegar samples was used to validate these three determinations. The precision parameters of the method for measuring delta13C (carbon isotopic deviation) were found to be similar to the values previously obtained for similar methods applied to wine ethanol or sugars extracted from fruit juices: the average repeatability (r) was 0.45 per thousand, and the average reproducibility (R) was 0.91 per thousand. As expected from previous in-house study of the uncertainties, the precision parameters of the method for measuring the 2H/1H ratio of the methyl site were found to be slightly higher than the values previously obtained for similar methods applied to wine ethanol or fermentation ethanol in fruit juices: the average repeatability was 1.34 ppm, and the average reproducibility was 1.62 ppm. This precision is still significantly smaller than the differences between various acetic acid sources (delta13C and delta18O) and allows a satisfactory discrimination of vinegar types. The precision parameters of the method for measuring delta18O were found to be similar to the values previously obtained for other methods applied to wine and fruit juices: the average repeatability was 0.15 per thousand, and the average reproducibility was 0.59 per thousand. The above values are proposed as repeatability and reproducibility limits in the current state of the art. On the basis of this satisfactory inter-laboratory precision and on the accuracy demonstrated by a spiking experiment, the authors recommend the adoption of the three isotopic determinations included in this study as official methods for controlling the authenticity of vinegar.

In situ sulfur isotope analysis of sulfide minerals by SIMS: Precision and accuracy, with application to thermometry of ~3.5Ga Pilbara cherts

USGS Publications Warehouse

Kozdon, R.; Kita, N.T.; Huberty, J.M.; Fournelle, J.H.; Johnson, C.A.; Valley, J.W.

2010-01-01

Secondary ion mass spectrometry (SIMS) measurement of sulfur isotope ratios is a potentially powerful technique for in situ studies in many areas of Earth and planetary science. Tests were performed to evaluate the accuracy and precision of sulfur isotope analysis by SIMS in a set of seven well-characterized, isotopically homogeneous natural sulfide standards. The spot-to-spot and grain-to-grain precision for δ34S is ± 0.3‰ for chalcopyrite and pyrrhotite, and ± 0.2‰ for pyrite (2SD) using a 1.6 nA primary beam that was focused to 10 µm diameter with a Gaussian-beam density distribution. Likewise, multiple δ34S measurements within single grains of sphalerite are within ± 0.3‰. However, between individual sphalerite grains, δ34S varies by up to 3.4‰ and the grain-to-grain precision is poor (± 1.7‰, n = 20). Measured values of δ34S correspond with analysis pit microstructures, ranging from smooth surfaces for grains with high δ34S values, to pronounced ripples and terraces in analysis pits from grains featuring low δ34S values. Electron backscatter diffraction (EBSD) shows that individual sphalerite grains are single crystals, whereas crystal orientation varies from grain-to-grain. The 3.4‰ variation in measured δ34S between individual grains of sphalerite is attributed to changes in instrumental bias caused by different crystal orientations with respect to the incident primary Cs+ beam. High δ34S values in sphalerite correlate to when the Cs+ beam is parallel to the set of directions , from [111] to [110], which are preferred directions for channeling and focusing in diamond-centered cubic crystals. Crystal orientation effects on instrumental bias were further detected in galena. However, as a result of the perfect cleavage along {100} crushed chips of galena are typically cube-shaped and likely to be preferentially oriented, thus crystal orientation effects on instrumental bias may be obscured. Test were made to improve the analytical precision of δ34S in sphalerite, and the best results were achieved by either reducing the depth of the analysis pits using a Köhler illuminated primary beam, or by lowering the total impact energy from 20 keV to 13 keV. The resulting grain-to-grain precision in δ34S improves from ± 1.7‰ to better than 0.6‰ (2SD) in both procedures. With careful use of appropriate analytical conditions, the accuracy of SIMS analysis for δ34S approaches ± 0.3‰ (2SD) for chalcopyrite, pyrite and pyrrhotite and ± 0.6‰ for sphalerite. Measurements of δ34S in sub-20 µm grains of pyrite and sphalerite in ∼ 3.5 Ga cherts from the Pilbara craton, Western Australia show that this analytical technique is suitable for in situ sulfur isotope thermometry with ± 50 °C accuracy in appropriate samples, however, sulfides are not isotopically equilibrated in analyzed samples.

Constraining new physics models with isotope shift spectroscopy

NASA Astrophysics Data System (ADS)

Frugiuele, Claudia; Fuchs, Elina; Perez, Gilad; Schlaffer, Matthias

2017-07-01

Isotope shifts of transition frequencies in atoms constrain generic long- and intermediate-range interactions. We focus on new physics scenarios that can be most strongly constrained by King linearity violation such as models with B -L vector bosons, the Higgs portal, and chameleon models. With the anticipated precision, King linearity violation has the potential to set the strongest laboratory bounds on these models in some regions of parameter space. Furthermore, we show that this method can probe the couplings relevant for the protophobic interpretation of the recently reported Be anomaly. We extend the formalism to include an arbitrary number of transitions and isotope pairs and fit the new physics coupling to the currently available isotope shift measurements.

A bacterial method for the nitrogen isotopic analysis of nitrate in seawater and freshwater

USGS Publications Warehouse

Sigman, D.M.; Casciotti, K.L.; Andreani, M.; Barford, C.; Galanter, M.; Böhlke, J.K.

