Instrumental INAA

In terms of atomic spectrometry, NAA is a method combining excitation by nuclear reaction with delayed de-excitation of the radioactive atoms produced by emission of ionising radiation (fi, y, X-ray). Measurement of delayed particles or radiations from the decay of a radioactive product of a neutron-induced nuclear reaction is known as simple or delayed-gamma NAA, and may be purely instrumental (INAA). The y-ray energies are characteristic of specific indicator radionuclides, and their intensities are proportional to the amounts of the various target nuclides in the sample. NAA can thus... 

The nondestructive instrumental (INAA) and destructive radiochemical (radiochemical neutron activation analysis — RNAA) procedures of this method are discussed later in this chapter. Specific problems, such as chain decays, cyclic activation, and interferences, as well as typical appKcations have recently been discussed by Alfassi (2001) and the references therein. 

Atomic absorption spectroscopy of VPD solutions (VPD-AAS) and instrumental neutron activation analysis (INAA) offer similar detection limits for metallic impurities with silicon substrates. The main advantage of TXRF, compared to VPD-AAS, is its multielement capability AAS is a sequential technique that requires a specific lamp to detect each element. Furthermore, the problem of blank values is of little importance with TXRF because no handling of the analytical solution is involved. On the other hand, adequately sensitive detection of sodium is possible only by using VPD-AAS. INAA is basically a bulk analysis technique, while TXRF is sensitive only to the surface. In addition, TXRF is fast, with an typical analysis time of 1000 s turn-around times for INAA are on the order of weeks. Gallium arsenide surfaces can be analyzed neither by AAS nor by INAA. 

Homogeneity Determinations with Instrumental Neutron Activation Analysis (INAA)... 

Different analytical procedures have been developed for direct atomic spectrometry of solids applicable to inorganic and organic materials in the form of powders, granulate, fibres, foils or sheets. For sample introduction without prior dissolution, a sample can also be suspended in a suitable solvent. Slurry techniques have not been used in relation to polymer/additive analysis. The required amount of sample taken for analysis typically ranges from 0.1 to 10 mg for analyte concentrations in the ppm and ppb range. In direct solid sampling method development, the mass of sample to be used is determined by the sensitivity of the available analytical lines. Physical methods are direct and relative instrumental methods, subjected to matrix-dependent physical and nonspectral interferences. Standard reference samples may be used to compensate for systematic errors. The minimum difficulties cause INAA, SNMS, XRF (for thin samples), TXRF and PIXE. 

HS-SPME Headspace solid-phase INAA Instrumental neutron activation... 

WVGES has not had analytical laboratory facilities since the 1970 s so contract geochemical analyses are a necessity. After considering a variety of sources for analytical work including both university and government laboratories, we decided to use a commercial lab, located in Ontario, which specializes in analyses for the mineral exploration industry (they have since expanded into the environmental field as well). For the sake of consistency, each sample is analyzed using the same set of techniques, a combination of Instrumental Neutron Activation Analysis (INAA) and Selective Extraction-Ignition Coupled Plasma spectroscopy that yield results for 49 elements - Au, Ag, As, Ba, Br, Ca, Co, Cr, Cs, Fe, Hf, Hg, Ir, Mo, Na, Ni, Rb, Sb, Sc, Se, Sn, Sr, Ta, Th, U, W, Zn, La, Ce, Nd, Sm, Eu, Tb, Yb, Lu, Cu, Pb, Mn, Cd,... 

Chemically pure reagents were used. Cadmium was added as its sulfate salt in concentrations of about 50 ppm. Lanthanides were added as nitrates. For the experiments with other metal ions so-called "black acid from a Nissan-H process was used. In this acid a large number of metal ions were present. To achieve calcium sulfate precipitation two solutions, one consisting of calcium phosphate in phosphoric acid and the other of a phosphoric acid/sulfuric acid mixture, were fed simultaneously in the 1 liter MSMPR crystallizer. The power input by the turbine stirrer was 1 kW/m. The solid content was about 10%. Each experiment was conducted for at least 8 residence times to obtain a steady state. During the experiments lic iid and solid samples were taken for analysis by ICP (Inductively Coupled Plasma spectrometry, based on atomic emission) and/or INAA (Instrumental Neutron Activation Analysis). The solid samples were washed with saturated gypsum solution (3x) and with acetone (3x), and subsequently dried at 30 C. The details of the continuous crystallization experiments are given in ref. [5]. 

