A 10-fold improvement in the precision of boron isotopic analysis by negative thermal ionization mass spectrometry

Boron isotopes are potentially very important to cosmochemistry, geochemistry, and paleoceanography. However, the application has been hampered by the large sample required for positive thermal ionization mass spectrometry (PTIMS), and high mass fractionation for negative-TIMS (NTIMS). Running as BO(2)(-), NTIMS is very sensitive and requires only nanogram sized samples, but it has rather poor precision (approximately 0.7-2.0 per thousand) as a result of the larger mass fractionation associated with the relatively light ion. In contrast, running as the much heavier molecule of Cs(2)BO(2)(+), PTIMS usually achieves better precision around 0.1-0.4 per thousand. Moreover, there is a consistent 10 per thousand offset in the (11)B/(10)B ratio for NIST SRM 951 standard boric acid between the NTIMS and the certified value, but the cause of this offset is unclear. In this paper, we have adapted a technique we developed earlier to measure the (138)La/(139)La using LaO(+) (1) to improve the NTIMS technique for BO(2). We were able to correct for instrumental fractionation by measuring BO(2)(-) species not only at masses of 42 and 43, but also at 45, which enabled us to normalize (45)BO(2)/(43)BO(2) to an empirical (18)O/(16)O value. We found that both I(45)/I(42) = ((11)B(16)O(18)O/(10)B(16)O(16)O) and (I(43)/I(42))(C) = ((11)B(16)O(16)O/(10)B(16)O(16)O) vary linearly with (I(45)/I(43))(C) x 0.5 = ((11)B(16)O(18)O/(11)B(16)O(16)O) x 0.5 = (18)O/(16)O. In addition, different activators and different chemical forms of B yield different slopes for the fractionation lines. After normalizing (11)B(16)O(18)O/(11)B(16)O(16)O x 0.5 to a fixed (18)O/(16)O value, we obtained a mean (11)B/(10)B value of NIST SRM 951 that matches the NIST certified value at 4.0430 +/- 0.0015 (+/-0.36 per thousand, n = 11). As a result, our technique can achieve precision and accuracy comparable to that of PTIMS with only 1 per thousand of the sample required. This new NTIMS technique for B isotopes is critical to the studies of early solids in the solar system and individual foraminifera in sediments that require both high sensitivity and precision.     

Investigation of uranium isotopic signatures in real-life particles from a nuclear facility by thermal ionization mass spectrometry

An improved method was recently developed for the isotopic analysis of single-reference uranium oxide particles for nuclear safeguards. This method is a combination of analytical tools including in situ SEM micromanipulation, filament carburization and multiple ion counting (MIC) detection, which is found to improve sensitivity for thermal ionization mass spectrometry (TIMS) isotope ratio analysis. The question was raised whether this method could be applied for the detection of nuclear signatures in real-life particles with unknown isotopic composition. Therefore, environmental dust was collected in different locations within a nuclear facility. The screening of the samples to find the uranium particles of interest was performed using a scanning electron microscope (SEM) equipped with an energy-dispersive X-ray (EDX) detector. The comparison of the measurement results to reference data evaluated by international safeguards authorities was of key importance for data interpretation. For the majority of investigated particles, detection of uranium isotopic signatures provided information on current and past nuclear feed operations that compared well with facility declarations.     

Determination of radium isotope ratios and abundances in geologic samples by thermal ionization mass spectrometry

We describe chemical separation and mass spectrometric procedures for the measurement of radium isotopes in geologic samples. These methods provide 226Ra/228Ra ratio measurements for 1 g or less of rock sample containing subpicogram amounts of radium with precision better than 1.5% (95% confidence level). Radium-226 concentrations were measured by isotope dilution for smaller sample sizes (100-500 mg) containing as little as 1-10 fg of total 226Ra with similar high precision.     