2001-01-01

We report a new method for measurement of the isotopic composition of nitrate (NO3-) at the natural-abundance level in both seawater and freshwater. The method is based on the isotopic analysis of nitrous oxide (N2O) generated from nitrate by denitrifying bacteria that lack N2O-reductase activity. The isotopic composition of both nitrogen and oxygen from nitrate are accessible in this way. In this first of two companion manuscripts, we describe the basic protocol and results for the nitrogen isotopes. The precision of the method is better than 0.2‰ (1 SD) at concentrations of nitrate down to 1 μM, and the nitrogen isotopic differences among various standards and samples are accurately reproduced. For samples with 1 μM nitrate or more, the blank of the method is less than 10% of the signal size, and various approaches may reduce it further.

Reflector and Shield Material Properties for Project Prometheus

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

J. Nash

2005-11-02

This letter provides updated reflector and shield preliminary material property information to support reactor design efforts. The information provided herein supersedes the applicable portions of Revision 1 to the Space Power Program Preliminary Reactor Design Basis (Reference (a)). This letter partially answers the request in Reference (b) to provide unirradiated and irradiated material properties for beryllium, beryllium oxide, isotopically enriched boron carbide ({sup 11}B{sub 4}C) and lithium hydride. With the exception of {sup 11}B{sub 4}C, the information is provided in Attachments 1 and 2. At the time of issuance of this document, {sup 11}B{sub 4}C had not been studied.

Interaction of water vapor with silicate glass surfaces: Mass-spectrometric investigations

NASA Astrophysics Data System (ADS)

Kudriavtsev, Yu.; Asomoza-Palacio, R.; Manzanilla-Naim, L.

2017-05-01

The secondary ion mass-spectroscopy technique was used to study the results of hydration of borosilicate, aluminosilicate, and soda-lime silicate glasses in 1H2 18O water vapor containing 97% of the isotope 18O. It is shown that hydration of the surface of the soda-lime silicate glass occurs as a result of the ion-exchange reaction with alkali metals. In the case of borosilicate and aluminosilicate glasses, water molecules decompose on the glass surface, with the observed formation of hydrogenated layer in the glass being the result of a solid-state chemical reaction—presumably, with the formation of hydroxides from aluminum and boron oxides.

Characterization Of Nuclear Materials Using Time-Of-Flight ICP-MS

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

Buerger, Stefan; Riciputi, Lee R; Bostick, Debra A

2006-01-01

The investigation of illicit trafficking of nuclear materials, nuclear safeguards analysis, and non-proliferation control requires sensitive and isotope-selective detection methods to gain crucial nuclear forensic information like isotope 'fingerprints' and multi-element signatures. The advantage of time-of-flight (TOF) mass spectrometry - quasi-simultaneous multi-mass analysis - combined with an inductively coupled plasma (ICP) ion source provides an analytical instrument with multi-element and multi-isotope capability and good detection limits. A TOF-ICP-MS system thus appears to be an advantageous choice for the investigation and characterization of nuclear materials. We present here results using a GBC OptiMass 8000 time-of-flight ICP-MS for the isotope screening ofmore » solid samples by laser ablation and the multi-element determination of impurities in uranium ore concentrates using matrix matched standards. A laser ablation system (New Wave Research, UP 213) coupled to the TOF-ICP-MS instrument has been used to optimize the system for analysis of non-radioactive metal samples of natural isotopic composition for a variety of elements including Cu, Sr, Zr, Mo, Cd, In, Ba, Ta, W, Re, Pt, and Pb in pure metals, alloys, and glasses to explore precision, accuracy, and detection limits. Similar methods were then applied to measure uranium. When the laser system is optimized, no mass bias correction is required. Precision and accuracy for the determination of the isotopic composition is typically 1 - 3% for elemental concentrations of as little as 50 ppm in the matrix, with no requirement for sample preparation. The laser ablation precision and accuracy are within ~10x of the instrumental limits for liquid analysis (0.1%). We have investigated the capabilities of the TOF-ICP-MS for the analysis of impurities in uranium matrices. Matrix matching has been used to develop calibration curves for a range of impurities (alkaline, earth-alkaline, transition metals, and rare earth elements). These calibration curves have been used to measure impurities in a number of uranium samples. The results from the TOF-ICP-MS will be compared with other mass spectrometric methods.« less

A double-spike method for K-Ar measurement: A technique for high precision in situ dating on Mars and other planetary surfaces

NASA Astrophysics Data System (ADS)

Farley, K. A.; Hurowitz, J. A.; Asimow, P. D.; Jacobson, N. S.; Cartwright, J. A.

2013-06-01

A new method for K-Ar dating using a double isotope dilution technique is proposed and demonstrated. The method is designed to eliminate known difficulties facing in situ dating on planetary surfaces, especially instrument complexity and power availability. It may also have applicability in some terrestrial dating applications. Key to the method is the use of a solid tracer spike enriched in both 39Ar and 41K. When mixed with lithium borate flux in a Knudsen effusion cell, this tracer spike and a sample to be dated can be successfully fused and degassed of Ar at <1000 °C. The evolved 40Ar∗/39Ar ratio can be measured to high precision using noble gas mass spectrometry. After argon measurement the sample melt is heated to a slightly higher temperature (˜1030 °C) to volatilize potassium, and the evolved 39K/41K ratio measured by Knudsen effusion mass spectrometry. Combined with the known composition of the tracer spike, these two ratios define the K-Ar age using a single sample aliquot and without the need for extreme temperature or a mass determination. In principle the method can be implemented using a single mass spectrometer. Experiments indicate that quantitative extraction of argon from a basalt sample occurs at a sufficiently low temperature that potassium loss in this step is unimportant. Similarly, potassium isotope ratios measured in the Knudsen apparatus indicate good sample-spike equilibration and acceptably small isotopic fractionation. When applied to a flood basalt from the Viluy Traps, Siberia, a K-Ar age of 351 ± 19 Ma was obtained, a result within 1% of the independently known age. For practical reasons this measurement was made on two separate mass spectrometers, but a scheme for combining the measurements in a single analytical instrument is described. Because both parent and daughter are determined by isotope dilution, the precision on K-Ar ages obtained by the double isotope dilution method should routinely approach that of a pair of isotope ratio determinations, likely better than ±5%.