With analytical methods such as x-ray fluorescence (XRF), proton-induced x-ray emission (PIXE), and instrumental neutron activation analysis (INAA), many metals can be simultaneously analyzed without destroying the sample matrix. Of these, XRF and PEXE have good sensitivity and are frequently used to analyze nickel in environmental samples containing low levels of nickel such as rain, snow, and air (Hansson et al. 1988 Landsberger et al. 1983 Schroeder et al. 1987 Wiersema et al. 1984). The Texas Air Control Board, which uses XRF in its network of air monitors, reported a mean minimum detectable value of 6 ng nickel/m (Wiersema et al. 1984). A detection limit of 30 ng/L was obtained using PIXE with a nonselective preconcentration step (Hansson et al. 1988). In these techniques, the sample (e.g., air particulates collected on a filter) is irradiated with a source of x-ray photons or protons. The excited atoms emit their own characteristic energy spectrum, which is detected with an x-ray detector and multichannel analyzer. INAA and neutron activation analysis (NAA) with prior nickel separation and concentration have poor sensitivity and are rarely used (Schroeder et al. 1987 Stoeppler 1984). 

First, we analyzed samples for a large number of elements to Identify any elements, regardless of toxicity or typical concentration, that would provide signals for the presence of material from certain types of sources. Both ambient samples and particles from sources were analyzed by Instrumental neutron activation analysis (INAA), by which one can often measure about 35 elements In Individual samples (17), As the Important elements Pb, N1 and Cd are not consistently, If ever, observed by INAA, they were often measured by other methods. As INAA Is sensitive to very small amounts of obscure elements, we have obtained reliable data for elements such as Ga, Hf, Sc, In, W and many rare earths which pose no known health hazard at present levels and contribute Insignificant amounts of mass to TSP. However, as discussed below, many trace elements have already been shown to be Important In receptor... 

In this work, we use a University of Washington low pressure impactor (LPI) and instrumental neutron activation analysis (INAA) to determine the elemental composition of aerosols from a two 430 MWe coal-utility boilers, ranging in diameter from less than 0.07 to about 10 )Jm, and to investigate the modification of the aerosol by a modern flue-gas desulfurization system. A preliminary account of the work is presented here. 

All impactor and filter samples were analyzed for up to 45 elements by instrumental neutron activation analysis (INAA) as described by Heft ( ). Samples were irradiated simultaneously with standard flux monitors in the 3-MW Livermore pool reactor. The x-ray spectra of the radioactive species were taken with large-volume, high-resolution Ge(Li) spectrometer systems. The spectral data were transferred to a GDC 7600 computer and analyzed with the GAMANAL code (1 ), which incorporates a background-smoothing routine and fits the peaks with Gaussian and exponential functions. 

During the late 1960s and early 1970s, neutron activation analysis provided a new way to measure bulk chemical composition. Neutron activation analysis utilizes (n,y) reactions to identify elements. A sample is placed in a nuclear reactor where thermal neutrons are captured by atoms in the sample and become radioactive. When they decay, the radioactive isotopes emit characteristic y-rays that are measured to determine abundances. Approximately 35 elements are routinely measured by neutron activation analysis. A number of others produce radioactive isotopes that emit y-rays, but their half-lives are too short to be useful. Unfortunately, silicon is one of these elements. Other elements do not produce y-ray-emitting isotopes when irradiated with neutrons. There are two methods of using neutron activation to determine bulk compositions, instrumental neutron activation analysis (INAA) and radiochemical neutron activation analysis (RNAA). 

Quantitative trace element analysis of diamond by LA-ICP-MS using different synthetic multielement carbon based standards (e.g., cellulose pellets) is discussed by Rege et al 2, whereby 13C was used for internal standardization. Concentrations of 41 elements were determined in two fibrous diamonds from Jwaneng Botswana (JWA 110 and 115) by relative sensitivity coefficients measured using the synthetic cellulose standard. The analytical data were verified by means of instrumental neutron activation analysis (INAA) and proton induced X-ray emission (PIXE).72... 

Methods and technology were developed and used at the NASA Plum Brook Reactor (PBR) to analyze trace elements in pollution-related samples by instrumental neutron activation analysis (INAA). This work is significant because it demonstrates that INAA is a useful analytic tool for monitoring trace elements in a variety of sample matrices related to environmental protection. In addition to coal, other samples analyzed for trace elements included fly ash, bottom ash, crude oil, fuel oil, residual oil, gasoline, jet fuel, kerosene, filtered air particulates, various ores, stack... 

Battelle has developed instrumental neutron activation analysis (INAA) techniques which permit very sensitive and accurate multielement analysis of approximately 40 elements in coal and fly ash. These techniques, which will be described in this work, form the basis for extensive environmental studies of the effluent from coal-powered generating facilities and other pollution sources. 