Determination of dissolved metal species by electrospray ionization mass spectrometry

The distribution of metal species in solution was determined using flow injection electrospray ionization mass spectrometry. Complexes formed by selected metal ions with added organic ligands in 50:50 water/acetonitrile and 50:50 water/methanol under acidic, neutral, and basic conditions were detected using electrospray ionization conditions optimized to best represent solution-phase interactions. Metal species containing acetate, nitrate, and solvent molecules predominated in acidic solution but became less abundant at higher pH. Interactions between metal ions and added organic ligands became more selective with increasing pH, showing the expected preference of hard and soft ligands for metal ions of the corresponding type. Species distributions also tended toward larger complexes as pH increased. Overall ion yield was greater for aqueous acetonitrile than for aqueous methanol solutions; however, reduction of copper(II) in aqueous acetonitrile resulted in the detection of copper(I) complexes for certain ligands. Experimental results for copper(II) and 8-hydroxyquinoline in 50:50 water/methanol showed good agreement with aqueous speciation predicted using the thermodynamic equilibrium model MINEQL. Detection of neutral complexes was achieved by protonation, deprotonation, or electrochemical oxidation during electrospray.     

Accurate measurement of ruthenium isotopes by negative thermal ionization mass spectrometry

The method for measurement of ruthenium isotopic composition as RuO(3)(-) by negative thermal ionization mass spectrometry (NTI-MS) is shown to be sensitive and accurate. Precise measurement of the (18)O/(16)O ratio, which is important for oxygen correction in NTI-MS, has also been made. Both Re and Pt filaments were tested, and the latter was proved to be more efficient for negative ion production. The mechanism of ion production with the addition of HI as a reducing reagent and Ba(NO(3))(2) as an ionizing enhancer was also studied. Sensitivity was found to be about 100 times higher than that of the positive mode. Factors related to negative ion formation are discussed, and parameters are optimized. The ionization efficiency has been improved to 0.7%. Ten nanograms of Ru yielded a total ion current of 3 × 10(-12) A for 1 h. The precisions of all Ru isotope ratios with a 100 ng sample size were better than 0.009%.     

Determination of iridium in natural waters by clean chemical extraction and negative thermal ionization mass spectrometry

Methods for the precise, routine measurement of Ir in seawater, riverwater, and estuarine water using isotope dilution negative thermal ionization mass spectrometry (ID-NTIMS) have been developed. After equilibration with a (191)Ir-enriched spike, Ir is separated from solution by coprecipitation with ferric hydroxide, followed by anion exchange chromatography using a reductive elution technique. UV irradiation is employed for the decomposition of trace organics, which interfere with negative ion production. IrO(2)(-) ions are produced in the mass spectrometer by heating the sample on a Ni-wire filament in the presence of Ba(OH)(2). Detection efficiencies ranged from 0.1% to 0.3%. We have used these procedures to determine the concentrations of Ir in 4 kg samples from the Pacific Ocean, the Atlantic Ocean, the Baltic Sea, and the rivers supplying the Baltic. Our chemical procedures introduce a total blank of ～2 × 10(8) atoms per sample. The distribution of Ir in the oceans is fairly uniform, averaging ～4 × 10(8) atoms kg(-)(1). The concentrations in the rivers supplying the Baltic Sea range from (17.4 ± 0.9) × 10(8) for a pristine river to (92.9 ± 2.2) × 10(8) atoms kg(-)(1) for a polluted river. The distribution, speciation, and transport of Ir in natural waters can now be subjected to intensive study.     

