Determination of bromine and iodine in biological and environmental materials using epithermal neutron activation analysis

Epithermal neutron activation analysis (ENAA) was applied to the determination of the contents of bromine and iodine in 40 biological and environmental standard reference materials and Chinese diets. Boron nitride (BN) for solid samples and BN+Cd for liquid samples were adopted as shield material. Irradiation was carried out in inner and outer irradiation sites in a Miniature Source Reactor (MNSR) for solid and liquid samples, respectively. The 443 keV photopeak of ¹²⁸I and the 616 keV photopeak of ⁸⁰Br were used. The precision of measurement (relative standard deviation) is 2∼6% for contents of iodine of more than 100 ng/g and 8∼12% in the 20∼100 ng/g range in solid samples, and 12∼18% at less than 100 ng/ml in liquid samples. For bromine, the precision of measurement is 2–8% for solid samples and lower than 13% for liquid samples. The detection limits under experimental conditions varied between 10∼30 ng/g, 55∼95 ng/g and 25∼68 ng/g for iodine and 50∼150 ng/g, 200∼450 ng/g and 100∼300 ng/g for bromine in ENAA with BN shield in inner irradiation sites, with Cd shield and BN+Cd shield in outer irradiation sites, respectively. Received: 13 June 1996 / Revised: 2 September 1996 / Accepted: 19 September 1996     

Development of the <Emphasis Type="Italic">k</Emphasis><Subscript>0</Subscript>-based cyclic neutron activation analysis for short-lived radionuclides

The k ₀-based cyclic neutron activation analysis (k ₀-CNAA) technique has been studied to explore the applicability at the Portuguese research reactor (RPI). In particular, for the determination of elements which form short-lived radionuclides, particularly fluorine (²⁰F, 11.16 s half-life) and selenium (^77mSe, 17.36 s half-life) in polymer, biological and environmental samples. The detection limits obtained for F and Se were about 50 and 0.01 mg kg⁻¹, respectively, in the investigated materials. The timing parameters for the procedure were 10 to 20 s for irradiation, 5 s decay, 10 to 20 s counting, 5 s waiting and performed with eight cycles. The k ₀-IAEA program was modified to use millisecond time resolution for irradiation, decay and counting times as needed for interpreting k ₀-CNAA data in terms of concentration, accuracy and detection limit. The quality control of the procedure was performed by preparing a standard solution containing fluorine with different contents as well as using the certified reference materials containing selenium from which the bias between the results and the certified values were within 15% for most elements at the investigated content ranges. The analytical results for several other elements producing short-lived or detectable radionuclides, e.g., Al, Ca, Cl, Cu, Dy, I, Mg, Mn, Ti, and V were also obtained by the k ₀-CNAA procedure with accuracy within 12%.     

Determination of Fluorine, Chlorine, and Bromine by Molecular Absorption Spectrometry

Fluorine was determined by molecular absorption spectrometry (MAS) in a graphite tube furnace, and fluorine, chlorine, and bromine were determined in a flame. For the fluorine work, aluminum nitrate was added as a reagent to produce aluminum fluoride molecules whose absorbance was monitored with emission from a platinum hollow cathode lamp (HCL) at 227.45 nm. A deuterium arc lamp was employed for background correction. For the furnace work, barium nitrate was used as a chemical modifier to increase the absorption signal. After optimization of the chemical and furnace conditions, a detection limit of 160 pg F was obtained, with a linear dynamic range of two orders of magnitude. Graphite furnace MAS was used to accurately determine fluoride in dental rinse and National Institute of Standards and Technology oyster tissue, but the precision was between 21 and 23%. Low recoveries were obtained for the determination of trifluoroacetic acid and l,2,2,3-tetrafluoropropan-1-ol by graphite furnace MAS. The detection limit for F by flame MAS was 13 mg liter⁻¹ which is a factor of 5 lower than the best reported flame MAS detection limit. Chlorine was determined by flame MAS with the aluminum chloride molecule. Excitation was done at 261.4 nm with a lead HCL. and a detection limit of 180mg liter⁻¹ was obtained. Flame MAS of bromine was done by use of AlBr (excitation at 279.0 nm with an arsenic HCL) and InBr (excitation at 284.3 nm with a chromium HCL), but very poor detection limits were obtained: 24.5 g liter⁻¹ and 500mg liter⁻¹, respectively.     

