Contribution of mine-derived airborne particulate matter to Ca, Fe, Mn and S content and distribution in the lichen Punctelia hypoleucites transplanted to Bajo de la Alumbrera mine, Catamarca (Argentina)

doi:10.21203/rs.3.rs-3125412/v1

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Contribution of mine-derived airborne particulate matter to Ca, Fe, Mn and S content and distribution in the lichen Punctelia hypoleucites transplanted to Bajo de la Alumbrera mine, Catamarca (Argentina)

https://doi.org/10.21203/rs.3.rs-3125412/v1

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published 07 Feb, 2024

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The aim of this work is to relate the contribution of mine-derived airborne particulate matter to Ca, Fe, Mn and S content and distribution in Punctelia hypoleucites transplanted to Bajo de la Alumbrera, an important open-pit mine in Catamarca, Argentina. Lichen samples were transplanted to four monitoring sites: two sites inside the mine, and two sites outside the mine. After three months, elemental distribution in samples were analyzed by micro-Particle induced X-ray emission, and elemental concentration was determined by specific techniques: Ca and Fe by instrumental neutron activation analysis; Mn by inductively coupled plasma atomic emission spectrometry; S by a turbidimetric method. As a result, a differential distribution of S and Ca in thalli transplanted inside-mine sites was detected compared to that of samples transplanted outside-mine sites. An overlap of Fe and S in the upper cortex of the apothecium section was observed, leading to infer a mineral association of both elements. Similar association was observed for Ca and S. In addition to these results, the significantly higher concentration detected for S and Mn in inside-mine sites samples suggests a contribution of Fe, S, Ca and Mn of mining origin to the content and distribution of these elements in P. hypoleucites. Micro PIXE complemented with Mössbauer spectroscopy analysis determined the presence of pyrite particles together with other iron-bearing minerals with different degrees of oxidation were detected. These results point out to a mining origin of the airborne particulate matter trapped by the lichen thalli transplanted to Bajo de la Alumbrera.

Bioindicator

open-pit mining

micro PIXE

Mössbauer spectroscopy

Open-pit mining impacts air quality, mainly through the emission of particulate matter. This fact is due to the extraction process itself, as well as crushing, grinding and the existence of deposits of sterile waste, among other associated activities. This extractive method involves the removal of a large amount of rock materials, which can possibly be dispersed in an area beyond the mine.

Pollution generated in the mining process has detrimental effects on ecosystems, due not only to the physical effect that atmospheric particles can produce, but also to their chemical composition. Particles from metalliferous mining can contain sulfides, heavy metals, metalloids and other chemical species wich provoke adverse effects on organisms and the environment as a whole (Odumo et al. 2018).

Bajo de la Alumbrera, one of the most important open-pit mines in Argentina, is located in the central west of the province of Catamarca. As part of the environmental controls for this mining project, atmospheric particulate matter monitoring is carried out at a limited number of fixed stations outside and inside its area. However, data about sites further away from the mine, that are potentially affected by pollution, is a key issue. Obtaining this kind of information requires the simultaneous placement of a large number of sampling stations even in remote areas, which is difficult due to economic and technical reasons (Cañas et al. 2017).

An alternative to traditional air quality monitoring methods, with low cost and relatively fast implementation and execution, is the use of lichens. These organisms can be used as accumulative biomonitors due to their ability to absorb and/or retain various elements from the atmosphere, combined with their longevity and resistance to environmental stress (Loppi and Bonini 2000; Garty 2001).

A lichen is a self-sustaining ecosystem formed by the interaction of an exhabitant fungus and an extracellular arrangement of one or more photosynthetic partners and an indeterminate number of other microscopic organisms (Hawksworth and Grube 2020). Photobionts can be blue-green cyanobacteria and/or unicellular green algae. The most common mycobionts are ascomycetes. Lichen thalli are emergent systems that generate a great variety of vegetative structures, growth forms, reproduction and special biotypes (Barreno 2004). On the basis of their overall habit lichens are traditionally divided into three main morphological groups: these are crustose, foliose and fruticose types (Büdel and Scheidegger 2008).