Preferential flow pathways revealed by field based stable isotope analysis of CO2 by mid-infrared laser spectroscopy

NASA Astrophysics Data System (ADS)

van Geldern, Robert; Nowak, Martin; Zimmer, Martin; Szizybalski, Alexandra; Myrttinen, Anssi; Barth, Johannes A. C.; Jost, Hj

2016-04-01

A newly developed and commercially available isotope ratio laser spectrometer for CO2 analyses has been tested during a 10-day field monitoring campaign at the Ketzin pilot site for CO2 storage in northern Germany. The laser instrument is based on tunable laser direct absorption in the mid-infrared. The instrument recorded a continuous 10-day carbon stable isotope data set with 30 minutes resolution directly on-site in a field-based laboratory container during a tracer experiment. To test the instruments performance and accuracy the monitoring campaign was accompanied by daily CO2 sampling for laboratory analyses with isotope ratio mass spectrometry (IRMS). The carbon stable isotope ratios measured by conventional IRMS technique and by the new mid-infrared laser spectrometer agree remarkably well within 2σ analytical precision (<0.3 ‰). This proves the capability of the new mid-infrared direct absorption technique to measure high precision and accurate real-time table isotope data directly in the field. The injected CO2 tracer had a distinct δ13C value that was largely different from the reservoir background value. The laser spectroscopy data revealed a prior to this study unknown, intensive dynamic with fast changing δ13C values. The arrival pattern of the tracer suggest that the observed fluctuations were probably caused by migration along separate and distinct preferential flow paths between injection well and observation well. The new technique might contribute to a better tracing of the migration of the underground CO2 plume and help to ensure the long-term integrity of the reservoir.

Subduction-like fluids in the genesis of Mt. Etna magmas: evidence from boron isotopes and fluid mobile elements

NASA Astrophysics Data System (ADS)

Tonarini, Sonia; Armienti, Pietro; D'Orazio, Massimo; Innocenti, Fabrizio

2001-11-01

New whole-rock B, Sr, Nd isotope ratios and 87Sr/ 86Sr on clinopyroxenes have been collected to study the enrichment of fluid mobile elements (FMEs) observed in Mt. Etna volcanics. Etna volcano, one of the most active in the world, is located in an extremely complex tectonic context at the boundary between colliding African and European plates. The analytical work focuses on current (1974-1998) and historic (1851-1971) eruptive activity, including some key prehistoric lavas, in order to interpret the secular shift of its geochemical signature to more alkaline compositions. Boron is used as a tool to unravel the role of fluids in the genesis of magmas, revealing far-reaching consequences, beyond the case study of Mt. Etna. Small variations are observed in δ 11B (-3.5 to -8.0‰), 87Sr/ 86Sr (0.70323-0.70370), and 143Nd/ 144Nd (0.51293-0.51287). Moreover, temporal evolution to higher δ 11B and 87Sr/ 86Sr, and to lower 143Nd/ 144Nd, is observed in the current activity, defining a regular trend. Sr isotopic equilibrium between whole-rock and clinopyroxene pairs indicates the successive introduction of three distinct magma types into the Etna plumbing system over time; these are characterized by differing degrees of FME enrichment. In addition, certain lavas exhibit evidence for country rock assimilation, magma-fluid interaction, or magma mixing in the shallow feeding system; at times these processes apparently lowered magmatic δ 11B and/or induced Sr isotopic disequilibrium between whole rock and clinopyroxene. The regular increase of δ 11B values is correlated with Nb/FME and 87Sr/ 86Sr ratios; these correlations are consistent with simple mixing between the mantle source and aqueous fluids derived from nearby Ionian slab. The best fit of Mt. Etna data is obtained using an enriched-MORB mantle source and a fluid phase with δ 11B of about -2‰ and 87Sr/ 86Sr of 0.708. We argue that the slab window generated by differential roll-back of subducting Ionian lithosphere (with respect to Sicily) allows the upwelling of asthenosphere from below the subduction system and provides a suitable path of rise for subduction-related fluids. The increasing geochemical signature of fluid mobile elements enrichment to Mt. Etna lavas is considered a consequence of the progressive opening of slab window through time.

High Acidification Rate of Norwegian Sea Revealed by Boron Isotopes in the Deep-Sea Coral Madrepora Oculata

NASA Astrophysics Data System (ADS)

Gonzalez, C.; Douville, E.; Hall-Spencer, J.; Montagna, P.; Louvat, P.; Gaillardet, J.; Frank, N.; Bordier, L.; Juillet-Leclerc, A.

