The Role of Carboxyl and Hydroxyl Groups of Humic Acid in Removing AuCl4- from Aqueous Solution

Sri Sudiono(1), Mustika Yuniarti(2), Dwi Siswanta(3), Eko Sri Kunarti(4), Triyono Triyono(5), Sri Juari Santosa(6*)

(1) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281
(2) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281
(3) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281
(4) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281
(5) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281
(6) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281
(*) Corresponding Author


Humic acid (HA) extracted from peat soil according to the recommended procedure of the International Humic Substances Society (IHSS) has been tested to remove AuCl4- from aqueous solution. The removal was optimum at pH 2.0 and it was mainly dictated by attachment through hydrogen bonding to unionized carboxyl (–COOH) groups and reduction by the action of the hydroxyl (–OH) groups to gold (Au) metal. The removal of AuCl4- improved after HA was purified through repeated immersion and shaking in a mixed solution containing 0.1 M HCl and 0.3 M HF. When the purification led to the sharp decrease in ash content from 39.34 to 0.85% (w/w) and significant increase in both the –COOH and –OH contents from 3240 to 3487 mmol/kg and from 4260 to 4620 mmol/kg, respectively; the removal of AuCl4- improved from 0.105 to 0.133 mmol/g. This improvement of AuCl4- removal by the purified HA was accompanied by higher ability in reduction to Au metal. The attached AuCl4- on –COOH groups of both crude and purified HAs was qualitatively observed by the characterization result of FT-IR spectroscopy, while the presence of Au metal on the surface of those HAs was verified by the characterization result of XRD.


Humic acid; carboxyl group; hydroxyl group; AuCl4-; removal

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[1] Yustiawati, Kihara, Y., Sazawa, K., Kuramitz, H., Kurasaki, M., Saito, T., Hosokawa, T., Syawal, M.S., Wulandari, L., Hendri, I., and Tanaka, S., 2015, Effects of peat fires on the characteristics of humic acid extracted from peat soil in Central Kalimantan, Indonesia, Environ. Sci. Pollut. Res., 22 (4), 2384–2395.

[2] Hough, R.M., Noble, R.R.P., and Reich, M., 2011, Natural gold nanoparticles, Ore Geol. Rev., 42, 55–61.

[3] Arbuzov, S.I., Rikhvanov, L.P., Maslov, S.G., Arhipov, V.S., and Belaeva, A.M., 2006, Anomalous gold contents in brown coals and peat in the south-eastern region of the Western-Siberian platform, Int. J. Coal Geol., 68 (3-4), 127–132.

[4] Loffredo, E., and Senesi, N., 2006, Soil and Water Pollution Monitoring, Protection and Remediation, in NATO Sciences Series IV, Earth, and Environmental Sciences, Vol. 69, Eds. Tardowski, I., Allen, H.E., and Haggblom, M.M., Springer, Berlin.

[5] Zhu, Y., An, F., and Tan, J., 2011, Geochemistry of hydrothermal gold deposits: A review, Geosci. Frontiers, 2 (3), 367–374.

[6] Baker, T., Bertelli, M., Blenkinsop, T., Cleverley, J.S., Mvlellan, J., Nugus, M., and Gillen, D., 2010, P-T-X conditions of fluids in the sunrise dam gold deposit, Western Australia, and implications for the interplay between deformation and fluids, Econ. Geol., 105 (5), 873–894.

[7] Lintern, M.J., Hough, R.M., Ryan, C.G., Watling, J., and Verrall, M., 2009, Ionic gold in calcrete revealed by LA-ICP-MS, SXRF and XANES, Geochim. Cosmochim. Acta, 73 (6), 1666–1683.

[8] Senesi, N., and Plaza, C., 2007, Role of humification processes in recycling organic wastes of various nature and sources as soil amendments, Clean-Soil, Air, Water, 35 (1), 26–41.

[9] Pramanik, P., and Kim, P.J., 2013, Fractionation and characterization of humic acids from organic amended rice paddy soils, Sci. Total Environ., 466-467, 952–956.

[10] Litvin, V.A., Galagan, R.L., and Minaev, B.F., 2012, Kinetic and mechanism formation of silver nanoparticles coated by synthetic humic substances, Colloids Surf., A, 414, 234–243.

[11] Lin, Y.H., and Su, P.H., 2010, Behavior of Aluminum adsorption in different compost-derived humic acids, Clean-Soil, Air, Water, 38 (10), 916–920.

[12] Erny, G.L., Gonçalves, B.M., and Esteves, V.I., 2013, Immobilized humic substances and immobilized aggregates of humic substances as sorbent for solid phase extraction, J. Chromatogr. A, 1306, 104–108.

[13] Tang, W.W. Zeng, G.M., Gong, J.L, Liang, J., Xu, P., Zhang C., and Huang, B.B., 2014, Impact of humic/fulvic acid on the removal of heavy metals from aqueous solutions using nanomaterials: A review, Sci. Total Environ., 468-469, 1014–1027.

