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Acarospora species (arrowed) colonize a range of extreme habitats with differing geology influenced by metals such as (A) acidic, iron sulphide mineralised boulders and mine spoil at Parys Mountain, 24 March 2008; (B) on calcareous, nutrient-enriched tombstones, 12 May 2004 and (C) denuded, metal-enriched soils in a region heavily influenced by acidic and particulate emissions from the former smelter at Zlatna, Romania, 1996 and (D) iron-stained quartz mica schists on the lower slopes of a recently exposed nunatak on the McLeod Glacier, Signy Island, South Orkney Islands. Inset approaching the nunatak across McLeod Glacier. 16 November 2009.
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One of the most successful mechanisms enabling fungi to survive in extreme subaerial environments is by formation of mutualistic symbioses with algae and/or cyanobacteria as lichens. Collections, field and mineral weathering studies and developments in modern instrumental and analytical techniques have considerably advanced knowledge in understandi...
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... organisms, Acarospora taxa colonize rocks, soils, bark, wood and other materials influenced by metals ( Figure 2). Acarospora sens. ...
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... sulphides are the principal acid-forming constituents of mine spoils which liberate dilute sulphuric acid as a result of bacterially assisted oxidative weathering and which leads to 'acid mine drainage', a major source of metal contamination ( Jenkins et al., 2000). The Acarosporion sinopicae com- munity, characterised by the obligate rust-coloured Acarospora sinopica, is characteristic of such acidic envi- ronments (Wirth, 1972) (Figure 2A). With particular refer- ence to sulphide-rich substrata, metamorphosed in greenschist facies, in central Scandinavia, the author's multi-disciplinary doctoral studies illustrated the complex- ity of the interrelationships between Cu and Fe minerals, pH and other ecological factors in determining assemblage composition (Purvis, 1985). ...
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... X-ray emission map for Pb mainly localized on the surface and medulla. (D) SEM micrographs of crystalline inclusions within the medulla of Acarospora rugulosa ( Figure 2D was difficult to see the hyphae ( Figure 4D). Infra red spec- tra and XRD from hand-picked material identified the blue phase as being the hydrated copper oxalate, moo- looite, CuC 2 O 4 . ...
Citations
... Acarospora cf. badiofusca, A. sinopica, A. smaragdula, A. rugulosa have been reported to induce weathering of peculiar rocks [43]. Xanthoria elegans, Bacidia stipata, Lecidea lapicida, Rhizocarpon geographicum dwelling on volcanic site aids in weathering process [17]. ...
The astonishing ability to adapt to most extremes of climates of earth makes saxicolous lichens an indispensable species of this planet. They can thrive on different categories of rocks viz. sandstone, granite, volcanic andesite, siliceous, ultramafic, non-ultramafic, basaltic, hornfels, coastal, calcareous cliffs, etc. These extremophiles have not only proven their endurance from Antarctica to the deserts but can also withstand the harsh conditions of outer space. Therapeutically, some species exhibited antioxidant, antimicrobial, and anticancer properties due to their diverse chemical composition. They play a vital role in facilitating weathering phenomena in rocks and have a unique ability to biomineralize heavy metals from the surrounding environment, which has enormous applications in the study of rock mineral compositions. Saxicolous lichens also served as an indicator of environmental pollution and hence remarked as an important biomonitoring tool. Several crustose lichens have been used in lichenometry to date rock substrates and their applications, from therapy to terraforming, make them not only new sources of inspiration for drug development, geochronological dating, and lithology but also for transforming mars.
... Due to their tendency to accumulate large levels of hazardous metals, foliose lichens are frequently used as biomonitors of metal pollution in the environment (Purvis, 2014). Our results indicate that the accumulation of lead in the lichen thalli causes a decrease in the content of C a , C b and total chlorophyll. ...
The assessment of the air quality is a major concern to the current time. The monitoring and maintenance of air quality necessarily pass by detecting and estimating the overall air pollution. The use of lichens must be an assessmenttool to be studied. In our work we were interested about the toxicity of lead on the various parameters of stress in the lichen Xanthoria parietina. For this purpose, lichen thalli have been incubated at lead concentrations of 0, 0.5, 1.0, 5.0 and 10.0 mM, for time scale of 0, 24, 48 and 96 hours. The obtained results showed that lead has an action on the various studied parameters, and the intensity of oxidative stress observed in lichens thalli depends on the concentration, and time of exposure. Lead induced a decrease in chlorophyll and protein contents, and an increase in the contents of catalase, hydrogen peroxide and reduced glutathione. Furthermore, the results also showed that high concentrations of lead caused total destruction of reduced glutathione.