2012-12-01

Ocean acidification and global warming due to the increase of anthropogenic CO2 are major threats for marine calcifying organisms, such as deep-sea corals, particularly in high-latitude regions. In order to evaluate the current anthropogenic perturbation and to properly assess the impacts and responses of calcifiers to previous changes in pH it is critical to investigate past changes of the seawater carbonate system. Unfortunately, current instrumental records of oceanic pH are limited, covering only a few decades. Scleractinian coral skeletons record chemical parameters of the seawater in which they grow. However, pH variability over multidecadal timescales remains largely unknown in intermediate and deep seawater masses. Here we present a study that highlights the potential of deep-sea-corals to overcome the lack of long-term pH records and that emphasizes a rapid acidification of high latitude subsurface waters of Norwegian Sea during the past decades. We have reconstructed seawater pH and temperature from a well dated deep-sea coral specimen Madrepora oculata collected alive from Røst reef in Norwegian Sea (67°N, 9°E, 340 m depth). This large branching framework forming coral species grew its skeleton over more than four decades determined using AMS 14C and 210Pb dating (Sabatier et al. 2012). B-isotopes and Li/Mg ratios yield an acidification rate of about -0.0030±0.0008 pH-unit.year-1 and a warming of 0.3°C during the past four decades (1967-2007). Overall our reconstruction technique agrees well with previous pH calculations (Hönisch et al., 2007 vs. Trotter et al., 2011 and McCulloch et al., 2012, i.e. the iterative method), but additional corrections are here applied using stable isotope correlations (O, C, B) to properly address kinetic fractionation of boron isotopes used for pH reconstruction. The resulting pH curve strongly anti-correlates with the annual NAO index, which further strengthens our evidence for the ocean acidification rate calculated here. If the rate of atmospheric CO2 emission is not reduced, the Røst reef will become undersaturated in aragonite by the end of century. Sabatier P. et al., 2012. Biogeosciences, 9, 1253-1265. Hönisch B. et al., 2007. Geochim. Cosmochim. Acta 71, 1636-1641. Trotter J. et al., 2011. Earth and Planetary Science Letters 303 (2011) 163-73. McCulloch M. et al., 2012. Geochim. Cosmochim. Acta 82, 154-162

Thermal equilibration of iron meteorite and pallasite parent bodies recorded at the mineral scale by Fe and Ni isotope systematics

NASA Astrophysics Data System (ADS)

Chernonozhkin, Stepan M.; Weyrauch, Mona; Goderis, Steven; Oeser, Martin; McKibbin, Seann J.; Horn, Ingo; Hecht, Lutz; Weyer, Stefan; Claeys, Philippe; Vanhaecke, Frank

2017-11-01

In this work, a femtosecond laser ablation (LA) system coupled to a multi-collector inductively coupled plasma-mass spectrometer (fs-LA-MC-ICP-MS) was used to obtain laterally resolved (30-80 μm), high-precision combined Ni and Fe stable isotope ratio data for a variety of mineral phases (olivine, kamacite, taenite, schreibersite and troilite) composing main group pallasites (PMG) and iron meteorites. The stable isotopic signatures of Fe and Ni at the mineral scale, in combination with the factors governing the kinetic or equilibrium isotope fractionation processes, are used to interpret the thermal histories of small differentiated asteroidal bodies. As Fe isotopic zoning is only barely resolvable within the internal precision level of the isotope ratio measurements within a single olivine in Esquel PMG, the isotopically lighter olivine core relative to the rim (Δ56/54Ferim-core = 0.059‰) suggests that the olivines were largely thermally equilibrated. The observed hint of an isotopic and concentration gradient for Fe of crudely similar width is interpreted here to reflect Fe loss from olivine in the process of partial reduction of the olivine rim. The ranges of the determined Fe and Ni isotopic signatures of troilite (δ56/54Fe of -0.66 to -0.09‰) and schreibersite (δ56/54Fe of -0.48 to -0.09‰, and δ62/60Ni of -0.64 to +0.29‰) may result from thermal equilibration. Schreibersite and troilite likely remained in equilibrium with their enclosing metal to temperatures significantly below their point of crystallization. The Ni isotopic signatures of bulk metal and schreibersite correlate negatively, with isotopically lighter Ni in the metal of PMGs and isotopically heavier Ni in the metal of the iron meteorites analyzed. As such, the light Ni isotopic signatures previously observed in PMG metal relative to chondrites may not result from heterogeneity in the Solar Nebula, but rather reflect fractionation in the metal-schreibersite system. Comparison between the isotope ratio profiles of Fe and Ni determined across kamacite-taenite interfaces (Δ56/54Fekam-tae = -0.51 to -0.69‰ and Δ62/60Nikam-tae = +1.59 to +2.50‰) and theoretical taenite sub-solidus diffusive isotopic zoning broadly constrain the cooling rates of Esquel, CMS 04071 PMGs and Udei Station IAB to between ∼25 and 500 °C/Myr.

Advances in the measurement of sulfur isotopes by multi-collector ICP-MS (MC-ICP- MS)

NASA Astrophysics Data System (ADS)

Ridley, W. I.; Wilson, S. A.; Anthony, M. W.

