Abstract
A combined approach based on multiple X-ray analytical techniques and conventional methods was adopted to investigate the distribution and speciation of Cr in a polluted agricultural soil, from the bulk-scale down to the (sub)micro-level. Soil samples were collected from two different points, together with a control sample taken from a nearby unpolluted site. The bulk characterization revealed that the polluted soils contained much higher concentrations of organic matter (OM) and potentially toxic elements (PTE) than the control. Chromium was the most abundant PTE (up to 5160 g kg−1), and was present only as Cr(III), as its oxidation to Cr(VI) was hindered by the high OM content. According to sequential extractions, Cr was mainly associated to the soil oxidisable fraction (74%) and to the residual fraction (25%). The amount of Cr potentially bioavailable for plant uptake (DTPA-extractable) was negligible. Characterization of soil thin sections by micro X-ray fluorescence (μXRF) and field emission scanning electron microscopy coupled with microanalysis (FEGSEM-EDX) showed that Cr was mainly distributed in aggregates ranging from tens micrometres to few millimetres in size. These aggregates were coated with an aluminosilicate layer and contained, in the inner part, Cr, Ca, Zn, P, S and Fe. Hyperspectral elaboration of μXRF data revealed that polluted soils were characterised by an exogenous organic-rich fraction containing Cr (not present in the control), and an endogenous aluminosilicate fraction (present also in the control), coating the Cr-containing aggregates. Analyses by high-resolution micro X-ray computed tomography (μCT) revealed a different morphology of the soil aggregates in polluted soils compared with the control. The finding of microscopic leather residues, combined with the results of bulk- and micro-characterizations, suggested that Cr pollution was likely ascribable to soil amendment with tannery waste-derived matrices. However, over the years, a natural process of Cr stabilization occurred in the soil thus reducing the environmental risks.
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References
Alfeld M, Janssens K (2015) Strategies for processing mega-pixel X-ray fluorescence hyperspectral data: a case study on a version of Caravaggio’s painting supper at Emmaus. J Anal Atom Spectrom 30:777–789. https://doi.org/10.1039/c4ja00387j
Allegretta I, Porfido C, Martin M, Barberis E, Terzano R, Spagnuolo M (2018) Characterization of As-polluted soils by laboratory X-ray-based techniques coupled with sequential extractions and electron microscopy: the case of Crocette gold mine in the Monte Rosa mining district (Italy). Environ Sci Pollut Res 25:25080–25090. https://doi.org/10.1007/s11356-018-2526-9
Barceló, J., and Poschenrieder, C. (1997) “Chromium in plants”, in Chromium Environmental Issues, eds. S. Canali, F. Tittarelli, P. Sequi (Milano, Italy: FrancoAngeli s.r.l.), 101-129
Barnhart J (1997) Occurrences, uses, and properties of chromium. Regul Toxicol Pharmacol 26:3–7. https://doi.org/10.1006/rtph.1997.1132
Bartlett RJ, and James BR (1996) “Chromium, methods of soil analysis”, in Methods of Soil Analysis, Part 3-Chemical Methods, ed. D. L. Sparks (Madison, WI: ASA/SSSA Press), 683-701
Bartlett RJ (1997). “Chromium redox mechanisms in soils: should we worry about Cr(VI)?”, in Chromium Environmental Issues, eds. S. Canali, F. Tittarelli, P. Sequi (Milano, Italy: FrancoAngeli s.r.l.), 1–20
Becquer T, Quantin C, Sicot M, Boudot JP (2003) Chromium availability in ultramafic soils from New Caledonia. Sci Total Environ 301:251–261. https://doi.org/10.1016/S0048-9697(02)00298-X
Brunetti G, Farrag K, Soler-Rovira P, Ferrara M, Nigro F, Senesi N (2012) Heavy metals accumulation and distribution in durum wheat and barley grown in contaminated soils under Mediterranean field conditions. J Plant Interact 7:160–174. https://doi.org/10.1080/17429145.2011.603438
Cassano A, Molinari R, Romano M, Drioli E (2001) Treatment of aqueous effluents of the leather industry by membrane processes - a review. J Membr Sci 181:111–126. https://doi.org/10.1016/S0376-7388(00)00399-9
