Copper isotope fractionation and transformation at the acid mine drainage-sediment interface in mining areas

LIU De-hong; CAO Kai-wen; LIAO Wen; HOU Dong-mei; ZHONG Song-xiong

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China Environmental Science ›› 2026, Vol. 46 ›› Issue (3) : 1533-1542.

Environmental Ecology

Copper isotope fractionation and transformation at the acid mine drainage-sediment interface in mining areas

LIU De-hong¹, CAO Kai-wen^1,2, LIAO Wen³, HOU Dong-mei², ZHONG Song-xiong¹

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Abstract

The heavy metal copper (Cu) in acid mine drainage (AMD) is an essential element for organisms but potentially toxic. To control its environmental impact, it is necessary to investigate the factors that influence Cu migration in AMD-sediment interfaces. This study investigated the isotopic composition and fractionation characteristics of Cu in AMD systems from three different mining areas in central China. By coupling these isotopic signatures with detailed physicochemical analyses, we elucidated the key factors and mechanisms controlling Cu adsorption and migration. The results revealed that the Cu isotope fractionation between solutions and sediments in the Dingjiashan gold-copper-sulfur mining area, the Guanchao lead-zinc mining area, and the Qiaolichong polymetallic mining area ranged from (0.3±0.01)‰ to (1.5±0.07)‰, (0.61±0.01)‰, and (1.03±0.02)‰, respectively. This indicates that Cu isotope fractionation in AMD systems varies across mining areas and at different locations within the same mining area. The trends in the primary Cu species in sediments are consistent with those in AMD systems, and exhibit a clear pattern: as sediment Fe-oxide content and the proportion of Fe-/Mn-oxide-bound Cu increase, the isotopic fractionation magnitude decreases; conversely, elevated sulfur/organic matters and a larger fraction of organic- sulfide-bound Cu amplify the fractionation scale, confirming that mineral adsorption and organic-sulfur complexation are the key factors governing Cu mobility and transformation in AMD systems. These results suggest that the characteristics of Cu stable isotope fractionation may serve as a potential tool to explore the key factors controlling Cu migration in AMD systems across different mining areas.

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acid mine drainage / sediment / copper / isotope fractionation / migration and transformation

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LIU De-hong, CAO Kai-wen, LIAO Wen, HOU Dong-mei, ZHONG Song-xiong. Copper isotope fractionation and transformation at the acid mine drainage-sediment interface in mining areas[J]. China Environmental Science. 2026, 46(3): 1533-1542

