СИЛИКАГЕЛЬ С КОВАЛЕНТНО ИММОБИЛИЗОВАННЫМ ТИОСЕМИКАРБАЗИДОМ ДЛЯ ТВЕРДОФАЗНОГО КОНЦЕНТРИРОВАНИЯ РТУТИ Джамиля Наибовна Коншина, Виктор Владимирович Опенько, Зауаль Ахлоович Темердашев, Валерий Викторович Коншин, Константин Андреевич Романовский

А new thiosemicarbazide modified silica gel sorbent was prepared and applied for preconcentration of trace mercury(II) prior to the measurement by spectrophotometry and atomic absorption spectroscopy. The optimization of some analytical parameters affecting the adsorption of the analyte such as acidity, shaking time, sample flow rate and volume, eluent condition, and interfering substances were investigated. At pH 2, the maximum static adsorption capacity of Hg(II) onto the thiosemicarbazide modified silica gel was 0.49 мМ∙g-1 . The sorbent was used to remove mercury in a dynamic mode. Changing the speed of pumping the solution (0.5 ml / min (0.25 cm / min) to 6 ml / min (3.2 cm / min)) as an increase in volume from 50 ml to 2000 ml to levels of concentrations (0.0125 mM / l, 0.0375mM / l, 0.075mM / l) did not affect the recovery of mercury. The quantitative recovery (95 %) of Hg(II) could be obtained using 5 mL of 6 mol L−1 HCl solution as eluent. Common coexisting substances did not interfere with the separation of mercury(II) under optimal conditions. The detection limit of sorption-spectrophotometric method definition of mercury was 0.07 µg L−1, and the relative standard deviation (RSD) was lower than 5.0 % . The prepared sorbent was successfully applied for the preconcentration of trace Hg(II) in mineralizate sample fish.Keywords: silica gel, thiosemicarbazide, sorption, mercury, spectrophotometry(Russian)DOI: http://dx.doi.org/10.15826/analitika.2014.18.4.012Dzh. N. Konshina, V.V. Open'ko, Z.A. Temerdashev, V.V. Konshin, K.A. Romanovskii Federal State Educational Institution of Higher Professional Education «Kuban State University», Krasnodar, Russian FederationREFERENCES1. Vlasova N.N, Oborina E.N, Grigor`eva O.Yu., Voronkov M.G. [Organosilicon ion-exchange and complexing adsorbents]. Russian Chemical Reviews, 2013, vol. 82, no. 5, pp. 449-465. doi:10.1070/RC2013v082n05ABEH004301 (in Russian).2. Kara D., Fisher A. Modified silica gel and their use for the preconcentration of trace elements. Separation and Purification Reviews, 2012, vol. 41. pp. 267-317. doi:10.1080/15422119.2011.608765.3. Sigma-aldrich. Available at: http://www.sigmaaldrich.com/catalog/search?interface= Allterm=silicaN=0mode=match%20partialmaxfocus=productlang=enregion=RU (accessed 1 August 2014).4. Silicycle. Available at: http://www.silicycle.com/ (accessed 1 August 2014).5. Lisichkin G.V., Fadeev A. Iu., Serdan A.A., Nesterenko P.N., Mingalev P.G., Furman D.B. Khimiia privitykh poverkhnostnykh soedinenii [Chemical compounds grafted surface]. Moscow, Fizmatlit, 2003, 592 p. (in Russian).6. Losev V.N., Mazniak N.V., Buiko E.I., Trofimchuk A.K. [Sorption-atomic-absorption and sorption-atomic-emission (with inductively coupled plasma) definition of metals in natural waters with silica gel chemically modified mercaptopropyle groups]. Analitika i Kontrol' [Analytics and Control], 2005, vol. 9, no. 1, pp. 81-85 (in Russian).7. Marguí E., Van Grieken R., Fontàs C., Hidalgo M, Queralt I. Preconcentration methods for the analysis of liquid samples by x-ray fluorescence techniques. Applied Spectroscopy Reviews, 2010, vol. 45, pp. 179-205. doi: 10.1080/05704920903584198.8. Zougagh M., Cano Pavon J. M., Garcia de Torres A. Chelating sorbents based on silica gel and their application in atomic spectrometry. Analytical and Bioanalytical Chemistry, 2005, vol. 381, pp. 1103-1113. doi:10.1007/s00216-004-3022-2.9. Soliman E.M., Saleh M. B., Salwa A. A. New solid phase