Foliose lichens are leaf-like, flat and only partially attached to a substrate. Foliose thalli are either homoiomerous (gelatinous lichens) or heteromerous. Typically they have a dorsiventral organization with distinct upper and lower surfaces. Often the thallus is divided into lobes. Foliose lichens develop a great range of thallus size and diversity. The majority of lichens develop internally stratified thalli. The main subdivisions in foliose lichens are upper cortex, photobiont layer, medulla, and lower cortex (Fig. 1).

Figure 1. A- Punctelia hypoleucites thallus. B- Thallus lobe perpendicular section. C- Apothecium perpendicular section. D- Microscopy image of the apothecium perpendicular section. The different parts of the thallus are marked by arrows and letters. Such structures are divided in these layers. Uc: Upper cortex, al: Layer containing the photobiont (in this case alga), m: Medulla / loosely packed hyphae, Lc: Lower cortex, ep: Epimenium. hy: Hymenium, Lc: Lower cortex, em: Empty space.

As occurs in most fungi, the vast majority of lichenized ascomycetes have a sexual and an asexual life cycle. Sexual reproduction in most lichens, as in non-lichenised ascomycetes, takes place through the production of ascomata, structures containing asci and ascospores. The ascomata are composed of hyphae that form the hymenium. Underneath the hymenium a generative layer (i.e. subhymenium) is present, which gives rise to the hymenium. Sometimes a hypothecium, underlying the subhymenium, can be developed. In the upper part of the hymenium there is usually a layer (epithecium) rich in pigments and/or crystals (oxalates) (Fig. 1). This is surrounded by an excipulum of sterile hyphae. The most common types of ascomata are: perithecia, apothecia, mazedia and lirelas. The apothecia are open, cup-shaped or disc-shaped with the hymenium exposed to the outside and with epithecium (Barreno and Pérez-Ortega 2003).

Different mechanisms can explain the accumulation of pollutants in the lichen thallus including particule deposition onto the lichen surface or entrapment in the interhyphal spaces of the medulla, extracellular binding of cations and intracellular uptake (Garty et al. 1979; Bargagli and Mikhailova 2002; Backor and Loppi 2009). The entrapment of metal-containing particles has been analyzed in detail by Garty (2001), while the origin and mode of interception and incorporation of particulate matter has been reviewed by Garty and Garty-Spitz (2015).

Several analytical techniques have been used to determine the distribution and concentration of elements in the lichen thallus (Garty et al. 1979; Conti and Tudino 2016). According to Budka et al. (2004) elemental microanalysis allows more accurate air pollution studies compared to bulk (macro) analysis. In this sense, microPIXE (Particle Induced X-ray Emission with a scanning microprobe) allows simultaneous 2D mapping of main, minor and trace elements (Z > 11) of a sample with micrometric precision, providing a quantitative determination of trace elements concentration with high sensitivity (µg.g^− 1 range). The typical detection limits of this technique for most elements are in the range of 1 − 10 µg.g^− 1 (Stoliar et al. 2004).

The irradiation with heavy ion micro-beams of tens of MeV energy shows significant improvement of the detection limits when analyzing heavy elements (de la Fournière et al. 2020 and references therein). In this work, a 50-MeV ¹⁶O beam was employed.

Although it is possible to obtain information on the multi-elemental content of a sample by micro-PIXE, techniques such as INAA and ICP-OES are more suitable for determining the total content of the certain elements when the sample is a complex matrix, such us a biological tissue or a lichen thallus. According to Nečemer et al. (2008). the advantages of the INAA results are their independence from matrix effects, and from sample inhomogeneities due to the rather large effective sample mass from which the information about the elemental content is obtained. ICP-OES is more suitable for the determination when the element concentrations are below the limits of detection for INAA (Ebrahim et al. 2017). Thus, both INAA and ICP-OES allow to obtain a representative value of the elemental content of a lichen sample when it consists of several thalli conveniently crushed and homogenized for analytical purposes.

