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Geochemistry of Mine Stream Sediments and the Control on Potentially Toxic Element Migration: A Case Study from the Baccatoio Basin (Tuscany, Italy)

Geochemie von bergbaulich geprägten Bachsedimenten und die Regulierung der Ausbreitung von potentiell toxischen Elementen – Eine Fallstudie aus dem Baccatoio Becken (Toskana, Italien)

Geoquímica de los sedimentos de los arroyos mineros y control de la migración de elementos potencialmente tóxicos - Un estudio de caso de la cuenca de Baccatoio (Toscana, Italia)

矿区河流沉积物地球化学及潜在有毒元素迁移控制—以Baccatoio盆地(意大利托斯卡纳)为例

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Abstract

The concentration of 14 potentially toxic elements (PTE), including emerging contaminants, was determined in mine tunnel sludges, streambed sediments, and in the bank-full channel load of the Baccatoio stream, in Tuscany (Italy), in a catchment affected by AMD. The geochemical profile of streambed piston-cored sediments and the solute concentrations of the hyporheic pore water and surface water were also determined. Sediments are characterized by high concentrations of As, Cd, Tl, Sb, Ni, Cu, Zn, besides Al, Mn, and Fe. The As and Fe are closely coupled, indicating that iron oxyhydroxide precipitation plays a major role in controlling As sequestration. Mn oxides likely act as a sorbent for Zn, Ni, Sb, and Pb. Downstream geochemical trends indicate that precipitation and sorption represent the natural attenuation processes controlling the PTE loading released from the contaminated acidic effluents. The obtained results highlight that the Baccatoio stream sediments may act as secondary pollution sources via redox cycling, allowing contaminant remobilization to surface- and ground-water across the streambed, affecting the stream environment and aquatic biota.

Zusammenfassung

Die Konzentrationen von 14 potentiell toxischen Elementen (PTE) einschließlich neu auftretender Schadstoffe wurde in Schlamm aus Bergbaustollen, Sedimenten aus einem Bachbett und aus dem Hauptkanal des Baccatoio Bachs in einem durch AMD geprägten Einzugsgebiet in der Toskana (Italien), untersucht. Darüber hinaus wurde auch das geochemische Profil von mittels Kolbenkernprobenehmer entnommener Sedimente sowie die gelösten Konzentrationen des hyporheisches Porenwassers und Oberflächenwassers bestimmt. Die Sedimente werden neben Al, Fe und Mn durch hohe Konzentrationen von As, Cd, Cu, Ni, Sb, Tl und Zn charakterisiert. Die enge Verknüpfung von As und Fe weist darauf hin, dass die Ausfällung von Eisenoxyhydroxiden eine entscheidende Rolle bei der Abscheidung von As spielt. Manganoxide sind mutmaßlich ein Sorbent für Ni, Pb, Sb und Zn. Geochemische Trends entlang des Fließpfades weisen darauf hin, dass die natürliche Ausfällung und Sorption die stromab gerichtet Befrachtung des Fließgewässers mit PTE aus den kontaminierten, sauren Abflüssen bestimmen. Die Ergebnisse der Studie zeigen, dass die Baccatoio Sedimente infolge natürlicher Redoxprozesse als sekundäre Schadstoffquellen wirken können. Dies ermöglicht eine Schadstoff-Remobilisierung in die Grund- und Oberflächenwasserressourcen im Bereich des Bachbetts, welche die Fließgewässerökologie und aquatischen Biota beeinträchtigt.

