The determination of carbon,nitrogen and oxygen in gases by neutron time-of-flight spectrometry

Carbon, nitrogen and oxygen were determined in gases by time-of-flight spectrometry of prompt neutrons from the respective reactions¹²C(d, n)¹³N,¹⁴N(d, n)¹⁵O and¹⁶O(d, n)¹⁷F, produced by a pulsed beam of deuterons of 2 MeV (for nitrogen) or 3 MeV. The analysis is non-destructive and requires about 15 min. per sample. The relative standard deviation for all three elements was about ±3%. Detection limits, using a total irradiation current of 20 millicoulombs, for carbon, nitrogen and oxygen, respectively, were 6·10⁻⁸ g, 2·10⁻⁷ g and 1.7·10⁻⁷ g per cm² cross-sectional area of irradiating beam.     

Statistical mechanics of Ar2+ in an inductively coupled plasma

In the mass spectrum of an argon inductively coupled plasma (ICP), there is a peak due to the presence of the argon dimer ion, Ar₂⁺. Using elementary statistical mechanics, an attempt is made to elucidate the mechanism responsible for this ion's presence in the ICP, The assumption of local thermodynamic equilibrium (LTE) in the ICP leads to three possible mechanisms that could be responsible for the presence of the argon dimer ion, however, the results of the calculations show that only one of the mechanisms agrees with experiment. The experimental measurements of the number density ratio of Ar₂⁺ to Ar⁺, against which the theoretical values are compared, were taken using inductively coupled plasma mass spectrometry (ICP-MS),     

Homogeneous and heterogeneous triplet — triplet annihilation in anthracene-doped phenanthrene crystals

Delayed and prompt fluorescence spectra and delayed fluorescence decay data for 10^?5?10^?6 M/M crystals of anthracene in phenanthrene are reported. It is shown that these data indicate that a heterogeneous (host-dopant) annihilation process takes place which produces the excited singlet state of the host molecule.     

Development and characterization of a 9-mm inductively-coupled argon plasma source for atomic emission spectrometry

A new 9-mm (i.d.) inductively-coupled plasma (ICP) torch is described which supports a stable, analytically useful plasma at less than 500 W of r.f. power and 7 l min^-1 total argon gas flow. Detection limits, working curves and other analytical characteristics of the new device are compared with those of both a miniature (13-mm i.d.) and conventional (19-mm i.d.) ICP. Although temperatures of the new plasma are somewhat lower than those in the larger plasmas, the new system offers promise for future, miniaturized ICP instruments.     

Analytical atomic spectroscopy using ion trap devices

Investigations using ion trap devices for analytical atomic spectroscopy purposes have focused on the use of an inductively coupled plasma (ICP) ion source with ion trap mass spectrometric (ITMS) detection. Initial studies were conducted with an instrument assembled by simply appending an ion trap as the detector to a fairly conventional ICP/MS instrument, i.e. leaving an intermediate linear quadrupole between the plasma source and the ion trap. The principal advantages found with this system include the destruction of nearly all problematic and typical ICP/MS polyatomic ions (e.g., ArH⁺, ArO⁺, ArCl⁺, Ar₂⁺, etc) and a dramatic reduction of the primary plasma source ion, Ar⁺. These results prompted the development of a second-generation plasma source ion trap instrument in which direct coupling of the ICP and ion trap has been effected (i.e. no intermediate linear quadrupole); the same performance benefits have been largely preserved. Initial operation of this instrument is described, characterized, and compared to the originally described ICP/ITMS and conventional ICP/MS systems. In addition, experiments aimed at improving ICP/ITMS sensitivity and selectivity using broadband resonance excitation techniques are described. Finally, the potential for laser optical detection of trapped ions for analytical purposes is speculated upon.     

Measurement of thermal neutron capture cross sections of 237Np and 242Pu using prompt gamma neutron activation

Several samples of ²³⁷Np and ²⁴²Pu were irradiated in the guided cold neutron beam of the prompt gamma activation analysis facility at the Budapest Research Reactor. The thermal neutron capture cross sections of ²³⁷ Np and ²⁴²Pu were evaluated from the obtained prompt and delayed gamma ray data. The thermal neutron capture cross sections for ²³⁷Np(n,γ)²³⁸Np was found to be $ \sigma_{0} ({}^{237}{\text{Np}}) = 170.4 \pm 7.4\,{\text{b}} $ and for ²⁴²Pu(n,γ)²⁴³Pu to be $ \sigma_{0} ({}^{242}{\text{Pu}}) = 19.6 \pm 3.9\,{\text{b}} $ .     

