litosphereЛитосфераLITHOSPHERE (Russia)1681-90042500-302XA.N. Zavaritsky Institute of Geology and Geochemistry10.24930/1681-9004-2018-18-6-928-941litosphere-262Research ArticleСтатьиArticlesЭлементный состав грунтовых вод и спелеотемы “лунное молокоˮ в карстовой пещере Прощальная (Дальний Восток)Element composition of ground water and speleothem “moon milkˮ in a karst cave Proshchal’naya (Far East)КондратьеваЛ. М.KondratyevaLubov’ M.

г. Хабаровск, ул. Ким Ю Чена, 65, 680000

65 Kim-Yu-Chen st., Khabarovsk 680000

ПолевскаяО. С.PolevskayaOksana S.

г. Хабаровск, ул. Ким Ю Чена, 65, 680000

65 Kim-Yu-Chen st., Khabarovsk 680000

oksasha.polevskaya@mail.ruГолубеваЕ. М.GolubevaEvgeniya M.

г. Хабаровск, ул. Ким Ю Чена, 65, 680000

65 Kim-Yu-Chen st., Khabarovsk 680000

ШтареваА. В.ShtarevaAnna V.

г. Хабаровск, ул. Ким Ю Чена, 65, 680000

65 Kim-Yu-Chen st., Khabarovsk 680000

КоноваловаН. С.KonovalovaNatal’ya S.

г. Хабаровск, ул. Ким Ю Чена, 65, 680000

65 Kim-Yu-Chen st., Khabarovsk 680000

Институт водных и экологических проблем ДВО РАНРоссияInstitute of water and ecological problems, Far East Branch of RASRussian FederationИнститут тектоники и геофизики им. Ю.А. Косыгина ДВО РАНРоссияYu.A.. Kosygin Institute of tectonics and geophysics, Far East Branch of RASRussian Federation20182812201806928941Copyright © Кондратьева Л.М., Полевская О.С., Голубева Е.М., Штарева А.В., Коновалова Н.С., 20182018Кондратьева Л.М., Полевская О.С., Голубева Е.М., Штарева А.В., Коновалова Н.С.Kondratyeva L.M., Polevskaya O.S., Golubeva E.M., Shtareva A.V., Konovalova N.S.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://www.lithosphere.ru/jour/article/view/262

Объект исследования. Целью работы являлся сравнительный анализ элементного состава грунтовых вод (капельной, трещинной), воды из внутреннего водотока, в карстовой пещере Прощальная (Хабаровский край) и поверхностных вод ближайшей реки Сагды-Селанка. Большой интерес представляло исследование спелиотемы (натечного образования) “лунное молоко” (moonmilk) в пещере Прощальная. Материалы и методы. Натечное образование “лунное молоко” исследовалось с помощью сканирующей электронной микроскопии (EVO-40HV, CarlZeiss, Германия) и кремний-дрейфового рентгеновского детектора X-MAX 80 мм2 . Методом ICP-MS проведен сравнительный анализ элементного состава грунтовых вод (капельной, трещинной), воды из внутреннего водотока в пещере Прощальная и поверхностных вод р. Сагды-Селанка. Результаты. Максимальные концентрации кальция, железа и марганца были установлены в весенний период в капельной воде, а магния – в проточных водах (внутренний водоток пещеры и р. Сагды-Селанка). Определено, что визуально пластичная и гомогенная масса спелеотемы “лунное молоко” гетерогенна и содержит различные микроструктуры. Трубчатые микроструктуры представлены более богатым элементным составом (C, O, Ca, Fe, Mn, Si, Al и S) по сравнению с булавовидными образованиями (C, O, Ca и Na). Связующей матрицей в составе “лунного молока” были сетчатые структуры, подобные мицелию актиномицетов и бактериальным пленкам. Выводы. Результаты проведенных исследований в условиях муссонного климата могут быть интересны при изучении карстовых процессов в других климатических зонах.