[14] Batista, A.P.S., Romão, L.P.C., Arguelho, M.L.P.M., and Garcia, C.A.B., 2009, Biosorption of Cr(III) using in natura and chemically treated tropical peats, J. Hazard. Mater., 163 (2-3), 517–523.

[15] Santosa, S.J., Siswanta, D., Sudiono, S., and Sehol, M., 2007, Synthesis and utilization of chitin–humic acid hybrid as sorbent for Cr(III), Surf. Sci., 601 (22), 5148–5153.

[16] Santosa, S.J., Sundari, S., Sudiono, S., and Rahmanto, W.H., 2006, A new type of adsorbent based on the immobilization of humic acid on chitin and its application to adsorb Cu(II), e-J. Surf. Sci. Nanotechnol., 4, 46.

[17] Santosa, S.J., Siswanta, D., Sudiono, S., and Sehol, M., 2010, Synthesis and utilization of chitin–humic acid hybrid as sorbent for Cr(III), Surf. Sci., 601 (22), 5148–5153.

[18] Hori, M., Shozugawa, K. and Matsuo, M., 2015, Reduction process of Cr(VI) by Fe(II) and humic acid analyzed using high time resolution XAFS analysis, J. Hazard. Mater., 285, 140–147.

[19] Yel, E., and Ahmetli, G., 2015, Environmental dilemma of humic substances: being adsorbents and being carcinogens, Int. J. Environ. Sci. Dev., 6 (1), 73–76.

[20] Santosa, S.J., Siswanta, D., Kurniawan, A., and Rahmanto, W.H., 2007, Hybrid of chitin and humic acid as high performance sorbent for Ni(II), Surf. Sci., 601 (22), 5155–5161.

[21] Santosa, S.J., Sudiono, S., and Sujandi, S., 2006, Peat soil humic acid immobilization on silica gel and its application as an adsorbent for the selective adsorption of Copper, e-J. Surf. Sci. Nanotechnol., 4, 602–608.

[22] Santosa, S.J., Santoso, U.T., Siswanta, D., and Jumina, 2009, “Toxic Metal Decontamination by Means of Peat Soil Derived Humic Acid Immobilized on Crab Shell Chitosan” in Handbook on Environmental Quality, Ed. Ertuo, K., Nova Science Publishers, New York.

[23] Santosa, S.J., Raharjo, B., Taftanzani, A., and Basuki, K.T., 2006, Synthesis and Utilization of Organic-Inorganic Hybrid of Humic Acid-Bentonite as Sorbent for Cs(I) and Am(III), Proc. 1st Int. IUPAC Conf. “Green-Sustainability Chemistry”, Dresden, Germany.

[24] Huang, S.W., Chiang, P.N., Liu, J.C., Hung, J.T., Kuan, W.H., Tzou, Y.M., Wang, S.L., Huang J.H., Chen, C.C., Wang, M.K., and Loeppert, R.H, 2012, Chromate reduction on humic acid derived from a peat soil – Exploration of the activated sites on HAs for chromate removal, Chemosphere, 87 (6), 587–594.

[25] Santosa, S.J., Sudiono, S., Siswanta, D., Kunarti, E.S., and Dewi, S.R., 2011, Mechanism of the removal of AuCl4 ions from aqueous solution by means of peat soil humin, Adsorpt. Sci. Technol., 29 (11), 733–746.

[26] Santosa, S.J., 2014, Sorption kinetics of Cd(II) species on humic acid‐based sorbent, Clean-Soil, Air, Water, 42 (6), 760–766.

[27] Ren, Z.L., Tella, M., Bravin, M.N., Comans, R.N.J., Dai, J., Garnier, J-M., Sivry, Y., Doelsch, E., Straathof, A., and Benedetti, M.F., 2015, Effect of dissolved organic matter composition on metal speciation in soil solutions, Chem. Geol., 398, 61–69.

[28] Santosa, S.J., Siswanta, D., Sudiono, S., and Utarianingrum, R., 2008, Chitin–humic acid hybrid as adsorbent for Cr(III) in effluent of tannery wastewater treatment, Appl. Suf. Sci., 254 (23), 7846-7850.

[29] Gunzler, H., and Gremlich, H-U, 2002, IR Spectroscopy, Wiley-VCH, Weinheim.

[30] Morris, M.C., McMurdie, H.F., Evans, E.H., Paretzkin, B., Parker, H.S., and Panagiotopoulos, N.C., 1981, Standard X-ray Diffraction Powder Patterns Section 18 Data for 58 Substances, National Bureau of Standards, Washington, DC 20234, 1–105.

[31] Baidoo, E., Ephraim, J.H., Darko, G., and Akoto, O., 2014, Potentiometric studies of the acid–base properties of tropical humic acids, Geoderma,
217-218, 18–25.

[32] Klučáková, M., and Kolajová, R., Dissociation ability of humic acids: Spectroscopic determination of pKa and comparison with multi-step mechanism, 2014, React. Funct. Polym., 78, 1–6.

[33] Rodríguez, F.J., Schlenger, P., and García-Valverde, M., 2014, A comprehensive structural evaluation of humic substances using several fluorescence techniques before and after ozonation. Part I: Structural characterization of humic substances, Sci. Total Environ., 476-477, 718–730.

