Migration and Enrichment of Heavy Metals During the Weathering Pedogenesis of Rocks in the Ningzhen Ore Cluster Area
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摘要:
岩石的风化成土作用造成重金属富集并导致土壤超标是一类特殊的地质成因土壤重金属污染现象，也被称为地质高背景问题，近年来受到学术界的高度关注。为弄清岩石风化成土过程中的重金属的物质来源、释放迁移和富集规律，本研究以宁镇矿集区代表性碳酸盐岩、岩浆岩和碎屑岩风化成土剖面为对象，通过野外调查、岩矿鉴定、相关性分析、上陆壳标准化蛛网图解、化学蚀变指数和质量平衡系数计算等方法，系统研究了重金属在岩石风化成土过程中迁移富集规律。结果表明：各剖面土壤与其下伏母岩具有物源继承关系；在同一气候条件下，重金属在风化剖面中的迁移规律受岩石岩性、剖面化学风化程度和重金属元素在岩石中赋存状态等多因素控制；岩浆岩和碎屑岩剖面土壤重金属表现出继承母岩化学成分组成和含量特征，重金属迁移能力与化学风化程度呈正比。而碳酸盐岩剖面重金属迁移能力与化学风化程度呈反比，导致碳酸盐岩剖面重金属呈现出（岩石）低背景、（土壤）高富集的地球化学特征，其中Cd、As的含量甚至超农用地土壤污染风险管制值，需要加以重视。在上述研究基础上，建立了重金属在岩石风化成土过程中的释放迁移模式。
Abstract:Weathering pedogenesis of rocks can release heavy metals to soil, and further accumulation of heavy metals in soil may exceed the national standard for safety soils. To understand the source, release, transport, and enrichment of heavy metals in the process of weathering pedogenesis, we systematically studied the migration and enrichment of heavy metals during rock weathering in the representative weathering pedogenesis profiles (carbonate rock, magmatic rock, and clastic rock) of the Ningzhen ore cluster area using a combination of field survey, rock and mineral identification, geochemical analysis and statistical analysis. The results showed that the soil of each profile has a provenance inheritance relationship with its underlying parent rock. The heavy metals in the soil of magmatic rock and clastic rock profiles showed similar chemical composition and content characteristics to the inherited parent rock. In contrast, the carbonate rock profile showed the geochemical characteristics of a low content of heavy metals in rocks and a high content in soil. In particular, the contents of Cd and As even exceeded the risk intervention values for soil contamination of agricultural land. It was revealed that the migration of heavy metals in weathering profiles of rocks under the same climatic conditions is controlled by multiple factors, such as rock lithology, the degree of chemical weathering of the profiles, and the occurrence state of heavy metals in rocks. The migration ability of heavy metals in magmatic rock and clastic rock profiles is proportional to the degree of chemical weathering, while the migration ability of heavy metals in carbonate rock profiles is inversely proportional to the degree of chemical weathering, leading to a higher potential for enrichment of heavy metals. Based on the above research, the release and migration pattern of heavy metals in the processes of rock weathering and soil formation was established.
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Key words:
- soil heavy metals /
- the chemical weathering /
- enrichment /
- mining areas /
- Ningzhen
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图 1 长江中下游成矿带矿集区分布图（a）（据张明超等, 2018）及研究区地质简图和采样位置分布（b）
Figure 1.
