Partitioning of OH-F-Cl between biotite and silicate melt: Experiments and an empirical model

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OriginalspracheEnglisch
Seiten (von - bis)155-179
Seitenumfang25
FachzeitschriftGeochimica et cosmochimica acta
Jahrgang317
Frühes Online-Datum8 Nov. 2021
PublikationsstatusVeröffentlicht - 15 Jan. 2022

Abstract

The partitioning of hydroxyl (OH), fluorine (F) and chlorine (Cl) between biotite and silicate melt has been experimentally investigated at 100–500 MPa and 850–975 °C. A variety of starting glasses was used, covering alkali-rich basalt, trachyandesite, trachyte, tephriphonolite and dacite, in order to investigate potential compositional effects of both melt and biotite on the partitioning behaviors. The investigated F contents in biotite and silicate melt are ranging within 0.2–8.2 wt% and 0.1–4.8 wt% respectively, yielding a Nernst-type partition coefficient DFBt-melt within 1.5–10. The investigated Cl contents in both biotite and silicate melt are much lower (≤0.15 wt% and ≤ 1.3 wt% respectively), and DClBt-melt values are < 1 (0.02–0.4). The results are used to estimate the exchange coefficients (ratio of D values) for F-OH and Cl-OH pairs expressed as KdF/OHBt-melt=XFBt/XOHBt/XFmelt/XOHmelt, and KdCl/OHBt-melt=XClBt/XOHBt/XClmelt/XOHmelt, in which XFBt, XClBt and XOHBt are mole fractions of F, Cl and OH in biotite, and XFmelt, XClmelt and XOHmelt are mole fractions of F, Cl and OH in silicate melt, respectively. KdF/OHBt-melt is in the range of 1–50, which is higher than KdCl/OHBt-melt (0.07–5) by about one order of magnitude, implying that the relative incorporation preference of F, OH and Cl between biotite and melt is highest for F, lower for OH and lowest for Cl. Biotite and melt compositions exert important effects on the OH-F-Cl partitioning between biotite and melt. Multiple linear regression of data from literature and this study allows us to propose the following empirical equations: lnKdF/OHBt-melt=0.995-1.619∗DASI+3.613∗XMgBt-17.523∗XTiBt (R2 = 0.83, sd = 0.31), lnKdCl/OHBt-melt=3.380-2.454∗CSI-0.398∗XMgBt-22.377∗XTiBt (R2 = 0.94, sd = 0.26), in which XMgBt = Mg/(Mg + Fe3++Fe2++Mn + Ti + AlVI) of biotite, XTiBt = Ti/(Mg + Fe3++Fe2++Mn + Ti + AlVI) of biotite, DASI (deviation from ASI of 1) = |1–ASI|, with ASI = molar Al2O3/(Na2O + K2O + CaO) of the melt, and CSI (chlorine solubility index) = molar (Al1/2 + Ca1/2 + Mg1/2 + Na)/Si of the melt. The empirical models confirm the so-called Mg-F preference and Mg-Cl avoidance rules in biotite, and also reveal that increasing Ti content in biotite tends to lower KdF/OHBt-melt and KdCl/OHBt-melt. Furthermore, DASI and CSI are effective parameters that reflect the incorporation abilities of F and Cl in melt as a function of melt composition. A wide prediction potential of the OH-F-Cl exchange partition model is expected, because fairly large ranges in temperature (640–975 °C), melt composition (ASI = 0.7–1.4; CSI = 0.6–1.6) and biotite composition (XMgBt = 0–0.88) are covered. Calculated KdF/OHBt-melt and KdCl/OHBt-melt from the models are in good agreement with experimentally determined values, and the deviation from the models are less than 20% relative in both cases. Applying the empirical models, we calculated melt F and Cl concentrations based on biotite compositions from several intrusive-volcanic rocks that are associated with different deposit types. The results show that the magmas associated with Mo and REE deposits are characterized by high F (up to ca. 10,000 ppm) but relatively low Cl. On the contrary, the magmas that have contributed to the formation of porphyry Cu and Au deposits contain much higher Cl (up to ca. 10,000 ppm) than F.

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Partitioning of OH-F-Cl between biotite and silicate melt: Experiments and an empirical model. / Zhang, Chao; Li, Xiaoyan; Behrens, Harald et al.
in: Geochimica et cosmochimica acta, Jahrgang 317, 15.01.2022, S. 155-179.

