CC BY
62
ства почв на 14-16%о. В карбонатных слоях почвенных образцов (40-50 см) Бурятии и Внутренней Монголии содержание изотопного состава составило от -7,90 до -7,85%о и -10, 57- -14,13%о соответственно.
Таким образом, полученные данные изотопного состава углерода 513С растительных и почвенных (органического вещества и карбонатного) образцов исследуемых фитоценозов вносят определенный вклад для выяснения механизма процессов почвообразования.
Литература:
1. http://ru.wikipedia.org/wiki
2. Моргун Е.Г., Ковда И.В., Рысков Я.Г., Олейник С.А. Возможности и проблемы использования методов геохимии стабильных изотопов углерода в почвенных исследованиях // Почвоведение. - 2008. - №3. - С. 299310.
3. Заварзин Г.А., Жилина Т.Н. Содовые озера - природная модель древней биосферы континента // Журн. общей биологии. - 1991.- Т.52. - С. 308-318.
Буянтуева Любовь Батомункуевна, кандидат биологических наук, доцент, кафедра экспериментальной биологии, Бурятский государственный университет, 670000, Улан-Удэ, ул. Смолина 24а, т. 8(3012)663992, blb 62@mail.ru.
Дамдинсурэн Болормаа, научный исследователь Монгольской ассоциации по менеджменту пастбищ Монголии, Монголия, Улан-Батор, район Баянзурх, микрорайон №3, bolormaa_d.gahoo.com
Дамбаев Вячеслав Борисович, кандидат биологических наук, младший научный сотрудник, Институт общей и экспериментальной биологии СО РАН, 670047, Улан-Удэ, ул. Сахьяновой, 6, slavadmb@rambler.ru
Намсараев Баир Бадмабазарович, доктор биологических наук, профессор, зав. лабораторией микробиологии, Институт общей и экспериментальной биологии СО РАН, 670047, Улан-Удэ, ул. Сахьяновой 6
Buyantueva Lyubov Batomunkuevna, candidate of biological sciences, assistant professor, Chair of Experimental Biology, Buryat State University, 670000, Ulan-Ude, Smolina St., 24a, blb62@mail.ru.
Dambaev Vyacheslav Borisovich, candidate of biological sciences, researcher, Institute of General and Experimental Biology SB RAS, 670047, Ulan-Ude, Sakhyanovoy St., 6, slavadmb@rambler.ru
Damdinsuren Bolormaa, researcher, Mongolian Society on Pasture Management, Mongolia, Ulaan-Baatar, Bayan-zurkh District 3, bolormaa_d.gahoo.com
Namsaraev Bair Badmabazarovich, Doctor of Biology, Professor, Head of Laboratory of Microbiology, Institute of General and Experimental Biology SB RAS, 670047, Ulan-Ude, Sakhyanovoy St., 6
УДК543 O. Bolormaa, S. Narantsetseg, B. Burmaa, P. Oyukhuu, Ts. Amartaivan
HUMAN HAIR ELEMENTAL ANALYSIS OF PATIENTS WITH VIRAL HEPATITIS AND LIVER CIRRHOSIS BY X-RAY FLUORESCENCE METHOD
Human hair of chronic viral hepatitis and liver cirrhosis patients in Ulaanbaatar were analyzed for elemental analysis by total X-ray Fluorescence spectrometry. Positive strong correlations were observed among the elements [Ti=f(Pb), f(Cu)], [Cu=f(K), f(Ti)] and [Sr=f(K), f(Fe)]. The mean concentrations of Ca, Fe, Ti and Sr were found higher than those in the hair of normal people in Japan, Mongolia, Iran and Indonesia though the level of Cu and Zn is not different. The concentrations of Ca, Ti and Sr in hair of the patients were found to be increased over that of normal Mongolian people reported by other researchers.
Keywords: trace element, human hair, viral hepatitis, liver cirrhosis
О. Болормаа, С. Нарантсэсэг, Б. Бурмаа, П. Оюхуу, Ц. Амартайван
ЭЛЕМЕНТНЫЙ АНАЛИЗ РЕНТГЕНО-ФЛУОРЕСЦЕНТНЫМ МЕТОДОМ ВОЛОС ЛЮДЕЙ, БОЛЬНЫХ ВИРУСНЫМ ГЕПАТИТОМ И ЦИРРОЗОМ ПЕЧЕНИ
Волосы больных хроническим вирусным гепатитом и циррозом печени в Улан-Баторе исследовали на элементный анализ рентгено-флуоресцентным спектрометром. Наблюдались положительно сильные корреляции среди элементов [Ti=f(Pb), f(Cu)], [Cu=f(K), f(Ti)] and [Sr=f(K), f(Fe)]. Найдено, что средние концентрации Ca, Ti, и Sr выше, чем в волосах обычных людей в Японии, Монголии, Иране и Индонезии, хотя уровень Сг и Ят не отличается. Концентрации Ca, Ti и Sr в волосах больных людей выше, чем у здоровых монголов, зарегистрированные другими исследователями.
