Multi-element analysis of biological material by RNAA using HPLC with on-line yield determination

The idea to use high performance liquid chromatography with continuous UV detection for multi-element radiochemical separation and simultaneous multi-element on-line yield determination is introduced. The validity of the concept was evaluated by demonstrating the constancy of the ratio of the signals for a main isotope (⁶⁰Co) and a carrier (⁵⁹Co) as a function of the elemental mass processed in the separation. The suitability of the method for practical purposes is demonstrated by its application to the RNAA determination of cobalt in biological materials. It is concluded that the method, although not yet completely developed, bears the potential of improving both accuracy and precision of multi-element RNAA.     

Low level determination of thallium in biological and environmental reference materials by RNAA using several counting methods

A new RNAA procedure was developed capable of low level determination of thallium in biological and environmental samples. After high fluence neutron irradiation in a nuclear reactor, wet ashing of samples and T1(I) separation by solvent extraction with sodium diethyldithiocarbamate at pH 13, several types of counting were employed to compare their detection limits and to utilize the self-validation principle of NAA. The following measurement modes were used: High efficiency counting of -rays of²⁰²T1 and Hg X-rays produced on decay of²⁰⁴T1 using a well-type HPGe detector, combined ^– ray and ^–-counting of²⁰⁴T1 with the aid of a HPGe planar detector, and liquid scintillation counting and counting of Cerenkov radiation of ^–-particles of²⁰⁴T1. The lowest detection limit of 0.034 ng of T1 was achieved on liquid scintillation counting of²⁰⁴T1. The method was applied for the analysis of biological NIST SRMs 1515, 1573a, 1577b and environmental NIST SRM 1633a. Good agreement was found between the thallium certified value in SRM 1633a and values determined in this work by all counting modes. For SRM 1573a, results in agreement were obtained by two counting modes, while counting of Hg X-rays of²⁰⁴T1 was only used for SRMs 1515 and 1577b.     

Neutron activation determination of gold in rocks using dibutyl sulfide extraction for gold separation

A rapid method for the determination of gold in rocks by neutron activation was developed. The method is based on the quantitative and specific separation of gold with dialkyl sulfide extraction.     

Metrological assessment of the high-accuracy RNAA method for determination of cobalt in biological materials

The paper summarizes work on the development of the high-accuracy RNAA method for the determination of trace amounts of cobalt in biological materials. The method is based on a combination of neutron activation with selective and quantitative isolation of the analyte in a state of high radiochemical purity by use of column chromatography followed by gamma-ray spectrometric measurements. The method was devised according to a set of rules, which were formulated to obtain high accuracy of the method. The procedure has been also equipped with several criteria as key factors in quality assurance. Qualification of the high-accuracy RNAA method as a primary ratio method has been demonstrated and its usefulness in the certification of the candidate reference materials tea leaves and mixed Polish herbs is presented.     

TLC technique for the detection and determination of gamma- BHC in biological material

Summary Five isomers present in technical benzene hexachloride were successfully separated by TLC on silica-gel G impregnated with silver nitrate solution. The -isomer was identified by running a control sample of -BHC. Measurement of the spot area was found suitable for the estimation of 5–20g of-BHC, and was applied to analysis of autopsy tissues. The limit of identification is 0.1g.

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Zusammenfassung Auf mit Silbernitratlösung imprägniertem Kieselgel G konnten dünn-schichtchromatographisch fünf Isomere aus technischem Hexachlorbenzol erfolgreich getrennt werden. Das-Isomere wurde mit Hilfe einer Vergleichsprobe identifiziert. Die Planimetrie der Flecken eignet sich zur Schätzung von 5–20 g-Hexachlorbenzol. Die Methode wurde zur Untersuchung von Autopsieproben angewendet. Die Nachweisgrenze beträgt 0,1g.

     

A two-group separation scheme for the determination of eleven trace elements in biological material by neutron activation analysis.

The applicability of solvent extraction with tri-n-octylphosphine oxide (TOPO) in the neutron activation analysis of biological material has been studied. A two-group radiochemical separation scheme is presented. After wet oxidation, As, Se, and Hg are removed by distillation and subsequent sulfide precipitation; Ca, Cd, Co, Fe, Mo, Sc, W, and Zn are then determined after extraction with TOPO. Chemical yield is determined for the volatile group by re-irradiation of the sulfide precipitate. No chemical yield determination is performed for the TOPO group. Results for six international biological standards are presented. The method is applicable to a wide variety of biological samples.     

Simultaneous determination of Rb and Cs by RNAA method

A RNAA method has been developed for the simultaneous determination of Rb and Cs in geological samples. The method is based on precipitation with sodium tetraphenylborate followed by NaI(Tl) gamma spectrometry. Three mica dust particulate samples and two USGS standard rocks, BCR-1 and W-1 were analyzed. Dipicrylamine (DPA) and 2-thenoyl-trifluoroacetone (TTA) in nitrobenzene were also used for solvent extraction. The precipitation method is better than solvent extraction.     

