Abstract
The ecotoxic effect of Zn species arising from the weathering of the marmatite-like sphalerite ((Fe, Zn)S) in Allium cepa systems was herein evaluated in calcareous soils and connected with its sulfide oxidation mechanism to determine the chemical speciation responsible of this outcome. Mineralogical analyses (X-ray diffraction patterns, Raman spectroscopy, scanning electron microscopy and atomic force microscopy), chemical study of leachates (total Fe, Zn, Cd, oxidation–reduction potential, pH, sulfates and total alkalinity) and electrochemical assessments (chronoamperometry, chronopotentiometry, cyclic voltammetry, and electrochemical impedance spectroscopy) were carried out using (Fe, Zn)S samples to elucidate interfacial mechanisms simulating calcareous soil conditions. Results indicate the formation of polysulfides (Sn2−), elemental sulfur (S0), siderite (FeCO3)-like, hematite (Fe2O3)-like with sorbed CO32− species, gunningite (ZnSO4·H2O)-like phase and smithsonite (ZnCO3)-like compounds in altered surface under calcareous conditions. However, the generation of gunningite (ZnSO4·H2O)-like phase was predominant bulk-solution system. Quantification of damage rates ranges from 75 to 90% of bulb cells under non-carbonated conditions after 15–30 days, while 50–75% of damage level is determined under neutral-alkaline carbonated conditions. Damage ratios are 70.08 and 30.26 at the highest level, respectively. These findings revealed lower ecotoxic damage due to ZnCO3-like precipitation, indicating the effect of carbonates on Zn compounds during vegetable up-taking (exposure). Other environmental suggestions of the (Fe, Zn)S weathering and ecotoxic effects under calcareous soil conditions are discussed.
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References
Afra, Z., Rezapour, S., Sabbaghtazeh, E., Dalalian, M. R., & Rafieyan, O. (2022). Long-term orchard practice affects the ecological and human health risk of soil heavy metals in a calcareous environment. Environmental and Monitoring Assessment, 194, 433. https://doi.org/10.1007/s10661-022-10084-x
Ahlberg, E., & Ásbjörnsson, J. (1994). Carbon paste electrodes in mineral processing: An electrochemical study of sphalerite. Hydrometallurgy, 36, 19–37. https://doi.org/10.1016/0304-386X(94)90039-6
Álvarez-Ayuso, E., & Abad-Valle, P. (2021). Application of different alkaline materials as polluted soil amendments: A comparative assessment of their impact on trace element mobility and microbial functions. Ecotoxicological and Environmental Safety, 227, 112927. https://doi.org/10.1016/j.ecoenv.2021.112927
ASTM. (1999). Standard test method for shake extraction of solid waste with water D3987-85, West Conshocken, PA.
ASTM. (2001). Standard test method for accelerated weathering of solid materials using a modified humidity cell D5744-96, West Conshocken, PA.
Babedi, L., Tadie, M., Neethling, P., & Von der Heyden, B. P. (2021). A fundamental assessment of the impacts of cation (Cd Co, Fe) substitution on the molecular chemistry and surface reactivity of sphalerite. Minerals Engineering, 160, 106695. https://doi.org/10.1016/j.mineng.2020.106695
Bao, Z., Al, T., Bain, J., Shrimpton, H. K., Finfrock, Y. Z., Ptacek, C. J., & Blowes, D. W. (2022). Sphalerite weathering and controls on Zn and Cd migration in mine waste rock: An integrated study from the molecular scale to the field scale. Geochimica Et Cosmochimica Acta, 318, 1–18. https://doi.org/10.1016/j.gca.2021.11.007
Castro-Larragoitia, J., Kramar, U., & Puchelt, H. (1999). 200 years of mining activities at La Paz/San Luis Potosí/Mexico-Consequences for environment and geochemical exploration. Journal of Geochemical Exploration, 58, 81. https://doi.org/10.1016/S0375-6742(96)00054-4
Chen, Z., & Yoon, R. H. (2000). Electrochemistry of copper activation of sphalerite at pH 9.2. International Journal of Mineral Processing, 58, 57–66. https://doi.org/10.1016/S0301-7516(99)00047-2
Chenglong, Z., & Youcai, Z. (2009). Mechanochemical leaching of sphalerite in an alkaline solution containing lead carbonate. Hydrometallurgy, 100, 56–59. https://doi.org/10.1016/j.hydromet.2009.10.004
Cronk, B. C. (2016). How to use IBM SPSS statistics: A step-by-step guide to analysis and interpretation. Routledge.