References

[1] Jones S N, Cetin B. Evaluation of waste materials for acid mine drainage remediation [J]. Fuel, 2017,188:294-309.
[2] Liakopoulos A, Lemiere B, Michael K, et al. Environmental impacts of unmanaged solid waste at a former base metal mining and ore processing site (Kirki, Greece) [J]. Waste Management & Research, 2010,28(11):996-1009.
[3] Frenkel A I, Korshin G V, Ankudinov A L. XANES study of Cu²⁺-binding sites in aquatic humic substances [J]. Environmental Science & Technology, 2000,34(11):2138-2142.
[4] Li D, Liu S A, Li S. Copper isotope fractionation during adsorption onto kaolinite: Experimental approach and applications [J]. Chemical Geology, 2015,396:74-82.
[5] Coutaud M, Méheut M, Glatzel P, et al. Small changes in Cu redox state and speciation generate large isotope fractionation during adsorption and incorporation of Cu by a phototrophic biofilm [J]. Geochimica et Cosmochimica Acta, 2018,220:1-18.
[6] Du Laing G, Rinklebe J, Vandecasteele B, et al. Trace metal behaviour in estuarine and riverine floodplain soils and sediments: a review [J]. Science of the total environment, 2009,407(13):3972-3985.
[7] Zheng X D, Han G L, Song Z L, et al. Biogeochemical cycle and isotope fractionation of copper in plant–soil systems: a review [J]. Reviews of Environmental Science and Biotechnology, 2024,23:21- 41.
[8] Mihaljevic M, Baieta R, Ettler V, et al. Tracing the metal dynamics in semi-arid soils near mine tailings using stable Cu and Pb isotopes [J]. Chemical Geology, 2019,515:61-76.
[9] Navarrete J U, Borrok D M, Viveros M, et al. Copper isotope fractionation during surface adsorption and intracellular incorporation by bacteria [J]. Geochimica et Cosmochimica Acta, 2011,75:784-799.
[10] Pokrovsky O S, Viers J, Emnova E E, et al. Copper isotope fractionation during its interaction with soil and aquatic microorganisms and metal oxy(hydr)oxides: possible structural control [J]. Geochimica et Cosmochimica Acta, 2008,72:1742-1757.
[11] Ratnayake D M, Tanaka R, Nakamura E. Novel nickel isolation procedure for a wide range of sample matrices without using dimethylglyoxime for isotope measurements using MC-ICP-MS [J]. Analytica Chimica Acta, 2021,1181:338934.
[12] Viers J, Grande J A, Zouiten C, et al. Are Cu isotopes a useful tool to trace metal sources and processes in acid mine drainage (AMD) context? [J]. Chemosphere, 2018,193:1071-1079.
[13] 肖文丹,叶雪珠,张棋,等.基于稳定同位素与多元素的土壤铅污染源解析 [J]. 中国环境科学, 2021,41(5):2319-2328. Xiao W D, Ye X Z, Zhang Q, et al. Source apportionment of lead pollution in soil based on the stable isotope and multi element characteristics [J]. China Environmental Science. 2021,41(5):2319- 2328.
[14] 刘明,杨雅迪,毕乃双,等.2015年调水调沙期间黄河悬浮颗粒Pb及其稳定同位素组成变化 [J]. 中国环境科学, 2019,39(7):3009-3017. Liu M, Yang Y D, Bi N S, et al. Variations of Pb and its stable isotopic composition of suspended particles in the Yellow River during water-sediment regulation scheme period in 2015 [J]. China Environmental Science, 2019,39(7):3009-3017.
[15] Shields W R, Goldich S S, Garner E L, et al. Natural variations in the abundance ratio and the atomic weight of copper [J]. Journal of Geophysical Research, 1965,70(2):479-491.
[16] Bigeleisen J. Chemistry of Isotopes: Isotope chemistry has opened new areas of chemical physics, geochemistry, and molecular biology [J]. Science, 1965,147(3657):463-471.
[17] Balistrieri L S, Borrok D M, Wanty R B, et al. Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water [J]. Geochimica et Cosmochimica Acta, 2008,72:311-328.
[18] Ryan B M, Kirby J K, Degryse F, et al. Copper isotope fractionation during equilibration with natural and synthetic ligands [J]. Environmental Science & Technology, 2014,48:8620-8626.
[19] Ehrlich S, Butler I, Halicz L, et al. Experimental study of the copper isotope fractionation between aqueous Cu(II) and covellite, CuS [J]. Chemical Geology, 2004,209:259-269.
[20] Jouvin D, Weiss D J, Mason T F M, et al. Stable isotopes of Cu and Zn in higher plants: evidence for Cu reduction at the root surface and two conceptual models for isotopic fractionation processes [J]. Environmental Science & Technology, 2012,46:2652-2660.
[21] Lv Y, Liu S A, Zhu J M, et al. Copper and zinc isotope fractionation during deposition and weathering of highly metalliferous black shales in central China [J]. Chemical Geology, 2016,445:24-35.
