李延河, 武占辉,李洁祥,于振子, 张波, 王心义,等.平顶山煤田岩溶地热水中稀土元素的分布特征及其影响因素[J].河南理工大学学报（自然科学版）,2025,44(1):88-99.

LI Y H, WU Z H,LI J X, et al. The distribution characteristics and its influencing factors of rare earth elements in the karst geothermal water in Pingdingshan Coalfield[J]. Journal of Henan Polytechnic University(Natural Science) , 2025, 44(1): 88-99.

平顶山煤田岩溶地热水中稀土元素的分布特征及其影响因素

李延河1, 武占辉2,李洁祥2,3,4,于振子1,5, 张波1,5, 王心义2,3,4

1.平顶山天安煤业股份有限公司，河南 平顶山  467099;2.河南理工大学 资源环境学院，河南 焦作  454000;3.煤炭安全生产与清洁高效利用省部共建协同创新中心，河南 焦作  454000;4.河南理工大学 矿业研究院，河南 焦作  454000;5.中国平煤神马集团 炼焦煤资源开发及综合利用国家重点实验室，河南 平顶山  467099

摘要:目的 为了探究华北型煤田深部岩溶地热水中稀土元素地球化学行为的指示意义， 方法  以平顶山煤田为例，通过野外调查取样，室内测试，再结合稀土元素配分模式分析和赋存形态模拟等手段，探究深层岩溶地热水中稀土元素（rare earth elements， REEs）的分布特征与迁移规律。 结果 结果表明，寒武系灰岩含水层中REEs质量浓度较低（0.054~0.244 μg/L），沿径流路径呈下降趋势；稀土元素（post-archean Australian shale， PAAS）标准化配分模式表现为MREEs和HREEs相对富集，LREEs相对亏损，并且具有明显的Eu正异常和程度不一的Ce负异常，且Ce负异常程度和Eu正异常程度从补给区到排泄区呈降低趋势；水化学平衡软件MINTEQ 3.1模拟结果表明，地热水中REEs以Ln(CO₃)₂^-和LnCO₃⁺络合态为主，随原子序数增大或pH升高，摩尔分数明显增大，而LnCO3摩尔分数依次递减，另外，地热水中还存在少量LnSO₄⁺，Ln³⁺, LnHCO₃²⁺,LnF²⁺和Ln(SO₄)₂^-其摩尔分数随原子序数增大依次减小，同时受地热水pH和HCO₃^-，SO₄^2-，F^-浓度共同控制；此外，岩溶地热水中还表现出明显的Y正异常和高ρ（Y） /ρ（Ho），可能与地热水富集Ca2+有关。 结论 研究结果拓展了稀土元素在煤田水文地球化学研究中的应用，可为揭示矿区深部岩溶地热水补径排过程提供重要依据。

关键词:平顶山煤田;岩溶地热水;水化学;稀土元素

doi: 10.16186/j.cnki.1673-9787.2023010018

基金项目:国家自然科学基金资助项目（41972254）；河南省创新型科技人才队伍建设工程资助项目（CXTD2016053）；河南省高校基本科研业务费专项项目（NSFRF200103）

收稿日期:2023/01/09

修回日期:2023/05/04

出版日期:2025/01/02

The distribution characteristics and its influencing factors of rare earth elements in the karst geothermal water in Pingdingshan Coalfield

LI Yanhe1, WU Zhanhui2,LI Jiexiang2,3,4, YU Zhenzi1,5, ZHANG Bo1,5, WANG Xinyi2,3,4

1. Pingdingshan Tianan Coal. Co.， Ltd.， Pingdingshan  467099， Henan， China; 2. School of Resources and Environment， Henan Polytechnic University， Jiaozuo  454000， Henan， China; 3. Collaborative Innovation Center of Coal Work Safety and Clean High Efficiency Utilization， Jiaozuo  454000， Henan， China; 4. Institute of Mining and Technology Research， Henan Polytechnic University， Jiaozuo  454000， Henan， China; 5. State Key Laboratory of Coking Coal Exploitation and Comprehensive Utilization China Pingmei Shenma Group， Pingdingshan  467099， Henan， China

Abstract: Objectives In order to understand the indicative significance of the geochemical behavior of rare earth elements （REEs） in deep karst geothermal water of the coalfield in North China. Methods Taking the Pingdingshan coalfield as an example， the distribution characteristics and migration pattern of REEs in the deep karst geothermal water were investigated through field sampling， laboratory testing， combined with analysis of rare earth element distribution patterns and simulation of occurrence forms. Results This study shows that the contents of REEs in the Cambrian reservoirs in Pingdingshan coalfield is raletively low （0.054~0.244 μg/L）， and decrease along the flowing path. The standardized distribution pattern of rare earth elements （PAAS） shows a relative enrichment of MREEs and HREEs and a relative depletion of LREEs， and obvious Eu positive anomalies and varying degrees of Ce negative anomalies. The degree of Ce negative anomalies and Eu positive anomalies decreases from the recharge area to the discharge area. The simulation results of MINTEQ show that the REEs in the geothermal water are dominated by complex species of Ln(CO₃)₂^- and LnCO₃⁺ the proportion of Ln(CO₃)₂^- increases significantly with increasing atomic number or pH value， while the content of LnCO₃⁺ decreases sequentially. In addition， there are still small amount of LnSO₄⁺，Ln³⁺, LnHCO₃²⁺,LnF²⁺，and Ln(SO₄)₂^- species in the geothermal fluid， whose contents decrease sequentially with the atomic number， controlled by the pH as well as HCO₃^-，SO₄^2- and F^- contents of geothermal water. In addition， there are obvious Y positive anomalies and high ρ(Y）/ρ（Ho） in karst geothermal water， which is closely related to the enrichment of Ca2+ in geothermal water. Conclusions The research results expand the application of REEs in the study of coalfield hydrogeochemistry， and can provide a basis for revealing the recharge， runoff， and discharge processes of deep karst geothermal water in mining areas.

Key words: Pingdingshan Coalfield; karst geothermal waters; hydrochemistry; rare earth elements （REEs）