1. ECODEFATTING Environmentally friendly natural products instead of chemical products in the degreasing phase of the tanning cycle LIFE13 ENV/IT/000470 Emilia Bramanti ICCOM-CNR 12 MONTH MEETING, October 22 2015 –Newport, Santa Croce, Pisa

2. Gantt chart

3. ACTION A.1, A.2 Study of the interaction between leather and the defatting agents (commercial and natural products, Action A2) by Fourier Transform Infrared Spectrometry (FTIR) and Thermogravimetric Analysis (TGA) ACTION C.1, C2, C3, C4 Analytical method to determine the metal content in the defatting wastewaters and also the fat content: ICP-MS, ICP-OES, atomic spectrometry (DMA80) and FTIR ACTION C.2, C3 (in progress) Metal content in the wastewaters obtained from the treatment with natural derived compounds (before and after microbial degradation). ECODEFATTING ACTIONS at ICCOM-PI in the first 12 months

4. Methods (A, B and C Actions) Infrared spectroscopy (ATR-FTIR) for the study of defatting agents/leather protein interactions and the residual fat content in leather Thermogravimetric Analysis (TGA) for the study of defatting agents/leather proteins ICP-MS, ICP-OES, DMA80 for the determination of metals A flow injection Dynamic Surface Tesion Detector for the determination of surface Active agents (?)

5. Agilent 7700 Series ICP-MS with a 3rd generation Octopole Reaction System with improved ion focusing and increased collision efficiency and a kinetic energy discrimination system (KED) Determination of the metal content in the defatting wastewaters from the treatment with commercial and natural products

6. ATR-FTIR analysis Sample in contact with penetrating radiation (evanescent wave) (d=0.5-5  m) Infrared beam from source To detector refractive index of the crystal must be significantly greater than that of the sample (2.38 and 4.01 at 2000 cm -1 ) (diamond or ZnSe or KRS-5 ie thallium iodide) Reflected bean is attenuated at characteristic wavelength (absorption bands) Diameter = 2 mm Solidsliquids

7. The frequency deconvolution procedure implemented in LabView

8. FTIR and TGA analysis of leather samples: -B1-B4 -COM1-COM4 -EDF1-EDF25 -Leather before the soaking process EDF20 -Leather before the soaking process SG50 -Pre-tanned leather EDF20 -Pre-tanned leather SG50 -Crust EDF20 -Wet-Blue EDF20 -FTIR of residual bath EDF19-EDF25 and B3 -Metal analysis by DMA80 (Hg) and ICP-OES and ICP-MS of residual baths of: -COM 1-4 -Rokanol -Etocas 15 -Tripropionin -Trietyl Citrate - Castor oil -Exilene Glycol -EDF20 -Leather before the soaking process EDF20 -Leather before the soaking process SG50 -Pre-tanned leather EDF20 -Pre-tanned leather SG50 Summary of samples analysed

9. Pictures of leather samples B1-B4 -COM1-COM4 -EDF1-EDF25

10. Area 1 Stretching CH2/CH3 Area 2 Stretching C=O Amide I Amide II ACTION A1, A2, B1 and B2 Study of the interaction between leather and the defatting agents (commercial and natural products) by Fourier Transform Infrared Spectrometry (FTIR)

11. ACTION A.1-A2 and B1-B2 Study of the fat content in leather samples treated or not (blanks) with defatting agents (commercial and natural products) by Fourier Transform Infrared Spectrometry (FTIR) CH2/CH3 stretching area (Area 1) Area 1 Area 2

12. ACTION A, B and C Lab demostration tests of defatting agents (commercial and natural products) COM 1: Anionic slightly Oxyethylenated COM 2: Synthetic oxo-alcohol ethoxylate COM 3: Polyglycol fatty chain linear COM 4: Non-ionic / anionic surfactant (*) extracted in dichloromethane Best ECODEFATTING product

14. ACTION C.1, C2, C3, C4 FTIR to determine the fat content in the wastewaters (baths) (dried films)

15. Amide I Amide II ACTION A1, A2, B1 and B2 Study of the interaction between leather and the defatting agents (commercial and natural products, Action A2) by Fourier Transform Infrared Spectrometry (FTIR) AII/AI ratios from FTIR SPECTRA of leather samples treated withcommercial and ECODEFATTING products

