Experimental release of elements from rock varnish by industrial compounds indicate increased risk to petroglyphs

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Experimental release of elements from rock varnish by industrial compounds indicate increased risk to petroglyphs
  • Australian Heritage Council. The Potential Outstanding Universal Value of the Dampier Archipelago Site and Threats to that Site; A report by the Australian Heritage Council to the Minister for Sustainability, Environment, Water, Population and Communities. Australian Heritage Council (2012).

  • Mulvaney, K. Without them – what then? People, petroglyphs and Murujuga. In Tacon P. S. C., May S. K., Frederick U. K., McDonald J., editors. Histories of Australian Rock Art (Terra Australis 55). ANU Press; Canberra. 2022. p155-172. (2022).

  • UNESCO. Murujuga Cultural Landscape. World Heritage listing. (2025).

  • Bednarik, R. G. The potential of rock patination analysis in Australian archaeology – part 1. Artefact 4, 14–38 (1979).

    Google Scholar 

  • Donaldson, M. Burrup rock art; Aboriginal rock art of Burrup Peninsula and Dampier Archipelago, Western Australia. Perth; Wildrocks Publications. (2009).

  • McDonald, J. & Veth, P. Dampier Archipelago petroglyphs; archaeology, scientific values and National Heritage Listing. Archael. Ocean 44, 49–69 (2009).

    Article 

    Google Scholar 

  • Mulvaney, K. About time; Towards a sequencing of the Dampier Archipelago petroglyphs of the Pilbara region, Western Australia. Records of the Western Australian Museum 2011, Suppl. 79 Pt 1:30–49. (2011).

  • Smith, B. W. et al. The impact of Industrial pollution on the rock art of Murujuga, Western Australia. Rock Art Res. 39, 1–14 (2022).

  • Vinnicombe, P. Petroglyphs of the Dampier Archipelago; Background to development descriptive analysis. Rock Art Res. 19, 2–27 (2002).

  • Mulvaney, K. Dating the dreaming; extinct fauna in the petroglyphs of the Pilbara region, Western Australia. Archaeol. Ocean. 44, 40–48 (2009).

    Article 

    Google Scholar 

  • Mulvaney, K. J. Murujuga Marni – Rock Art of the Macropod Hunters and the Mollusc Harvesters. Perth; UWA Press, (2015).

  • McDonald, J. I must go down to the seas again; or, what happens when the sea come to you? Murujuga rock art as an environmental indicator for Australia’s north-west. Quat. Int. 385, 124–135 (2015).

    Article 

    Google Scholar 

  • Gara, T. The Flying Foam massacre; an incident on the northwest frontier, Western Australia. Paper presented to the Archaeology at ANZAAS 1983, 53rd ANZAAS Congress, Perth, Western Australia. (1983).

  • Bednarik, R. G. Australian apocalypse; The story of Australia’s greatest cultural monument. Melbourne, Australia. Australian Rock Art Research Association; Occ. AURA Publ. No. 14. (2006).

  • Donaldson, M. Understanding the rocks; Rock art and the geology of Murujuga (Burrup Peninsula). Rock Art Res. 28, 35–43 (2011).

  • Bednarik, R. G. The science of Dampier rock art – Part 1. Rock Art Res. 24, 209–246 (2007).

  • Pillans, B. & Fifield, L. K. Erosion rates and weathering history of rock surfaces associated with Aboriginal rock art engravings (petroglyphs) on Burrup Peninsula, Western Australia, from cosmogenic and nuclide measurements. Quat. Sci. Rev. 69, 98–106 (2013).

    Article 

    Google Scholar 

  • Bednarik, R. G. The survival of the Murujuga (Burrup) petroglyphs. Rock Art Res. 19, 29–40 (2002).

  • Black, J. L. Scientific evidence supports the degradation of globally significant palaeoart by industrial emissions on Murujuga, Western Australia. CMAS. 26, 318–340 (2024).

  • Dorn, R. I. Rock varnish revisited. Prog. Phys. Geogr. 48, 1–39 (2024).

    Article 

    Google Scholar 

  • Chaddha, A. S., Sharma, A., Singh, N. K., Shamsad, A. & Banerjee, M. Biotic-abiotic mingle in rock varnish formation: A new perspective. Chem. Geol. 2024, 648–121961 (2024).

    Google Scholar 

  • Dorn, R. I. Anthropogenic interactions with rock varnish. In Dontsova K., Balogh-Brunstad Z., Roux G. L., editors, Biogeochemical cycles; ecological drivers and environmental impact. Geophysical Monograph 251, American Geophysical Union and John Wiley and Sons, Inc. p. 267–283 (2020).

  • Lingappa, U. F. et al. An ecophysiological explanation for manganese enrichment in rock varnish. Proc. Nat. Acad. Sci. USA 118, e2025188118 (2021).