Continuous automatic determination of ammonia by using an integrated separation/detection unit

An automatic continuous-flow photometric method for the determination of ammonia is proposed. It is based on the Berthelot reaction, the product of which is temporarily immobilized on a suitable support (Sephadex QAE) located in the flow-cell. The retained product is eluted after measurement by a cationic surfactant contained in the carrier solution. The method allows the determination of the analyte between 0.4 and 20.0 gmg/ml, with an RSD of 0.8%, at a sampling frequency of 13/hr. The determination limit can be reduced by a factor of ten by using a flow-cell with a two-fold longer path length, but the sampling frequency is also reduced as a result. The method was applied to the determination of this analyte in agricultural samples (plants and soils) and compared with standard methods for these types of samples.     

Assay of platinum and gold in biological material by neutron activation analysis

Compounds of both gold and platinum are used in medicine, the former as salts to treat arthritides and the latter as the metal complex cisplatin to treat cancer. We have investigated neutron activation analysis with the Slowpoke II reactor as an assay method for both elements using human blood plasma as a matrix. Neutron activation of platinum gives rise to 3.15 day¹⁹⁹Au while that of gold produces 2.7 day¹⁹⁸Au. Activated samples are dissolved during heating in test tubes and the gold extracted by adding dibutyl sulphide to the same tube. The latter is formed to able to quantitate Pt down to 60 ng and Au down to 60 pg. The dissolution technique and possible interferences in the assay are discussed.     

Chromatographic separation and colorimetric determination of gold

Gold(III) is selectively sorbed from 1M hydrochloric acid by a short column containing a special acrylate resin. Then the gold is eluted from the column with acetone-hydrochloric acid, and the absorbance of the effluent is measured at 340 nm. Gold(III) may be successfully separated and determined in samples containing many other metal ions.     

Simplified sample preparation for fluoride determination in biological material

A simple and rapid preparation method for the determination of fluoride in biological materials (blood and food) of various origins, is described. A homogenized sample was placed in a plastic diffusion cell and calcium phosphate added, it was then dried at 55 degrees C and treated with 70% HClO4 and 40% AgClO4. After digestion for 24 h at 55 degrees C, the fluorides released were fixed on the upper part of a diffusion cell containing a thin layer of NaOH. The analyses of the diffused fluoride were carried out with an ion-selective electrode. The proposed microdiffusion method, without mineralization, enables quantitative separation of the fluoride from the biological samples.     

DPASV determination of mercury in plant material after a preliminary separation via gas phase and gold trap

A new separation procedure was developed which solves problems of organic interferences in the analysis of mercury traces in environmental matrices using differential pulse anodic stripping voltammetry (DPASV). The separation combines the volatilization of metallic mercury and its absorption on Au-wool, followed by a quantitative anodic dissolution of the mercury into a pure electrolyte solution. This procedure prolongs the analysis time for about 2 min, but offers an interference-free determination of mercury using the standard DPASV method without deterioration of sensitivity and precision. The method was tested with plant reference material olive leaves (BCR No 62).     

A definitive RNAA method for determination of selenium in biological samples: uncertainty evaluation and assessment of degree of accuracy

This article describes work on the development of a highly accurate RNAA method for determination of selenium in biological samples. The analytical post-irradiation procedure is based on a combination of cation-exchange and extraction chromatography with final selective and quantitative fixation of selenium on a column packed with 3,3′-diaminobenzidine (DAB) supported on Amberlite XAD4, followed by gamma-ray spectrometric measurement. The suitability and accuracy of the method was demonstrated by analysing CRMs with certified selenium content. The uncertainty budget for Se determination in standard reference material Peach Leaves NBS 1547 was estimated; the combined standard uncertainty was calculated as 1.7%. The described method fulfils all the criteria for definitive methods. It was subsequently used for determination of selenium in biological materials intended as new CRMs and proficiency test samples.     

The determination of phanquone in biological material by gas-liquid chromatography.

A gas-liquid chromatographic method for the quantitative determination of phanquone is described, based on the formation of a dimethoxine prior to its extraction from biological material. The sensitivity of the procedure is about 15 ng/ml in biological fluid.     

RNAA of trace iridium in Precambrian-Cambrian boundary samples by thiourea type chelate resin separation

A RNAA procedure is described for the determination of trace Ir in Precambrian-Cambrian boundary samples. After irradiation, the powdered sample is transferred to a graphite crucible to expel the massive silicon with mixed acid (HF–HCl–HNO₃) by heating. The residue is then fused with mixed fusion (Na₂O₂–NaOH) in a muffle furnace at 700°C for 15 minutes. After cooling, the fused mixture is leached with hot water. The final solution is adjusted to pH 1.5–2.0 and then passed through a column filled with thiourea type chelate resin. The resin absorbed with¹⁹²Ir is measured for 4000–10 000 s by means of SCORPIO-3000 multi-channel computer — Ge(Li) detector system. Experiments with radioactive tracer are carried aout for checking radiochemical separation yield. The accuracy and precision of the method are evaluated by the analysis of U.S. geological SRMs DTS-1 and AG-Bohor-1. The method is used for the determination of trace Ir in several sets of Precambrian-Cambrian boundary samples collected from Yunnan province in China and the Ir anomaly is observed.