Object of research. The aim of this work was the comparative analysis of element composition of groundwater (drip, fracture), water from the interior of the watercourse in a karst cave Proshchal’naya (Khabarovsk Territory) and the surface water of the nearest river Sagdy-Selanka. The great interest was the study of speleothem (dropstones) “moon milk” in the cave Proshchal’naya. Materials and methods. Speleothem “moon milk” was investigated with a scanning electron microscope (EVO-40HV, CarlZeiss, Germany) and silicon-drift x-ray detector X-MAX 80 мм2 . By ICP-MS method a comparative analysis of element composition of groundwater (drip, fracture), water from an internal stream in the cave Proshchal’naya and surface water of the river Sagdy-Selenka were carried out. Results. Maximum concentrations of calcium, iron and manganese was installed in the spring, between drip and fracture water and magnesium – in flowing waters (inland watercourse caves and Sagdy-Selanka R.). It was determined that visually plastic and homogeneous mass of speleothem “moon milk” is heterogeneous and contains various microstructures. Tubular microstructures were represented by richer elemental compo sition (C, O, Ca, Fe, Mn, Si, Al, and S) compared with club-shaped formations (C, O, Ca, and Na). The binding matrix in the composition of the “moon milk” were reticular structures similar to actinomycente mycelium and bacterial films. Findings. The results of studies conducted in a monsoon climate may be interesting for researchers which study karst processes in other climatic zones.

