Evaluation of Carbon Rod Atomizer for Routine Analysis of Vanadium in Crude Oil by Atomic Absorption Spectroscopy

Abstract

The Carbon Rod Atomizer (CRA) was evaluated for routine trace analysis of vanadium in crude oil by atomic absorption spectroscopy with a carbon (graphite) tube as a micro-furnace. Two crude oil samples were analyzed, both by standard addition and standard working curve methods, and the results confirmed by analysis with flame atomic absorption spectroscopy using a fuel-rich nitrous oxide-acetylene flame. Because of the relative involatility of vanadium at the temperature of the CRA, quantitative recoveries of vanadium in crude oil occur only when the vanadium content of the sample injected into the CRA does not exceed the limit of about 1 × 10^?8 g. A sensitivity (weight/1% absorption) of 7.0 × 10^?11 g and detection limit (signal-to-root-mean-square-noise equal to two) of 6.9 × 10^?12 are reported.     

氢化物原子吸收与常规雾化火焰原子吸收法测定锑的几个问题

本文就氢化物原子吸收法与常规雾化火焰原子吸收法用于锑含量的测定中所存在的共存元素的干扰,"记忆效应"及锑的价态变化等几个方面的问题进行了试验考察和分析,对两种方法的灵敏度、精密度及测定线性范围进行了比较,结果表明:氢化物原子吸收法的最大优点是灵敏度高(可达pp～b级)能满足含有微量锑试样的分析要求。雾化火焰原子吸收法测定锑,由于不存在"记忆"效应,样品之间的更换瞬间即可完成,因而适宜大量样品的检测分析。     

Atomic Absorption Spectrometry of Silver with Absorption Tube Having Nebulization Chamber

In the atomic absorption spectrometry with the long absorption tube using a hydrogen-air flame, only the total consumption type of the burners, e.g., Beckman¹ or ring burners², have been used for the input of a sample solution to the flame. The use of the indirect input method with nebulization chamber has never been attempted, though, by use of a commercially available apparatus with nebulization chamber, the large increase of the sensitivity has been easily obtained by heating the chamber and nebulizing air^3–5.     

Indirect Amplification Determination of Thorium by Atomic Absorption Spectroscopy

Thorium may not be determined by direct atomic absorption spectroscopy in flame media with appreciable sensitivity because of inefficient atomisation. Earlier papers from this laboratory have described indirect amplification procedures for similarly difficult elements e.g. niobium¹ and titanium² by atomic absorption spectroscopy· Madison and Guyon³ have developed a solution spectrophotometric procedure for thorium in which the heteropoly acid complex of thorium with phosphomolybdic acid is formed and reduced to the ‘heteropoly blue’. Strict adherence to time of addition of reagents is required in this procedure, and. it is necessary to effect an initial separation of the thorium from most other cations present in the sample.     

The Use of a Triple Pass Optical Arrangement for the Determination of Arsenic and Selenium by Atomic Absorption Spectroscopy in an Inert Gas Shielded Nitrous Oxide-Acetylene Flame

The utility of the inert gas shielded nitrous oxide-acetylene flame for the determination of arsenic and selenium by atomic absorption spectrometry has been demonstrated elsewhere¹. The low background absorbance of the fuel-rich, 50 mm path-length flame (ca 4 and 5% at the As 193.7 and Se 196.0 nm lines respectively) permits the attainment of detection limits which are equal to, or somewhat superior to, those obtainable with the air-acetylene flame. The AAS sensitivity (that concentration producing 1% absorption), however, is decreased; this is the result of the shorter path length of this flame compared to that employed for air-acetylene (100 mm) and the lower concentration of analyte produced in the larger volume of gas used to support the flame.     

Study of traces of elements on a universal laser photoionization spectrometer

A new complex laser analytical spectrometer operating synchronously in the atomic beam regime and in the flame regime is developed. Analytical potentialities of the spectrometer are demonstrated by the example of determining sodium and calcium content in standard solutions and aluminum alloys. Processes of thermal atomization of Ca and Na in vacuum and the effect of the basis of a sample on the element determined are studied. Efficient excitation via Rydberg states is realized for these elements. The contents of Ca and Na in aluminum alloys are determined at levels of 10^?2 and 10^?3%, respectively.     

