Neutron with radiochemical separations

Trace Elements in Coal by Neutron Activation Analysis with Radiochemical Separations... 

Procedures for the determination of 11 elements in coal—Sb, As, Br, Cd, Cs, Ga, Hg, Rb, Se, U, and Zn—by neutron activation analysis with radiochemical separation are summarized. Separation techniques include direct combustion, distillation, precipitation, ion exchange, and solvent extraction. The evaluation of the radiochemical neutron activation analysis for the determination of mercury in coal used by the Bureau of Mines in its mercury round-robin program is discussed. Neutron activation analysis has played an important role in recent programs to evaluate and test analysis methods and to develop standards for trace elements in coal carried out by the National Bureau of Standards and the Environmental Protection Agency. 

For a trace element concentration to be certified by NBS, it must be determined by at least two independent methods, the results of which must agree within a small experimental error range of 1% to 10%, depending on the nature of the sample and the concentration level of the element. Such accuracy in determining some trace elements for certification of coal SRM is achieved most easily by NAA with radiochemical separation. Scientists at NBS have extensively tested a neutron activation method that involves a combustion separation procedure on coal as well as on several other matrices to be certified as standard reference materials. The procedures they have thus developed to determine mercury (12), selenium (13), and arsenic, zinc, and cadmium (14) are outlined in a following section on methods for determining specific elements in coal. 

As mentioned before, two interlaboratory studies were organised prior to certification, involving ca. 15 laboratories using techniques such as cold vapour atomic absorption spectrometry, direct current plasma atomic emission spectrometry (DCP-AES), differential pulse anodic stripping voltammetry (DPASV), microwave plasma atomic emission spectrometry (MIP-AES), electrothermal atomic absorption spectrometry (ETAAS) and neutron activation analysis with radiochemical separation (RNAA). 

RFNAA Activation with fast neutrons and radiochemical separation... 

Nuclear Methods - Neutron Activation Analysis with Radiochemical Separation (RNAA)... 

Some relevant terms for activation analysis are activation analysis, neutron activation analysis (NAA), instrumental neutron activation analysis (INAA), neutron activation analysis with radiochemical separation (RNAA), photon activation, neutron capture prompt gamma activation analysis (PGAA), charged particle activation, autoradiography, liquid scintillation counting, nuclear microprobe analysis, radiocarbon (and other element) dating, radioimmunoassay, nuclear track technique, other nuclear and radiochemical methods. Briefly, the salient features of some of the more popular techniques are as follows ... 

Gallium may be estimated in low-temperature coal ash by neutron activation analysis, with radiochemical separation. Amounts in the range 1—10 p.p.m. were determined. 

In radiochemical activation analysis (RAA), the various techniques of activation analysis (AA), i.e., neutron activation analysis (NAA), photon activation analysis (PAA), and charged particle activation analysis (CPAA) are combined with radiochemical separation procedures with the intention of extending the capabilities offered by the purely instrumental methods. 

Geochemists were some of the first researchers to realize the enormous benefits of ICP-MS for the determination of trace elements in digested rock samples. Until then, they had been using a number of different techniques, including neutron activation analysis (NAA), thermal ionization mass spectrometry (TIMS), ICP-OES, x-ray techniques, and GFAA. Unfortunately, they all had certain limitations, which meant that no one technique was suitable for all types of geochemical samples. For example, NAA was very sensitive, but when combined with radiochemical separation techniques for the determination of rare earth elements, it was extranely slow and expensive to run. TIMS was the technique of choice for carrying out isotope ratio studies because it offered excellent precision, but unfortunately was painfully slow. Plasma... 

The NAA measurements on the paper samples were made at the Breazeale Nuclear Reactor Facility at the Pennsylvania State University with a TRIGA Mark III reactor at a flux of about 1013 n/cm2-sec. Samples were irradiated from 2 to 20 min and counted for 2000 sec, after a 90 min decay time for Ba and a 60 hr decay for Sb, Analyses were performed instrumentally, without radiochemical separation, using a 35cm3 coaxial Ge-Li detector and a 4096-channel pulse height analyzer. With these procedures, detection limits for Ba and Sb were 0.02ug and 0.001 ug, respectively. These sensitivities are comparable to those obtained by GA s radiochemical separation procedure, and are made possible by the use of the higher neutron output from the more powerful reactor and in combination with the higher resolution solid state detector... 

