Anhydrous sulfate minerals are abundant in the active fumaroles with highly oxidizing conditions on the scoria cones of the Tolbachik volcano. The mineral itelmenite, ideally Na 2 CuMg 2 (SO 4 ) 4 , containing isomorphous admixture of Zn, was described in 2018, whereas glikinite, ideally Zn 3 O(SO 4 ) 2 , was described in 2020. Synthetic analogs of both minerals were obtained during studies of phase formation in the Na 2 SO 4 –CuSO 4 –MgSO 4 –(ZnSO 4 ) systems which lead to essentially different results. Solid-state syntheses resulted in formation of several compounds previously known as minerals only. Both Zn- and Mg-containing analogs of itelmenite were prepared and exhibit slight deviations from the ideal Na 2 CuM 2 (SO 4 ) 4 stoichiometry. The Mg compound could be prepared single-phase which allowed the study of its thermal expansion and IR spectroscopy. Na 2 CuMg 2 (SO 4 ) 4 and Na 2 CuZn 2 (SO 4 ) 4 were evaluated for Na + -ion diffusion. For the Zn compound, several by-products were observed which are synthetic analogs of puninite Na 2 Cu 3 O(SO 4 ) 2 , as well as hermannjahnite CuZn(SO 4 ) 2 and glikinite-type (Zn,Cu) 3 O(SO 4 ) 2 . All of them were prepared via solid-state reactions in open systems. The Na 2 CuMg 2 (SO 4 ) 4 , Na 2 CuZn 2 (SO 4 ) 4 and (Zn,Cu) 3 O(SO 4 ) 2 were structurally characterized by the single-crystal XRD. In the Zn-bearing system, the admixture of Cu 2+ likely controls the formation of itelmenite-type and glikinite-type phases. The results of the experiments allowed to deduce possible scenarios of the formation processes of itelmenite and some other endemic fumarolic minerals. Our study shows that outstanding mineralogical diversity observed in the fumaroles of the Tolbachik scoria cones is not only due to the formation from the gas enriched by transition metals and involves also intensive exchange with the host basaltic scoria. Similar processes seem also to be responsible for the recrystallization of many other mineral species observed in high-temperature fumaroles resulted from the recent eruptions.

中文翻译：

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一锅中的喷气孔：钛铁矿的 Zn- 和 Mg-类似物和 glikinite 的合成类似物的合成、晶体结构和性质

在托尔巴奇克火山的火山渣锥上具有高度氧化条件的活性喷气孔中富含无水硫酸盐矿物。矿物钛铁矿，理想情况下是 Na 2 CuMg 2 (SO 4 ) 4 ，含有 Zn 的同晶混合物，于 2018 年进行了描述，而 glikinite，理想情况下为 Zn 3 O(SO 4 ) 2 ，于 2020 年进行了描述。这两种矿物的合成类似物是在 Na 2 SO 4 –CuSO 4 –MgSO 4 –(ZnSO 4 ) 系统中的相形成研究期间获得的，这导致了本质上不同的结果。固态合成导致形成了几种以前仅称为矿物质的化合物。制备了含锌和含镁的钛铁矿类似物，它们与理想的 Na 2 CuM 2 (SO 4 ) 4 化学计量略有偏差。Mg 化合物可以单相制备，从而可以研究其热膨胀和红外光谱。评价Na 2 CuMg 2 (SO 4 ) 4 和Na 2 CuZn 2 (SO 4 ) 4 的Na + -离子扩散。对于 Zn 化合物，观察到几种副产物，它们是石榴石 Na 2 Cu 3 O(SO 4 ) 2 的合成类似物，以及绿铁石 CuZn(SO 4 ) 2 和水杨石型 (Zn,Cu) 3 O(所以 4) 2。它们都是通过开放系统中的固态反应制备的。Na 2 CuMg 2 (SO 4 ) 4 、Na 2 CuZn 2 (SO 4 ) 4 和(Zn,Cu) 3 O(SO 4 ) 2 的结构通过单晶XRD表征。在含锌系统中，Cu 2+ 的混合物可能控制了钛铁矿型和水铝石型相的形成。实验结果可以推断出钛铁矿和其他一些地方性延胡索矿物的形成过程的可能情景。我们的研究表明，在 Tolbachik 火山渣锥的喷气孔中观察到的显着矿物学多样性不仅是由于富含过渡金属的气体形成的，而且还涉及与宿主玄武质火山渣的强烈交换。类似的过程似乎也导致了在最近喷发产生的高温喷气孔中观察到的许多其他矿物物种的重结晶。我们的研究表明，在 Tolbachik 火山渣锥的喷气孔中观察到的显着矿物学多样性不仅是由于富含过渡金属的气体形成的，而且还涉及与宿主玄武质火山渣的强烈交换。类似的过程似乎也导致了在最近喷发产生的高温喷气孔中观察到的许多其他矿物物种的重结晶。我们的研究表明，在 Tolbachik 火山渣锥的喷气孔中观察到的显着矿物学多样性不仅是由于富含过渡金属的气体形成的，而且还涉及与宿主玄武质火山渣的强烈交换。类似的过程似乎也导致了在最近喷发产生的高温喷气孔中观察到的许多其他矿物物种的重结晶。