Ключевые слова: следовый элемент, человеческий волос, вирус гепатита, цирроз печени.
Scalp human hair is well known to accumulate metal concentrations over time, thus containing a higher concentration than found in blood, serum or urine samples [1-3]. In recent years considerable effort has been made to measure trace metal levels in various human tissues to determine inter element correlations with different diseases [3-5] by several analytical techniques [3-8]. TXRF (total reflection X-ray fluorescence) is a technique that has many advantageous features such as multielemental capability, high sensitivity and precision, short time of analysis as well as offering the possibility of direct sample analysis with the use of very small sample manipulation. Usually, an analysis by TXRF involves the dissolution of sample; an aliquot of the solution is placed on a quartz plate, and, after drying, the plate with the sample is used as an emitter. To analyze biological materials, a thin micro section of the material to be analyzed (a microtome) is sometimes prepared. Being placed on a quartz support, it is used as an emitter. This feature makes the technique very attractive for monitoring environmental pollution and in analyzing biological materials [9-10]. Viral hepatitis and liver cirrhosis are very common diseases among Mongolian people and number of morbidity due to liver disorders have being increased for the last years in through statistic survey in last 5 years in Mongolia [11].
In the present paper the TXRF method was applied to chemical analysis of the human hair of the acute viral hepatitis patients in Ulaanbaatar, capital city of Mongolia.
Experimental
Apparatus.TXRF spectrometer installed at Nuclear Research Center, National University of Mongolia. The spectrometer consists of a total reflection unit (Atominstitut Oesterreichischen Univ., Vienna, Austria), an X-ray spectrometry unit (a semiconductor Si(Li) detector, model S1 18080) (CAMBERRA, USA) 160 eV resolution at 5.9 keV Mn Ka line, an X-ray generator, model IS0-3000 SEIFERT, and data was collected with a measurement time of 200 s in a PC based NUCLEUS computer (USA). The AXIL software provides the calculation of components using the internal standard method (Ga is used as a reference material). In the experiments, an X-ray tube with molybdenum anode operated under the following conditions: voltage V=50 kV, current i=10 mA.
Reagents. Analytical grade acetone and distilled water were used for washing human hair samples; 14N nitric acid (HNO3) pure for analysis and 30% hydrogen peroxide (H2O2) were used for acid digestion of human hair samples. The gallium (Ga) element standard, 1000 ^g/ml was served for internal standardization by TXRF.
Samples. The scalp hair samples were collected from the same place on the backside of head, namely from the occipital region using a pair of stainless steel scissors. The age range of individuals was 19 to 70 years (mean: 43.9). Samples were stored in sealed plastic bags, which were mar-ked with personal information regarding age, sex, hair color and doctor’s diagnosis of diseases. The main problem of using hair is external contamination. The samples were thoroughly washed to remove external contamination by 1% soap solution rinsed with distilled water, then placed for one hour in acetone and finally washed again by distilled water and air-dried. The weight of the samples was about 25-30 mg. Hair samples were dissolved in a mixture of HNO3 and H2O2. The weighed hair sample (25-30 mg) was placed into the chemical beaker and added
0.3 mL ultra pure nitric acid and then heated in the microwave oven within 3 min at 120oC. Then to the residue was added 0.1 mL of 30% hydrogen peroxide and heated less than 100oC for 2 min. After this, the solution was evaporated almost to dryness and 0.6 mL of 0.1 M nitric HNO3 added to the mixture. Finally the solution was again evaporated almost to dryness at 130-140oC. The residue was dissolved in 1.0 mL of 0.1 M HNO3 to produce a final sample solution.
