Mercury(II) reduction and sulfite oxidation in aqueous systems: kinetics study and speciation modeling
Kurt L. B. Solis A , Go-un Nam A and Yongseok Hong A BA Department of Environmental Engineering, Daegu University, Gyeongsan-si, Gyeongsangbuk-do, 712714, Republic of Korea.
B Corresponding author. Email: yshong@daegu.ac.kr
Environmental Chemistry 14(3) 151-159 https://doi.org/10.1071/EN16169
Submitted: 6 October 2016 Accepted: 16 December 2016 Published: 23 January 2017
Environmental context. Wastewater contains various substances such as sulfur-containing chemicals and heavy metals including mercury ions. Several technologies have been developed to trap mercury ions; however, mercury can undergo reactions with sulfite and change to its vapour form, which easily escapes to the atmosphere. Here, we devised a model to predict the formation of vapour-phase mercury as a function of sulfite concentration, temperature and water acidity based on coal-fired power plant wastewater.
Abstract. The re-emission of mercury (Hg) as a consequence of the formation and dissociation of the unstable complex HgSO3 is a problem encountered in flue gas desulfurisation treatment in coal-fired power plants. A model following a pseudo-second-order rate law for Hg2+ reduction was derived as a function of [SO32–], [H+] and temperature and fitted to experimentally obtained data to generate kinetics rate values of 0.120 ± 0.04, 0.847 ± 0.07, 1.35 ± 0.4 mM–1 for 40 °C, 60 °C and 75 °C respectively. The rate of reduction of Hg2+ increases with a temperature increase but shows an inverse relationship with proton concentration. Plotting the model-fit kinetics rate constants yields ΔH = 61.7 ± 1.82 kJ mol–1, which is in good agreement with literature values for the formation of Hg0 by SO32–. The model could be used to better understand the overall Hg2+ re-emission due to SO32– happening in aquatic systems such as flue gas desulfurisation wastewaters.
Additional keywords: redox chemistry, water chemistry, wastewater.
References
[1] Her Majesty’s Inspectorate of Pollution, Risk Perception and Communication 1995 (Environmental Agency: London).[2] United Nations Environment Programme (UNEP), Global Mercury Assessment 2013: Sources, Emissions, Releases, and Environmental Transport 2013 (UNEP Chemicals Branch: Geneva, Switzerland).
[3] US Environment Protection Agency (EPA), Mercury Study Report to Congress 1997 (US Government Printing Office: Washington, DC).
[4] A. Kumari, B. Kumar, S. Manzoor, U. Kulshrestha, Status of atmospheric mercury research in South Asia: a review. Aerosol Air Qual. Res. 2015, 15, 1092.
| Status of atmospheric mercury research in South Asia: a review.Crossref | GoogleScholarGoogle Scholar |
[5] T. Barkay, I. Wagner-Dobler, Microbial transformations of mercury: potentials, challenges, and achievements in controlling mercury toxicity in the environment. Adv. Appl. Microbiol. 2005, 57, 1.
| Microbial transformations of mercury: potentials, challenges, and achievements in controlling mercury toxicity in the environment.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28Xot1GktLo%3D&md5=2e4093a605d4a722a934388ef0e5ae4dCAS |
[6] H. Gibb, K. G. O’Leary, Mercury exposure and health impacts among individuals in the artisanal and small-scale gold mining community: a comprehensive review. Environ. Health Perspect. 2014, 122, 667.
| 1:CAS:528:DC%2BC2cXhvVCisb3N&md5=463f450d931c21da37214656ebc20cebCAS |
[7] R. B. Turaga, Perceptions of mercury risk and its management. Hum. Ecol. Risk Assess. 2014, 20, 1385.
| Perceptions of mercury risk and its management.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXhs12qtrbP&md5=352fbe6547507bfe42aa85153c32999eCAS |
[8] K.-H. Kim, E. Kabir, S. A. Jahan, A review on the distribution of Hg in the environment and its human health impacts. J. Hazard. Mater. 2016, 306, 376.