表 1 宁镇矿集区岩石−土壤剖面特征
Table 1. Characters of the rock-soil profiles in Ningzhen ore cluster area
剖面 基岩 岩石特征 剖面特征 海拔（m） 坡度（°） 土地利用方式 KY1 石英二长斑岩 斑状结构，块状构造。斑晶为斜长石（25%）、钾长石（20%），次为黑云母（10%）及少量角闪石和石英，含黄铁矿和黄铜矿等硫化物 剖面厚度（指岩-土界面以上部分，下同）150 cm，其中土壤层厚100 cm，呈黄棕色黏土状，下伏50 cm厚的粉状岩母质层，向下逐渐过渡到弱风化-新鲜母岩 145 5～10 林地 KY3 石英闪长斑岩 斑状结构，块状构造。斑晶为斜长石（35%）、黑云母（3%）以及少量石英和角闪石 剖面厚度约180 cm，土壤层厚105 cm，风化壳成棕色黏土状，下伏75 cm厚的砂糖状母质层，向下逐渐过渡到弱风化-新鲜母岩 66 8 林地 KY7 中三叠统黄马青组
长石石英砂岩细粒结构。主要矿物成分为石英（70%）、长石（20%）及少量灰岩、泥岩碎屑和云母碎片 剖面厚度70 cm，其中土壤层厚45 cm，下伏25 cm厚的砂糖状母质层，向下逐渐过渡到弱风化母岩 83 3～5 林地 KY8 中三叠统青龙组灰岩
（简称“青龙灰岩”）细晶结构。矿物主要为方解石（98%）和少量黏土、石英等，见铁质分布于方解石上及晶粒间 岩-土界面清晰，剖面发育较薄（67 cm），其呈红棕色黏土状，缺失C层，土壤体（A+B层）直接与下伏基岩接触 90 5 林地 KY9 下二叠统栖霞组含生物碎屑灰岩（简称“栖霞灰岩”） 微晶-细晶结构。矿物为方解石（80%）和生物碎屑（12%）。生物碎屑由纤维状方解石、泥晶方解石组成。矿物间充填铁质、泥质 岩-土界面清晰，剖面发育极薄（10 cm），土层呈红棕色黏土状，顶部有机质层和腐殖质层已被侵蚀，缺A层和残存部分B层，C层不发育，下伏基岩 97 2 林地 
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表 2 岩石风化剖面主量元素（%）、惰性元素（m/kg）含量及CIA值
Table 2. Concentrations of major (%), immobile (mg/kg) elements and CIA values in rock weathering profles
剖面
（母岩）KY1
（石英二长斑岩）KY3
（石英闪长斑岩）KY8
（青龙灰岩）KY9
（栖霞灰岩）（KY7）
长石石英砂岩UCC 发生层 A层 B层 C层 R层 A层 B层 C层 R层 A层 B层 R层 B层 R层 A层 B层 C层 R层 SiO2 65.21 70.82 67.22 59.79 64.70 64.22 63.51 63.73 62.85 57.87 6.32 34.18 0.02 64.89 60.28 63.53 59.05 66* Al2O3 16.87 13.87 18.29 16.64 15.78 16.93 17.23 16.82 13.99 18.72 1.40 17.55 0.29 16.29 18.70 17.82 20.61 15.2* Fe2O3 2.71 2.97 3.10 5.04 1.49 3.49 4.11 4.81 0.91 5.36 0.44 7.11 0.03 5.64 6.70 6.10 6.00 5* FeO 1.61 0.94 0.44 0.52 2.89 1.28 0.56 0.22 2.80 1.25 0.22 1.17 0.10 1.20 1.20 0.55 0.18 MgO 1.03 0.86 0.76 2.70 1.17 1.53 1.63 1.41 0.96 1.68 0.37 1.27 0.38 1.11 1.36 1.42 1.55 2.2* CaO 1.29 0.72 0.28 3.51 1.25 1.04 1.14 1.27 4.19 2.67 50.23 15.87 55.44 0.39 0.36 0.33 0.68 4.2* Na2O 2.30 1.73 0.40 3.85 2.85 2.38 2.70 4.17 2.14 0.61 0.05 0.20 0.02 0.62 0.54 0.71 1.34 3.9* K2O 2.63 2.39 2.55 2.72 2.62 2.97 3.00 3.05 2.42 2.23 0.49 2.07 0.04 2.17 2.28 2.62 3.01 3.4* MnO 0.08 0.04 0.04 0.13 0.06 0.07 0.17 0.09 0.07 0.14 0.04 0.20 0.02 0.08 0.07 0.04 0.05 0.08* TiO2 0.54 0.67 0.43 1.01 0.63 0.65 0.58 0.64 0.52 0.56 0.06 0.52 0.01 0.89 0.81 0.67 0.72 0.5* P2O5 0.15 0.06 0.08 0.44 0.22 0.21 0.27 0.38 0.10 0.19 0.03 0.11 0.01 0.06 0.06 0.07 0.07 0.16* LOI 5.27 4.63 