Characterization of Acid Mine Drainage-Influenced Sediments near

Huanuni Mine, Bolivia: A Preliminary Mineralogical Study

Isabella Conelian Fabbrona, *, Jérémie Garniera, b
a University of Brasilia, Institute of Geosciences, Graduate Program in Geology. Asa Norte, 70910-900, Brasilia, DF,
Brazil
bJoint International Laboratory LMI OCE “Observatory of Environmental Change’, UnB/IRD, 70910-900, Brasilia,
Distrito Federal, Brazil

*Corresponding author.
E-mail address: Isabella.fabbron@gmail.com (I.C.Fabbron).

Highlights

• Secondary sulfates, such as jarosite and melanterite, reveal AMD processes in mining
zones.
• X-ray diffraction reveals the absence of crystalline iron oxides, suggesting amorphous
phases.
• Metal mobility is influenced by sulfides and secondary mineral phases in AMD areas.

Abstract
Acid mine drainage (AMD) is a persistent environmental challenge, resulting from the oxidation
of sulfide minerals such as pyrite, leading to the release of metals and acidity into surrounding
ecosystems. This study focuses on the Huanuni mining district in Bolivia, an area heavily
affected by AMD, to characterize the mineralogical composition of sediments and evaluate
metal mobility. Four sediment samples were analyzed using X-ray diffraction (XRD) to identify
primary and secondary mineral phases. Primary minerals, including quartz, rutile, and illite,
reflect the geological background, while secondary minerals, such as jarosite,
hydroniumjarosite, copiapite, coquimbite, and melanterite, highlight the influence of AMD
processes. The detection of sulfide minerals, including pyrite and pyrrothite, further emphasizes
the region’s mining impact. Secondary sulfates and sulfides were found to contribute
significantly to metal mobility and acidity transfer, posing risks to downstream ecosystems. The
absence of crystalline iron oxides or hydroxides suggests poorly crystalline phases undetectable
by XRD. To better understand metal associations and environmental risks, complementary
analyses, such as SEM-EDS and sequential extraction, are recommended. This preliminary
study provides essential insights into AMD impacts and supports future remediation efforts for
the Huanuni mining district.