2006-12-01

The demonstrated capability to measure 34S/32S by MC-ICP-MS with a precision (2ó) of ~0.2 per mil has many potential applications in geochemistry. However, a number of obstacles limit this potential. First, to achieve the precision indicated above requires sufficient mass resolution to separate isobaric interferences of 16O2 and 17O2 on 32S and 34S, respectively. These requirements for high resolution mean overall instrument sensitivity is reduced. Second, current methods preclude analysis of samples with complex matrices, a common characteristic of sulfur-bearing geologic materials. Here, we describe and discuss a method that provides both efficient removal of matrix constituents, and provides pre-concentration of S, thus overcoming these obstacles. The method involves the separation of sulfur from matrix constituents by high pressure (1000 psi) ion chromatography (HPIC), followed by isotope measurement using MC-ICP-MS. This combination allows for analysis of liquid samples with a wide range of S concentrations. A powerful advantage of this technique is the efficient separation of many sulfur species from matrix cations and anions (for instance in a seawater or acid mine drainage matrix), as well as the separation of sulfur species, e.g., sulfate, sulfite, thiosulfate, thiocynate, from each other for isotope analysis. The automated HPIC system uses a carbonate-bicarbonate eluent with eluent suppression, and has sufficient baseline separation to collect the various sulfur species as pure fractions. The individual fractions are collected over a specific time interval based upon a pre-determined elution profile and peak retention times. The addition of a second ion exchange column into the system allows pre-concentration of sulfur species by 2-3 orders of magnitude for samples that otherwise would have sulfur concentrations too low to provide precise isotopic ratios. The S isotope ratios are measured by MC-ICP-MS using a desolvating sample introduction system, a standard-sample bracketing method employing standards that are well characterized for sulfur isotope composition using stable isotope gas mass spectrometry. Data are collected in time-resolved mode, which reduces analytical time and allows for flexibility in data integration. Preliminary data indicates that sulfur species do not fractionate during the column chemistry.

Laboratory technology and cosmochemistry

PubMed Central

Zinner, Ernst K.; Moynier, Frederic; Stroud, Rhonda M.

2011-01-01

Recent developments in analytical instrumentation have led to revolutionary discoveries in cosmochemistry. Instrumental advances have been made along two lines: (i) increase in spatial resolution and sensitivity of detection, allowing for the study of increasingly smaller samples, and (ii) increase in the precision of isotopic analysis that allows more precise dating, the study of isotopic heterogeneity in the Solar System, and other studies. A variety of instrumental techniques are discussed, and important examples of discoveries are listed. Instrumental techniques and instruments include the ion microprobe, laser ablation gas MS, Auger EM, resonance ionization MS, accelerator MS, transmission EM, focused ion-beam microscopy, atom probe tomography, X-ray absorption near-edge structure/electron loss near-edge spectroscopy, Raman microprobe, NMR spectroscopy, and inductively coupled plasma MS. PMID:21498689

Oxygen isotope analysis of shark teeth phosphates from Bartonian (Eocene) deposits in Mangyshlak peninsula, Kazakhstan

NASA Astrophysics Data System (ADS)

Pelc, Andrzej; Hałas, Stanisław; Niedźwiedzki, Robert

2011-01-01

We report the results of high-precision (±0.05‰) oxygen isotope analysis of phosphates in 6 teeth of fossil sharks from the Mangyshlak peninsula. This precision was achieved by the offline preparation of CO2 which was then analyzed on a dual-inlet and triple-collector IRMS. The teeth samples were separated from Middle- and Late Bartonian sediments cropping out in two locations, Usak and Kuilus. Seawater temperatures calculated from the δ18O data vary from 23-41°C. However, these temperatures are probably overestimated due to freshwater inflow. The data point at higher temperature in the Late Bartonian than in the Middle Bartonian and suggest differences in the depth habitats of the shark species studied.

Trace metals in corals--hind casting environmental chemical changes in the tropical Atlantic waters

NASA Astrophysics Data System (ADS)

Holmes, C. W.; Koenig, A.; Ridley, W. I.; Wilson, S. A.

2002-12-01

As corals grow, they secrete a calcareous skeleton with the aid of photosynthetic activity of endosymbiotic dinoflagellates (zooxanthellae). The rate of this secretion varies inter-annually. Entrapped with the carbonate are trace substances that record the chemistry of the surrounding ocean. Detailing changes in chemistry requires careful and very tedious high-resolution sampling. The advent of laser ablation inductive couple plasma/mass spectroscopy (LA-ICP/MS) circumvents this sampling problem. This method also permits a continuous scan of the entire coral skeleton. Another problem has been the lack of a carbonate standard which appears to be resolved with the creation of an artificial carbonate standard (USGS MAC-1). This standard is presently undergoing rigorous analysis, but preliminary results are very positive. The LA-ICP/MS data of three Atlantic corals reveals an intriguing distribution of trace metals and boron that may be related to climatic driven chemical changes during the last hundred years. The distribution of the trace metals appears to have an association with three climate signals: 1. the strength of the North Atlantic Oscillation (NAO), 2. the local effects of El Nino in the Florida region and 3. change in oceanic chemistry, possibly due to rising CO2. Aluminum and titanium levels vary with the strength of the NAO. The highest concentrations occur at the time of strong positive NOA when there is large amount of sediment transported off the deserts of North Africa. This relationship is particularly strong in the coral from the Cape Verde Islands. Along the eastern seaboard of the Atlantic, the relationship is not as pronounced but still observable. Nutrients and anthropogenic trace metals, such as zinc, lead, and mercury appear to correlate with local conditions and show a weak correspondence to the El Nino as it affects south Florida. Boron variation is directly related to the high-density bands of the corals. The long-term record of boron concentrations in a coral collected at Looe Key shows an increase of approximately 25 percent from 1885 to a peak in the early 1970s. From the peak until 1983, the time of collection, boron decreases about 15 percent. Boron in the twenty-year record in the Cape Verde coral shows a similar decrease. Hemming and others (1986) found that the boron concentration and the heavy isotope of carbon, 13C are concentrated in the annual high-density bands. They proposed that this phenomenon is the result of the physiological processes leading to the precipitation of the carbonate structure. Assuming that the zooanthellae are driving the photosynthetic processes, the explanation of high boron and associated high δ13C is the result of increased primary productivity. As a result, 12C is preferentially utilized within the cell leaving the extracelluar fluids in the region between the basal ectoderm and exoskeleton enriched in 13C. In addition, this increased activity increases HCO3^{-} leading to the higher pH in these fluids. This increase in pH, favors an increase in the reactive species, B(OH)_{4}$-which leads to increased boron precipitation within the carbonate structure. If this model is correct, our data suggest that increases in boron reflect increases in photosynthesis from the 1800s till about 1970, then have slightly decreased.