Determination of129I in ambient air by inductively coupled plasma mass spectrometry (ICP/MS)

The detection of¹²⁹I by Inductively Coupled Plasma Mass Spectrometry (ICP/MS) in environmental samples can be used to determine anthropogenic release of this long-lived radionuclide, which is a definitive indicator of certain nuclear activities. By using selective precipitation techniques with on-line ICP/MS detection, low levels of¹²⁹I can be detected. The major interference for the ICP/MS detection of¹²⁹I is due the presence of natural¹²⁹Xe found in water samples at a concentration of about 1 ng/ml. This work will demonstrate a instrument detection of less than 50 fg¹²⁹I from environmental air samples and shows promise for a rugged ICP/MS technique to monitor¹²⁹I levels in ambient air for nonproliferation monitoring purposes.     

Beta decay of the fission product Sb and a new complete evaluation of absolute gamma ray transition intensities

The radionuclide ¹²⁵Sb is a long-lived fission product, which decays to ¹²⁵Te by negative beta emission with a half-life of 1008 day. The beta decay is followed by the emission of several gamma radiations, ranging from low to medium energy, that can suitably be used for high-resolution detector calibrations, decay heat calculations and in many other applications. In this work, the beta decay of ¹²⁵Sb has been studied in detail. The complete published experimental data of relative gamma ray intensities in the beta decay of the radionuclide ¹²⁵Sb has been compiled. The consistency analysis was performed and discrepancies found at several gamma ray energies. Evaluation of the discrepant data was carried out using Normalized Residual and RAJEVAL methods. The decay scheme balance was carried out using beta branching ratios, internal conversion coefficients, populating and depopulating gamma transitions to ¹²⁵Te levels. The work has resulted in the consistent conversion factor equal to 29.59(13) %, and determined a new evaluated set of the absolute gamma ray emission probabilities. The work has also shown 22.99% of the delayed intensity fraction as outgoing from the 58 d isomeric 144 keV energy level and 77.01% of the prompt intensity fraction reaching to the ground state from the other excited states. The results are discussed and compared with previous evaluations. The present work includes additional experimental data sets which were not included in the previous evaluations. A new set of recommended relative and absolute gamma ray emission probabilities is presented.     

Comparison of temperature measurements in ICP and MIP with Ar and He as plasma gas

Various temperature measurements have been carried out in microwave induced plasmas (MIP) generated with a surfatron and inductivcly coupled plasmas (ICP) both with argon and helium as plasma gas. Iron has been used for the determination of excitation temperature, and OH and N⁺₂ for rotational temperatures. In the case of the Ar ICP, equilibrium is attained between the various temperatures (4500 K), as previously described. On the other hand, in the He ICP and the MIPs, iron provides the highest temperature (4500 K) but discrepancies are obtained with results from N⁺₂ and OH. These two species show lower values, especially OH (2000 K).     

Near‐field laser ablation inductively coupled plasma mass spectrometry: a novel elemental analytical technique at the nanometer scale

An analytical technique utilizing a near‐field effect (to enhance the incident light energy on the thin tip of an Ag needle) in a laser ablation inductively coupled plasma mass spectrometry (NF‐LA‐ICP‐MS) procedure was developed. To produce the thin needles with a tip diameter in the hundreds of nm range a robust needle etching procedure was established. The ‘sample‐to‐tip’ distance was controlled via the measurement of a tunnel current between the needle and sample surface. The NF‐LA‐ICP‐MS technique thus developed was applied for the analysis of copper isotopic standard reference material NIST SRM 976 and tungsten‐molybdenum alloy NIST SRM 480 in the nm resolution range. The observed craters ranged from 200 nm to about 2 µm in diameter and were dependent on the needle used as well as on the ‘sample‐to‐tip’ distance. The mass spectrometric measurements of ⁶³Cu⁺ ion intensity on NIST SRM 976 showed that using near‐field enhancement in laser ablation allowed a roughly 6‐fold increase in the ion intensity of the analyte when the needle was about 100 nm (and below) from the surface, in contrast to when it was far away (e.g. 10 µm) from the sample. The relative standard deviation (RSD) of the ⁶⁵Cu⁺/⁶³Cu⁺ isotopic ratio measurements by NF‐LA‐ICP‐MS was 3.9% (n = 9). The detection efficiencies obtained for the compared LA‐ICP‐MS and NF‐LA‐ICP‐MS methods were found to be 4.6 * 10^?3 counts per second (cps)/ablated atom and 2.7 * 10^?5 cps/ablated atom, respectively. Copyright © 2008 John Wiley & Sons, Ltd.     