карсткапельная водатрещинная воданатечное образование “лунное молоко”karstdrip waterwater of fracturingdropstones“moonmilk”ReferencesАбдрахманов Р.Ф., Попов В.Г. (2010) Геохимия и формирование подземных вод Южного Урала. Уфа: АН РБ, Гилем, 420 с.Abdrakhmanov R.F., Popov V.G. (2010) Geokhimiya i formirovanie podzemnykh vod Yuzhnogo Urala [Geochemistry and formation of groundwater in the South Urals]. (Ed. V.N. Puchkov). Ufa, AN RB, Gilem Publ., 420 p. (In Russian)Багринцева К.И. (1999) Условия формирования и свойства карбонатных коллекторов нефти и газа. M.: РГГУ (II), 285 с.Aloisi G., Gloter A., Krüger M., Wallmann K., Guyot F., Zuddas P. (2006) Nucleation of calcium carbonate on bacterial nanoglobules. Geology, 34, 1017-1020.Берсенёв Ю.И. (1989) Карст Дальнего Востока. М.: Наука, 172 с.Bagrintseva K.I. (1999) Usloviya formirovaniya i svoistva karbonatnykh kollektorov nefti i gaza [Conditions of formation and properties of carbonate reservoirs of oil and gas]. Moscow, RGGU. Publ. (II), 285 p. (In Russian)Дублянский В.Н., Дублянская Г.Н. (2004) Карстоведение. Ч. I. Общее карстоведение. Пермь: Пермский гос. университет, 306 с.Benzerara K., Miot J., Morin G., Ona-Nguema G., SkouriPanet F., Ferard C. (2011) Significance, mechanisms and environmental implications of microbial Biomineralization. C. R. Geosci., 343(2-3), 160-167.Гресов А.И., Обжиров А.И., Коровицкая Е.В., Шакиров Р.Б. (2009) Метаноностность и перспективы освоения ресурсов метана угольных пластов бассейнов юга Дальнего Востока. Тихоокеан. геология, 28(2), 103-116.Bersenev Yu.I. (1989) Karst Dal’nego Vostoka [Karst of the Far East]. Moscow, Nauka Publ., 172 p. (In Russian)Жабинская Т.Б. (2003) Формирование химического состава подземных вод Воронцовского карстового массива (Западный Кавказ). Записки горного института, 155(2), 27-29.Bindschedler S., Cailleau G., Braissant O., Millière L., Job D., Verrecchia E.P. (2014) Unravelling the enigmatic origin of calcitic nanofibres in soils and caves: purely physicochemical or biogenic processes? Biogeosci., 11, 2809-2825.Кадебская О.И. (2016) Процессы современного минералообразования в карбонатных пещерах Урала, связанные с различными микроклиматическими обстановками. Географ. вестник, 1(36), 5-17.Bindschedler S., Millière L., Cailleau G., Job D., Verrecchia E.P. (2012) An ultrastructural approach to analogies between fungal structures and needle fibre calcite. Geomicrobiol. J., 29, 301-313.Кондратьева Л.М., Литвиненко З.Н. (2014) Формирование биопленок микробными комплексами подземных вод in vitro. Биотехнология, 3, 73-82.Blyth A.J., Frisia S. (2008) Molecular evidence for bacterial mediation of calcite formation in cold highaltitude caves. Geomicrobiol. J., 25, 101-111.Кондратьева Л.М., Полевская О.С. (2017) Микроорганизмы и образование спелеотемы “лунное молоко” в карстовых пещерах. Биосфера, 9(2),152-165.Bontognali T.R., Vasconcelos C., Warthmann R., Dupraz C., Bernasconi S.M., McKenzie J.A. (2008) Microbes produce nanobacteria-like structures, avoiding cell entombment. Geology, 36, 663-666.Крайнов С.Р., Рыженко Б.Н., Швец В.М. (2012) Геохимия подземных вод. Теоретические, прикладные и экологические аспекты. М.: ЦентрЛитНефтеГаз, 672 с.Cailleau G., Verrecchia E.P., Braissant O., Emmanuel L. (2009) The biogenic origin of needle fibre calcite. Sedimentol., 56, 1858-1875.Кулаков В.В., Кондратьева Л.М., Голубева Е.М. (2010) Геологические и биогеохимические условия формирования повышенного содержания железа и марганца в воде р. Амур. Тихоокеан. геология, 29(6), 66-76.Canaveras J.C., Cuezva S., Sanchez-Moral S., Lario J., Laiz L., Gonzalez J.M., Saiz-Jimenez C. (2006) On the origin of fiber calcite crystals in moonmilk deposits. Naturwissenschaften, 93, 27-32.Мазина С.Е., Семиколенных А.А. (2010) Различные формы лунного молока пещер России в свете проблемы генезиса. Пермь. Пещеры. Вып. 33, 34-44.Cuthbert M.O., Rau G.C., Andersen M.S., Roshan H., Rutlidge H., Marjo C.E., Markowska M., Jex C.N., Graham P.W., Mariethoz G., Acworth R.I., Baker A. (2014) Evaporative cooling of speleothem drip water. Sci. Rep., 4:5162. doi: 10.1038/srep05162.