Neutron activation analysis of zeolite catalysts

A new method for the determination of aluminum and silicon has been developed for zeolite catalysts. In contrast to previous methods, thermal neutrons are used for the analysis of both elements, and cadmium absorbers are not needed. The silicon determination utilizes a one-hour irradiation to observe the³¹Si produced by the (n, ) reaction of³⁰Si. A 15-second irradiation is used for the²⁷Al(n, )²⁸Al reaction. The²⁸Al activity is corrected for the contribution from the²⁸Si(n,p)²⁸Al reaction by using the analyzed weight of silicon in the sample and the data for a silicon standard irradiated simultaneously with the zeolite and the aluminum standard. The quantitation limits are 0.012 g for silicon and 3.3×10^–5 g for aluminum. Sodium presents a significant interference, but this element can be removed by taking advantage of the ion exchange properties of these materials.     

Cyclic neutron activation analysis for determination of selenium in food samples using <Superscript>77m</Superscript>Se

Cyclic neutron activation analysis method was conducted for determination of Se in food samples. High accuracy and good precision were proved by analyzing certified reference materials (CRMs) of chicken (GBW10018), rice (GBW10010) and cabbage (GBW10014). The detection limits for the three CRMs reached 0.16, 0.66 and 1.2 ng after 6 cycles at the 161.9 keV γ-peak from ^77mSe, under a neutron flux of 9.0 × 10¹¹ n cm⁻² s⁻¹ and the conditions of 30 s irradiation, 2 s decay, 30 s counting and 2 s waiting, significantly lower than those of conventional neutron activation analysis without any cycles, which were 0.94, 3.6 and 4.3 ng, respectively.     

Fluorine analysis by activation with an isotopic fast-neutron source and counting Nitrogen-16

A rapid, nondestructive method has been developed for determination of fluorine by activation with fast neutrons from a²⁴¹Am-²⁴²Cm-Be source and counting the 6–7 MeV γ rays of the product nitrogen-16. The total neutron output of the source is 4.8·10⁹ unmoderated neutrons per second and the flux is 1.4·10⁸ fast n·cm⁻²· sec⁻¹. The γ-ray detectors consist of two opposing, matched cylindrical NaI(Tl) crystals 10 cm long and 10 cm in diameter. The sample is irradiated for 30 seconds, cooled for 4 seconds, and then counted for 30 seconds. The sensitivity is 4.8·10⁴ counts nitrogen-16 per gram fluorine, and the limit of detection is 0.4 mg fluorine in a 10-gram sample. A reproducibility of 0.24% is achieved. The relative standard deviation of the specific count rate of nitrogen-16 for 11 fluorine compounds is 1.31%.     

Proton microprobe determination of fluorine depth distributions and surface multielement characterization in dental enamel

Particle induced X-ray emission analysis (PIXE) and nuclear reaction analysis have been applied to multielemental analysis of human dental enamel in a proton microprobe. The PIXE technique was excercised for the characterization of multielemental lateral distributions on and just below the sample surface. For the assessment of depth distributions of fluorine the resonant nuclear reaction¹⁹F(p,aλ)¹⁶O was used. The combination of two analytical techniques comprising both atomic and nuclear interactions in a microprobe was applied to enamel samples of different origins. One sample constituted a healthy enamel and the other one enamel from a restored tooth. The microprobe in the combined mode was demonstrated to permit the establishment of lateral, concentration gradients of elements heavier than phosphorus with a resolution of 15 μm in enamel and simultaneously of depth distributions of fluorine better than 0.7 μm. The detection limits approached, 10–25 ppm for most of the elements considered. Supported by the Swedish Natural Science Research Council     

Oxygen isotope measurement by instrumental neutron activation analysis using reactor neutron—Revisited

The oxygen isotopes¹⁶O and¹⁸O were determined using reactor instrumental neutron activation analysis by utilizing the¹⁶O(n, p)¹⁶N and the¹⁸O(n, )¹⁹O reaction in the UCI 250 kw TRIGA research reactor.¹ Such measurements were used to follow an exchange reaction between H₂ ¹⁸O and finely ground coal. The best conditions for the determination were explored and interference reactions quantified. Single irradiation/count sequences were used to determine 30 parts per thounsand of¹⁶O and 1 part per thousand of¹⁸O in a 400 mg sample of an HVA rank coal to a 25% (1) precision. Reactor pulses were shown to improve these detection limits significantly. Special attention was given to correcting for the high count rates from other induced activites.     

