the characterisation of volatile organic compounds · pdf filethe characterisation of volatile...

THE CHARACTERISATION OF VOLATILE ORGANIC COMPOUNDS IN LEATHER - 1 -

THE CHARACTERISATION OF VOLATILE ORGANIC COMPOUNDS IN

LEATHER

Tomaselli M.*, Naviglio B.*, Naviglio D.**, Comite G.*, Calvanese G.*

* Experimental station for the Leather and Tanning products Industry- Naples-Italy

** Department of Nutritional Science – University of Naples “Federico II” - Italy

Introduction

The aim of this work is to characterise the volatile substances present in leather while also

investigating the provenance of such compounds, that is the processing phase during which they

may be fixed to the leather.

The emerging environmental restrictions, which also regard the finished product (leather) deriving

from so-called eco-friendly consumption, motivate a deeper investigation of the presence of

substances released by the finished leather. This aspect is particularly important as regards the

quality of the air in an internal environment, such as the passenger compartment of a vehicle or the

room of an apartment. It is in fact known that internal furnishings made from leather must only

release a limited quantity of volatile substances but, at the same time, produce that typical “leather

smell”. The volatile substances are therefore also responsible for important organoleptic properties

of the leather product such as the smell, characterising not just the quality of the article, intentional

and pleasant smells, but in some cases imperfections connected with bad smells. In short, for leather

material the ideal is to have a perceptible but not strong smell so as not to be overly disturbing.

But what is smell? A smell may be defined as any emanation perceived through the sense of smell.

An essential condition therefore for a smell to be perceived is that it can be “smelt”; in practice this

means that the odorous substances must be in an aeriform state so as to be inhaled and come into

contact with the olfactory receptors of the nasal mucous membrane.

For the assessment and determination of the intensity of a smell, for quality control or olfactory

disturbance, the olfactometer is generally used. This consists of the sensorial analysis of an

osmogen “panel test” mixture, which is presented to a jury of selected persons (panel), and the


processing of the results obtained. This olfactory panel test is today regulated by a European

technical regulation, the EN 13725 for the standardisation of olfactometric analysis.

Unlike chemical analysis, olfactometric analysis does not provide the identification of a substance

or group of substances, but the units of odour of the gaseous mixture: this way the olfactory impact

can be calculated, although remaining a subjective sensation. By knowing the number of dilutions

required for the smell to be perceived by the panel, the number of units of odour per cubic metre of

the examined sample is calculated. This measurement technique permits an evaluation of the

possible synergic and masking effects too so that the concentration of smell (OU/mc) of a mixture

of compounds is not the algebraical sum of the single substances but the result of more complex

phenomena and relations. The instrument which makes it possible to carry out the right dilutions is

the olfactometer, by means of which the group of panellists judges the perceptibility of the sample.

This investigation method, while useful for the purposes of assessing the olfactory-disturbance

impact of a gaseous mixture and for commercial purposes given that it provides hedonistic

information about a product, does not however permit the identification of the various compounds

causing the smell within the gaseous mixture constituting the smell, nor their quantitative

evaluation.

This study attempts to evaluate whether it is possible to conduct a broad investigation for the

qualitative-quantitative definition of the odour of leather or of other “tannery” smells using

analytic-instrumental methods so as to define the characteristics in an objective manner but also to

identify the possible causes of olfactory disturbance in some leather articles. Against such

advantages however it is presumable that these methods will have the disadvantage of a reduced

sensitivity compared to the human “instrument” in detecting some compounds to which the sense of

smell is particularly sensitive (very low threshold for the perception of the smell), especially in the

case of mixtures of substances which together produce smells that are particularly difficult to

reproduce in the laboratory or to associate with one or a group of chemical substances.

The technical scientific approach was that of extracting the volatile substances from the leather

using the “purge and trap” technique which consists of stripping the substances from the sample at a

controlled temperature using a flow of inert gas (helium) which strips off and transports the volatile

substances to an absorbent trap where they are concentrated to then be thermally desorbed and

channelled to a gas-chromatography system connected to a mass detector for the resolution of the

volatile mixture and the identification of each single volatile component.


This technique enhances the result of the analysis of the volatile substances present in traces unlike

another commonly used sampling technique, the “static head space”, which only enables the

detection of the most plentiful substances and present in a concentration determined by the

equilibrium with the sample and the environment with which it is in contact.