气相色谱-质谱测定化妆品中的硝基麝香类化合物

建立了化妆品中5种硝基麝香含量的气相色谱-质谱联用检测方法。采用丙酮/正己烷混合液超声提取化妆品中的硝基麝香,提取液经过浓缩,由气相色谱-质谱联用仪检测,以氘代二甲苯麝香内标法定量。该方法对化妆品中5种硝基麝香的加标回收率在85.21%~110.2%之间,相对标准偏差(RSD)不大于7.15%,在50μg/L~5000μg/L范围内呈现良好的线性关系,灵敏度高,最低检测限分别达到20~50μg/kg;选择性好,能有效消除复杂基体干扰。可用于常见化妆品中硝基麝香类化合物含量的检测。     

Major factors affecting the isotopic measurement of chlorine based on the Cs2Cl+ ion by thermal ionization mass spectrometry

The factors that affect isotopic measurement of chlorine based on Cs2Cl+ ion by thermal ionization mass spectrometry were studied. Graphite is essential for the emission of Cs2Cl+ ion from CsCl. No Cs2Cl+ ions are detected in the absence of graphite on the filament. The emission of Cs2Cl+ ion and the measured 37Cl/35Cl ratio were affected by different varieties of graphite, the pH value of the sample solution, and impurities in the solution. High-precision isotopic measurement of chlorine based on Cs2Cl+ ion is achieved only by using graphite with a perfect crystal structure. The measured 37Cl/35Cl ratios were much higher, and even the emission of Cs2Cl+ ion becomes impossible when pH values of the sample solution were higher than 6, corresponding to the presence of excess Cs. The measured 37Cl/35Cl ratios were higher when SO4(2-) and NO3- anions were present. The results show that the measured 37Cl/35Cl ratios are weakly related to the amount of chlorine on filament in a range from 1 to 500 microg.     

Determination of dissociation constants for protein-ligand complexes by electrospray ionization mass spectrometry

A fully automated biophysical assay based on electrospray ionization mass spectrometry (ESI-MS) for the determination of the dissociation constants (KD) between soluble proteins and low molecular mass ligands is presented. The method can be applied to systems where the relative MS response of the protein and the protein-ligand complexes do not reflect relative concentrations. Thus, the employed approach enables the use of both electrostatically and nonpolar bound complexes. The dynamic range is wider than for most biological assays, which facilitates the process of establishing a structure-activity relationship. This fully automated ESI-MS assay is now routinely used for ligand screening. The entire procedure is described in detail using hGHbp, a 25-kDa extracellular soluble domain of the human growth hormone receptor, as a model protein.     

Unnatural isotopic composition of lithium reagents

Isotopic analysis of 39 lithium reagents from several manufacturers indicates that seven were artificially depleted in (6)Li significantly in excess of the variation found in terrestrial materials. The atomic weight of lithium in analyzed reagents ranged from 6.939 to 6.996, and δ(7)Li, reported relative to L-SVEC lithium carbonate, ranged from -11 to +3013‰. This investigation indicates that (6)Li-depleted reagents are now found on chemists' shelves, and the labels of these (6)Li-depleted reagents do not accurately reflect the atomic and (or) molecular weights of these reagents. In 1993, IUPAC issued the following statement: "Commercially available Li materials have atomic weights that range between 6.94 and 6.99; if a more accurate value is required, it must be determined for the specific material." This statement has been found to be incorrect. In two of the 39 samples analyzed, the atomic weight of Li was in excess of 6.99.     

Electrostatic-spray ionization mass spectrometry

An electrostatic-spray ionization (ESTASI) method has been used for mass spectrometry (MS) analysis of samples deposited in or on an insulating substrate. The ionization is induced by a capacitive coupling between an electrode and the sample. In practice, a metallic electrode is placed close to but not in direct contact with the sample. Upon application of a high voltage pulse to the electrode, an electrostatic charging of the sample occurs leading to a bipolar spray pulse. When the voltage is positive, the bipolar spray pulse consists first of cations and then of anions. This method has been applied to a wide range of geometries to emit ions from samples in a silica capillary, in a disposable pipet tip, in a polymer microchannel, or from samples deposited as droplets on a polymer plate. Fractions from capillary electrophoresis were collected on a polymer plate for ESTASI MS analysis.     

