ERSİN ÖNEM, HÜSEYİN ATA KARAVANA, ALİ YORGANCIOĞLU, BAHRİ BAŞARAN

Deri Sanayinde İhracatı Tehdit Eden Yasaklı Maddelerin Ayakkabılık Mamul Derilerde Araştırılması

Deri sanayi büyük ölçüde ihracata yönelik olarak faaliyet göstermektedir. Günümüzde deri sektöründe artan rekabet koşulları kalite kriterlerinin değişmesine neden olmuştur. Çevre bilincinin ve insan sağlığına verilen değerin artmasıyla deri işlemede kullanılan zararlı kimyasalların kullanımı kaldırılmakta, yahut sınırlandırılmaktadır. Bu çalışmada, toksik etkisi olan ve deri ürünlerinde bulunması istenmeyen ya da belli sınırlandırmaları olan bazı bileşenler üzerinde durulmuştur. Bu amaçla mamul hale gelmiş ayakkabılık derilerde azo boyarmadde, fitalat, formaldehit, krom(VI), alkil fenol etoksilat (APEO), nonil fenol etoksilat (NPEO) ve kısa zincirli klorlanmış parafin (SCCP) analizleri gerçekleştirilmiş ve ayakkabılık derilerdeki içerikleri araştırılmıştır. Sonuçlar ayakkabılık derilerin azo boyarmadde, krom(VI) ve NPEO içeriklerinin sırasıyla 35 ppm, 5.4 ppm ve 1520 ppm değerleri ile tanımlanan limit değerlerin üzerinde olduğunu göstermiştir.

Investigation of the Restricted Substances Threaten to Exports in Finished Upper Leather Products

Leather industry widely trades intended to exports. Nowadays, increasing competition conditions in the sector caused to change the quality criterias. Use of the hazardous chemicals in leather processing is removed or restricted with the inreased environmental conscious and increased conscious for the human health. In this study, it was put emphasis on the some substances having toxic effect and undesirable or restricted ones in terms of the leather products. In this context, analyses of azo dye, phthalate, formaldehyde, chromium(VI), alkylphenol ethoxylate (APEO), nonylphenol ethoxylate (NPEO) and short chain chlorinated paraffin (SCCP) in finished upper leathers were carried out and restricted substances were investigated. Results showed that azo dye, chromium(VI) and NPEO contents of the upper leathers were higher than the described limit values with 35 ppm, 5.4 ppm and 1520 ppm, respectively.

