Trace element proxies of seafloor hydrothermal fluids based on secondary ion mass spectrometry (SIMS) of black smoker chimney linings
Trace element proxies of seafloor hydrothermal fluids based on secondary ion mass spectrometry (SIMS) of black smoker chimney linings
复制标题
基于黑烟囱内衬二次离子质谱 (SIMS) 的海底热液微量元素代理
DOI：
10.1016/j.gca.2019.09.038
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发表时间：
2020
影响因子：
5
通讯作者：
Rouxel, O.J.
中科院分区：
文献类型：
--
作者：
Evans, G.N.;Tivey, M.K.;Monteleone, B.;Shimizu, N.;Seewald, J.S.;Rouxel, O.J.
成对的黑色烟囱衬里和海底热液喷口流体的采样有助于在严格限制的物理化学条件下分析矿物和流体之间的微量元素分配，从而支持硫化物矿物沉积环境中微量元素替代物的开发。在这里，使用二次离子质谱仪(SIMS)测量了黄铜矿衬里的22个黑色烟囱中的Co、Ni、Ga、Ag和In的浓度(其中Co、Ag和In为29个)，并与电感耦合等离子体质谱(ICP-MS)和NIST可溯源参考溶液进行了校准。为了提供更多关于所研究的29个黑色烟囱衬里中19个的喷口流体对微量元素浓度的数据，本文还提供了33个热液喷口流体的电感耦合等离子体质谱(ICPMS)数据，这些流体来自刘展布中心东部和Value Fa山脊的Tahi Moana-1、Abe、Tu‘i Malila和Mariner喷口区域。所研究的黄铜矿黑色烟囱衬里代表了不同的温度(269-395 °C)、化学成分(例如，pH(在25 °C下) = 2.3-4.4)和地质条件。电子探针结果表明，矿物化学计量比范围从化学计量比黄铜矿到摩尔铜：摩尔Fe = 为0.65。SIMS获得的微量元素含量为：Co(<；2 ng/g-760 μg/g)、Ni(<；17 ng/g-454 μg/g)、Ga(<；0.9 ng/g-48 μg/g)、Ag(60 μg/g-3800 μg/g)、In(<；0.5 ng/g-270 μg/g)。黄铜矿中的银浓度与成对喷口流体中的{Ag+}：{Cu2+}的自由离子活度比密切相关，黄铜矿中的高银浓度表明其形成于含低铜浓度的近中性喷口流体或含银浓度较高的低pH喷口流体，可归因于地下银的再动员。低pH富铜流体中的低银黄铜矿不受广泛的银再活化作用的影响。黄铜矿中Ga和In的浓度随喷口流体pH的变化呈负相关，可能反映了Ga和In-OH-−络合物的强度。因此，Ga和In的浓度区分了由近中性贫铜喷口流体形成的富银黄铜矿或由富银低pH喷口流体形成的富银黄铜矿。相比之下，Co和Ni与流体数据没有显示出趋势，但与矿物Cu：Fe比值相关，可能反映了Fe(II)晶格位置的更大可用性或2+离子的配对替代。总体而言，这项研究证明了配对的喷口流体和黑色烟囱样品可能提供对硫化物矿物沉积环境中痕量元素分配的洞察以及重要流体参数(如pH和金属浓度)的相关替代。这项研究还证明了SIMS在高空间分辨率和低检测限下精确分析黄铜矿中痕量元素的实用价值。
Sampling of paired black smoker chimney linings and seafloor hydrothermal vent fluids supports the development of trace element proxies for sulfide mineral deposition environments by facilitating analyses of trace element partitioning between mineral and fluid phases under well-constrained physiochemical conditions. Here, concentrations of Co, Ni, Ga, Ag, and In in chalcopyrite lining 22 black smoker chimneys (29 for Co, Ag, and In) are measured using secondary ion mass spectrometry (SIMS) calibrated against inductively coupled plasma mass spectrometry (ICP-MS) and NIST-traceable reference solutions. To provide additional data on the trace element concentrations of vent fluid pairs for 19 of the 29 black smoker chimney linings investigated, this paper also presents new ICP-MS data for 33 hydrothermal vent fluids collected from the Tahi Moana-1, ABE, Tu’i Malila, and Mariner vent fields on the Eastern Lau Spreading Center and Valu Fa Ridge.The chalcopyrite black smoker chimney linings investigated represent a variety of temperature (269–395 °C), chemical (e.g., pH (at 25 °C) = 2.3–4.4), and geologic conditions. Electron microprobe results indicate that mineral stoichiometry ranges from stoichiometric chalcopyrite to mol Cu : mol Fe = 0.65. Trace element concentrations obtained by SIMS are: Co (<2 ng/g–760 μg/g), Ni (<17 ng/g–454 μg/g), Ga (<0.9 ng/g–48 μg/g), Ag (60 μg/g–3800 μg/g), In (<0.5 ng/g–270 μg/g). Concentrations of Ag in chalcopyrite strongly correlate with the free ion activity ratio of {Ag+}:{Cu+} in paired vent fluids, with high Ag concentrations in chalcopyrite indicating formation from near neutral vent fluids containing low Cu concentrations or low-pH vent fluids with high Ag concentrations attributable to subsurface Ag remobilization. Chalcopyrite with low Ag precipitates from low-pH Cu-rich fluids unaffected by extensive Ag remobilization. Concentrations of Ga and In in chalcopyrite exhibit a negative trend with vent fluid pH, possibly reflecting the strength of Ga and In OH−complexes. Thus, Ga and In concentrations differentiate Ag-rich chalcopyrite formed from near-neutral Cu-poor vent fluids or that formed from Ag-rich low-pH vent fluids. In contrast, Co and Ni exhibit no trend with fluid data, but correlate with mineral Cu:Fe ratios, possibly reflecting the greater availability of Fe(II) lattice sites or paired substitution of 2+ ions.Overall, this study demonstrates the potential of paired vent fluid and black smoker chimney samples to provide insight into the partitioning of trace elements in sulfide mineral deposition environments and related proxies of important fluid parameters such as pH and metal concentrations. This study also demonstrates the utility of SIMS to precisely analyze trace elements in chalcopyrite at high spatial resolutions and low detection limits.
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作者：
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通讯作者：
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DOI：
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期刊：
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DOI：
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发表时间：
2008
期刊：
Journal of Geophysical Research 113
影响因子：
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通讯作者：
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