Isotopic Resonance Hypothesis: Experimental Verification by Escherichia coli Growth Measurements

NASA Astrophysics Data System (ADS)

Xie, Xueshu; Zubarev, Roman A.

2015-03-01

Isotopic composition of reactants affects the rates of chemical and biochemical reactions. As a rule, enrichment of heavy stable isotopes leads to progressively slower reactions. But the recent isotopic resonance hypothesis suggests that the dependence of the reaction rate upon the enrichment degree is not monotonous. Instead, at some ``resonance'' isotopic compositions, the kinetics increases, while at ``off-resonance'' compositions the same reactions progress slower. To test the predictions of this hypothesis for the elements C, H, N and O, we designed a precise (standard error +/-0.05%) experiment that measures the parameters of bacterial growth in minimal media with varying isotopic composition. A number of predicted resonance conditions were tested, with significant enhancements in kinetics discovered at these conditions. The combined statistics extremely strongly supports the validity of the isotopic resonance phenomenon (p << 10-15). This phenomenon has numerous implications for the origin of life studies and astrobiology, and possible applications in agriculture, biotechnology, medicine, chemistry and other areas.

Accessory Mineral Records of Early Earth Crust-Mantle Systematics: an Example From West Greenland

NASA Astrophysics Data System (ADS)

Storey, C. D.; Hawkesworth, C. J.

2008-12-01

Conditions for the formation and the nature of Earth's early crust are enigmatic due to poor preservation. Before c.4 Ga the only archives are detrital minerals eroded from earlier crust, such as the Jack Hills zircons in western Australia, or extinct isotope systematics. Zircons are particularly powerful since they retain precise records of their ages of crystallisation, and the Lu-Hf radiogenic isotope and O stable isotope systematics of the reservoir from which they crystallised. In principle, this allows insight into the nature of the crust, the mantle reservoir from which the melt was extracted and any reworked material incorporated into that melt. We have used in situ methods to measure U-Pb, O and Lu-Hf within single zircon crystals from tonalitic gneisses from West Greenland in the vicinity of the Isua Supracrustal Belt. They have little disturbed ages of c.3.8 Ga, mantle-like O isotope signatures and Lu-Hf isotope signatures that lie on the CHUR evolution line at 3.8 Ga. These samples have previously been subjected to Pb isotope feldspar and 142Nd whole rock analysis and have helped constrain models in which early differentiation of a proto-crust must have occurred. The CHUR-like Lu-Hf signature, along with mantle-like O signature from these zircons suggests juvenile melt production at 3.8 Ga from undifferentiated mantle, yet the other isotope systems preclude this possibility. Alternatively, this is further strong evidence for a heterogeneous mantle in the early Earth. Whilst zircons afford insight into the nature of the early crust and mantle, it is through the Sm-Nd system that the mantle has traditionally been viewed. Titanite often contains several thousand ppm Nd, making it amenable to precise analysis, and is a common accessory phase. It has a reasonably high closure temperature for Pb and O, and it can retain cores with older ages and distinct REE chemistry. It is often the main accessory phase alongside zircon, and it is the main carrier of Nd within the whole rock such that Nd isotope analysis of titanite may be able to see-through later alteration that may have partially reset the whole rock system. We present new in-situ U-Pb, O and Sm-Nd and high-precision U-Pb ID-TIMS and Sm-Nd MC- ICPMS data from individual or fragmented titanite grains. We discuss how these data complement the zircon data and may help to resolve long-standing debates in ancient gneiss terranes, with utility to the nature and formation of crust on the early Earth.

Boron and strontium isotope ratios and major/trace elements concentrations in tea leaves at four major tea growing gardens in Taiwan.

PubMed

Chang, Cheng-Ta; You, Chen-Feng; Aggarwal, Suresh Kumar; Chung, Chuan-Hsiung; Chao, Hung-Chun; Liu, Hou-Chun

2016-06-01

Isotopic compositions of B and Sr in rocks and sediments can be used as tracers for plant provincial sources. This study aims to test whether tea leaf origin can be discriminated using (10)B/(11)B and Sr isotopic composition data, along with concentrations of major/trace elements, in tea specimens collected from major plantation gardens in Taiwan. The tea leaves were digested by microwave and analyzed by multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). The data showed significant variations in (87)Sr/(86)Sr ratios (from 0.70482 to 0.71462), which reflect changes in soil, groundwater or irrigation conditions. The most radiogenic tea leaves were found at the Taitung garden and the least radiogenic ones were from the Hualien garden. The δ (11)B was found to change appreciably (δ (11)B = 0.38-23.73 ‰) which could be due to fertilizers. The maximum δ (11)B was also observed in tea samples from the Hualien garden. Principal component analysis combining (87)Sr/(86)Sr, δ (11)B and major/trace elements results successfully discriminated different sources of major tea gardens in Taiwan, except the Hualien gardens, and this may be due to rather complicated local geological settings.

