Comparative study of toxic chlorophenolic compounds generated in various bleaching sequences of wheat straw pulp

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This study compared the chlorophenolic compounds generated during the bleaching of wheat straw pulp. The six different bleaching sequences used in present study were: (i) chlorine-extraction-hypo (CEH); (ii) persulphate-peroxide-chlorine-extraction-hypo (Px-P-CEH); (iii) oxygen-chlorine-extraction-hypo (OCEH); (iv) chlorine dioxide-extraction-chlorine dioxide (DED); (v) persulphate-peroxide-chlorine dioxide-extraction-chlorine dioxide (Px-P-DED); and (vi) oxygen-chlorine dioxide-extraction-chlorine dioxide (ODED) bleaching. The concentrations of a large number of identified chlorophenolic compounds often exceed their threshold concentrations in CEH effluent. Therefore, the untreated effluent generated from the CEH bleaching sequence of wheat straw pulp can be considered toxic. Prebleaching (PxP) reduces the generation of chlorophenolic compounds by 36 % in the (PxP)CEH sequence. Oxygen prebleaching reduces the generation of chlorophenolic compounds by 86 % in the OCEH bleaching effluent. The PxP also reduces the generation of chlorophenolic compounds by 46 % in the (PxP)DED bleaching sequence and oxygen delignification substantially reduces the generation of the compounds by 78 %.

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  1. Antongiovanni M, Sargentini C (1991) Variability in chemical composition of straws. Options Médit Sér Sémin 16:49–53

  2. Axegård P (1986) Substituting chlorine dioxide for elemental chlorine makes bleach plant effluent less toxic. TAPPI J 69(10):54–59

  3. Axegård P, Renberg L (1998) The minimal impact of bleached kraft mill effluent. Pulp Pap Can J 99(4):85–90

  4. Axegård P, Dahlman O, Haglind I, Jacobson B, Morck R, Strömberg L (1993) Pulp bleaching and environment—the situation. Nord Pulp Pap Res J 4:365

  5. Berry RM, Luthe CE, Voss RH, Wrist PE, Axegard P, Gellerstedt G, Lindblad PO, Pöpke IJ (1991) The effects of recent changes in bleached softwood kraft mill technology on organochlorine emissions: an international perspective. Pulp Pap Can J 92(6):155–165

  6. Bright D, Hodson P, Lehtinen KJ, McKague AB, Rodgers J, Solomon K (1993) Evaluation of ecological risks associated with the use of chlorine dioxide for the bleaching of pulp—scientific progress since. Report prepared for Alliance for Environmental Technology

  7. Davis JC, Hoos RAW (1975) Use of sodium pentachlorophenate and dehydroabietic acid as reference toxicants for salmonid bioassays. J Fish Res Board Can 32:411–416

  8. Earl PF, Reeve DW (1989) Chlorinated organic matter in bleached chemical pulp production—the effect of chlorination stage variables on chlorinated organic matter in effluent. TAPPI J 72(10):183–188

  9. EC (2001) EC Decision 2455/2001/ED of European Parliament and the Council of Nov. 20, establishing the list of priority substances in the field of water policy and amending directive 2000/60 EC (L331 of 15-12-2002)

  10. Folke J (1985) Organics in wheat and rye straw pulp bleaching and combined mill effluents (I) chemical characterization and bio-degradation studies. Toxicol Environ Chem 10:1–24

  11. Freire CSR, Silvestre AJD, Pascoal NC (2003) Carbohydrate derived chlorinated compounds in ECF bleaching of hardwood pulps: formation, degradation & contribution to AOX in a bleached kraft pulp mill. J Environ Sci Technol 37(4):811–814

  12. Hayward K (1998) Drinking water contaminant hit list for US EPA. Water 21, Sept–Oct, 4

  13. Hedjazi S, Kordsachia O, Rudolf P, Latibarid AJ, Tschirnere U (2009) Alkaline sulfite–anthraquinone (AS/AQ) pulping of wheat straw and totally chlorine free (TCF) bleaching of pulps. Ind Crops Prod 29:27–36

  14. Huang G, Shi JX, Langrish TAG (2007) A new pulping process for wheat straw to reduce problems with the discharge of black liquor. Bioresour Technol 98:2829–2835

  15. Jimenez L, Rodrıguez A, Perez A, Moral A, Serrano L (2008) Alternative raw materials and pulping process using clean technologies. Ind Crops Prod 28:11–16

  16. Kahm L, Le Bigot Y, Delmas M, Avignon G (2005) Delignification of wheat straw using a mixture of carboxylic acids and peroxoacids. Ind Crops Prod 21:9–15

  17. Keith LH, Telliard WA (1979) Priority pollutants: a prospective view. Enviorn Sci Technol J 13(4):416–424

  18. Leach JM, Chung LTK (1978) Development of a chemical toxicity assay for pulp mill effluents. Grant No. R804977010. EPA, Cincinnati, OH

  19. Liebergott N, Van Lierop B, Nolin A, Faubert M, Laflamme J (1991) Modifying the bleaching process to decrease AOX formation. Pulp Pap Can J 92(3):84–89

  20. Lindstrom K, Nordin J (1976) Gas chromatography mass spectrometry of chlorophenols in spent bleach liquors. J Chromatogr 128:13–26

  21. Mathur S, Kumar S, Rao NJ (2001) Application of commercial xylanases in bleaching—a review. IPPTA J 13(1):13–24

  22. Mattson K, Lehtinen K-J, Tana J, Harding J, Kukkonen J, Nakari T, Engström C (2001) Effects of pulp mill effluents and restricted die on growth and physiology of rainbow trout (Oncorhynchus mykins). Ecotoxicol Environ Saf J 49:144–154

