Abstract Zinc-rich fluor-elbaite from Piława Górna, Poland, was studied by electron microprobe (EPMA), single-crystal X‑ray difraction (SREF), and Raman spectroscopy (RS) to check the possibility of the application of RS to draw crystal-chemical conclusions for Al-rich and Li-bearing tourmalines on basis of the O–H stretching vibrations in the spectral range 3400–3800 cm–1. This tourmaline, forming a thin metasomatic zone around gahnite, features varying compositions with a ZnO content reaching in the studied fragment of 5.70(12) wt%. The crystal structure of this Zn-rich fluor-elbaite [a = 15.921(1), c = 7.127(1) Å] was refined with a R1 value of 1.67%. Its formula was determined on the basis of electron-microprobe and structure refinement as X(Na0.84◻0.14Ca0.01)Σ1.00Y(Al1.06Li0.84Zn0.69 F e 0.32 2 + M n 0.09 Σ 3.00 Z A l 6 B O 3 3 T S i 6 O 18 V ( O H ) 3 W F 0.65 O H 0.26 O 0.09 . ${\left.\mathrm{Fe}_{0.32}^{2+}{\mathrm{Mn}}_{0.09}\right)}_{\Sigma3.00}{}^{\mathrm Z}\mathrm{Al}_6{\left({\mathrm{BO}}_3\right)}_3\left({}^{\mathrm T}\mathrm{Si}_6{\mathrm O}_{18}\right)^{\mathrm V}(\mathrm{OH})_3{}^{\mathrm W}\left({\mathrm F}_{0.65}{\mathrm{OH}}_{0.26}{\mathrm O}_{0.09}\right).$The deconvolution of the O–H stretching vibration bands, performed by fitting of an input model of component bands with Gaussian function shapes for the empirical spectrum, indicates that each of the three maxima assigned for VOH bonded to YAl3+, Y2+, and YLi+ and with the total integral intensity of at least 75% of the total OH content could be resolved into 1 to 3 bands, depending on the X-site occupation (vacancies, Na+, and Ca2+). The deconvolution indicates further that several low intense bands of WO–H modes above a Raman shift of 3600 cm–1, totally reaching ≤25%, are dependent on the occupation of triplets of YYY cations bonded to the hydroxyl. These WO–H modes are also influenced by the X-site occupation. Due to ordering of all octahedral cations (except Al) at the Y site and a complete occupation of the Z site by Al and the V site by OH, it seems possible to evaluate the Li and OH contents in a Al-rich and Li-bearing tourmaline directly from the Raman spectrum. By using the ratio VOHIYAlZAlZAl/(VOHIYZZ + WOHIYYY) as evaluated from RS, corresponding to the ratio YAl/V+WOH in the crystal, the formula of the Zn-rich fluor-elbaite can be calculated as X ( Na 0.85 □ 0.14 Ca 0.01 ) ∑1.00 Y ( Al 1.11 Y 1.11 2+ Li 0.78 ) ∑3.00 Z Al 6 ( BO 3 ) 3 ( Si 6 O 18 ) ( OH ) 3 ( F 0.65 OH 0.13 O 0.22 ), $^{\text{X}}{{\left( \text{N}{{\text{a}}_{\text{0}\text{.85}}}{{\square }_{0.14}}\text{C}{{\text{a}}_{0.01}} \right)}_{\sum 1.00}}^{\text{Y}}{{\left( \text{A}{{\text{l}}_{\text{1}\text{.11}}}\text{Y}_{\text{1}\text{.11}}^{\text{2+}}\text{L}{{\text{i}}_{\text{0}\text{.78}}} \right)}_{\sum \text{3}\text{.00}}}^{\text{Z}}\text{A}{{\text{l}}_{\text{6}}}{{\left( \text{B}{{\text{O}}_{\text{3}}} \right)}_{\text{3}}}\left( \text{S}{{\text{i}}_{\text{6}}}{{\text{O}}_{\text{18}}} \right){{\left( \text{OH} \right)}_{\text{3}}}\left( {{\text{F}}_{\text{0}\text{.65}}}\text{O}{{\text{H}}_{\text{0}\text{.13}}}{{\text{O}}_{\text{0}\text{.22}}} \right),$where Y2+ = Zn + Fe + Mn. The formula, determined only on basis of EPMA and deconvolution of RS in the O–H stretching bands, corresponds very well (≤1 SD range of EPMA) to the formula determined on basis of EPMA and SREF. This result implicates that the O–H stretching vibrations, measured by Raman spectroscopy, could be applied for Al-rich and Li-bearing tourmalines as a useful tool for providing additional information for determining the crystal-chemical formula. It is also very helpful when crystal structural data are not available.

