Environmental Science and Pollution Research

, Volume 26, Issue 30, pp 30584–30595 | Cite as

Enhanced reductive dechlorination of 1,1,1-trichloroethane using zero-valent iron-biochar-carrageenan microspheres: preparation and microcosm study

  • Changling Ji
  • Liang MengEmail author
  • Hualin Wang
Water Environment Protection and Contamination Treatment


In this study, a composite remediation material for the enhanced reductive dechlorination (ERD) of 1,1,1-trichloroethane (1,1,1-TCA) in aqueous solution was prepared. This material was comprised of biochar as the carrier and adsorbent, and carrageenan (CG) as the embedding medium to entrap the organic carbon sources and zero-valent iron (ZVI). We determined the suitable biochar dosage and organic carbon source in the composite alongside the optimal preparation conditions. Furthermore, using an anaerobic microcosm study, we discussed the performance and possible mechanisms of the composite on 1,1,1-TCA removal in aqueous solution. From this, we found that the suitable dosage of biochar in water during the preparation of composite microspheres was 0.2% (w/v). Under this condition, the biochar had a strong capacity to adsorb 1,1,1-TCA with a removal efficiency of 84.2%. Soluble starch was selected as the appropriate organic carbon source, because starch-microspheres show an excellent slow-release effect in water. The optimal preparation conditions of microspheres were identified as follows: 2% CG (w/v) colloidal solution, 6% CaCl2 (w/v) solution, and a 12-h curing time. After 25-day incubation with the composite prepared under optimized conditions, the removal efficiency of 1,1,1-TCA was 95.68%, which was 24.69% higher than that observed in the microcosm with a commercial remediation material. The scanning electron microscopy (SEM) images show that the amounts of ZVI and soluble starch inside the microsphere decreased obviously, while the biochar amount remained about the same. This indicates that 1,1,1-TCA in aqueous solution was mainly removed via soluble starch-enhanced biotic reductive dechlorination and ZVI-enhanced abiotic reductive dechlorination. The changes in microbial community structure demonstrate that the composite stimulated the activities of functional anaerobic bacteria, in particular, regarding dechlorination and fermentation abilities in the microcosm, therefore enhancing the anaerobic biodegradation of 1,1,1-TCA. This study suggests that the composite, entrapping biochar, ZVI, and organic carbon source in CG microspheres can significantly enhance the reductive dechlorination of 1,1,1-TCA in aqueous solution. We anticipate this novel remediation material could be successfully applied to the in situ ERD remediation of natural groundwater mainly contaminated with 1,1,1-TCA.


1,1,1-Trichloroethane Enhanced reductive dechlorination Biochar Zero-valent iron Organic carbon source Entrapment Composite 



This work was supported by the National Natural Science Foundation of China (41401357), the Shanghai Professional Development Funding, China (201528), the Shanghai Science and Technology Commission of Shanghai Municipality, China (17DZ1202003), the Shanghai Municipal Natural Science Foundation, China (13ZR1460200), the National High Technology Research and Development Program of China (SS2013AA062608).

Supplementary material

11356_2018_1235_MOESM1_ESM.docx (1.8 mb)
ESM 1 (DOCX 1864 kb)