Detection and Quantitation Of Several Atomic Species By Intra-cavity Quenching Of Laser Emission

Until recently laser research has been the province of the physicist wherein lasers have been utilized extensively as sources of coherent, highly monochromatic energy. The thrust of this research has been to employ the organic solution laser output as an analytical signal from which information about a particular system may be extracted. Preliminary investigations in this laboratory showed that a great number of variables are active in the achievement of lasing from an organic solution. More significantly, concurrent work in this laboratory produced some anomalous results which were subsequently attributed to a cavity defect. This suggested that small energy losses at discrete wavelengths within the resonant cavity of an organic solution laser could result in quenching of broad band laser emission at those specific wavelengths. These considerations led to investigations in which atoms and mlecules were purposefully introduced into the resonant cavity of an organic solution laser.¹ A search of the literature revealed that investigators at The National Bureau of Standards had previously observed this phenomenon and had reported on the intra-cavity absorption of a pulsed rhodamine 6G laser emission by sodium vapor.² In a follow-up paper Keller and co-workers demonstrated the enhancement of absorption for Eu(NO₃)₃) when placed within the cavity of a rhodamine 6G laser. Concurrently absorption was observed from Ba and Sr in an air-acetylene flame within a dye laser cavity by, Thrash et al.⁴ Hansch and co-workers⁵ duplicated the intra-cavity absorption experiment with iodine vapor and compared the sensitivity of this result with measurements obtained from conventional absorption techniques. At about the same time Latz, Wyles, and Green¹ reported data which dennnstrated that the extent of intra-cavity absorption for nitrogen dioxide was linearly related to its concentration. Investigation into the use of a laminar flow burner with an air-acetylene flame within a dye laser cavity showed part per billion (ppb) detection limits for sodium as well as the detection of barium and mercury. The completion of these intracavity absorption studies in the visible region of the spectrum yielded the results which are reported here as well as quantitative intyacavity absorption data for Eu⁺³. In an independent study Konjevic also reported detection of sodium by intra-cavity absorption from an airnatural gas flame⁶.     

Flame Furnace Atomic Absorption Spectrometry: A Review

Abstract

Flame atomic absorption spectrometry (FAAS) is one of the most widespread traditional analytical techniques for trace element determination, but it often suffers from poor sensitivity due to the low nebulization efficiency and the short residence time of free atoms in the flame. On the basis of conventional FAAS, flame furnace atomic absorption spectrometry (FF-AAS) is developed with a tube (flame furnace) placed on top of the FAAS burner for the atomization. Sample is introduced via beam injection (BIFF-AAS) or thermospray (TS-FF-AAS). Due to the total sample introduction and prolonged residence time of free atoms in the flame furnace, marked sensitivity improvement is obtained for volatile and semivolatile elements over conventional FAAS. TS-FF-AAS can be employed as an element-selective detector for GC, HPLC, or CE for studying of metal speciation analysis and metallomics. In addition, three newly developed sample introduction methods, including ultrasonic nebulization, hydride generation, and pneumatic nebulization, are discussed. The analytical figures of merit and practical applications of FF-AAS in analytical atomic spectrometry are reviewed in this article.     

Fundamental noise sources in a high-sensitivity two-tone frequency modulation spectrometer and detection of CO2 at 1.6 μm and 2 μm

2 , and its sensitivity is 7(2)×10^-8 in a 1-Hz bandwidth. The corresponding minimum detectable concentration of CO₂ in air has been estimated to be 1 ppm · m. This opens the possibility of a detection at ppb levels at 2 μm, where a two orders of magnitude increase in the CO₂ absorption signal is demonstrated. Received: 06 April 1998/Revised version: 02 July 1998     

Determination of Silver by Chemical Vapor Generation with In Situ Trapping Flame Atomic Absorption Spectrometry