CE with on‐line detection by ICP‐MS for studying the competitive binding of zinc against cadmium for glutathione

Development of a feasible method for studying the competitive interaction between a pair of antagonists is essential for understanding the antagonism of trace metals in biological systems. Herein, we report the application of CE on‐line coupled with ICP mass spectroscopy (CE‐ICP‐MS) to investigate the competitive binding of Zn²⁺ against Cd²⁺ for glutathione (GSH), which is related to the detoxification of Cd²⁺ in biological system, and introduce a method to evaluate the kinetics and thermodynamics for the competitive binding of Zn²⁺ against Cd²⁺ for GSH. The CE‐ICP‐MS hybrid technique allows easy and sensitive probing of the competitive binding of Zn²⁺ against Cd²⁺ for GSH and quantitative determination of the important thermodynamic and kinetic parameters of the competitive binding of Zn²⁺ against Cd²⁺ for GSH. Owing to the high sensitivity and element selectivity with multi‐elements detection capacity of ICP‐MS, we detailed the evaluation of the kinetics and thermodynamics describing the competition of Zn²⁺ against Cd²⁺ for GSH from the systematic data obtained by CE‐ICP‐MS. The competitive binding of Zn²⁺ against Cd²⁺ for GSH was demonstrated exothermic and thermodynamically favorable (ΔG=?7.2 kJ/mol) and driven entirely by a large favorable enthalpy decrease (ΔH=?15.1 kJ/mol) but with an unfavorable entropy decrease (ΔS=?25.6 J/mol/K). The kinetic data were fit to a second‐order equation with the reaction rate constant (k) of (2.18±0.10)×10² L/(mol·s) under the simulated physiological condition.     

Evaluation of metal and radionuclide data from neutron activation and acid-digestion-based spectrometry analyses of background soils: Significance in environmental restoration

A faster, more cost-effective, and higher-quality data acquisition for natural background-level metals and radionuclides in soils is needed for remedial investigations of contaminated sites. The advantages and disadvantages of neutron activation analysis (NAA) compared with those of acid-digestion-based spectrometry (ADS) methods were evaluated using Al, Sb, As, Cr, Co, Fe, Mg, Mn, Hg, K, Ag,²³²Th,²³⁵U,²³⁸U, V, and Zn data. The ADS methods used for this project were inductively coupled plasma (ICP), ICP-mass spectrometry (ICP-MS), and alpha spectrometry. Scatter plots showed that the NAA results for As, Co, Fe, Mn,²³²Th, and²³⁸U are reasonably correlated with the results from the other analytical methods. Compared to NAA, however, the ADS methods underestimated Al, Cr, Mg, K, V, and Zn. Because of the high detection limits of ADS methods, the scatter plots of Sb, Hg, and Ag did not show a definite relationship. The NAA results were highly correlated with the alpha spectrometry results for²³²Th and²³⁸U but poorly correlated for²³⁵U. The NAA, including the delayed neutron counting, was a far superior technique for quantifying background levels of radionuclides (²³²Th,²³⁵U, and²³⁸U) and metals (Al, Cr, Mg, K, V, and Zn) in soils.     

