Automation of the standard additions method in flame atomic absorption spectrometry

Two manifolds allowing the automation of the standard additions method in flame atomic absorption spectrometry by using two computer-controlled variable-speed peristaltic pumps operating in a programmed way are presented in this article. One of the pumps increases and the other decreases its turning speed linearly with time, so that the flow-rate supplied to the nebulizer is constant. In the first manifold, one pump moves the sample solution, while the other pump propels a standard solution, so that a continuously changing on-line mixture of both the solutions is obtained. In the second manifold, both pumps, one of which also pumps a standard solution, while the other pumps a diluent solution, propel the sample solution. This second manifold that exactly reproduces the standard additions method, is automatic and allows releaser solutions to be used. Both the procedures present the additional advantage over the conventional batch procedure of the very high number of data that can be acquired by the computer. The theoretical background of both manifolds is presented and their correct operation is experimentally verified.     

Gamma spectrometry of 234Th (238U) in environmental samples

Environmental samples from a wide-range of aquatic and soil deposits, mainly of Scandinavian origin, were analysed for 234Th (238U) using low-level gamma-spectrometry. The diversity of the samples, in terms of composition and ages, allowed a detailed evaluation of the analytical problems associated with gamma-ray spectrometry with focus on the reliability of the 234Th peaks for absolute determination of the 234Th activities. The X-ray contributions in the 93 keV peak were compared with the corresponding self-absorption corrected activities of the 63 keV peak. These X-ray contributions were, also, correlated with the 238U, 232Th, 235U, 40K and 137Cs activities of the samples. Despite the difficulties imposed by the self-absorption corrections, the 63 keV peak is still the best option. Large variability in the 93 keV peak interferences, due to X-rays from Th, exists in sediment and soil samples. Only in the case of young ombrotrophic peat samples was it possible to conclude that the 93 keV peak is free from X-ray contributions and can be as good as the 63 keV Monte-Carlo self-absorption corrected peak. X-ray contributions in the samples correlated with the 238U and 232Th activities, only, in closed environmental systems where a secular equilibrium with the daughters of the U/Th series can occur.     

Gamma ray spectroscopy with ultra-high precision

The energy of gamma rays emitted after thermal neutron capture can nowadays be measured with parts-per-million precision. This precision allows one to measure tiny Doppler effects caused by recoil due to the preceding emission of gamma rays or neutrinos. The study of the Doppler profiles of gamma rays has given rise to new applications in nuclear and solid state physics     

Gamma ray spectrum smoothing by one-pass method

One-pass method with a piecewise cubic polynomial was used as a smoothing technique in gamma ray spectrum analysis. By this method, smoothed results of spectrum region is represented to several divided intervals each of which are fitted with a cubic polynomial calculated by least square technique, respectively. From the smoothing procedure of simulated photoelectric peaks and actual gamma ray spectra, following results were obtained. Photoelectric peaks which had more than 10 channels of FWHM (full width at half maximum) were fitted correctly and low count spectra of about 100 counts per channel could also be fitted smoothly. These smooth results can not easily be obtained by Savitzky's convolution technique. In conclusion, this one-pass method was found to be effective for gamma ray spectra, especially for photoelectric peaks of large FWHM and Compton region.     

Optimising precision in standard additions determinations

Summary The effect of the size of the added increment in standard additions determination on precision is evaluated by computer simulation. The precision obtained for different modes of calculating results is compared for double and single additions. The use of double additions up to the top of the linear range, combined with calculation of results by a weighted linear regression, is recommended.

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Optimierung der Präzision bei Bestimmungen mit der Standardzugabe-Methode

Zusammenfassung Der Effekt der Größe des zugesetzten Inkrements auf die Präzision bei Standardzugabe-Verfahren wird mit Hilfe einer Computersimulation ausgewertet. Die Präzision wird bei verschiedenen Berechnungsarten für einfache und doppelte Zugaben verglichen. Empfohlen wird die Verwendung doppelter Zugaben bis zur oberen Grenze des linearen Bereichs, kombiniert mit der Berechnung der Ergebnisse durch gewichtete lineare Regression.