[22] Little S H, Munson S, Prytulak J, et al. Cu and Zn isotope fractionation during extreme chemical weathering [J]. Geochimica et Cosmochimica Acta, 2019,263:85-107.
[23] Liu Y, Xia Y, Wang Z, et al. Lithologic controls on the mobility of Cd in mining-impacted watersheds revealed by stable Cd isotopes [J]. Water Research, 2022,220:118619.
[24] Rennert T. Wet-chemical extractions to characterise pedogenic Al and Fe species–a critical critical review [J]. Soil Research, 2018,57(1): 1-16.
[25] Ren M, Zhuang Q, He X, et al. Speciation and possible origins of organosulfur compounds in rice paddy soils affected by acid mine drainage [J]. Environmental Science & Technology, 2024,58(17): 7357-7366.
[26] Li W Q, Jackson S E, Pearson N J, et al. Copper isotopic zonation in the Northparkes porphyry Cu-Au deposit, SE Australia [J]. Geochimica et Cosmochimica Acta, 2010,74:4078-4096.
[27] Wang R R, Yu H M, Cheng W H, et al. Copper migration and isotope fractionation in a typical paddy soil profile of the Yangtze Delta [J]. Science of the Total Environment, 2022,821:153201.
[28] 邹献中,陈勇,谢卓文,等.离子强度对可变电荷表面吸附性铜离子解吸的影响:高岭石 [J]. 土壤学报, 2018,55(3):664-672. Zou X Z, Chen Y, Xie Z W, et al. Effect of ionic strength on the desorption of copper ions adsorbed on variable-charge surfaces: Kaolinite [J]. Acta Pedologica Sinica, 2018,55(3):664-672.
[29] Fulton J L, Hoffmann M M, Darab J G, et al. Copper(I) and copper(II) coordination structure under hydrothermal conditions at 325℃: an X-ray absorption fine structure and molecular dynamics study [J]. The Journal of Physical Chemistry A, 2000,104(49):11651-11663.
[30] Peacock C L, Sherman D M. Copper (II) sorption onto goethite, hematite and lepidocrocite: a surface complexation model based on ab initio molecular geometries and EXAFS spectroscopy [J]. Geochimica et Cosmochimica Acta, 2004,68(12):2623-2637.
[31] Kimball B E, Mathur R, Dohnalkova A C, et al. Copper isotope fractionation in acid mine rainage [J]. Geochimica et Cosmochimica Acta, 2009,73(2009):1247-1263.
[32] Ijichi Y, Ohno T, Sakata S. Copper isotopic fractionation during adsorption on manganese oxide: effects of pH and desorption [J]. Geochemical Journal, 2018,52:e1-e6.
[33] 刘健,牛少勋,黄恩惠,等.酸性矿山废水灌溉对稻田土壤铁碳的影响及微生物群落结构响应 [J]. 中国环境科学, 2025,45(5):2654- 2663. Liu J, Niu S X, Huang E H, et al, Effects of acid mine drainage irrigation on iron and carbon in paddy soils and the response of microbial community structure [J]. China Environmental Science, 2025,45(5):2654-2663.
[34] Dotor-Almazan A, Armienta-Hernandez M A, Talavera-Mendoza O, et al. Geochemical behavior of Cu and sulfur isotopes in the tropical mining region of Taxco, Guerrero (southern Mexico) [J]. Chemical Geology, 2017,471:1-12.
[35] Liu S A, Teng F Z, Li S G, et al. Copper and iron isotope fractionation during weathering and pedogenesis: insights from saprolite profiles [J]. Geochimica et Cosmochimica Acta, 2014,146:59-75.
[36] Tang D M, Qin K Z, Su B X, et al. Sulfur and copper isotopic signatures of chalcopyrite at Kalatongke and Baishiquan: Insights into the origin of magmatic Ni-Cu sulfide deposits [J]. Geochimica et Cosmochimica Acta, 2020,275:209-228.
[37] 王小芳,李方晓,黄涛,等.安徽铜陵铜尾矿硫形态及硫同位素分布特征 [J]. 中国环境科学, 2019,39(4):1664-1671. Wang X F, Li F X, Huang T, et al. Distribution characteristics of sulfur species and isotopes in a copper tailing at Tongling, Anhui Province [J]. China Environmental Science, 2019,39(4):1664-1671.
[38] Bigalke M, Weyer S, Wilcke W. Copper isotope fractionation during complexation with insolubilized humic acid. [J]. Environmental Science & Technology, 2010,44:5496-5502.
[39] Sherman D M, Little S H. Isotopic disequilibrium of Cu in marine ferromanganese crusts: Evidence from ab initio predictions of Cu isotope fractionation on sorption to birnessite [J]. Earth and Planetary Science Letters, 2020,549:116540.
[40] He, L H, Liu, J H, Zhang, H, et al. Copper and zinc isotope variations in ferromanganese crusts and their isotopic fractionation mechanism [J]. Acta Oceanologica Sinica, 2021,40:43-52.
[41] Fonseca E M D A, Baptista J A, Mcalister J, et al. The role of the humic substances in the fractioning of heavy metals in Rodrigo de Freitas Lagoon, Rio de Janeiro-Brazil [J]. Anais da Academia Brasileira de Ciências, 2013,85(4):1289-1301.
[42] Mathur R, Godfrey L, Frimmel H E, et al. Copper isotopic evidence of microbial gold fixation in the Mesoarchean Witwatersrand Basin [J]. Geochimica et Cosmochimica Acta, 2025,388:114-126.