Progress of Cryogenics and Isotopes Separation , ISSN: 1582-2575
2019, Volume 22, Issue 2
Pages 55-64

Reductive dechlorination of α-hexachlorocyclohexane by iron sulfide nanoparticles in batch experiments mimics its anaerobic biodegradation in environment - preliminary results

Silviu Laurentiu Badea * , Diana Ionela Popescu , Violeta Niculescu , Stanica Enache , Amalia Soare , Roxana Elena Ionete

National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm. Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania

*Corresponding author: Silviu Laurentiu Badea, e-mail: silviu.badea@icsi.ro

Received 10 September 2019Received in revised form 21 October 2019Accepted 01 November 2019Available online 20 November 2019


Abstract

Iron sulfide (FeS) is a reductive mineral naturally occurring in many anoxic environments. It is associated with sulfate-reducing bacteria that grow in anoxic aquifers and sediments. Many previously studies have reported the capacity of FeS for reductive dehalogenation of various halogenated organic pollutants. Therefore, a new method for FeS nanoparticles synthesis was developed in this study, to be used in reductive dechlorination of α-hexachlorocyclohexane (α-HCH), mimicking its transformation pathways in anoxic environments. To synthesize the FeS nanoparticles, a solution of 0.2M Na2S was added over a solution of 0.2M FeSO4, under a N2 flow. The XRD analysis showed an almost amorphous phase of FeS nanoparticles, while the Raman and FTIR spectra were in accordance with the ones of FeS phases from the literature. The dehalogenation reaction was performed by mixing 1g of FeS nanoparticles with 100 mL N2 flushed-water and by adding α-HCH from a stock solution in acetone to a final concentration in water of 9.80 mg/L. The dechlorination reaction was performed for 20 days in an incubator at 30°C and 125 rpm. For sampling, 14 mL aliquots of α-HCH solution were taken with syringes at determined intervals for gas chromatography-mass spectrometry (GC-MS) analysis. The degradation products identified by GC-MS were β-pentachlorocyclohexene, benzene and 1,2,4 trichlorbenzene, showing that the dehydrochlorination is the main degradation pathway of α-HCH by FeS. The experiment highlighted that the synthesized FeS nanoparticles degraded the α-HCH to an extent of about 53%, demonstrating their potential in dehalogenation of HCH isomers.


References

  • Badea, S. L., Vogt, C., Weber, S., Danet, A. F., Richnow, H. H. (2009)
    Stable isotope fractionation of γ-hexachlorocyclohexane (lindane) during reductive dechlorination by two strains of sulfate-reducing bacteria
    Environmental Science & Technology, 43(9), 3155-3161. https://doi.org/10.1021/es801284m

  • Badea, S. L., Vogt, C., Gehre, M., Fischer, A., Danet, A. F., Richnow, H. H. (2011)
    Development of an enantiomer‐specific stable carbon isotope analysis (ESIA) method for assessing the fate of α‐ hexachlorocyclohexane in the environment
     Rapid Communications in Mass Spectrometry, 25(10), 1363-1372. https://doi.org/10.1002/rcm.4987

  • Butler, E. C., Hayes, K. F. (1998)
    Effects of solution composition and pH on the reductive dechlorination of hexachloroethane by iron sulfide
     Environmental Science & Technology, 32(9), 1276-1284. https://doi.org/10.1021/es9706864 

  • He, Y. T., Wilson, J. T., Wilkin, R. T. (2010)
    Impact of iron sulfide transformation on trichloroethylene degradation
     Geochimica et Cosmochimica Acta, 74(7), 2025-2039. https://doi.org/10.1016/ j.gca.2010.01.013

  • Hurma, T., Aksay, S. (2018)
    Investigations of structural vibrational and optical properties of mackinawite nanostructured FeS film
    Revista Română de Materiale/Romanian Journal of Materials, 48(1), 18-23

  • Kaschl, A., Vogt, C., Uhlig, S., Nijenhuis, I., Weiss, H., Kästner, M., Richnow, H. H. (2005)
    Isotopic fractionation indicates anaerobic monochlorobenzene biodegradation
    Environmental Toxicology and Chemistry: An International Journal, 24(6), 1315-1324. https://doi.org/10.1897/04-321R.1