     

Interpolation in the standard additions method

The standard additions method (SAM) has traditionally been performed by using extrapolation. This practice is suboptimal because predictions are affected by even slight departures of calibration points from a straight line. Despite this, most textbooks and papers in analytical chemistry still refer exclusively to extrapolation. In contrast, the use of interpolation is recommended in this paper as a way to get predictions on the central part of the regression line and thus minimize the bias in the prediction and the variance associated with the analytical result. Several scenarios were studied, with concentration errors simulated in different calibration solutions. It was found that translational effects due to variations at the central part of the calibration caused the lowest disturbances on the predicted concentrations. The differences between the interpolated and extrapolated predictions can be as large as ±30%. The confidence interval associated with the extrapolation result is wider than that due to interpolation by as much as 100%. It is shown that commonly used equations underestimate the correct confidence intervals. Both, absence of bias and improved precision, are of relevance in quality assurance, method validation and error propagation.     

Gamma ray attenuation coefficient measurement for neutron-absorbent materials

The compounds Na₂B₄O₇, H₃BO₃, CdCl₂ and NaCl and their solutions attenuate gamma rays in addition to neutron absorption. These compounds are widely used in the shielding of neutron sources, reactor control and neutron converters. Mass attenuation coefficients of gamma related to the four compounds aforementioned, in energies 662, 778.9, 867.38, 964.1, 1085.9, 1173, 1212.9, 1299.1,1332 and 1408 keV, have been determined by the γ rays transmission method in a good geometry setup; also, these coefficients were calculated by MCNP code. A comparison between experiments, simulations and Xcom code has shown that the study has potential application for determining the attenuation coefficient of various compound materials. Experiment and computation show that H₃BO₃ with the lowest average Z has the highest gamma ray attenuation coefficient among the aforementioned compounds.     

气相色谱-质谱联用测定环境样品中三氯生

建立了气相色谱质谱联用(GC-MS)分析自然水体中三氯生的方法,采用C(18)固相萃取柱处理水样.利用N-甲基-N(三甲基硅)-三氟乙酰胺(MSTFA)对目标物进行衍生化.GC-MS分析中以菲-D10为内标,利用内标法对三氯生进行定量.河水海水中不同浓度加标的三氯生回收率为73%～101%,相对标准偏差(RSD)在4.5%～11.3%之间,方法检出限为0.2 ng/L.该方法适用于河水海水水体中三氯生的测定.     

Natural radioactivity studies of Bidar soil samples using gamma spectrometry

The activity of the terrestrial primordial radionuclides ²²⁶Ra, ²³²Th and ⁴⁰K are measured for Bidar soil samples. The collected soil samples are analyzed using HPGe detector based on high resolution gamma spectrometric system. The activity of the three radionuclides ²²⁶Ra, ²³²Th and ⁴⁰K were found to be in the range of BDL–47.68, 7.65–59.08 and BDL–260.65 Bq kg^?1 respectively. The mean gamma absorbed dose rate in air above 1 m from ground is estimated to be 34.47 nGy h^?1. Annual effective dose equivalent and the radium equivalent activity were within the limits in the present study and it is found that the activity of the radionuclides are comparable with the worldwide literature values. Also the external hazard indices for the soil samples of Bidar district were within the limit of unity.     

