Use of Multiple Irradiations and Reference Materials as Comparators in Quality Control of Neutron Activation Analysis Data of Biological Samples.

We propose that several different reactor irradiation times followed by assaying of activity for differential counting periods may be employed for quality control (QC) of neutron activation analysis (NAA) data of biological samples. It is also recommended that three to four reference materials (RMs) of similar matrix but from different agencies such as National Institute of Standards and Technology (NIST, USA), International Atomic Energy Agency (IAEA, Vienna), Institute of Nuclear Chemistry and Technology (INCT, Poland), and National Institute of Environmental Studies (NIES, Japan) including a synthetic multielemental primary standard should always be analyzed simultaneously along with the samples. Finally, the mean ± σ values so obtained may be considered as more reliable after statistical analysis. Our analytical data for Na and K in three RMs (SRM 1572, CRM H-9, and Bowen's Kale) using different irradiation periods of 15 m, 2 h, 6 h, and 1 day were comparable with the certified values within error range of + 0.2 to - 2.7%. We report our data for 20 elements in two candidate RMs corn flour (INCT-CF-3) and soya bean flour (INCT-SBF-4) from the INCT, Poland, where Z-score values for most elements are in reasonable range of certified values.

Identification of new phytoconstituents and antimicrobial activity in stem bark of Mangifera indica (L.).

Mangifera indica, commonly called mango or amra belonging to a family of Anacardiaceae, is an important medicinal plant widely used in a variety of Ayurvedic preparations. Extract of its bark, leaves, flowers and kernels are being extensively used for curing various chronic diseases. Mango wood is used in yagya as base fire through which medicated smoke is generated. Three new compounds have been isolated from methanolic and hexane extracts of stem bark: 1,2-benzenedicarboxylic acid, mono(2-ethylhexyl)ester and 9,12-tetradecadiene-1-ol-acetate from the hexane extract and 3-chloro-N-(2-phenylethyl) propanamide from the methanolic extract. These were first separated by thin layer chromatography and later in a silica gel column and identified by characteristic infrared bands corresponding to respective functional groups. The compounds were further confirmed on the basis of GC-MS fragmentation pattern after comparing the data with NIST mass spectral database. All three compounds exhibited antimicrobial activity due to triterpenoids and flavonoids. Elemental analyses by INAA show it to be enriched in essential nutrient elements such as Ca, Fe, K, Mn and Zn which all play an important role in enzymatic processes.

Availability of essential elements in nutrient supplements used as antidiabetic herbal formulations.

Five brands of antidiabetic herbal formulations as tablets, Diabetex, Divya Madhu Nashini, Jambrushila, Diabeticin, and Madhumeh Nashini, from different pharmacies were analyzed for six minor (Na, K, Ca, Cl, Mg, and P) and 20 trace (As, Ba, Br, Ce, Co, Cr, Cs, Cu, Fe, Hg, La, Mn, Rb, Sb, Sc, Se, Sm, Th, V, and Zn) elements by thermal neutron irradiation followed by high-resolution gamma ray spectrometry. Further Ni, Cd, and Pb were determined by atomic absorption spectrophotometry. Most elements vary in a narrow range by a factor of 2-4 while a few others vary in a wide range, e.g., Na (0.05-0.67 mg/g), Mn (26.7-250 microg/g), and V (0.26-2.50 microg/g). All the five brands contain K, Cl, Mg, P, and Ca as minor constituents along with mean trace amounts of Cr (2.11 +/- 0.67 microg/g), Cu (15.7 +/- 7.11 microg/g), Fe (459 +/- 171 microg/g), Mn (143 +/- 23 microg/g), Se (238 +/- 112 ng/g), and V (0.99 +/- 0.93 microg/g). Jambrushila is enriched in Na, Ca, Mg, Cl, Fe, Cu, Se, and Zn, essential nutrients responsible for curing diabetes. Dietary intake of Mn, Fe, and Cu are greater than 10% of the recommended dietary allowance, whereas that for Zn and Se is less than 2%. Mean contents of toxic elements (As, Cd, Hg, and Pb) were found below permissible limits except in Jambrushila. Cr and Zn were inversely correlated with r = -0.81, whereas Rb and Cs exhibit linear correlation (r = 0.93) in five brands. C, H, N analysis showed C approximately 55%, H approximately 12%, and N approximately 2% with a total of approximately 70% organic matter. However, thermal decomposition studies at 700 degrees C suggest less than 5% nonvolatile metal oxides. Herbal formulations contain minor and trace elements in bioavailable forms that favorably influence glucose tolerance and possibly increase the body's ability to ameliorate development of diabetes.