| A review on the distribution of Hg in the environment and its human health impacts.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC28Xhs1Gjtb8%3D&md5=f52bc86ee016a7f1e2fde15c74f642c9CAS |
[9] F. Rosso, W. Jin, A. L. Pisello, M. Ferrero, M. Ghandehari, Translucent marbles for building envelope applications: weathering effects on surface lightness and finishing when exposed to simulated acid rain. Constr. Build. Mater. 2016, 108, 146.
| Translucent marbles for building envelope applications: weathering effects on surface lightness and finishing when exposed to simulated acid rain.Crossref | GoogleScholarGoogle Scholar |
[10] H. Soud, Developments in FGD 2000 (IEA Clean Coal Center, Technology Collaboration Programme: London).
[11] P. Córdoba, Status of flue gas desulphurisation (FGD) systems from coal-fired power plants: overview of the physic-chemical control processes of wet limestone FGDs. Fuel 2015, 144, 274.
| Status of flue gas desulphurisation (FGD) systems from coal-fired power plants: overview of the physic-chemical control processes of wet limestone FGDs.Crossref | GoogleScholarGoogle Scholar |
[12] M. J. Holmes, K. E. Redinger, A. P. Evans, P. S. Nolar, 4th International Conference on Managing Hazardous Air Pollutants 1997, pp. 4-58–4-75 (EPRI: Washington, DC).
[13] P.-R. Kim, Y.-J. Han, T. M. Holsen, S.-M. Yi, Atmospheric particulate mercury: concentrations and size distributions. Atmos. Environ. 2012, 61, 94.
| Atmospheric particulate mercury: concentrations and size distributions.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XhsVansrzM&md5=7e9673634af07f73d41b86cc86708b9eCAS |
[14] J. H. Pavlish, M. D. Mann, Air and Waste Management 91st Annual Meeting and Exhibition 1998 (The Association: San Diego, CA).
[15] T. Higgins, T. Sandy, S. Givens, Flue Gas Desulfurization in Dual-Alkali System 2009 (POWER). Available at http://www.powermag.com/flue-gas-desulfurization-wastewater-treatment-primer/ [Accessed 22 March 2016].
[16] W. Lidong, W. Juan, X. Peiyao, L. Qiangwei, Z. Wendi, C. Shuai, Selectivity of transition metal catalysts in promoting the oxidation of solid sulfites in flue gas desulfurization. Appl. Catal. A Gen. 2015, 508, 52.
| Selectivity of transition metal catalysts in promoting the oxidation of solid sulfites in flue gas desulfurization.Crossref | GoogleScholarGoogle Scholar |
[17] B. Zhao, Y. Li, H. Tong, Y. Zhuo, L. Zhang, J. Shi, C. Chen, Study on the reaction rate of sulfite oxidation with cobalt ion catalyst. Chem. Eng. Sci. 2005, 60, 863.
| Study on the reaction rate of sulfite oxidation with cobalt ion catalyst.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXhtVGisLfL&md5=9f727be68d90412ae919f486b08cc93cCAS |
[18] C. L. Senior, J. R. Morency, G. P. Huffman, F. Huggins, T. Peterson, B. Wu, Air and Waste Management Association 91st Annual Meeting and Exhibition 1998, Paper 98-RA79B.04 (The Association: San Diego, CA).
[19] L. Van Loon, E. Mader, S. L. Scott, Reduction of the aqueous mercuric ion by sulfite: UV spectrum of HgSO3 and its intramolecular redox reaction. J. Phys. Chem. A 2000, 104, 1621.
| Reduction of the aqueous mercuric ion by sulfite: UV spectrum of HgSO3 and its intramolecular redox reaction.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXovVSisA%3D%3D&md5=39cfbbca6fef2187e8f6e5af882204acCAS |
[20] European Commission, Integrated Pollution Prevention and Control 2008 (European Commission: Seville, Spain). Available at http://www.envirocentre.ie/includes/documents/2008 June Integrated Poll Prev Control190608.pdf [Accessed 14 May 2016].