X射线荧光光谱法测定土壤污染样品中9种重金属

采用粉末压片法制样,利用理学ZSX PrimusⅡX射线荧光光谱仪,用国家标准物质土壤(GSS系列)、沉积物(GSD系列)、环境保护部标准样品研究所研制的土壤标准样品GSB Z 50011-88(黑钙土)、GSB Z 50012-88(棕壤)、GSB Z 50013-88(红壤)、GSB Z 50014-88(褐土)、湖南污染土壤标准(GBW0732729)做标准样品,建立XRF方法测定农业地质土壤污染物样品中的Cu、Pb、Cr、Ni、Zn、Co、As、Mn、V这9种重金属元素的方法,采用经验系数法校正谱线重叠干扰和基体校正。用3个土壤考核样和环境保护部标准样品研究所研制的GSB07-3272-2015作为样品评估该方法的准确度和精密度,结果符合《全国土壤污染状况详查土壤样品分析测试方法技术规定》中上述元素的规定检测方法质量要求。     

Flameless atomic absorption determination of barium in natural waters using the technique of standard additions

Summary A simple method for the determination of barium in natural waters by flameless atomic absorption spectrometry using the carbon rod is proposed. Barium in highly salted waters is previously separated from the interfering ions by ion-exchange chromatography, using Dowex 50 W-X8 resin, and eluted with 0.1M EDTA solution. Mineral waters with low salinity are transferred directly to the furnace and the standard addition method is performed. The detection limit is 90 pg Ba for 10l injections. The method was applied to samples from the Atlantic Ocean and from Araruama Lake. Barium in commercially available waters was also determined.

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Bestimmung von Barium in natürlichen Wässern durch flammenlose Atomabsorptionsbestimmung unter Verwendung des Standard-Zugabe- Verfahrens

Zusammenfassung In salzreichen Wässern enthaltenes Barium wird von störenden Ionen durch Ionen-Austausch-Chromatographie über Dowex 50 W-X8 getrennt und mit 0,1M EDTA ausgewaschen. Mineralwässer mit geringem Salzge- halt werden unmittelbar in den Ofen eingebracht und die Standard-Zugabe- Methode angewendet. Die Nachweisgrenze liegt bei 90pg/10l. Die Methode wurde zur Untersuchung von Proben aus dem Atlantischen Ozean sowie aus dem Araruama-See angewendet. Außerdem wurde Barium in handelsüblichen Trinkwässern bestimmt.

     

Application of the H-point standard additions method by using absorbance increment values as analytical signals

This paper demonstrates how the absorbance increment (DeltaA) between two wavelengths selected according to the fundamental criteria for application of the H-Point standard additions method (HPSAM) are only related to the analyte concentration. A procedure for calculation of the unknown analyte concentration with no bias error by applying HPSAM to DeltaA values in much the same way as the method of standard additions (MOSA), is reported. The method was also applied to a calibration with a single standard. The results obtained on 6 samples with maximal separations between 65 and 0 nm are reported. Finally, the proposed method was applied to the resolution of different phenol-o-cresol mixtures.     

Exploiting monosegmented flow analysis to perform in-line standard additions using a single stock standard solution in spectrophotometric sequential injection procedures

The robustness of sequential injection analysis (SIA) was combined with the monosegmented flow analysis (MSFA) approach, in which there is no dispersion of the reaction zone with carrier, to develop a methodology to perform in-line dilution. This approach allows one to know accurately the dilution of sample and reagent inside the monosegment, without the need for determination of dispersion coefficients. As a consequence, the methodology allowed the mechanization of procedures to perform standard additions and to construct analytical curves using a single stock standard solution, with very simple and conventional computation of the sample concentration. The method was illustrated with experiments using the bromothymol blue (BTB) dye, in which no reactions are involved, as well as with the spectrophotometric methodology for determination of Fe(II) using o-1,10-phenanthroline as chromogenic reagent. The resulting method presented a sampling frequency of 30 analyses per hour and a detection limit of 25 μg l⁻¹.     

