1. BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E) LIFE12 ENV/IT/352 Determination of trace elements in traditional dyes, naturalized dyes and commercial dyes Alessandro D’Ulivo

2. BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E) LIFE12 ENV/IT/352 DyesTypeNotes Disperse Blue 27 Blue Teratop Commercial  90% Additives   10% Dye Disperse Red 202Traditional Acid Dye Disperse Yellow 42Traditional Acid Dye Disperse Blue 27, Purified Traditional Acid DyeExtracted from Blue Teratop Disperse Orange 30Traditional Acid Dye Red NatNaturalized DyeNaturalized Red 202 Blue NatNaturalized Dye18C UNIFI, DB27 Yellow NatNaturalized Dye17D UNIFI, DY42 Orange NatNaturalized Dye12D UNIFI, D030 Analized Dyes

3. Trace element Determination Pressurized MW Digestion, HNO 3 + H 2 O 2 Determination by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) Perkin Elmer Optima 8000 Elements: Hg, Cd, Pb, Tl Mn, Cr, V, Co, Ni, Cu, Zn B, As, Sb, Se Be, Ba Al, Fe LIFE12 ENV/IT/352 BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E)

4. Direct Determination of Mercury Direct determination of Hg in solid and liquid samples Digestion not required No Hg losses No Hg contamination Typical Sample size 100 - 500 mg L.O.Q < 20 pg Hg (< 0.2 ppb) DMA-80: fully compliant with US EPA method 7473 and with ASTM method D-6722-01. Mercury Determination at sub p.p.b. Level LIFE12 ENV/IT/352 BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E)

5. Direct Determination of Mercury Results LIFE12 ENV/IT/352 BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E) Detected Elements in at least one of the Dyes Hg, Se, Pb, Cr, V, Be, Ni, Mn, Zn, Al, Cu, Fe, B, Ba Above Limit of quantification L.O.Q. = 10 s Elements Non-Detected in any dyes Tl  0.17 ; Cd  0.1; As  1.0; Co  0.17 [Sb  1.7 ] (mg/kg) Below the reported L.O.Q. Indicators of potential hazard level

6. Direct Determination of Mercury LIFE12 ENV/IT/352 BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E) Red202Yell 42Blue 27 Orang 30 Red Nat Yell Nat Blue Nat Orang Nat Blue COM LOQ mg/kg Hg 0,0890,0560,0030,0110,0130,0120,0220,019 0,660,0002 Se - (*)2,4-------1,7 Pb 1,32,03,71,5-2,2-- 3,50,8 Cr 0,6 1,1-4,50,82,10,42,8 0,17 V -0,7-1,11,2 1,01,31,80,4 Be ---0,30,270,31-0,3 0,07 Ni --0,5-2,1-1,22,1 0,42 Mn 0,30,9-0,250,56-0,250,1959,1 0,08 Zn 1,64,61,70,66,417,715,52,810,6 0,17 Al -64,3--6,6--0,926,1 0,8 Cu 1,40,41,0-----11,4 0,3 Fe 33,729,22,01,849,71,72,11,0112,4 0,08 B 293,6------64 0,83 Ba -1,705--0,170-0,1860,0252,991 0,02 (*)  LOQ ; Below LOQ in all samples: Co  0.17; Sb  1.7; As  1.0; Tl  1.7; Cd  0.1 mg/kg

7. Direct Determination of MercuryTotal Metal Content LIFE12 ENV/IT/352 BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E) Hg, Cd, Pb, Tl Mn, Cr, V, Co, Ni, Cu, Zn B, As, Sb, Se Be, Ba + Al, Fe 160 mg/kg 298 mg/kg Commercial Disperse Blue27 Blue Teratop

8. Direct Determination of MercuryMercury and Lead LIFE12 ENV/IT/352 BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E) (1) Red202 (2) Yellow (3) Blue 27 (purified)) (4) Orange30 (5) Red202Nat (6) Yellow Nat ( 7) Blue Nat (8) OrangeNat (9) Disperse Blue 27 – Blue Teratop