extractors for selective separation and preconcentration of mercury (II) based on silica gel immobilized aliphatic amines 2-thiophenecarboxaldehyde Schiff’s bases. Analytica Chimica Acta, 2004, vol. 523, pp. 133-140. doi: 10.1016/j.aca.2004.07.002.10. Wu Q., Chang X., He Q., Zhai Y., Cui Y., Huang X. Silica gel modified with diaminothiourea as selective solid-phase extractant for determination of Hg(II) in biological and natural water samples. International Journal of Environmental Analytical Chemistry, 2008, vol. 88, pp. 245-254. doi: 10.1080/03067310701648278.11. Zhang L., Chang X., Zheng Hu Z., Zhang L., Shi J.,Gao R. Selective solid phase extraction and preconcentration of mercury(II) from environmental and biological samples using nanometer silica functionalized by 2,6-pyridine dicarboxylic acid. Microchimica Acta, 2010, vol. 168, pp. 79-85. doi:10.1007/s00604-009-0261-0.12. Chen D., Hu B., Huang C. Chitosan modified ordered mesoporous silica as micro-column packing materials for on-line flow injection-inductively coupled plasma optical emission spectrometry determination of trace heavy metals in environmental water samples. Talanta, 2009, vol. 78, pp. 491-497. doi: 10.1016/j.talanta.2008.11.046.13. Fan J., Wu C., Wei Y., Peng C., Peng P. Preparation of xylenol orange functionalized silica gel as a selective solid phase extractor and its application for preconcentration - separation of mercury from waters. Journal of Hazardous Materials, 2007, vol. 145, pp. 323-330. doi: 10.1016/j.jhazmat.2006.11.025.14. Zhou Y., Hu X., Zhang M., Zhuo X., Niu J. Preparation and characterization of modified cellulose for adsorption of Cd(II), Hg(II), and acid fuchsin from aqueous solutions. Industrial and Engineering Chemistry Research, 2013, vol. 52, pp. 876-884. doi:10.1021/ie301742h.15. Mahmoud M.E. Selective solid phase extraction of mercury(II) by silica gel-immobilized-dithiocarbamate derivatives. Analytica Chimica Acta, 1999, vol. 398, pp. 297-304. doi: 10.1016/S0003-2670(99)00429-8.16. Kirillov A.I., Panezhda E.V., Vlasova N.N., Pozhidaev Iu.N., Belousova L.I., Voronkov M.G. [Silicone polymer with thioacetamide group for a concentration of Hg(II), Cd(II), Zn (II), Ni(II), Co (II)]. Analitika i Kontrol' [Analytics and Control], 2000, vol. 4, no. 1, pp. 62-65 (in Russian).17. Simonova L.N., Bruskina I.M., Trofimchuk A.K., Triashin A.S. [Sorption photometric determination of different forms of mercury by means of silica gel grafted with N-benzoyl -N'-propylthiourea]. Zhurnal analiticheskoi khimii [Journal of Analytical Chemistry], 1989, vol. 44, no. 4, pp. 661-665.18. Bai L., Hu Y., Fu W., Wan J., Cheng X., Zhuge L., Xiong L., Chen Q. Synthesis of a novel silica-supported dithiocarbamate adsorbent and its properties for the removal of heavy metal ions. Journal of Hazardous Materials, 2011, vol. 195, pp.261-275. doi: 10.1016/j.jhazmat.2011.08.038.19. Perrin D. D. Organic complexing reagents: structure, behavior, and application to inorganic analysis. New York, Interscience (Wiley), 1964. 365 p. (Rus. Ed.: Perrin D. Organicheskie analiticheskie reagenty. Мoscow, Мir, 1967. 407 p.)20. Konshina Dzh.N., Temerdashev Z.A., Konshin V.V., Byshkina E.I. [Surface functionalization of cellulose thiosemicarbazide groups to create sorbent for concentration and determination of heavy metals in water]. Analitika i Kontrol' [Analytics and Control], 2013, vol. 17, no. 4, pp. 393-400 (in Russian).21. Temerdashev Z.A., Konshina Dzh. N., Logacheva E. Yu., Konshin V.V. Sorbtion properties of cellulose filters with covalently immobilized thiosemicarbazide. Journal of Analytical Chemistry, 2011, vol. 66, no. 10, pp. 930-936. doi: 10.1134/S1061934811100157.22. Temerdashev Z.A., Konshin V.V., Konshina Dzh.N., Logacheva E.Yu. Sposob polucheniia 2,3-ditiosemikarbazontselliulozy i ee primenenie dlia kontsentrirovaniia tiazhelykh metallov iz rastvorov v analiticheskikh tseliakh [Method of producing 2,3-dithiosemicarbazone cellulose and use thereof in concentrating heavy metals from solutions for analytical purposes]. Patent RF, no. 2417231, 2011 (in Russian).23. Vrancken K.C., Possemiers K., Van Der Voort P., Vansant P. Surface modification of silica gels with aminoorganosilanes. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 1995, vol 98, no. 3, pp. 235-241. doi: 10.1016/0927-7757(95)03119-X.24. Lur'e Iu. Iu. Spravochnik po analiticheskoi khimii [Handbook of Analytical Chemistry]. Moscow, Khimiia, 1979. 480 p. (in Russian).25. Radi S., Toubi Y., Attayiba A., Bacquet M. New polysiloxane-chemically immobilized C,C-bipyrazolic receptor for heavy metals adsorption. Journal of Applied Polymer Science, 2011, vol. 121, pp. 1393-1399. doi: 10.1002/app.33541.26. Leyden D.E., Howard L.G., Patterson T.A. Silica gel with immobilized chelating groups as an analytical sampling tool. Analytical Letters, 1975, vol. 8, pp. 51-56. doi:10.1080/00032717508060360.27. Venkatesan K.A., Srinivasan T.G., Vasudeva P.R. Removal of complexed mercury from aqueous solutions using dithiocarbamate grafted on silica gel. Separation Science and Technology, 2002, vol. 37, pp. 1417-1429. doi: 10.1081/SS-120002619.28. Radi S., Attayibat A. [Functionalized SiO2 with S-donor thiophene: synthesis, characterization, and its heavy metals adsorption phosphorus, sulfur, and silicon and the related elements. Phosphorus, sulfur and silicon and the related elements, 2010, vol. 185, pp. 2003-2013. doi: 10.1080/10426500903440042.29. Brown J., Mercier L., Pinnavaia T.J. Selective adsorption of Hg2+ by thiol-functionalized nanoporous silica. Chemical Communications, 1999, no.1, pp. 69-70. doi: 10.1039/A807249C.30. He D., He X., Wang K., Zhao Y., Zou Z. Regenerable multifunctional mesoporous silica nanocomposites for simultaneous detection and removal of mercury (II). Langmuir, 2013, vol. 29, pp. 5896-5904. doi: 10.1021/la400415h31. Johari K., Saman N., Ma H. A comparative evaluation of mercury (II) adsorption equilibrium and kinetics onto silica gel and sulfur-functionalised silica gels adsorbents. The Canadian Journal of Chemical Engineering, 2014, vol. 92, no. 6, pp.1048-1058. doi: 10.1002/cjce.21949.32. Kester D.R., Duedall I.W., Connors D.N., Pytkowicz R. M. Preparation of artificial seawater. Limnology and Oceanography: Methods, 1967, vol. 12, no. 1, pp. 176-179. doi: 10.4319/lo.1967.12.1.0176.33. Reznikov A.A., Mulikovskaia E.P., Sokolov I. Iu. Metody analiza prirodnykh vod [Methods for analysis of natural waters]. Moscow, Nedra, 1970. 488 p. (in Russian)34. Chai X., Chang X., Hu Z., He Q., Tu Z., Li Z. Solid phase extraction of trace Hg(II) on silica gel modified with 2-(2-oxoethyl)hydrazine carbothioamide and determination by ICP-AES. Talanta, 2010, vol. 82, pp. 1791-1796. doi: 10.1016/j.talanta.2010.07.076.35. Fan J., Qin Y., Ye C., Peng P., Wu C. Preparation of the diphenylcarbazone-functionalized silica gel and its application to on-line selective solid-phase extraction and determination of mercury by flow-injection spectrophotometry. Journal of Hazardous Materials, 2008, vol. 150, pp. 343-350. doi: 10.1016/j.jhazmat.2007.04.111.