Abstract
Goethite is an effective adsorbent for hexavalent chromium (Cr(VI)). Oxalic acid and other organic acids will affect the release, immobilization, and bioavailability of Cr(VI) in nature on the mineral surface. Mn(II) can accelerate the reduction of Cr(VI) with oxalic acid. Herein, the effects of oxalic acid and Mn(II) on the mobilization and transformation of adsorbed Cr(VI) on the surface of goethite were investigated in this study. The results revealed that Mn(II) could increase the adsorption of Cr(VI) by increasing the positive charge on the surface of goethite. The complexation of oxalic acid with the surface of goethite caused the adsorbed Cr(VI) to be released into the solution. Moreover, oxalic acid could undergo redox with adsorbed Cr(VI) through electron conduction on the surface of goethite, thereby resulting in the transformation of adsorbed Cr(VI) to Cr(III). During the reaction in the presence of oxalic acid, the concentration of Cr(III) increased from 0 to 13.9 mg/L. In addition, Mn(II), oxalic acid, and Cr(VI) could form unstable ester-like species in the solution, which accelerated the reduction of Cr(VI) to Cr(III). These findings of this study may enrich our understanding of the behaviors of Cr(VI) in the coexistence of goethite, oxalic acid, and Mn(II).








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References
Babel S, Kurniawan TA (2004) Cr(VI) removal from synthetic wastewater using coconut shell charcoal and commercial activated carbon modified with oxidizing agents and/or chitosan. Chemosphere 54:951–967
Bhuvaneswari R, Divya Bharathi M, Anbalagan G, Chakkaravarthi G, Sakthi Murugesan K (2018) Molecular structure, vibrational spectroscopic (FT-IR, FT-Raman), NBO, HOMO and LUMO analysis of morpholinium oxalate by density functional method. J Mol Struct 1173:188–195
Brose DA, James BR (2013) Hexavalent chromium reduction in solution and in chromite ore processing residue-enriched soil by tartaric acid with isopropyl alcohol and divalent manganese as co-reductants. J Environ Qual 42:766–773
Cheah SF, Kraemer SM, Cervini-Silva J, Sposito G (2003) Steady-state dissolution kinetics of goethite in the presence of desferrioxamine B and oxalate ligands: implications for the microbial acquisition of iron. Chem Geol 198:63–75
Cui J, Zhu N, Luo D, Li Y, Wu P, Dang Z, Hu X (2019) The role of oxalic acid in the leaching system for recovering indium from waste liquid crystal display panels. ACS Sustain Chem Eng 7:3849–3857
Dalal U, Reddy SN (2019) A novel nano zero-valent iron biomaterial for chromium (Cr6+ to Cr3+) reduction. Environ Sci Pollut Res 26:10631–10640
Deng B, Stone AT (1996) Surface-catalyzed chromium(VI) reduction: reactivity comparisons of different organic reductants and different oxide surfaces. Environ Sci Technol 30:2484–2494
Fang D, Wei S, Xu Y, Xiong J, Tan W (2019) Impact of low-molecular weight organic acids on selenite immobilization by goethite: understanding a competitive-synergistic coupling effect and speciation transformation. Sci Total Environ 684:694–704
Flynn ED, Catalano JG (2018) Influence of oxalate on Ni fate during Fe(II)-catalyzed recrystallization of hematite and goethite. Environ Sci Technol 52:6920–6927
Fu Z, Wu F, Song K, Lin Y, Bai Y, Zhu Y, Giesy JP (2013) Competitive interaction between soil-derived humic acid and phosphate on goethite. Appl Geochem 36:125–131
Gadol HJ, Flynn ED, Catalano JG (2017) Oxalate-promoted trace metal release from crystalline iron oxides under aerobic conditions. Environ Sci Technol Lett 4:311–315