In mining areas, lichens have been used as passive biomonitors, i.e. as analyzers of the elemental accumulation in specimens in situ (Balabanova et al. 2009, 2012; Saunier et al. 2013; Odumo et al. 2014, 2018). They have also been used as active biomonitors through the application of transplantation techniques (Demková et al. 2019, 2020). With both methodologies, lichens have proven to be useful for estimating air pollution and the impact of mining activity on air quality.

Fifteen years ago, an air quality study with transplanted lichens was conducted within the Farallón Negro Volcanic Complex and its area of influence in the western region of Catamarca (Argentina). The study included four transplant sites: Bajo de la Alumbrera Cu-Mo mine and three localities potentially affected by mining emissions. In that study, P. austrosinense (Zahlbr.) Hale and Canomaculina consors (Nyl.) Elix and Hale were used as biomonitors. Active biomonitoring using both species showed to be suitable in order to relate air quality to natural or anthropogenic factors in the monitoring sites. Also, P. austrosinense and C. consors allowed to detect air pollutants from open-pit mining and proved that active biomonitoring is an adequate methodology to determine air quality in the study area (Cañas et al. 2017).

At present, the lichen Punctelia hypoleucites (Nyl.) Krog is being evaluated as bioindicator/biomonitor of air pollution in Bajo de la Alumbrera mining project and its surroundings. To interpret the bioindicator response it is important to know how the elements are distributed in different lichen structures. Knowing the origin of the accumulated elements is also important for associating this response to a specific source of pollution.

The aim of this work is to establish the contribution of mine-derived airborne particulate matter to Ca, Fe, Mn and S content and distribution in the biomonitor Punctelia hypoleucites transplanted to Bajo de la Alumbrera mine, Catamarca (Argentina).

2.1. Study area

The study area is located at the Central-Western region of Catamarca Province, in the extreme North of the morphostructural unit of the North-Western Pampean Ranges (Caminos 1979). The area is characterized by the presence of narrow valleys and wide closed intermountain depressions (bolsones), alternating with uplifted basement blocks whose western slopes are usually steeper than the eastern ones. Geologically, it consists of a precambrian igneous-metamorphic basement, mainly covered by quaternary alluvial deposits. The climate is warm arid; precipitations are very scarce with only about 150 to 300 mm per year, mostly in summer (about 60–70% of the total precipitation); prevailing winds blow from NE. Phytogeographically, it is located in the Monte Phytogeographic Province in the Chaqueño Domain of the Neotropical region (Morlans 1995).

In the region, there are important Au, Ag, Cu and Mo deposits currently in operation. The first large scale mining operation of Argentina - Bajo de la Alumbrera - is located there. It is an open-pit copper-gold-molibdenum (Cu-Au-Mo) mine, which corresponds to a porphyry-type deposit included in Farallón Negro volcanic complex (Gutiérrez et al. 2006). This mine began operating in 1997 and when this work began (2018) it was in the closure phase. In its place, a copper and gold deposit located 4 km from Bajo de la Alumbrera, Bajo El Durazno, was in open-pit mining and it has been in operation since 2015.

The study area is sparsely populated: the main locality is Andalgalá (12,600 inhabitants), the third largest city of the province. There are also little villages such as Amanao (29 inhabitants), Los Nacimientos (215 inhabitants) and Hualfín (987 inhabitants) (INDEC 2010). The four towns are located in intermountain depressions: Amanao and Andalgalá at the North end of the Bolsón de Pipanaco, Hualfin and Los Nacimientos in the Hualfin Valley. Given their relative proximity to Bajo de la Alumbrera, these human settlements are considered environmentally vulnerable. For this reason, Hualfin was chosen as a monitoring site for this study (Fig. 2).