Cruz, R., Bertrand, V., Monroy, M., & González, I. (2001b). Effect of sulfide impurities on the reactivity of pyrite and pyritic concentrates: A multi-tool approach. Applied Geochemistry, 16, 803–819. https://doi.org/10.1016/S0883-2927(00)00054-8
Cruz, R., Mendez, B. A., Monroy, M., & González, I. (2001a). Cyclic voltammetry applied to evaluate reactivity in sulfide mining residues. Applied Geochemistry, 16, 1631–1640. https://doi.org/10.1016/S0883-2927(01)00035-X
Doner, H. E., & Lynn, W. C. (1989). Carbonate, halide, sulfate, and sulfide minerals. In Minerals in soil environments, 2nd (pp. 279–330). https://doi.org/10.2136/sssabookser1.2ed.c6.
Eaton, A. D., Clesceri, L. S., & Greenberg, A. E. (1995). APHA. AWWA, WEF, standard methods for the examination of water and wastewater, 19th edn (pp. 1–6). Washington, DC.
EPA. SW-846. (1986). In: Test method 9038: Sulfate (Turbidimetric), hazardous waste test method. U.S. Environmental Protection Agency U.S., Washington, DC, USA.
Gamiño-Gutiérrez, S. P., González-Pérez, C. I., Gonsebatt, M. E., & Monroy-Fernández, M. G. (2013). Arsenic and lead contamination in urban soils of Villa de la Paz (Mexico) affected by historical mine wastes and its effect on children’s health studied by micronucleated exfoliated cells assay. Environmental Geochemistry and Health, 35, 37–51. https://doi.org/10.1007/s10653-012-9469-8
García-Gómez, C., Obrador, A., González, D., Babín, M., & Fernández, M. D. (2018). Comparative study of the phytotoxicity of ZnO nanoparticles and Zn accumulation in nine crops grown in a calcareous soil and an acidic soil. Science of the Total Environment, 644, 770–780. https://doi.org/10.1016/j.scitotenv.2018.06.356
Ghosh, M., Jana, A., Sinha, S., Jothiramajayam, M., Nag, A., Chakraborty, A., Mukherjee, A., & Mukherjee, A. (2016b). Effects of ZnO nanoparticles in plants: Cytotoxicity, genotoxicity, deregulation of antioxidant defenses, and cell-cycle arrest. Mutation Research: Genetic Toxicology and Environmental Mutagenesis, 807, 25. https://doi.org/10.1016/j.mrgentox.2016.07.006
Ghosh, M., Sinha, S., Jothiramajayam, M., Jana, A., Nag, A., & Mukherjee, A. (2016a). Cyto-genotoxicity and oxidative stress induced by zinc oxide nanoparticle in human lymphocyte cells in vitro and Swiss albino male mice in vivo. Food Chemistry and Toxicology, 97, 286–296. https://doi.org/10.1016/j.fct.2016.09.025
Giannetta, M. G., Soler, J. M., Queralt, I., & Cama, J. (2023). Natural attenuation of heavy metals via secondary hydrozincite precipitation in an abandoned PbZn mine. Journal of Geochemical Exploration, 251, 107236. https://doi.org/10.1016/j.gexplo.2023.107236
Gleisner, M., & Herbert, R. B., Jr. (2002). Sulfide mineral oxidation in freshly processed tailings: Batch experiments. Journal of Geochemical Exploration, 76, 139–153. https://doi.org/10.1016/S0375-6742(02)00233-9
Hiller, E., Petrák, M., Tóth, R., Lalinská-Voleková, B., Jurkovič, Ľ, Kučerová, G., & Vozár, J. (2013). Geochemical and mineralogical characterization of a neutral, low-sulfide/high-carbonate tailings impoundment, Markušovce, eastern Slovakia. Environmental Sciences and Pollution Research, 20, 7627–7642. https://doi.org/10.1007/s11356-013-1581-5
Islas-Valdez, S., López-Rayo, S., Arcos, J., Menéndez, N., & Lucena, J. J. (2020). Effect of Fe: Ligand ratios on hydroponic conditions and calcareous soil in Solanum lycopersicum L. and Glycine max L. fertilized with heptagluconate and gluconate. Journal of the Science of Food and Agriculture, 100, 1106–1117. https://doi.org/10.1002/jsfa.10119
Jalali, M., & Moradi, F. (2013). Competitive sorption of Cd, Cu, Mn, Ni, Pb and Zn in polluted and unpolluted calcareous soils. Environmental and Monitoring Assessing, 185, 8831–8846. https://doi.org/10.1007/s10661-013-3216-1
Jebril, N., Boden, R., & Braungardt, C. (2021). The effect of pH, calcium, phosphate and humic acid on cadmium availability and speciation in artificial groundwater. In Journal of Physics: Conference Series (Vol. 1879, No. 2, p. 022020). IOP Publishing. https://doi.org/10.1088/1742-6596/1879/2/022020.