Galan B, Castaneda D, Ortiz I (2005) Removal and recovery of Cr(VI) from polluted ground waters: a comparative study of ion-exchange technologies. Water Res 39:4317–4324
Gao WG, Liu XC, Chen MF (2017) In situ ATR-FTIR investigation and theoretical calculation of the interactions of chromate and citrate on the surface of haematite (α-Fe2O3). RSC Adv 7:41011–41016
Gao W, Yan J, Qian L, Han L, Chen M (2018) Surface catalyzing action of hematite (α-Fe2O3) on reduction of Cr(VI) to Cr(III) by citrate. Environ Technol Innov 9:82–90
Gheju M, Balcu I (2017) Assisted green remediation of chromium pollution. J Environ Manag 203:920–924
Gheju M, Balcu I (2019) Sustaining the efficiency of the Fe(0)/H2O system for Cr(VI) removal by MnO2 amendment. Chemosphere 214:389–398
Guo X, Yang C, Wu Y, Dang Z (2014) The influences of pH and ionic strength on the sorption of tylosin on goethite. Environ Sci Pollut Res 21:2572–2580
Jin X, Liu Y, Tan J, Owens G, Chen Z (2018) Removal of Cr(VI) from aqueous solutions via reduction and absorption by green synthesized iron nanoparticles. J Clean Prod 176:929–936
Kabir-ud-Din, Hartani K, Khan Z (2001) Effect of micelles on the oxidation of oxalic acid by chromium(VI) in the presence and absence of manganese(II). Colloids Surf A Physicochem Eng Asp 193:1–13
Kabir-ud-Din, Hartani K, Khan Z (2002) One-step three-electron oxidation of tartaric and glyoxylic acids by chromium(VI) in the absence and presence of manganese(II). Transit Met Chem 27:617–624
Kaya A, Onac C, Korkmaz Alpoguz H (2016) A novel electro-driven membrane for removal of chromium ions using polymer inclusion membrane under constant D.C. electric current. J Hazard Mater 317:1–7
Kretschmer I, Senn AM, Martin Meichtry J, Custo G, Halac EB, Dillert R, Bahnemann DW, Litter MI (2019) Photocatalytic reduction of Cr(VI) on hematite nanoparticles in the presence of oxalate and citrate. Appl Catal B Environ 242:218–226
Kumar V, Parihar RD, Sharma A, Bakshi P, Singh Sidhu GP, Bali AS, Karaouzas I, Bhardwaj R, Thukral AK, Gyasi-Agyei Y, Rodrigo-Comino J (2019) Global evaluation of heavy metal content in surface water bodies: a meta-analysis using heavy metal pollution indices and multivariate statistical analyses. Chemosphere 236:124364
Liao S, Wang J, Zhu D, Ren L, Lu J, Geng M, Langdon A (2007) Structure and Mn2+ adsorption properties of boron-doped goethite. Appl Clay Sci 38:43–50
Litter MI (2017) Last advances on TiO2-photocatalytic removal of chromium, uranium and arsenic. Curr Opin Green Sustain Chem 6:150–158
Liu Y, Liu X, Zhao Y, Dionysiou DD (2017) Aligned α-FeOOH nanorods anchored on a graphene oxide-carbon nanotubes aerogel can serve as an effective Fenton-like oxidation catalyst. Appl Catal B Environ 213:74–86
Mo X, Yang Z, Xu H, Zeng G, Huang J, Yang X, Song P, Wang L (2015) Combination of cathodic reduction with adsorption for accelerated removal of Cr(VI) through reticulated vitreous carbon electrodes modified with sulfuric acid-glycine co-doped polyaniline. J Hazard Mater 286:493–502
Mu Y, Jiang X, Ai Z, Jia F, Zhang L (2018) Mn2+ promoted Cr(VI) reduction with oxalic acid: the indispensable role of in-situ generated Mn3+. J Hazard Mater 343:356–363
Persson P, Axe K (2005) Adsorption of oxalate and malonate at the water-goethite interface: molecular surface speciation from IR spectroscopy. Geochim Cosmochim Acta 69:541–552
Polowczyk I, Urbano BF, Rivas BL, Bryjak M, Kabay N (2016) Equilibrium and kinetic study of chromium sorption on resins with quaternary ammonium and N-methyl-D-glucamine groups. Chem Eng J 284:395–404