Procedures. The analysis of human hair was performed by using methodology previously developed by us [12]. To prepare emitters, an aliquot of the solution of up to 1,0 ml was taken and weighed in a special vessel using an AG204 electronic balance (Mettler-Toledo, Switzerland). Next, 10 ^L of a standard solution of Ga with a concentration of 1000 ppm was added, and the solution was weighed again. After stirring, an aliquot of 5 ^L was taken, applied to quartz reflector, dried using an infrared lamp, and used as an emitter. The acquisition time is 200 s. The performance parameters of the developed procedure were estimated. Limits of detection cmin were calculated using the 3 ^-criterion [13], and the determination of standard deviation characterizing the scatter of background values was made using several blank emitters prepared by applying diluted HNO3 (1:99) to quartz reflectors. The values of cmin are 2, 8, 2, 10, 7 and 3 ng for Zn, Ca, Cu, K, Fe and Pb respectively. The reproducibility (sr,b) of the procedure was estimated using the obtained results for hair analysis. The values of sr,b are 6,8,13,21 and 20% for Zn, Cu, Ca, K and Fe respectively. The accuracy was verified using an IAEA-086 certified reference sample of hair.
Results and discussion
The accuracy was checked by the analysis of a standard reference material, IAEA-086 unspiked human hair, including statistical and repeatable errors, whose elemental concentrations are presented in table 1. Errors mainly come from the preparation of targets for irradiation, spectrum fitting, and partially from the detection efficiency. The results obtained are in a good agreement with the certified values.
Table 1
Comparison of elemental concentrations (^g g-1) in IAEA -086 standard sample and certified valuesl
This work Certified value
Ca 81+11 112+11
Cu 1.98+0.34 1.76+0.13
Fe 20.1+3.2 12.3+1.5
Mn 0.88+0.15 0.96+0.08
Sc 1.5+0.2 1.4+0.2
Se 0.12+0.06 0.10+0.02
Zn 18.3+2.5 16.7+1.1
Estimated concentrations of elements are presented in table 2, 3. From the present results, it can be seen the levels of elements Ca, Ti, Fe, and Cu, are higher and K and Zn are lower in the patients of chronic viral hepatitis and liver cirrhosis than those observed in the normal people.
Table 2
Results of human hair samples (B Virus) Element
Content K Ca Fe Cu Zn Sr Pb Ti
Max, mg/kg 1211 8625 : 336 84 434 115 144 389
Min, mg/kg 73 555 7 2 6 5 120 4.5 23 6
Mean, mg/kg 511 2016 5 5 5 6 205 32 62 163
Standard 3.17 19.4 1.2 0.45 0.9 1.08 1.08 0.21
deviation, %
Table 3
Results of human hair samples (C Virus)
Element
Content K Ca Fe Cu Zn Sr Pb Ti
Max, mg/kg 802 8625 641 115 531 77 134 453
Min, mg/kg 43.3 455 31 21 53 7 16 10
Mean, mg/kg 364 2254 210 55 244 31 55 146
Standard 317 19.24 1.2 0.45 0.9 1.1 1.2 0.2
deviation, %
The elemental concentrations in biological samples vary considerably due to geographical differences, nutritional status and environmental factors. The present results were compared with other results reported by several researchers and the ranges of word wide mean values. Table 4 shows the comparative results. The mean concentrations of Ca, Fe, Ti and Sr in this work were found higher than those of normal people in Japan, Mongolia, Iran and Indonesia. The level of elements Cu and Zn observed in human hair of liver cirrhosis and chronic viral hepatitis patients are in agreement with those determined in normal human hair of Japan, Mongolia, Iran and Indonesia. It is interesting to note that concentrations of Ca, Ti, Ni, As, Br and Sr in the human hair of the cirrhosis and chronic viral hepatitis patients were higher than Mongolian normal human hair which are have been analyzed by other researchers.
Some researchers have been observed that cancer of the respiratory tract can be attributed to the inhalation of nickel compounds. To determine the interaction between elements in hair correlation coefficients were calculated. Positive strong correlations were observed among the elements [Ti=f(Pb), f(Cu)], [Cu=f(K), f(Ti)] and [Sr=f(K), f(Fe)]. The correlation matrix gives us information about relationships between two metals but does not take into consideration of the presence of other elements.
