The elemental and isotopic abundances of halogens (F, Cl, Br, I) are used to constrain planetary volatile loss and volatile delivery processes, but their behavior during magmatic differentiation in general, and sulfide liquid segregation in particular, is currently not well constrained. To test whether sulfide liquid segregation could affect halogen behavior during magmatic processes, we performed high-pressure experiments to systematically quantify the sulfide liquid – silicate melt partition coefficients (Dsulliq-silmelt values, defined as the ratio between the wt.% concentration of the halogen in the sulfide liquid and silicate melt, respectively) of F, Cl, Br and I at a pressure of 1 GPa and temperatures of 1683–1883 K. Results show that dry-polishing target surfaces is crucial for obtaining representative halogen concentrations of sulfide liquids. The results also show that no appreciable amounts of F partition into sulfide liquids, whereas Cl, Br and I behave increasingly chalcophile with increasing atomic radius (i.e., DF sulliq-silmelt 1) in several experiments. In contrast to previous observations, DCl/Br sulliq-silmelt was found to be <1. The DCl,Br,I sulliq-silmelt predominantly vary with sulfide liquid melt composition, showing an increase with increasing O in the sulfide liquid, which itself is correlated with more oxidizing conditions (i.e., higher fO2) or silicate melt FeO contents. The DCl,Br,I sulliq-silmelt values remain constant and/or potentially decrease again at the highest O concentrations of the sulfide liquids in this study (∼2.5 wt.% O). Results indicate that the magnitude of halogen depletions in the terrestrial, martian and lunar mantle are not strongly affected by segregation of sulfide liquids during their accretion, given the expected low modal abundance of sulfide liquids and/or relatively low DCl,Br,I sulliq-silmelt values. Core formation remains the most important process in establishing iodine depletion in the terrestrial mantle, whereas volatility-related loss seems most likely for F, Cl, Br and I, in case of the martian mantle. However, segregation of sulfide liquids during accretion could have resulted in a relative increase of the offset between the mantle depletions of the lighter and heavier halogens. The experimental results confirm the previously proposed feasibility of sulfide liquids as reservoirs for halogens in magmatic sulfide ore environments. As proposed by Mungall and Brenan (2003), fractional crystallization of these sulfide liquids in the absence of a silicate melt can lead to the formation of halide melts or fluids, consistent with the association between halide minerals and magmatic sulfide ores in some localities.

中文翻译：

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F、Cl、Br 和 I 的亲硫行为的实验评估：对行星吸积和岩浆矿床形成过程中卤素命运的影响

卤素（F、Cl、Br、I）的元素和同位素丰度用于限制行星挥发物损失和挥发物输送过程，但它们在一般岩浆分异过程中的行为，特别是硫化物液体偏析，目前没有得到很好的限制。为了测试硫化物液体偏析是否会影响岩浆过程中的卤素行为，我们进行了高压实验以系统地量化硫化物液体 - 硅酸盐熔体分配系数（Dsulliq-silmelt 值，定义为卤素的重量百分比浓度之间的比率）在 1 GPa 的压力和 1683-1883 K 的温度下，分别在 F、Cl、Br 和 I 的硫化物液体和硅酸盐熔体中）。结果表明，干抛光目标表面对于获得硫化物液体的代表性卤素浓度至关重要。结果还表明，在几个实验中，没有可观数量的 F 分配到硫化物液体中，而 Cl、Br 和 I 随着原子半径的增加（即 DF sulliq-silmelt 1）表现出越来越亲硫性。与之前的观察结果相反，发现 DCl/Br sulliq-silmelt <1。DCl,Br,I sulliq-silmelt 主要随硫化物液体熔体组成而变化，随着硫化物液体中 O 的增加而增加，这本身与更多的氧化条件（即更高的 fO2）或硅酸盐熔体 FeO 含量相关。DCl,Br,I sulliq-silmelt 值在本研究中硫化物液体的最高 O 浓度（~2.5 wt.% O）下保持不变和/或可能再次下降。结果表明，鉴于硫化物液体的预期低模态丰度和/或相对较低的 DCl,Br,I sulliq-锡熔值。地核形成仍然是确定地幔中碘耗竭的最重要过程，而在火星地幔的情况下，F、Cl、Br 和 I 似乎最有可能发生与波动相关的损失。然而，在吸积过程中硫化物液体的分离可能导致较轻和较重卤素的地幔消耗之间的偏移量相对增加。实验结果证实了先前提出的硫化物液体作为岩浆硫化物矿环境中卤素储层的可行性。