  1. Ahmad M, Lee SS, Rajapaksha AU, Vithanage M, Zhang M, Cho JS, Lee SE, Ok YS (2013) Trichloroethylene adsorption by pine needle biochars produced at various pyrolysis temperatures. Bioresour Technol 143:615–622. CrossRefGoogle Scholar
  2. Amato KR, Yeoman CJ, Kent A, Righini N, Carbonero F, Estrada A, Gaskins HR, Stumpf RM, Yildirim S, Torralba M (2013) Habitat degradation impacts black howler monkey (Alouatta pigra) gastrointestinal microbiomes. ISME J 7(7):1344–1353. CrossRefGoogle Scholar
  3. Atashgahi S, Lu Y, Zheng Y, Saccenti E, Suarez-Diez M, Ramiro-Garcia J, Eisenmann H, Elsner M, Stams AJM, Springael D, Dejonghe W, Smidt H (2016) Geochemical and microbial community determinants of reductive dechlorination at a site biostimulated with glycerol. Environ Microbiol 19:968–981CrossRefGoogle Scholar
  4. Baric M, Majone M, Beccari M, Papini MP (2012) Coupling of polyhydroxybutyrate (PHB) and zero valent iron (ZVI) for enhanced treatment of chlorinated ethanes in permeable reactive barriers (PRBs). Chem Eng J 195–196:22–30CrossRefGoogle Scholar
  5. Blandino A, Macías M, Cantero D (1999) Formation of calcium alginate gel capsules: influence of sodium alginate and CaCl2 concentration on gelation kinetics. J Biosci Bioeng 88(6):686–689. CrossRefGoogle Scholar
  6. Broholm MM, Hunkeler D, Tuxen N, Jeannottat S, Scheutz C (2014) Stable carbon isotope analysis to distinguish biotic and abiotic degradation of 1, 1, 1-trichloroethane in groundwater sediments. Chemosphere 108:265–273. CrossRefGoogle Scholar
  7. Caporaso J, Kuczynski J, Stombaugh J (2010) QIIME allows analysis of high-throughput community sequencing data. Nat Methods 7(5):335–336. CrossRefGoogle Scholar
  8. Cha JS, Park SH, Jung SC, Ryud C, Jeone JK, Shinb MC, Park YK (2016) Production and utilization of biochar: a review. J Ind Eng Chem 40:1–15. CrossRefGoogle Scholar
  9. Chang J, Woo H, Ko MS, Lee J, Lee S, Yun ST, Lee S (2015) Targeted removal of trichlorophenol in water by oleic acid-coated nanoscale palladium/zero-valent iron alginate beads. J Hazard Mater 293:30–36. CrossRefGoogle Scholar
  10. Collins R, Higgs P (2012) Testing the infinitely many genes model for the evolution of the bacterial core genome and pangenome. Mol Biol Evol 29(11):3413–3425. CrossRefGoogle Scholar
  11. Comba S, Molfetta AD, Sethi R (2011) A comparison between field applications of nano-, micro-, and millimetric zero-valent iron for the remediation of contaminated aquifers. Water Air Soil Pollut 215(1-4):595–607. CrossRefGoogle Scholar
  12. Craun GF (1984) Health aspects of groundwater pollution. In: Bitton G, Gerba CP (eds) Groundwater pollution microbiology. Wiley, New York, pp 135–179Google Scholar
  13. Daâssi D, Rodríguez-Couto S, Nasri M, Mechichi T (2014) Biodegradation of textile dyes by immobilized laccase from Coriolopsis gallica into Ca-alginate beads. Int Biodeter Biodegr 90:71–78. CrossRefGoogle Scholar
  14. Datta S, Christena LR, Rajaram YRS (2013) Enzyme immobilization: an overview on techniques and support materials. 3. Biotech 3:1–9Google Scholar
  15. Duarte K, Justino CIL, Freitas AC, Duarte AC, Rocha-Santos TAP (2014) Direct-reading methods for analysis of volatile organic compounds and nanoparticles in workplace air. Trac Trend Anal Chem 53:21–32. CrossRefGoogle Scholar
  16. Duman O, Tunç S, Bozoğlan BK, Polat TG (2016) Removal of triphenylmethane and reactive azo dyes from aqueous solution by magnetic carbon nanotube-κ-carrageenan-Fe3O4 nanocomposite. J Alloy Compd 687:370–383. CrossRefGoogle Scholar
  17. Dumanoglu Y, Kara M, Altiok H, Odabasi M, Elbir T, Bayram A (2014) Spatial and seasonal variation and source apportionment of volatile organic compounds (VOCs) in a heavily industrialized region. Atmos Environ 98:168–178. CrossRefGoogle Scholar
  18. Edgar RC (2013) UPARSE: highly accurate OTU sequences from microbial amplicon reads. Nat Methods 10(10):996–998. CrossRefGoogle Scholar
  19. Farias S, Mayer DA, de Oliveira D, Souza S, Souza A (2017) Free and Ca-alginate beads immobilized horseradish peroxidase for the removal of reactive dyes: an experimental and modeling study. Appl Biochem Biotechnol 99:1–17Google Scholar