9. Direct Determination of MercuryChromium and Vanadium LIFE12 ENV/IT/352 BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E) (1) Red202 (2) Yellow (3) Blue 27 (purified)) (4) Orange30 (5) Red202Nat (6) Yellow Nat ( 7) Blue Nat (8) OrangeNat (9) Disperse Blue 27 – Blue Teratop

10. Direct Determination of MercuryNickel and Manganese LIFE12 ENV/IT/352 BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E) (1) Red202 (2) Yellow (3) Blue 27 (purified)) (4) Orange30 (5) Red202Nat (6) Yellow Nat ( 7) Blue Nat (8) OrangeNat (9) Disperse Blue 27 – Blue Teratop

11. Direct Determination of MercuryZinc and Copper LIFE12 ENV/IT/352 BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E) (1) Red202 (2) Yellow (3) Blue 27 (purified)) (4) Orange30 (5) Red202Nat (6) Yellow Nat ( 7) Blue Nat (8) OrangeNat (9) Disperse Blue 27 – Blue Teratop

12. Direct Determination of MercuryAluminum and Iron LIFE12 ENV/IT/352 BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E) (1) Red202 (2) Yellow (3) Blue 27 (purified)) (4) Orange30 (5) Red202Nat (6) Yellow Nat ( 7) Blue Nat (8) OrangeNat (9) Disperse Blue 27 – Blue Teratop

13. Direct Determination of MercuryBoron and Barium LIFE12 ENV/IT/352 BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E) (1) Red202 (2) Yellow (3) Blue 27 (purified)) (4) Orange30 (5) Red202Nat (6) Yellow Nat ( 7) Blue Nat (8) OrangeNat (9) Disperse Blue 27 – Blue Teratop

14. BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E) LIFE12 ENV/IT/352 Commercial Dye mixture containing additves present a much higher content of hazardous elements with respect to both traditional acid and naturalized dyes. Contamination in commercial dyes is probably due to use of additives with low degree of purity. Naturalized dyes, needing none additives, present a much lower environmental impact for hazardous elements with respect to traditional acid dyes. Conclusion

15. BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E) LIFE12 ENV/IT/352 Screening of hazardous elements will be expanded to more samples: Commercial Dyes (containing additives) Acid Dyes (Extracted from Commercial) -Teratop Yellow GWL - Yellow DY42 -Terasil Brown 2RFL - Orange D030 -Foron Bruno Giallo S-2RFL - Red 202 -Foron Rosso Brillante Future Activities

16. Toxic metals /elements (mg/kg or ppm) con ICP-OES Traditional Dyes Naturalized DyesCommercial Dyes Disperse RED 202 Disperse Yellow 42 Disperse Blue 27 (purified) Disperse Orange 30 Red 202 Red nat 17D Unifi DY42 Yellow nat 18 C Unifi DB27 Blue nat 12D Unifi D030 Orange nat Disperse Blue 27 Blue Teratop L.O.Q. mg/kg Dyes Hg (*) 0,0890,0560,0030,0110,0220,0120,0190,0130,66 0,0002 B 29,03,6------64,0 0,83 V -0,7- 1,11,2 1,11,31,8 0,42 Cr 0,6 1,1 4,50,82,10,42,8 0,17 Mn 0,30,9- 0,30,6-0,30,259,0 0,08 Ni --0,5-2,1 -1,2 -2,2 0,42 Cu 1,40,41,0- - - -- 12,0 0,33 Zn 1,64,61,70,66,417,715,52,811,0 0,17 Be - - - 0,3 - - 0,07 Ba -1,7--0,2- 0,03,0 0,02 Pb 1,32,03,71,5- 2,2--3,5 0,83 Se -2,4- -- -- -- 1,67 Total Me 34,418,08,03,815,222,320,45,0160,0 In all samples : Co  0.17; Sb  1.7; As  1.0; Tl  1.7; Cd  0.1 mg/kg. (*) Direct mercury analysis, DMA80 BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E) LIFE12 ENV/IT/352