Figure 2. A- Map of the study area showing the outside mine transplant sites (E7 and W). B- Map of Bajo de la Alumbrera showing inside mine sites (E1 and E8). The sources of particulate matter emissions from mining are also indicated (Open Pit, Durazno Pit, Tailings dam, Primary crusher, Stock pile and Flotation plant).

2.2. Mineralization

Bajo El Durazno deposit: Mineralization of Cu-Au and in minor proportion Ag and Mo present in the veins between the stock (andesitic porphyry) and bedrock, accompanied by quartz, calcite, magnetite, pyrite (FeS₂), chalcopyrite (CuFeS₂) and a minor content of sericite, chlorite, orthoclase, biotite, siderite, molybdenite, bornite, sphalerite, galena, tetrahedrite-tenantite and gold. Potassic Zone: potassium feldspar-biotite, in addition to disseminated mineralisation of pyrite and chalcopyrite with magnetite, hematite, bornite, sphalerite and molybdenite. Sericite-clay (or phyllic) zone: abundant sulphate minerals such as jarosite (KFe₃ ^+ 3(SO₄)₂(OH)₆), natrojarosite (NaFe₃(SO₄)₂(OH)₆), gypsum (CaSO₄), with greater dissemination and veinlets of pyrite than in the potassic zone. Propylitic zone: (the minerals are not described here but in the La Alumbrera deposit the typical associations of this alteration are named) (Allison 1986; Sasso 1997; Alderete 1999).

Bajo de la Alumbrera deposit: Primary mineralisation: chalcopyrite + pyrite ± magnetite. Potassic zone: gold-copper, secondary biotite-potassium feldspar-magnetite-quartz ± anhydrite. Propylitic zone: epidote-chlorite-albite ± magnetite. Phyllic zone (after potassic and propylitic alterations): Sericite-pyrite-quartz (González 1975; Godeas and Svetliza 1980; Sasso 1997; Angera 1999).

2.3. Sampling procedure

In february 2018, thalli of the lichen Punctelia hypoleucites (Nyl.) Krog were collected from a clean site within the North-Western Pampean Ranges region. Lichen bags were prepared and transplanted to four monitoring sites: two sites inside the mine closed to particulate matter emission sources (E1, E8), one 25 km away from the mine (E7) and another one 70 km away from the mine outside of Farallon Negro Volcanic Complex (W) (Fig. 2). At each transplant site, three bags were exposed for three months.

2.4. Elemental distribution analyses by micro PIXE.

2D ¹⁶O⁵⁺ maps of Ca, Fe, Mn and, S elemental concentration were obtained by micro PIXE, scanning a 50-MeV ¹⁶O⁵⁺ beam over cryosectioned lichen samples, at the Tandar accelerator (CNEA - Buenos Aires - Argentina). Data acquisition and processing were performed with the OMDAQ-3 (Oxford Microbeams Ltd, UK) computer code. In order to analyze the elemental distribution in lichen thalli, at least 2 lobes and 2 apothecia were separated from lichen bags and were immediately frozen by using the protocol of Llabador and Moretto (1998). A mounting medium (Cryoplast®, Biopack, Argentina) was employed to avoid ice crystals formation. Afterwards, transversal cross-sections of lichens (Fig. 3) were obtained using a cryomicrotome at the set temperature of -20°C to avoid ions migration which could alter in vivo distribution. Histological cross-sections were transferred to a 4 mm ultrapure polypropylene film supported by a polycarbonate washer and then freeze-dried (Southworth-Daviesa et al. 2007). Thin samples of 10 µm thickness can easily break during handling then special care was taken to only irradiate those cuts which kept cell integrity as tested by optical microscopy.