Kabata-Pendias, A., & Mukherjee, A. B. (2007). Trace elements from soil to human. In eBook packages earth and environmental science, earth and environmental science (RO). Berlin, Heidelberg: Springer. https://doi.org/10.1007/978-3-540-32714-1.
Karimi, S., Ghahreman, A., Rashchi, F., & Moghaddam, J. (2017). The mechanism of electrochemical dissolution of sphalerite in sulfuric acid media. Electrochimica Acta, 253, 47–58. https://doi.org/10.1016/j.electacta.2017.09.040
Kaur, M., Bhatti, S. S., Soodan, R. K., Katnoria, J. K., Bhardwaj, R., Nagpal, A. K., & Xu, M. (2021). Physico-chemical characterization of agricultural soil samples and their modulatory effects on cytogenetic and biochemical parameters of Allium cepa. Journal of Soil Science and Plant Nutrition, 21, 1890–1903. https://doi.org/10.1007/s42729-021-00488-y
Khoshgoftar, A. H., Shariatmadari, H., Karimian, N., Kalbasi, M., Van der Zee, S. E. A. T. M., & Parker, D. R. (2004). Salinity and zinc application effects on phytoavailability of cadmium and zinc. Soil Science Society of America Journal, 68, 1885–1889. https://doi.org/10.2136/sssaj2004.1885
Langman, J. B., & Moberly, J. G. (2018). Weathering of a mined quartz-carbonate, galena-sphalerite ore and release and transport of nanophase zinc carbonate in circumneutral drainage. Journal of Geochemical Exploration, 188, 185–193. https://doi.org/10.1016/j.gexplo.2018.01.024
Lara, R. H., Vazquez-Arenas, J., Ramos-Sanchez, G., Galvan, M., & Lartundo-Rojas, L. (2015). Experimental and theoretical analysis accounting for differences of pyrite and chalcopyrite oxidative behaviors for prospective environmental and bioleaching applications. Journal of Physical Chemistry C, 119, 18364–18379. https://doi.org/10.1021/acs.jpcc.5b05149
Leme, D. M., & Marin-Morales, M. A. (2009a). Allium cepa test in environmental monitoring: A review on its application. Mutation Research/reviews in Mutation Research. https://doi.org/10.1016/j.mrrev.2009.06.002
Leme, D. M., & Marin-Morales, M. A. (2009b). Allium cepa test in environmental monitoring: A review on its application. Mutation Research-Reviews in Mutation Research, 682, 71–81. https://doi.org/10.1016/j.mrrev.2009.06.002
Lillo, J., Oyarzun, R., Esbrí, J. M., García-Lorenzo, M. L., & Higueras, P. (2015). Pb–Zn–Cd–As pollution in soils affected by mining activities in central and southern Spain: A scattered legacy posing potential environmental and health concerns. Environment, Energy and Climate Change I: Environmental Chemistry of Pollutants and Wastes. https://doi.org/10.1007/698_2014_278
Liu, J., Wen, S., Xian, Y., Deng, J., & Huang, Y. (2012). Dissolubility and surface properties of a natural sphalerite in aqueous solution. Mining Metallurgy and Exploration, 29, 113–120. https://doi.org/10.1007/BF03402402
Moshiri, F., Ebrahimi, H., Ardakani, M. R., Rejali, F., & Mousavi, S. M. (2019). Biogeochemical distribution of Pb and Zn forms in two calcareous soils affected by mycorrhizal symbiosis and alfalfa rhizosphere. Ecotoxicology and Environmental Safety, 179, 241–248. https://doi.org/10.1016/j.ecoenv.2019.04.055
Navarro, M. C., Pérez-Sirvent, C., Martínez-Sánchez, M. J., Vidal, J., Tovar, P. J., & Bech, J. (2008). Abandoned mine sites as a source of contamination by heavy metals: A case study in a semi-arid zone. Journal of Geochemical Exploration, 96, 183–193. https://doi.org/10.1016/j.gexplo.2007.04.011
Ning, X., Wang, S., Long, S., Dong, Y., Li, L., & Nan, Z. (2023). Temporal distribution and accumulation pattern of cadmium and arsenic in the actual field calcareous soil-maize system, northwest China. Science of the Total Environment, 870, 162012. https://doi.org/10.1016/j.scitotenv.2023.162012