Ciavatta C, Manoli C, Cavani L, Franceschi C, Sequi P (2012) Chromium-containing organic fertilizers from tanned hides and skins: a review on chemical, environmental, agronomical and legislative aspects. J Environ Prot 3:1532–1541. https://doi.org/10.4236/jep.2012.311169
Cook KR (2000) In situ treatment of soil and groundwater contaminated with chromium – technical resource guide. EPA/625/R-00/005. U.S. Environmental Protection Agency Press, Ohio
Cubadda F, Ciardullo S, D’Amato M, Raggi A, Aureli F, Carcea M (2010) Arsenic contamination of the environment-food chain: a survey on wheat as a test plant to investigate phytoavailable arsenic in Italian agricultural soils and as a source of inorganic arsenic in the diet. J Agric Food Chem 58:10176–10183. https://doi.org/10.1021/jf102084p
Dhal B, Thatoi HN, Das NN, Pandey BD (2013) Chemical and microbial remediation of hexavalent chromium from contaminated soil and mining/metallurgical solid waste: a review. J Hazard Mater 250–251:272–291. https://doi.org/10.1016/j.jhazmat.2013.01.048
Ertani A, Mietto A, Borin M, Nardi S (2017) Chromium in agricultural soils and crops: a review. Water Air Soil Pollut 228:190. https://doi.org/10.1007/s11270-017-3356-y
Förstner U, Salomons W (1980) Trace metal analysis of polluted sediments. Environ Sci Technol Lett 1:494–505. https://doi.org/10.1080/09593338009384006
Gattullo CE, D’Alessandro C, Allegretta I, Porfido C, Spagnuolo M, Terzano R (2018a) Alkaline hydrothermal stabilization of Cr(VI) in soil using glass and aluminum from recycled municipal solid wastes. J Hazard Mater 344:381–389. https://doi.org/10.1016/j.jhazmat.2017.10.035
Gattullo CE, Pii Y, Allegretta I, Medici L, Cesco S, Mimmo T et al (2018b) Iron mobilization and mineralogical alterations induced by iron-deficient cucumber plants (Cucumis sativus L.) in a calcareous soil. Pedosphere 28:59–69. https://doi.org/10.1016/S1002-0160(15)60104-7
Gualtieri AF (2000) Accuracy of XRPD QPA using the combined Rietveld-RIR method. J Appl Crystallogr 33:267–278. https://doi.org/10.1107/S002188989901643X
Gupta V, Jatav PK, Verma R, Kothari SL, Kachhwaha S (2017) Nickel accumulation and its effect on growth, physiological and biochemical parameters in millets and oats. Environ Sci Pollut Res 24:23915–23925. https://doi.org/10.1007/s11356-017-0057-4
Hänsch R, Mendel RR (2009) Physiological functions of mineral micronutrients (Cu, Zn, Mn, Fe, Ni, Mo, B, Cl). Curr Opin Plant Biol 12:259–266. https://doi.org/10.1016/j.pbi.2009.05.006
Indorante SJ, Hammer RD, Koenig PG, Follmer LR (1990) Particle-size analysis by a modified pipette procedure. Soil Sci Soc Am J 54:560–563. https://doi.org/10.2136/sssaj1990.03615995005400020047x
Italian Legislative Decree n. 152 (2006). Decreto legislativo 3 aprile 2006, n. 152. Norme in Materia Ambientale (Gazzetta Ufficiale Della Repubblica Italiana n. 88. Supplemento Ordinario n. 96, 14 aprile 2006)
Italian Legislative Decree n. 99 (1992). Decreto legislativo 27 gennaio 1992, n. 99. Attuazione della direttiva 86/278/CEE concernente la protezione dell’ambiente, in particolare del suolo, nell’utilizzazione dei fanghi di depurazione in agricoltura (Gazzetta Ufficiale Della Repubblica Italiana n.28. Supplemento Ordinario n. 38, 15 Febbraio 1992)
Italian Ministerial Decree n. 186/, (2006). Decreto del Ministero dell’Ambiente e della Tutela del Territorio 5 aprile 2006, n. 186. Regolamento recante modifiche al decreto ministeriale 5 febbraio 1998 (Gazzetta Ufficiale della Repubblica Italiana n. 115, 19 maggio 2006)
IUSS Working Group WRB. 2006. World reference base for soil resources. World Soil Resources Reports No. 103. FAO, Rome
James BR, Petura JC, Vitale RJ, Mussoline GR (1995) Hexavalent chromium extraction from soils - a comparison of 5 methods. Environ Sci Technol 29:2377–2381. https://doi.org/10.1021/es00009a033
Kabata-Pendias, A., and Mukherjee, A. B. (2007). “Chromium”, in Trace Elements from Soil to Human, eds. A. Kabata-Pendias, A.B. Mukherjee (Berlin Heidelberg, Germany: Springer Verlag), 173–183