INAA of fluorine in plastics using the medium-flux McMaster Nuclear Reactor

The fluorine contents of plastics, ranging from about 20 μg·g⁻¹ to 66%, may be measured instrumentally using a conventional research nuclear reactor, an automated sample irradiation and counting system, and a set of well-calibrated, in-house, fluorine standards. Plastics with low to medium fluorine contents may be analyzed using ²⁰F by placing the gamma-ray detector at appropriate distances from the irradiated sample. For high-F plastics, samples may be irradiated in a cadmium lined irradiation site, using ¹⁹O and ²⁰F. Counting statistics of <3% translate into reproducibility of measurements within ±3% and analytical accuracies of ±1% to ±10%.     

Activation analysis with cyclotron-produced fast neutrons. Application to instrumental multi-element analysis and to the radiochemical determination of fluorine

Fast neutrons produced by irradiation of a thick beryllium target with 20–50 MeV deuterons are used for activation analysis. The spatial neutron flux distribution around the target is measured. A rotating sample holder is used for the simultaneous irradiation of samples and standards. Instrumental analysis can be applied for a number of elements. As an example, results for calcium and strontium in some reference materials are given. The¹⁹F(n, 2n)¹⁸F reaction is used for the radiochemical determination of fluorine in rocks with a fluorine concentration ranging from 9 to 5400 μg·g⁻¹ Aspirant of the N.F.W.O.     

Fast and precise determination of fluorine in geological samples by 14 MeV neutron activation analysis

A fast and precise method of determining fluorine in geological matrices is proposed. The 0.20 MeV photopeak of¹⁹O, induced by the¹⁹F(n, p)¹⁹O reaction, was used for this assay. Neutron flux monitoring was achieved by adding an internal standard monitor (20 mg Ce) to each sample and counting the activity due to the 0.74 MeV photopeak of^139m Ce, produced in the¹⁴⁰Ce(n, 2n)^139m Ce reaction. This activity was considered to be proportional to the neutron flux during the sample irradiation. This method of fluorine determination was checked on two fluorine geological standards, mica and apatite, containing 1.50 and 2.90% fluorine, respectively. The sensitivity of the method, obviously depending upon the matrix composition, was 1.46 mg for the mica standard.     

Epithermal instrumental neutron activation analysis of biological reference materials for iodine

Epithermal instrumental neutron activation analysis (EINAA) methods have been optimized and applied to several biological reference materials and selected food items for the determination of iodine. The method involves irradiation of the samples for different periods in epi-cadmium and/or epi-boron flux of the Dalhousie University SLOWPOKE-2 reactor and direct counting without any pre-treatment on a 25-cm³ hyperpure Ge detector. The 443 keV photopeak of ¹²⁸I is used for assaying the iodine content. Precision of measurements, expressed as the relative standard deviation, is 10–15% at 200–500 ppb and 3–12% at 500–6000 ppb levels of iodine. Accuracy of iodine measurements is within 5%. The detection limits for iodine in several biological materials with cadmium and boron, either alone or a combination of the two, as thermal neutron shields have been found to vary between 0.1 and 0.4 mg · kg^–1 for different periods of irradiation, decay and counting. The results suggest that the EINAA methods can be successfully applied to biological materials for routine analysis of iodine at levels higher than 200 ppb.     