The work done, moreover, permitted the creation of a sort of identificatory “spectrum” of the skins

represented by the gas-chromatogram showing the volatile substances eluted, a sort of leather

identity card, depending on the article (e.g. upper, clothing, furnishings) and in perspective, before

a long series of characterisations, on the tannery district of provenance.

Experimental part

11 skins at various stages of processing and for different types of article, as described below, were

investigated:

� no.4 sheepskins processed for clothing and specifically: one at the pickled state of African

provenance (called “Africa”) (sample no.1), one at the wet blue state (sample no.2), one at

the crust state (sample no.3) and one at the finished state (sample no.4)

� no.3 sheepskins processed for footwear and specifically: one at the wet blue state of

European origin (called “Europe”) (sample no.5), one at the crust stage (sample no.6) and

one at the finished state (sample no.7)

� no.1 bovine skin for footwear at the crust state (sample no.8)

� no.1 buffalo skin for furnishings at the finished state (sample no.9)

� no.1 split leather of the “by cast” article type (sample no.10)

� no.1 goatskin for footwear at the finished stage (sample no.11), with an unpleasant smell

so as to be able to compare the analytical results obtained both for skins of the same origin but at

different stages of processing, from the pickel stage to the finished product through the semi-

processed skins, and for skins at the same stage but processed so as to obtain different articles

(clothing/footwear, sheep/bovine). Such a comparison proves interesting if made relative to the

skins at different stages of the same process (samples from no.1 to no.4 and from no.5 to no.7).


Lastly the chromatogram relative to the finished leather with a clear defect due to the presence of

pungent, unpleasant smell (sample no. 11), was compared to all the rest to validate this analytic-

methodological approach as a technique for identifying the volatile substances responsible for smell.

About 1 gram of sample, of each type of skin mentioned above, was cut into pieces of

approximately 0.3÷04 cm2 and put into a glass container (vassel) closed hermetically inside the

“purge and trap”, system as shown in Fig. 1 in the photograph of the system used. The sample was

then heated with an infrared lamp to a temperature of 50°C, so as to speed up the removal of the

volatile substances (kinetic effect). In the “purge and trap” phase the substances are stripped using a

flow of helium at approximately 40 linear metres/min for a period of 20 minutes and then

forwarded to the absorbent trap type T10 (TENAX / Silica gel / carbon molecular sieve) kept at

room temperature (see the diagram of Fig. 2). The system then automatically activates the thermic

desorption phase (see the “desorb” diagram in Fig. 3) of the substances in the trap at a temperature

of 190 °C, to then direct them to the gas-chromatograph, fitted with a column input system, the high

temperature split/splitless, by means of a heated transfer line, thus avoiding the condensation of

some less volatile component. At the exit of the gas-chromatograph the eluted components are

directed to a quadruple type mass detector which, thanks to a dedicated software and a sufficient

library of mass spectrums of chemical substances, enables their identification and consequently the

characterisation of the mixture of volatile substances emitted by the leather.

Below are the sampling and analysis conditions adopted:

Purge and trap system make O I Analytical mod. ECLIPSE 4 F3390 :

� Purge:

transport gas = helium

flow = 40 linear metres/min

temperature = 50 °C;

time = 20 min

trap temperature = 20 °C

� Desorb:

temperature = 190 °C;

time = 2 min

Gas-chromatochromic system GC/MS make HP mod. 6890 Series and 5973 Mass Selective

detector:


� Injector split/splitless:

transport gas = helium

flow = 1 linear metre/min

injector temperature = 280 °C;

split ratio= 1/1

� Temperature Programme: 40 °C (5 min.) � (5 °C/min.) 200 ° C

200 ° C � (10 °C/min.) 250 °C (5 min.)

� Column:

Superchrom DB1 L=60m; ID=0,25mm; F=1µm

� Detector:

Quadrupole MS detector type HP mod.

Results and discussions

From the analysis of the gas-chromatography results, specific families of volatile organic

compounds can be identified and they or the single compounds can be associated with the leather

article produced, the animal origin of the leather and lastly the state of the leather (pickeled, wet-

blue, crust, finished).

The compounds identified were then grouped into the following families:

� Paraffinic and oleofin hydrocarbons

� Non aromatic cyclic hydrocarbons

� Mono aromatic hydrocarbons

� Polycyclic aromatic hydrocarbons

� Aldehydes

� Ketones

� Alcohols

� Esters

Table 1 shows a summary of the analytical results for each sample analysed, giving the number and

total percentage area of the compounds belonging to the families described above.