Максимович Н.Г., Бельтюкова Н.В. (1981) Вторичные минералы карбонатных карстовых пещер. Пермь. Пещеры. Вып. 18, 59-70.Dublyanskii V.N., Dublinskaya G.N. (2004) Karstovedenie. Ch. I [Karstology. Pt I]. Perm, Perm. Stat. Univ. Publ., 306 p. (In Russian)Махинов А.Н., Крюкова М.В., Махинова А.Ф. (2015) Роль карстовых явлений в формировании долинного ландшафта реки Сагды-Селанка (центральный Сихотэ-Алинь). Вестн. ДВО РАН, (5), 86-93.Dupraz C., Reid R.P., Braissant O., Decho A.W., Norman R.S., Visscher P.T. (2009) Processes of carbonate precipitation in modern microbial mats. Earth-Sci. Rev., 96, 141-162.Петров Е.С., Новороцкий П.В., Леншин В.Т. (2000) Климат Хабаровского края и Еврейской автономной области. Владивосток: Дальнаука, 173 с.Fairchild I.J., Borsato A., Tooth A.F., Frisia S., Hawkesworth C.J., Huang Y.M., McDermott F., Spiro B. (2000) Controls on trace element (Sr–Mg) compositions of carbonate cave waters: implications for speleothem climatic records. Chem. Geol., 166, 255-269.Потехина Ж.С. (2006) Метаболизм Fe(III) восстанавливающих бактерий. Тольятти: ИЭВБ РАН, 225 с.Fru E.С., Piccinelli P., Fortin D. (2012) Insights into the Global Microbial Community Structure Associated with Iron Oxyhydroxide Minerals Deposited in the Aerobic Biogeosphere. Geomicrobiol. J., 29(7), 587-610.Шварцев С.Л. (2010) Внутренняя эволюция геологической системы вода–порода. Вестник РАН, (3), 242- 251.Gresov A.I., Obzhirov A.I., Korovitskaya Ye.V., Shakirov R.B. (2009) Methane-bearing and prospects of methane resources development from coal layers in the south of Far East basins. Tikhookean. Geol., 28(2), 103- 116. (In Russian)Шварцев С.Л., Рыженко Б.Н., Алексеев В.А. (2007) Геологическая эволюция и самоорганизация системы вода–порода. Новосибирск: Изд-во СО РАН, 389 с.Hill C.A., Forti P. (2007) Cave mineralogy and the NSS: past, present, future. J. Cave Karst Stud., 69, 35-45.Aloisi G., Gloter A., Krüger M., Wallmann K., Guyot F., Zuddas P. (2006) Nucleation of calcium carbonate on bacterial nanoglobules. Geology, 34, 1017-1020.Kadebskaya O.I. (2016) Processes of modern mineral formation in the carbonate caves of the Urals, associated with various microclimatic conditions. Geogr. Vestn., 1(36), 5-17. (In Russian).Benzerara K., Miot J., Morin G., Ona-Nguema G., SkouriPanet F., Ferard C. (2011) Significance, mechanisms and environmental implications of microbial Biomineralization. C. R. Geosci., 343(2-3), 160-167.Kondrat’yeva L.M., Litvinenko Z.N. (2014) Formation of biofilms by microbial complexes of groundwater in vitro. Biotekhnol., (3), 73-82. (In Russian)Bindschedler S., Cailleau G., Braissant O., Millière L., Job D., Verrecchia E.P. (2014) Unravelling the enigmatic origin of calcitic nanofibres in soils and caves: purely physicochemical or biogenic processes? Biogeosci., 11, 2809-2825.Kondrat’yeva L.M., Polevskaya O.S. (2017) Microorganisms and the formation of speleothem “moonmilk” in karst caves. Biosfera, 9(2), 152-165. (In Russian)Bindschedler S., Millière L., Cailleau G., Job D., Verrecchia E.P. (2012) An ultrastructural approach to analogies between fungal structures and needle fibre calcite. Geomicrobiol. J., 29, 301-313.Kondrat’yeva L.M., Polevskaya O.S., Litvinenko Z.N., Golubeva E.M., Konovalova N.S. (2016) Role of the Microbial Community in Formation of Speleothem (Moonmilk) in the Snezhnaya Carst Cave (Abkhaziya). Microbiol., 85(5), 629-637.Blyth A.J., Frisia S. (2008) Molecular evidence for bacterial mediation of calcite formation in cold highaltitude caves. Geomicrobiol. J., 25, 101-111.Konhauser K., Riding R. (2012) Bacterial Biomineralization. Fundamentals of Geobiology. (Eds H. Knoll, D.E. Canfield, K.O. Konhauser). John Wiley & Sons, Ltd., 105- 130.Bontognali T.R., Vasconcelos C., Warthmann R., Dupraz C., Bernasconi S.M., McKenzie J.A. (2008) Microbes produce nanobacteria-like structures, avoiding cell entombment. Geology, 36, 663-666.Kraynov S.R., Ryzhenko B.N., Shvets V.M. (2012) Geokhimiya podzemnykh