  23. McKague AB, Chew W, Zhu S, Reeve DW (1998) Proceedings of the International Pulp Bleaching Conference, Helsinki, Finland 1, pp 205–212

  24. Mocarelli P, Brambilla P, Gerthoux PM, Patterson DG Jr, Needham LL (1996) Changes in sex ratio with exposure to dioxin. Lancet 348:409

  25. NORAD-COURSE (1993) Laboratory manual for pulp and paper laboratory. The Norwegian Institute of Technology, Department of Chemical Engineering, University of Trondheim, Trondheim

  26. Okumura R, Yamashita Y, Kohno Y, Nagasaka H (2004) Historical trends of PCDD/Fs and Co-PCBs in a sediment core collected in Sendai Bay. Jpn Water Res J 38(16):3511–3522

  27. Panwar S, Gupta MK, Mishra S (2002) Environmental impact of toxic chlorinated phenolics released in pulp and paper industry and its control measures. In: Interaction meet on environmental impact of toxic substances released in pulp & paper industry, Proceedings, pp 69–73

  28. Ray AK, Kumar V, Dutt D, Mittal KC, Upadhyaya JS (2005) Comparison of ECF bleaching sequences of bagasse pulp. In: IPPTA convention, pp 77–82

  29. Roncero MB, Torres AL, Colom JF, Vidal T (2003a) TCF bleaching of wheat straw pulp using ozone and xylanase. Part A: paper quality assessment. Bioresour Technol 87:305–314

  30. Roncero MB, Torres AL, Colom JF, Vidal T (2003b) TCF bleaching of wheat straw pulp using ozone and xylanase. Part B: kinetic studies. Bioresour Technol 87:315–323

  31. Servizi JA, Gordon RW, Martens DW (1968) Toxicity of two chlorinated catechols, possible components of kraft pulp mill bleach waste. International Pacific Salmon Fisheries Commission progress report no 17

  32. Sharma C, Mohanty S, Kumar S, Rao NJ (1996a) Gas chromatographic analysis of chlorophenolic, resin and fatty acids in chlorination and caustic extraction effluent from Kahi-grass. Analyst 121:1963–1967

  33. Sharma C, Mohanty S, Kumar S, Rao NJ (1996b) Gas chromatographic analysis of chlorophenolic, resin and fatty acids in effluents from bleaching processes of agricultural residues. Int J Environ Anal Chem 64:289–300

  34. Sharma C, Mohanty S, Kumar S, Rao NJ (1997) Gas chromatographic determination of pollutants in the chlorination and caustic extraction stage effluent from the bleaching of a bamboo pulp. Talanta 44(10):1911–1918

  35. Singh RP (1979) Bleaching of pulp, 3rd edn. TAPPI Press, Atlanta, pp 29–89

  36. Singh S, Dutt D, Tyagi CH, Upadhyaya JS (2011) Bio-conventional bleaching of wheat straw soda-AQ pulp with crude xylanases from SH-1 NTCC-1163 and SH-2 NTCC-1164 strains of Coprinellus disseminatus to mitigate AOX generation. N Biotechnol 28(1):47–57

  37. Svenningsen NW (2001) Network for industrial environmental management—a new approach to old challenges in the Asia-Pacific pulp and paper industry. Paperex India, pp 50–51

  38. Takeuchi K, Suwa Y, Yamagishi T, Yonezawa Y (2000) Anaerobic transformation of chlorophenols in methanogenic sludge unexposed to chlorophenols. Chemosphere 41:1457–1462

  39. TAPPI (1992) Test methods, T-236 cm-85. Kappa number of pulp. TAPPI Press, Atlanta, Georgia, pp 1–3

  40. TAPPI (2000–2001) Test methods, standards methods for pulp & paper. TAPPI Press, Atlanta

  41. Tatum VL, Fisher RP (1995) The endocrine active chemical issue. In: Proceedings of the 1995 international environmental conference. TAPPI Press, Atlanta, pp 365–368

  42. Tremblay L, Van Der Kraak G (1999) Comparison between the effects of phytoserol β-sitosterol and pulp and paper mill effluents on sexually immature rainbow trout. Environ Toxicol Chem J 18:329–336

  43. Voss RH, Wearing JT, Mortimer RD, Kovacs T, Wong A (1980) Chlorinated organics in kraft bleachery effluents. Paperi ja Puu 62(12):809–814

  44. Voss RH, Wong A, Wearing JT (1981) Effect of softwood chlorination on the formation of toxic chlorinated compounds. Pulp Pap Can J 82(2):97–105

  45. Xie T-M, Lu Z-J (1987) A preliminary study of chlorophenolics in non-wood pulp bleaching effluents. Nordic Pulp Pap Res J 2:56–60

  46. Zhang H, He Z, Yonghao N (2011) Improvement of high-yield pulp properties by using a small amount of bleached wheat straw pulp. Bioresour Technol 102:2829–2833

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Correspondence to Sudheer Kumar Shukla.

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Malhotra, R., Prakash, D., Shukla, S.K. et al. Comparative study of toxic chlorophenolic compounds generated in various bleaching sequences of wheat straw pulp. Clean Techn Environ Policy 15, 999–1011 (2013) doi:10.1007/s10098-013-0578-6

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  • Bleaching effluent
  • Chlorophenolic compounds
  • Effluent toxicity
  • Wheat straw pulp