Danxia Red Caused by Surface Iron Coating: Study on the Occurrence State of Iron in Typical Danxia Strata in Southern China
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摘要: 丹霞地貌在我国南方地区广泛发育，其红色的特征是主要的地貌判别标志之一. 前人的研究成果显示丹霞的红色成因与地层中的铁有关，但是对于铁的赋存状态并未进行深入研究. 通过对采自广东省丹霞山及江西省龙虎山两个典型丹霞地貌区的样品进行矿物组成、地球化学及铁的赋存状态研究，结果表明：（1）广东丹霞山及江西龙虎山丹霞地层样品的岩性主要为砾岩与砂岩，主要的矿物组成是石英与长石，含有少量的粘土及铁氧化物，岩体致密坚硬，固结程度高，多为铁质胶结.（2）地球化学分析显示，二者的SiO2的含量最高，Al2O3次之，TFe2O3与FeO的含量较低，铁氧化物主要是赤铁矿，它是极高效的显色剂，通过高效的地球化学过程，以最显色的矿物形式，富集在了颗粒表面.（3）穆斯堡尔谱分析显示二者地层中铁均以氧化物铁及粘土铁的形式赋存，其中三价铁离子远高于二价铁离子的含量. 综合来看，铁在丹霞地层中的含量较低，但是以铁氧化物的形式吸附和沉淀在石英、长石等矿物的表面，以及粘土矿物的表面和层间，形成极薄的赤铁矿包膜，致使地层呈现红色.Abstract: Danxia landform is widely developed in southern China, and its red feature is one of the main distinguishing marks of landform. Previous research results have shown that the red color of Danxia landforms is related to iron in the strata, but no in-depth study has been conducted on the state of iron occurrence. In this paper, the mineral composition, geochemistry and iron occurrence of samples from Danxia Mountain in Guangdong Province and Longhu Mountain in Jiangxi Province are studied. The results show that: (1)The Danxia landform stratigraphic samples in Guangdong Province and Longhu Mountain in Jiangxi Province show that the main mineral composition is quartz and feldspar, containing a small amount of clay and iron oxides, with a high degree of consolidation, and some layers contain gravel. (2) Geochemical analysis shows that the content of SiO2 in both is the highest, followed by Al2O3. The content of TFe2O3 (0.81%~1.63%) and FeO (0.08%~0.16%) is lower, indicating that the content of iron minerals is not the main factor causing redness. (3)The iron in the Danxia Formation of Danxia Mountain in Guangdong and Longhu Mountain in Jiangxi mainly exists in the form of clay iron and oxide iron, among which trivalent iron ions (oxides-Fe3+: 41.3% and 44.3%, clay-Fe3+: 49.7% and 47.6%) are much higher than the content of divalent iron ions (clay-Fe2+: 9.0% and 8.1%). All indicate that the content of iron in the Danxia Formation is relatively low, but it may be in the form of an iron oxide coating that exists on the surface of minerals such as quartz and feldspar, causing the formation to appearred.
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图 1 广东丹霞山及江西龙虎山丹霞地层手标本及岩石样品单偏光镜下照片
a. 广东丹霞山丹霞地层暗红色砾岩；b. 广东丹霞山丹霞地层暗红色粗砂岩；c. 江西龙虎山丹霞地层暗红色中粗粒砂岩；d. 广东丹霞山样品单偏光下照片；e. 江西龙虎山样品单偏光下照片
Fig. 1. Photographs of hand specimens and rock samples of Danxia strata in Danxia Mountain, Guangdong Province and Longhu Mountain, Jiangxi Province under partially polarized light
图 2 南方典型丹霞地层矿物组合XRD分析结果
Qz. 石英；Cy. 粘土类矿物；Fp. 长石；Io. 铁氧化物；Sf. 硫化物
Fig. 2. Mineral association of typical Danxia Formation in southern China
图 3 南方典型丹霞地层穆斯堡尔谱图
Fig. 3. Mossbauer spectrum of typical Danxia strata in southern China
表 1 南方典型丹霞地层地球化学成分（%）
Table 1. The typical Danxia strata chemical composition in southern China (%)
序号 样品名称 样品性质 SiO2 TiO2 Al2O3 TFe2O3 MnO MgO CaO Na2O K2O P2O5 LOI FeO SUM 1 sg01 砾岩 85.61 0.11 7.86 0.81 0.01 0.70 0.05 0.10 2.21 0.02 2.19 0.08 99.66 2 sg02 砂岩 73.22 0.14 13.82 1.63 0.03 1.45 0.40 0.60 5.40 0.02 2.81 0.16 99.53 3 yt01 砂岩 80.75 0.26 6.72 1.18 0.04 0.40 3.89 1.25 1.61 0.02 3.97 0.12 100.10 注：全铁=FeO+Fe2O3；sg01和sg02为广东丹霞山早白垩世丹霞组地层样品；yt01为江西龙虎山晚白垩世赣州群丹霞地层样品；FeO的含量采用化学滴定法测定. 
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表 2 南方典型丹霞地层样品化学指标
Table 2. The Typical Danxia strata samples chemical indicators in southern China
样品号 样品类型 颜色 氧化还原指标 CIA风化指数 sg01 粗砾岩 暗红色 10.13 0.75 sg02 粗砂岩 暗红色 10.19 0.65 yt01 粗砂岩 暗红色 9.83 0.53 注：氧化还原指标：TFe2O3/FeO；化学风化指标CIA={(Al2O3)/[(A12O3)+(CaO*)+(Na2O)+(K2O)]}×100%，表达式中主成分均以摩尔分数表示，CaO*指硅酸盐中的CaO，即全岩中的CaO扣除掉化学沉积的CaO的摩尔分数，CIA实际反映了含铝硅酸盐矿物尤其是长石风化成粘土矿物的程度，CIA值越高，指示硅酸盐矿物中Na、K和Ca矿物从母岩中淋失越多，化学风化越强.由于实验过程中很难精确地分离纯化沉积物样品中的硅酸盐矿物，本文采用McLennan提出的校正方法，即根据自然界硅酸盐矿物中Na和Ca的平均组成，依据沉积物样品中的CaO/Na2O的摩尔比值来计算CIA：如果比值> 1, 以Na2O的摩尔含量代替CaO含量；而若比值< 1，则直接以CaO摩尔含量来计算CIA.
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表 3 南方典型丹霞地层样品穆斯堡尔谱拟合参数结果及铁的赋存状态
Table 3. The result of fitting parameters of Mossbauer spectrum and the occurrence state of iron in typical Danxia formation samples in southern China
样品号 化学种 相对含量（%） IS（mm/s） QS(mm/s) HW(mm/s) H/T sg01 clay-Fe2+ 9.00±0.21 1.079±0.005 2.217±0.010 0.099±0.003 clay-Fe3+ 49.70±0.29 0.292±0.003 0.754±0.005 0.099±0.003 oxides-Fe3+ 41.30±0.32 0.361±0.001 -0.095±0.001 0.099±0.003 45.3±0.14 yt01 clay-Fe2+ 8.10±0.38 1.337±0.008 2.039±0.002 0.169±0.006 clay-Fe3+ 47.60±0.50 0.296±0.003 0.676±0.006 0.169±0.006 oxides-Fe3+ 44.30±0.54 0.351±0.005 -0.102±0.001 0.169±0.006 50.39±0.24
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