6.11 3.30 6.05 4.92 4.80 3.09 8.74 8.42 40.02 19.44 43.53 6.34 7.33 5.85 6.41 — Zr 159.0 298.0 144.0 181.0 206.0 187.0 165.0 160.0 202.0 145.0 23.50 109.00 10.30 275.0 229.0 188.0 196.0 190* Th 9.89 11.60 9.73 6.05 9.13 7.56 7.02 7.47 9.14 10.40 1.00 10.31 0.48 14.20 12.60 12.60 13.30 10.7* U 2.62 2.80 2.19 1.76 2.25 2.23 1.93 1.79 2.82 4.02 2.69 5.34 2.07 2.75 2.93 3.06 3.19 2.8* CIA 65.26 67.25 82.30 51.49 61.68 65.20 63.81 57.40 59.10 80.83 67.10 85.74 70.70 79.94 82.30 79.46 75.44 40.2 注：*上陆壳元素平均含量（UCC）（Taylor et al., 1985）；LOI.烧失量；R.基岩；C.母质层；B.淀积层；A.淋溶层；CIA.化学蚀变指数，CIA=Al2O3/[（Al2O3+K2O+Na2O+CaO*）]×100，摩尔比，CaO*采用S.M. Mclennan（1993）方法校正。
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表 3 岩石风化剖面重金属（mg/kg）、有机质（%）含量及pH值
Table 3. Characteristics of average contents of heavy metals in soils from rocks Concentrations of heavy metals (mg/kg), organic matter (%) and pH value in rock weathering profles
母岩 剖面 分层 重金属元素 pH值 有机质 As Cd Cr Cu Hg Zn Ni Pb 石英二长斑岩 KY1 A 3.51 0.26 38.60 61.00 0.024 99.30 17.40 71.00 6.38 1.26 B 4.76 0.10 44.50 58.30 0.03 57.30 18.80 26.80 5.06 0.98 C 3.49 0.07 38.50 51.20 0.01 43.80 14.20 19.50 5.45 0.35 R 1.77 0.13 78.60 63.20 0.003 110.00 61.70 16.30 — — 石英闪长斑岩 KY3 A 6.05 0.17 34.5 32.7 0.035 82.7 20.7 23.3 7.13 2.25 B 5.46 0.09 29.7 33.2 0.024 76.3 21.4 20.8 7.83 0.71 C 12.1 0.11 26.7 46.9 0.018 68.5 22.1 58.6 7.44 0.47 R 3.65 0.05 22.10 25.10 0.003 73.00 17.6 12.30 — — 长石石英砂岩 KY7 A 20.00 0.13 87.80 41.20 0.039 135.00 35.60 86.30 5.58 0.83 B 22.80 0.12 96.00 49.90 0.035 173.00 43.40 101.00 5.53 0.81 C 29.60 0.28 63.8 56.20 0.033 239.00 31.50 140.00 5.66 0.40 R 26.00 0.28 61.2 50.9 0.029 240 35.3 159 — — 细晶灰岩 KY8 A 18.9 0.56 47.5 29.2 0.051 101.00 20.70 48.10 8.09 2.51 B 49.00 0.37 95.3 53.3 0.04 183.00 47.80 46.30 8.15 0.77 R 11 0.34 9.53 8.83 0.01 56.30 6.65 13.80 — — 含生物屑微晶-
细晶灰岩KY9 B 224.00 5.37 194.00 44.50 0.31 221.00 111.00 36.80 8.35 0.89 R 4.70 0.26 13.10 1.35 0.022 8.76 1.74 1.99 — — 宁镇扬丘陵深层（150～200 cm）
土壤背景值（廖启林，2004）11.3 0.094 84 29 0.03 69 38 24.5 — — 农用地土壤风险筛选值
（GB 15618-2018）5.5＜pH≤6.5 30 0.4 250 50 0.5 200 70 100 — — 6.5＜pH≤7.5 25 0.6 300 100 0.6 250 100 140 — —
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表 4 重金属与主量元素含量相关系数（r）
