Application of radioisotope excited energy dispersive X-ray fluorescence determination of palladium in catalysts and doped venezuelan laterites

A rapid procedure for determining palladium in catalysts and geoiogical materials is presented. This method involves the use of an²⁴¹Am (100 mC) source for excitation and employs a PDP-11/05 processor for the data acquisition and analysis by energy-dispersive X-ray fluorescence. The relative standard deviation for 5 independent determinations is less than 3% for 100 seconds of fluorescent time. The calculated and measured values agreed well for both, the prepared standards and the doped Venezuelan laterites. Finally, data on the different sources of error is given including counting time, sample preparation, and total error. This investigation was funded in parts by CONICIT (Consejo Nacional de Investigaciones Científicas y Technológicas).     

Distribution of <Superscript>137</Superscript>Cs activities in clams, <Emphasis Type="Italic">Tivela mactroidea</Emphasis> collected along the northern coast of Venezuela and the island of Margarita

Clam meats were obtained directly from the fishermen on the beaches in front of where the clams were collected at eight sites; seven along the northern coast of Venezuela and one on the northern coast of the island of Margarita (Venezuela). Marine sediments were also collected in the same corresponding areas as the clams. ¹³⁷Cs was determined both in clam meats and the marine sediments by high resolution gamma-ray spectrometry employing a hyperpure germanium detector. About 5 kg portions of clam meats were washed and dried in the laboratory, before 500 cm³ volumes were transferred and weighed in the measuring containers. Similarly, 500 cm³ volumes of marine sediments that were dried and ground to pass a 85 μm sieve were transferred to the measuring containers. The samples were counted for 150,000 seconds of real time. The ¹³⁷Cs activity of the clam meats ranged from <0.011 Bq·kg⁻¹ (our detection limit) to 0.36 Bq·kg⁻¹ (dried weigh). These values are all within the range of values considered for environmental fallout from the nuclear weapons tests. Finally, all the values for the corresponding marine sediments were below our detection limit of 0.1 Bq·kg⁻¹ of ¹³⁷Cs (dried weigh).     

Environmental radioactivity at the Venezualan Institute for Scientific Research (IVIC)

The concentration of¹³⁷Cs, potassium, thorium and uranium for 6 monitoring sites and 32 other sites at the Venezuelan Institute for Scientific Research (IVIC) were presented, as well as, the estimated air dose and exposure rates for each site. The concentration of¹³⁷Cs was found to be much higher at many sites at IVIC in respect to the average estimated value of¹³⁷Cs in Venezuela. But, this was determined to be due to a natural cause, the cloud forest which surrounds the higher elevations. The values of potassium, thorium and uranium were compared to values from other parts of northern Venezuela and were found to agree for sites at similar elevations. They were also shown to be about two to three times higher than global estimates. Thus, the air dose and exposure rates were correspondingly two to three times higher too, but the annual dose from the primordial radionuclides in the soil was estimated to be less than 0.1 mSv, which is considered negligible for health risks.     

Monitoring of Radon Anomalies in the Rio Casanay and a Thermal Spring Near the El Pilar Fault Shortly After the July 9, 1997 Earthquake (Mw=6.9) in the State of Sucre (Venezuela)

Immediately, after the July 9, 1997 earthquake (Ms = 6.8) in the state of Sucre, Venezuela, we began measuring radon in water to investigate the possible correlations with the seismic activity and to study the meteorological affects. Sampling periods were for 3–5 days with 4–8 weeks in between each. During the first two sampling periods, the seismic activity was high with several minor events (Mb4.0) and anomalous radon concentrations were measured and considered as possible precursors for the events. We have also shown that the radon activity was stable except for daily meteorological effects during periods of low seismic activity. The radon activity during the first year after the major event on July 9, 1997, at the beginning of the rainy season increased from about 50 pCi/l to about 350 pCi/l for all sampling points. Then abruptly dropped to 100 pci/l at the beginning of the next rainy season for points #1 and #2 in the Casanay river and stayed relativelystable during the second year. At the start of the third year, the values began to increase again, similarly to the first year. We concluded that this was caused by the heavy rainfall at the beginning of the rainy season. While at the sampling points at Hotel Cristal, thermal spring pool, it decreased slowly during the second year but increased again at the onset of the third year. Finally, we have concluded as other investigators, that monitoring radon activity alone is insufficient to predict minor earthquakes (Mb4.0), but in some cases it can be considered as a precursor.     