... Nevertheless, Raman spectroscopy has its (Jones et al., 1981;Wilson & Jones, 1984;Purvis, 1984;Purvis & James, 1985;192 Purvis & Halls, 1996;Sarret et al., 1998;Purvis et al., 2008); (b) Microenvironment of 193 naturally metal-enriched ultrabasic rocks and serpentinites (Wilson et al., 1980;1981;Jones et 194 al., 1981); and, if taken into consideration, (c) Iron-rich dolomites (Ascaso et al., 1982). The 195 occurrence of metallic oxalates can be expected more in metal-hyperaccumulator species 196 rather than in pollution-tolerant species (Sarret et al., 1998), even though the term 197 "hyperaccumulator" is best avoided in the case of lichens when the fixation of metals is 198 extracellular (Purvis, 2014), which is the case of lichen metallic oxalates depositions. ...
... The origin of metals included in the structure of metallic oxalate has still not been 1981); (c) Enriched water "run-off" from secondary minerals (Czehura, 1977;Purvis 1984;305 Chisholm et al., 1987;Purvis, 2014); and (d) Polluted wet and dry atmospheric deposition 306 (Sarret et al., 1998). The existent literature upon organic acid-mineral interaction is sparse (Barman et al., 1992;Varadachari et al., 1994;Drever & Stillings, 1997) and this gap in 308 knowledge offers the space for another review. ...
Lichens are generally acknowledged as the main agents of the initial bioweathering of rock substrates. The most direct evidence of a chemical interaction between lichens and their mineral substrata is the production of oxalic acid, of which interaction with ions present in a close lichen environment occasionally results in the precipitation of metal oxalates. In the past, only a few studies revealed the presence of metal oxalates in lichens, and currently, almost no new discoveries are arriving. Therefore, the main goal of this review is to bring the focus back to this phenomenon. To date, only Mg oxalate dihydrate, Mn oxalate dihydrate, Cu oxalate hemihydrate, Zn oxalate dihydrate, and anhydrous Pb oxalate have been detected in lichens. The most reliable diagnostic methods of metal oxalates in lichens are powder X-ray diffraction (pXRD), infrared spectroscopy (IR), extended X-ray absorption fine structure (EXAFS) spectroscopy, and Raman spectroscopy. Prospective lichen specimens for investigations may be found in anthropogenically-polluted environment or naturally metal-rich rock substrata. This review acts as an initial guide that provides analytical options for field lichenologists, offers a few suggestions for further research on this matter, and encourages to new biomineral discoveries in the scope of mineralogy. Survival in the metal-toxic environment, ability to produce oxygen, and extremophile nature, are the reasons why lichens are good subjects for research within the context of currently expanding astrobiology sciences, as well.
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CITE AS: Krajanová, V. 2023: Discoveries and identification methods of metal oxalates in lichens and their mineral associations: A review of past studies and analytical options for lichenologists. Fungal Biology Reviews, Volume 43, 2023, 100287,
ISSN 1749-4613.
https://doi.org/10.1016/j.fbr.2022.09.003.
... Literature indicates that lichens can serve as metal chelators [62] due to the production of metabolites playing a role in metal complexation [63]. This capability depends on the lichen metabolites and cation type [62,63] and ensures the survival of lichens in harsh environmental conditions [64]. For example, depsidone produced by Hypogymnia physdes-physodalic acid, can uptake Cu 2+ but not Fe 2+ [65,66], whereas Cu 2+ uptake is also promoted by other lichenic compounds, (+)-usnic acid or divaricatic acid [67]. ...
Lichens are a source of various biologically active compounds. However, the knowledge about them is still scarce, and their use in medicine is limited. This study aimed to investigate the therapeutic potential of the lichen Platismatia glauca and its major metabolite caperatic acid in regard to their potential application in the treatment of central nervous system diseases, especially neurodegenerative diseases and brain tumours, such as glioblastoma. First, we performed the phytochemical analysis of the tested P. glauca extracts based on FT-IR derivative spectroscopic and gas chromatographic results. Next the antioxidant properties were determined, and moderate anti-radical activity, strong chelating properties of Cu2+ and Fe2+ ions, and a mild effect on the antioxidant enzymes of the tested extracts and caperatic acid were proved. Subsequently, the influence of the tested extracts and caperatic acid on cholinergic transmission was determined by in vitro and in silico studies confirming that inhibitory effect on butyrylcholinesterase is stronger than against acetylcholinesterase. We also confirmed the anti-inflammatory properties of P. glauca extracts and caperatic acid using a COX-2 and hyaluronidase inhibition models. Moreover, our studies show the cytotoxic and pro-apoptotic activity of the P. glauca extracts against T98G and U-138 MG glioblastoma multiforme cell lines. In conclusion, it is possible to assume that P. glauca extracts and especially caperatic acid can be regarded as the source of the valuable substances to finding new therapies of central nervous system diseases.