Determination of fluorine in coral skeletons by instrumental neutron activation analysis

Summary A systematic and non-destructive technique is proposed for the determination of fluorine in coral samples by instrumental neutron activation analysis using the ¹⁹F(n,γ)²⁰F reaction. About 50 to 80-mg samples in polypropylene capsules were irradiated for 15 seconds in the pneumatic transfer tube system (PN-3) of JRR-3M reactor. After the irradiation at a thermal neutron flux of 1.5 ^. 10¹³ n ^. cm^{-2 .} s^-1, the coral samples and standards were cooled for 6 seconds and the g-rays emitted were measured for 15 seconds with a Ge detector. The sequence from sample irradiation to g-ray counting was performed under a computer-control mode. The analytical precision was ~5% for the JCp-1 coral standard. The present method was applied to the determination of fluorine in corals from Thailand, Okinawa and the Philippines. The advantage of one method over destructive techniques is discussed by comparing the analytical results obtained for the JCp-1 coral standard using INAA, ion chromatography and spectrophotometry. Factors that may control the levels of fluorine in corals are also discussed.     

Chemical, sensory and microbiological changes of gamma irradiated coconut cream powder

A study was carried out to determine optimum decontamination dose for a locally manufactured coconut cream powder. Samples were gamma irradiated (0–15 kGy) and ageing process was achieved using GEER oven at 60 °C for 7 days, which is equivalent to one-year storage at room temperature. Iodine value (IV), ranging from 4.8 to 6.4, was not affected by radiation doses and storage, however peroxide value and thiobarbituric acid (TBA) generally increased with radiation doses. In most samples, peroxide value (meq/kg) reduced after storage, whilst the TBA (mg malonaldehyde/kg), indicator for product quality, slightly increased. The sensory evaluation conducted using 25 taste panellists indicated that scores on odour, creamy taste and overall acceptance for all irradiated samples at more than 5 kGy were significantly lower (P<0.05) than the control. However, the panellists could not detect any significant differences among the irradiation doses (P>0.05). All stored products were significantly different in colour, creamy taste, odour and overall acceptance (P<0.05) when compared to the non-stored non-irradiated control. Microbiological count of the samples prior to irradiation was in the range of 1×10²–1.7×10³ cfu/g with no detection of Salmonella sp. and Escherichia coli. No microbial colonies were detected after irradiation. Based on the TBA and overall sensory acceptance, gamma irradiation of 5 kGy was found to be the optimum dose and lower doses can be considered to decontaminate coconut cream powder.     

Development of a microextraction by packed sorbent with gas chromatography‐mass spectrometry method for quantification of nitroexplosives in aqueous and fluidic biological samples

A new method for quantification of 12 nitroaromatic compounds including 2,4,6‐trinitrotoluene, its metabolites and 2,4,6‐trinitrophenyl‐N‐methylnitramine with microextraction by packed sorbent followed by gas chromatography and mass spectrometric detection in environmental and biological samples is developed. The microextraction device employs 4 mg of C₁₈ silica sorbent inserted into a microvolume syringe for sample preparation. Several parameters capable of influencing the microextraction procedure, namely, number of extraction cycles, washing solvent, volume of washing solvent, elution solvent, volume of eluting solvent and pH of matrix, were optimized. The developed method produced satisfactory results with excellent values of coefficient of determination (R² > 0.9804) within the established calibration range. The extraction yields were satisfactory for all analytes (> 89.32%) for aqueous samples and (> 87.45%) for fluidic biological samples. The limits of detection values lie in the range 14–828 pg/mL.     

Method for the simultaneous determination of the most problematic families of organic pollutants in compost and compost-amended soil

