litosphereЛитосфераLITHOSPHERE (Russia)1681-90042500-302XA.N. Zavaritsky Institute of Geology and Geochemistry10.24930/2500-302X-2024-24-5-864-885litosphere-2148Research ArticleСтатьиArticlesМорфогенетические разновидности оксигидроксидов железа в мерцающих курильщиках-диффузерах на гидротермальном поле Рейнбоу (36°13′ с.ш., 33°54′ з.д., Срединно-Атлантический хребет): данные ЛА-ИСП-МС для развития теории гальмиролизаMorphogenetic varieties of iron oxyhydroxides in shimmering smokers-diffusers of the Rainbow hydrothermal field (36°13′ N, 33°54′ W, Mid-Atlantic Ridge): LA-ICP-MS data for the development of halmyrolysis theoryМасленниковВ. В.MaslennikovV. V.

456317, г. Миасс

Miass 456317

ЛеинА. Ю.LeinA. Yu.

117997, г. Москва, Нахимовский пр-т, 36

36 Nakhimovsky av., Moscow 117997

АюповаН. Р.AyupovaN. R.

456317, г. Миасс

Miass 456317

ЦелуйкоА. С.TseluykoA. S.

456317, г. Миасс

Miass 456317

АртемьевД. С.ArtemyevD. S.

456317, г. Миасс

Miass 456317

КотляровВ. А.KotlyarovV. A.

456317, г. Миасс

Miass 456317

Институт минералогии Южно-Уральского федерального научного центра минералогии и геоэкологии УрО РАНРоссияInstitute of Mineralogy, South ural Federal Scientific Center for Mineralogy and Geoecology, ural Branch of the Russian Academy of SciencesRussian FederationИнститут океанологии им. П.П. Ширшова РАНРоссияP.P. Shirshov Institute of Oceanology, RASRussian Federation202406112024245864885Copyright © Масленников В.В., Леин А.Ю., Аюпова Н.Р., Целуйко А.С., Артемьев Д.С., Котляров В.А., 20242024Масленников В.В., Леин А.Ю., Аюпова Н.Р., Целуйко А.С., Артемьев Д.С., Котляров В.А.Maslennikov V.V., Lein A.Y., Ayupova N.R., Tseluyko A.S., Artemyev D.S., Kotlyarov V.A.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/2148

Объектами исследования являются оксигидроксиды железа, покрывающие и замещающие трубы мерцающих курильщиков-диффузеров гидротермального поля Рейнбоу (САХ). Цель работы. Определить концентрации и ассоциации химических элементов в разновидностях оксигидроксидов железа для выявления закономерностей геохимической дифференциации в условиях гальмиролиза сульфидных труб курильщиков-диффузеров. Материалы и методы. Образцы отобраны во время погружения на глубине 2317 м с использованием ручного манипулятора обитаемого аппарата “Мир-2” (рейс №50, судно “Академик Мстислав Келдыш”, 2005 г.). Разновидности оксигидроксидов железа диагностированы с применением сканирующих электронных (РЭММА-202М с ЭДС LZ-5 Link и Tescan Vega 3 sbu с энергодисперсионным анализатором Oxford Instruments X-act) и электронно-зондового (Jeol Superprobe 733 с ЭДС Oxford Instruments INCAx-sight) микроскопов, порошковой рентгеновской дифрактометрии (рентгеновский дифрактометр SHIMADZU XRD-6000, CuK-α излучение с монохроматором) и проанализированы методом масс-спектрометрии с индуктивно связанной плазмой и лазерной абляцией (ЛА-ИСП-МС) в Центре коллективного пользования Южно-Уральского федерального научного центра минералогии и геоэкологии УрО РАН. Результаты. Микрослоистые агрегаты гетита, содержащие примесь барита, кальцита, арагонита, опала, самородной серы, ковеллина, сфалерита и рентгеноаморфной оксигидроксидной фазы железа, покрывают трубы мерцающих курильщиков-диффузеров. По направлению к внутренним частям оболочек труб они сменяются псевдоморфозами лепидокрокита по пириту и пирротину, а затем радиально-пластинчатыми и бактериоморфными крустификациями лепидокрокита. Методом ЛА-ИСП-МС установлено, что все разновидности оксигидроксидов железа характеризуются повышенными содержаниями Zn и Co в ассоциации с другими элементами, свойственными для среднетемпературных гидротермальных флюидов (Cd, Mn, Ni, Ga, Sn, Pb и Sb) при отсутствии существенных концентраций элементов высокотемпературной гидротермальной ассоциации (Se, Bi, Te). По мере перехода от поверхностных слоистых агрегатов гетита к агрегатам лепидокрокита роль элементов гидрогенной ассоциации (Mg, Na, К, Sr, U, V, As, Mo, Ni, P, B, W, Cs и РЗЭ) снижается. Для элементов с разной валентностью (U, V, Mo, As, Cr, Eu) предлагаются различные механизмы накопления в условиях гальмиролиза сульфидов и осаждения на локальных окислительно-восстановительных барьерах. Предполагается, что часть микроэлементов (Sr, V, As, P, PЗЭ), обнаруженных в гетите, являются продуктами сорбции на гидроксидах железа или входят в состав невидимых Fe-Ca гидроксофосфатов. Вывод. Выявлено влияние гальмиролиза сульфидов на дифференциацию химических элементов. 