Speciation Analysis of Thallium by Reversed‐phase Liquid Chromatography ‐ Inductively Coupled Plasma Mass Spectrometry

An inductively coupled plasma mass spectrometer (ICP‐MS) was used as a liquid chromatographic detector for the speciation analysis of thallium in environmental samples. In this study, ionic thallium species, namely Tl(I) and Tl(III) were well separated by reversed‐phase high performance liquid chromatography (RP‐HPLC) with a C8‐HPLC column as the stationary phase and 1 mmol L^?1 tetrabutylammonium phosphate (TBAP), 2 mmol L^?1 diethylenetriamine pentaacetic acid (DTPA) in 1% v/v methanol solution (pH 6) as the mobile phase. Effluent from the HPLC column was delivered to the nebulizer of the ICP‐MS for the determination of thallium. The separation was complete in less than 3 min. Detection limit was 0.002 μg L^?1 for both Tl(I) and Tl(III) compounds based on peak height. The relative standard deviation of the peak areas for five injections of a mixture containing 1 μg Tl L^?1 was better than 3.4%. The concentrations of Tl compounds were determined in standard reference materials, including NIST SRM 1643e Trace Elements in Water and NRCC NASS‐5 Open Ocean Seawater and water samples collected in Kaohsiung area, Taiwan. The HPLC‐ICP‐MS results of the reference samples agreed with the reference values. This method has also been applied to determine Tl(I) and Tl(III) compounds in custard apple (Annona squamosa) leaves collected from Chai‐shan Mountain, Kaohsiung and Taitung City, Taiwan. The thallium species were quantitatively leached from the leaves with a 5 mmol L^?1 DTPA in 100 mmol L^?1 ammonium acetate solution in an ultrasonic bath during a period of 30 min. The HPLC‐ICP‐MS result that was obtained after the analysis of leaves sample showed a satisfactory agreement with the total thallium concentration obtained by ICP‐MS analysis of completely dissolved sample.     

Rapid pre-concentration of Escherichia coli in a microfluidic paper-based device using ion concentration polarization

We report a microfluidic paper based analytical device implementing ion concentration polarization (ICP) for rapid pre-concentration of Escherichia coli in water. The fabricated device consists of a paper channel with a Nafion^® membrane and in-built micro wire electrodes to supply electric voltage to induce the ICP effect. E. coli cells were stained with SYTO 9 and fluorescence was used as a sensing method. The device achieved high concentration factor up to 2 × 10⁵ within minutes. The effect of total ion concentration, on ICP and fluorescence intensity was studied. The reported device and method are suitable and effective for detection of E. coli during ballast water quality monitoring, coastal water quality monitoring where high salinity water is present.     

Measurement of k0-Factors in Prompt Gamma-Ray Neutron Activation Analysis

The guided thermal neutron beam at 100 MW Dhruva research reactor facility of Bhabha Atomic Research Centre (BARC) was used to carry out prompt gamma-ray neutron activation analysis (PGNAA). The prompt k ₀-factors have been determined for the isotopes of the elements H, B, K, Co, Cu, Ca, Ti, Cr, Cd, Ba, Hg and Gd with respect to 1951 keV gamma-line of ³⁶Cl. The prompt k ₀-factors for H, Cl and Cu were also measured with respect to the 1381 keV gamma-line of ⁴⁹Ti. Different samples like NH₄Cl, Ti metal, cobalt chloride and other stoichiometric compounds and pure metals were used for this purpose. Prompt gamma-rays were accumulated using a 22% HPGe detector connected to a PC based 8k MCA in single mode counting. The energy calibration in the range of 100–8500 keV was carried out using gamma-rays from ¹⁵²Eu and ⁶⁰Co, and the prompt gamma-rays from ³⁶Cl whereas the absolute detection efficiency for this energy range was determined using ¹⁵²Eu and prompt gamma-rays from ³⁶Cl and ⁴⁹Ti.     

Determination of trace elements in quartz glass by use of LINA-Spark–ICP–MS as a new method for bulk analysis of solid samples

The determination of trace elements in pure quartz glass samples has been performed by coupling an ICP quadrupole mass spectrometer with the LINA-Spark-Atomizer, an IR laser ablation system dedicated to direct bulk and surface analysis of solid samples. Linear calibration curves were obtained for nine elements (Na, Al, Ca, Ti, Cr, Mn, Zr, Ba, and Pb) in the ng g^–1 range with detection limits of less than 10 ng g^–1 for Ca, Cr, Mn, Zr, Ba, and Pb and in the range of 120–220 ng g^–1 for Na, Al, and Ti. The distance between the laser focal point and the sample surface has a significant influence on signal intensity and precision, both of which can be improved by a factor of approximately two by focusing the laser 15 mm behind the sample surface. Aerosol moistening reduced the standard deviation of the signal intensity by a factor of 2–4. Signal instability, which resulted from different ablation rates or variations in the transmission of the mass spectrometer, were compensated by use of the simultaneously measured SiAr⁺ ion as an internal standard. Under these conditions precision was usually better than 5% RSD. The results were compared with those obtained by use of a commercial LA–ICP–MS system. With this instrumentation linear calibration curves were achieved for three elements only (Al, Ti, and Pb), showing that LA–ICP–MS is less appropriate for bulk analysis in the ng g^–1 range.     

