BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E) LIFE12 ENV/IT/352 Determination...

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


LIFE12 ENV/IT/352

Dyes Type Notes

Disperse Blue 27Blue Teratop

Commercial ~ 90% Additives~ 10% Dye

Disperse Red 202 Traditional Acid Dye

Disperse Yellow 42 Traditional Acid Dye

Disperse Blue 27, Purified

Traditional Acid Dye Extracted from Blue Teratop

Disperse Orange 30 Traditional Acid Dye

Red Nat Naturalized Dye Naturalized Red 202

Blue Nat Naturalized Dye 18C UNIFI, DB27

Yellow Nat Naturalized Dye 17D UNIFI, DY42

Orange Nat Naturalized Dye 12D UNIFI, D030

Analized Dyes

Trace element Determination • Pressurized MW Digestion, HNO3 + H2O2

• Determination by Inductively Coupled PlasmaOptical Emission Spectrometry (ICP-OES)Perkin Elmer Optima 8000Elements: Hg, Cd, Pb, Tl

Mn, Cr, V, Co, Ni, Cu, Zn B, As, Sb, Se

Be, Ba Al, Fe

LIFE12 ENV/IT/352


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


Direct Determination of MercuryResults

LIFE12 ENV/IT/352


Hg Tl Cd Se As Co Pb Cr V Be Ni Mn Zn Al Cu Fe B Ba

1E-3

0,01

0,1

1

10

DECRETO MINISTERIALE 12 giugno 2003, n. 185«Regolamento recante norme tecniche per il riutilizzodelle acque reflue in attuazione dell’articolo26, comma 2, del D.Lgs. 11 maggio 1999, n. 152».(G.U. 23 luglio 2003, n. 169)

Max

imun

Con

cent

ratio

n (m

g/L)

Metal

Concentration Limits for reusing waste waters

Detected Elements inat 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-Detectedin 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

Direct Determination of Mercury

LIFE12 ENV/IT/352


Red202 Yell 42 Blue27

Orang 30

Red Nat

Yell Nat

Blue Nat

Orang Nat

Blue COM

LOQ mg/kg

Hg 0,089 0,056 0,003 0,011 0,013 0,012 0,022 0,019 0,66 0,0002

Se - (*) 2,4 - - - - - - - 1,7

Pb 1,3 2,0 3,7 1,5 - 2,2 - - 3,5 0,8

Cr 0,6 0,6 1,1 - 4,5 0,8 2,1 0,4 2,8 0,17

V - 0,7 - 1,1 1,2 1,2 1,0 1,3 1,8 0,4

Be - - - 0,3 0,27 0,31 - 0,3 0,07

Ni - - 0,5 - 2,1 - 1,2 2,1 0,42

Mn 0,3 0,9 - 0,25 0,56 - 0,25 0,19 59,1 0,08

Zn 1,6 4,6 1,7 0,6 6,4 17,7 15,5 2,8 10,6 0,17

Al - 64,3 - - 6,6 - - 0,9 26,1 0,8

Cu 1,4 0,4 1,0 - - - - - 11,4 0,3

Fe 33,7 29,2 2,0 1,8 49,7 1,7 2,1 1,0 112,4 0,08

B 29 3,6 - - - - - - 64 0,83

Ba - 1,705 - - 0,170 - 0,186 0,025 2,991 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

Direct Determination of MercuryTotal Metal Content

LIFE12 ENV/IT/352


1 2 3 4 5 6 7 8 90

50

100

150

200

250

300Total Metal Content B-Comm

Met

als

(mg/

kg)

Dyes

Traditional Naturalized

1 2 3 4 5 6 7 8 90

20

40

60

80

100

120

140

160

B-Comm

RN YN BN ONOB*Y

Tot

al M

etal

s (m

g/kg

)

Dyes

RTraditional Naturalized

Total Metal Content

Al and Fe not included

Hg, Cd, Pb, TlMn, Cr, V, Co, Ni, Cu, Zn

B, As, Sb, SeBe, Ba

+ Al, Fe

160 mg/kg 298 mg/kgCommercialDisperse Blue27Blue Teratop

Direct Determination of MercuryMercury and Lead

LIFE12 ENV/IT/352


1 2 3 4 5 6 7 8 90,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

B-Comm

Naturalized

Traditional

Hg

(mg/

kg)

Dyes

MercuryLOQ=0.0002 mg/kg

1 2 3 4 5 6 7 8 90

1

2

3

4

5

6

7

L e a dLOQ=0.83 mg/kg

B-Comm

Pb

(mg/

kg)