  20. Fu F, Dionysiou DD, Liu H (2014) The use of zero-valent iron for groundwater remediation and wastewater treatment: a review. J Hazard Mater 267:194–205. CrossRefGoogle Scholar
  21. Harding-Marjanovic KC, Yi S, Weathers TS, Sharp JO, Sedlak DL, Alvarez-Cohen L (2016) Effects of aqueous film-forming foams (AFFFs) on trichloroethene (TCE) dechlorination by a Dehalococcoides mccartyi-containing microbial community. Environ Sci Technol 50(7):3352–3361. CrossRefGoogle Scholar
  22. Huang BB, Lei C, Wei CH, Zeng GM (2014) Chlorinated volatile organic compounds (Cl-VOCs) in environment—sources, potential human health impacts, and current remediation technologies. Environ Int 71:118–138. CrossRefGoogle Scholar
  23. Kao CM, Liao HY, Chien CC, Tseng YK, Tang P, Lin CE, Chen SC (2016) The change of microbial community from chlorinated solvent-contaminated groundwater after biostimulation using the metagenome analysis. J Hazard Mater 302:144–150. CrossRefGoogle Scholar
  24. Kim H, Hong HJ, Jung J, Kim SH, Yang JW (2010) Degradation of trichloroethylene (TCE) by nanoscale zero-valent iron (nZVI) immobilized in alginate bead. J Hazard Mater 176(1-3):1038–1043. CrossRefGoogle Scholar
  25. Kocur CMD, Lomheim L, Molenda O, Weber K, Austrins L, Sleep B (2016) Long-term field study of microbial community and dechlorinating activity following carboxymethyl cellulose-stabilized nanoscale zero-valent iron injection. Environ Sci Technol 50(14):7658–7670. CrossRefGoogle Scholar
  26. Kumari S, Panesar PS, Bera MB, Chopra HK (2014) Comparative studies on physico-chemical characterization of yeast cells entrapped with alginate and hybrid beads. Iran Polym J 23(2):111–119. CrossRefGoogle Scholar
  27. Langwaldt JH, Puhakka JA (2000) On-site biological remediation of contaminated groundwater: a review. Environ Pollut 107(2):187–197. CrossRefGoogle Scholar
  28. Lawrinenko M, Laird DA, van Leeuwen JH (2016) Sustainable pyrolytic production of zero-valent iron. ACS Sustain Chem Eng 5:767–773CrossRefGoogle Scholar
  29. Li BZ, Li L, Lin KF, Zhang W, SG L, Luo QS (2013) Removal of 1,1,1-trichloroethane from aqueous solution by a sono-activated persulfate process. Ultrason Sonochem 20(3):855–863. CrossRefGoogle Scholar
  30. Liang SH, Kuo YC, Chen SH, Chen CY, Kao CM (2013) Development of a slow polycolloid-releasing substrate (SPRS) biobarrier to remediate TCE-contaminated aquifers. J Hazard Mater 254:107–115CrossRefGoogle Scholar
  31. Lin HY, Chen ZL, Megharaj M, Naidu R (2013) Biodegradation of TNT using Bacillus mycoides immobilized in PVA-sodium alginate-kaolin. Appl Clay Sci 83–84:336–342CrossRefGoogle Scholar
  32. Mallardi A, Angarano V, Magliulo M, Torsi L, Palazzo G (2015) General approach to the immobilization of glycoenzyme chains inside calcium alginate beads for bioassay. Anal Chem 87(22):11337–11344. CrossRefGoogle Scholar
  33. Miura T, Yamazoe A, Ito M, Ohji S, Hosoyama A, Takahata Y, Fujita N (2015) The impact of injections of different nutrients on the bacterial community and its dechlorination activity in chloroethene-contaminated groundwater. Microbes Environ 30(2):164–171. CrossRefGoogle Scholar
  34. Mohan D, Sarswat A, Ok YS, Charles U, Pittman J (2014) Organic and inorganic contaminants removal from water with biochar, a renewable, low cost and sustainable adsorbent—a critical review. Bioresour Technol 160:191–202. CrossRefGoogle Scholar
  35. Patil SS, Adetutu EM, Aburto-Medina A, Menz IR, Ball AS (2014) Biostimulation of indigenous communities for the successful dechlorination of tetrachloroethene (perchloroethylene)-contaminated groundwater. Biotechnol Lett 36:75–83CrossRefGoogle Scholar
  36. Peale JGD, Mueller J, Molin J (2010) Successful ISCR-enhanced bioremediation of a TCE DNAPL source utilizing EHC® and KB-1®. Remediat J 20(3):63–81. CrossRefGoogle Scholar
  37. Phenrat T, Kumloet I (2016) Electromagnetic induction of nanoscale zerovalent iron particles accelerates the degradation of chlorinated dense non-aqueous phase liquid: proof of concept. Water Res 107:19–28. CrossRefGoogle Scholar
  38. Phenrat T, Schoenfelder D, Kirschling TL, Tilton RD, Lowry GV (2015a) Adsorbed poly(aspartate) coating limits the adverse effects of dissolved groundwater solutes on Fe0 nanoparticle reactivity with trichloroethylene. Environ Sci Pollut Res. CrossRefGoogle Scholar