________________________________________________________________________________________Table 4.
Inter comparison of trace element concentrations (ug g-1) in human hair
Element Our study, patients (TXRF) Prev. study, patients15 (PIXE) Iran1 (INAA) Pakistan5 (AAS) Indonesia16 (AAS) Japan14 (PIXE)
K 387 NA NA NA NA NA
Ca 1919 2257 862 1232 NA 1890
Fe 161 55.2 NA 21 242 29.1
Cu 51 19.7 9.7 NA 29 42.7
Zn 211 296 170 184 228 238
Sr 28 15.8 NA NA NA 6.04
Pb 53.6 2.5 NA NA NA 0.23
Ti 132 141 NA NA NA 10.4
NA-not available
Conclusion
The trace elemental analysis is carried out in the human hair of the liver cirrhosis and chronic viral hepatitis patients by employing TXRF technique. It is confirmed that the present method of analyzing human hair can serve as a powerful one for evaluation of human environment. From the present results, it has illustrated that the levels of elements Ca, Fe, Ti and Sr higher in the human hair of the cirrhosis and chronic viral hepatitis patients than those observed by different researchers for normal people from Iran, Japan and Indonesia. The elements Cu and Zn observed in the in the hair of the liver cirrhosis and chronic viral hepatitis patients similar to those determined in normal human hair. Positive strong correlations were observed among the elements [Ti=f(Pb), f(Cu)], [Cu=f(K), f(Ti)] and [Sr=f(K), f(Fe)]. However, no visible correlation was determined. To provide more credible data more statistics (more populated cohort of patients) is needed.
References
1. Hindmarsh T.J. Caveats in hair analysis in chronic arsenic poisoning // Clinical Biochemistry. - 2002. - V.35. - P. 1-11.
2. Valcovic V. Human Hair II // CRC. Press, Inc., - 1988
3. Forte G., Alimonti A., Violente N. et al. Calcium, copper, iron, magnesium, silicon and zinc content of hair in
Parkinson's disease // J. Trace Elem. Med. Biol. - 2005. - V.19. - P. 195-201.
4. Ovesen J., Moller-Madsen B., Nielsen P.T. et al. Differences in zinc status between patients with osteoarthritis
and osteoporosis // J. Trace Elem.Med.Biol. - 2009. - V.23. P. 1-8.
5. Lloyd G.R., Ahmad S., Wasim M., Rereten R.G. Pattern recognition of Inductively Coupled Plasma Atomic Emission Spectroscopy of human scalp hair for discriminating between healthy and Hepatitis C patients // Analytica Chimica Acta. - 2009. - V.649. P. 33-42.
6. Tavakkoli A., Ahmadiniar A., Shirini R. Determination of hair element content in Iranian population using INAA // Anal. Radioanal. Nucl. Chem. - 2000. - V.243, №3. - P. 731-735.
7. Sera K., Futatsugawa S., Murao S. Quantitative analysis of untreated hair samples for monitoring human exposure to heavy metals // Nucl. Inst. and Meth. in Phys. Res B. - 2002. - V.189. - P. 174-179
8. Kolmogorov Y., Kovoleva V., Gonchar A. Analysis of trace elements in scalp hair of healthy people, hyperplasia and breast cancer patients with XRF method // Nucl. Instrum. Methods A. - 2000. - V.448. - P. 457-460.
9. Khuder A., Bakir M.A., Karjou J., Sawan M.Kh. XRF and TXRF techniques for multi-element determination of trace elements in whole blood and human hair samples // J. Radioanal. Nucl. Chem. - 2007. - V.273, №2. P. 435442.
10. Khuder A., Bakir M.A., Hasan R., Mohammad A. Determination of nickel, copper, zinc and lead in human scalp hair n Syrian occupationally exposed workers by total reflection X-ray fluorescence // Environ. Monit. Assess. -2008. - V.143. - P. 67-74.
11. Health statistics of Mongolia. - 2010.
12. Pavlinskii G.V., Smagunova A.N., Karpukova O.M., Bolormaa O., Dorj D. Sources of Error in Total Reflection X-Ray Fluorescence Analysis and Error Correction using the internal standard method // J. Anal. Chem. - 2002. -V.37, №3. - P. 231-239.
13. Smagunova A.N., A.Kozlov V. Primeri primeneniya matematicheskoi theorii eksperimenta v rentgeno-flourestsentnom analize (Application of Matematical Experiment Theory in X-ray Fluorescence Analysis). - Irkutsk, Irkutsk State Univ, 1990. - 232 p.
14. Murao S., Daisa E., Sera K., Maglambayan V.B., Futatsugawa S. PIXE measurement of human hairs from a small-scale-mining site of the Philippines // Nucl. Instr. and Meth.in Phys. Res. B. - 2002. - V. 189. - P. 168-173.
15. Bolormaa O., Tsuji M., Kawasaki K., Narantsetseg S. PIXE analysis of trace elements in human hair of patients with liver disorders // IJPIXE. - 2006. - V. 16, №1-2. P. 29-38.
