176 Fluoride Vol. 35 No. 3 176-184 2002 Research Report DETERMINATION OF FLUORIDE IN WATER RESIDUES BY PROTON INDUCED GAMMA EMISSION MEASUREMENTS AKM Fazlul Hoque,a M Khaliquzzaman,b MD Hossain,c AH Khand Dhaka, Bangladesh SUMMARY: A multielement proton induced gamma emission (PIGE) method has been developed to analyze fluoride in water residues obtained by evapo- ration. In this method, 200 mL of water sample mixed with 100 mg of cellulose powder is evaporated, and the residue is made into standard pellets that are then irradiated with a 2.9 MeV proton beam. The emitted γ-rays from the decay of the excited fluorine nuclei are detected with a high resolution, high purity germanium (HPGe) detector and analyzed using a commercial gamma ray spectrum unfolding software. For concentration calibration, synthetic fluoride standards of different concentrations, as NaF in a CaCO3 matrix, were pre- pared and homogenized by dispersing them in methanol. The method thus developed was applied to determine the concentration of fluoride in 85 water samples collected from different city supplies of Bangladesh. The concentra- tion ranged from 0.03 to 1.10 mg/L with the mean of 0.32 ± 0.21 mg/L. Keywords: Bangladesh, Fluoride analysis, Proton induced gamma emission, Water fluo- ride concentration, Water residue. INTRODUCTION Pollution of the biosphere with fluoride is a human health concern in many parts of the world. The fluoride content of drinking water is a very important factor from the health point of view. Dental researchers have reported that the supplementation of fluoride in drinking water improves the resistance to dental caries.1-3 However, recent studies by public health dentists in New Zealand, Canada, the United Kingdom, and the United States have indicated that no such benefit from water fluoridation is ob- served.4-7 On the other hand, there are reports that excessive fluoride in- take causes fluorosis, cancer, arthritis, and other diseases.8-12 It has also been observed that fluorine in excess affects human intelligence, espe- cially in children, who are most susceptible to early fluoride toxicity.9,12 Chronic fluoride intoxication (fluorosis) has been reported not only in humans but also in domestic animals, such as, cattle, buffaloes, sheep, and goats.13 Different analytical methods using nuclear reactions have been re- ported for determination of fluoride in samples related to geology, odon- tology, medicine, metallurgy, environment, etc.14-19 Determination of fluoride using photon activation analysis is very sensitive but it requires pyrolysis or hydropyrolysis or distillation to separate fluoride from inter- ——————————————— aFor Correspondence: Dr AKM Fazlul Hoque, Accelerator Facilities Division, Atomic En- ergy Centre, P.O. Box 164, Dhaka - 1000, Bangladesh. E-mail: [email protected] bWorld Bank Dhaka office, Consultant, Environment Team, 3A Paribagh, Dhaka; cPhys- ics Department, Jahangirnagar University, Savar, Dhaka; dChemistry Department, Dhaka University, Dhaka, Bangladesh. Fluoride analysis by proton induced gamma emission 177 fering substances.15 In fast neutron activation analysis using 19F(n, α)16N, 19F(n, γ)20F, etc, the sensitivity is not sufficient to determine more than a few µg/g (ppm) of fluoride in samples.15 In ion beam analysis with 19F(p, - + 16 α1 e e ) O de-excitation takes place mainly through internal pair pro- duction, by which an electron and a positron are created and the inelasti- cally scattered particles are detected in coincidence with the emitted photon.16 A signal with very low background is obtained, but the yield is very low because of the coincidence condition. Proton induced gamma emission (PIGE) is also a nuclear reaction based analytical method. Initially, it was developed at the 3 MeV Van de Graaff Accelerator Laboratory of the Atomic Energy Centre, Dhaka (AECD) for non-destructive analysis of fluoride in human teeth.19 Subse- quently, knowing the multielement capability of the method, it was em- ployed for analyzing the light elements in environmental samples in- cluding fluoride in drinking water. The present work is thus an expansion of the scope of the application of PIGE in environmental and human health studies, where it is neces- sary to analyze water, food, etc. for specific information of human health significance. Generally, fluoride ions in water are analyzed by spectrophotometry, ion sensitive electrode (ISE), and ion-chromatography. Each of the meth- ods has its own limitations and advantages.20 Spectrophotometry of fluo- ride in water using alizarin is not interference free, and for low concen- trations it requires distillation, which is time consuming. Ion chromatog- raphy is costly, and although it can analyze multianionic samples, high concentrations of chloride ion interfere with the determination of fluo- ride. ISE is a very useful method for quantitative analysis of fluoride ions in