Research subject. Iron oxyhydroxides covering and replacing the chimneys of shimmering water smokers-diffusers of the Rainbow hydrothermal field (MAR). Aim. To identify features of the concentration and associations of chemical elements in varieties of iron oxyhydroxides to recognize patterns of geochemical differentiation under conditions of halmyrolysis of sulfide chimneys-diffusers. Materials and methods. Samples were collected during a dive to a depth of 2300 m using the manual manipulator of the Mir-2 manned vehicle (travel No. 50, research vessel Akademik Mstislav Keldysh, 2005). Varieties of iron ohyhydroxides were identified using electron microscopes (REMMA-202М with LZ-5 Link system, Tescan Vega 3 sbu with an Oxford Instruments X-act energy-dispersive analyzer, and Jeol Superprobe 733 with an EDA Oxford Instruments INCAx-sight) and a powder X-ray diffractometer (SHIMADZU XRD-6000, CuK-α radiation with monochromator). Further, a mass spectrometry with inductively coupled plasma and laser ablation (LA-ICP-MS) analysis was conducted at the South Urals Federal Scientific Center of Mineralogy and Geoecology, Ural Branch of the Russian Academy of Sciences. Results. Microlayered goethite aggregates containing admixtures of barite, calcite, aragonite, native sulfur, covellite, sphalerite, and an X-ray amophoric oxyhydroxide phase of iron cover the shimmering diffusers. Towards the inner parts of the chimney walls, they are replaced by pseudomorphs of lepidocrocite after pyrite and pyrrhotite, and then by radial and bacteriomorphic crustifications of lepidocrocite. The use of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) showed that goethite varieties have the increased contents of Zn and Co associated with other elements of medium-temperature hydrothermal fluids (Cd, Mn, Ni, Ga, Sn, Pb and Sb) in the absence of significant concentrations of a high-temperature hydrothermal association (Se, Bi, Te). The role of elements of seawater association (Mg, Na, K, Sr, U, V, As, Mo, Ni, P, B, W, Cs, REE) decreases from the surface layered goethite aggregates to crustification varieties of lepidocrocite. Different scenarios of accumulation under conditions of sulfide halmyrolysis and precipitation on local reduction barriers are proposed for elements with different valences (U, V, Mo, As, Cr, Eu). It is assumed that some of the microelements (Sr, V, As, P, REE) found in goethite are products of sorption on iron hydroxides or are part of invisible Fe-Ca hydroxyphosphates. Conclusion. The influence of sulfide halmyrolysis on the differentiation of chemical elements has been revealed.

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