2.5. Analysis of elemental content

2.5.1. Analysis of Ca and Fe content (INAA)

Instrumental Neutron Activation Analysis (INAA) was used to determine Ca and Fe concentration (Jasan et al. 2011). Samples were ground in a Spex Centi Prep 6750 criogenic mill and lyophilized for 24 h. About 300 mg of lyophilized material was pelletized and wrapped-up in aluminum foil for irradiation, together with two certified reference materials, NIST SRM 1633b Coal Fly Ash and IAEA Lichen 336, for calibration purposes. Irradiations were done at the RA-3 reactor (thermal flux 3.10¹³ cm^− 2 s^− 1, 8 MW) of the Argentine National Atomic Energy Commission (Ezeiza Atomic Centre) for 4 h. Two measurements were performed after 7 and 30 day-decay using GeHP detectors (30% efficiency, 1.9 KeV resolution for 1332.5 KeV ⁶⁰Co peak), coupled to an Ortec 919E multichannel buffer module. Concentration of Ca and Fe were calculated using a software developed at NAA laboratory. GBW07405 soil was used as control sample. For all determined elements, experimental values showed good agreement with those in the material’s certificate. The concentration was expressed in mg g^− 1 dry weight.

2.5.2. Analysis of Mn content (ICP-AES)

An accurately weighed portion of each sample (0.5 g) was placed in a porcelain crucible and ashed at 600°C for 2 hours. The ashes were digested by adding 6 ml of a 5:1 mixture of HCl (36%) and HNO3 (65%) and heated until boiling. It was filtered under vacuum to separate the solid residue. Finally, the liquid fraction was diluted to a volume of 25 ml with ultrapure water (tridistilled and deionized). Analyses for Mn were conducted with a Perkin Elmer Optima 8300 inductive plasma coupling emission spectrophotometer (ICP-OES). Metal concentrations were calculated on a dry weight basis. The precision of analysis was estimated by the relative standard deviation of three replicates and was found to be 5–10%.

2.5.3. Certified Reference Materials

A standard reference solution NIST SRM #3132 (Merck) was used for the quality control of ICP-OES measurements and GBW07405 soil was used as control sample for INAA analysis. For all determined elements, experimental values showed good agreement with those in the material’s certificate.

2.5.4. Analysis of sulphur content.

So as to analyse the sulphur content, a 2.5 ml of Mg(NO₃)₂ saturated solution was added to 0.25 g of lichen samples and dried in an electric heater. Subsequently, the sample was heated in an oven for 2 h at 500°C. The ashes were then suspended in HCl 6M, filtered, and the resulting solution was boiled for 3 min. The solution was brought to 25 ml with tridistilled and deionized water. The amount of SO₄²⁻ in the solution was determined by turbidimetric method with barium chloride (González and Pignata 1994) which thus allowed for the calculation of sulphur content in each sample. The concentration was expressed in mg of total sulphur g^− 1 dry weight.

2.6. Statistical analysis

One way ANOVA was used to compare the elemental concentration of Punctelia hypoleucites transplanted to the monitoring sites. LSD Fisher´s test for multiple comparisons were made to identify sites with significantly different elemental content (p-value < 0.05).

2.7. Iron minerals identification -Mössbauer spectroscopy

Mössbauer Spectroscopy was performed in the transmission mode using a ⁵⁷Co source in a Rh matrix. Samples for this purpose were pulverized in an agate mortar and then compacted in an acrylic holder. The spectrum was collected at room temperature (RT) and then fitted with the Normos software (Brand 2010). Isomer shift (IS) values were taken relative to that of α-Fe at RT.

Elemental distribution maps corresponding to the different transplant sites show that Fe is only detected on the lichen surface, in the upper and lower cortex of thallus and epimenium of apothecium (Fig. 3–6).

Sulphur was preferentially distributed in the algal layer of lichen thallus lobe and apothecia of the off-mine and control site samples (Fig. 3, 4). A high concentration of sulphur in the algal layer was already reported by Budka et al. (2002), Clark et al. (1999) and Paul et al. (2003). The algal layer is metabolically the most active part of the lichen thallus, producing photosynthates that are necessary for the growth of the whole lichen (Palmqvist 2000).