Legacy of contaminant N sources to the NO3− signature in rivers: a combined isotopic (δ15N-NO3−, δ18O-NO3−, δ11B) and microbiological investigation

PubMed Central

Briand, Cyrielle; Sebilo, Mathieu; Louvat, Pascale; Chesnot, Thierry; Vaury, Véronique; Schneider, Maude; Plagnes, Valérie

2017-01-01

Nitrate content of surface waters results from complex mixing of multiple sources, whose signatures can be modified through N reactions occurring within the different compartments of the whole catchment. Despite this complexity, the determination of nitrate origin is the first and crucial step for water resource preservation. Here, for the first time, we combined at the catchment scale stable isotopic tracers (δ15N and δ18O of nitrate and δ11B) and fecal indicators to trace nitrate sources and pathways to the stream. We tested this approach on two rivers in an agricultural region of SW France. Boron isotopic ratios evidenced inflow from anthropogenic waters, microbiological markers revealed organic contaminations from both human and animal wastes. Nitrate δ15N and δ18O traced inputs from the surface leaching during high flow events and from the subsurface drainage in base flow regime. They also showed that denitrification occurred within the soils before reaching the rivers. Furthermore, this study highlighted the determinant role of the soil compartment in nitrate formation and recycling with important spatial heterogeneity and temporal variability. PMID:28150819

In situ observations of the isotopic composition of methane at the Cabauw tall tower site

NASA Astrophysics Data System (ADS)

Röckmann, Thomas; Eyer, Simon; van der Veen, Carina; Popa, Maria E.; Tuzson, Béla; Monteil, Guillaume; Houweling, Sander; Harris, Eliza; Brunner, Dominik; Fischer, Hubertus; Zazzeri, Giulia; Lowry, David; Nisbet, Euan G.; Brand, Willi A.; Necki, Jaroslav M.; Emmenegger, Lukas; Mohn, Joachim

2016-08-01

High-precision analyses of the isotopic composition of methane in ambient air can potentially be used to discriminate between different source categories. Due to the complexity of isotope ratio measurements, such analyses have generally been performed in the laboratory on air samples collected in the field. This poses a limitation on the temporal resolution at which the isotopic composition can be monitored with reasonable logistical effort. Here we present the performance of a dual isotope ratio mass spectrometric system (IRMS) and a quantum cascade laser absorption spectroscopy (QCLAS)-based technique for in situ analysis of the isotopic composition of methane under field conditions. Both systems were deployed at the Cabauw Experimental Site for Atmospheric Research (CESAR) in the Netherlands and performed in situ, high-frequency (approx. hourly) measurements for a period of more than 5 months. The IRMS and QCLAS instruments were in excellent agreement with a slight systematic offset of (+0.25 ± 0.04) ‰ for δ13C and (-4.3 ± 0.4) ‰ for δD. This was corrected for, yielding a combined dataset with more than 2500 measurements of both δ13C and δD. The high-precision and high-temporal-resolution dataset not only reveals the overwhelming contribution of isotopically depleted agricultural CH4 emissions from ruminants at the Cabauw site but also allows the identification of specific events with elevated contributions from more enriched sources such as natural gas and landfills. The final dataset was compared to model calculations using the global model TM5 and the mesoscale model FLEXPART-COSMO. The results of both models agree better with the measurements when the TNO-MACC emission inventory is used in the models than when the EDGAR inventory is used. This suggests that high-resolution isotope measurements have the potential to further constrain the methane budget when they are performed at multiple sites that are representative for the entire European domain.

In-situ observations of the isotopic composition of methane at the Cabauw tall tower site

NASA Astrophysics Data System (ADS)

Röckmann, Thomas; Eyer, Simon; van der Veen, Carina; E Popa, Maria; Tuzson, Béla; Monteil, Guillaume; Houweling, Sander; Harris, Eliza; Brunner, Dominik; Fischer, Hubertus; Zazzeri, Giulia; Lowry, David; Nisbet, Euan G.; Brand, Willi A.; Necki, Jaroslav M.; Emmenegger, Lukas; Mohn, Joachim

2017-04-01

High precision analyses of the isotopic composition of methane in ambient air can potentially be used to discriminate between different source categories. Due to the complexity of isotope ratio measurements, such analyses have generally been performed in the laboratory on air samples collected in the field. This poses a limitation on the temporal resolution at which the isotopic composition can be monitored with reasonable logistical effort. Here we present the performance of a dual isotope ratio mass spectrometric system (IRMS) and a quantum cascade laser absorption spectroscopy (QCLAS) based technique for in-situ analysis of the isotopic composition of methane under field conditions. Both systems were deployed at the Cabauw experimental site for atmospheric research (CESAR) in the Netherlands and performed in-situ, high-frequency (approx. hourly) measurements for a period of more than 5 months. The IRMS and QCLAS instruments were in excellent agreement with a slight systematic offset of +0.05 ± 0.03 ‰ for δ13C-CH4 and -3.6 ± 0.4 ‰ for δD-CH4. This was corrected for, yielding a combined dataset with more than 2500 measurements of both δ13C and δD. The high precision and temporal resolution dataset does not only reveal the overwhelming contribution of isotopically depleted agricultural CH4 emissions from ruminants at the Cabauw site, but also allows the identification of specific events with elevated contributions from more enriched sources such as natural gas and landfills. The final dataset was compared to model calculations using the global model TM5 and the mesoscale model FLEXPART-COSMO. The results of both models agree better with the measurements when the TNO-MACC emission inventory is used in the models than when the EDGAR inventory is used. This suggests that high-resolution isotope measurements have the potential to further constrain the methane budget, when they are performed at multiple sites that are representative for the entire European domain.