water down to the concentration of 0.1 mg/L. However, the ionic strength of the solution has to be adjusted for different samples to mini- mize interference. If organic acids and boron are present in water, distil- lation is necessary. Compared to these methods of fluoride analysis in water, the PIGE method has the advantage of being isotopic in nature with virtually no interference; sensitivity is high, and it has the multielement capability like ion chromatography. Sample preparation steps are mostly physical in nature, and thus sample contamination is minimal. Moreover, since the same experimental setup is used for determining fluoride in teeth, with the only expense being that of sample preparation, the method provides a nondestructive procedure for analysis that is advantageous for large-scale screening where sensitivity is important. PIGE analysis of fluoride reported in this work is based on the detec- tion of the gamma rays emitted on proton interaction with 19F. The en- Fluoride 35 (3) 2002 178 Hoque, Khaliquzzaman, Hossain, Khand ergy of the gamma ray indicates the isotope that is present, and the inten- sity is a measure of the concentration of the isotope in the sample. MATERIALS AND METHODS Sample preparation: A 200 mL water sample together with 100 mg of ash- less cellulose powder (Whatman) was evaporated to dryness in a porcelain dish on a steam bath and then under an infra-red lamp. The residue was cooled at room temperature in a desiccator for 1 hr. The powdered sample was then weighed and sealed in a polythene bag and stored in a desiccator. A 50 mg sample was pressed into a 10 mm diameter pellet with 3 tons of pressure in a graduated hydraulic press. The pellet was mounted on a 35 mm slide frame with adhesive tape and preserved in a desiccator until irradiated. A 200 mL de-ionized water mixed with 100 mg of cellulose was prepared in the same way as the blank and analyzed for any contamination in sample preparation. Concentration calibration: In order to determine the concentration of fluo- ride in water samples for concentration calibration shown in Figure 1, AnalaR grade NaF in the concentration range of 10-500 mg/kg in a CaCO3 matrix was used. The nuclear reaction 19F(p, p′ γ)19F is used to construct the calibration curve. 600 t y = 1.0469x 2 450 R = 0.9983 300 150 Fluoride (mg/kg) in sample pelle 0 0 100 200 300 400 500 Counts per µC Figure 1. Calibration curve for the determination of fluoride in water residue. NaF standards were homogeneously dispersed in 100 mg of CaCO3 with methanol, and the resulting matrices were dried under an infrared lamp. Fluoride 35 (3) 2002 Fluoride analysis by proton induced gamma emission 179 Weighed 50 mg samples were then pressed into pellets. As a test for homo- geneity, irradiation of three 50 mg pellets gave reproducible results within ± 5%. The calibration curve was correct within this uncertainty. In real sample analysis, this calibration was used to determine the concentration of fluoride in water residues on dry weight basis (mg/kg). These data were then con- verted to mg F/L of water samples with respect to 200 mL of each analyte sample. Method of analysis: The schematic diagram of both the internal/external beam PIGE setup is shown in Figure 2. Two tantalum collimators, each of 2 mm diameter, and a 4 mm diameter cleanup aperture, were used to obtain a finely collimated beam. In internal beam PIGE, sample excitation and gamma-ray emission are performed within the vacuum chamber. A high pu- rity germanium (HPGe) detector in the first position in Figure 2 is used for γ-ray analysis. Figure 2. Schematic diagram of the external/internal beam of the PIGE experimental system. In the external beam technique, samples are irradiated in air, where a wide variety of samples can be irradiated easily by extracting the proton beam through the Be window sufficiently strong to hold vacuum in the accelerator tube. The great advantage of the external beam technique is the reduction of charge build up on the sample during irradiation. Polyimide films (Kapton brand) of 1.12 mg/cm2 thickness were used to extract the proton beams from the beam port into the air. The set up is de- Fluoride 35 (3) 2002 180 Hoque, Khaliquzzaman, Hossain, Khand signed to hold a 35 mm slide frame for solid samples at an angle of 45° relative to the beam direction, and the characteristic γ-rays are detected at 90° with respect to the beam. The total proton charge on the sample and the kapton window, from the beam port and the collimators, was integrated with a charge integrator. The external beam is most useful for irradiation of samples of different shape and size. Because of limitations in geometry, internal beam irradiation is more restrictive. The analyzed proton beam energy was 2.9 MeV. The proton energy on the target after absorption at the exit window and the air between the window and the sample is estimated to be 2.3 MeV.