Common Features of NAA Procedures. In all of the procedures discussed in this article, irradiations are made in a high thermal neutron flux (1011 to 1013 neutrons cm"2 sec 1) simultaneously with the samples and standard(s) sealed in polyethylene containers for a short irradiation or in silica containers for a long irradiation. The standard is a known amount, or solution of known concentration, of a pure compound of the element to be determined. The concentration of the element in the sample is determined by comparing its radioactivity with that of the standard, which is either subjected to the same radiochemical separation as the sample with an inactive matrix or diluted. The radioactivity is counted directly if the sample is measured in solution. The radiochemical yield of precipitated samples is determined directly by weighing and that of solutions of samples by aliquot re-irradiation. 

Neutron activation analysis (NAA) with a rapid radiochemical separation has been the method generally used in recent years, but requires substantial investment, has high operating cost and limited availability. Modem flameless atomic absorption (AAS) instruments provide sensitivity approaching that of NAA and offer a viable alternative for the detection of firearms discharge residue. 

Dyhczynski, R.S. 50 years of adventures with neutron activation analysis with the special emphasis on radiochemical separations. J. Radioanal. Nucl. Chem. 303, 1067-1090 (2015). doi 10.1007/sl0967-014-3822-6... 

An accuracy of 0.2 ng has been reached in the analysis of biological and environmental samples containing about 4 ng Au on irradiation in the thermal neutron flux of 1 x 1013 n cm 2 s 1 during 6 days652 and subsequent radiochemical separation. 4.7 ppb and 1.9 ppb of Au was detected653 by INAA in two human kidney stones (one oxalate and one phosphate). There are indications that the trace element content of hair correlates with the body stores of these elements, particularly with those of bone654. The INAA of hair samples taken from osteoporosis patients showed 2.32 1.32 ngg 1 content of Au in osteoporotic hair and 3.57 1.90 ngg-1 in normal hair655. 

The availability of high flux thermal neutron irradiation facilities and high resolution intrinsic Ge and lithium drifted germanium (Ge(Li)) or silicon (Si(Li)) detectors has made neutron activation a very attractive tool for determining trace elemental composition of petroleum and petroleum products. This analytical technique is generally referred to as instrumental neutron activation analysis (INAA) to distinguish it from neutron activation followed by radiochemical separations. INAA can be used as a multi-elemental method with high sensitivity for many trace elements (Table 3.IV), and it has been applied to various petroleum materials in recent years (45-55). In some instances as many as 30 trace elements have been identified and measured in crude oils by this technique (56, 57). 

The fundamental principle behind analysis by activation analysis is activation or excitation of an atomic nucleus by exposure to radiation such as neutrons, protons or high-energy photons with subsequent measurement of emitted sub-atomic particles or radiation. The most common aspect of the technique involves activation with neutrons in a nuclear reactor and measurement of delayed emitted gamma rays, denoted neutron activation analysis, either instrumental neutron activation analysis (INAA) or neutron activation followed by radiochemical separation (RNAA) in which the element of interest is chemically separated from the matrix after irradiation to provide for better, unimpeded counting. 

Geological and sediment CRMs Many Seal into PE capsules or high-purity silica vials [N/MT] Irradiate with thermal neutrons in nuclear reactor (1-3 min, 5-lOh, 20 h), count irradiated samples or radiochemically separated fractions [N/MT-INAA INAA-SEP/ CONC-RNAA] Kucera (1995)... 

It is generally agreed that neutron activation analysis has shown great sensitivity for many elements. Absolute sensitivities of detection depend on the atomic weight of the element, the fractional abundance of the target nuclide, and its cross section for thermal neutrons (which are fixed values) as well as on the available neutron flux, the irradiation time, the decay period, and the counting efficiency of the detector (which are variable parameters). The formulae described under Fundamentals (vide supra) will make it clear that, unless conditions are exactly specified, published values cannot easily be compared especially as the definitions for sensitivity chosen by the investigators may be different. Experimental sensitivities may be idealized because of matrix problems, difficulties in radiochemical separations, and other analytical problems associated with the analysis of complex, real samples. 

UNILAC was extended to Cm targets (Kratz et al. 1986) because this reaction was predicted to have a higher cross section. Comprehensive aqueous- and gas-phase radiochemical separation techniques were used to isolate SHE fractions that were then assayed for SF activity, including fission-fragment total kinetic energies, and neutron emission. Again, the results were negative with upper cross-section limits of 10 cm for half-lives of minutes to hours and 4 X 10 cm for half-lives from days to several years. 

A special place is reserved for methods of activation analysis, involving slow and fast neutrons, charged particles, or photon.s, applied either directly or in combination with some type of radiochemical separation (Section 1.6.13). These methods quickly became almost indispen.sable, especially in extreme trace analysis of the ele-... 

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