Keywords: Acid mine drainage, Huanuni, Sulphates, X-ray diffraction, Metal mobility
1. Introduction
Acid Mine Drainage (AMD) is a major environmental challenge associated with mining
activities around the world. It arises when sulfide minerals, primarily pyrite (FeS₂), are exposed
to oxygen and water, producing sulfuric acid. This acid dissolves and spreads heavy metals and
metalloids like copper (Cu), lead (Pb), zinc (Zn), arsenic (As), and cadmium (Cd) into nearby
soils and water, creating toxic conditions that harm ecosystems and pose health risks (Blowes et
al., 2014; Nordstrom and Alpers, 1997). Due to its persistence and severe environmental impact,
AMD remains a critical concern, particularly in fragile ecosystems and regions with a long
history of mining.
The mobility, transport, and toxicity of metals in AMD environments are highly influenced by
geochemical factors such as pH, redox potential, and secondary mineral formation, which
control metal solubility and movement (Alpers and Blowes, 1993). Under the low pH conditions
typical of AMD sites, metals remain dissolved and mobile, spreading through surface and
groundwater, which complicates treatment efforts (Daraz et al., 2023; Jamieson et al., 2015).
Research conducted in regions such as the Iberian Pyrite Belt and Appalachian coalfields has
shown that these conditions exacerbate AMD's environmental impact, leading to contamination
that can persist for decades or even centuries (DRISCOLL et al., 2001; Sarmiento et al., 2012).
Studies in AMD-affected sites, such as the Pan de Azúcar mine in Argentina, have documented
the formation of secondary minerals like jarosite, melanterite, and coquimbite, which play a
critical role in metal storage, acidity transfer, and seasonal mobility in semi-arid climates
(Murray et al., 2014).
While significant research has been conducted on AMD in various global mining regions, few
studies have specifically focused on the Huanuni mining district in Bolivia, an area with a long
history of mineral extraction. AMD heavily impacts the Huanuni district, which drains toward
the Poopó Lake Basin. Identifying the sources of contamination, as well as understanding the
mobility and environmental risks of metals in this specific mining area, is essential for
developing sustainable environmental management practices.
In this work, we present preliminary results from mineralogical analyses of AMD-impacted
sediments in the Huanuni district. These initial findings aim to provide an early understanding
of metal distribution patterns and mineral phases of sediments in AMD-affected zones.
2. Geological Background
The Poopó Lake Basin, located in the Bolivian Altiplano, is an extensive endorheic watershed
characterized by its high-altitude semi-arid climate and significant mining activity. Positioned in
the Oruro Department of Bolivia, this basin encompasses Lake Poopó, a shallow saline lake
covering approximately 2,500 square kilometers, which has historically been impacted by
inflows from regional mining operations. The lake serves as a terminal sink for runoff and
effluents from mining sites, leading to the accumulation of metal-rich sediments and waters with
elevated acidity.
The Poopó Basin hosts two prominent mining districts, Huanuni and Morococala, which are
both integral parts of Bolivia’s central Andean Tin Belt (Mlynarczyk and Williamsjones, 2005).
These districts have a long history of mineral extraction, focusing on economically significant
metals such as tin (Sn), lead (Pb), silver (Ag), and zinc (Zn).
The Huanuni mining district, located approximately 45 km southeast of Oruro, is a major tin
producer. The mineralization is hosted within Ordovician to Cretaceous sedimentary formations,
including the Llallagua and Uncía formations Only capitalized when a name, which comprise
quartzites, sandstones, and shales. Structural deformation resulting from Andean orogeny events
created fault and fold systems that were later intruded by Miocene porphyritic dikes. These
intrusions provided the hydrothermal fluids essential for mineral deposition (references needed).
The central parts of the district are dominated by cassiterite (SnO₂) and stannite (Cu₂FeSnS₄),
whereas peripheral areas have higher concentrations of sphalerite (ZnS) and galena (PbS),
reflecting a thermal mineral zonation (Cacho et al., 2019).
3. Materials and Methods
Contamination in the Poopó Lake Basin was assessed, focusing on the tributaries of the
Desaguadero River near the Huanuni mining district. A total of 4 sediment samples from
riverbed soils were collected and analyzed for their mineralogical properties.
The mineralogical composition of sediment samples was determined using X-Ray Diffraction
(XRD) analysis. The samples were first dried at room temperature and then powdered to ensure
a uniform particle size and minimize orientation effects. The powdered samples were mounted
on glass sample holders to create a flat and evenly distributed surface suitable for diffraction.
Measurements were conducted on a Rigaku Ultima IX diffractometer in the X-ray Diffraction
Laboratory of the University of Brasília (UnB), using CuKα radiation (λ = 1.54056 Å). The
equipment was operated at 40 kV and 40 mA. Diffraction patterns were recorded over a 2θ
range of 2° to 60° with a step size of 0.05° and a scan speed of 5° per minute.
The identification of mineral phases was performed using the International Centre for
Diffraction Data (ICDD) PDF-2 database with the aid of the Jade® 9 software for interpretation
of diffraction patterns. While this method provided reliable identification of crystalline phases
and an overview of mineralogical composition, it has limitations. XRD is less sensitive to
detecting amorphous materials or poorly crystalline phases, which may be present in significant
amounts but remain unidentified. Additionally, factors such as overlapping peaks and
preferential orientation in the samples could affect the accuracy of phase quantification
(Alderton, 2021). These limitations are inherent to the XRD technique and should be considered
when interpreting the results.
4. Results
The X-ray diffraction analysis of four sediment samples from the Huanuni mining district
revealed the presence of both primary and secondary minerals (Table 1), reflecting the influence
of detrital sources and acid mine drainage (AMD) processes. Peaks in the diffractograms
corresponded to several distinct mineral phases, and their identification provided insights into
the geochemical processes occurring in the region (Fig.1).