ABSTRACT

The hyphenation of chemical vapor generation with an integrated atom trap system for flame atomic absorption spectrometry (CVG-IAT-FAAS) was evaluated for determination of silver in real samples (coal fly ash, sediment, and nickel alloy). The volatile species of silver were formed by reaction with sodium tetrahydroborate(III) in the presence of nitric acid. A new CVG-IAT-FAAS design (versus a water-cooled single silica tube, double-slotted quartz tube) significantly improved the sensitivity and detection limits compared with conventional flame atomic absorption spectrometry (FAAS) for determination of silver. The concentration limit of detection was 0.7 ng mL^?1 for Ag. The overall efficiency of the vapor generation process was estimated to be ca. 12%. For a 2 min in situ preconcentration time, sensitivity was enhanced 143-fold for Ag using the vapor generation atom trapping technique, compared to conventional FAAS. Sensitivity can be further improved by increasing the collection time. The precision of measurement at 10 ng mL^?1 of Ag was 10% RSD. The accuracy of this method was validated by analyses of NRC GBW 07302 (Stream Sediment), BCS CRM No. 346 (Nickel Alloy), NIST SRM 2710 (Montana Soil), NRCC LUTS-1 (Lobster Hepatopancreas), and NIST SRM 1643e (Trace Element in Water) certified reference materials. The measured Ag contents in these five reference materials were in satisfactory agreement with the certified values (spanning the range of 0.066–35 µg g^?1).     

原子吸收光谱法测定粉煤灰中氧化钾、氧化钠

采用火焰原子吸收光谱法测定粉煤灰中氧化钾、氧化钠含量。采用氢氟酸-高氯酸混合酸分解样品,以氯化锶消除其他元素的干扰。本方法操作简便、再现性好、灵敏度高,适用于粉煤灰中氧化钾、氧化钠含量的测定。     

Increasing the sensitivity of atomic absorption determination of iron

We have studied the effect of the nature and concentration of surfactants on the atomic absorption of iron. We show that using sodium dodecylbenzenesulfonate as the modifier in flame atomic absorption determination of iron in real samples makes it possible to make the measurements in a low-temperature flame (propane-butane-air type) with increased sensitivity and selectivity and also a lower detection limit for iron. We have developed a procedure for atomic absorption determination of iron in food products using sodium dodecylbenzenesulfonate as the modifier. The detection limit for iron is C_min = 0.008 μg/cm³. Report given at the International Congress of Analytical Sciences, ICAS-2006, 20–30 June 2006, Moscow, Russia __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 263–266, March–April, 2007.     

Use of Zeeman Atomic Absorption Flame Spectrometry for Measurements in C2H2/Air and C2H2/N2O Flames

The Hitachi Zeeman atomic absorption spectrometer system is used to evaluate the influence of observation height and C₂H₂ flow rate upon the atomic absorption sensitivity (slope of calibration curve) and upon the atomic absorption signals for 6 elements in an C₂H₂/Air flame and for 3 elements in an C₂H₂/N₂O flame. Fuel-rich conditions result in greater absorption signals and sensitivities in all cases even though there is a significant temperature drop. Optimal observation heights for each case are evaluated. Greater linearity of analytical calibration curves occurs for fuel-rich conditions under Zeeman background correction than under no background correction. The Zeeman atomic absorption flame spectrometer should find more use in the future.     

Selective optothermal detection of NO2 and H2O with a frequency-tuned CO waveguide laser

The results are reported of the CO-laser optothermal (OT) detection of impurity gases when their absorption spectra overlap with those of an interfering gas. The influence of the latter was avoided using low gas pressures corresponding to a maximum of the OT sensitivity. Frequency tuned in the 5.2–6.3 m wavelength range, ¹²C¹⁶O and ¹³C¹⁶O waveguide lasers were used. The fine frequency tuning at 490 MHz was achieved for 150 laser transitions of both molecules. The OT sensitivity was estimated by NO₂ detection in the presence of water vapor. The minimal detectable concentration proved to be 60 ppb at P _19–18(14) transition of a ¹²C¹⁶O laser for NO₂ and 75 ppb on P _12–11(13) transition of a ¹³C¹⁶O laser for H₂O.     

Direct Determination of Mercury at 0.2 ppm Level by Flame AA Using a Thermospray Atomizer and a Circular Burner

A circular flame atomizer system using a quartz T flame adapator has been developed for the direct determination of mercury. A thermospray nebulizer was used as a sample introduction device to the atomizer. This design gave a sensitivity (1% absorption) of 0.20 ppm and detection limits of 10 ppb at 1.0 mL/min solvent flow at 253.7 nm. The absolute sensitivity was 25 ng and absolute detection limits was 1.5 ng.     