Niu, Y., Sun, F., Xu, Y., Cong, Z., & Wang, E. (2014). Applications of electrochemical techniques in mineral analysis. Talanta, 127, 211–218. https://doi.org/10.1016/j.talanta.2014.03.072
Obrador, A., Novillo, J., & Alvarez, J. M. (2003). Mobility and availability to plants of two zinc sources applied to a calcareous soil. Soil Science Society of America Journal, 67, 564–572. https://doi.org/10.2136/sssaj2003.5640
Oubane, M., Khadra, A., Ezzariai, A., Kouisni, L., & Hafidi, M. (2021). Heavy metal accumulation and genotoxic effect of long-term wastewater irrigated peri-urban agricultural soils in semiarid climate. Sciences of the Total Environment, 794, 148611. https://doi.org/10.1016/j.scitotenv.2021.148611
Peng, L., Shah, S. S. A., & Wei, Z. (2018). Recent developments in metal phosphide and sulfide electrocatalysts for oxygen evolution reaction. Chinese Journal of Catalysis, 39, 1575–1593. https://doi.org/10.1016/S1872-2067(18)63130-4
Puigdomenech, I. (2015). HYDRA: Hidrochemical Equilibrium-constant Data base Software Royal Institute of Technology, Sweeden (2004). https://sites.google.com/site/chemdiagr/download.
Razo, I., Carrizales, L., Castro, J., Díaz-Barriga, F., & Monroy, M. (2004). Arsenic and heavy metal pollution of soil, water and sediments in a semi-arid climate mining area in Mexico. Water Air and Soil Pollutution, 152, 129–152. https://doi.org/10.1023/B:WATE.0000015350.14520.c1
Redwan, M., Rammlmair, D., & Berkh, K. (2021). Secondary minerals in a calcareous environment: An example from Um Gheig Pb/Zn mine site, Eastern Desert, Egypt. Environmental Earth Sciences, 80, 1–19. https://doi.org/10.1007/s12665-021-09590-x
Schippers, A., Tanne, C., Stummeyer, J., & Graupner, T. (2019). Sphalerite bioleaching comparison in shake flasks and percolators. Minerals Engineering, 132, 251. https://doi.org/10.1016/j.mineng.2018.12.007
Sharma, G. K., Jena, R. K., Ray, P., Yadav, K. K., Moharana, P. C., Cabral-Pinto, M. M., & Bordoloi, G. (2021). Evaluating the geochemistry of groundwater contamination with iron and manganese and probabilistic human health risk assessment in endemic areas of the world’s largest River Island, India. Environmental Toxicology and Pharmacology, 87, 103690. https://doi.org/10.1016/j.etap.2021.103690
Shen, H., Christie, P., & Li, X. (2006). Uptake of zinc, cadmium and phosphorus by arbuscular mycorrhizal maize (Zea mays L.) from a low available phosphorus calcareous soil spiked with zinc and cadmium. Environmental Geochemistry and Health, 28, 111–119. https://doi.org/10.1007/s10653-005-9020-2
Sosa-Rodríguez, F. S., Vazquez-Arenas, J., Ponce-Peña, P., Aragón-Piña, A., Mallet, M., Trejo-Córdova, G., & Lara, R. H. (2023). Sphalerite oxidation simulating acidic, circumneutral and alkaline conditions to account for weathering behavior. Journal of Geochemical Exploration. https://doi.org/10.1016/j.gexplo.2023.107163
Sun, Z., Xiong, T., Zhang, T., Wang, N., Chen, D., & Li, S. (2019). Influences of zinc oxide nanoparticles on Allium cepa root cells and the primary cause of phytotoxicity. Ecotoxicology, 28, 175–188. https://doi.org/10.1007/s10646-018-2010-9
Tice, R. R., Agurell, E., Anderson, D., Burlinson, B., Hartmann, A., Kobayashi, H., et al. (2000). Single cell gel/comet assay: Guidelines for in vitro and in vivo genetic toxicology testing. Environmental and Molecular Mutagenesis, 35, 206–221. https://doi.org/10.1002/(sici)1098-2280(2000)35:3%3c206::aid-em8%3e3.0.co;2-j.
