Research Progress of Aluminum−Phase Secondary Minerals and Their Environmental Significance in Acid Mine Water
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摘要:
酸性矿山排水（AMD）是硫化矿床矿山环境污染防治的难点，因而持续受到国内外学者的关注。众多的学者对矿区AMD中次生矿物进行了研究。为深入了解AMD中次生矿物的形成和演化，为AMD污染防治提供科学依据，笔者对前人不同环境下AMD中的次生矿物类型、次生矿物形成顺序，以及铝相次生矿物的形成、特征、环境危害及意义进行了简要综述。目前与AMD有关的主要次生矿物存在3种类型，即铁相次生矿物、铝相次生矿物和其他相次生矿物，AMD中的pH、Eh和温度对于次生矿物的形成具有控制性的作用。铁、铝相次生矿物具有吸附金属能力，这一性质有助于在一定程度上实现河流的自净化作用。由于AMD形成条件高，矿物相不稳定，目前有关AMD中铝相次生矿物及“酸性白水”的研究成果有限。因此，加强铝相次生矿物以及“酸性白水”的研究，可以更好地解析蒿坪河流域石煤矿区河流酸性磺水–酸性白水的形成演化机制，以及铝相次生矿物吸附重金属的地球化学过程。
Abstract:Acid mine drainage (AMD) is a difficult point in the prevention and control of environmental pollution in sulfide ore deposits, has attracted the attention of scholars at home and abroad. Numerous scholars have studied secondary minerals in AMD in different mining areas. In order to understand the formation and evolution of secondary minerals in AMD, it provides scientific basis for AMD pollution prevention and control. This paper briefly reviews the types of secondary minerals, the formation order of secondary minerals, and the formation, characteristics, environmental hazards and significance of secondary minerals in aluminum phase in AMD under different environments. There are currently three main types of secondary minerals associated with AMD, including: iron−phase secondary minerals, aluminum−phase secondary minerals and other−phase secondary minerals. The pH, Eh and temperature in AMD have a controlling effect on the formation of secondary minerals. Fe− and Al−phase secondary minerals have strong adsorption capacity for several metals in AMD, which can achieve a certain degree of water self−purification. At present, due to the high formation conditions of AMD and unstable mineral phases, there are limited research results on aluminum−phase secondary minerals and “acidic white water” in AMD. Therefore, the study of aluminum−phase secondary minerals and “acidic white water” can better analyze the formation and evolution mechanism of acidic sulfonated water and acidic white water in rivers in the stone coal mines area of Haoping river basin from the perspective of prevention and control, as well as the geochemical process of heavy metal adsorption by aluminum−phase secondary minerals.
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表 1 AMD中次生矿物种类（据Alpers et al.，1994修改）
Table 1. Species of secondary minerals in AMD
