Abstract
Most tanneries use high proportions of Na2S and CaO during the dehairing step, resulting in effluents of high alkalinity and large amounts of suspended solid, besides the risk of liberating the toxic H2S. Solid waste rich in protein is another environmental problem of tanneries. Enzymes are an interesting technological tool for industry due to their biodegradability, nontoxic nature, and nonpolluting effluent generation. In the leather industry, proteases have been chosen as a promising eco-friendly alternative to Na2S/CaO dehairing. Extracts with high proteolytic activity have been obtained from fruits of Bromeliaceae species: Bromelia balansae Mez (Bb), Bromelia hieronymi Mez (Bh), and Pseudananas macrodontes (Morr.) Harms (Pm). In this work, Bb, Bh, and Pm have been studied for application in the leather industry, focusing in their dehairing properties. Enzymatic activities were measured against collagen, keratin, elastin, and epidermis while a dehairing assay was performed by employing cowhide. All extracts showed similar activity on collagen and epidermis, while Bh and Pm were the most active against keratin at the same caseinolytic unit (CU) values; Bh was the only extract active against elastin. Bb (1 CU/ml), Bh (1.5 CU/ml), and Pm (0.5 CU/ml) were able to depilate cowhide. Desirable characteristics of dehairing were observed for all extracts since hair pores did not show residual hair, grain surface was clean and intact, and collagen fiber bundles of dermis were not damaged. In conclusion, results here presented show that proteolytic extracts of Bromeliaceae species are promising eco-compatible tools for leather industry.
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References
Aftab MN, Hameed A, Haq I-u, Chen R-s (2006) Biodegradation of leather waste by enzymatic treatment. Chin J Process Eng 6(3):462–465
Andrioli E, Petry L, Gutterres M (2015) Environmentally friendly hide unhairing: enzymatic-oxidative unhairing as an alternative touse of lime and sodium sulphide. Process Saf Environ 93:9–17. https://doi.org/10.1016/j.psep.2014.06.001
Arunachalam C, Saritha K (2009) Protease enzyme: an eco-friendly alternative for leather industry. Indian J Sci Technol 2(12):29–32
Brullo A (2003) Isolation, purification and characterization of cysteine endopeptidases in fruits of Pseudananas macrodontes (Morr.) Harms (Bromeliaceae). Dissertation, National University of La Plata, Argentina (in Spanish) Available at http://sedici.unlp.edu.ar/bitstream/handle/10915/2246/Documento_completo__.pdf?sequence=23
Bruno MA, Pardo MF, Caffini NO, López LMI (2003) Hieronymain I. A new cysteine peptidase isolated from unripe fruits of Bromelia hieronymi Mez (Bromeliaceae). J Protein Chem 22(2):127–134. https://doi.org/10.1023/A:1023418812832
Bruno MA, Trejo SA, Avilés XF, Caffini NO, López LMI (2006) Isolation and characterization of hieronymain II, another peptidase isolated from fruits of Bromelia hieronymi Mez. Protein J 25(3):224–231. https://doi.org/10.1007/s10930-006-9005-8
Bruno MA, Trejo S, Caffini NO, López LMI (2008) Purification and characterization of hieronymain III. Comparison with other proteases previously isolated from Bromelia hieronymi Mez. Protein J 27(7-8):426–433. https://doi.org/10.1007/s10930-008-9152-1
Cantera CS, Goya L, Galarza B, Garro ML, Lopez LMI (2003) Hair saving unhairing process. Part 5 Characterisation of enzymatic preparations applied in soaking and unhairing processes. J Soc Leath Tech Chem 87(2):69–77
Choudhary RB, Jana AK, Jha MK (2004) Enzyme technology applications in leather processing. Indian J Chem Technol 11:659–671
Dettmer A, Ayub MA, Gutterres M (2011) Hide unhairing and characterization of commercial enzymes used in leather manufacture. Braz J Chem Eng 28(3):373–380. https://doi.org/10.1590/S0104-66322011000300003
Dettmer A, Cavalli É, Ayub MA, Gutterres M (2012) Optimization of the unhairing leather processing with enzymes and the evaluation of inter-fibrillary proteins removal: an environment-friendly alternative. Bioprocess Biosyst Eng 35(8):1317–1324. https://doi.org/10.1007/s00449-012-0719-z
Dixit S, Yadav A, Dwivedi PD, Das M (2015) Toxic hazards of leather industry and technologies to combat threat: a review. J Clean Prod 87:39–49. https://doi.org/10.1016/j.jclepro.2014.10.017
Foroughi F, Keshavarz T, Evans CS (2006) Specificities of proteases for use in leather manufacture. J Chem Technol Biotechnol 81(3):257–261. https://doi.org/10.1002/jctb.1367
George N, Chauhan PS, Kumar V, Puri N, Gupta N (2014) Approach to ecofriendly leather: characterization and application of an alkaline protease for chemical free dehairing of skins and hides at pilot scale. J Clean Prod 79:249–257. https://doi.org/10.1016/j.jclepro.2014.05.046
Jaouadi NZ, Jaouadi B, Hlim HB, Reki H, Belhou M, Hmidi M, Bejar S (2014) Probing the crucial role of Leu31 and Thr33 of the Bacillus pumilus CBS alkaline protease in substrate recognition and enzymatic depilation of animal hide. PLoS One 9(9):e108367. https://doi.org/10.1371/journal.pone.0108367