Elemental characterization of trifala powders and tablets by instrumental neutron activation analysis, thermal analysis and spectral studies of gallic acid.

Trifala is one of the most popular herbal formulations, marketed either as powder or a tablet and is used in all parts of India. It is an effective laxative, antioxidant, anticancer and antidiabetic agent, and is used to refresh the eyes. In order to understand the therapeutic uses of trifala, the powder and tablet forms from Zandu Pharmaceuticals, Mumbai, were analyzed for six minor (Na, K, Mg, Ca, Cl and P) and 23 trace (Al, Ba, Br, Cd, Co, Cr, Cs, Cu, Fe, Eu, Hf, Hg, La, Mn, Ni, P, Pb, Rb, Sb, Se, Th, V and Zn) elements. The elements were determined by employing instrumental neutron activation analysis (INAA) and atomic absorption spectrophotometry (AAS). A comparison of the elemental contents in the powder and tablets showed wide variations. The powder was rich in Cr, Fe, Se and Zn, whereas the tablet contained a four-fold higher Mn compared to the powder. Column and thin layer chromatography (TLC) in ethyl acetate/methanol (7:3) were used for the separation of gallic acid in ethanolic extract. It was further confirmed by elemental analysis and spectral methods and quantitatively estimated to the extent of approximately 2%. Thermogravimetric decomposition studies show a three stage process, first a slow process with approximately 20% wt loss at temperatures up to 200 degrees C followed by a fast process losing another 30-35% wt at approximately 300 degrees C for both the powder and tablets. At 700 degrees C metal oxide residue of 7.5 and approximately 16% were left for powder and tablets, respectively.

Bhasmas: unique ayurvedic metallic-herbal preparations, chemical characterization.

Bhasmas are unique Ayurvedic metallic preparations with herbal juices/fruits, known in the Indian subcontinent since the seventh century BC and widely recommended for treatment of a variety of chronic ailments. Twenty bhasmas based on calcium, iron, zinc, mercury, silver, potassium, arsenic, copper, tin, and gemstones were analyzed for up to 18 elements by instrumental neutron activation analysis, including their C, H, N, and S contents. In addition to the major constituent element found at % level, several other essential elements such as Na, K, Ca, Mg, V, Mn, Fe, Cu, and Zn have also been found in microg/g amounts and ultratrace (ng/g) amounts of Au and Co. These seem to remain chelated with organic ligands derived from medicinal herbs. The bhasmas are biologically produced nanoparticles and are taken along with milk, butter, honey, or ghee (a preparation from milk); thus, this makes these elements easily assimilable, eliminating their harmful effects and enhancing their biocompatibility. Siddha Makaradhwaja, a mercury preparation is found to be stoichiometrically HgS without any traces of any other element. Similarly, Swet Parpati is stoichiometrically KNO3 but is found to have Mn, Cu, Zn, Na, P, and Cl as well. An attempt has been made to correlate the metallic contents with their medicinal importance. Na and K, the two electrolytic elements, seem to be well correlated, although K/Na varies in a wide range from 0.06 to 95, with specifically low values for Ca-, Fe-, and Zn-based bhasmas. K/P also varies in a wide range from 0.23 to 12, although for most bhasmas (n = 12), it is 2.3 +/- 1.2. Further, Fe/Mn is linearly correlated (r = 0.96) with Fe in nine noniron bhasmas.

Analysis of Indian mint (Mentha spicata) for essential, trace and toxic elements and its antioxidant behaviour.

Mint, belonging to the genus Mentha in the family Labiatae (Lamiaceae) is pungent in taste with post digestive effects and hot potency. Ten samples of mint leaves, collected from four different locations in North-West parts of India (Roorkee, Dehradun, Baghpat and Uttarkashi) were analysed for seven minor (Al, Na, K, Ca, Cl, Mg, and P) and 20 trace (As, Au, Ba, Br, Co, Cr, Cs, Eu, Fe, Hf, Hg, La, Mn, Rb, Sb, Sc, Se, Sn, Th and Zn) elements by instrumental neutron activation analysis (INAA). Also Ni, Cu and Cd were determined by atomic absorption spectrophotometry (AAS). Samples along with reference materials (RMs) and synthetic primary standard were irradiated at approximately 10(13) n cm-2s-1 and its gamma-activity was measured using HPGe detector and MCA system. Most elements were found in widely varying amounts depending on the location, e.g. Na (0.21-0.86 mg/g), K (12.4-53.3 mg/g) and Ca (5.82-16.8 mg/g) whereas mean contents of other nutrient elements in mint were: Fe (108+/-22 microg/g), Mg (4.83+/-0.92 mg/g), Mn (53.5+/-9.6 microg/g), P (3.88+/-0.94 mg/g), Cu (16.9+/-1.8 microg/g), Zn (21.0+/-4.7 microg/g) and Se (0.18+/-0.03 microg/g). Further, DPPH free radical scavenging activity test in diethyl ether extract showed 100% activity at approximately 40 microg/L suggesting it to be antioxidant in accordance with literature reports.