From the analysis of these results it may be deduced that the contribution to the emission of volatile

substances differs depending on the state of the leather. The chromatograms relative to the analysis

of the samples indicated in Figures from 4 to 14 show the identification made by the mass detector

of the volatile substances, where the figure shown in brackets alongside the name gives the

percentage of recognition.

For skins in the pickeled (see chromatogram of Fig.4) and wet-blue states (see chromatograms of

Fig.5 and Fig.8) one may deduce a preponderant presence of mono aromatic hydrocarbons such as

the alkyl-benzenes, in particular the polymethylbenzenes such as Xylene, Prenitol (Benzene,

1,2,3,4-tetramethyl-), Isodurene (Benzene, 1,2,3,5-tetramethyl-), Enimellitene (Benzene, 1,2,3-

trimethyl-) and Durene (Benzene, 1,2,4,5-tetramethyl-) and derived toluene alkyls. These

compounds may derive from the use of solvents made from oil distillates in the degreasing stages or

as stabilisers in chemical products made from surfactants and/or emulsified preservatives. This

consideration is supported by the contemporary presence, even though in relatively small quantities,

of paraffinic hydrocarbons and aromatic polycyclics such as azulene, naphthalene, indano and

tetralin (Naphthalene, 1,2,3,4-tetrahydro).

The analysis of skins at the crust state (see chromatograms of Figures 6, 9 and 11) showed a high

percentage concentration of aldehydes, ketones, esters and alcohols. As regards the aldehydic

compounds the main aldehydes identified were as follows: benzaldehyde, esanale, eptanale and

nonanale.

These aldehydes are normally contained in essential oils and/or natural resins. The presence of

aldehydes, especially those of nonanale, esanale, eptanale and benzaldehyde, is due to the use of

essential oils in the fatliquoring stage, but probably also to the so called retanning products, as

residues of synthesis (untransformed reagents). This consideration is supported moreover by the

fact that the relative integration areas of the peaks corresponding to the aldehydes decreases in

percentage terms when moving from the crust stage to the finished stage in the same process (see

chromatograms of Figures 6 with 7 and of Figures 9 with 10).

The presence of ketones is linked mainly to the use during retanning of chemical products

containing ketonic based solvents, very widely used given their low cost, high solvent effect and

anti-oxidant properties. The percentage area relative to the ketones increases considerably for the

finished leather, having a strong solvent effect on many of the polymers used in the finishing phase.

Specifically those most commonly found were isoforone (2-Cyclohexen-1-one, 3,5,5-trimethyl) and

an alkyl derivative of butirrone (4-Heptanone, 2,6-dimethyl-), and to a lesser extent alkyl


derivatives of eptanone, esanone and pentanone, of which the 2,2,4,4-tetrametil 3-Pentanone proved

preponderant.

The esters were found only in the skins in the crust and finished states. In fact they have a

considerable solvent effect on resins. Specifically those most utilised are butyl and exyl acetate

(Acetic acid, 2-ethylhexyl ester), as shown in the gas chromatograph analysis.

The alcohols found derive from the use of watery emulsions of organic compounds, in their role as

stabilisers of such emulsions and non-ionic surfactants, but also as solvents of the spray solutions

used in the finishing phase. Specifically, from the survey conducted 2-etil-1-esanolo and 2,6-

dimetil-4-eptanolo were found most frequently, often present as solvents, and 2,6-dimetil-2-butossi-

4-eptanolo often indicated as the stabiliser of watery emulsions or as a surfactant component.

The comparison of the chromatograms relative to skins in the same state but for different destined

uses (articles) proves interesting. From table 1 it can be seen how the gas-chromatograph analysis

of the crust relative to sample 3 (sheepskin – clothing) gave similar results to the crust in sample 6,

also of sheepskin origin but with a different destination (footwear rather than clothing), but with

very similar percentage values for the aldehyde, ketone and alkylbenzene areas in the first (% area

aldehydes=26.08 ketones=18.72 and alkylbenzenes=17.86), while in the second the percentage

composition of ketones and esters was considerably higher than the others (% area ketones=25.19

and esters=21.7 against the alkylbenzenes=8.83). The analysis of sample no.8 (crust/bovine/

footwear), however, gave totally different chromatographic results from the sheepskin crusts, with a

much higher concentration of aldehydes than of the other families of compounds (no.8 total % area

aldehydes of 63.33), almost totally characterising, to the exclusion of the alkylbenzenes (% area of

14.68), the emission of SOV from the leather.