[21] L. L. Van Loon, E. a. Mader, S. L. Scott, Sulfite stabilization and reduction of the aqueous mercuric ion: kinetic determination of sequential formation constants. J. Phys. Chem. A 2001, 105, 3190.
| Sulfite stabilization and reduction of the aqueous mercuric ion: kinetic determination of sequential formation constants.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXhs1ags70%3D&md5=e33615d34bdaf9ace3cfa098c2e7a12eCAS |
[22] J. Munthe, Z. Xiao, Q. Lindqvist, The aqueous reduction of divalent mercury by sulfite. Water Air Soil Pollut. 1991, 56, 621.
| The aqueous reduction of divalent mercury by sulfite.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3MXms1aqur4%3D&md5=60e1bdf58f543b9c03b2d9cc4f8124c6CAS |
[23] J. L. Ticknor, H. Hsu-Kim, M. A. Deshusses, A robust framework to predict mercury speciation in combustion flue gases. J. Hazard. Mater. 2014, 264, 380.
| A robust framework to predict mercury speciation in combustion flue gases.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXitVWjtL7E&md5=29f620eb060b1fbd4ddd10f336658a5aCAS |
[24] M.L. Pudvay, I. Degremont, Operating Experience on the Treatment on FGD Scrubber Blowdown from Existing Generating Stations 2011 (Infilco Degremont: Richmond, VA)
[25] A. N. Ermakov, A. P. Purmal, Catalysis of HSO3–/SO32– oxidation by manganese ions. Kinet. Catal. 2002, 43, 249.
| Catalysis of HSO3–/SO32– oxidation by manganese ions.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XktVGhs7g%3D&md5=0eb24360e55d772710a74dcfe2b89a26CAS |
[26] N. Omine, C. Romero, H. Kikkawa, S. Wu, S. Eswaran, Study of elemental mercury re-emission in a simulated wet scrubber. Fuel 2012, 91, 93.
| Study of elemental mercury re-emission in a simulated wet scrubber.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhtlGiurfL&md5=674fadafa5e1128eda33ec42d8e3644cCAS |
[27] J.-Z. Zhang, F. J. Millero, The rate of sulfite oxidation in seawater. Geochim. Cosmochim. Acta 1991, 55, 677.
| The rate of sulfite oxidation in seawater.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3MXhvFWqt7Y%3D&md5=ead35a743afca9b4ae63c9924262befcCAS |
[28] US EPA, Method 1631: Mercury in Water by Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectrometry. EPA 821-R-96–012. 1996 (US Environmental Protection Agency, Office of Water: Washington, DC).
[29] F. Vidal B., P. Ollero, A kinetic study of the oxidation of S(IV) in seawater. Environ. Sci. Technol. 2001, 35, 2792.
| A kinetic study of the oxidation of S(IV) in seawater.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXjvVWitbk%3D&md5=72815662b2cbecdf3e4c402772fa985cCAS |
[30] D. C. Harris, Nonlinear least-squares curve fitting with Microsoft Excel solver. J. Chem. Educ. 1998, 75, 119.
| Nonlinear least-squares curve fitting with Microsoft Excel solver.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXhtFyksQ%3D%3D&md5=78ee35bba7e1bb5ac624c04ce649fa06CAS |
[31] R. Chang, Physical Chemistry for the Biosciences 2005 (University Science Books: Sausalito, CA).
[32] J.-s. Mo, Z.-b. Wu, C.-j. Cheng, B.-h. Guan, W.-r. Zhao, Oxidation inhibition of sulfite in dual alkali flue gas desulfurization system. J. Environ. Sci. 2007, 19, 226.
| Oxidation inhibition of sulfite in dual alkali flue gas desulfurization system.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXjt1Smur4%3D&md5=263cf1aa87d098944739515cba145964CAS |
[33] P. Hui, H. Palmer, Uncatalyzed oxidation of aqueous sodium sulfite and its ability to simulate bacterial respiration. Biotechnol. Bioeng. 1991, 37, 392.