Publikation: Beitrag in FachzeitschriftArtikelForschungPeer-Review

Zhang C, Li X, Behrens H, Holtz F. Partitioning of OH-F-Cl between biotite and silicate melt: Experiments and an empirical model. Geochimica et cosmochimica acta. 2022 Jan 15;317:155-179. Epub 2021 Nov 8. doi: 10.1016/j.gca.2021.10.031
Zhang, Chao ; Li, Xiaoyan ; Behrens, Harald et al. / Partitioning of OH-F-Cl between biotite and silicate melt : Experiments and an empirical model. in: Geochimica et cosmochimica acta. 2022 ; Jahrgang 317. S. 155-179.
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@article{bbcd84b1c9a341dfb2c7dd2d553ee4be,
title = "Partitioning of OH-F-Cl between biotite and silicate melt: Experiments and an empirical model",
abstract = "The partitioning of hydroxyl (OH), fluorine (F) and chlorine (Cl) between biotite and silicate melt has been experimentally investigated at 100–500 MPa and 850–975 °C. A variety of starting glasses was used, covering alkali-rich basalt, trachyandesite, trachyte, tephriphonolite and dacite, in order to investigate potential compositional effects of both melt and biotite on the partitioning behaviors. The investigated F contents in biotite and silicate melt are ranging within 0.2–8.2 wt% and 0.1–4.8 wt% respectively, yielding a Nernst-type partition coefficient DFBt-melt within 1.5–10. The investigated Cl contents in both biotite and silicate melt are much lower (≤0.15 wt% and ≤ 1.3 wt% respectively), and DClBt-melt values are < 1 (0.02–0.4). The results are used to estimate the exchange coefficients (ratio of D values) for F-OH and Cl-OH pairs expressed as KdF/OHBt-melt=XFBt/XOHBt/XFmelt/XOHmelt, and KdCl/OHBt-melt=XClBt/XOHBt/XClmelt/XOHmelt, in which XFBt, XClBt and XOHBt are mole fractions of F, Cl and OH in biotite, and XFmelt, XClmelt and XOHmelt are mole fractions of F, Cl and OH in silicate melt, respectively. KdF/OHBt-melt is in the range of 1–50, which is higher than KdCl/OHBt-melt (0.07–5) by about one order of magnitude, implying that the relative incorporation preference of F, OH and Cl between biotite and melt is highest for F, lower for OH and lowest for Cl. Biotite and melt compositions exert important effects on the OH-F-Cl partitioning between biotite and melt. Multiple linear regression of data from literature and this study allows us to propose the following empirical equations: lnKdF/OHBt-melt=0.995-1.619∗DASI+3.613∗XMgBt-17.523∗XTiBt (R2 = 0.83, sd = 0.31), lnKdCl/OHBt-melt=3.380-2.454∗CSI-0.398∗XMgBt-22.377∗XTiBt (R2 = 0.94, sd = 0.26), in which XMgBt = Mg/(Mg + Fe3++Fe2++Mn + Ti + AlVI) of biotite, XTiBt = Ti/(Mg + Fe3++Fe2++Mn + Ti + AlVI) of biotite, DASI (deviation from ASI of 1) = |1–ASI|, with ASI = molar Al2O3/(Na2O + K2O + CaO) of the melt, and CSI (chlorine solubility index) = molar (Al1/2 + Ca1/2 + Mg1/2 + Na)/Si of the melt. The empirical models confirm the so-called Mg-F preference and Mg-Cl avoidance rules in biotite, and also reveal that increasing Ti content in biotite tends to lower KdF/OHBt-melt and KdCl/OHBt-melt. Furthermore, DASI and CSI are effective parameters that reflect the incorporation abilities of F and Cl in melt as a function of melt composition. A wide prediction potential of the OH-F-Cl exchange partition model is expected, because fairly large ranges in temperature (640–975 °C), melt composition (ASI = 0.7–1.4; CSI = 0.6–1.6) and biotite composition (XMgBt = 0–0.88) are covered. Calculated KdF/OHBt-melt and KdCl/OHBt-melt from the models are in good agreement with experimentally determined values, and the deviation from the models are less than 20% relative in both cases. Applying the empirical models, we calculated melt F and Cl concentrations based on biotite compositions from several intrusive-volcanic rocks that are associated with different deposit types. The results show that the magmas associated with Mo and REE deposits are characterized by high F (up to ca. 10,000 ppm) but relatively low Cl. On the contrary, the magmas that have contributed to the formation of porphyry Cu and Au deposits contain much higher Cl (up to ca. 10,000 ppm) than F.",
keywords = "Biotite, Chlorine, Fluorine, HO, Partitioning, Silicate melt",
author = "Chao Zhang and Xiaoyan Li and Harald Behrens and Francois Holtz",
note = "Funding Information: We thank Renat Almeev and Eric Wolff for their helps with EPMA, and Andr{\'e} Stechern, S{\"o}ren Wilke, Robert Balzer and Stefan Linsler for their helps with IHPV. This study was supported by DFG ( German Research Foundation ) Project BE 1720/40 . We acknowledge gratefully the critical and constructive journal reviews made by Brian Tattitch, Stamatis Flemetakis and another anonymous reviewer.",
year = "2022",
month = jan,
day = "15",
doi = "10.1016/j.gca.2021.10.031",
language = "English",
volume = "317",
pages = "155--179",
journal = "Geochimica et cosmochimica acta",
issn = "0016-7037",
publisher = "Elsevier Ltd.",