Analysis of essential elements in Pragya-peya--a herbal drink and its constituents by neutron activation.

Ayurvedic herbal formulations are a good source of several nutrient elements essential for metabolic processes. Pragya-peya, a herbal drink and its 12 herbal constituents have been analyzed for 7 minor (Al, Ca, Cl, Mg, Na, K, P) and 15 trace (Ba, Br, Co, Cr, Cs, Fe, Hg, La, Mn, Rb, Sc, Se, Th, V, Zn) elements by instrumental neutron activation analysis (INAA). The method involves thermal neutron irradiation in a reactor followed by counting at several intervals. Also Cd, Cu, Ni and Pb contents were determined by atomic absorption spectrometry (AAS). Elemental data were validated by simultaneously analysing reference materials (RMs) such as mixed Polish herbs (INCT-MPH-2) and peach leaves (SRM-1547). Sample homogeneity was tested by analysing samples from three different batches collected at different intervals. Pragya-peya has been found to be especially rich in several nutrient elements such as Ca, K, V, Fe, Mn, Se and Zn whereas no single constituent is enriched in all the nutrient elements. Concentrations of elements are discussed vis-a-vis their medicinal/therapeutic uses. Several elements such as Na, K, P, Ca, Fe, Co, and Zn seem to be well correlated in 12 constituent herbs.

Use of gold as monostandard for the determination of elemental concentrations in environmental SRMs and Ganga river sediments by the k0 method.

Instrumental neutron activation analysis (INAA) using the k0 method by employing gold as monostandard has been used for the determination of 18 elements (As, Ba, Br, Cl, Cr, Co, Cs, Dy, Fe, Hf, Ga, In, La, Mn, Na, Rb, Sc and Th) in standard reference materials (SRMs) of environmental origin and four sediment samples collected from the Ganga river in northern parts of India. Data obtained for SRMs agree within +/- 5-10% with the certified values for most elements. Merits and demerits of the k0 method are discussed. An attempt has been made to identify the sources of heavy metal pollutants in the sediment samples and study the mobility pattern for toxic heavy metals originating from the tanneries along with the river flow.

Trace element correlations in the blood of Indian women with breast cancer.

Fourteen minor (Na, K, P, Fe) and trace (Br, Co, Cr, Cs, Hg, Rb, Sb, Se, Sr, Zn) elements have been determined in pre- and postoperative blood samples of 10 breast-cancer-affected. Indian women and compared with controls. The study showed elevation of Cr, Hg, Fe, Rb, Sb, and Zn and lowering of Se, K, P, and Sr contents in the blood of cancer patients. Most elemental contents in pre- and postoperative stages remain unaltered except Br, Co, and Sb. Statistical significance of Fe, Se, Zn, and Hg levels has been tested by box plots. Lowering of Se in blood (-54.4%) is correlated with its enhancement in cancerous breast tissue (94.7%) of various clinical stages. Se/Zn and Se/Fe ratios are lowered in the blood of cancer patients, whereas Na/K ratio is only marginally enhanced. An attempt has been made to correlate Se levels with the dietary intake and breast cancer risk vis-a-vis American and Japanese women.

Availability of essential trace elements in Ayurvedic Indian medicinal herbs using instrumental neutron activation analysis.

Specific parts of several plants (fruits, leaves, stem, bark, and roots) often used as medicines in the Indian Ayurvedic system have been analysed for 20 elements (As, Ba, Br, Ca, Cl, Co, Cr, Cu, Fe, K, Mn, Mo, Na, P, Rb, Sb, Sc, Se, Sr and Zn) by employing instrumental neutron activation analysis (INAA). The samples were irradiated with thermal neutrons in a nuclear reactor and the induced activity was counted using high resolution gamma ray spectrometry. Most of the medicinal herbs have been found to be rich in one or more of the elements under study.

