The solid-state reduction kinetics of pre-oxidized vanadium-titanium magnetite concentrate was studied. The phase and microstructure of the reduction product were characterized by XRD, SEM and EDS methods, based on wh...The solid-state reduction kinetics of pre-oxidized vanadium-titanium magnetite concentrate was studied. The phase and microstructure of the reduction product were characterized by XRD, SEM and EDS methods, based on which the mechanism of the solid-state reduction was investigated. The results showed that using coal as reductant at 950-1100 °C, the solid-state reduction of the pre-oxidized vanadium-titanium magnetite concentrate was controlled by interface chemical reaction and the apparent activation energy was 67.719 k J/mol. The mineral phase transformation during the reduction process can be described as follows: pre-oxidized vanadium-titanium magnetite concentrate → ulvospinel → ilmenite → Fe Ti2O5 →(FenTi1-n)Ti2O5. M3O5-type(M can be Fe, Ti, Mg, Mn, etc) solid solutions would be formed during the reduction process of the pre-oxidized vanadium-titanium magnetite concentrate at 1050 °C for 60 min. The poor reducibility of iron in M3O5 solid solutions is the main reason to limit the reduction property of pre-oxidized vanadium-titanium magnetite concentrate.展开更多
In China, most Precambrian banded iron formations (BIFs) are situated in the North China Craton. The Yuanjiacun iron depos- it, located in the Ltlliang area, is arguably the most representative Superior-type BIF. Th...In China, most Precambrian banded iron formations (BIFs) are situated in the North China Craton. The Yuanjiacun iron depos- it, located in the Ltlliang area, is arguably the most representative Superior-type BIF. This iron deposit is coherent with the sedimentary rock succession of the Yuanjiacun Formation in the lower Lliliang Group, and was interpreted to be deposited at 2.3-2.1 Ga, based on ages of overlying and underlying volcanic strata. This age overlaps with the time range of the Great Oxidation Event (GOE, 2.4-2.2 Ga). The Yuanjiacun BIF consists mainly of subhedral-xenomorphic magnetite and quartz and rarely other minerals with a lower degree of metamorphism, from greenschist to lower amphibolite facies. The geochemical characteristics of this BIF are similar to those of Superior-type BIFs. Prominent positive La, Y, and Eu anomalies normalized by the Post Archean Australian Shale (PAAS) indicate that the primary chemical precipitate is a result of solutions that repre- sent mixtures of seawater and high-T hydrothermal fluids. The contamination from crustal detritus found is negligible based on low abundances of Al2O3 and TiO2 (〈0.5%) and of trace elements such as Th, Hf, Zr, and Sc (〈1.5 ppm), as well as the lack of co-variations between Al2O3 and TiO2. In particular, the Yuanjiacun BIF samples do not display significant negative Ce anom- alies like those of the Archean iron formations, but rather, the Yuanjiacun BIF samples exhibit prominent positive Ce anoma- lies, low Y/Ho ratios, and high light to heavy REE ((Pr/Yb)sN) ratios, which are essentially consistent with the late Paleoprote- rozoic (〈2.0 Ga) BIFs around the world. These characteristics of the Yuanjiacun BIF samples imply that the ancient ocean (2.3-2.1 Ga) was redox-stratified from oxic shallow water to deeper anoxic water. The specific redox conditions of the ancient ocean may be related to the GOE, which gave rise to the oxidation of Ce and Mn in the upper water, and to the presence of a Mn oxide shuttle in the ocean, resulting in varying REE patterns due to the precipitation and dissolution of this Mn oxide shut tle under different redox states. Therefore, the Yuanjiacun BIF appears to have formed near the redoxcline and lower-level reduced marine water.展开更多
The more oxidized mantle peridotites above subducting slabs than stable continental areas have been attributed to the infiltration of some oxidizing fluids released from the subducting slabs. However, knowledge for th...The more oxidized mantle peridotites above subducting slabs than stable continental areas have been attributed to the infiltration of some oxidizing fluids released from the subducting slabs. However, knowledge for the redox states of the slabs itself is very limited. Until now, few oxybarometers can be directly used to constrain the redox states of the subducting slabs.The rutile-ilmenite oxybarometer was proposed and successfully applied to constrain the oxygen fugacity of mantle assemblages.However, its application to rocks equilibrated at crustal P-T conditions has been hampered by some uncertainties in an early solid solution model of ilmenite. With a newly-released solid solution model for the ilmenite, we have conducted high-P experiments(at 3 and 5 GPa, and 900–1300°C) to test the accuracy of this oxybarometer. The experiments were performed with their oxygen fugacities controlled by the CCO buffer(i.e., C+O_2=CO_2). We demonstrated that the oxygen fugacities calculated for our high-P experimental products by using the rutile-ilmenite oxybarometer were in excellent agreement with the fO_2 dictated by the CCO buffer, suggesting a wide applicability of this oxybarometer to crust rocks. As examples, the rutile-ilmenite oxybarometer has been used to constrain the oxygen fugacities of some metamorphic rocks such as eclogite, granulite and amphibolite usually observed from the subduction zones.展开更多
基金Project(NCET-10-0834)supported by the Program for New Century Excellent Talents in University,China
文摘The solid-state reduction kinetics of pre-oxidized vanadium-titanium magnetite concentrate was studied. The phase and microstructure of the reduction product were characterized by XRD, SEM and EDS methods, based on which the mechanism of the solid-state reduction was investigated. The results showed that using coal as reductant at 950-1100 °C, the solid-state reduction of the pre-oxidized vanadium-titanium magnetite concentrate was controlled by interface chemical reaction and the apparent activation energy was 67.719 k J/mol. The mineral phase transformation during the reduction process can be described as follows: pre-oxidized vanadium-titanium magnetite concentrate → ulvospinel → ilmenite → Fe Ti2O5 →(FenTi1-n)Ti2O5. M3O5-type(M can be Fe, Ti, Mg, Mn, etc) solid solutions would be formed during the reduction process of the pre-oxidized vanadium-titanium magnetite concentrate at 1050 °C for 60 min. The poor reducibility of iron in M3O5 solid solutions is the main reason to limit the reduction property of pre-oxidized vanadium-titanium magnetite concentrate.
