The Role of Gypsum Salt Layer in the Mineralization Process of Skarn Type Iron Deposits: A Case Study of Hanxing Area
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摘要:
矽卡岩型铁矿床是中国富铁矿床的重要类型，其储量占全部富铁矿的60%左右。膏盐层在矽卡岩型铁矿成矿过程中的作用一直是广大学者所关注的重点。研究表明，邯邢地区矽卡岩型铁矿层中硫酸盐、硫化物的δ34S值分别为24‰～29‰、11‰～20‰，具有海相沉积岩的S同位素组成特征，沉积膏盐层物质参与矽卡岩型铁矿的成矿过程。以邯邢地区矽卡岩型铁矿床为例，系统地分析了矿床中硫化物、硬石膏等含硫矿物的δ34S的主要组成，阐述了膏盐层在矽卡岩型铁矿成矿过程中的作用。①膏盐层中的Na+、Cl−等物质作为矿化剂加入气水热液，富碱的气水热液令接触区附近的闪长岩体出现钠长石化现象，析出Fe，并以铁氯酸钠络合物和铁卤化物的形式随热液运移。②膏盐层中的硫酸盐在高温条件下具有高氧化活性，与还原性的富铁热液发生氧化还原反应，提高热液氧逸度，热液中的Fe2+被氧化成Fe3+，从而产生Fe3O4，磁铁矿在围岩层间富集、沉淀，形成富铁矿床。③膏盐层物质溶解后在碳酸盐岩层间形成各种溶（熔）蚀空隙，为岩浆侵入和矿体就位提供有利的成矿空间，是矽卡岩磁铁矿矿床形成的重要地质条件之一。膏盐层在矽卡岩型铁矿成矿过程中具有提供矿化剂、氧化剂和储矿空间的作用。
Abstract:The Skarn-type iron deposit is an important type of iron-rich deposits in China with reserves accounting for about 60% of all iron-rich ores. In recent, the role of gypsum salt layer in the mineralization process of Skarn iron deposits has been the focus of attention of scholars. The results show that the δ34S values of sulfate and sulfide in the Skarn-type iron deposits in the Hanxing area range from 24‰ to 29‰ and from 11‰ to 20‰, respectively, and have the characteristics of sulfur isotope composition of marine sedimentary rocks. These data imply that sedimentary gypsum-salt layer material is involved in the mineralization of skarn-type iron deposits. Taking the skarn iron deposit in the Hanxing area in this study, the compositions of δ34S of the sulfides, gypsums, and other sulfur-containing minerals in this area were systematically analyzed, and the role of the gypsum salt layer in the mineralization process was clarified. ① Na+, Cl− and other substances, as mineralizer, in the gypsum salt layer are added to the gas-water hydrothermal fluid. The alkali-rich gas-water hydrothermal fluid causes the albitization of the diorite near the contact area, which precipitates Fe and migrates iorn in the form of sodium chlorate complex and iron halide. ② the sulfate in the gypsum salt layer has high oxidation activity under high temperature conditions, and it would cause a redox reaction with the reducing iron-rich hydrothermal fluid to increase the oxygen fugacity. The Fe2+ in the hydrothermal fluid, therefore, is oxidized to Fe3+, resulting in the formation of magmatite (i.e., Fe3O4). Hence, the magnetite is enriched and precipitated among the surrounding rock layers to form an iron-rich deposit. ③ various dissolution erosion voids are formed in the carbonate rock layers after the dissolution of the gypsum salt layer material, which provides a favorable mineralization space and is one of the important geological conditions for the formation of skarn magnetite deposits. In conlusion, gypsum salt layer has important significance in providing mineralizer, oxidant and ore-contained space in the process of skarn iron mineralization.