... They tolerate these high metal concentrations by sequestrating metals in the extracellular space as oxalate crystals, after the mycobiont's production of organic short-chain acids (oxalic, citric, and malic) [17]. Complexing them with the lichen's secondary metabolites, such as phenolic acids [18] (depsides, depsidones [19], and dibenzofurans [20]), leads to another storage form of metals in this space. ...
This study aims to complete our research on Usnea barbata (L.) Weber ex F.H. Wigg (U. barbata) from the Călimani Mountains, Romania, with an elemental analysis and to explore its antibacterial and antifungal potential. Thus, we analyzed twenty-three metals (Ca, Fe, Mg, Mn, Zn, Al, Ag, Ba, Co, Cr, Cu, Li, Ni, Tl, V, Mo, Pd, Pt, Sb, As, Pb, Cd, and Hg) in dried U. barbata lichen (dUB) by inductively coupled plasma mass spectrometry (ICP-MS). For the second study, we performed dried lichen extraction with five different solvents (ethyl acetate, acetone, ethanol, methanol, and water), obtaining five U. barbata dry extracts (UBDE). Then, using an adapted disc diffusion method (DDM), we examined their antimicrobial activity against seven bacterial species—four Gram-positive (Staphylococcus aureus, Enterococcus casseliflavus, Streptococcus pyogenes, and Streptococcus pneumoniae) and three Gram-negative (Escherichia coli, Klebsiella pneumoniae, and Pseudomonas aeruginosa)—and two fungi species (Candida albicans and Candida parapsilosis). Usnic acid (UA) was used as a positive control. The ICP-MS data showed a considerable Ca content (979.766 µg/g), followed by, in decreasing order, Mg, Mn, Al, Fe, and Zn. Other elements had low levels: Ba, Cu, Pb, and Cr (3.782–1.002 µg/g); insignificant amounts (
... Only those species that have passive physicochemical defense www.nature.com/scientificreports/ mechanisms selectively grow on such substrates, since they are able to bind copper in the form of intracellular organometallic complexes and in the form of extracellular copper oxalates [27][28][29][30] . Such lichens include the L. inops species, in which moolooite from Karelia was found. ...
The present work focuses on the revealing the patterns of copper oxalates formation under the influence of lichens and fungi by combination of the results of field studies and model experiments. These findings create the scientific basis for the potential microbial technology applications (ore enrichment, monuments conservation, environment bioremediation, etc.). Copper oxalate moolooite Cu(C 2 O 4 )·H 2 O was discovered in saxicolous lichen Lecidea inops on the weathered chalcopyrite ore of Voronov Bor deposit (Central Karelia, Russia). Bioinspired syntheses of moolooite and wheatleyite Na 2 Cu(C 2 O 4 ) 2 2H 2 O with the participation of the microscopic fungi Aspergillus niger (active producer of oxalic acid) were carried out on weathered Cu-ore from the Voronov Bor deposit. It was shown that morphology of moolooite crystals is controlled both by the underlying rock and by the species composition of microorganisms. Iron ions (sourced from the underlying rock) in the crystallization medium inhibits the moolooite formation. The observed intensive dissolution of moolooite crystals are well explained by washing effect of the intratalline solutions which depends on repeatedly dehydration / rehydration cycles in the lichens. Joint interpretation of original and published data shows that moolooite along with other cooper oxalates are biominerals.
... They can colonize extreme environments (boreal forest, arctic tundra, lava fields and tide-flooded areas) and they are good bio-indicators for monitoring pollution by heavy metals or sulfur dioxide. However, some lichens prove to be resistant to sulfur dioxide because of their surface hydrophobicity (Hauck et al., 2008) and to metals due to oxalate production (Purvis, 2014). In this Research Topic, two articles dealing with lichens are included. ...
... Certain species are able to effectively colonise various natural and anthropogenic sites that are strongly enriched with heavy metals (Cuny et al., 2004a;Purvis and Halls, 1996;Osyczka, 2014, 2018). Some of them show a high tolerance to metal pollution; however, only a limited number of species appears insensitive to extreme metal contamination of the substrate (Osyczka and Rola, 2013a;Purvis, 2014). Those lichens that demonstrate the unique ability for extraordinary accumulation of elements in thalli are considered as hyperaccumulators; there are, for instance, Diploschistes muscorum (Cuny et al., 2004b;Sarret et al., 1998), Acarospora rugulosa (Chisholm et al., 1987), Stereocaulon japonicum (Nakajima et al., 2013) and Lecanora polytropa (Pawlik-Skowro nska et al., 2006). ...
