case study: levels of contamination of chemical auxiliaries for ......case study: levels of...

Case study: levels of contamination of

chemical auxiliaries for spinning and weaving

Bartolini Giuseppe, Franchi Andrea and Dall’Anese Riccardo (BuzziLab – Prato)

July, 18 2017

© - Copyright Laboratorio Buzzi July, 18 2017

April - May 2017: Laboratorio Analisi Buzzi, in collaboration with CID:

study on level of contamination of spinning and weaving auxiliaries

Chemical analysis of four of the 11 priority groups of Detox MRSL

Parameter MRSL DETOX Limit

Ethoxylated Alkylphenols - APEOS 1 mg/kg

Perfluorinated Compounds - PFC 0.01mg/kg

Chlorophenols 0.05 mg/kg

Phthalates 10 mg/kg


Involved Companies (CID members)

DAYKEM – Chemicals producer

MANIFATTURA ILARIA – Yarn producer

FURPILE IDEA – Fabric producer

FILATI BIAGIOLI MODESTO - Yarn producer

PECCI FILATI - Yarn producer

ALBERTO BARDAZZI - Fabric producer

INDUSTRIA ITALIANA FILATI - Yarn producer

LANIFICIO dell’OLIVO - Yarn producer

FILATI BE.MI.VA - Yarn producer

LANIFICIO EUROPA - Fabric producer

BERTO INDUSTRIA TESSILE – produttori di tessuto

COTONIFICIO FERRARI - Fabric producer


ANALYTICAL SECTION

PERFLUORINATED COMPOUNDS - PFC

Analytical Method: in-house method developed by BuzziLab (ref. to UNI

CEN TS 15968)

Brief description of the method:

A weighted amount of sample is dissolved in organic solvent; analysis is

performed by GC-MSMS (for PFC telomers) and LC-MSMS (for other

PFCs)

Limit of Detection: 0,001mg/kg

Limit of Quantification (Detox MRSL): 0.01mg/kg


PERFLUORINATED COMPOUNDS- PFC

LC-MS Agilent 6495 Triple Quadrupole GC-MS Agilent 7010 Triple Quadrupole

ANALYTICAL SECTION


APEOS / CHLOROPHENOLS / PHTHALATES

Test Method: in-house method (developed by Buzzi Lab) was used by high-

resolution mass spectrometry/time-of-flight liquid chromatography (LC-QTOF

equipment).

Brief description of test method: a weighted sample of dye is dissolved in organic

solvent and directly analized by LC-QTOF.

This equipment permit the quantitative analysis of APEOS, Chlorophenols and

Phthalates in a single injection, using high-resolution mass spectrometry (exact

masses) with also low-limit of detection.

Limit of Detection: APEOS and Chlorophenols: 0.01mg/kg – Phthalates: 0.1mg/kg

Limit of Quantification (MRSL): APEOS: 1mg/kg – Chlorophenols: 0.05mg/kg –

Phthalates: 10mg/kg

ANALYTICAL SECTION


APEOS / CHLOROPHENOLS / PHTHALATES

LC-Q-TOF

Agilent 6545

ANALYTICAL SECTION


RESULTS


Chemical Auxiliaries

Total: 68

of 8 different classes


0

5

10

15

20

25

30

35

40

antistatics Non-SlipAgent

Detergent SizingAgent

Gluingagent

Lubricant Paraffinwax

MoistRegain

12

1 1 3

1

38

8

1

Auxiliaries: tot. 68


On the total of 68 samples:

• Only one sample (classified as non-slip agent) is

free of contamination

• frequent contamination is due to PFC Telomer

(FTOH 4:2 and FTOH 6:2 - 30.9%) followed by

APEOS (19.1%) and Phthalates (14,4%);

• Contamination by Chlorophenols regarded only 3

sample (4.4%).