A review of intercomparison exercises run by NPL from 1989–1997

The flux of cold neutrons that is obtainable from various high energy netron sources is studied for a particular model of a cold neutron source when the cold moderation region of the apparatus is at 20, 70, and 298K. The maximum flux obtained with a californium-252 source was 2.7·10^?3 cold neutron per (cm²·second (source neutron)). This flux was obtained when the cold moderation region of the apparatus was at 20K and when the thermal moderator is either polyethylene or trimethylbenzene and the cold moderator is polyethylene. This flux should allow sensitive prompt and delayed neutron activation analysis measurements.     

Prompt gamma rays from triton-induced reactions on oxygen and their use for analysis

Triton-induced reactions on oxygen were studied with a view to using the prompt γ-rays for analytical purposes. Five γ-rays were found to be potentially useful, of which three had a high intensity, the n(1, 0), n(2, 0) and p(1, 0) γ-rays, the other two being the n(3, 0) and the unresolved pair α(1, 0)–α(2, 0). The γ-rays are labelled according to the conventions(a,b), wheres is the light prompt product and the γ-photon is emitted by de-excitation from levela tob in the heavy product nucleus. The method had a relative precision of 2 to 3.5% for surface oxygen concentrations from 50 to 3 μg/cm². The sensitivity with 1 900 keV tritons was 0.13 μg/cm² on surfaces of steel or copper which did not yield interfering γ-rays, but 0.45 μg/cm² on aluminium where interfering γ-rays were emitted.     

Rapid and direct speciation of methyltins in seawater by an on-line coupled high performance liquid chromatography-hydride generation-ICP/MS system

A novel on-line coupled HPLC-hydride generation (HG)-ICP/MS system was developed for rapid, direct and sensitive speciation of methyltins in seawater without any pretreatment step. Methyltin compounds were separated by reversed phase HPLC, and then on-line reacted with potassium borohydride and acetic acid to generate volatile hydride products. The volatile derivatization products were separated in the spray chamber of ICP/MS and then introduced into ICP/MS by argon gas for detection. Monomethyltin (MMT), dimethyltin (DMT) and trimethyltin (TMT) were baseline separated in less than 15 min by reversed phase HPLC. The influence of KBH₄ concentration and type of acid on the system performance was investigated and optimized. Calibration curves, based on peak heights against concentration, were linear in the range of 0.5-50 ng (Sn) mL⁻¹ of methyltins with correlation coefficients of 0.9990, 0.9990 and 0.9996 for MMT, DMT and TMT, respectively. The relative standard deviations measured at 10 ng (Sn) mL⁻¹ for these three methyltins were in the range of 0.6-1.4% (n = 5), and the calculated detection limits (S/N = 3) for MMT, DMT and TMT were 0.266, 0.095 and 0.039 ng (Sn) mL⁻¹, respectively. This method was successfully applied to the speciation of methyltins in seawater with spiked recovery in the range of 95.4-106.9%. MMT and DMT were detected in all the seawater samples with concentrations in the range of 1.0-1.5 and 0.30-0.57 ng (Sn) mL⁻¹ for MMT and DMT, respectively.     

The use of delayed nuclear track counting for determining bismuth

The predominant use of the nuclear track technique (NTT) in analytical chemistry has been to measure the prompt charged particle emission from neutron induced reactions with stable or fissile nuclides of selected elements. This work describes the use of the NTT for determining bismuth via delayed alpha particle emission from the decay of²¹⁰P. This technique is sensitive and reliable since alpha track counting is highly efficient and can provide information, on elemental spatial distributions. Bismuth determinations in various materials by this technique appears possible to at least the 1.0 microgram per gram level.