Kanagaraj J, Tamil Selvi A, Senthilvelan T, Chandra Babu NK, Chandrasekar B (2014) Evaluation of new bacteriocin as a potential short-term preservative for goat skin. Am J Microbiol Res 2:86–93. https://doi.org/10.12691/ajmr-2-3-2
Khandelwal HB, More SV, Kalal KM, Laxman RS (2015) Eco-friendly enzymatic dehairing of skins and hides by C. brefeldianus protease. Clean Techn Environ Policy 17:393–405. https://doi.org/10.1007/s10098-014-0791-y
Köleli N (2004) Speciation of chromium in 12 agricultural soils from Turkey. Chemosphere 57:1473–1478. https://doi.org/10.1016/j.chemosphere.2004.08.068
Kolomaznik K, Adamek M, Andel I, Uhlirova M (2008) Leather waste—potential threat to human health, and a new technology of its treatment. J Hazard Mater 160:514–520. https://doi.org/10.1016/j.jhazmat.2008.03.070
Lindsay WL, Norwell WA (1978) Development of DTPA of soil test for Zn, Fe, Mn and Cu. J Am Soil Sci 42:421–428. https://doi.org/10.2136/sssaj1978.03615995004200030009x
Lombi E, Susini J (2009) Synchrotron-based techniques for plant and soil science: opportunities, challenges and future perspectives. Plant Soil 320:1–35. https://doi.org/10.1007/s11104-008-9876-x
Majumdar S, Peralta-Videa JR, Castillo-Michel H, Hong J, Rico CM, Gardea-Torresdey JL (2012) Applications of synchrotron μ-XRF to study the distribution of biologically important elements in different environmental matrices: a review. Anal Chim Acta 755:1–16. https://doi.org/10.1016/j.aca.2012.09.050
Mehta N, Cocerva T, Cipullo S, Padoan E, Dino GA, Ajmone-Marsan F, Cox SF, Coulon F, de Luca DA (2019) Linking oral bioaccessibility and solid phase distribution of potentially toxic elements in extractive waste and soil from an abandoned mine site: case study in Campello Monti, NW Italy. Sci Total Environ 651:2799–2810. https://doi.org/10.1016/j.scitotenv.2018.10.115
Morrison JM, Goldhaber MB, Lee L, Holloway JM, Wanty RB, Wolf RE, Ranville JF (2009) A regional-scale study of chromium and nickel in soils of northern California, USA. Appl Geochem 24:1500–1511. https://doi.org/10.1016/j.apgeochem.2009.04.027
Oze C, Fendorf S, Bird DK, Coleman RG (2004) Chromium geochemistry of serpentine soils. Int Geol Rev 46:97–126. https://doi.org/10.2747/0020-6814.46.2.97
Parra S, Bravo MA, Quiroz W, Moreno T, Karanasiou A, Font O, Vidal V, Cereceda F (2014) Distribution of trace elements in particle size fractions for contaminated soils by a copper smelting from different zones of the Puchuncaví Valley (Chile). Chemosphere 111:513–521. https://doi.org/10.1016/j.chemosphere.2014.03.127
Pettine M, Capri S (2005) Digestion treatments and risks of Cr(III)-Cr(VI) interconversions during Cr(VI) determination in soils and sediments - a review. Anal Chim Acta 540:231–238. https://doi.org/10.1016/j.aca.2005.03.040
Qian J, Shan X, Wang Z, Tu Q (1996) Distribution and plant availability of heavy metals in different particle-size fractions of soil. Sci Total Environ 187:131–141. https://doi.org/10.1016/0048-9697(96)05134-0
Sahuquillo A, López-Sánchez JF, Rubio R, Rauret G, Thomas RP, Davidson CM, Ure AM (1999) Use of certified reference material for extractable trace metals to assess sources of uncertainty in the BCR three-stage sequential extraction procedure. Anal Chim Acta 382:317–327. https://doi.org/10.1016/S0003-2670(98)00754-5
Shahid M, Shamshad S, Rafiq M, Khalid S, Bibi I, Niazi NK, Dumat C, Rashid MI (2017) Chromium speciation, bioavailability, uptake, toxicity and detoxification in soil-plant system: a review. Chemosphere 178:513–533. https://doi.org/10.1016/j.chemosphere.2017.03.074
Shanker AK, Cervantes C, Loza-Taverac H, Avudainayagam S (2005) Chromium toxicity in plants. Environ Int 31:739–753. https://doi.org/10.1016/j.envint.2005.02.003
Silva MDM, Barajas-Aceves M, Araújo ASF, Araújo FF, Melo WJ (2014) Soil microbial biomass after three-year consecutive composted tannery sludge amendment. Pedosphere 24:469–475. https://doi.org/10.1016/S1002-0160(14)60033-3