Field-based stable isotope analysis of carbon dioxide by mid-infrared laser spectroscopy for carbon capture and storage monitoring.

PubMed

van Geldern, Robert; Nowak, Martin E; Zimmer, Martin; Szizybalski, Alexandra; Myrttinen, Anssi; Barth, Johannes A C; Jost, Hans-Jürg

2014-12-16

A newly developed isotope ratio laser spectrometer for CO2 analyses has been tested during a tracer experiment at the Ketzin pilot site (northern Germany) for CO2 storage. For the experiment, 500 tons of CO2 from a natural CO2 reservoir was injected in supercritical state into the reservoir. The carbon stable isotope value (δ(13)C) of injected CO2 was significantly different from background values. In order to observe the breakthrough of the isotope tracer continuously, the new instruments were connected to a stainless steel riser tube that was installed in an observation well. The laser instrument is based on tunable laser direct absorption in the mid-infrared. The instrument recorded a continuous 10 day carbon stable isotope data set with 30 min resolution directly on-site in a field-based laboratory container during a tracer experiment. To test the instruments performance and accuracy the monitoring campaign was accompanied by daily CO2 sampling for laboratory analyses with isotope ratio mass spectrometry (IRMS). The carbon stable isotope ratios measured by conventional IRMS technique and by the new mid-infrared laser spectrometer agree remarkably well within analytical precision. This proves the capability of the new mid-infrared direct absorption technique to measure high precision and accurate real-time stable isotope data directly in the field. The laser spectroscopy data revealed for the first time a prior to this experiment unknown, intensive dynamic with fast changing δ(13)C values. The arrival pattern of the tracer suggest that the observed fluctuations were probably caused by migration along separate and distinct preferential flow paths between injection well and observation well. The short-term variances as observed in this study might have been missed during previous works that applied laboratory-based IRMS analysis. The new technique could contribute to a better tracing of the migration of the underground CO2 plume and help to ensure the long-term integrity of the reservoir.

[Measurements of stable isotopes in atmospheric CO2 and H2O by open-path Fourier transform infrared spectrometry].

PubMed

Wang, Wei; Liu, Wen-Qing; Zhang, Tian-Shu

2013-08-01

The development of spectroscopic techniques has offered continuous measurement of stable isotopes in the ambient air. The method of measuring environmental stable isotopes based on Fourier transform infrared spectrometry (FTIR) is described. In order to verify the feasibility of the method for continuous measurement of the stable isotopes, an open-path FTIR system was used to measure stable isotopes of CO2 and H2O in ambient air directly in a seven-day field experiment, including 12CO2, 3CO2, H2 16O and HD16 O. Also, the time course of carbon isotopic ratio delta13 C and deuterium isotope composition deltaD was calculated. The measurement precision is about 1.08 per thousand for delta13 C and 1.32 per thousand for deltaD. The measured stable isotopes of CO2 and H2O were analyzed on different time scales by Keeling plot methods, and the deuterium isotopic ratios of evapotranspiration were determined. The results of the field experiment demonstrate the potential of the open-path FTIR system for continuous measurement of stable isotopes in the air.

Determination of tin isotope ratios in cassiterite by femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Schulze, Marie; Ziegerick, Marco; Horn, Ingo; Weyer, Stefan; Vogt, Carla

2017-04-01

In comparison to isotope analysis of dissolved samples femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry (fs-LA-MC-ICP-MS) enables precise isotope ratio analyses consuming much less sample material and with a minimum effort in sample preparation. This is especially important for the investigation of valuable historical objects for which visual traces of sampling are unwanted. The present study provides a basis for tin isotope ratio measurements using LA-MC-ICP-MS technique. For this, in house isotope standards had to be defined. Investigations on interferences and matrix effects illustrate that beside Sb only high Te contents (with values above those to be expected in cassiterite) result in a significant shift of the measured tin isotope ratios. This effect can partly be corrected for using natural isotope abundances. However, a natural isotope fractionation of Te cannot be excluded. Tin beads reduced from cassiterite were analysed by laser ablation and after dissolution. It was shown that tin isotope ratios can be determined accurately by using fs-LA-MC-ICP-MS. Furthermore the homogeneity of tin isotope ratios in cassiterite was proven.

Selenium isotope ratios as indicators of selenium sources and oxyanion reduction

USGS Publications Warehouse

Johnson, T.M.; Herbel, M.J.; Bullen, T.D.; Zawislanski, P.T.

1999-01-01

Selenium stable isotope ratio measurements should serve as indicators of sources and biogeochemical transformations of Se. We report measurements of Se isotope fractionation during selenate reduction, selenite sorption, oxidation of reduced Se in soils, and Se volatilization by algae and soil samples. These results, combined with previous work with Se isotopes, indicate that reduction of soluble oxyanions is the dominant cause of Se isotope fractionation. Accordingly, Se isotope ratios should be useful as indicators of oxyanion reduction, which can transform mobile species to forms that are less mobile and less bioavailable. Additional investigations of Se isotope fractionation are needed to confirm this preliminary assessment. We have developed a new method for measurement of natural Se isotope ratio variation which requires less than 500 ng Se per analysis and yields ??0.2??? precision on 80Se/76Se. A double isotope spike technique corrects for isotopic fractionation during sample preparation and mass spectrometry. The small minimum sample size is important, as Se concentrations are often below 1 ppm in solids and 1 ??g/L in fluids. The Se purification process is rapid and compatible with various sample matrices, including acidic rock or sediment digests.