基金supported by the Major State Basic Research Programme of the People’s Republic of China(Grant No.2012CB416601)the Knowledge Innovation Programme of the Chinese Academy of Sciences(Grant No.KZCX2-YW-Q04-07)
文摘In China, most Precambrian banded iron formations (BIFs) are situated in the North China Craton. The Yuanjiacun iron depos- it, located in the Ltlliang area, is arguably the most representative Superior-type BIF. This iron deposit is coherent with the sedimentary rock succession of the Yuanjiacun Formation in the lower Lliliang Group, and was interpreted to be deposited at 2.3-2.1 Ga, based on ages of overlying and underlying volcanic strata. This age overlaps with the time range of the Great Oxidation Event (GOE, 2.4-2.2 Ga). The Yuanjiacun BIF consists mainly of subhedral-xenomorphic magnetite and quartz and rarely other minerals with a lower degree of metamorphism, from greenschist to lower amphibolite facies. The geochemical characteristics of this BIF are similar to those of Superior-type BIFs. Prominent positive La, Y, and Eu anomalies normalized by the Post Archean Australian Shale (PAAS) indicate that the primary chemical precipitate is a result of solutions that repre- sent mixtures of seawater and high-T hydrothermal fluids. The contamination from crustal detritus found is negligible based on low abundances of Al2O3 and TiO2 (〈0.5%) and of trace elements such as Th, Hf, Zr, and Sc (〈1.5 ppm), as well as the lack of co-variations between Al2O3 and TiO2. In particular, the Yuanjiacun BIF samples do not display significant negative Ce anom- alies like those of the Archean iron formations, but rather, the Yuanjiacun BIF samples exhibit prominent positive Ce anoma- lies, low Y/Ho ratios, and high light to heavy REE ((Pr/Yb)sN) ratios, which are essentially consistent with the late Paleoprote- rozoic (〈2.0 Ga) BIFs around the world. These characteristics of the Yuanjiacun BIF samples imply that the ancient ocean (2.3-2.1 Ga) was redox-stratified from oxic shallow water to deeper anoxic water. The specific redox conditions of the ancient ocean may be related to the GOE, which gave rise to the oxidation of Ce and Mn in the upper water, and to the presence of a Mn oxide shuttle in the ocean, resulting in varying REE patterns due to the precipitation and dissolution of this Mn oxide shut tle under different redox states. Therefore, the Yuanjiacun BIF appears to have formed near the redoxcline and lower-level reduced marine water.
基金supported by the National Natural Science Foundation of China(Grant Nos.41520104004&41502038)the China Postdoctoral Science Foundation(Grant No.2015M570009)
文摘The more oxidized mantle peridotites above subducting slabs than stable continental areas have been attributed to the infiltration of some oxidizing fluids released from the subducting slabs. However, knowledge for the redox states of the slabs itself is very limited. Until now, few oxybarometers can be directly used to constrain the redox states of the subducting slabs.The rutile-ilmenite oxybarometer was proposed and successfully applied to constrain the oxygen fugacity of mantle assemblages.However, its application to rocks equilibrated at crustal P-T conditions has been hampered by some uncertainties in an early solid solution model of ilmenite. With a newly-released solid solution model for the ilmenite, we have conducted high-P experiments(at 3 and 5 GPa, and 900–1300°C) to test the accuracy of this oxybarometer. The experiments were performed with their oxygen fugacities controlled by the CCO buffer(i.e., C+O_2=CO_2). We demonstrated that the oxygen fugacities calculated for our high-P experimental products by using the rutile-ilmenite oxybarometer were in excellent agreement with the fO_2 dictated by the CCO buffer, suggesting a wide applicability of this oxybarometer to crust rocks. As examples, the rutile-ilmenite oxybarometer has been used to constrain the oxygen fugacities of some metamorphic rocks such as eclogite, granulite and amphibolite usually observed from the subduction zones.