  39. Phenrat T, Thongboot T, Lowry GV (2015b) Electromagnetic induction of zerovalent iron (ZVI) powder and nanoscale zerovalent iron (NZVI) particles enhances dechlorination of trichloroethylene in contaminated groundwater and soil: proof of concept. Environ Sci Technol 50:872–880CrossRefGoogle Scholar
  40. Pierro L, Matturro B, Rossetti S (2016) Polyhydroxyalkanoate as a slow-release carbon source for in situ bioremediation of contaminated aquifers: from laboratory investigation to pilot-scale testing in the field. New Biotechnol 72:152–161Google Scholar
  41. Srirattana S, Piaowan K, Lowry GV, Phenrat T (2017) Electromagnetic induction of foam-based nanoscale zerovalent iron (NZVI) particles to thermally enhance non-aqueous phase liquid (NAPL) volatilization in unsaturated porous media: proof of concept. Chemosphere 183:323–331. CrossRefGoogle Scholar
  42. Sun Z, Zheng S, Ayoko GA, Frost RL, Xi YF (2013) Degradation of simazine from aqueous solutions by diatomite-supported nanosized zero-valent iron composite materials. J Hazard Mater 263:768–777. CrossRefGoogle Scholar
  43. Tan XF, Liu YG, YL G, Xu Y, Zeng GM, Hua XJ, Liu SB, Wang X, Liu SM, Lia J (2016) Biochar-based nano-composites for the decontamination of wastewater: a review. Bioresour Technol 212:318–333. CrossRefGoogle Scholar
  44. USEPA (2015) Human health ambient water quality criteria: 2015 update. EPA 820-F-15-001 Office of Water. U.S. Environmental Protection Agency, WashingtonGoogle Scholar
  45. Wang W, Wang S, Zhang J, ZH H, Zhang XD, Sierra MJ (2016) Degradation kinetics of pentachlorophenol and changes in anaerobic microbial community with different dosing modes of co-substrate and zero-valent iron. Int Biodeter Biodegr 113:126–133. CrossRefGoogle Scholar
  46. Xie T, Reddy KR, Wang CW, Erin Y, Kurt S (2015) Characteristics and applications of biochar for environmental remediation: a review. Crit Rev Environ Sci Technol 45(9):939–969. CrossRefGoogle Scholar
  47. Xin J, Zheng X, Han J, Shao H, Kolditz O (2015) Remediation of trichloroethylene by xanthan gum-coated microscale zero valent iron (XG-mZVI) in groundwater: effects of geochemical constituents. Chem Eng J 271:164–172. CrossRefGoogle Scholar
  48. Yang J, Meng L, Guo L (2017) In situ remediation of chlorinated solvent-contaminated groundwater using ZVI/organic carbon amendment in china: field pilot test and full-scale application. Environ Sci Pollut Res. CrossRefGoogle Scholar
  49. Yu SY, Lee PK, Hwang SI (2015) Groundwater contamination with volatile organic compounds in urban and industrial areas: analysis of co-occurrence and land use effects. Environ Earth Sci 74:3661–3677CrossRefGoogle Scholar
  50. Yu H, Feng CH, Liu XP, Yi XY, Ren Y, Wei CH (2016) Enhanced anaerobic dechlorination of polychlorinated biphenyl in sediments by bioanode stimulation. Environ Pollut 211:81–89. CrossRefGoogle Scholar
  51. Zhang W, Chen L, Zhang R, Lin KF (2015) High throughput sequencing analysis of the joint effects of BDE209-Pb on soil bacterial community structure. J Hazard Mater 301:1–7CrossRefGoogle Scholar
  52. Zhao X, Liu W, Cai ZQ, Han B, Qian TW, Zhao DY (2016) An overview of preparation and applications of stabilized zero-valent iron nanoparticles for soil and groundwater remediation. Water Res 100:245–266. CrossRefGoogle Scholar
  53. Zhou YZ, Yang J, Wang XL, Pan YQ, Li H, Zhou D, Liu YD, Wang P, JD G, Lu Q, Qiu YF, Lin KF (2014) Bio-beads with immobilized anaerobic bacteria, zero-valent iron, and active carbon for the removal of trichloroethane from groundwater. Environ Sci Pollut Res 21(19):11500–11509. CrossRefGoogle Scholar
  54. Zia KM, Tabasum S, Nasif M, Sultan N, Aslam N, Noreen A, Zuber M (2016) A review on synthesis, properties and applications of natural polymer based carrageenan blends and composites. Int J Biol Macromol 95:282–301Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, School of Resource and Environmental EngineeringEast China University of Science and TechnologyShanghaiPeople’s Republic of China
  2. 2.Shanghai Academy of Environmental SciencesShanghaiPeople’s Republic of China

Personalised recommendations