For the samples corresponding to the inside-mine sites (E1 and E8) sulphur was located superficially in some sectors of the upper cortex and epimenium, in addition to the algal layer. Moreover, an overlap of S and Fe maximum concentration in the upper cortex of the apothecium section was observed, suggesting a mineralogical association of these elements (Fig. 5, 6). Mineralisation at Alumbrera is abundant in S and Fe-bearing compounds such as sulphides (pyrite and chalcopyrite) and sulphates (jarosite and natrojarosite) (Sasso 1997; Alderete 1999). The higher concentrations of Fe and S detected in thalli exposed at in-mine sites (Table 1) would contribute to associate these elements with the geochemistry of the deposit thus attributing their presence to particles of mining origin trapped in the lichen structures.

At all sites Ca is preferentially distributed in the medulla and in the epimenium (Fig. 3–6) High levels of Ca, in the form of oxalate crystal deposits have been observed in the medulla of some lichens (Baran and Monje 2008; Modenesi et al. 2000; Paul et al. 2003), suggesting that they have a physiological function. These deposits might serve as a kind of reservoir to provide minimal but essential water levels for the photosynthetic activity of the photobiont during prolonged dry periods and generate light reflection to the algal cells, therefore helping to maximize the efficiency of photosynthesis (Clark et al. 2001).

Figure 3. Elemental distribution (Ca, Fe, Mn, and S) in perpendicular section of structures that constitute this species (thallus lobe and apothecium), taken from the samples transplanted to the control site (W). Apothecium microscopy image from right to left shows epithecium, thecium, hypothecium, algal layer, medulla, algal layer, and upper cortex. Micro PIXE conditions: 50 MeV 16O5 + beam, scan size (300×300–500×500) µm² (see scale bar), spot size 5×5µm2. The pixels change colour from blue to red with the increase of the elemental concentration.

Figure 4. Elemental distribution (Ca, Fe, Mn, and S) in perpendicular section of two structures that constitute this species (thallus lobe and apothecium), taken from the samples transplanted to the outside-mine site (E7). Apothecium microscopy image from right to left shows epithecium, thecium, hypothecium, algal layer, medulla, algal layer, and upper cortex. Thallus lobe from bottom to top show upper cortex, algal layer, and medulla. Lower cortex is not distinguishable in this cut. Same micro PIXE conditions as in Fig. 3. Scan size (300 ×300–500×500) µm² (see scale bar).

Figure 5. Elemental distribution (Ca, Fe, Mn, and S) in perpendicular section of two structures that constitute this species (thallus and apothecium), taken from the samples transplanted to the in-mine site (E1). Apothecium microscopy image from right to left shows upper cortex, algal layer, medulla. Hypothecium, thecium, and epithecium, are not clearly distinguishable in this cut by the quality of the histological slice. Thallus lobe from bottom to top show upper cortex, algal layer, and medulla. Lower cortex is distinguishable in this cut. Same micro PIXE conditions as in Fig. 3. Scan size (300×300–500×500) µm² (see scale bar).

Figure 6. Elemental distribution (Ca, Fe, Mn, and S) in perpendicular section of two structures that constitute this species (thallus and apothecium), taken from samples transplanted to the in-mine site (E8). Apothecium microscopy image from right to left shows upper cortex, medulla, and algal layer. Epithecium, thecium, and hypothecium are not distinguishable in this cut. Thallus lobe from left to right show medulla, algal layer, and upper cortex. Lower cortex is not distinguishable in this cut. Same micro PIXE conditions as in Fig. 3. Scan size (450×450) µm² (see scale bar).