    Article 
    CAS 
    PubMed 
    PubMed Central 

    Google Scholar 

  • Chaddha, A. S., Sharma, A., Singh, N. K., Patel, D. K. & Satyanarayana, G. N. V. Rock Varnish: Nature’s Shield. ACS Earth Space Chem. 7, 1516–1527 (2023).

    Article 
    CAS 

    Google Scholar 

  • Thiagarajan, N. & Lee, C.-T. A. Trace-element evidence for the origin of desert varnish by direct aqueous atmospheric deposition. Earth Planet. Sci. Lett. 224, 131–141 (2004).

    Article 
    CAS 

    Google Scholar 

  • Potter, R. M. & Rossman, G. R. Desert varnish; the importance of clay minerals. J. Sci. 196, 1446–1448 (1977).

    CAS 

    Google Scholar 

  • Liu, T. & Broecker, W. S. How fast does rock varnish grow? Geol. 28, 183–186 (2000).

  • Garvie, L. A. J., Barr, D. M. & Buseck, P. R. Nanometer-scale complexity, growth, and diagenesis in desert varnish. Geol. 36, 215–218 (2008).

  • Xu, X. et al. Characteristics of desert varnish from nanometer to micrometer scale; A photo-oxidation model on its formation. J. Chem. Ecol. 522, 55–70 (2019).

    CAS 

    Google Scholar 

  • Krinsley, D., Ditto, J., Langworthy, K., Dorn, R. I. & Thompson, T. Varnish microlaminations; new insights from focused ion beam preparation. Phys. Geogr. 34, 159–173 (2013).

    Article 

    Google Scholar 

  • Dorn, R. I. Revisiting the importance of clay minerals in rock varnish. Am. Miner. 110, 1341–1342 (2025).

    Article 

    Google Scholar 

  • Goldsmith, Y., Stein, M. & Enzel, Y. From dust to varnish; Geochemical constraints on rock varnish formation in the Negev Desert, Israel. Geochim. Cosmochim. Acta 126, 97–111 (2014).

    Article 
    CAS 

    Google Scholar 

  • Black, J. L., MacLeod, I. D. & Smith, B. W. Theoretical effects of industrial emissions on colour change at rock art sites on Burrup Peninsula, Western Australia. J. Archaeol. Sci. Rep. 12, 457–462 (2017).

    Google Scholar 

  • Bothe, H. The Cyanobacterium Chroococcidiopsis and its potential for life on Mars. J. Astrobiol. Space Sci. Rev. 2, 398–412 (2019).

    Google Scholar 

  • WA EPA. Report 1379. Technical Ammonium Nitrate Production Facility, Burrup Peninsula. Western Australia Environmental Protection Authority, (2011).

  • National Pollution Inventory. (2023).

  • MacLeod, I. & Fish, W. Determining decay mechanisms on engraved rock art sites using pH, chloride ion and redox measurements with an assessment of the impact of cyclones, sea salt and nitrate ions on acidity. Paper presented to the ICOM-CC 19th Triennial Conference Preprints, Beijing, 17-21 May (2021).

  • Kits, K. D. et al. Kinetic analysis of a complete nitrifier reveals an oligotrophic lifestyle. Nature 549, 269–272 (2017).

    Article 
    CAS 
    PubMed 
    PubMed Central 

    Google Scholar 

  • MacLeod, I. D. Surface chemistry of Burrup rock art at Yara monitoring sites, September 2021. (2021).

  • MacLeod, I. Effects of moisture, micronutrient supplies and microbiological activity on the surface pH of rocks in the Burrup Peninsula. Triennial meeting (14th), The Hague, 12-16 September 2005, London: James & James. p. 386–393 (2005).

  • Shen, J., Zerkle, A. L., Stueeken, E. & Claire, M. W. Nitrates as a potential N supply for microbial ecosystems in hyperarid Mars analog system. Life 9, 79 (2019).

    Article 
    PubMed 
    PubMed Central 

    Google Scholar 

  • Liu, X. et al. Nitrate determines the bacterial specialization and impacts microbial functions in a surface karst cave. Front. Microbiol. 14 (2023).

  • Dakal, T. C. & Cameotra, S. S. Microbially induced deterioration of architectural heritage: routes and mechanisms involved. Environ. Sci. Eur. 24, 6 (2012).

  • Gadd, G. M. Geomicrobiology of the built environment. Nat. Microbiol. 2, 16275 (2017).

    Article 
    CAS 
    PubMed 

    Google Scholar 

  • Reboah, P. et al. The biological contribution to the weathering of limestone monuments in a vegetated urban area: results of a 5-year exposure. Herit. Sci. 12, 270 (2024).

