Determination of activities and condensation temperatures of GaO1.5 and InO1.5 in anorthite-diopside eutectic melts by Knudsen Effusion Mass Spectrometry
Lukas Bischof , Paolo A. Sossi , Dmitry Sergeev , Michael Müller , Max W. Schmidt
{"title":"Determination of activities and condensation temperatures of GaO1.5 and InO1.5 in anorthite-diopside eutectic melts by Knudsen Effusion Mass Spectrometry","authors":"Lukas Bischof , Paolo A. Sossi , Dmitry Sergeev , Michael Müller , Max W. Schmidt","doi":"10.1016/j.gca.2023.08.027","DOIUrl":null,"url":null,"abstract":"<div><p>The group 13 elements Ga and In are overabundant in bulk silicate Earth (BSE) when compared to lithophile elements of similar 50% nebular condensation temperature <span><math><mrow><mfenced><mrow><msubsup><mi>T</mi><mrow><mi>c</mi></mrow><mn>50</mn></msubsup></mrow></mfenced></mrow></math></span>. To understand whether evaporation from silicate melts provides a more accurate description of volatility during the later stages of planetary accretion, namely, at higher temperatures and oxygen fugacities than in the solar nebula, knowledge of the activities of GaO<sub>1.5</sub> and InO<sub>1.5</sub> in silicate melts and their stable gaseous species are required. To this end, we doped anorthite-diopside (An-Di) eutectic glasses with ∼1000 and ∼10,000 ppm of Ga and In and determined their equilibrium partial pressures above the silicate liquid by Knudsen Effusion Mass Spectrometry (KEMS) using Ir cells at 1550–1740 K over the log(<em>f</em>O<sub>2</sub>) range ΔIW+1.5 to ΔIW+2.5 (IW = iron-wüstite buffer). We detect Ga<sup>0</sup> and In<sup>0</sup> as the dominant vapour species and determine activity coefficients of <em>γ</em>(GaO<sub>1.5</sub>) = 0.036(6) at 1700 K and of <em>γ</em>(InO<sub>1.5</sub>) = 0.017(12) at 1674 K. Using these activity coefficients, we calculate partial pressures of Ga and In, together with those of similarly volatile elements, K and Zn and show that their relative volatilities from An-Di eutectic melts are in the in order Ga > K ∼ In > Zn, different from those predicted from their <span><math><mrow><msubsup><mi>T</mi><mrow><mi>c</mi></mrow><mn>50</mn></msubsup></mrow></math></span> under nebular conditions but in line with their relative abundances in the BSE. This substantiates the view that the abundances of volatiles in BSE, such as Ga and In, may have been set by evaporation from silicate melts under oxidising conditions at later stages of planetary accretion. Moreover, chondrules likely never underwent significant evaporation during melting and their volatile-depleted nature is likely inherited from the earliest solid condensates.</p></div>","PeriodicalId":327,"journal":{"name":"Geochimica et Cosmochimica Acta","volume":"360 ","pages":"Pages 1-15"},"PeriodicalIF":4.5000,"publicationDate":"2023-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Geochimica et Cosmochimica Acta","FirstCategoryId":"89","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0016703723004295","RegionNum":1,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"GEOCHEMISTRY & GEOPHYSICS","Score":null,"Total":0}
引用次数: 0
Abstract
The group 13 elements Ga and In are overabundant in bulk silicate Earth (BSE) when compared to lithophile elements of similar 50% nebular condensation temperature . To understand whether evaporation from silicate melts provides a more accurate description of volatility during the later stages of planetary accretion, namely, at higher temperatures and oxygen fugacities than in the solar nebula, knowledge of the activities of GaO1.5 and InO1.5 in silicate melts and their stable gaseous species are required. To this end, we doped anorthite-diopside (An-Di) eutectic glasses with ∼1000 and ∼10,000 ppm of Ga and In and determined their equilibrium partial pressures above the silicate liquid by Knudsen Effusion Mass Spectrometry (KEMS) using Ir cells at 1550–1740 K over the log(fO2) range ΔIW+1.5 to ΔIW+2.5 (IW = iron-wüstite buffer). We detect Ga0 and In0 as the dominant vapour species and determine activity coefficients of γ(GaO1.5) = 0.036(6) at 1700 K and of γ(InO1.5) = 0.017(12) at 1674 K. Using these activity coefficients, we calculate partial pressures of Ga and In, together with those of similarly volatile elements, K and Zn and show that their relative volatilities from An-Di eutectic melts are in the in order Ga > K ∼ In > Zn, different from those predicted from their under nebular conditions but in line with their relative abundances in the BSE. This substantiates the view that the abundances of volatiles in BSE, such as Ga and In, may have been set by evaporation from silicate melts under oxidising conditions at later stages of planetary accretion. Moreover, chondrules likely never underwent significant evaporation during melting and their volatile-depleted nature is likely inherited from the earliest solid condensates.
在块状硅酸盐土(BSE)中,13族元素Ga和In相对于50%星云凝结温度Tc50的亲石元素来说是过丰富的。要了解硅酸盐熔体的蒸发是否能更准确地描述行星吸积后期的挥发性,即在比太阳星云更高的温度和氧逸度下,需要了解硅酸盐熔体中高1.5和InO1.5的活动及其稳定的气态物质。为此,我们在钙长石透辉石(An-Di)共晶玻璃中掺杂了~ 1000 ppm和~ 10,000 ppm的Ga和In,并使用Ir细胞在1550-1740 K下在log(fO2)范围ΔIW+1.5至ΔIW+2.5 (IW =铁- w stite缓冲液)上通过Knudsen Effusion Mass Spectrometry (KEMS)测定了它们在硅酸盐液体上的平衡分压。我们检测到Ga0和In0是主要的蒸汽种类,并确定了γ(GaO1.5)在1700 K = 0.036(6)和γ(InO1.5)在1674 K = 0.017(12)的活度系数。利用这些活度系数,我们计算了Ga和In的分压,以及类似挥发性元素K和Zn的分压,并表明它们在An-Di共晶熔体中的相对挥发度依次为Ga >K ~ In >Zn,与星云条件下Tc50的预测值不同,但与它们在BSE中的相对丰度一致。这证实了这样一种观点,即BSE中挥发物的丰度,如Ga和in,可能是由行星吸积后期氧化条件下硅酸盐熔体的蒸发决定的。此外,球粒在融化过程中可能从未经历过明显的蒸发,它们挥发性耗尽的性质可能继承自最早的固体凝析物。
期刊介绍:
Geochimica et Cosmochimica Acta publishes research papers in a wide range of subjects in terrestrial geochemistry, meteoritics, and planetary geochemistry. The scope of the journal includes:
1). Physical chemistry of gases, aqueous solutions, glasses, and crystalline solids
2). Igneous and metamorphic petrology
3). Chemical processes in the atmosphere, hydrosphere, biosphere, and lithosphere of the Earth
4). Organic geochemistry
5). Isotope geochemistry
6). Meteoritics and meteorite impacts
7). Lunar science; and
8). Planetary geochemistry.