LIFE12 ENV/IT/352
Action C5 - Monitoring of the benefits from dyeing leather with naturalised colorants.
Determination of trace elements in commercial dyes,
crude chromophore, purified dyes and naturalized dyes
Alessandro D’Ulivo
BIONAD 24 Month Meeting
January 27th, 2016, UNIFI Premises , Florence (I)
LIFE12 ENV/IT/352
Analized Dyes & Chromophore
Crude
Chromophore
Commercial Dye
[Crude Chromophores
+ Additives ]
Purified
Chromophore
Naturalized
Dyes
[From commercial Dyes]
[from Purified Dyes]
YELLOW
Disperse Yellow
42
Teratop Brown
GWL
Disperse Yellow
42
DY42 Nat
ORANGE
Disperse Orange
30
Foron Brown Yellow
S-2RFL 150
Disperse Orange
30
D030 Nat
RED
Disperse Red
202
Foron Brilliant Red
S-RGL 200
Disperse Red
202
DR202 Nat
BLUE
NA*
Teratop Blue
GLF
Disperse Blue 27
DB27
(*) Not commercially available
BIONAD 24 Month Meeting
January 27th, 2016, UNIFI Premises , Florence (I)
LIFE12 ENV/IT/352
Trace element Determination
• Pressurized MW Digestion, HNO3 + H2O2
• 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
BIONAD 24 Month Meeting
January 27th, 2016, UNIFI Premises , Florence (I)
LIFE12 ENV/IT/352
Mercury
Direct
Determination
Determination
at of
subMercury
p.p.b. Level
•
•
•
•
•
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.
BIONAD 24 Month Meeting
January 27th, 2016, UNIFI Premises , Florence (I)
LIFE12 ENV/IT/352
Results of Mercury
Direct Determination
10
Concentration Limits for reusing waste waters
Maximun Concentration (mg/L)
DECRETO MINISTERIALE 12 giugno 2003, n. 185
«Regolamento recante norme tecniche per il riutilizzo
delle acque reflue in attuazione dell’articolo
26, comma 2, del D.Lgs. 11 maggio 1999, n. 152».
(G.U. 23 luglio 2003, n. 169)
1
0,1
Indicators of potential hazard level
0,01
1E-3
Hg Tl Cd Se As Co Pb Cr
V Be Ni Mn Zn Al Cu Fe B Ba
Metal
Detected Elements in
Hg, Se, Pb, Cr, Cd, Pb, V, Be,
at least one of the Dyes Ni, Mn, Zn, Al, Cu, Fe, B, Ba
Elements Non-Detected
in any dyes
Tl  0.17 ; Co  0.17 (mg/kg)
BIONAD 24 Month Meeting
Above Limit of quantification
L.O.Q. = 10 s
Below the reported L.O.Q.
January 27th, 2016, UNIFI Premises , Florence (I)
LIFE12 ENV/IT/352
Additives
Commercial Dyes
Commercial
«Crude»
Chromophores
Soxhlet
Extraction
Purified
Chromophores
BIONAD 24 Month Meeting
Lactose
Naturalised Dyes
January 27th, 2016, UNIFI Premises , Florence (I)
LIFE12 ENV/IT/352
Commercial Dyes
Element
Al
As
B
Ba
Be
Cd
Co
Cr
Cu
Fe
Hg
Mn
Ni
Pb
Sb
Se
Tl
V
Zn
Totalb
Teratop
Brown
GWL
Crude Chromophores
LOQm
Foron
Brilliant
Red
S-RGL200
(mg/kg)
Teratop
Blue
GLF
Disperse
Yellow
42
Disperse
Orange
30
Disperse
Red
202
(mg/kg)
Foron
Brown
Yellow
S-2RFL150
(mg/kg)
(mg/kg)
(mg/kg)
(mg/kg)
(mg/kg)
(mg/kg)
32.7
49.8
47.6
26.1
64.3
-
-
0.83
8.1
-a
7.5
-
0.94
-
-
0.83
-
-
-
64.1
3.6
-
29.0
0.83
0.84
0.63
4.8
3.0
1.7
-
-
0.02
-
-
-
-
-
0.30
-
0.07
0.10
0.13
-
-
0.15
-
-
0.08
-
-
-
-
-
-
-
0.17
-
3.8
3.3
2.8
0.59
0.60
0.17
-
-
-
11.4
0.40
1.4
0.33
21.5
49.9
44.5
112.4
29.2
1.8
33.7
0.08
0.0070
0.46
0.0017
0.66
0.060
0.010
0.090
8.510-5
11.2
18.3
12.9
59.1
0.91
0.25
0.34
0.08
-
2.4
2.4
2.1
0.42
-
-
-
-
3.5
2.0
1.5
1.3
0.83
2.1
1.9
-
-
-
-
-
1.70
3.9
2.2
2.0
-
2.4
-
1.70
-
-
-
-
-
-
-
1.70
9.8
14.3
22.1
1.8
0.73
1.1
2.9
-
-
10.6
4.6
0.62
1.6
0.17
97.7
148.6
147.1
299.4
114.8
13.2
75.1
[10.4]c
0.42
0.42
a - concentrations that are not reported are below LOQm.