16. Ponzetta MT, Nardi S., Calliari I., Lucchese M. Trace elements in human scalp hair and soil in Irian Jaya // Bi-
ol. Trace. Elem Res. - 1998. - V.62. - P. 199-212.
Bolormaa O., associate professor, Department of Inorganic and Analytical Chemistry, School of Chemistry and Chemical Engineering, National University of Mongolia, Ulaanbaatar, Mongolia
Narantsetseg S., Professor, Head of Gastroenterology Department, Shastin Central Hospital, Ulaanbaatar, Mongolia Burmaa B., master student, Department of Inorganic and Analytical Chemistry, School of Chemistry and Chemical Engineering, National University of Mongolia, Ulaanbaatar, Mongolia
Oyukhuu P., Head of Gastroenterology Department, Shastin Central Hospital, Ulaanbaatar, Mongolia Amartaivan Ts., associate professor, Head Section of Nuclear Analytical Techniques, Nuclear Research Center, National University of Mongolia, Ulaanbaatar, Mongolia
Болорма O., доцент, факультет неорганической и аналитической химии, школа химии и инженерной химии, Монгольский государственный университет, Улан-Батор, Монголия
Нарансэсэг S., профессор, заведующий отделом гастроэнтерологии, центральный гоститаль, Улан-Батор, Монголия.
Бурмаа B., магистрант, факультет неорганической и аналитической химии, школа химии и инженерной химии, Монгольский национальный университет, Улан-Батор, Монголия.
Оюхуу P., отдел гастроэнтерологии, центральный гоститаль, Улан-Батор, Монголия.
Амартайван Ts., доцент, руководитель отдела ядерных аналитических технологий, Ядерный исследовательский центр, Монгольский национальный университет, Улан-Батор, Монголия.
УДК 544 © O. Bolormaa, M. Tsuji, S. Murao, B. Ochirkhuyag
LEACHABILITY OF ARSENIC BY SEDIMENTS IN BOROO AREA, MONGOLIA
The leachability of arsenic and other constituents was studied by a diphasic distribution technique. Chemical analyses were carried out using particle-induced X-ray emission spectrometry and ion chromatography for aqueous phase. Showed that these sediments contain Hg, Se, As and Pb at different levels along with other metals. A 10-20 ppm level of As (III) was released by one of these samples into aqueous solution at higher pH values.
Keywords: arsenic, sediment, heavy metals, leachability, diphase Distribution
О. Болормаа, М. Цужи, С. Мурао, Б. Очирхуяг ВЫЩЕЛАЧИВАНИЕ МЫШЬЯКА ДОННЫМИ ОСАДКАМИ В РАЙОНЕ БОРОО, МОНГОЛИЯ
Изучено вымывание мышьяка и других составляющих методом двуфазного распределения. Химические анализы проводились с использованием рентгено-эмиссионной спектрометрии и ионной хроматографии для водной фазы. Показано, что осадки содержат Hg, Se, As и Pb на различных уровнях наряду с другими металлами. Уровень мышьяка (III) 10-20 ppm был высажен одним из образцов в водном растворе при повышенных значениях рН.
Ключевые слова: мышьяк, осадки, тяжелые металлы, способность к вымыванию.
In the gold mining practiced in several Asian developing countries including Mongolia, mercury is found to form an amalgam with gold. The process of gold purification is mainly performed by small-scale miners with a low level of technical knowledge and skills, with no strict regulation. This leads to serious potential health and environmental risks in the areas of gold mining. Waste streams in mining industry often contain arsenic and other heavy metals. It could migrate through geological structure and might pollute water sources with potential hazardous contamination of drinking water. Discharge of heavy metals such as Hg, As and Pb, associated with gold mining, has been reported. It includes Inner Mongolia [1], Central Portugal [2], Indonesia [3] and USA, Philippines [4, 5], Tangania and Zimbabwe [6]. These heavy metals are redistributed between sediments, depending upon the ion exchange adsorption properties of sediments. Hence, it is important to understand such chemical properties of sediments comprising basically aluminosilicates, and insoluble oxides and/ or hydroxides of metals in order to predict the redistribution behavior. The total As, Sb, and Bi concentrations in surface soil samples were found in the mine dump sites due to mineralization associated with those metalloids, with the average values of 2500, 54 and 436 ^g g-1, respectively. The guideline for As of 6.0 ^g g-1 in agricultural land has set in Korea [7]. In the area of Boroo Mongolia, which