Summary


Total Contaminations

13 (19%)

21 (30,9%)

10 (15%)

3 (4%)

APEOS

PFC

Phthalates

Chlorophenols


SINGLE CLASS RESULTS

1 - LUBRICANTS


5

15

6 1

Lubricants: tot 38

APEOS

PFC

Phthalates

Chlorophenols


0

1

2

3

4

5

6

7

0 - 1 mg/kg 1 - 5 mg/kg 5 - 10 mg/kg > 10mg/kg 0 - 1 mg/kg 1 - 5 mg/kg 0 - 1 mg/kg 0 - 1 mg/kg

FTOH 4:2 FTOH 6:2 PFOA H4PFOS

4

7

1 1

4

1

2

1

Lubricants - PFC


0

1

2

3

4

5

0 - 10 mg/kg 10 - 100 mg/kg 10 - 100 mg/kg 0 - 10 mg/kg

DEHP DINP DIBP

0

2

1

3

Lubricant - Phthalates


0

1

2

3

4

5

0 - 10 mg/kg 10 - 100 mg/kg

APEOS

2

3

Lubricant - APEOS


0

200

400

600

800

1000

1200

1400

1227 mg/kg

Lubricant - Chlorophenols

OPP



2 – ANTISTATIC

AGENTS


1

3

2

Antistatics: tot 12

APEOS

PFC

Phthalates


0

1

2

3

4

5

6

7

8

9

10

FTOH 4:2 FTOH 4:2 FTOH 4:2 FTOH 6:2

2,92

6,83

4,15

1,51

Antistatics - PFC (mg/kg)


0

2

4

6

8

10

12

14

DETP DIBP

6 mg/kg 9 mg/kg

Antistatics - Phthalates


0

1

2

3

4

5

6

7

8

9

10

NPEO 8mg/kg

Antistatics - APEOS (mg/kg)



3 – PARAFFIN

WAX and OILS


3

1

2

Paraffins: tot 8

APEOS

PFC

Phthalates


0

1

2

3

0 - 1 mg/kg 1 - 10 mg/kg

APEOS

1

2

Paraffin - APEOS


0

1

2

3

0 - 1 mg/kg 1 - 10 mg/kg

DIBP

0

2

Paraffin - Phthalates


0

0,05

0,1

0,15

0,11 mg/kg

Paraffin - PFC

FTOH 4:2



4 – DETERGENT

AGENTS


1

Detergent: tot 1

PFC


0

0,5

1

1,5

2

2,5

3

3,5

3,08 mg/kg

Detergent - PFC

FTOH 4:2



5 – SIZING

AGENTS


4

Sizing Agents: tot 6

APEOS


0

1

2

3

4

5

0 - 10 mg/kg 10 - 20 mg/kg

0

4

Sizing Agents - APEOS



6 – GLUING

AGENTS


1

Gluing Agent: tot 1

clorofenoli


0

2

4

6

8

10

12

14

16

18

20

CMP 18,9mg/kg

Gluing Agent - Chlorophenols



7 – MOIST

REGAIN AGENTS


1 1

Moist Regain Agents: tot 1

PFC

Chlorophenols


0

0,5

1

1,5

2

2,5

3

3,5

4

4,5

5

OPP 4,65mg/kg

Moist Regain- Chlorophenols


0

1

2

3

4

5

6

7

8

9

10

4,84 mg/kg

Moist regain- PFC

FTOH 4:2


Comparison:

levels of contaminations for

compliance

to

Detox MRSL of Prato textile District


CONSOLIDATED

RESULTS


3

6,8

1,5

4,1 3,1

5,7

1,2

4,4

6,3

0,02 1,3

0,6 0,03 1,1 0,04 0,03 0,4 2,7

4,2

2,7 0,8 0,8 0,9 0,3 0,15 0,6

13,4

0,11

4,8

0

2

4

6

8

10

12

14

16

PFC - MRSL Detox Limit: 0,01mg/kg

Note: unit on y-axis: mg/kg


19

1227

4,6

0

200

400

600

800

1000

1200

1400

CMP OPP OPP

Chlorophenols - MRSL Detox Limit: 0,05mg/kg



8

18 18

16

18

11

8

11 11

7 2

9 9

0

2

4

6

8

10

12

14

16

18

20

APEOS - MRSL Detox Limit: 1mg/kg



6 9 11

36

5 7 7

99

5 6 0

20

40

60

80

100

120

DETP DIBP DEHP DINP DIBP DIBP DIBP DEHP DIBP DIBP

Phthalates - MRSL Detox Limit: 10mg/kg



CONSOLIDATED

RESULTS for

EACH CLASS


2,92

6,83

4,15

1,51

0

1

2

3

4

5

6

7

8

9

10

FTOH 4:2 FTOH 4:2 FTOH 4:2 FTOH 6:2

Antistatics - PFC (mg/kg)