vod. Teoreticheskie, prikladnye i ekologicheskie aspekty [Geochemistry of groundwater. Theoretical, applied and environmental aspects]. Moscow, TsentrLitNefteGaz Publ., 672 p. (In Russian)Cailleau G., Verrecchia E.P., Braissant O., Emmanuel L. (2009) The biogenic origin of needle fibre calcite. Sedimentol., 56, 1858-1875.Kulakov V.V., Kondrat’eva L.M., Golubeva E.M. (2010) Geological and biogeochemical conditions for the formation of a high content of iron and manganese in the water of the Amur River. Tikhookean. Geol., 29(6), 66- 76. (In Russian)Canaveras J.C., Cuezva S., Sanchez-Moral S., Lario J., Laiz L., Gonzalez J.M., Saiz-Jimenez C. (2006) On the origin of fiber calcite crystals in moonmilk deposits. Naturwissenschaften, 93, 27-32.Lacelle D., Lauriol B., Ian D. (2004) Seasonal isotopic imprint in moonmilk from Caverne de l’Ours (Quebec, Canada): implications for climatic reconstruction. Can. J. Earth Sci., 41(12), 1411-1423.Cuthbert M.O., Rau G.C., Andersen M.S., Roshan H., Rutlidge H., Marjo C.E., Markowska M., Jex C.N., Graham P.W., Mariethoz G., Acworth R.I., Baker A. (2014) Evaporative cooling of speleothem drip water. Sci. Rep., 4: 5162. doi: 10.1038/srep05162.Liu H., Liu Z., Macpherson G.L., Yang R., Chen B., Sun H. (2015) Diurnal hydrochemical variations in a karst spring and two ponds, Maolan Karst Experimental Site, China: Biological pump effects. J. Hydrol., 522, 407-417.Dupraz C., Reid R.P., Braissant O., Decho A.W., Norman R.S., Visscher P.T. (2009) Processes of carbonate precipitation in modern microbial mats. Earth-Sci. Rev., 96, 141-162.Maciejewska M., Adam D., Naômé A., Martinet L., Tenconi E., Całusińska M., Delfosse P., Hanikenne M., Baurain D., Compère P., Carnol M., Barton H.A., Rigali S. (2017) Assessment of the Potential Role of Streptomyces in Cave Moonmilk Formation Front. Microbiol., 8, 1181-1199.Fairchild I.J., Borsato A., Tooth A.F., Frisia S., Hawkesworth C.J., Huang Y.M., McDermott F., Spiro B. (2000) Controls on trace element (Sr–Mg) compositions of carbonate cave waters: implications for speleothem climatic records. Chem. Geol., 166, 255-269.Maciejewska M., Pessi I.S., Arguelles-Arias A., Noirfalise P., Luis G., Ongena M., Barton H., Carnol M., Rigali S. (2015) Streptomyces lunaelactis sp. nov., a novel ferroverdin A-producing Streptomyces species isolated from a moonmilk speleothem. (Antonie van Leeuwenhoek). J. Microbiol., 107(2), 519-531.Fru E.С., Piccinelli P., Fortin D. (2012) Insights into the Global Microbial Community Structure Associated with Iron Oxyhydroxide Minerals Deposited in the Aerobic Biogeosphere. Geomicrobiol. J., 29(7), 587-610.Makhinov A.N., Kryukova M.V., Makhinova A.F. (2016) The role of karst phenomena in the formation of the valley landscape of the Sagdi-Selanka River (central Sikhote-Alin). Vestn. DVO RAN, (5), 86-93. (In Russian)Hill C.A., Forti P. (2007) Cave mineralogy and the NSS: past, present, future. J. Cave Karst Stud., 69, 35-45.Maksimovich N.G., Bel’tyukova N.V. (1981) Secondary minerals of carbonate karst caves. Perm. Peshchery. V. 18, 59-70. (In Russian)Konhauser K., Riding R. (2012) Bacterial Biomineralization. Fundamentals of Geobiology. (Eds H. Knoll, D.E. Can field, K.O. Konhauser). John Wiley & Sons, Ltd., 105- 130.Mazina S., Semikolennykh A. (2010) Different forms of moonmilk of the caves of Russia in the light of the problem of genesis. Perm. Peshchery. V. 33, 34-44. (In Russian)Kondratyeva L.M., Polevskaya O.S., Litvinenko Z.N., Golubeva E.M., Konovalova N.S. (2016) Role of the Microbial Community in Formation of Speleothem (Moonmilk) in the Snezhnaya Carst Cave (Abkhaziya). Microbiol., 85(5), 629-637.Musgrove M., Banner J.L. ( 2004) Controls on the spatial and temporal variability of vadosedripwater geochemistry: Edwards Aquifer, central Texas. Geochim. Cosmochim. Acta., 68(5), 1007-1020.Lacelle D., Lauriol B., Ian D. (2004) Seasonal isotopic imprint in moonmilk from Caverne de l’Ours (Quebec, Canada): implications for climatic reconstruction. Canadian J. Earth Sci., 41(12), 1411-1423.Petrov