16. ACTION A.1-A2 and B1-B3 Study of the interaction between leather and the defatting agents (commercial and natural products) by Fourier Transform Infrared Spectrometry (FTIR) FTIR spectra of leather samples EDF 20 Crust and EDF 20 Wet Blue Area 1 Stretching CH2/CH3 Area 2 Stretching C=O

17. ACTION A.1-A2 and B1-B3 Study of the interaction between leather and the defatting agents (commercial and natural products) by FTIR- peak fitting analysis

21. Rinverdimento Calcinaio Spaccatura/scarnatura??? 1° lavaggio purga 2°lavaggio purga Pikel preconcia EDF20 or PolauseSG50 0,2% w/w EDF20 or PolauseSG50 0,1% w/w EDF20 or PolauseSG50 0,2% w/w

22. ACTION A.1, A.2. Study of the interaction between leather and the defatting agents (commercial and natural products) by Thermogravimetric Analysis (TGA) COM 1 COM 2 COM 3 COM 4

23. B3EDF 20 Leather Crust EDF 20Leather Wet Blue EDF 20 Leather before the soaking process EDF 20 Pretanning leather EDF 20 Leather before the soaking process SG 50 Pretanning leather SG 50 ACTION A.1, A.2. Study of the interaction between leather and the defatting agents (commercial and natural products) by Thermogravimetric Analysis (TGA)

24. Leather Sample Peak 1 (°C)Peak 3 (°C)Peak 4 (°C) Peak 5 (°C) Peak 6 (°C)Peak 7 (°C) Residuo finale % B163315392 5198877,3 B263315395 5388145,3 B366315394 5238637,1 B464312389 4987775,2 COM163306403 482 3,3 COM266309417 485 3,8 COM368311413 482 4 COM458316395434487 5,3 Ref1_972310411 6,6 Ref267313396 5348705,7 EDF168317383 476 5,7 EDF271309402 5 EDF370308392433 5,2 EDF474312413 477 6,1 EDF572313 479 4,9 EDF668302385 4947947,6 EDF769315388 4998838,3 EDF863327391 4878677,8 EDF965316381 4698507,7 EDF1071312386 503 11,2 EDF1162318391 511 16,4 EDF1259320385 50178913,7 EDF1361315391 51879114,7 EDF1464314390 51478711,3 EDF1565313397 5377966,7 EDF1671310394 5318906,7 EDF1767312393 5217939,7 EDF1870314392 52189411,4 EDF19613193894244978137,4 EDF2063314389 5028596,1 EDF21613173934275058186,4 EDF2264306403 5258824,9 EDF2364312394 5087746,7 EDF2464310393 5248786 EDF25553213894245018475,9 ACTION A.1, A.2. Study of the interaction between leather and the defatting agents (commercial and natural products) by Thermogravimetric Analysis (TGA)

25. TGA Peak 306-329 °C TGA Peak 380-417 °C TGA Peak 482-606 °C Residual (%) ACTION A.1, A.2. Study of the interaction between leather and the defatting agents (commercial and natural products) by Thermogravimetric Analysis (TGA)

26. ACTION C.2, C3 Metal content in the wastewaters obtained from the treatment with natural and commercial defatting agents

27. ACTION C.2, C3 Metal content in the wastewaters obtained from the treatment with natural and commercial defatting agents (mg/Kg, ppm)

28. ACTION C.2, C3 Metal content in the wastewaters obtained from the treatment with natural and commercial defatting agents (mg/Kg, ppm)

29. ACTIONS A1-A2 PEAK FITTING of Fourier Transform Infrared Spectrometry (FTIR) Thermogravimetric Analysis (TGA) Correlation with several leather chemical physical parameters (ICCOM/INESCOP) ACTIONS C1-C2- C3 Analytical method to determine the metal content in the defatting wastewaters and in the wastewaters obtained from the lab and semi-industrial treatment with natural derived compounds (before and after microbial degradation). ECODEFATTING ACTIONS of the next 6 months

30. ECODEFATTING PEOPLE @ ICCOM-PI Emilia Bramanti Alessandro D’Ulivo Massimo Onor Manuela Cempini Emanuela Pitzalis Marco Carlo Mascherpa Simona Biagi Valentina Della Porta