At the inside-mine site E8, Ca was also distributed in the upper cortex, although to a lesser extent. Mineralisation at Bajo El Durazno is rich in gypsum (CaSO₄) and calcite (CaCO₃) (Sasso 1997; Alderete 1999). Considering that the inside-mine sites are close to sources of particulate matter emissions from the mineralized zone, surface Ca could be associated with this source. Although the distribution of Ca in the lichen structures could therefore infer a mining origin, the concentration of this element in the thalli was similar in all transplant sites (Table 1).

The maps do not show a detailed Mn distribution in the lichen due to the fact that its concentration is much lower than that for the other elements. However, from the lobe maps corresponding to E1 and E8 sites and the apothecia map of E8 site, where more concentrated points can be identified in some sectors, Mn seems to have the same distribution as Fe (Fig. 3–6). It should be noticed that Mn is used as a mining indicator in Minera Alumbrera Ltd environmental impact reports (Alvarez 2017) and is a representative element of Bajo el Durazno and Bajo la Alumbrera deposits (Gutiérrez et al. 2006). A significantly higher concentration of Mn was detected in lichens transplanted to the E8 site in comparison to the other transplant sites (Table 1). This result, added to the similar distribution of Mn and Fe in the thalli transplanted to inside-mine sites, would allow to infer that both elements are associated to atmospheric particles of the same origin.

Table 1

Elemental concentrations (mean ± standard deviation) in lichens transplanted to inside-mine sites (E1, E8), an offside mine site (E7) and a control site (W).
Sites	Ca	Fe	Mn	S
W	49533 ± 7292	6153 ± 463ab	77 ± 13b	1668 ± 24b
E7	53133 ± 7427	5188 ± 97c	76 ± 6b	1416 ± 60c
E1	54933 ± 1021	5735 ± 678bc	80 ± 4b	1954 ± 177a
E8	53667 ± 2802	6757 ± 511a	102 ± 9a	1875 ± 165ab
ANOVA	NS	*	*	*

^{Values correspond to mean data obtained from the whole thalli. Values followed by the same letter do not differ significantly at a p < 0.05 (LSD Fisher´s test). NS: non−significant differences}.

The RT spectra for samples obtained from lichens transplanted to E1 and E8 sites (inside mine sites) are displayed in Fig. 7. The scarce amount of sample available from lichens transplanted to E1 was detrimental to a good signal-to-noise ratio. Nevertheless, some information could be obtained from the spectrum by comparing it with that corresponding to E8 sample, with enough mass to perform the analysis.

Figure 7. Mössbauer spectra of samples E8 (upper) and E1 (lower) at RT. The corresponding subspectra were identified as S1. S2 and S3 (sextets) and D1 and D2 (doublets).

Both spectra were fitted to three broad sextets and two quadrupole doublets. On one hand, the sextet with hyperfine field around 51 T (S1) is characteristic of hematite while the sextet around 48 T (S2) is typical of partially oxidized magnetite, and the last one around 38 T (S3) is ascribed to a minor contribution of goethite (Murad and Johnston, 1987). On the other hand, the major doublet (D1) with quadrupole splitting (QS) 0.72 mms^− 1 and IS 0.28 mm s^− 1 is attributed to pyrite (FeS₂) (Stevens et al. 2005), and the other one (D2) with QS 2.30 mm s^− 1 and IS 1.25 mm s^− 1 is ascribed to ferrous sulphate (FeSO₄). (Dong et al. 2002). Due to the scarce amount of sample available from lichens or the lack of Fe-bearing compounds no RT spectra could be obtained for lichens samples transplanted to E7 and W sites.