Qian X, Ren M, Zhu Y, Yue D, Han Y, Jia J, Zhao Y (2017) Visible light assisted heterogeneous Fenton-like degradation of organic pollutant via α-FeOOH/mesoporous carbon composites. Environ Sci Technol 51:3993–4000
Rahimi S, Moattari RM, Rajabi L, Derakhshan AA, Keyhani M (2015) Iron oxide/hydroxide (α,γ-FeOOH) nanoparticles as high potential adsorbents for lead removal from polluted aquatic media. J Ind Eng Chem 23:33–43
Ren HT, Jia SY, Liu Y, Wu SH, Han X (2012) Effects of Mn(II) on the sorption and mobilization of As(V) in the presence of hematite. J Hazard Mater 217-218:301–306
Sarkar B, Naidu R, Krishnamurti GSR, Megharaj M (2013) Manganese(II)-catalyzed and clay-minerals-mediated reduction of chromium(VI) by citrate. Environ Sci Technol 47:13629–13636
Shi Z, Li F, Yao S (2010) Effect of small organic acid anions on the adsorption of phosphate anions onto synthetic goethite from aqueous solution. Adsorpt Sci Technol 28:885–893
Simanova AA, Loring JS, Persson P (2011) Formation of ternary metal-oxalate surface complexes on α-FeOOH particles. J Phys Chem C 115:21191–21198
Sitthichai S, Pilapong C, Thongtem T, Thongtem S (2015) CMC-coated Fe3O4 nanoparticles as new MRI probes for hepatocellular carcinoma. Appl Surf Sci 356:972–977
Su M, Fang Y, Li B, Yin W, Gu J, Liang H, Li P, Wu J (2019) Enhanced hexavalent chromium removal by activated carbon modified with micro-sized goethite using a facile impregnation method. Sci Total Environ 647:47–56
Wang T, Zhang L, Li C, Yang W, Song T, Tang C, Meng Y, Dai S, Wang H, Chai L, Luo J (2015) Synthesis of core-shell magnetic Fe3O4@poly(m-phenylenediamine) particles for chromium reduction and adsorption. Environ Sci Technol 49:5654–5662
Wang Y, Ma J, Chen K (2013) Adsorptive removal of Cr(VI) from wastewater by α-FeOOH hierarchical structure: kinetics, equilibrium and thermodynamics. Phys Chem Chem Phys 15:19415–19421
Wilson D, Langell MA (2014) XPS analysis of oleylamine/oleic acid capped Fe3O4 nanoparticles as a function of temperature. Appl Surf Sci 303:6–13
Wu T, Sun Q, Fang G, Cui P, Liu C, Alves ME, Qin W, Zhou D, Shi Z, Wang Y (2019) Unraveling the effects of gallic acid on Sb(III) adsorption and oxidation on goethite. Chem Eng J 369:414–421
Xie J, Gu X, Tong F, Zhao Y, Tan Y (2015) Surface complexation modeling of Cr(VI) adsorption at the goethite-water interface. J Colloid Interface Sci 455:55–62
Yang X, Liu L, Zhang M, Tan W, Qiu G, Zheng L (2019) Improved removal capacity of magnetite for Cr(VI) by electrochemical reduction. J Hazard Mater 374:26–34
Yu B, Jia SY, Liu Y, Wu SH, Han X (2013) Mobilization and re-adsorption of arsenate on ferrihydrite and hematite in the presence of oxalate. J Hazard Mater 262:701–708
Zhang Y, Yang J, Du J, Xing B (2019) Goethite catalyzed Cr(VI) reduction by tartaric acid via surface adsorption. Ecotoxicol Environ Saf 171:594–599
Zubir NA, Yacou C, Motuzas J, Zhang X, Diniz da Costa JC (2014) Structural and functional investigation of graphene oxide-Fe3O4 nanocomposites for the heterogeneous Fenton-like reaction. Sci Rep 4:4594
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This research was financially supported by the National Natural Science Foundation of China (No. 51978174) and Natural Science Foundation of Guangdong Province (No. 2018A030313099).
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Liang, C., Tang, B., Zhang, X. et al. Mobility and transformation of Cr(VI) on the surface of goethite in the presence of oxalic acid and Mn(II). Environ Sci Pollut Res 27, 26115–26124 (2020). https://doi.org/10.1007/s11356-020-09016-4
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DOI: https://doi.org/10.1007/s11356-020-09016-4