b - sum of concentrations includes LODm whenever the determined values cannot be quantified.
c - sum of LOQm.
BIONAD 24 Month Meeting
January 27th, 2016, UNIFI Premises , Florence (I)
LIFE12 ENV/IT/352
Purified Chromophores
from Commercial Dyes
Element
Al
As
B
Ba
Be
Cd
Co
Cr
Cu
Fe
Hg
Mn
Ni
Pb
Sb
Se
Tl
V
Zn
Totalb
Disperse
Yellow
42
(mg/kg)
8.2
0.37
0.13
0.00015
3.7
6.8
25.3
Disperse
Orange
30
(mg/kg)
0.0012
1.7
10.4
Naturalised Dyes
Disperse
Red
202
(mg/kg)
3.9
0.0001
12.6
Disperse
Blue
27
(mg/kg)
1.1
1.0
2.0
0.0030
0.50
3.7
1.7
17.6
LOQm
DY42
Nat
D030
Nat
DR202
Nat
DB27
Nat
(mg/kg)
0.31
0.85
1.7
0.010
2.2
1.2
17.7
31.0
(mg/kg)
0.90
0.03
0.29
0.45
1.0
0.020
0.19
1.3
2.8
13.0
(mg/kg)
6.6
0.17
0.27
4.5
49.7
0.010
0.57
2.1
1.2
6.4
71.4
(mg/kg)
0.19
2.1
2.1
0.020
0.25
1.2
1.0
15.5
97.7
a - concentrations that are not reported are below LOQm;
b - sum of concentrations includes LODm whenever the determined values cannot be quantified;
c - sum of LOQm
BIONAD 24 Month Meeting
January 27th, 2016, UNIFI Premises , Florence (I)
(mg/kg)
0.83
0.83
0.83
0.02
0.07
0.08
0.17
0.17
0.33
0.08
8.510-5
0.08
0.42
0.83
1.70
1.70
1.70
0.42
0.17
[10.4]c
LIFE12 ENV/IT/352
Non quantifiable Elements (Conc ≤ LOQm)
10
Number of Elements below LOQm
9
Purified
Chromophores
8
Naturalised
Dyes
7
6
5
4
Commercial
Dyes
Crude
Chromophores
Al
B
Be
Co
Mn
Tl
V
3
2
1
0
Be
Co
Tl
Co
Sb
Tl
B
Ba
Co
Cr
Cu
Sb
Se
Tl
Dyes
BIONAD 24 Month Meeting
January 27th, 2016, UNIFI Premises , Florence (I)
LIFE12 ENV/IT/352
DirectTotal
Determination
Element Content
of Mercury
360
Total Metal Concentration ( mg / kg)
320
Commercial
280
240
200
160
120
Crude
Chromophore
Naturalized
80
40
Purified
Cromophore
0
Dyes
BIONAD 24 Month Meeting
January 27th, 2016, UNIFI Premises , Florence (I)
LIFE12 ENV/IT/352
Direct Determination
Mercury of Mercury
700
600
Commercial
Dyes
Mercury Concentration
500
Mercury (g/kg)
400
100
Commercial
Chromophores
50
Naturalised Dyes
Purified Dyes
Dyes & Chromophores
BIONAD 24 Month Meeting
January 27th, 2016, UNIFI Premises , Florence (I)
LIFE12 ENV/IT/352
Conclusion
In general total elements content follow the order:
Commercial Dyes > Crude Chromophore ≥ Naturalized Dyes > Purified Dyes
Similar trend is found for mercury.
Contamination of commercial dyes can be addressed to the use of additives
with low degree of purity.
Naturalized dyes, presents some problems of contamination by Zn, Fe and Al,
probably arising from the apparatus employed in synthesis/purification.
BIONAD 24 Month Meeting
January 27th, 2016, UNIFI Premises , Florence (I)