As regards the finished leather for furnishings (sample no.9), unlike the others, a greater percentage

area was observed for the alcohols and ketones (no.5 alcohols total area %=34.26 and no. 4 ketones

of total area %=15.88) and specifically, respectively 2-butossi- ethanol and the ketones 2-butanone

and cicloesanone.

The split leather sample with “by cast finish” (sample no. 10), rather, showed a preponderant

presence of alkyl benzenes (19 substances area % equal to 27.51) compared to the other families of

compounds (area % no.3 aldehydes=0.92 no.3 ketones=1.64 no.4 alcohols=2.04 and no.3

esters=4.54).


Lastly, from the analysis of the leather with the unpleasant smell (sample no. 11) the presence was

observed of organic substances not found in the other leathers analysed, such as D-limonene, also

known as p-menta-1,8-diene or dipentene or citrene, a substance with a characteristic odours,

perceivable in low concentrations and unsaturated hydrocarbons such as 3-ottene. In this regard it

should be noted that during the finishing phase of this leather a caseinic binding agent was used

containing dipentene.

Conclusions

In this study it has been seen how the Purge and Trap investigation technique used with gas

chromatography and the mass detector is useful in identifying the volatile organic substances

emitted by leather and skins.

It proved possible in fact to characterise the gaseous emission of various leather articles as well as

samples of skins not yet tanned, investigating the possible presence of substances important for the

quality of the product (organoleptic properties) and the quality of the air of the confined space in

which such products are used.

This identification, as we have seen, if performed for the same skins at various stages of processing

enables the identification of the processing stage during which specific volatile substances are fixed

to the leather and which, if not eliminated thoroughly during the subsequent processing phases, will

be found on the finished article.

Lastly we have seen how this technique may prove useful in identifying the cause of some leather

defects such as the emission of bad smells or, in other cases, in identifying the volatile substances

responsible for so-called fogging.


Fig. 1: Photograph of the P&T system used connected to the GC/MS


Fig. 2: flow diagram of the “purge” phase


Fig. 3: flow diagram of the “desorb” phase


Table 1: no. of compounds and total gas-chromatogram percentage areas grouped by family of organic substances