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Key words:
- skarn type iron ore deposits /
- gypsum salt layer /
- mineralizer /
- metallogenic space /
- redox reaction
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表 1 邯邢式矽卡岩型铁矿的硫同位素组成表
Table 1. Sulfur isotope composition of Hanxing type skarn type iron ore
矿床 硫化物δ34SV-CDT/‰ 硫酸盐δ34SV-CDT/‰ 数据来源 变化范围 平均 变化范围 平均 蒸发沉积石膏
（中奥陶统地层）21.3～31.6 27.9(30） 蔡本俊等，1987 沉积变质石膏
（中奥陶统地层）27.2～27.6 27.4 热液形成石膏
（中奥陶统地层）21.3～25.5 23.4 符山铁矿 11～14 13（6） 21.3～31.6 27.9（35） 赵瑞，1986；
蔡本俊等，1987；
章百明等，1996矿山村铁矿 14～18 16（17） 玉石洼铁矿 11～18 16（9） 马庄铁矿 15～19 16（6） 钢铁沟铁矿 12～18 16（3） 三王村铁矿 15～18 16（15） 北河铁矿 11.6～14.2 13.3（3） 西石门铁矿 14～18.6 16.2（13） 24～29.1 26.3（4） 文广，2017 北洺河铁矿 12.2～16.5 14.06（5） 24～29.1 26.3（5） 章百明等，1996；
王艳娟，2011符山铁矿 6.3～8.6 7.5（5） 息朝庄等，2022；
王艳娟，2012矿山村和武安岩体 6.4～18.8 12.2 徐文炘等，1987 煤层中黄铁矿 −26～3.3 −14（4） 注：括号内数字为样品个数。 
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表 2 常压下盐类矿物的物理化学性质表
Table 2. Physical and chemical properties of salt minerals under atmospheric pressure
矿物 钾石盐 石盐 硫酸钾 方解石 白云石 石膏 钾长石 斜长石 角闪石 辉石 橄榄石 分子式 KCl NaCl K2SO4 CaCO3 CaMg（CO3）2 CaSO4 K（AlSi3O8） （Ca, Na）AlSi3O8 （Ca, Mg, Fe）
Si3O22（OH）2（Ca, Mg, Fe）2
（Si, Al）2O6（Ca, Mg,
Fe）2SiO4分解温度（℃） 560～580 850～920 810～950 1100 ～1190 熔融温度（℃） 776 801 1030 ～1070 1290 ～1340 2800 1300 ～1450 1075 ～1200 1120 ～1550 1100 ～1200 1200 ～1400 1205 ～1 890晶格能（千卡） 156 179 358 647 1385 622 2400 ～3000 2500 ～3800 3800 4100 4200 ～4800 注：数据来自草广金，1978。
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表 3 过渡性金属成矿元素的络合物和卤化物形式
Table 3. Complexes and halide forms of transitional metal-forming elements
金属元素 络合物 卤化物 金属元素/形式 络合物 卤化物 Fe R（Fe3+Cl4）、R2（Fe2+Cl4） FeCl2、FeF2 W R2（WF8）、WOCl4 WCl6、WF6 Cu R2（CuCl4） CuCl、CuF Mo R2（MoCl6） MoCl4、MoF4 Pb R2（PbCl4） PbCl2、PbF2 Sn R2（SnCl6） SnCl4、SnF4 Zn R2（ZnCl4） ZnCl2、ZnF2 Au R（AuCl2）、R（AuCl4） AuCl3、AuF3 注：R为K+、Na+等碱金属离子。
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表 4 邯邢地区部分铁矿岩石钠化前后的化学元素占比变化表
Table 4. Changes in proportion of chemical elements before and after sodification of some iron ore rocks in Hanxing area
矿区 带入元素（%） 带出元素（%） 数据来源 SiO2 Al2O3 Na2O K2O CaO MgO Fe2O3+FeO 中关铁矿 原岩 51.15 13.56 2.47 4.98 7.97 9.56 5.14 贾木欣等，2006 钠化岩石 57.94 16.19 7.19 1.61 5.71 2.82 3.83 白涧铁矿 原岩 59.16 15.58 4.54 2.55 4.78 3.38 5.68 赵书梅等，2011 钠化岩石 58.83 15.8 7.08 1.08 5.83 2.9 4.08 西石门铁矿 原岩 59.01 16.63 8.2 0.28 6.65 2.05 4.2 魏宏飞，2011 钠化岩石 73.23 12.78 8.69 0.13 2.61 0.01 0.41
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