Occupational exposure amongst locomotive shed workers and welders using neutron activation analysis of scalp hair.

Elemental analysis of scalp hair of locomotive shed workers and industrial welders was used to study occupational exposure. Instrumental neutron activation analysis (INAA) was used for the determination of 17 elements, Ba, Br, Ca, Co, Cr, Cu, Fe, Hg, K, Mn, Na, P, Sb, Sc, Se, Th and Zn. Most elements show normal distribution at 95% confidence level. Further statistical significance was tested by correlation coefficient and regression coefficients (r2). Comparison of mean elemental contents of the subjects with controls shows a significant enhancement of Ca, Cr, Fe, Co, Na, Sc and Th, but declining trends for Br, Cu, P, Sb and Zn in locomotive shed workers. In the case of welders: Ba, Co, Cu, K, Mn, Sc and Sb show enhancement whereas Br, Cr, Hg, Se, Th and Zn exhibit depletion. Elemental contents have been correlated with possible sources of origin. Comparison of mean elemental data for the present population around Nagpur city matches well with the reported data for Bombay and Delhi. Comparative data from other countries are also presented.

Minor and trace elemental determination in the Indian herbal and other medicinal preparations.

Medicinal plants described in the Indian "Ayurvedic" literature viz. Tulsi (Ocimum sanctum), Gulvel (Tinospora cardifolia), bitter Neem (Azadirachta indica), Kanher (Nerium Andicum), Vekhand (Acorus calamus), and Peacock's feather (ash) were analyzed for minor and trace elements by instrumental neutron activation analysis. The samples and the standards from the National Institute of Standards and Technology, USA and IAEA, Vienna were irradiated for 5 min, 1 h, 5 h, and 10 h with thermal neutrons at a flux of 10(12)-10(13) n cm-2 s-1 in APSARA and CIRUS reactor at BARC, Bombay. High resolution gamma ray spectrometry was performed using a 45 cm3 HPGe detector and a 4096 MCA system. Concentrations of 13 elements were determined. Zinc, manganese, and sodium were significantly higher in Tulsi leaves while zinc is higher in Neem leaves. Peacock's feathers were found to be rich in manganese, iron, copper, and zinc. A high concentration of mercury was also found in the peacock's feather ash. The therapeutic significance in restoring ionic balance is discussed.

An evaluation of the environmental implications of petroleum refinery emissions by multielemental neutron activation analysis of rumen fluid ash of buffaloes.

In order to study environmental pollution in and around a petroleum refinery complex, a multielemental instrumental neutron activation analysis (INAA) method was used to assay concentrations of As, Ba, Br, Cl, Co, Cr, Cs, Cu, Fe, Hg, La, Mn, Mo, K, Na, P, Sc, Rb, Se, Sr, W and Zn in the rumen fluid ash samples of buffaloes from the vicinity of the refinery. Corresponding samples from a control area 300 km away from the refinery were analysed. Standard Reference Materials, Bovine liver (SRM 1577a), Oyster tissue (SRM 1566a) and Animal bone (CRM H-5) were also analysed for quality control. Samples were irradiated with thermal neutrons at 10(12)-10(13) n cm-2 s-1 and counted by high-resolution gamma spectrometry. Mean elemental concentrations of As, Ba, Br, Cr, Hg and Fe were found to be enhanced, whereas those of Na, K, Cl, Cu, Mn and P were depleted in samples from the vicinity of the refinery complex compared to controls. The environmental implications of anomalous elemental concentrations are discussed.

An elemental correlation study in cancerous and normal breast tissue with successive clinical stages by neutron activation analysis.

Influence of trace elements in body metabolism and their physiological importance in various diseases have motivated their accurate and quantitative determination in biological tissues and fluids. Instrumental Neutron Activation Analysis (INAA) using short and long term irradiation has been employed to determine five minor elements (Cl, K, Na, Mg, P) and 15 trace elements (As, Br, Co, Cr, Cs, Cu, Fe, Hg, Mn, Rb, Sb, Se, Sc, Sr, and Zn) in cancerous and normal breast tissue from 30 patients of four clinical stages. Several elements show enhancement in cancerous breast tissue. Selenium shows maximum enhancement of 94.7% followed by K (81.6%), Sc (66.7%), Cu (58.2%) Na (48.5%), P (44.4%), and Zn (39.2%). Some elements, such as Fe, Cr, and Mn, are depressed by 30.8, 30.1, and 12.8%, respectively. These elements compete for binding sites in the cell, change its enzymatic activity and exert direct or indirect action on the carcinogenic process accelerating the growth of tumors. This is further evidenced by histopathological examination of cancerous cells showing poor cytological differentiation. An attempt has been made to correlate trace element concentrations of Se, Cu, Zn, Rb, Br, Hg, As, Co, Fe, Cr, and Mn and the ratios of Se/Zn, K/P, Cu/Zn, Na/K, and Se/Fe with the clinical stages of cancer. Inhibition of enzymatic activity caused by variation in trace element concentrations results in immunological breakdown of the body system.