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富锌氟橡胶中OH伸缩振动的晶体结构和拉曼光谱研究 富锌氟橡胶中OH伸缩振动的拉曼光谱研究

摘要 通过电子显微探针 (EPMA)、单晶 X 射线衍射 (SREF) 和拉曼光谱 (RS) 研究了波兰 Piława Górna 的富锌氟锂基于光谱范围 3400-3800 cm-1 内的 O-H 伸缩振动的富铝和含锂电气石的晶体化学结论。这种碧玺在 gahnite 周围形成一个薄的交代带，具有不同的成分，ZnO 含量在所研究的碎片中达到 5.70(12) wt%。这种富含锌的氟橡胶 [a = 15.921(1), c = 7.127(1) Å] 的晶体结构经过精炼，R1 值为 1.67%。根据电子探针和结构精修确定其分子式为 X(Na0.84◻0.14Ca0.01)Σ1.00Y(Al1.06Li0.84Zn0.69 F e 0.32 2 + M n 0.09 Σ 3。00 ZA l 6 BO 3 3 TS i 6 O 18 V (OH) 3 WF 0.65 OH 0.26 O 0.09。${\left.\mathrm{Fe}_{0.32}^{2+}{\mathrm{Mn}}_{0.09}\right)}_{\Sigma3.00}{}^{\mathrm Z}\ mathrm{Al}_6{\left({\mathrm{BO}}_3\right)}_3\left({}^{\mathrm T}\mathrm{Si}_6{\mathrm O}_{18}\right )^{\mathrm V}(\mathrm{OH})_3{}^{\mathrm W}\left({\mathrm F}_{0.65}{\mathrm{OH}}_{0.26}{\mathrm O }_{0.09}\right).$O-H 伸缩振动带的去卷积，通过对具有高斯函数形状的成分带输入模型进行拟合，用于经验谱，表明分配给 VOH 的三个最大值中的每一个与 YAl3+、Y2+ 和 YLi+ 键合，并且总积分强度至少为总 OH 含量的 75% 可以分解为 1 到 3 个带，具体取决于 X 位点占据（空位、Na+ 和 Ca2+）。解卷积进一步表明，拉曼位移 3600 cm-1 以上的几个低强度 WO-H 模式带，完全达到≤25%，取决于与羟基键合的 YYY 阳离子三重态的占据。这些 WO-H 模式也受 X 位点占用的影响。由于所有八面体阳离子（Al 除外）在 Y 位点的排序以及 Z 位点被 Al 完全占据，V 位被 OH 完全占据，似乎可以评估富含 Al 和 Li-的 Li 和 OH 含量。轴承直接来自拉曼光谱的电气石。通过使用由 RS 计算的 VOHIYAlZAlZAl/(VOHIYZZ + WOHIYYY) 比值，对应于晶体中的 YAl/V+WOH 比值，富锌氟橡胶的分子式可以计算为 X ( Na 0.85 □ 0.14 Ca 0.01 ) ∑1.00 Y ( Al 1.11 Y 1.11 2+ Li 0.78 ) ∑3.00 Z Al 6 ( BO 3 ) 3 ( Si 6 O 18 ) ( OH ) 3 ( F 0. 65 OH 0.13 O 0.22 ), $^{\text{X}}{{\left( \text{N}{{\text{a}}_{\text{0}\text{.85}}}{ {\square }_{0.14}}\text{C}{{\text{a}}_{0.01}} \right)}_{\sum 1.00}}^{\text{Y}}{{\left ( \text{A}{{\text{l}}_{\text{1}\text{.11}}}\text{Y}_{\text{1}\text{.11}}^{ \text{2+}}\text{L}{{\text{i}}_{\text{0}\text{.78}}} \right)}_{\sum \text{3}\text {.00}}}^{\text{Z}}\text{A}{{\text{l}}_{\text{6}}}{{\left( \text{B}{{\text {O}}_{\text{3}}} \right)}_{\text{3}}}\left( \text{S}{{\text{i}}_{\text{6}} }{{\text{O}}_{\text{18}}} \right){{\left( \text{OH} \right)}_{\text{3}}}\left( {{\ text{F}}_{\text{0}\text{.65}}}\text{O}{{\text{H}}_{\text{0}\text{.13}}}{{ \text{O}}_{\text{0}\text{.22}}} \right),$其中 Y2+ = Zn + Fe + Mn。该公式仅基于 EPMA 和 O-H 伸缩带中 RS 的解卷积确定，与基于 EPMA 和 SREF 确定的公式非常吻合（EPMA 的 ≤1 SD 范围）。该结果表明，通过拉曼光谱测量的 O-H 伸缩振动可应用于富铝和含锂电气石，作为为确定晶体化学式提供额外信息的有用工具。当晶体结构数据不可用时，它也非常有用。