According to the description of the mineralization detailed in the Study Area section for the Bajo el Durazno deposit, the main Fe minerals composing the deposit are sulphides (pyrite, chalcopyrite and bornite), oxides (magnetite and haematite) and sulphates (jarosite and natrojarosite) and to a lesser extent chlorite, biotite, siderite and tetrahedrite-tenantite. All Fe minerals detected in lichens by this analysis are consistent with the minerals described for the porphyry-type deposit, with the exception of goethite. Goethite is a secondary mineral, a product of surface alteration of primary minerals such as pyrite, marcasite, arsenopyrite, chalcopyrite, siderite, magnetite and others that have been exposed to atmospheric conditions (Tabelin et al. 2020). As a result of this oxidation of sulphides, hydrated oxides and oxihydroxides are formed, which give the characteristic colours (orange, reddish or brownish) to the deposits of barren material after a certain time. Therefore, the presence of goethite in lichens transplanted to inside mine sites would indicate the incorporation into the thalli of particles from sulphides mine tailings (waste dumps, stock-piles and tailing dump) subjected to oxidative processes.

By means of micro PIXE, a differential distribution of S and Ca could be detected in relation to that corresponding to the sample coming from the location of the transplant site. In the inside-mine sites an overlap of Fe and S in the upper cortex of the apothecium section was observed, leading to deduce a mineral association of both elements. Something similar was observed for Ca and S. These results, added to the significantly higher concentration detected for S and Mn in inside-mine site samples, allow inferring a contribution of Fe, S, Ca and Mn to the content and natural distribution of these elements in P. hypoleucites; then, it can be concluded that this input comes from mining-derived particulate matter in the thalli specimens transplanted to the Bajo de la Alumbrera open-pit mining project.

Sulphur and Fe distribution obtained by micro PIXE complemented with Mössbauer spectroscopy analysis determined the presence of pyrite (FeS₂) and ferrous sulfate particles in the apothecia of lichens located inside the mine. Mössbauer spectra characteristic of other iron-bearing minerals in different degrees of oxidation were also identified in the structures, in particular goethite. These results trace the mining origin of the airborne particulate matter trapped by the lichen in the mining area.

The information obtained from this study is valuable, as P. hypoleucites revealed to be an excellent air quality biomonitor in the Bajo de la Alumbrera mine area.

Funding: This work was supported by Secretariat of Science and Technology of the National University of Catamarca (RES. C.S. N° 031/18), Government secretariat for science, technology and productive innovation (RESOL-2018-70-APN-SGCTEIP#MCT) and National Council for Scientific and Technical Research (RES. D. N° 1406/14)

Competing Interests: The authors have no relevant financial or non-financial interests to disclose.

Author Contributions: Juan Martín Hernández, Martha Susana Cañas and Emmanuel Marie de la Fournière contributed to the study conception, design and data collection. Sampling and material preparation were performed by Juan Martín Hernández. Analysis and validation of experiments were performed by Juan Martín Hernández, Emmanuel Marie de la Fournière, Cinthia Paula Ramos, Raquel Clara Jasan, Rita Rosa Plá, Rodrigo Invernizzi and Luis Germán Rodríguez Brizuela. The first draft of the manuscript was written by Juan Martín Hernández and Martha Susana Cañas and Emmanuel Marie de la Fournière, Cinthia Paula Ramos and Rita Rosa Plá commented on previous versions of the manuscript. All authors read and approved the final manuscript. Martha Susana Cañas obtained financial support for this research.

Data Availability: The datasets generated during the current study are available from the corresponding author on reasonable request.

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Contribution of mine-derived airborne particulate matter to Ca, Fe, Mn and S content and distribution in the lichen Punctelia hypoleucites transplanted to Bajo de la Alumbrera mine, Catamarca (Argentina)

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Abstract

Figures

INTRODUCTION

MATERIALS & METHODS

2.1. Study area

2.2. Mineralization

2.3. Sampling procedure

2.4. Elemental distribution analyses by micro PIXE.

2.5. Analysis of elemental content

2.5.1. Analysis of Ca and Fe content (INAA)

2.5.2. Analysis of Mn content (ICP-AES)

2.5.3. Certified Reference Materials

2.5.4. Analysis of sulphur content.

2.6. Statistical analysis

2.7. Iron minerals identification -Mössbauer spectroscopy

RESULTS AND DISCUSSION

CONCLUSIONS

Declarations

References

Status:

Journal Publication

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