Instrumental neutron activation analysis of ambient air dust particulates from metropolitan cities in India.

Ambient air dust samples were collected from industrial, commercial and residential areas of four metropolitan cities (Delhi, Calcutta, Madras and Cochin) in India, and were analysed for 27 elements (As, Ba, Br, Ce, Co, Cr, Cs, Cu, Eu, Hf, Hg, Fe, Ga, La, Lu, Na, P, Sb, Sc, Se, Sr, Ta, Tb, Th, Rb, Yb and Zn) by Instrumental Neutron Activation Analysis (INAA). Samples were irradiated with thermal neutrons in a nuclear reactor for 1 day and counted by high resolution gamma spectrometry at different intervals. Several environmental standards such as Coal (SRM 1932b); Urban Particulate Matter (SRM 1648) from NIST, USA; Vehicle Exhaust from NIES, Japan; and Soil-5 from IAEA, Vienna were also analysed for quality assurance. The results reveal that the concentrations of several pollutant elements in dust samples from the four cities are highly variable. Wide differences were observed for elemental concentrations of As, Ba, Br, Cu, Cr, Hg, Fe, Sb, Se and Zn and these variations are explained in terms of their possible sources of origin.

Radiochemical neutron activation analysis of Fe, Co, Zn, Sb and Se in biomedical and environmental samples.

A radiochemical neutron activation method has been developed for the simultaneous determination of Fe, Co, Zn, Sb and Se levels in cancerous breast tissue, milk samples and fugitive cement dust particulates. Various Standard Reference Materials from NIST, USA (Bovine Liver 1577a, Milk Powder 1549, Coal Fly Ash 1633a and Urban Particulate Matter 1648), IAEA Vienna (Animal Muscle H-4, Milk powder A-11 and Soil-5) and NIES Japan (Pond Sediment) were also analysed for quality control. Samples together with standards were irradiated at a thermal neutron fluence of 10(13) ncm-2s-1 for 2 weeks. After dissolution/fusion together with carriers, the Fe was first separated by extracting with diethyl ether followed by extraction with cupferron in chloroform. From the aqueous phase Co and Zn were extracted using alpha-nitroso-beta-naphthol in chloroform and 2-thenoyltrifluoroacetone in isobutylmethyl ketone, respectively. From another aliquot, Se was first complexed with o-phenylenediamine and extracted in benzene. Later Sb was extracted using KI and 4-(2-pyridylazo)-resorcinol (PAR) in benzene. The method yields reasonably accurate data for monitoring of trace elements in biomedical and environmental specimens.

Minor and trace elemental contents of cancerous breast tissue measured by instrumental and radiochemical neutron activation analysis.

Many minor and trace elements influence the permeability of cell membranes by competing for binding sites, and exert direct or indirect action on the carcinogenic process. Instrumental and radiochemical neutron activation analysis has been employed for the determination of more than 20 elements in normal and cancerous breast tissues of 6 patients. Most trace elements, viz., Zn, Cu, Mn, Co, Se, Br, As, Sb and Cd, are elevated in cancerous tissue, whereas lower levels are observed for Fe, Cs, I, and Sr. Similarly, concentrations of minor constituents, such as Na, K, P, Cl, and Mg, are enhanced compared to normal tissue. Several elements incorporate into the normal cell, change its enzymatic activity, and accelerate the growth of tumor.

Neutron activation analysis of respirable mica samples and their pathological effects in lungs of rats.

Instrumental and radiochemical neutron activation analyses (INAA, RNAA) have been used to quantify the different elements present in mica samples derived from Indian mines and a factory, together with USGS standards using high-resolution gamma-ray spectrometry. Both samples revealed the presence of several toxic elements in appreciable quantities. When tested in a rat model system over a period of 360 days after intratracheal injection of mica samples of respirable size (50 mg/animal), the animals which received the factory sample containing shellac exhibited enhanced dust-induced pulmonary reaction together with characteristic abscess formation at later periods. The significance of these findings is discussed.