In most obsidian provenance studies, the ability to employ compositional differences to discriminate between sources depends, to a certain extent, on the number of elements measured. Because instrumental neutron activation analysis (INAA) is capable of measuring 25-30 elements in obsidian with excellent precision, numerous combinations of trace and major elements are available for comparing differences between sources. The main requirements for success are that all sources have been located and analyzed, and that the internal variation measured within the sources be smaller than the compositional differences measured between the sources (23). 

Until recently, there was no systematic survey, documentation, and chemical and physical analyses of western Mediterranean obsidian sources. Recently, Tykot completed an extensive survey and documentation of western Mediterranean obsidian sources on the islands of Sardinia, Palmarola, Lipari, and Pantelleria (24-27) for a more detailed discussion. Samples from these sources were analyzed at MURR by INAA and/or XRF and LA-ICP-MS. As expected, INAA (and XRF and LA-ICP-MS) of geologic samples from these sources demonstrated that obsidian from each island had a unique chemical signature(s). In the case of Sardinia, six compositional groups were identified. Because of the analytical cost and semi-destructive nature of INAA, artifacts were analyzed by LA-ICP-MS rather than INAA. XRF would have provided a viable analytical alternative, but many of the artifacts were smaller than the minimum size required for this analysis on a standard laboratory-based stationary XRF instrument... 

Until now, little attention has been given to the analysis of ancient copper alloys with LA-ICP-MS. This type of material is usually analyzed with fast or instrumental neutron activation analysis (FNAA or INAA), particle induced X-ray emission (PIXE), X-ray fluorescence (XRF), inductively coupled plasma-atomic emission spectrometry or inductively coupled plasma-atomic absorption spectrometry (ICP-AES or ICP-AAS). Some of these techniques are destructive and involve extensive sample preparation, some measure only surface compositions, and some require access to a cyclotron or a reactor. LA-ICP-MS is riot affected by any of these inconveniences. We propose here an analytical protocol for copper alloys using LA-ICP-MS and present its application to the study of Matisse bronze sculptures. 

Trace elemental analysis of ancient ceramics has been proven a very useful tool for tracing the circulation of this material. Instrumental neutron activation analysis (INAA) was for years the analytical technique of choice to measure the composition of ceramics because of the large number of elements it could determine and its good sensitivity. Lately, a few publications have shown that laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) could provide similar results as INAA more quickly and at lower cost. A protocol has been developed to determine 51 elements using LA-ICP-MS and tested it on Wari period ceramics previously analyzed using INAA. We show how INAA and LA-ICP-MS analysis lead to the same conclusion in terms of sample groupings. 

Trace element studies of ceramics have been undertaken for the purpose of locating source regions for archaeological materials since the 1960s. While a number of techniques have been used for this purpose, by far the most common and most effective has been instrumental neutron activation analysis (INAA), largely due to its excellent sensitivity, precision, accuracy and the large number of elements it can measure simultaneously. 

The relative ability of the two techniques to produce comparable data structure is impacted by a number of factors. Clearly, instrumental sensitivity, precision, and accuracy play a role for certain elements. INAA, for instance, reported nickel concentrations below detection in all but one sample in the dataset, PRW209, for which a concentration of 20.9 ppm was measured. Using LA-ICP-MS, a concentration of 20.8 ppm was measured for this same sample. However, this technique was also able to detect measurable concentrations of Ni in all other samples, ranging from 13 to 23 ppm. For other elements, high background noise to signal ratios limit the sensitivity, precision and accuracy of measurement by LA-ICP-MS. This is particularly a problem for two elements... 

Forty-four of the 55 samples were chemically characterized by X-ray fluorescence (XRF). Thirty-seven of these samples were also characterized mineralogically by X-ray diffraction (XRD). Finally, 11 out of the 44 samples analyzed by XRD (4 specimens from La Cueva Pintada site and 7 from the San Francisco s convent) were analyzed by instrumental neutron activation analysis (INAA). Additionally, 11 samples from San Francisco convent, which had an insufficient weight to be characterized by XRF, were analyzed by INAA as well. XRD analyses are now being conducted for the 18 samples not yet characterized. 

The following section focuses on the variability of the clay bodies or pastes of the glazed ceramics previously characterized by LA-ICP-MS and LA-TOF-ICP-MS. The purpose of this study is to compare the variation in the ceramic pastes with the different glaze decorative technologies through time. The variability in the ceramic pastes will be characterized through instrumental neutron activation analysis (INAA) and petrographic analysis. 

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