Developing micro-Raman mass spectrometry for measuring carbon isotopic composition of carbon dioxide

We investigated the applicability of micro-Raman spectroscopy for determining carbon isotopic compositions (13C/12C) of minute CO2 fluid inclusions in minerals. This method is nondestructive and has sufficiently high spatial resolution (1 microm) to measure each fluid inclusion independently. Raman spectra of CO2 fluid have 12CO2-origin peaks at about 1285 cm(-1) and 1389 cm(-1) (V(-)([12]) and V+[12]) and a 13CO2-origin peak at about 1370 cm(-1) (V+[13]). The relationship between carbon isotopic compositions and peak intensity ratios of V+[12] and V+[13] was calibrated. Considering several factors affecting the peak intensity ratio, the error in obtained carbon isotopic composition was 2% (20%). The reproducibility of the intensity ratio under the same experimental environment was 0.5% (5%). Within these error values, we can distinguish biogenic CO2 from abiogenic CO2.     

Chiral analysis by electrospray ionization mass spectrometry/mass spectrometry. 2. Determination of enantiomeric excess of amino acids

The determination of enantiomeric excess (ee) of amino acids was achieved by investigating the collision-induced dissociation spectra of protonated trimers that were formed by electrospray ionization of amino acids in the presence of one of the following chiral selectors: L- or D-N-tert-butoxycarbonylphenylalanine, L- or D-N-tert-butoxycarbonylproline, and L- or D-N-tert-butoxycarbonyl-O-benzylserine. The protonated trimers were dissociated to form protonated dimers, and the observed dissociation efficiency r (i.e., the intensity ratio of protonated dimers to protonated trimers) for an enantiomeric mixture was found to be related to its ee value by the following equation: r = a + b/(c + ee), where a, b, and c were constants. A linear calibration plot was obtained by plotting r versus 1/(c + ee), where c was calculated with the MATLAB software, or by plotting 1/(r - r0) versus 1/ee, where r0 was the r value for the racemic mixture. The latter "two-reciprocal" method was more convenient for application. Another practical method for ee determination was the "three-point" method, whereby the ee of an unknown sample with a measured r value could be derived from the equation ee = 100?1/(rL - r0) - 1/(rD - r0)?/?2/(r - r0) - 1/(rL - r0) - 1/(rD - r0)?, with rL and rD being the r values for the enantiomerically pure L- and D-forms of the sample, respectively. A calibration plot was not required. The ee determination was achieved with acceptable precision even for the worst case of acceptable chiral recognition with a particular chiral selector, suggesting that the ee determination of all 19 common amino acids could be achieved by the present method. The ee of a histidine sample was determined both by the two-reciprocal method, giving an error of 0.2% ee (1.1% relative error) and consuming only approximately 5.3 nmol of sample, and by the three-point method, giving an error of 0.4% ee and consuming only approximately 2.3 nmol of sample. In the latter case, it took 27 min for the mass spectrometric measurements of the three calibration standards and an additional 9 min for the unknown sample. The direct ee determination of more than one amino acid in a mixture was also demonstrated in the study.     

Determination of iodine in oyster tissue by isotope dilution laser resonance ionization mass spectrometry

The technique of laser resonance ionization mass spectrometry has been combined with isotope dilution analysis to determine iodine in oyster tissue. The long-lived radioisotope, 129I, was used to spike the samples. Samples were equilibrated with the 129I, wet ashed under controlled conditions, and iodine separated by coprecipitation with silver chloride. The analyte was dried as silver ammonium iodide upon a tantalum filament from which iodine was thermally desorbed in the resonance ionization mass spectrometry instrument. A single-color, two-photon resonant plus one-photon ionization scheme was used to form positive iodine ions. Long-lived iodine signals were achieved from 100 ng of iodine. The precision of 127I/129I measurement has been evaluated by replicate determinations of the spike, the spike calibration samples, and the oyster tissue samples and was 1.0%. Measurement precision among samples was 1.9% for the spike calibration and 1.4% for the oyster tissue. The concentration of iodine determined in SRM 1566a, Oyster Tissue, was 4.44 micrograms/g with an estimate of the overall uncertainty for the analysis of +/- 0.12 microgram/g.