Linear alkylbenzene sulfonates (LAS), nonylphenol ethoxylates (NPE; sum of nonylphenol, nonylphenol monoethoxylate, and nonylphenol diethoxylate), and di-(2-ethylhexyl)phthalate (DEHP) are the most problematic organic pollutants in sludge owing to their high concentrations and the concentration limits of 2,600, 50, and 100 mg/kg, respectively, proposed in the European Union directive draft for land application of sludge. In this paper, an analytical method for the simultaneous determination of the C₁₀, C₁₁, C₁₂, and C₁₃ LAS homologues, the nonylphenolic compounds nonylphenol, nonylphenol monoethoxylate, and nonylphenol diethoxylate, and di(2-ethylhexyl)phthalate in compost and compost-amended soil is proposed. The method is based on sonication-assisted extraction, cleanup by solid-phase extraction, and determination by high-performance liquid chromatography with diode-array and fluorescence detectors. The mean recoveries of LAS, NPE, and DEHP were 83, 87, and 79%, respectively, in compost samples, and 77, 96, and 99%, respectively, in compost-amended soil samples. The limits of detection and quantification in compost samples were lower than 6.77 and 22.3 mg/kg dry matter, respectively, for LAS; lower than 7.34 and 22.8 mg/kg dry matter, respectively, for NPE; and 0.78 and 1.18 mg/kg dry matter, respectively, for DEHP. The limits of detection and quantification in compost-amended soil samples were lower than 0.03 and 0.10 mg/kg dry matter, respectively, for LAS; lower than 0.04 and 0.12 mg/kg dry matter, respectively, for NPE; and 0.03 and 0.10 mg/kg dry matter, respectively, for DEHP. The method was successfully applied to compost and compost-amended soil samples from Seville (south of Spain).     

Fluorine concentration profile determination in MAGNOX reactor fuel canning material

The role of fluorine, as a corrosion inhibitant was investigated by determining fluorine concentration profiles in corroded MAGNOX reactor fuel cladding material. A nuclear convolution method was employed, based on the¹⁹F(p, αγ)¹⁶O resonant reaction and prompt gamma detection. The investigation was carried out for scale thicknesses of 3.5 and 4.5 μm as determined using 4.5 MeV protons and a broad resonance in¹⁶O(p, p)¹⁶O back-scattering cross-section. The results indicate the presence of thin fluorine concentration layers near to the scale surface on both etched and pre-oxidized magnesium alloy samples. Furthermore, an additional lower concentration distribution was also observed throughout the scale of the pre-oxidized sample.     

Trace element determination in high-purity scandium by neutron activation analysis and pre-irradiation matrix separation

A pre-irradiation separation procedure has been developed for the determination of trace elements in high-purity scandium by neutron activation analysis. The sample is dissolved in high-purity concentrated hydrochloric acid and scandium is extracted with the same volume of a solution of 50 vol.% bis(2-ethyl hexyl)-orthophosphoric acid (HDEHP) in toluene. The scandium matrix is removed from the most important trace impurities and the residual amount of Sc is in the range of 0.001%. The separation is carried out in the vial to be used in irradiation to prevent sample contamination. Detection limits in the ppb range were achieved with a sample of 10 mg, a thermal neutron flux of 2 · 10¹³ n · cm^–2 · s^–1 and an irradiation time of 48 hours. Most of the elements sought in two samples of high-purity scandium were below the detection limits.     

Effects of Fluorine Deposition on the Chemistry of Acid Luvisols

Abstract

The deposition of airborne fluorine by an aluminum smelter in Upper Austria (Central Europe) during 50 years caused a storage of fluorine in the soils up to 170 g m^?2, corresponding to an annual deposition up to 3.7 g m^?2. The proportion of 1:50 water extractable fluorine increased with total fluorine and ranges from 25% to 37% of the total deposition, indicating an increasing risk of groundwater pollution through further fluorine input. The deposited fluorine increased the solubility of exchangeable and ammonium oxalate soluble aluminum. This is explained by ligand exchange of OH^?-groups at the surface of amorphous Al-oxides with consequent dissolution of Al. Subsequently, aluminum was leached and the contents of exchangeable and oxidic aluminum in the topsoils decreased. The released OH^? neutralized protons (H⁺) dissociating from organic matter, causing a significant decrease of the base neutralization capacity, and raising the pH of the soils.     

Dosage non destructif de l’hafnium par activation neutronique et spectrometrie γ de179mHf et de178mHf (periodes respectives: 19.0 et 4.8 s)

A non-destructive method for the determination of hafnium in zirconium and various alloys, based on the formation of^178mHf and^179mHf, is proposed. For a neutron flux of 10⁹ n _th ·cm⁻²·sec⁻¹, the limit of determination is about 0.5 μg. This limit can fall to 50 ng with the multiple irradiation runs system (ten runs at 92-second cycles). The simple determination is complete within 15 minutes, whereas the multiple irradiation runs method requires about 15 minutes longer time.