E.S., Novorotskii P.V., Lenshin V.T. (2000) Klimat Khabarovskogo kraya i Evreyskoi avtonomnoi oblasti [The climate of the Khabarovsk Territory and the Jewish Autonomous Region]. Vladivostok; Khabarovsk, Dal’nauka Publ., 173 p. (In Russian)Liu H., Liu Z., Macpherson G.L., Yang R., Chen B., Sun H. (2015) Diurnal hydrochemical variations in a karst spring and two ponds, Maolan Karst Experimental Site, China: Biological pump effects. J. Hydrol., 522, 407-417.Potekhina Zh.S. (2006) Metabolizm Fe(III) vosstanavlivayushchikh bakterii [The Methabolism of Fe (III)-reducing bacteria]. Tol’yatti, IEVB RAN, 225 p. (In Russian)Maciejewska M., Pessi I.S., Arguelles-Arias A., Noirfalise P., Luis G., Ongena M., Barton H., Carnol M., Rigali S. (2015) Streptomyces lunaelactis sp. nov., a novel ferroverdin A-producing Streptomyces species isolated from a moonmilk speleothem. (Antonie van Leeuwenhoek). J. Microbiol., 107(2), 519-531.Richter D.K., Immenhauser A., Neuser R.D. (2008) Electron backscatter diffraction documents randomly orientated c-axes in moonmilk calcite fibres: evidence for biologically induced precipitation. Sedimentol., 55, 487-497.Maciejewska M., Adam D., Naômé A., Martinet L., Tenconi E., Całusińska M., Delfosse P., Hanikenne M., Baurain D., Compère P., Carnol M., Barton H.A., Rigali S. (2017) Assessment of the Potential Role of Streptomyces in Cave Moonmilk Formation. Front. Microbiol., 8, 1181-1199.Sanchez-Moral S., Portillo M.C., Janices I., Cuezva S., Fernandez-Cortes A., Cañaveras J.C., Gonzalez J.M. (2012) The role of microorganisms in the formation of calcitic moonmilk deposits and speleothems in Altamira. Cave. Geomorphology, 139(2), 285-292.Musgrove M., Banner J.L. ( 2004) Controls on the spatial and temporal variability of vadosedripwater geochemistry: Edwards Aquifer, central Texas. Geochim. Cosmochim. Acta., 68(5), 1007-1020.Sánchez-Román M., Vasconcelos C., Schmid T., Dittrich M., McKenzie J.A., Zenobi R., Rivadeneyra M.A. (2008) Aerobic microbial dolomite at the nanometer scale: Implications for the geologic record. Geology, 36(11), 879-882.Richter D.K., Immenhauser A., Neuser R.D. (2008) Electron backscatter diffraction documents randomly orientated c-axes in moonmilk calcite fibres: evidence for biologically induced precipitation. Sedimentol., 55, 487-497.Shankar N., Achyuthan H. (2007) Genesis of calcic and petrocalcic horizons from Coimbatore, Tamil Nadu: Micromorphology and geochemical studies. Quat. Int., 175, 140-154.Sanchez-Moral S., Portillo M.C., Janices I., Cuezva S., Fernandez-Cortes A., Cañaveras J.C., Gonzalez J.M. (2012) The role of microorganisms in the formation of calcitic moonmilk deposits and speleothems in Altamira. Cave. Geomorphol., 139(2), 285-292.Shvartsev S.L. (2012) Internal evolution of the geological water-rock system. Vestn. Ross. Akad. Nauk, (3), 242- 251. (In Russian)Sánchez-Román M., Vasconcelos C., Schmid T., Dittrich M., McKenzie J.A., Zenobi R., Rivadeneyra M.A. (2008) Aerobic microbial dolomite at the nanometer scale: Implications for the geologic record. Geology, 36(11), 879-882.Shvartsev S.L., Ryzhenko B.N., Alekseyev V.A. (2007) Geologicheskaya evolyutsiya i samoorganizatsiya sistemy voda–poroda [Geological evolution and self-organization of the water–rock system]. Novosibirsk, SO RAN Publ., 389 p. (In Russian).Shankar N., Achyuthan H. (2007) Genesis of calcic and petrocalcic horizons from Coimbatore, Tamil Nadu: Micromorphology and geochemical studies. Quaternary International, 175, 140-154.Smith A.C., Wynn P.M., Barker P.A., Leng M.J. (2015) Drip water electrical conductivity as an indicator of cave ventilation at the event scale. Sci. Total Environ., 1(532), 517-527.Smith A.C., Wynn P.M., Barker P.A., Leng M.J. (2015) Drip water electrical conductivity as an indicator of cave ventilation at the event scale. Sci. Total Environ., 1(532), 517-527.Spötl C., Fohlmeister J., Cheng H., Boch R. (2016) Modern aragonite formation at near-freezing conditions in an alpine cave, Carnic Alps, Austria. Chem. Geol., 435, 60- 