Solé VA, Papillon E, Cotte M, Walter P, Susini J (2007) A multiplatform code for the analysis of energy-dispersive X-ray fluorescence spectra. Spectochim Acta B 62:63–68. https://doi.org/10.1016/j.sab.2006.12.002
Soriano-Disla JM, Speir TW, Gómez I, Clucas LM, McLaren RG, Navarro-Pedreño J (2010) Evaluation of different extraction methods for the assessment of heavy metal bioavailability in various soils. Water Air Soil Pollut 213:471–483. https://doi.org/10.1007/s11270-010-0400-6
Sparks DL (1996) Methods of soil analysis, part 3, chemical methods. In: SSSA Book Series No 5. ASA/SSSASA Press, Madison
Terzano R, Spagnuolo M, Vekemans B, De Nolf W, Janssens K, Falkenberg G et al (2007) Assessing the origin and fate of Cr, Ni, Cu, Zn, Pb, and V in an industrial polluted soil by combined microspectroscopic techniques and bulk extraction methods. Environ Sci Technol 41:6762–6769. https://doi.org/10.1021/es070260h
Terzano R, Denecke MA, Falkenberg G, Miller B, Paterson D, Janssens K (2019) Recent advances in analysis of trace elements in environmental samples by X-ray based techniques (IUPAC technical report). Pure Appl Chem 91:1029–1063. https://doi.org/10.1515/pac-2018-0605
Thouin H, Le Forestier L, Gautret P, Hube D, Laperche V, Dupraz S et al (2016) Characterization and mobility of arsenic and heavy metals in soils polluted by the destruction of arsenic-containing shells from the Great War. Sci Total Environ 550:658–669. https://doi.org/10.1016/j.scitotenv.2016.01.111
USEPA, Method 3060A (1996). Alkaline digestion for hexavalent chromium. Washington: United States Environmental Protection Agency
USEPA, Method 7196A (1992) Chromium, hexavalent (colorimetric). United States Environmental Protection Agency, Washington
Vanhoof C, Corthouts V, Tirez K (2004) Energy-dispersive X-ray fluorescence systems as analytical tool for assessment of contaminated soils. J Environ Monit 6:344–350. https://doi.org/10.1039/b312781h
Wang X-S, Qin Y, Chen Y-K (2006) Heavy meals in urban roadside soils, part 1: effect of particle size fractions on heavy metals partitioning. Environ Geol 50:1061–1066. https://doi.org/10.1007/s00254-006-0278-1
Wen J, Li Z, Huang B, Luo N, Huang M, Yang R, Zhang Q, Zhai X, Zeng G (2018) The complexation of rhizosphere and nonrhizosphere soil organic matter with chromium: using elemental analysis combined with FTIR spectroscopy. Ecotox Environ Safe 154:52–58. https://doi.org/10.1016/j.ecoenv.2018.02.014
Wong JWC, Li K, Fang M, Su DC (2001) Toxicity evaluation of sewage sludges in Hong Kong. Environ Int 27:373–380. https://doi.org/10.1016/S0160-4120(01)00088-5
Yarlagadda PS, Matsumoto MR, VanBenschoten JE, Kathuria A (1995) Characteristics of heavy metals in contaminated soils. J Environ Eng 121:276–286. https://doi.org/10.1061/(ASCE)0733-9372(1995)121:4(276)
Acknowledgements
The authors thank Mrs. Rosaria Mininni of the University of Bari for the technical support given in soil analyses. X-ray analyses were performed at the “Micro X-ray Lab” of the University of Bari. The work was supported by the Research Programme “FutureIn-Research” (Regione Puglia, Italy).
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This study was supported by the Research Programme “FutureIn-Research” (Regione Puglia, Italy).
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Conceptualization: Concetta Eliana Gattullo and Roberto Terzano; Methodology: Concetta Eliana Gattullo, Ignazio Allegretta and Roberto Terzano; Formal analysis and investigation: Concetta Eliana Gattullo, Ignazio Allegretta, Carlo Porfido and Ida Rascio; Writing - original draft preparation: Concetta Eliana Gattullo; Reviewing: Matteo Spagnuolo and Roberto Terzano; Funding acquisition: Matteo Spagnuolo and Roberto Terzano; Supervision: Roberto Terzano.
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Gattullo, C.E., Allegretta, I., Porfido, C. et al. Assessing chromium pollution and natural stabilization processes in agricultural soils by bulk and micro X-ray analyses. Environ Sci Pollut Res 27, 22967–22979 (2020). https://doi.org/10.1007/s11356-020-08857-3
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DOI: https://doi.org/10.1007/s11356-020-08857-3