PAR

AFF

INIC

A

ND

OL

EO

FIN

IC

HY

DR

OC

AR

BO

NS

CY

CL

IC

HY

DR

OC

AR

BO

NS

MO

NO

A

RO

MA

TIC

H

YD

RO

CA

RB

ON

S PO

LY

CY

CL

IC

AR

OM

AT

IC

HY

DR

OC

AR

BO

NS

AL

DE

HY

DE

S

KE

TO

NE

S

AL

CO

HO

LS

EST

ER

S

no. o

f co

mpo

unds

tota

l are

a %

no. o

f co

mpo

unds

tota

l are

a %

no. o

f co

mpo

unds

tota

l are

a %

no. o

f co

mpo

unds

tota

l are

a %

no. o

f co

mpo

unds

tota

l are

a %

no. o

f co

mpo

unds

tota

l are

a %

no. o

f co

mpo

unds

tota

l are

a %

no. o

f co

mpo

unds

tota

l are

a %

Sam

p 1

AFRICA SHEEPSKIN CLOTHING PICKELED

1 0.04 1 0.21 23 75.26 4 7.63 2 0.64 - - - - - -

Sam

p 2 AFRICA SHEEPSKIN

CLOTHING 1 0.78 - - 21 72.51 4 9.79 - - 1 0.4 2 0.25 - -

Sam

p 3 AFRICA SHEEPSKIN

CLOTHING CRUST 5 2 - � 12 17.86 1 0.59 6 26.08 5 18.72 3 8.45 4 10.82

Sam

p 4

AFRICA SHEEPSKIN CLOTHING FINISHED

6 4.57 - - 14 29.19 1 1.05 6 12.87 6 22.49 1 2.70 3 18.48

Sam

p 5

SHEEPSKIN EUROPEAN FOOTWEAR WET-BLUE

9 19.97 3 1.83 18 32.1 4 7.75 - - 2 0.68 1 0.27 - -

Sam

p 6

SHEEPSKIN EUROPEAN

FOOTWEAR CRUST3 3.58 4 2.01 9 8.83 1 0.46 4 11.44 6 25.19 4 16.96 4 21.7

Sam

p7

SHEEPSKIN EUROPEAN FOOTWEAR FINISHED

5 5.79 2 16.17 12 9.67 1 0.37 4 6.79 5 25.87 3 17.76 1 1.9

Sam

p 8 BOVINE ITALY

FOOTWEAR CRUST 3 1.83 1 2.47 12 14.68 1 1.17 8 63.33 1 0.16 1 1.19 2 3.69

Sam

p 9

BUFFALO ITALY FURNISHING

FINISHED5 3.88 1 3.0 5 1.93 1 0.1 6 4.49 4 15.88 5 34.26 1 3.52

Sam

pl0

SPLIT LEATHER BY CAST ARTICLE

1 0.27 - - 19 27.51 7 4.82 3 0.92 3 1.64 4 2.04 3 4.54

Sam

pl1

GOATSKIN FINISHED

FOOTWEAR "BAD SMELLING "

12 9.37 3 2.28 10 21.42 1 1.62 8 36.7 3 3.67 1 0.89 2 5.79


.1. Fig.4: gas-chromatogram sample no.1

15 20 25 300,0

5,0x10 6

1,0x10 7

1,5x10 7

2,0x10 7

2,5x10 7

3,0x10 7

12

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

2728

29 30

31

1 Hexanal (72%)2 p-Xylene (91%)3 Heptanal (93%)4 Benzene, 1,3-dimethyl- (97%)5 Benzene, (1-methylethyl)- (80%)6 Benzene, propyl- (91%)7 Benzene, 1-ethyl-3-methyl- (94%)8 Benzene, 1,3,5-trimethyl- (94%)9 Benzene, 1-ethyl-3-methyl- (91%)10 Furan, 2-pentyl- (80%)11 Benzene, 1,2,3-trimethyl- (94%)12 Decane (90%)13 1,2,4-Trimethylbenzene (91%)14 Indane (76%)15 Benzene, 1-methyl-3-propyl- (90%)16 Benzene, 1,2,4,5-tetramethyl- (91%)17 Benzene, 1,2-diethyl- (94%)18 Benzene, (1-methylpropyl)- (94%)19 Benzene, 4-ethyl-1,2-dimethyl- (91%)20 Benzene, 1,2,4,5-tetramethyl- (93%)21 Benzene, 2-ethyl-1,3-dimethyl- (95%)22 Benzene, 1-methyl-4-(2-methylpropy (53%)23 Benzene, 1-ethyl-2,3-dimethyl- (97%)24 Benzene, 1,2,4,5-tetramethyl- (94%)25 Benzene, 1,2,4,5-tetramethyl- (97%)26 Benzene, 1,3-diethyl-5-methyl- (91%)27 1H-Indene, 2,3-dihydro-4-methyl- (91%)28 Benzene, 1,2,3,4-tetramethyl- (97%)29 Naphthalene, 1,2,3,4-tetrahydro- (90%)30 Benzene, 1,4-dimethyl-2-(2-methylp (52%)31 Azulene (91%)

Sample no.1SHEEPSKIN AFRICAAFRICAPICKELED - CLOTHING

Abundancecounts

Time, min


Fig.5: gas-chromatogram sample no.2

15 20 25 300,0

2,0x10 6

4,0x10 6

6,0x10 6

8,0x10 6

1,0x10 7

1,2x10 7

1,4x10 7

1,6x10 7

1,8x10 7

1 2

34 5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

2122

23

24

25 26

27

2829 3031

Sample no.2SHEEPSKIN AFRICA

WET BLUE - CLOTHING

1 Cyclohexanone (91%)2 1,2-Ethanediamine, N-(phenylmethyl (45%)3 Benzene, 1-ethyl-4-methyl- (91%)4 Benzene, 1,3,5-trimethyl- (91%)5 Benzene, 1-ethyl-4-methyl- (91%)6 Piperidine (81%)7 Benzene, 1,3,5-trimethyl- (94%)8 Benzene, 1,2,3-trimethyl- (96%)9 Indane (87%)10 Benzene, 1-methyl-3-propyl- (93%)11 Benzene, 1,2,4,5-tetramethyl- (93%)12 Benzene, 1,2-diethyl- (94%)13 Benzene, (1-methylpropyl)- (93%)14 Benzene, 1-ethyl-2,4-dimethyl- (95%)15 Benzene, 1-ethyl-2,3-dimethyl- (91%)16 Benzene, 2-ethyl-1,3-dimethyl- (95%)17 Benzene, 1-methyl-4-(2-methylpropy (72%)18 Benzene, 4-ethyl-1,2-dimethyl- (96%)19 Benzene, 1,2,4,5-tetramethyl- (96%)20 Benzene, 1,2,4,5-tetramethyl- (96%)21 Nonane, 3,7-dimethyl- (53%)22 Hydroxylamine, O-decyl- (64%)23 1H-Indene, 2,3-dihydro-4-methyl- (91%)24 Benzene, 1,2,3,4-tetramethyl- (97%)25 Naphthalene, 1,2,3,4-tetrahydro- (46%)26 Benzene, 2-ethyl-1,3-dimethyl- (64%)27 Naphthalene (95%)28 Benzene, pentamethyl- (91%)29 Benzene, pentamethyl- (91%)30 1-Octanol, dimethyl- (35%)31 2-Nonen-1-ol, (E)- (50%)