}

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TY - JOUR

T1 - Partitioning of OH-F-Cl between biotite and silicate melt

T2 - Experiments and an empirical model

AU - Zhang, Chao

AU - Li, Xiaoyan

AU - Behrens, Harald

AU - Holtz, Francois

N1 - Funding Information: We thank Renat Almeev and Eric Wolff for their helps with EPMA, and André Stechern, Sören Wilke, Robert Balzer and Stefan Linsler for their helps with IHPV. This study was supported by DFG ( German Research Foundation ) Project BE 1720/40 . We acknowledge gratefully the critical and constructive journal reviews made by Brian Tattitch, Stamatis Flemetakis and another anonymous reviewer.

PY - 2022/1/15

Y1 - 2022/1/15

N2 - The partitioning of hydroxyl (OH), fluorine (F) and chlorine (Cl) between biotite and silicate melt has been experimentally investigated at 100–500 MPa and 850–975 °C. A variety of starting glasses was used, covering alkali-rich basalt, trachyandesite, trachyte, tephriphonolite and dacite, in order to investigate potential compositional effects of both melt and biotite on the partitioning behaviors. The investigated F contents in biotite and silicate melt are ranging within 0.2–8.2 wt% and 0.1–4.8 wt% respectively, yielding a Nernst-type partition coefficient DFBt-melt within 1.5–10. The investigated Cl contents in both biotite and silicate melt are much lower (≤0.15 wt% and ≤ 1.3 wt% respectively), and DClBt-melt values are < 1 (0.02–0.4). The results are used to estimate the exchange coefficients (ratio of D values) for F-OH and Cl-OH pairs expressed as KdF/OHBt-melt=XFBt/XOHBt/XFmelt/XOHmelt, and KdCl/OHBt-melt=XClBt/XOHBt/XClmelt/XOHmelt, in which XFBt, XClBt and XOHBt are mole fractions of F, Cl and OH in biotite, and XFmelt, XClmelt and XOHmelt are mole fractions of F, Cl and OH in silicate melt, respectively. KdF/OHBt-melt is in the range of 1–50, which is higher than KdCl/OHBt-melt (0.07–5) by about one order of magnitude, implying that the relative incorporation preference of F, OH and Cl between biotite and melt is highest for F, lower for OH and lowest for Cl. Biotite and melt compositions exert important effects on the OH-F-Cl partitioning between biotite and melt. Multiple linear regression of data from literature and this study allows us to propose the following empirical equations: lnKdF/OHBt-melt=0.995-1.619∗DASI+3.613∗XMgBt-17.523∗XTiBt (R2 = 0.83, sd = 0.31), lnKdCl/OHBt-melt=3.380-2.454∗CSI-0.398∗XMgBt-22.377∗XTiBt (R2 = 0.94, sd = 0.26), in which XMgBt = Mg/(Mg + Fe3++Fe2++Mn + Ti + AlVI) of biotite, XTiBt = Ti/(Mg + Fe3++Fe2++Mn + Ti + AlVI) of biotite, DASI (deviation from ASI of 1) = |1–ASI|, with ASI = molar Al2O3/(Na2O + K2O + CaO) of the melt, and CSI (chlorine solubility index) = molar (Al1/2 + Ca1/2 + Mg1/2 + Na)/Si of the melt. The empirical models confirm the so-called Mg-F preference and Mg-Cl avoidance rules in biotite, and also reveal that increasing Ti content in biotite tends to lower KdF/OHBt-melt and KdCl/OHBt-melt. Furthermore, DASI and CSI are effective parameters that reflect the incorporation abilities of F and Cl in melt as a function of melt composition. A wide prediction potential of the OH-F-Cl exchange partition model is expected, because fairly large ranges in temperature (640–975 °C), melt composition (ASI = 0.7–1.4; CSI = 0.6–1.6) and biotite composition (XMgBt = 0–0.88) are covered. Calculated KdF/OHBt-melt and KdCl/OHBt-melt from the models are in good agreement with experimentally determined values, and the deviation from the models are less than 20% relative in both cases. Applying the empirical models, we calculated melt F and Cl concentrations based on biotite compositions from several intrusive-volcanic rocks that are associated with different deposit types. The results show that the magmas associated with Mo and REE deposits are characterized by high F (up to ca. 10,000 ppm) but relatively low Cl. On the contrary, the magmas that have contributed to the formation of porphyry Cu and Au deposits contain much higher Cl (up to ca. 10,000 ppm) than F.