| Uncatalyzed oxidation of aqueous sodium sulfite and its ability to simulate bacterial respiration.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3MXpvFyltw%3D%3D&md5=91cf855a67e41f293e53bb16e10fa493CAS |
[34] L. Wang, Y. Zhao, Kinetics of sulfite oxidation in wet desulfurization with catalyst of organic acid. Chem. Eng. J. 2008, 136, 221.
| Kinetics of sulfite oxidation in wet desulfurization with catalyst of organic acid.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXhsVekur4%3D&md5=7f6450b1f1327cc04098f091b1597230CAS |
[35] D. Karatza, M. Prisciandaro, A. Lancia, D. Musmarra, Reaction rate of sulfite oxidation catalyzed by cuprous ions. Chem. Eng. J. 2008, 145, 285.
| Reaction rate of sulfite oxidation catalyzed by cuprous ions.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXht12ls7fN&md5=45f6d4a8d77ce42b4e042f30532f4609CAS |
[36] E. Hayon, A. Treinin, J. Wilf, Electronic spectra, photochemistry, and autoxidation mechanism of the sulfite–bisulfite–pyrosulfite systems. SO2–, SO3–, SO4–, and SO5– radicals. J. Am. Chem. Soc. 1972, 94, 47.
| Electronic spectra, photochemistry, and autoxidation mechanism of the sulfite–bisulfite–pyrosulfite systems. SO2–, SO3–, SO4–, and SO5– radicals.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE38Xlt1yltg%3D%3D&md5=37232f33bfd54a178d47ec71e86275deCAS |
[37] M. A. Vincent, I. J. Palmer, I. H. Hillier, E. Akhmatskaya, Exploration of the mechanism of the oxidation of sulfur dioxide and bisulfite by hydrogen peroxide in water clusters using ab initio methods. J. Am. Chem. Soc. 1998, 120, 3431.
| Exploration of the mechanism of the oxidation of sulfur dioxide and bisulfite by hydrogen peroxide in water clusters using ab initio methods.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXitVyqtL4%3D&md5=69da184b803aa809319abca85eea43ecCAS |
[38] A. G. Clarke, M. Radojevic, Oxidation rates of SO2 in sea-water and sea-salt aerosols. Atmos. Environ. 1984, 18, 2761.
| Oxidation rates of SO2 in sea-water and sea-salt aerosols.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL2MXhtF2hsr8%3D&md5=8208da561d41c1cfe78ee9964de997cfCAS |
[39] K. J. A. De Waal, J. C. Okeson, The oxidation of aqueous sodium sulphite solutions. Chem. Eng. Sci. 1966, 21, 559.
| The oxidation of aqueous sodium sulphite solutions.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaF28Xks12itbc%3D&md5=1de5b09468c3a9f2cb6b5069a7becd34CAS |
[40] V. Linek, J. Mayrhoferová, J. Mayrhoferova, J. Mayrhoferová, The kinetics of oxidation of aqueous sodium sulphite solution. Chem. Eng. Sci. 1970, 25, 787.
| The kinetics of oxidation of aqueous sodium sulphite solution.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE3cXkt12gu7o%3D&md5=dc5ef5d0d9f98cc914c5adae894ceb20CAS |
[41] T. Reith, W. J. J. Beek, The oxidation of aqueous sodium sulphite solutions. Chem. Eng. Sci. 1973, 28, 1331.
| The oxidation of aqueous sodium sulphite solutions.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE3sXksVKiu7c%3D&md5=eef0ba9a5bf245c13d7420dff0fa08aaCAS |
[42] Y. Liu, Y. Wang, Z. Wu, S. Zhou, H. Wang, A mechanism study of chloride and sulfate effects on Hg2+ reduction in sulfite solution. Fuel 2011, 90, 2501.
| A mechanism study of chloride and sulfate effects on Hg2+ reduction in sulfite solution.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXltl2mtbo%3D&md5=6f944db88ea05c6e671b649e876d0d48CAS |
[43] J. D. Cox, D. Wagman, V. A. Medvedev, CODATA Key Values for Thermodynamics 1989 (Hemisphere Publishing Corporation: New York, NY). Available at http://www.codata.org/ [Accessed 30 April 2016].