Осуществлен синтез силикагеля с химически иммобилизованным тиосемикарбазидом (степень функционализации 0.49 мМ/г). Изучены некоторые параметры, влияющие на адсорбционную способность полученного материала по отношению к ртути, такие как рН, время контакта фаз, объем раствора и элюента, а также селективность сорбции в присутствии посторонних ионов. Максимальная сорбционная емкость полученного силикагеля по отношению к ионам ртути при рН = 2 составила 0.48 ± 0.04 мМ/г. Изменение скорости пропускания (от 0.5 мл/мин (0.25 см/мин) до 6 мл/мин (3.2 см/мин)) как и увеличение объема пропускаемого раствора от 50 мл до 2000 мл для уровней концентраций 0.0125, 0.0375 и 0.075мМ/л не влияет на степень извлечения ртути. Количественной десорбции ртути можно добиться при использовании 5 мл 6 МНСl. В выбранных условиях концентрирования ртути присутствие в растворе Fe3+, Zn2+ Cu2+, Pb2+, Co2+, Ni2+ и Cd2+ в n∙102 мольных избытках не влияет на степень её извлечения. Полученный сорбционный материал был применен для сорбционно-спектрофотометрического определения ртути в минерализате, полученном после СВЧ автоклавного разложения образца рыбы.Ключевые слова: силикагель, тиосемикарбазид, сорбция, ртуть, спектрофотометрия DOI: http://dx.doi.org/10.15826/analitika.2014.18.4.012 ЛИТЕРАТУРА1. Кремнийорганические ионообменные и комплексообразующие сорбенты / Н.Н. Власова [и др.] // Успехи химии. 2013. T. 82, №5. C. 449-464.2. Kara D., Fisher A. Modified silica gel and their use for the preconcentration of trace elements // Separation and purification reviews. 2012. V. 41. P. 267-317.3. Sigma-aldrich // [электронный ресурс]: http://www.sigmaaldrich.com/catalog/ search?interface=Allterm=silicaN=0mode=match%20partialmaxfocus=productlang=enregion=RU (дата обращения 01.08. 2014).4. Silicycle // [электронный ресурс]: http://www.silicycle.com/ (дата обращения 01.08. 2014).5. Химия привитых поверхностных соединений / Г.В. Лисичкин [и др.]. М.: Физматлит, 2003. 592 с.6. Сорбционно-атомно-абсорбционное и сорбционно-атомно-эмиссионное (с индуктивно связанной плазмой) определение металлов в природных водах с использование силикагеля, химически модифицированного меркаптопропильными группами / В.Н. Лосев [и др.] // Аналитика и контроль. 2005. Т. 9, № 1. С. 81-85.7. Preconcentration methods for the analysis of liquid samples by x-ray fluorescence techniques /E. Margui[et al.] // Appl. Spectrosc. Rev. 2010. V. 45. P. 179-205.8. Zougagh M., Cano Pavon J. M., Garcia de Torres A. Chelating sorbents based on silica gel and their application in atomic spectrometry // Anal. Bioanal. Chem. 2005. V. 381. P. 1103-1113.9. Soliman E.M., Saleh M. B., Salwa A.A. New solid phase extractors for selective separation and preconcentration of mercury (II) based on silica gel immobilized aliphatic amines 2-thiophenecarboxaldehyde Schiff’s bases // Anal. Chim. Acta. 2004. V. 523. P. 133-140.10. Silica gel modified with diaminothiourea as selective solid-phase extractant for determination of Hg(II) in biological and natural water samples / Q. Wu [et al.] // Intern. J. Environ. Anal. Chem. 2008. V. 88. P. 245-254.11. Selective solid phase extraction and preconcentration of mercury(II) from environmental and biological samples using nanometer silica functionalized by 2,6-pyridine dicarboxylic acid / L. Zhang [et al.] // Microchim. Acta. 2010. V. 168. P. 79-85.12. Chen D., Hu B., Huang C. Chitosan modified ordered mesoporous silica as micro-column packing materials for on-line flow injection-inductively coupled plasma optical emission spectrometry determination of trace heavy metals in environmental water samples // Talanta. 2009. V. 78. P. 491-497.13. Preparation of xylenol orange functionalized silica gel as a selective solid phase extractor and its application for preconcentration - separation of mercury from waters / J. Fan [et al.] // J. Hazard. Mater. 