  • Lal, R., Pandey, G., Sharma, P., Kumari, K., Malhotra, S., Pandey, R., Raina, V., Kohler, H. P. E., Holliger, C., Jackson, C., Oakeshott, J. G. (2010)
    Biochemistry of microbial degradation of hexachlorocyclohexane and prospects for bioremediation
    Microbiology and Molecular Biology Reviews, 74(1), 58-80. DOI: 10.1128/MMBR.00029-09

  • Li, D., Peng, P. A., Yu, Z., Huang, W., Zhong, Y. (2016)
    Reductive transformation of hexabromocyclododecane (HBCD) by FeS
     Water Research, 101, 195-202. https://doi.org/10.1016/j.watres.2016.05.066

  • Liu, X., Peng, P. A., Fu, J., Huang, W. (2003)
    Effects of FeS on the transformation kinetics of γ-hexachlorocyclohexane
    Environmental Science & Technology, 37(9), 1822-1828. https://doi.org/10.1021/es0259178

  • Liu, Y., Wu, L., Kohli, P., Kumar, R., Stryhanyuk, H., Nijenhuis, I., Lal, R., Richnow, H. H. (2019)
    Enantiomer and Carbon Isotope Fractionation of α-Hexachlorocyclohexane by Sphingobium indicum Strain B90A and the Corresponding Enzymes
    Environmental Science & Technology, 53(15), 8715-8724. https://doi.org/10.1021/acs.est.9b01233 

  • Liu, Y., Bashir, S., Stollberg, R., Trabitzsch, R., Weiß, H., Paschke, H., Nijenhuis, I., Richnow, H. H. (2017)
    Compound specific and enantioselective stable isotope analysis as tools to monitor transformation of hexachlorocyclohexane (HCH) in a complex aquifer system
    Environmental Science & Technology, 51(16), 8909-8916. https://doi.org/10.1021/acs.est.6b05632

  • Schilling, I. E., Hess, R., Bolotin, J., Lal, R., Hofstetter, T. B., Kohler, H. P. E. (2019)
    Kinetic Isotope Effects of the Enzymatic Transformation of γ-Hexachlorocyclohexane by the Lindane Dehydrochlorinase Variants LinA1 and LinA2
    Environmental Science & Technology, 53(5), 2353-2363. https://doi.org/10.1021/acs.est.8b04234

  • Srivastava, V., Srivastava, T., Kumar, M. S. (2019)
    Fate of the persistent organic pollutant (POP) Hexachlorocyclohexane (HCH) and remediation challenges
    International Biodeterioration &Biodegradation, 140, 43-56. https://doi.org/10.1016/j.ibiod.2019.03.004

  • Vijgen, J., Abhilash, P. C., Li, Y. F., Lal, R., Forter, M., Torres, J., Singh N., Yunus M., Tian C., Schäffer A., Weber, R. (2011)
    Hexachlorocyclohexane (HCH) as new Stockholm Convention POPs—a global perspective on the management of Lindane and its waste isomers
    Environmental Science and Pollution Research, 18(2), 152-162. https://doi.org/10.1007/s11356-010-0417-9

  • Wacławek, S., Silvestri, D., Hrabák, P., Padil, V. V., Torres-Mendieta, R., Wacławek, M., Černík, M., Dionysiou, D. D. (2019)
    Chemical oxidation and reduction of hexachlorocyclohexanes: A review
    Water Research, 162, 302-319. https://doi.org/10.1016/j.watres.2019.06.072

  • Zhang, N., Bashir, S., Qin, J., Schindelka, J., Fischer, A., Nijenhuis, I., Herrmann, H., Wick, L. Y., Richnow, H. H. (2014)
    Compound specific stable isotope analysis (CSIA) to characterize transformation mechanisms of α-hexachlorocyclohexane
    Journal of Hazardous Materials, 280, 750-757. https://doi.org/10.1016/j.jhazmat.2014.08.046

  • Zhou, L., Liu, J., Dong, F. (2017)
    Spectroscopic study on biological mackinawite (FeS) synthesized by ferric reducing bacteria (FRB) and sulfate reducing bacteria (SRB): Implications for in-situ remediation of acid mine drainage
    Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 173, 544-548. https://doi.org/10.1016/j.saa.2016.09.053.


  • Keywords

    Reductive dechlorination, iron sulfide, anaerobic degradation


    Tag search Reductive dechlorination iron sulfide anaerobic degradation