[34] Muscolo, A., Sidari, M., and Nardi, S., 2013, Humic substance: Relationship between structure and activity. Deeper information suggests univocal findings, J. Geochem. Explor., 129, 57–63.

[35] Li, J., Safarzadeh, M.S., Moats, M.S., Mille, J.D., LeVier, K.M., Dietrich, M., and Wan, R.Y., 2012, Thiocyanate hydrometallurgy for the recovery of gold. Part I: Chemical and thermodynamic considerations, Hydrometallurgy, 113-114, 1–9.

[36] Patil, Y.B., 2012, Development of a low-cost industrial waste treatment technology for resource conservation – An urban case study with gold-cyanide emanated from SMEs, Proc. Soc. Behav. Sci., 37, 379–388.

[37] Choi, C., and Hu, N., 2013, The modeling of gold recovery from tetrachloroaurate wastewater using a microbial fuel cell, Bioresour. Technol., 133, 589–598.

[38] Gurung, M., Adhikari, B.B., Kawakita, H., Ohto, K., Inoue, K., and Alam, S., 2013, Recovery of gold and silver from spent mobile phones by means of acidothiourea leaching followed by adsorption using biosorbent prepared from persimmon tannin, Hydrometallurgy, 133, 84–93.

[39] Chen, X., Lam, K.F., Mak, S.F., and Yeung, K.L., 2011, Precious metal recovery by selective adsorption using biosorbents, J. Hazard. Mater., 186 (1), 902–910.

[40] Adhikari, C.R., Parajuli, D., Kawakita, H., Chand, R., Inoue, K., and Ohto, K., 2007, Recovery and separation of precious metals using waste paper, Chem. Lett., 36 (10), 1254–1255.

[41] Huang, X., Wang, Y., Liao, X., and Shi, B., 2010, Adsorptive recovery of Au3+ from aqueous solutions using bayberry tannin-immobilized mesoporous silica, J. Hazard. Mater., 183 (1-3), 793–798.

[42] Castro, L., Blázquez, M.L., González, F., Muñoz, J.A., and Ballester, A., 2010, Extracellular biosynthesis of gold nanoparticles using sugar beet pulp, Chem. Eng. J., 164, 92–97.

[43] Mata, Y.N., Torres, E., Blazquez, M.L., and Ballester, A., 2009, Gold(III) biosorption and bioreduction with the brown alga Fucus vesiculosus, J. Hazard. Mater., 166 (2-3), 612–618.

[44] Litvin, V.A., and Minaev, B.F., 2014, The size-controllable, one-step synthesis and characterization of gold nanoparticles protected by synthetic humic substances, Mater. Chem. Phys., 144 (1-2), 168–178.

[45] Calze, P., Vione, D., and Minero, C., 2014, The role of humic and fulvic acids in the phototransformation of phenolic compounds in seawater, Sci. Total Environ., 493, 411–418.

[46] Doskočil, L., Grasset, L., Válková, D., and Pekař, M., 2014, Hydrogen peroxide oxidation of humic acids and lignite, Fuel, 134, 406–413.

[47] Aquino, A.J.A., Tunega, D., Schaumann, G.E., Haberhauer, G., Gerzabek, M.H., and Lischka, H., 2014, Proton transfer processes in polar regions of humic substances initiated by aqueous aluminum cation bridges: A computational study, Geoderma, 213, 115–123.

[48] Hamamoto, K., Kawakita, H., Ohto, K., and Inoue, K., 2009, Polymerization of phenol derivatives by the reduction of gold ions to gold metal, React. Funct. Polym., 69 (9), 694–697.

[49] Nakajima, A., Ohe, K., Baba, Y., and Kijima, T., 2003, Mechanism of gold adsorption by persimmon tannin gel, Anal. Sci., 19 (7), 1075–1077.

[50] Narayanan, K.B., and Sakthihel, N., 2008, Coriander leaf mediated biosynthesis of gold nanoparticles, Mater. Lett., 62 (30), 4588–4590.

[51] Zhang, Y., Xu, Q., Zhang, S., Liu, J., Zhou, J. Xu, H., Xiao, H., and Li, J., 2013, Preparation of thiol-modified Fe3O4@SiO2 nanoparticles and their application for gold recovery from dilute solution, Sep. Purif. Technol., 116, 391–397.

[52] Al-Saidi, H.M., 2016, The fast recovery of gold(III) ions from aqueous solutions using raw date pits: Kinetic, thermodynamic and equilibrium studies, J. Saudi Chem. Soc., 20 (6), 615–624.

[53] Chen, C., Wang, X., Jiang, H., and Hu, W., 2007, Direct observation of macromolecular structures of humic acid by AFM and SEM, Colloids Surf., A, 302 (1-3), 121–126.

[54] Shofiyani, A., Narsito, Santosa, S.J., Noegrohati, S., Zahara, T.A. and Sayekti, E., 2015, Cadmium adsorption on chitosan/chlorella biomass sorbent prepared by ionic-imprinting technique, Indones. J. Chem., 15 (2), 163–171.


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