Anomalously high activities of <Superscript>137</Superscript>Cs in soils and vegetation on and near a diabase outcrop in La Sierra de Lema,Venezuela

As a result of routine soil sampling to determine the ¹³⁷Cs background activities country-wide in Venezuela, it was decided to further investigate El Mirador (Lookout) area at the base of the Sierra de Lema mountain range. In April 2003 (A), soil samples were collected at eight sites on and around the edge of the diabase outcrop to confirm that this area had anomalously high ¹³⁷Cs activities. In July 2003 (B), not only soil samples were collected again, but also black mat, palm tree leaves and trunks, fruit bushes leaves and its fruit and fern leaves. The ¹³⁷Cs content was measured by high resolution gamma-ray spectroscopy by a comparative method with reference materials. The ¹³⁷Cs activity values range from 16.3 to 30.8 Bq·kg-1 in the soil samples collected in July 2003, 20.7–32.1 Bq·kg⁻¹ for the black mat, 26.3–38.4 Bq·kg⁻¹ for the palm leaves, 16.8–31.2 Bq·kg⁻¹ for the palm trunks and 17.6–27.3 Bq·kg⁻¹ for the fruit bush leaves, while, the ¹³⁷Cs activity values for the whole fruit were between 23.4 and 30.7 Bq·kg⁻¹; but, the value of the ¹³⁷Cs activity in the center of the fruit (the edible part) was 51.6 Bq·kg⁻¹, and the value of the ¹³⁷Cs activity for the fern leaves was 51.8 Bq·kg⁻¹. Thus, most of the ¹³⁷Cs activity values determined in the soil, black mat and vegetation samples from El Mirador (Lookout) were considered anomalously high with respect to those found near the equator and in other areas of Venezuela. Only the center of the fruit from the Clusia grandiflora bushes and the fern leaves had high activity ratios, about a factor of three and could be considered as biomonitors that concentrate and retain the ¹³⁷Cs. Finally, these anomalously high ¹³⁷Cs activities have been attributed not only to the rich organic soils, as sinks, but also due to the affect of the cloud forests.     

Environmental radioactivity near the central coast of Venezuela and its radiological impact

The concentrations of⁴⁰K,²²⁶Ra,²³²Th and¹³⁷Cs were determined in the upper layers of soils in the central coastal region of Venezuela. The activities of¹³⁷Cs are higher in the areas where the forest is well developed, oriented towards the wind and at higher elevations. The origin of the¹³⁷Cs deposition is from water input from the clouds directly in the cloudforest and rainfall from the northeast trade winds. Even though the values of¹³⁷Cs are much higher in these areas, there is little or no significant increase in the health risk. The natural radioactivity is correlated with the geology in the region except in the area of Urama. The values for the natural radiation background are as follows: for potassium between 1–3%, for radium between 1–3 ppm and for thorium the range was 6–39 ppm. The corresponding amounts of absorbed dose rates in air, the exposure rates and the annual effective dose equivalents are in the following ranges respectively: 11–39 pGy/s, 4–16 uR/h and 0.25–0.86 mSv/y. The annual effective dose equivalents include the contribution of the global average (2.57 mSv/y) of the rest of the natural sources of radiation. Finally, the largest natural radioactivity background, was found near Chichiriviche as a result of the massive granite deposits in this area, but again there is no significant health risk.     