6 9

0

2

4

6

8

10

12

14

DETP DIBP

Antistatics - Ftalati (mg/kg)

8

0

1

2

3

4

5

6

7

8

9

10

Antistatics - APEOS (mg/kg)

Parameter MRSL DETOX

Limit

APEOS 1 mg/kg

PFC 0.01mg/kg


Phthalates 10 mg/kg



3,08

0

0,5

1

1,5

2

2,5

3

3,5

Detergent - PFC (mg/kg)

FTOH 4:2

0

4

0

1

2

3

4

5

0 - 10 mg/kg 10 - 20 mg/kg

Sizing agents - APEOS

18,9

0

2

4

6

8

10

12

14

16

18

20

Gluing agent - Chlorophenols (mg/kg)

CMP


Limit

APEOS 1 mg/kg

PFC 0.01mg/kg


Phthalates 10 mg/kg



11

8

11 11

7

0

2

4

6

8

10

12

NPEO NPEO NPEO NPEO NPEO

Lubricants - APEOS

5,7

1,2

4,4

6,3

0,02

1,3 0,6

0,03 1,1

0,04 0,03 0,4

2,7

4,2

2,7

0,8 0,8 0,9 0,3 0,15 0,6

13,4

0

2

4

6

8

10

12

14

16

Lubricants - PFC


Limit

APEOS 1 mg/kg

PFC 0.01mg/kg


Phthalates 10 mg/kg



11

36

5 7 7

99

0

20

40

60

80

100

120

DEHP DINP DIBP DIBP DIBP DEHP

Lubricants - Phthalates

1227

0

200

400

600

800

1000

1200

1400

Lubricants - Chlorophenols (mg/kg)

OPP


Limit

APEOS 1 mg/kg

PFC 0.01mg/kg


Phthalates 10 mg/kg



0,11

0

0,02

0,04

0,06

0,08

0,1

0,12

FTOH 4:2

Paraffin - PFC

5 6

0

1

2

3

4

5

6

7

8

9

10

DIBP DIBP

Paraffin - Phthalates

2

9 9

0

1

2

3

4

5

6

7

8

9

10

NPEO NPEO NPEO

Paraffin - APEOS Parameter MRSL DETOX

Limit

APEOS 1 mg/kg

PFC 0.01mg/kg


Phthalates 10 mg/kg



4,84

0

1

2

3

4

5

6

7

8

9

10

Moist regain- PFC (mg/kg)

FTOH 4:2

4,65

0

0,5

1

1,5

2

2,5

3

3,5

4

4,5

5

Moist regain- Chlorphenols (mg/kg)

OPP


Limit

APEOS 1 mg/kg

PFC 0.01mg/kg


Phthalates 10 mg/kg



CONCLUSIONS

Only one sample (classified as non-slip agent) is free of

contamination

frequent contamination is due to PFC Telomer (FTOH 4:2 and FTOH

6:2 - 30.9%) followed by APEOS (19.1%) and Phthalates (14,4%);

Contamination by Chlorophenols regarded only 3 sample (4.4%).

Contamination due to PFC, Chlorophenols and APEOS is higher

than Detox MRSL limits, while Phthalate contamination is

generally lower than Detox MRSL limit (except in two cases)


ACTION PLAN

This is the first analytical screening on chemical auxiliaries for spinning

and weaving: successive steps will involve:

1- new screening on the same samples provided by same suppliers to

verify presence/abscence of contaminations in new batches;

2- potential screening (chemical analysis) on same kind of samples if

available from different suppliers;

3- possible extentions of chemical analysis to other priority groups of

Detox MRSL


Complete data of this study

is strictly reserved to CID

members.

Thank you


Giuseppe Bartolini [email protected]

Andrea Franchi [email protected]

Riccardo Dall’Anese [email protected]

Buzzi Lab

Laboratorio di Analisi, Prove e

Ricerche Industriali - ITIS T. Buzzi

59100 - PRATO - V.le della

Repubblica,9

Tel + 39 (0)574 - 58.98.87

fax + 39 (0) 574 - 58.98.90

www.buzzilab.it

mailto:[email protected]



http://www.buzzilab/



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