铁相次生矿物 化学式 铝相次生矿物 化学式 其他相次生矿物 化学式 水绿矾 FeSO4·7H2O 铝叶绿矾 Al2/3Fe4（SO4）6（OH）2·20H2O 胆矾 CuSO4·5H2O 铁矾 FeSO4·5H2O 铁明矾 FeAl2（SO4）4·22H2O 三水胆矾 CuSO4·3H2O 水铁矾 FeSO4·H2O 镁明矾 MgAl2（SO4）4·22H2O 水胆矾 Cu4（SO4）·（OH）6 叶绿矾 FeFe4（SO4）6（OH）2·20H2O 锰明矾 MnAl2（SO4）4·22H2O 柱钠铜矾 Na2Cu（SO4）·22H2O 粒铁矾 FeFe2（SO4）4·14H2O 毛矾石 Al2（SO4）3·17H2O 斜蓝铜矾 Cu4（SO4）（OH）6·2H2O 针绿矾 Fe2（SO4）3·9H2O 斜铝矾 Al（SO4）（OH）·5H2O 水铜铝矾 Cu4Al2（SO4）（OH）12·24H2O 板铁矾 （H3O）Fe（SO4）2·3H2O 明矾石 KAl3（SO4）2（OH）6 水氯铜矿 CuCl2·2H2O 纤铁矾 Fe（SO4）（OH）·5H2O 钠明矾石 NaAl3（SO4）2（OH）6 砷铁矾 Fe6（AsO3）4（SO4）（OH）4·4H2O 红铁矾 Fe（SO4）（OH）·3H2O 羟铝矾 Al4（SO4）（OH）10·4H2O 石膏 CaSO4·2H2O 基铁矾 Fe（SO4）（OH）·2H2O 矾石 Al4（SO4）（OH）4·7H2O 泻利盐 MgSO4·7H2O 黄钾铁矾 KFe3（SO4）2（OH）6 斜钠明矾 NaAl（SO4）2·6H2O 水镍钴矾 Co6Ni3Mn（SO4）·6H2O 黄铵铁矾 NH4Fe3（SO4）2（OH）6 三水铝石 Al（OH）3 钴铝矾 （Co,Mg）Al2（SO4）4·22H2O 黄钠铁矾 NaFe3（SO4）2（OH）6 赤矾 CoSO4·7H2O 柱钾铁矾 K2O·Fe2O3·4SO3·8H2O 白钠镁矾 Na6Mg（SO4）2·4H2O 施威特曼石 Fe8O8（SO4）（OH）6 李时珍石 ZnFe2（SO4）4·14H2O 锡铁山石 Fe8（Cl）（SO4）·6H2O 针铁矿 α-FeOOH 纤铁矿 γ-FeOOH 褐铁矿 Fe2O3·nH2O 赤铁矿 Fe2O3 
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表 2 铝相次生矿物的性质（据Bigham et al.，2000修改）
Table 2. Properties of aluminum phase secondary minerals
矿物名称 水羟铝矾石
Al4（OH）10SO4·15H2O羟铝矾
Al4（OH）10SO4·4H2O水羟铝矾
Al12（OH）26（SO4）5·20H2O矾石
Al2（OH）4SO4·7H2O变矾石
Al2（OH）4SO4·5H2O晶系 单斜晶系 单斜晶系 三斜晶系 单斜晶系 单斜晶系 空间群 P21 P1 P21/c P21/m 晶胞尺寸 a=14.911
b=9.993
c=13.640
β=112.24°a=12.954
b=10.004
c=11.064
β=104.1°a=18.475
b=19.454
c=3.771
α=95.24°
β=91.48°
γ=80.24°a=7.440
b=15.583
c=11.700
β=110.18°a=7.930
b=16.879
c=7.353
β=106.73°颜色 白色至浅黄棕色 白色 白垩色/
含铜时为浅蓝绿色白色 丝白色 结构及结晶度 粘土状，
通常潮湿和可塑粘土状，
贝壳状断口密堆积的微-
隐晶质聚集体泥状、易碎、
结节状细小纤维结节状微晶线状
聚集体和凝结物最强XRD间距（Å） 12.6, 6.18, 5.29, 4.70 9.39, 4.73, 3.69, 1.438 18.1 8.98, 7.79, 4.70 8.46, 4.52, 4.39, 3.54 稳定性 易脱水为羟铝矾 由水羟铝矾石脱水而成 在环境条件下脱水 在55 ℃下脱水为矾石
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表 3 铝羟基硫酸盐矿物中铝沉淀物的组成（%）（据Bigham et al.，2000修改）
Table 3. Composition (%) of Al hydroxysulfate minerals
水合
明矾石羟铝矾 水羟
铝矾石A B C D E F C1 C2 C3 理论值 分析值 Al2O3 38.80 45.80 31.70 46.40 44.75 36.20 42.80 47.00 39.00 40.10 44.10 CaO 0.30 0.40 0.77 1.50 Na2O 0.00 0.05 0.18 1.20 0.10 K2O 0.00 0.04 0.00 0.50 0.00 0.00 H2O 20.57 36.30 55.90 33.40 35.60 46.9 40.80 39.50 46.00 45.60 35.00 SO3 40.63 17.90 12.40 17.40 18.10 10.70 12.40 8.70 17.40 11.60 22.30 总计 100.00 100.00 100.00 97.20 98.75 94.20 96.90 96.90 104.20 97.40 101.40 X射线衍射 羟铝矾 羟铝矾 无定形 无定形 无定形 明矾石 无定形 无定形 电子衍射 羟铝矾 无定形 无定形 无定形 结晶 无定形 羟铝矾 注：样品A来自Bannister等（1948a）；样品B来自Clayton（1980）；样品C来自Nordstrom（1984）；样品D来自Headden（1905）、Cunningham等（1996）；样品E来自Ball（1989）；样品F来自Charles等（1967）合成沉淀。
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