The primary minerals identified include quartz, the most abundant phase across all
samples, and illite, a clay mineral classified as a primary phase in this study due to its
association with the sediment’s original geochemical conditions. Both minerals
displayed strong and well-defined peaks, confirming their crystallinity and prevalence.
Rutile was also present as a minor but consistent phase, suggesting its origin from
stable, weathering-resistant detrital inputs.
Table 1. Identified primary and secondary minerals in sediment samples from the Huanuni mining district based on
X-ray diffraction analysis.

The secondary minerals identified reflect the AMD impact on the sediment composition.
Jarosite and hydroniumjarosite were detected, with their characteristic peaks indicative of
sulfide oxidation under acidic conditions. Sulfate-rich phases such as copiapite, coquimbite and
melanterite were identified, highlighting the dissolution and precipitation processes driven by
the interaction of AMD with the surrounding environment. Minor amounts of alunogen were
also detected, further supporting the acidic and sulfate-rich conditions.
Sulfide minerals were represented by pyrite and pyrrothite, which were prominent in several
samples and consistent with mining-related sulfide mineralization in the district. Sphalerite was
detected in certain samples, reflecting the region’s zinc mineralization. Additionally, the
identification of diaspore and schorl suggests contributions from aluminosilicate-rich sources,
likely associated with the geological formations of the area.
The absence of detectable crystalline iron oxides or hydroxides, likely due to poor crystallinity,
underscores the need for complementary methods to capture these phases.
Figure 1. X-ray diffraction patterns of sediment samples from the Huanuni mining district. The diffractograms
illustrate the presence of primary minerals and secondary minerals identified through characteristic diffraction peaks.
List of abbreviations: qtz = quartz, cop = copiapite, coq = coquimbite, jt = jarosite, hjt = hydroniumjarosite, dia =
diaspore, sch = schorl, rut = rutile, alu = alunogen, mel = melanterite, gyp = gypsum, il = illite, py = pyrite, pyr =
pyrrhotite, sph = sphalerite.

5. Discussions and Conclusion

The mineralogical analysis of sediments from the Huanuni mining district reveals the interplay
between primary phases and secondary minerals formed under the influence of acid mine
drainage (AMD). Quartz and rutile, identified as primary phases, reflect the region's geological
background due to their chemical stability and resistance to weathering. Illite, while often
formed during diagenetic processes, is considered a primary phase due to its presence as a
dominant mineral associated with the sediment’s background. Together, these minerals highlight
the influence of both detrital contributions and in-situ mineral formation.
Secondary minerals identified in the samples, including jarosite, hydroniumjarosite, copiapite,
coquimbite, and melanterite, are indicative of intense AMD processes. These minerals form
because of sulfide oxidation, primarily from pyrite and pyrrothite, under acidic and sulfate-rich
conditions. The detection of melanterite in one sample underscores localized conditions of high
sulfate concentration and minimal oxidation, further demonstrating the heterogeneity of AMD
impacts within the region. These observations align with findings in other AMD-affected mining
areas where secondary sulfates are characteristic products of sulfide mineral alteration.
The absence of detectable crystalline iron oxides or hydroxides in the samples suggests these
phases may be poorly crystalline or amorphous, which are undetectable by XRD. This
characteristic is common in AMD environments, where iron precipitates in less ordered forms.
Advanced methods such as SEM-EDS and Mössbauer spectroscopy could further elucidate the
composition and distribution of these phases and their role in AMD processes. Additionally,
sequential extraction and microanalytical techniques are recommended to assess metal mobility,
stability, and associated environmental risks. These findings provide a foundation for
understanding AMD impacts and developing effective remediation strategies in the Huanuni
mining district.
Funding
This research did not receive any specific grant from funding agencies in the public, commercial,
or not-for-profit sectors.
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.
CRediT authorship contribution statement
Isabella Conelian Fabbron: Writing– review & editing, Writing original draft, Visualization,
Validation, Methodology, Conceptualization. Jérémie Garnier: Writing– review & editing,
Visualization, Supervision, Resourses Project administration, Conceptualization.
Acknowledgments
We thank Tati de Almeida and Frédéric Satgé for fieldwork support.
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