Isolation of Pu-isotopes from environmental samples using ion chromatography for accelerator mass spectrometry and alpha spectrometry

A radiochemical method for the isolation of plutonium-isotopes from environmental samples, based on the use of specific extraction chromatography resins for actinides (TEVA^®, Eichrom Industries, Inc.), has been set up in our laboratory and optimised for their posterior determination by alpha spectrometry (AS) or accelerator mass spectrometry (AMS). The proposed radiochemical method has replaced in our lab a well-established one based on the use of a relatively un-specific anion-exchange resin (AG^® 1X8, Bio-rad Laboratories, Inc.), because it is clearly less time consuming, reduces the amounts and molarities of acid wastes produced, and reproducibly gives high radiochemical yields.In order to check the reliability of the proposed radiochemical method for the determination of plutonium-isotopes in different environmental matrixes, twin aliquots of a set of samples were prepared with TEVA^® and with AG^® 1X8 resins and measured by AS. Some samples prepared with TEVA^® resins were measured as well by AMS. As it is shown in the text, there is a comfortable agreement between AS and AMS, which adequately validates the method.     

Plutonium determination in bioassay samples using radiochemical thermal ionization mass spectrometry

Summary A new high-sensitivity plutonium bioassay program employing thermal ionization mass spectrometry (TIMS) has been developed to monitor Savannah River Site employees for intakes of PuO₂. The U.S. Department of Energy requires bioassay laboratories which have the ability to detect a 100 mRem, 50-year committed effective dose equivalent (CEDE) intake of radioactive material. For PuO₂, traditional alpha-spectrometry methods are not sensitive enough to meet this specification. To comply with this requirement, a radiochemical TIMS method was developed to determine Pu in urine bioassay samples. Four radiochemical separation steps were used to purify Pu from urine to ensure samples were free from matrix effects that interfere with TIMS analysis. These included precipitation, ion-extraction chromatography, electrodeposition, and ion-exchange chromatography. A batch of reagent blanks determined the detection limit for this method was 0.59 fg ²³⁹Pu/l (1.3 µBq ²³⁹Pu/l). The ²³⁹Pu concentration was also measured in 20 urine blank samples to determine the minimum ²³⁹Pu concentration that would indicate an occupational intake. A Probit plot was constructed for the results and the 99 th percentile of the urine blanks showed that the minimum ²³⁹Pu concentration that would indicate an uptake was 2.4 fg/l (5.5 µBq/l).     

Gamma ray irradiation for sludge solubilization and biological nitrogen removal

This study was conducted to investigate the effects of gamma ray irradiation on the solubilization of waste sewage sludge. The recovery of an organic carbon source from sewage sludge by gamma ray irradiation was also studied. The gamma ray irradiation showed effective sludge solubilization efficiencies. Both soluble chemical oxygen demand (SCOD) and biochemical oxygen demand (BOD₅) increased by gamma ray irradiation. The feasibility of the solubilized sludge carbon source for a biological nitrogen removal was also investigated. A modified continuous bioreactor (MLE process) for a denitrification was operated for 20 days by using synthetic wastewater. It can be concluded that the gamma ray irradiation was useful for the solubilization of sludge and the recovery of carbon source from the waste sewage sludge for biological nitrogen removal.     

Analysis of submicroliter samples using micro thermospray flame furnace atomic absorption spectrometry

A recently described thermospray flame furnace atomic absorption spectrometric (TS-FF-AAS) system has been modified in order to extend the applicability of the method for the determination of elemental traces in very small sample volumes (microliter or submicroliter). As an easily available, effective thermospray vaporizer, a fused silica capillary was used and the liquid sample was transported by 1 MPa (10 bar) gas pressure delivered by a standard gas cylinder. A 0.3 microL sample volume can be analyzed with a higher power of detection than using 3 orders of magnitude larger sample volumes with conventional flame atomic absorption spectrometry. The relative standard deviations (N=12) for 0.3 microL volumes and 5 microg/mL Pb samples amount to 3.1% and 3.8% in signal height and signal area, respectively. The detection limit was found to be 69 ng/mL. Initial experiments with other elements (Cd, Hg, Tl, Zn) led to similar results.