Table 4. The correlation coeficient (r) between heavy metals and major elements content
SiO2 Al2O3 Fe2O3 FeO MgO CaO Na2O K2O MnO OM pH CIA As −0.975** 0.226 0.564 −0.079 0.164 0.960** −0.486 −0.542 0.711** −0.091 0.458 0.512 Cd −0.948** 0.114 0.435 −0.010 0.042 0.983** −0.380 −0.477 0.670* −0.004 0.459 0.397 Cr −0.901** 0.328 0.738** −0.113 0.164 0.814** −0.703* −0.772** 0.596* −0.150 0.256 0.710** Cu 0.108 0.346 0.356 −0.642* −0.055 −0.167 −0.357 −0.126 −0.048 −0.580* −0.531 0.394 Hg −0.949** 0.087 0.456 0.023 0.050 0.978** −0.390 −0.522 0.657* 0.024 0.447 0.403 Zn −0.634* 0.460 0.776** −0.140 0.444 0.446 −0.622* −0.523 0.328 −0.202 0.144 0.633* Ni −0.965** 0.330 0.701* −0.106 0.272 0.886** −0.572 −0.623* 0.709** −0.150 0.400 0.612* Pb 0.039 0.310 0.532 −0.266 0.264 −0.229 −0.325 −0.117 −0.129 −0.269 −0.383 0.325 OM 0.050 −0.659* −0.664* 0.971** −0.329 0.117 0.508 −0.105 −0.153 1 0.342 −0.624* pH −0.564 0.015 −0.100 0.416 0.487 0.583* 0.264 0.08 0.674* 0.342 1 −0.245 CIA −0.481 0.695* 0.839** −0.574 0.104 0.291 −0.963** −0.621* 0.202 −0.624* −0.245 1 注：**. 在 0.01 水平（双侧）上显著相关，*. 在 0.05 水平（双侧）上显著相关。
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表 5 剖面土壤重金属元素质量平衡系数
Table 5. The mass-balance calculation of heavy metal elements in profiles
岩石 剖面 τAs τCd τCr τCu τHg τZn τNi τPb 平均值 石英二长斑岩 KY1-A 1.26 1.28 −0.44 0.10 8.11 0.03 −0.68 3.96 1.70 KY1-B 0.63 −0.53 −0.66 −0.44 5.07 −0.68 −0.81 0.00 0.32 KY1-C 1.48 −0.32 −0.38 0.02 3.19 −0.50 −0.71 0.50 0.41 平均值 1.12 0.14 −0.49 −0.11 5.46 −0.39 −0.73 1.49 0.81 石英闪长斑岩 KY3-A 0.29 1.75 0.21 0.01 8.06 −0.12 −0.09 0.47 1.32 KY3-B 0.28 0.60 0.15 0.13 5.84 −0.11 0.04 0.45 0.92 KY3-C 2.21 1.22 0.17 0.81 4.82 −0.09 0.22 3.62 1.62 平均值 0.93 1.19 0.18 0.32 6.24 −0.11 0.06 1.51 1.29 长石石英砂岩 KY7-A −0.45 −0.67 0.02 −0.42 −0.04 −0.60 −0.28 −0.61 −0.38 KY7-B −0.25 −0.63 0.34 −0.16 0.03 −0.38 0.05 −0.46 −0.18 KY7-C 0.19 0.04 0.09 0.15 0.19 0.04 −0.07 −0.08 0.07 平均值 −0.17 −0.42 0.15 −0.14 0.06 −0.31 −0.10 −0.38 −0.17 青龙灰岩 KY8-A −0.80 −0.81 −0.42 −0.62 −0.41 −0.79 −0.64 −0.59 −0.63 KY8-B −0.28 −0.82 0.62 −0.02 −0.35 −0.47 0.16 −0.46 −0.20 平均值 −0.54 −0.82 0.10 −0.32 −0.38 −0.63 −0.24 −0.53 −0.42 栖霞灰岩 KY9-B 3.50 0.95 0.40 2.11 0.33 1.38 5.03 0.75 1.81
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