    Article 

    Google Scholar 

  • Dragovich, D. Weathering of desert varnish by lichens. Perth: Readings in Australian Geography. Proc. 21st IAG Conf. 21, 407–412 (1987).

    Google Scholar 

  • Dragovich, D. Distribution and chemical composition of microcolonial fungi and rock coatings from arid Australia. Phys. Geogr. 14, 323–341 (1993).

    Article 

    Google Scholar 

  • MRAMP. Murujuga Rock Art Monitoring Program: Monitoring Studies Report 2023. Technical Report on Monitoring Studies completed from March 2022 to March 2023. Available on request from the Department of Water and Environmental Regulation, Western Australia. (2023).

  • Neumann, J. T. et al. Artificial weathering of rock types bearing petroglyphs for Murujuga, Western Australia. Herit. Sci. 10, 77 (2022).

    Article 
    CAS 

    Google Scholar 

  • Watkins, R. T. et al. Experimental leaching of weathered gabbro and granophyre from Burrup Peninsula, Western Australia using synthetic solutions of known local contaminants; A foundation evaluation of the chemical threats to Murujuga rock art. Unpublished scientific report for the Murujuga Rock Art Conservation Project. Perth: Environmental Geochemistry Services. (2023).

  • Bruker A. X. S. DIFFRAC.EVA version 5.1.0.5, (2024).

  • Bruker A. X. S. TOPAS version 5, (2024).

  • Wenziker, K., McAlpine, K., Apte, S. & Masini, R. Background quality of costal marine waters off the North West Shelf, Western Australia. Technical Report; North West Shelf Joint Environmental Study. ISBN 1 921061 97 9. (2006).

  • Fasola, S., Muggeo, V. M. R. & Kuchenhoff, K. A heuristic, iterative algorithm for change-point detection in abrupt change models. Comput. Stat. 33, 997–1015 (2018).

    Article 

    Google Scholar 

  • R Core Team. R; A language and environment for statistical computing. R Foundation for Statistical Computing, Vienna, Austria. (2021).

  • Dorn, R. I. Rock varnish. In Nash D. J., McLaren S. J. editors. Geochemical Sediments and Landscapes. New Jersey, Wiley-Blackwell. p. 246–297 (2007).

  • Saleh, D. K., Abdollahi, H., Noaparast, M. & Nosratabad, A. F. Dissolution of aluminium from metakaolin with oxalic, citric and lactic acids. Clay Min. 54, 1–27 (2019).

    Google Scholar 

  • Mendes, G. D. O. et al. Oxalic acid is more efficient than sulfuric acid for rock phosphate solubilization. Miner. Eng. 155, (2020).

  • Zhang, P. & Sparks, D. L. Dissolution of synthetic crystalline and noncrystalline iron oxides by organic and mineral acids. Langmuir 1, 584–589 (1985).

    Google Scholar 

  • Dorn, R. I. Quaternary alkalinity fluctuations recorded in rock varnish microlaminations on western U.S.A. volcanics. Palaeogeogr. Palaeoclimatol. Palaeoecol. 76, 291–310 (1990).

    Article 

    Google Scholar 

  • Lefkowitz, J. P., Rouff, A. A. & Elzinga, E. J. Influence of pH on the reductive transformation of birnessite by aqueous Mn(II). Environ. Sci. Technol. 47, 10364–10371 (2013).

    Article 
    CAS 
    PubMed 

    Google Scholar 

  • Neumann, J. T. Experimental weathering of Aboriginal rock art from the Murujuga Peninsula, Western Australia: Do emissions from the local industry have an impact on the rock art weathering rate? Dissertation, Rheinische Friedrich-Wilhelms-Universität Bonn. pp 204 (2025).

  • Black, J. L. & Diffey, S. M. Reanalysis of the colour and mineralogy changes from 2004 to 2014 on Burrup Peninsula rock art sites. Report to DER from reanalysis of CSIRO provided data to WA government. May. (2016).

  • Smith, B. W., Black, J. L., Mulvaney, K. J. & Hœrlé, S. Monitoring rock art decay: Archival images of petroglyphs on Murujuga, Western Australia. CMAS 23, 198–220 (2022b).

    Google Scholar 

  • MRAMP. Murujuga Rock Art Monitoring Program: Monitoring studies report 2024. Technical report on monitoring studies completed from April 2023 to March 2024. Available on request from the Department of Water and Environmental Regulation, Western Australia. (2024).

  • Australian Government. 2025. Statement of Reasons for Approval under the Environment Protection and Biodiversity Conservation Act 1999. DCCEEW.gov.au John Gorton Building – King Edward Terrace, Parkes ACT 2600 Australia (2025).