70.Spötl C., Fohlmeister J., Cheng H., Boch R. (2016) Modern aragonite formation at near-freezing conditions in an alpine cave, Carnic Alps, Austria. Chem. Geol., 435, 60- 70.Summers E.A., Paoletti M.G., Beggio M., Dorigo L., Pamio A., Gomiero T., Furlan C., Brilli M., Dreon A.L., Bertoni R., Squartini A. (2013) Comparative microbial community composition from secondary carbonate (moonmilk) deposits: implications for the Cansiliella servadeii cave hygropetric food web. Int. J. Speleol., 42(3), 181-192.Summers E.A., Paoletti M.G., Beggio M., Dorigo L., Pamio A., Gomiero T., Furlan C., Brilli M., Dreon A.L., Bertoni R., Squartini A. (2013) Comparative microbial community composition from secondary carbonate (moonmilk) deposits: implications for the Cansiliella servadeii cave hygropetric food web. Int. J. Speleol., 42(3), 181-192.Tisato N., Torriani S.F., Monteux S., Sauro F., De Waele J., Tavagna M.L., De Angeli I.M., Chailloux D., Renda M., Eglinton T.I., Bontognali T.R. (2015) Microbial mediation of complex subterranean mineral structures. Sci. Rep., 5:15525. doi: 10.1038/srep15525.Tisato N., Torriani S.F., Monteux S., Sauro F., De Waele J., Tavagna M.L., De Angeli I.M., Chailloux D., Renda M., Eglinton T.I., Bontognali T.R. (2015) Microbial mediation of complex subterranean mineral structures. Sci. Rep., 5:15525. doi: 10.1038/srep15525.Vesper D.J., Loop C.M., White W.B. (2001) Contaminant transport in karst aquifers. Theoret. Appl. Karstol., (13- 14), 101-111.Vesper D.J., Loop C.M., White W.B. (2001) Contaminant transport in karst aquifers. Theoret. Appl. Karstol., (13- 14), 101-111.Wassenburg J.A., Immenhauser A., Richter D.K., Jochum K.P., Fietzke J., Deininger M., Goos M., Scholz D., Sabaoui A. (2012) Climate and cave control on Pleistocene/Holocene calcite-to-aragonite transitions in speleothems from Morocco: Elemental and isotopic evidence. Geochim. Cosmochim. Acta, 92, 23-47.Wassenburg J.A., Immenhauser A., Richter D.K., Jochum K.P., Fietzke J., Deininger M., Goos M., Scholz D., Sabaoui A. (2012) Climate and cave control on Pleistocene/Holocene calcite-to-aragonite transitions in speleothems from Morocco: Elemental and isotopic evidence. Geochim. Cosmochim. Acta, 92, 23-47.Wong C.I., Banner J.L., Musgrove M. (2011) Seasonal drip water Mg/Ca and Sr/Ca variations driven by cave ventilation: implications for and modeling of speleothem paleoclimate records. Geochim. Cosmochim. Acta, 75, 3514-3529.Wong C.I., Banner J.L., Musgrove M. (2011) Seasonal drip water Mg/Ca and Sr/Ca variations driven by cave ventilation: implications for and modeling of speleothem paleoclimate records. Geochim. Cosmochim. Acta, 75, 3514-3529.Yang H., Lu R., Downs R.T., Costin G. (2006) Goethite, α-FeO(OH), from single-crystal data. Acta Crystallographica, 62, 250-252.Yang H., Lu R., Downs R.T., Costin G. (2006) Goethite, α-FeO(OH), from single-crystal data. Acta Crystallograph., 62, 250-252.Zeng C., Liu Z., Zhao M., Yang R. (2016) Hydrologicallydriven variations in the karst-related carbon sink fluxes: Insights from high-resolution monitoring of three karst catchments in Southwest China. J. Hydrol., 533, 74-90.Zeng C., Liu Z., Zhao M., Yang R. (2016) Hydrologically-driven variations in the karst-related carbon sink fluxes: Insights from high-resolution monitoring of three karst catchments in Southwest China. J. Hydrol., 533, 74-90.Zhabinskaya T.B. (2003) Formation of the chemical composition of the ground waters of the Vorontsov karst massif (Western Caucasus). Zapiski Gornogo Instituta, 155(2), 27-29. (In Russian)Zhang F., Xu H., Konishi H., Shelobolina E.S., Roden E. (2012) Polysaccharide-catalyzed nucleation and growth of disordered dolomite: A potential precursor of sedimentary dolomite. Amer. Miner., 97(4), 556-567.Zhang F., Xu H., Konishi H., Shelobolina E.S., Roden E. (2012) Polysaccharide-catalyzed nucleation and growth of disordered dolomite: A potential precursor of sedimentary dolomite. Amer. Miner., 97(4), 556-567.

The authors declare that there are no conflicts of interest present.