Kanagaraj J, Velappan KC, Chandra Babu NK, Sadulla S (2006) Solid wastes generation in the leather industry and its utilization for cleaner environment—a review. J Sci Ind Res 65:541–548
Kruger NJ (2009) The Bradford method for protein quantitation. In: Walker JM (ed) The protein protocols handbook. Springer Protocols Handbooks. Humana Press, Totowa, pp 17–24. https://doi.org/10.1385/0-89603-268-X:9
López LM, Sequeiros C, Natalucci CL, Caffini NO, Brullo A, Maras B, Barra D (2000) Purification and characterization of macrodontain I, a cysteine peptidase from unripe fruits of Pseudananas macrodontes (Morr.) Harms (Bromeliaceae). Protein Expr Purif 18(2):133–140. https://doi.org/10.1006/prep.1999.1165
López LM, Sequeiros C, Trejo SA, Pardo MF, Caffini NO, Natalucci CL (2001) Comparison of two cysteine endopeptidases from Pseudananas macrodontes (Morr.) Harms (Bromeliaceae). Biol Chem 382(5):875–878. https://doi.org/10.1515/BC.2001.108
López LMI, Viana CA, Errasti ME, Garro ML, Martegani JE, Mazzilli GA, Freitas CDT, Araújo IMS, Da Silva RO, Ramos MV (2017) Latex peptidases of Calotropis procera for dehairing of leather as an alternative to environmentally toxic sodium sulfide treatment. Bioprocess Biosyst Eng 40(9):1391–1398. https://doi.org/10.1007/s00449-017-1796-9
Madhavi J, Srilakshmi J, Rao MR, Rao KRSS (2011) Efficient leather dehairing by bacterial thermostable protease. Int J Biosci Biotechnol 3(4):11–26
Pardo MF (2004) Endopeptidases of Bromelia balansae Mez and its application in the modification of alimentary proteins. Dissertation, National University of La Plata, Argentina (in Spanish)
Pardo MF, López LM, Canals F, Avilés FX, Natalucci CL, Caffini NO (2000) Purification of balansain I, an endopeptidase from unripe fruits of Bromelia balansae Mez (Bromeliaceae). J Agric Food Chem 48(9):3795–3800. https://doi.org/10.1021/jf0002488
Ramasami T, Rao JR, Chandrababu NK, Parthasarathi K, Rao PG, Saravanan P, Gayathri R, Sreeram KJ (1999) Beamhouse and tanning operations: process chemistry revisited. J Soc Leath Tech Chem 83(1):39–45
Saran S, Mahajan RV, Kaushik R, Isar J, Saxena RK (2013) Enzyme mediated beam house operations of leather industry: a needed step towards greener technology. J Clean Prod 54:315–322. https://doi.org/10.1016/j.jclepro.2013.04.017
Saravanan P, Renitha TS, Gowthaman MK, Kamini NR (2014) Understanding the chemical free enzyme based cleaner unhairing process in leather manufacturing. J Clean Prod 79:258–264. https://doi.org/10.1016/j.jclepro.2014.05.022
Sivasubramanian S, Manohar BM, Rajaram A, Puvanakrishnan R (2008a) Ecofriendly lime and sulfide free enzymatic dehairing of skins and hides using a bacterial alkaline protease. Chemosphere 70(6):1015–1024. https://doi.org/10.1016/j.chemosphere.2007.09.036
Sivasubramanian S, Manohar BM, Puvanakrishnan R (2008b) Mechanism of enzymatic dehairing of skins using a bacterial alkaline protease. Chemosphere 70(6):1025–1034. https://doi.org/10.1016/j.chemosphere.2007.07.084
Thanikaivelan P, Rao JR, Nair BU, Ramasami T (2004) Progress and recent trends in biotechnological methods for leather processing. Trends Biotechnol 22(4):181–188. https://doi.org/10.1016/j.tibtech.2004.02.008
Thompson VF, Saldaña S, Cong J, Goll DE (2000) A BODIPY fluorescent microplate assay for measuring activity of calpains and other proteases. Anal Biochem 279(2):170–178. https://doi.org/10.1006/abio.1999.4475
Valeika V, Beleška K, Valeikienė V, Kolodzeiskis V (2009) An approach to cleaner production: from hair burning to hair saving using a lime-free unhairing system. J Clean Prod 17(2):214–221. https://doi.org/10.1016/j.jclepro.2008.04.010
Acknowledgements
María Eugenia Errasti is member of the Scientific Research Commission of the Province of Buenos Aires (CIC-PBA) Researcher Career. Laura María Isabel López is member of the National Council of Scientific and Technical Research (CONICET) Researcher Career. The present work was supported by grants from National Council of Scientific and Technical Research (PIP 00297) and Scientific Research Commission of the Province of Buenos Aires (PIT-AP-BA 2016). Authors want to thank Germán Mazzilli from technical staff of the Centro de Investigaciones de Tecnología del Cuero (CITEC), who performed the soaking process.
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Scanning electron micrographs (2000 X) of cross section of cowhides after treatment with: (a) 1 CU/ml of Bb; (b) 1.5 CU/ml of Bh; (c) 0.5 CU/ml of Pm; (d) 0.2 CU/ml of New1875; (e) reaction buffer (Control) (PDF 192 kb).
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Errasti, M.E., Caffini, N.O. & López, L.M.I. Proteolytic extracts of three Bromeliaceae species as eco-compatible tools for leather industry. Environ Sci Pollut Res 25, 21459–21466 (2018). https://doi.org/10.1007/s11356-017-1096-6
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DOI: https://doi.org/10.1007/s11356-017-1096-6