The synthesis of various unique secondary metabolites by lichens is the result of mutualistic symbiotic association between the mycobiont and autotrophic photobiont. The function of these compounds and causal factors for their production are not fully understood. This paper examines the effect of heavy-metal bioaccumulation and physiological parameters related to photosynthesis and carbon metabolism on the production of lichen substances in hyperaccumulator Diploschistes muscorum. The obtained model of secondary metabolite concentrations in the thalli demonstrates that the carbon source provided by the photobiont and associated polyols produced by the mycobiont have positive impact on the production; on the contrary, the increased intracellular load of heavy metals and excessive loss of cell membrane integrity adversely affected secondary metabolite contents. Additionally, the production of secondary metabolites appears to be more dependent on intracellular metal concentrations than on soil pollution level. To compensate for metal stress, both efficient functioning of algal component and sufficient production of secondary metabolites are required. The balanced physiological functioning of mycobiont and photobiont constitutes the complex protective mechanism to alleviate the harmful effects of heavy metal stress on primary and secondary metabolism of lichens.
... Since the lichens have no root, they depend mainly on atmospheric inputs for their mineral nutrition [13,14]. Lichens lack a protective outer cuticle and stomata, and thalli can absorb mineral elements over their surface, including heavy metals [3,15]. ...
... The total concentration of Cu in the Cladonia pyxidata was found to be 3.10 ± 0.92 and 46 ± 14.4 for a sample collected from the forest and spoil mine heap, respectively ( Table 2). These results are in good agreement with previous studies explaining the effect of the surrounding environment on the heavy metals accumulation in lichens [7][8][9][10][11][12][13][14]. On the other hand, the lowest concentration of Cu was found in Pseudevernia furfuracea collected from the forest site. ...
Lichens have widely been used as bioindicators to reflect the quality of the environment. The present study was conducted to investigate the lichens diversity that grows on the surface of waste heaps from an abandoned old copper mine in Mlynky, Slovakia. In spite of the heavy metalcontaminated environment, we documented twenty species of lichens in the selected site. Taxonomically the most numerous group were represented by Cladonia with seven species, as well other species; namely, Acarospora fuscata, Cetraria islandica, Dermatocarpon miniatum, Hypogymnia physodes, Hypogymnia tubulosa, Lecanora subaurea, Lepraria incana, Physcia aipolia, Porpidia macrocarpa, Pseudevernia furfuracea, Rhizocarpon geographicum and Xanthoria parietina. The content of selected heavy metals (Cu, Fe, and Zn) in the predominant lichens Cetraria islandica, Cladonia digitata, Cladonia pyxidata, Hypogymnia physodes and Pseudevernia furfuracea were analyzed. The highest content of Cu, Fe, and Zn was found in Cladonia pyxidata collected from mine-spoil heaps with concentration 46 ± 4.4, 82.5 ± 22.6, 4.8 ± 1.6 mg/kg, respectively. Interestingly, Cladonia pyxidata collected from the forest surrounding the location showed 15 times lower concentration for Cu. Additionally, similar results were found for Fe and Zn.
... Our findings suggest that Cs is not readily transferred to new tissues, and that Cs is stored more strongly than ion exchange in the barks. This means that Cs is possibility present in an immobilisation form due to, for instance, transportation intracellularly by chelation and sequestration [65], and formation of metal compounds by lichen secondary metabolites [65][66][67]. ...
We investigated the radiocaesium content of nine epiphytic foliose lichens species and the adjacent barks of Zelkova serrata (Ulmaceae, "Japanese elm") and Cerasus sp. (Rosaceae, "Cherry tree") at the boundary of the Fukushima Dai-ichi Nuclear Power Station six years after the accident in 2011. Caesium-137 activities per unit area (the 137 Cs-inventory) were determined to compare radiocaesium retentions of lichens (65 specimens) and barks (44 specimens) under the same growth conditions. The 137 Cs-inventory of lichens collected from Zelkova serrata and Cerasus sp. were respectively 7.9-and 3.8-times greater than the adjacent barks. Furthermore, we examined the radiocaesium distribution within these samples using autoradiography and on the surfaces with an electron probe micro analyzer (EPMA). Autoradiographic results showed strong local spotting and heterogeneous distributions of radioactivity in both the lichen and bark samples, although the intensities were lower in the barks. The electron microscopy analysis demonstrated that particulates with similar sizes and compositions were distributed on the surfaces of the samples. We therefore concluded that the lichens and barks could capture fine particles, including radiocaesium particles. In addition, radioactivity was distributed more towards the inwards of the lichen samples than the peripheries. This suggests that lichen can retain 137 Cs that is chemically immobilised in particulates intracellularly, unlike bark.