Torres, M. A., West, A. J., & Li, G. (2014). Sulphide oxidation and carbonate dissolution as a source of CO2 over geological timescales. Nature, 507, 346–349. https://doi.org/10.1038/nature13030
Vázquez-Sánchez, E. E., Robledo-Cabrera, A., Tong, X., & López-Valdivieso, A. (2020). Raman spectroscopy characterization of some Cu, Fe and Zn sulfides and their relevant surface chemical species for flotation. Physicochemical Problems of Mineral Processing. https://doi.org/10.37190/ppmp/119763.
Voegelin, A., Jacquat, O., Pfister, S., Barmettler, K., Scheinost, A. C., & Kretzschmar, R. (2011). Time-dependent changes of zinc speciation in four soils contaminated with zincite or sphalerite. Environmental Science and Technology, 45, 255–261. https://doi.org/10.1021/es101189d
Wahba, M., Fawkia, L. A. B. İB., & Zaghloul, A. (2019). Management of calcareous soils in arid region. International Journal of Environmental Pollution and Environmental Modelling, 2, 248–258.
Wan, Y., Jiang, B., Wei, D., & Ma, Y. (2020). Ecological criteria for zinc in Chinese soil as affected by soil properties. Ecotoxicology and Environmental Safety, 194, 110418. https://doi.org/10.1016/j.ecoenv.2020.110418
Wang, C., Liu, R., Sun, W., Jing, N., Xie, F., & He, Q. Z. D. (2021). Selective depressive effect of pectin on sphalerite flotation and its mechanisms of adsorption onto galena and sphalerite surfaces. Minerals Engineering, 170, 106989. https://doi.org/10.1016/j.mineng.2021.106989
Yadav, K. K., Gupta, N., Kumar, V., Choudhary, P., & Khan, S. A. (2018). GIS-based evaluation of groundwater geochemistry and statistical determination of the fate of contaminants in shallow aquifers from different functional areas of Agra city, India: Levels and spatial distributions. RSC Advances, 8, 15876–15889. https://doi.org/10.1039/C8RA00577J
Acknowledgements
This work has been partially supported by the Science and Technology Council of the State of Durango (COCYTED), through the STEM-2021-977 project and by Promotion of Applied Research with Character of Regional Development and Social, Environmental and Economic Relevance Program, through the 24450 project number. Fabiola S. Sosa-Rodríguez acknowledges the support from SECTEI through project No. 2284c23, “Monitoreo de la calidad del agua en los sistemas de captación de agua de lluvia (SCALL) y evaluación del programa de cosecha de agua de lluvia en la Ciudad de México”. The authors appreciate the contributions from Ing. Erasmo Mata Martínez (IG-UASLP) for sphalerite samples obtaining, conditioning and preparation for mineralogical analyses; to Dr. Angel G. Rodríguez (CIACYT-UASLP), and Dr. Jaime C. Rojas-Montes (CONAHCYT-TecNM/ITD) for Raman spectroscopy and XRD facilities, respectively. We are specially indebted with Dr. Manuel Dossot from LCPME-Université de Lorraine due to important comments to strength Raman interpretation. Hugo Ramírez-Aldaba thanks to CONAHCYT for his postdoctoral fellowship (grant number 4766117).
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RHL and JV-A contributed to the methodology, resources, software, funding, supervision, investigation and conceptualization, writing—original draft and review analysis, and project administration. FSS-R, PP-P, ARL-O, and GAA-V were involved in the methodology, supervision, resources and investigation. HR-A, MAG, GT, ER-B, and IL assisted in the formal analysis.
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There is a lack of studies regarding linkage between sphalerite weathering, including the effect of carbonates in the stability of secondary compounds, and the transitional stages of Zn (and Cd) bioaccumulation and exposure to plant systems in calcareous soil. The present work contributes to disclose these stages to better assess the transitory processes of Zn exposure to vegetable systems and ecotoxic damage rate affected by sphalerite weathering.
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Ponce-Peña, P., López-Ortega, A.R., Anguiano-Vega, G.A. et al. Ecotoxic effect in Allium cepa due to sphalerite weathering arising in calcareous conditions. Environ Geochem Health 46, 87 (2024). https://doi.org/10.1007/s10653-024-01857-z
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DOI: https://doi.org/10.1007/s10653-024-01857-z