Detection of atomic oxygen in flames by absorption spectroscopy

The absolute concentration of atomic oxygen in an atmospheric pressure hydrogen/air flame has been measured using Intracavity Laser Spectroscopy (ICLS) based on a dye laser pumped by an argon-ion laser. Absorptions at the highly forbidden transitions at 630.030 nm and 636.380 nm were observed at an equivalent optical length of up to 10 km. The relatively low intensity of the dye laser avoids photochemical interferences that are inherent to some other methods for detecting atomic oxygen. The detection sensitivity is about 6 × 10¹⁴ atom/cm³ and can be improved with better flame and laser stabilization.     

火焰原子吸收法测定10种中成药中钠、铬、镍、锰和镁的含量

采用火焰原子吸收分光光度法测定10种中成药物中Na,CR,Ni,Mn和Mg五种金属元素的含量。结果显示，药物中金属元素含量丰富，但含量具有一定差异。其中含Na元素最多的是脑塞通；Mg元素含量最高的是中风回春片；Mn元素含量最高的是强力天麻杜仲丸；而消栓通络胶囊中Cr,Ni含量较高。测定结果为探讨中药微量元素与治疗脑血管疾病的关系提供了有用的数据。     

Limits of sensitivity of laser spectrometers

Theoretical considerations are given on the sensitivity of laser spectrometers in which the molecular transition is observed by a photoelectric detector, a photoconductive detector, or a diode. It is shown that the single-pass absorption spectrometer has extremely high sensitivity at a relatively high gas pressure and with optimum laser power. The holeburning spectrometer is less sensitive, though in offers much higher resolution of the homogeneous width at a low gas pressure. The nonlinear fluorescence method is characterized by both high resolution and high sensitivity, provided the fluorescence from the laser-excited level can be observed. The minimum detectable number of absorbing molecules is calculated to be 10² to 10⁶ depending on the parameters of the spectrometer. Thus a concentration of absorbing molecules lower than 10⁻¹² is expected to be detectable in some cases.     

Photoacoustic spectroscopy for trace gas detection with cryogenic and room-temperature continuous-wave quantum cascade lasers

The main characteristics that a sensor must possess for trace gas detection and pollution monitoring are high sensitivity, high selectivity and the capability to perform in situ measurements. The photacoustic Helmholtz sensor developed in Reims, used in conjunction with powerful Quantum Cascade Lasers (QCLs), fulfils all these requirements. The best cell response is # 1200 V W⁻¹ cm and the corresponding ultimate sensitivity is j 3.3 × 10⁻¹⁰ W cm⁻¹¹ Hz^−11/2. This efficient sensor is used with mid-infrared QCLs from Alpes Lasers to reach the strong fundamental absorption bands of some atmospheric gases. A first cryogenic QCL emitting at 7.9 μm demonstrates the detection of methane in air with a detection limit of 3 ppb. A detection limit of 20 ppb of NO in air is demonstrated using another cryogenic QCL emitting in the 5.4 μm region. Real in-situ measurements can be achieved only with room-temperature QCLs. A room-temperature QCL emitting in the 7.9 μm region demonstrates the simultaneous detection of methane and nitrous oxide in air (17 and 7 ppb detection limit, respectively). All these reliable measurements allow the estimated detection limit for various atmospheric gases using quantum cascade lasers to be obtained. Each gas absorbing in the infrared may be detected at a detection limit in the ppb or low-ppb range.     

An airborne diode laser spectrometer for the simultaneous measurement of H2O and HNO3 content of stratospheric cirrus clouds

We describe a tunable diode laser spectrometer for the in situ simultaneous detection of the nitric acid and the water vapour by means of high resolution absorption spectroscopy on rovibronic lines, using a single laser emitting in the mid-infrared (5.8 μm) and a multipass cell. The instrument was designed to be installed on a high altitude aircraft, as a part of a composite payload for atmospheric aerosol studies. The instrument design criteria are discussed and the expected performances are compared with results of laboratory and field operation. Due to the high chemical activity of HNO₃, that makes difficult to use a reference cell, a fast sweep detection of direct absorption was used for the measurement. An absorption sensitivity of about 2×10⁻⁴ was achieved with an integration time of 2.5 s, corresponding to a concentration of about 4 ppb of HNO₃ in the cell and 0.1 ppb in the external aerosol. The data acquisition and processing techniques, based on the full molecular lineshape fitting are also shown and discussed, including some examples of the data acquired during the scientific flights.