2007. V. 145. P. 323-330.14. Preparation and characterization of modified cellulose for adsorption of Cd(II), Hg(II), and acid fuchsin from aqueous solutions / Y. Zhou [et al.] // Ind. Eng. Chem. Res. 2013. V. 52. P. 876-884.15. Mahmoud M. E. Selective solid phase extraction of mercury(II) by silica gel-immobilized-dithiocarbamate derivatives // Anal. Chim. Acta. 1999. V. 398. P. 297-30416. Cорбционное извлечение Hg(II), Cd(II), Zn (II), Ni(II), Co (II) кремнийорганическим полимером с тиоацетомидной группировкой / А.И. Кириллов [и др.] // Аналитика и контроль. 2000. Т. 4, № 1. С. 62-65.17. Сорбционно-фотометрическое определение различных форм ртути с помощью силикагеля с привитой N-бензоил -N’-пропилтиомочевиной / Л. Н. Симонова [ и др.] // Журн. аналит. химии. 1989. № 4. С. 661-665.18. Synthesis of a novel silica-supported dithiocarbamate adsorbent and its properties for her removal of heavy metal ions / L. Bai [et al.] // J. Hazard. Mater. 2011. V. 195. P. 261-275.19. Перрин Д. Органические аналитические реагенты: пер. с англ. М.: Мир, 1967. 407 с.20. Функционализация поверхности целлюлозы тиосемикарбазидными группами с целью создания сорбента для концентрирования и определения металлов в водах / Дж.Н. Коншина [и др.] // Аналитика и контроль. 2013. Т. 17, № 4. С. 393-400.21. Сорбционные свойства целлюлозных фильтров с ковалентно иммобилизованным тиосемикарбазидом / З.А. Темердашев [и др.] // Журн. аналит. химии. 2011. Т. 66, № 10. С. 1048-1054.22. Патент 2417231 РФ, МПК СО8B 15/06 G01N 31/22. Способ получения 2,3-дитиосемикарбазонцеллюлозы и ее применение для концентрирования тяжелых металлов из растворов в аналитических целях. / Темердашев З.А., Коншин В.В, Коншина Д.Н., Логачева Е.Ю. (RU). №2009149712/05; заявл. 30.12.2009; опубл. 27.04.2011, Бюл. №12. 23. Surface modification of silica gels with aminoorganosilanes / K.C. Vrancken [et al.] // Colloids Surf. Part A. 1995. V. 98. P. 235-241.24. Лурье Ю.Ю. Справочник по аналитической химии. М.: Химия, 1979. 480 с.25. New polysiloxane-chemically immobilized C,C-bipyrazolic receptor for heavy metals adsorption / S. Radi[ et al.] // J. Appl. Polym. Sci. 2011. V. 121. P. 1393-1399.26. Leyden D.E., Howard L.G., Patterson T.A. Silica gel with immobilized chelating groups as an analytical sampling tool // Аnal. lett. 1975. V.8. P. 51-56.27. Venkatesan K.A., Srinivasan T.G., Vasudeva P.R. Removal of complexed mercury from aqueous solutions using dithiocarbamate grafted on silica gel // Sep. Sci. Technol. 2002. V. 37. P. 1417-1429.28. Radi S., Attayibat A. Functionalized SiO2 with S-donor thiophene: synthesis, characterization, and its heavy metals adsorption phosphorus, sulfur, and silicon and the related elements // Phosphorus, Sulfur Silicon Relat. Elem. 2010. V. 185. P. 2003-2013.29. Brown J., Mercier L., Pinnavaia T.J. Selective adsorption of Hg2+ by thiol-functionalized nanoporous silica // Chem. Commun. 1999. № 1. P. 69-70.30. Regenerable multifunctional mesoporous silica nanocomposites for simultaneous detection and removal of mercury(II) / D. He [et al.] // Langmuir. 2013. V. 29. P. 5896-5904.31. Johari K., Saman N., Ma H. A comparative evaluation of mercury (II) adsorption equilibrium and kinetics onto silica gel and sulfur-functionalised silica gels adsorbents // Can. J. Chem. Eng. 2014. V. 92. P. 1048-1058.32. Preparation of artificial seawater / D.R. Kester [et al.] // Limnol. Oceanogr. 1967. V. 12, № 1. Р. 176-179.33. Резников А.А., Муликовская Е.П., Соколов И.Ю. Методы анализа природных вод. М.: Недра, 1970. 488 с.34. Solid phase extraction of trace Hg(II) on silica gel modified with 2-(2-oxoethyl)hydrazine carbothioamide and determination by ICP-AES / X. Chai [et al.] // Talanta. 2010. V. 82. P. 1791-1796.35. Preparation of the diphenylcarbazone-functionalized silica gel and its application to on-line selective solid-phase extraction and determination of mercury by flow-injection spectrophotometry / J. Fan [et al.] // J. Hazard. Mater. 2008. V. 150. P. 343-350.