PDF

___

[1] Özçörekçi M, Öngüt E. 2005. Dünyada ve Türkiye'de Deri ve Deri Ürünleri Sanayiinin Gelişme Eğilimleri ve Geleceği. DPT (T.C. Başbakanlık Devlet Planlama Teşkilatı), İktisadi Sektörler ve Koordinasyon Genel Müdürlüğü, 335s.
[2] Çelebi H, Kara EE. 2007. Niğde İli Bor İlçesi Tabakhanelerinden Çıkan Atıksuların Tarım Topraklarının Kirliliğine Olan Etkisinin Araştırılması. Uluslararası Küresel İklim Değişikliği ve Çevresel Etkileri Konferansı, 18-20 Ekim, Konya, 379-383.
[3] Çolak SM. 2015. Hazardous Chemicals Used in Leather Production and Effects on Human Health. 3rd International Leather Engineering Congress, Innovative Aspects for Leather Industry, 21-22 Mayıs, İzmir, 295-305.
[4] Sojka-Ledakowicz J, Olczyk J, Polak J, Graz M, Jarosz-Wilkolazka A. 2015. Dyeing of Textile Fabrics with Bio-Dyes, Fibres and Textiles in Eastern Europe, Cilt. 23, s. 120- 125.
[5] Lee SC, Shin EC, Kim WJ. 2014. Dyeing Properties of Natural Leather Using Red Natural Dyes, Journal of the Society of Leather Technologists and Chemists, Cilt. 98, s. 252-258.
[6] Dave H, Ledwani L, Nema SK. 2016. Surface Modification by Atmospheric Pressure Air Plasma Treatment to Improve Dyeing with Natural Dyes: An Environment Friendly Approach for Leather Processing, Plasma Chemistry and Plasma Processing, Cilt. 36, s. 599- 613. DOI: 10.1007/s11090-015- 9687-9
[7] Velmurugan P, Shim J, Seo SK, Oh BT. 2016. Extraction of Natural Dye from Coreopsis tinctoria Flower Petals for Leather Dyeing - An Ecofriendly Approach, Fibers and Polymers, Cilt. 17, s. 1875-1883. DOI: 10.1007/s12221-016-6226-0
[8] Kanagaraj J, Senthilvelan T, Panda RC, Kavitha S. 2015a. Eco-Friendly Waste Management Strategies for Greener Environment Towards Sustainable Development in Leather Industry: A Comprehensive Review, Journal of Cleaner Production, Cilt. 89, s. 1-17. DOI: 10.1016/j.jclepro.2014.11.013
[9] Kanagaraj J, Senthilvelan T, Panda RC. 2015b. Degradation of Azo Dyes by Laccase: Biological Method to Reduce Pollution Load in Dye Wastewater, Clean Technologies and Environmental Policy, Cilt. 17, s. 1443-1456. DOI: 10.1007/s10098-014-0869-6
[10] Herva M, Alvarez A, Roca E. 2011. Sustainable and Safe Design of Footwear Integrating Ecological Footprint and Risk Criteria, Journal of Hazardous Materials, Cilt. 192, s. 1876-1881. DOI: 10.1016/j.jhazmat.2011.07.028
[11] Covington AD. 2009. Tanning Chemistry, The Science of Leather. The University of Northampton, Northampton, UK, 520s.
[12] Bayramoglu EE, Onem E, Yorgancioglu A. 2012. Reduction of Hexavalent Chromium Formation in Leather with Various Natural Products (Coridothymus capitatus, Olea europaea, Corylus avellana, and Juglans regia), Ekoloji, Cilt. 21, s. 114-120. DOI: 10.5053/ekoloji.2011.8413
[13] Colak SM, Dandar U, Kilic E. 2014. Antioxidant Effect of Tannic Acid on Formation of Formaldehyde and Hexavalent Chromium Compounds in Leather, Tekstil ve Konfeksiyon, Cilt. 24, s. 105-110.
[14] Ozgunay H, Yilmaz O, Dandar U, Colak S, Zengin G, Afsar A, Simion D, Gaidau C. 2016. The Effect of Valonea and Henna Treatment and Post-Mordanting on Cr (VI) and Free Formaldehyde Formation in Leather, Tekstil ve Konfeksiyon, Cilt. 26, s. 327-334.
[15] Yilmaz B, Onem E, Yorgancioglu A, Bayramoglu EE. 2016. UV Protection Against Photoageing of Garment Leathers by ZnO Nanoparticles: Application of Nano ZnO in Finishing Process as Photocatalyst, Journal of the Society of Leather Technologists and Chemists, Cilt. 100, s. 321-326.
[16] Bayramoglu EE, Onem E, Yorgancioglu A. 2013. Analysis of Release of Free Formaldehyde Originated from THP Salt Tannages in Leather by High Performance Liquid Chromatography: Origanum onites Essential Oil as Free Formaldehyde Scavenger, Journal of the American Leather Chemists Association, Cilt. 108, s. 411-419.
[17] Zhang SX, Chai XS, Huang BX, Mai XX. 2015. A Robust Method for Determining Water-Extractable Alkylphenol Polyethoxylates in Textile Products by Reaction-Based Headspace Gas Chromatography, Journal of Chromatography A, Cilt. 1406, s. 94-98. DOI: 10.1016/j.chroma.2015.06.001
[18] Van Mourik LM, Leonards PEG, Gaus C, De Boer J. 2015. Recent Developments in Capabilities for Analysing Chlorinated Paraffins in Environmental Matrices: A review, Chemosphere, Cilt. 136, s. 259-272. DOI: 10.1016/j.chemosphere.2015.05.0 45
[19] Rey A, Blanc N, Cannot JC, Berthod A. 2011. Determination of Short Polychlorinated Alkanes in Leather Using Gas ChromatographyElectron Capture Negative Chemical Ionization Mass Spectrometry, Journal of the American Leather Chemists Association, Cilt. 106, s. 294-302.
[20] TS EN ISO 17234-1. 2014. Deri - Boyalı Derilerde Belirli Azo Boyar Maddelerin Tayini İçin Kimyasal Deneyler - Bölüm 1: Azo Boyar Maddelerden Türetilen Belirli Aromatik Aminlerin Tayini. Türk Standartları Enstitüsü, 21s, Ankara.
[21] TS EN 14372. Deri - Kimyasal Deneyler - Fitalat Tayini.
[22] TS EN ISO 17226-1. 2009. Deri - Fomaldehit İçeriğinin Kimyasal Tayini - Bölüm 1: Yüksek Performans Sıvı Kromotografik Yöntem. Türk Standartları Enstitüsü, 17s, Ankara.
[23] TS EN ISO 17075. 2008. Deri - Kimyasal Deneyler - Krom 6 Tayini. Türk Standartları Enstitüsü, 19s, Ankara.
[24] American Apparel & Footwear Association (AAFA), 2016. Restricted Substances List (RSL), April, Seventeenth Edition.
[25] Bennett J, Miah YA, Varsani DS, Salvadori E, Sheriff TS. 2016. Selective Oxidative Degradation of Azo Dyes by Hydrogen Peroxide Catalysed by Manganase(II) Ions, RSC Advances, Cilt. 6, s. 103372- 103381. DOI: 10.1039/c6ra23067a
[26] Aslan A. 2009. Determination of Heavy Metal Toxicity of Finished Leather Solid Waste, Bulletin of Environmental Contamination and Toxicology, Cilt. 82, s. 633-638. DOI: 10.1007/s00128-009-9656-1
[27] Karavana HA, Basaran B, Aslan A, Bitlisli BO, Gulumser G. 2011. Heavy Metal Contents of Bootee Leathers Tanned with Different Process Recipes, Tekstil ve Konfeksiyon, Cilt. 21, s. 305-310.
[28] Aravindhan R, Madhan B, Rao JR. 2011. Studies on TaraPhosphonium Combination Tannage: Approach Towards A Metal Free Eco-Benign Tanning System, Journal of the American Leather Chemists Association, Cilt. 110, s. 80-87.
[29] Wang XC, Ren LF, Qiang TT. 2009. Novel Way of Transformation of Tannery Waste to Environmentally Friendly Formaldehyde Scavenger, Environmental Progress & Sustainable Energy, Cilt. 28, s. 285- 290. DOI: 10.1002/ep.10329