Resumen

Se determinó la concentración de 14 elementos potencialmente tóxicos (ETP), incluidos los contaminantes emergentes, en los lodos de los túneles de la mina, en los sedimentos del cauce y en la carga del cauce del arroyo Baccatoio, en la Toscana (Italia), en una cuenca afectada por AMD. También se determinó el perfil geoquímico de los sedimentos con núcleo de pistón del arroyo y las concentraciones de solutos del agua de poro hiporreica y del agua superficial. Los sedimentos se caracterizan por sus altas concentraciones de As, Cd, Tl, Sb, Ni, Cu, Zn, además de Al, Mn y Fe. El As y el Fe están estrechamente acoplados, lo que indica que la precipitación de oxihidróxido de hierro desempeña un papel importante en el control del secuestro de As. Los óxidos de Mn probablemente actúan como sorbentes para el Zn, Ni, Sb y Pb. Las tendencias geoquímicas aguas abajo indican que la precipitación y la sorción representan los procesos naturales de atenuación que controlan la carga de TEP liberada por los efluentes ácidos contaminados. Los resultados obtenidos destacan que los sedimentos del arroyo Baccatoio pueden actuar como fuentes secundarias de contaminación a través del ciclo redox, permitiendo la removilización de contaminantes a las aguas superficiales y subterráneas a través del lecho del arroyo, afectando al medio ambiente del arroyo y a la biota acuática.

抽象的

测定了意大利托斯卡纳(Tuscany)地区受酸性矿山废水(AMD)影响的Baccatoio河的河道淤泥, 河床沉积和平滩河道泥沙的14种潜在有毒元素(PTE)和新出现污染物的浓度. 测定了河床沉积物柱状岩芯的地球化学剖面以及潜流孔隙水和地表水的溶质浓度. 河床沉积物特征表现为除Al、Mn和Fe外, 还含有高浓度As, Cd, Tl, Sb, Ni, Cu和Zn. As与Fe密切耦合, 表明铁氢氧化物的沉淀过程对As捕获封存起控制作用. 锰氧化物很可能是Zn, Ni, Sb和Pb的吸附剂. 下游地球化学趋势表明, 沉淀和吸附是控制酸性污染废水(AMD)释放潜在有毒元素(PTE)负荷的主要自然衰减过程. 研究进一步表明, Bacatoio河流沉积物可能通过氧化-还原循环作用成为二次污染源, 污染物穿过河床再次迁移到地表水和地下水, 影响河流环境和水生生物.

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Acknowledgements

M. D’Orazio performed ICP-MS and HHXRF analysis on the sediments and is sincerely acknowledged. I. Baneschi helped during sediment coring. C. Biagioni is thanked for helpful discussions.

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Authors and Affiliations

  1. Dipartimento di Scienze della Terra, Università di Pisa, via S. Maria 53, 56126, Pisa, Italy

    Lisa Ghezzi, Roberto Giannecchini & Riccardo Petrini

  2. Dipartimento di Scienze della Terra, Università di Firenze, via La Pira 4, 50121, Firenze, Italy

    Antonella Buccianti

  3. IGG-CNR, via G. Moruzzi 1, 56124, Pisa, Italy

    Antonella Buccianti & Massimo Guidi

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Fig. 1S

Concentrations (mg/kg) of a Fe, Al, Mn, Ni, Cu, Zn, As, and Cd, and b Sb, Tl, Pb, Sr, and Ba in bank-full channel sediment samples, ordered from the headwater downstream stations. The distance from head source is also labelled in (b). Solid line: 0–20 cm depth; dashed line: 40–80 cm depth (PPTX 72 KB)

Supplementary file2 (PPTX 61 KB)

Fig. 2S

Fe, As, Sr, Ba, S, Ni, Mn, Sb (a) and Pb, Zn, Ca, K (b) concentration (mg/kg) profile in streambed sediment core (PPTX 57 KB)

Supplementary file4 (PPTX 49 KB)

Fig. 3S

a Fe(II) oxidation rate and b Fe(II) concentration pattern in the Baccatoio stream water increasing distance from Pollone AMD input to station C7-2 (PPTX 42 KB)

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Ghezzi, L., Buccianti, A., Giannecchini, R. et al. Geochemistry of Mine Stream Sediments and the Control on Potentially Toxic Element Migration: A Case Study from the Baccatoio Basin (Tuscany, Italy). Mine Water Environ 40, 722–735 (2021). https://doi.org/10.1007/s10230-021-00789-9

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