Dyes

Traditional

Naturalized

(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

Direct Determination of MercuryChromium and Vanadium

LIFE12 ENV/IT/352


1 2 3 4 5 6 7 8 90

1

2

3

4

5

6

ChromiumLOQ = 0.17 mg/kg

B-Comm

Cr (m

g/kg

)

Dyes

Traditional

Naturalized

1 2 3 4 5 6 7 8 90,0

0,5

1,0

1,5

2,0B-Comm

V (m

g/kg

)

Dyes

VanadiumLOQ=0.4 mg/kg

Traditional

Naturalized




Direct Determination of MercuryNickel and Manganese

LIFE12 ENV/IT/352


1 2 3 4 5 6 7 8 90,0

0,5

1,0

1,5

2,0

B-Comm

Ni (

mg/

kg)

Dyes

NickelLOQ=0.4 mg/kg

Traditional

Naturalized

1 2 3 4 5 6 7 8 90

10

20

30

40

50

60

B-Comm ManganeseLOQ=0.08 mg/kg

Naturalized

Mn

(mg/

kg)

Dyes

Traditional




Direct Determination of MercuryZinc and Copper

LIFE12 ENV/IT/352


1 2 3 4 5 6 7 8 90

2

4

6

8

10

12

14

16

18

20

22 ZincLOQ=0.2 mg/kg

B-CommZn

(mg/

kg)

Dyes

Traditional

Naturalized

1 2 3 4 5 6 7 8 90

2

4

6

8

10

12 CopperLOQ=0.3 mg/kg B-Comm

Cu

(mg/

kg)

Dyes

Traditional

Naturalized




Direct Determination of MercuryAluminum and Iron

LIFE12 ENV/IT/352


1 2 3 4 5 6 7 8 90

10

20

30

40

50

60

70

80

90

100 AluminumLOQ=0.83 mg/kg

B-Comm

Al (

mg/

kg)

Dyes

Traditional

Naturalized

1 2 3 4 5 6 7 8 90

20

40

60

80

100

120 B-Comm I r o nLOQ=0.08 mg/kg

Fe

(mg/

kg)

Dyes

Traditional

Naturalized




Direct Determination of MercuryBoron and Barium

LIFE12 ENV/IT/352


1 2 3 4 5 6 7 8 90

10

20

30

40

50

60 BoronLOQ=0.83 mg/kg

B-Comm

B (m

g/kg

)

Dyes

Traditional

Naturalized

1 2 3 4 5 6 7 8 90,0

0,5

1,0

1,5

2,0

2,5

3,0

Ba

(mg/

kg)

Dyes

BariumLOQ=0.02 mg/kg

Traditional

Naturalized





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


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

Toxic metals /elements (mg/kg or ppm) con ICP-OESTraditional Dyes Naturalized Dyes Commercial Dyes

Disperse RED 202

Disperse Yellow 42

Disperse Blue 27

(purified)

Disperse Orange

30Red 202 Red nat

17D Unifi DY42 Yellow

nat

18 C Unifi DB27

Blue nat

12D Unifi D030

Orange natDisperse Blue 27

Blue TeratopL.O.Q .

mg/kg Dyes

Hg (*) 0,089 0,056 0,003 0,011 0,022 0,012 0,019 0,013 0,66 0,0002

B 29,0 3,6 - - - - - - 64,0 0,83

V - 0,7 - 1,1 1,2 1,2 1,1 1,3 1,8 0,42

Cr 0,6 0,6 1,1 4,5 0,8 2,1 0,4 2,8 0,17

Mn 0,3 0,9 - 0,3 0,6 - 0,3 0,2 59,0 0,08

Ni - - 0,5 - 2,1 - 1,2 - 2,2 0,42

Cu 1,4 0,4 1,0 - - - - - 12,0 0,33

Zn 1,6 4,6 1,7 0,6 6,4 17,7 15,5 2,8 11,0 0,17

Be - - - 0,3 0,3 0,3 - 0,3 - 0,07

Ba - 1,7 - - 0,2 - 0,2 0,0 3,0 0,02

Pb 1,3 2,0 3,7 1,5 - 2,2 - - 3,5 0,83

Se - 2,4 - - - - - - - 1,67

Total Me 34,4 18,0 8,0 3,8 15,2 22,3 20,4 5,0 160,0

In all samples : Co 0.17; Sb 1.7; As 1.0; Tl 1.7; Cd 0.1 mg/kg . (*) Direct mercury analysis, DMA80


LIFE12 ENV/IT/352

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BIONAD 18 Month Meeting July 7th, 2015, Inescop Premises, Elda (E) LIFE12 ENV/IT/352 Determination...

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