AB - The partitioning of hydroxyl (OH), fluorine (F) and chlorine (Cl) between biotite and silicate melt has been experimentally investigated at 100–500 MPa and 850–975 °C. A variety of starting glasses was used, covering alkali-rich basalt, trachyandesite, trachyte, tephriphonolite and dacite, in order to investigate potential compositional effects of both melt and biotite on the partitioning behaviors. The investigated F contents in biotite and silicate melt are ranging within 0.2–8.2 wt% and 0.1–4.8 wt% respectively, yielding a Nernst-type partition coefficient DFBt-melt within 1.5–10. The investigated Cl contents in both biotite and silicate melt are much lower (≤0.15 wt% and ≤ 1.3 wt% respectively), and DClBt-melt values are < 1 (0.02–0.4). The results are used to estimate the exchange coefficients (ratio of D values) for F-OH and Cl-OH pairs expressed as KdF/OHBt-melt=XFBt/XOHBt/XFmelt/XOHmelt, and KdCl/OHBt-melt=XClBt/XOHBt/XClmelt/XOHmelt, in which XFBt, XClBt and XOHBt are mole fractions of F, Cl and OH in biotite, and XFmelt, XClmelt and XOHmelt are mole fractions of F, Cl and OH in silicate melt, respectively. KdF/OHBt-melt is in the range of 1–50, which is higher than KdCl/OHBt-melt (0.07–5) by about one order of magnitude, implying that the relative incorporation preference of F, OH and Cl between biotite and melt is highest for F, lower for OH and lowest for Cl. Biotite and melt compositions exert important effects on the OH-F-Cl partitioning between biotite and melt. Multiple linear regression of data from literature and this study allows us to propose the following empirical equations: lnKdF/OHBt-melt=0.995-1.619∗DASI+3.613∗XMgBt-17.523∗XTiBt (R2 = 0.83, sd = 0.31), lnKdCl/OHBt-melt=3.380-2.454∗CSI-0.398∗XMgBt-22.377∗XTiBt (R2 = 0.94, sd = 0.26), in which XMgBt = Mg/(Mg + Fe3++Fe2++Mn + Ti + AlVI) of biotite, XTiBt = Ti/(Mg + Fe3++Fe2++Mn + Ti + AlVI) of biotite, DASI (deviation from ASI of 1) = |1–ASI|, with ASI = molar Al2O3/(Na2O + K2O + CaO) of the melt, and CSI (chlorine solubility index) = molar (Al1/2 + Ca1/2 + Mg1/2 + Na)/Si of the melt. The empirical models confirm the so-called Mg-F preference and Mg-Cl avoidance rules in biotite, and also reveal that increasing Ti content in biotite tends to lower KdF/OHBt-melt and KdCl/OHBt-melt. Furthermore, DASI and CSI are effective parameters that reflect the incorporation abilities of F and Cl in melt as a function of melt composition. A wide prediction potential of the OH-F-Cl exchange partition model is expected, because fairly large ranges in temperature (640–975 °C), melt composition (ASI = 0.7–1.4; CSI = 0.6–1.6) and biotite composition (XMgBt = 0–0.88) are covered. Calculated KdF/OHBt-melt and KdCl/OHBt-melt from the models are in good agreement with experimentally determined values, and the deviation from the models are less than 20% relative in both cases. Applying the empirical models, we calculated melt F and Cl concentrations based on biotite compositions from several intrusive-volcanic rocks that are associated with different deposit types. The results show that the magmas associated with Mo and REE deposits are characterized by high F (up to ca. 10,000 ppm) but relatively low Cl. On the contrary, the magmas that have contributed to the formation of porphyry Cu and Au deposits contain much higher Cl (up to ca. 10,000 ppm) than F.

KW - Biotite

KW - Chlorine

KW - Fluorine

KW - HO

KW - Partitioning

KW - Silicate melt

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U2 - 10.1016/j.gca.2021.10.031

DO - 10.1016/j.gca.2021.10.031

M3 - Article

AN - SCOPUS:85119922934

VL - 317

SP - 155

EP - 179

JO - Geochimica et cosmochimica acta

JF - Geochimica et cosmochimica acta

SN - 0016-7037

ER -

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