  • Bao, H., Michalski, G. M. & Thiemens, M. H. Sulfate oxygen-17 anomalies in desert varnishes. Geochim. Cosmochim. Acta 65, 2029–2036 (2001).

    Article 
    CAS 

    Google Scholar 

  • Chaddha, A. S., Singh, N. K., Malviya, M. & Sharma, A. Birnessite-clay mineral couple in the rock varnish; a nature’s electrocatalyst. Sustain. Energ. Fuels. 6, 2553–2569 (2022).

    CAS 

    Google Scholar 

  • Charola, A. E. & Ware, R. Acid deposition and the deterioration of stone: a brief review of a broad topic. Geol. Soc. Spec. Publ. 205, 393–406 (2002).

    Article 
    CAS 

    Google Scholar 

  • Spiker, E. C., Hosker, R. P., Weintraub, V. C. & Sherwood, S. I. Laboratory study of SO2 dry deposition on limestone and marble: Effects of humidity and surface variables. Water Air Soil Pollut. 85, 2679–2685 (1995).

    Article 
    CAS 

    Google Scholar 

  • Kuhlman, K. R. et al. Diversity of Microorganisms within Rock Varnish in the Whipple Mountains, California. Appl. Environ. Microbiol. 72, 1708–1715 (2006).

    Article 
    CAS 
    PubMed 
    PubMed Central 

    Google Scholar 

  • Koretsky, C. The significance of surface complexation in hydrologic systems: a geochemist’s perspective. J. Hydrol. 230, 127–171 (2000).

    Article 
    CAS 

    Google Scholar 

  • Sokolova, T. A. Decomposition of clay minerals in model experiments and in soils; Possible mechanisms, rates, and diagnostics (analysis of literature). Eurasia Soil Sci. 46, 182–197 (2013).

    Article 
    CAS 

    Google Scholar 

  • van Breemen, N. & Wielemaker, W. G. Buffer intensities and equilibrium pH of minerals and soils. SSSAJ 38, 55–70 (1974).

    Article 

    Google Scholar 

  • Chou, L. & Wollast, R. Study of the weathering of albite at room temperature and pressure with a fluidized bed reactor. Geochim. Cosmochim. Acta 48, 2205–2217 (1984).

    Article 
    CAS 

    Google Scholar 

  • Appelo, C. & Postma, D. Geochemistry, Groundwater and Pollution. Rotterdam, Balkema, 2nd Edition. (2005).

  • Kowacz, M. & Putnis, A. The effect of specific background electrolytes on water structure and solute hydration: Consequences for crystal dissolution and growth. Geochim. Cosmochim. Acta 72, 4476–4487 (2008).

    Article 
    CAS 

    Google Scholar 

  • Rabbachin, L. et al. Diversity of fungi associated with petroglyph sites in the Negev Desert, Israel, and their potential role in bioweathering. Front. Fungal Biol. 5, 1400380 (2024).

    Article 
    PubMed 
    PubMed Central 

    Google Scholar 

  • Camuffo, D. Deterioration processes of historical monuments. Environ. Sci. 30, 189–221 (1986).

    CAS 

    Google Scholar 

  • Webb, A. H., Bawden, R. J., Busby, A. K. & Hopkins, J. N. Studies on the effects of air pollution on limestone degradation in Great Britain. Atmos. Environ. B 26, 165–181 (1992).

    Article 

    Google Scholar 

  • O’Brien, P. F., Bell, E., Orr, T. L. L. & Cooper, T. P. Stone loss rates at sites around Europe. Sci. Total Environ. 167, 111–121 (1995).

    Article 

    Google Scholar 

  • Livingston, R. A. Acid rain attack on outdoor sculpture in perspective. Atmos. Environ. 146, 332–345 (2016).

    Article 
    CAS 

    Google Scholar 

  • Cioban, L. A., Dochia, M., Mureşan, C. & Chambre, D. R. Weathering and deterioration of carbonate stones from historical monuments: A review. Sci. Tech. Bull. -Chem. Food Sci. Eng. 19, 15–33 (2022).

    Google Scholar 

  • Yan, Y. & Wang, Y. A review of atmospheric deterioration and sustainable conservation of calcareous stone in historical buildings and monuments. Sustainability 16, 10751 (2024).

    Article 
    CAS 

    Google Scholar 

  • Crits-Christoph, A. et al. Colonization patterns of soil microbial communities in the Atacama Desert. Microbiome 1, 28 (2013).

  • Gurgen, G. Impact of acid precipitation on historical monuments and statues. GJEA 7, 02–06 (2017).

    Google Scholar 

  • Prakash, J., Agrawal, S. B. & Agrawal, M. Global trends of acidity in rainfall and its impact on plants and soil. J. Soil. Sci. Plant Nutr. 23, 298–419 (2023).

    Article 

    Google Scholar 

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