Spatial distribution of cesium-137 in surface soils on the Araya and Paria Peninsulas (Venezuela)

The activity of cesium-137 (Bq/kg) in surface soils between 2-5 cm was determined for more than ninety sample sites on the Araya Peninsula, the Paria Peninsula and the isthmus in between them in the state of Sucre (Venezuela). The measurements were performed by high-resolution gamma-ray spectroscopy, employing a compatible IBM computer with a Nucleus analog to digital interface card. In general, the values for the ¹³⁷Cs activities were much greater on the Paria Peninsula than the Araya Peninsula and slightly lower on the isthmus. Even though the peninsulas are only separated by a small isthmus, their environmental characteristics are very different. The large difference in the annual rainfall of the peninsulas could have resulted in a greater amount of deposition of ¹³⁷Cs on the Paria Peninsula, as well as other environmental characteristics, such as altitude and vegetation. The difference of the environmental characteristics could also affect the degree of disturbances of the soils by natural processes on the peninsulas and the isthmus, which could also have affected the ¹³⁷Cs activity distribution. Finally, an anomalous high ¹³⁷Cs activity distribution was found at the farthest southeastern sample sites and one of lesser extent at the most northern sample sites. These anomalies are possibly due the direct affect of the northeasterly winds which transported the ¹³⁷Cs fallout from the nuclear weapon test sites.     

Temporal variation patterns of radon in mineral waters along the Cota Mil Highway, Caracas, Venezuela

Measurements of radon in potable mineral waters along the Cota Mil Highway at two sites, La Castellana with five sampling points within 20 meters of each other and two collection points at the San Jose site were carried out from November, 1997 to December, 1998. Temporal radon variation patterns will be presented for the seven sampling points, which had very different water flow rates and short-term variations. The extraction of the radon from mineral waters was accomplished in the laboratory a few hours after sampling and the measurements were performed employing a radiation monitor with a scintillation cell 18 hours latter to insure that the radon and its decay products were in equilibrium. The results suggest that the increase of radon from the middle of February to the middle of November can be related to the decrease in atmospheric temperature and rainfall. The large differences in the minimum and maximum values of radon and the short-term variations show the need for many measurements over a year to quantify a correct annual value to be employed in dose calculation for radiological impact studies on human health. Finally, we have also concluded that water sampling points with very low water flow rates are more suitable for investigating the possible relation between radon anomalies and seismic events.     

Sensitivities for eight medium Z-elements with eleven different radionuclides using a new radiometric X-ray analysis technique

In this work we shall discuss the preliminary results of employing eleven different radionuclides for elemental X-ray analysis using a new analytical technique. This new technique mixes the radioisotope directly with the sample and this source sample is directly placed on the detector window which is protected by a thin plastic film from contamination. An equal atomic mixture of eight elements (Ti, Mn, Zn, Br, Zr, Ag, Sn and Ag) was prepared and doped separately with the eleven different isotopes (Pm-147, S-35, Ni-63, Na-22, Co-137, Co-57, Cd-109, I-125, Am-241, Zn-65 and Fe-55). The spectrum of each is shown herein with a discussion of the background, signal to noise ratio, corrected peak intensities, etc. Finally, the possible future applications of this technique with some of the isotopes are presented.     

The simultaneous determinations of cobalt,nickel and molybdenum in hydrodesulfurization catalysts by photon induced X-ray fluorescence

A rapid radioisotope induced energy-dispersive X-ray fluorescence procedure for the simultaneous determinations of Cobalt, Nickel and Molybdenum in hydrodesulfurization catalysts is presented. A¹⁰⁹Cd (7 mCi) source is used as the excitation system coupled to a high resolution Si(Li) detector. A PDP-11/05 processor is employed as a multichannel analyzer and also to automatically control the complete system by means of a prewritten computer program. The relative standard deviations for the three determinations (CoO, NiO and MoO₃) are less than 5% for 300 seconds of fluorescent time for a typical sample. Finally a comparison of results by different methods is given to check the accuracy since no standard reference materials are available for catalytic material. This project was funded by Consejo Nacional de Investigaciones Científicas y Tecnológicas (CONICIT).