Abundance,counts

Time, min



15 20 25 30

0,0

2,0x10 6

1

2

3 4

5

6

7

8

9

1011

12

13

14

15

16

17

18

19

20

21 22

23

242526

27

28

29

30

31

3233

34

35 36

37

38

20 Cyclohexanone, 3,3,5-trimethyl- (80%)21 Benzene, cyclopropyl- (64%)22 Benzene, 1-methyl-3-propyl- (90%)23 Benzene, 1-ethyl-2,3-dimethyl- (87%)24 2-Butoxyethyl acetate (72%)25 Benzene, 1-methyl-4-propyl- (50%)26 Benzene, 2-ethyl-1,4-dimethyl- (90%)27 Nonanal (87%)28 Tetradecane (95%)29 2-Cyclohexen-1-one, 3,5,5-trimethy (94%)30 Benzene, 1,2,4,5-tetramethyl- (91%)31 Acetic acid, 2-ethylhexyl ester (90%)32 2-Nonenal, (E)- (89%)33 Bicyclo[2,2,1]heptan-2-one, 1,7,7- (96%)34 3,4-Dihydroxymandelic acid, ethyl (59%)35 Ethanol, 2-methoxy- (16%)36 Dodecane, 2-methyl-6-propyl- (46%)37 Azulene (81%)38 Dodecane (94%)

Sample no.3SHEEPSKIN AFRICA

CRUST- CLOTHING

1 Toluene (90%)2 Hexanal (87%)3 Acetic acid, butyl ester (64%)4 Tetrachloroethylene (95%)5 Ethylbenzene (87%)6 Benzene, 1,3-dimethyl- (97%)7 Heptanal (91%)8 Ethanol, 2-butoxy- (64%)9 Nonane (52%)10 Benzaldehyde (91%)11 Benzene, propyl- (64%)12 3-Pentanone, 2,2,4,4-tetramethyl- (89%)13 Benzene, 1-ethyl-4-methyl- (80%)14 2-Heptanone, 4,6-dimethyl- (78%)15 Octanal (55%)16 Cyclotetrasiloxane, octamethyl- (53%)17 Decane (93%)18 1-Hexanol, 2-ethyl- (83%)19 Benzene, 1-ethyl-3-methyl- (91%)

Abundance,counts

Time, min



15 20 25 300

1x10 6

2x10 6

3x10 6

4x10 6

5x10 6

12

34

5

6 78 9

10

11

12

13

14

15

16 17

18

1920

21

2223

24

25

26

27

2829

30

31

32

33 34

35

36

37 38

20 Benzene, 1-methyl-3-propyl- (90%)21 Benzene, 2-ethyl-1,4-dimethyl- (90%)22 2-Butoxyethyl acetate (50%)23 Benzene, (1-methylpropyl)- (53%)24 Benzene, 1-ethyl-2,3-dimethyl- (91%)25 Nonanal (80%)26 Tetradecane (86%)27 2-Cyclohexen-1-one, 3,5,5-trimethy (91%)28 Benzene, 1,2,4,5-tetramethyl- (91%)29 Benzene, 1-methyl-4-(1-methylethyl (91%)30 Acetic acid, 2-ethylhexyl ester (90%)31 Bicyclo[2,2,1]heptan-2-one, 1,7,7- (97%)32 Phenethylamine, N-methyl-,beta,,3, (50%)33 Tetracontane, 3,5,24-trimethyl- (43%)34 Decane, 3,8-dimethyl- (46%)35 1H-Indene, 1-methylene- (81%)36 Dodecane (95%)37 Undecane, 2,6-dimethyl- (96%)38 4-Octanone (52%)

Sample no.4SHEEPSKIN-AFRICA

FINISHED - CLOTHING1 Toluene (90%)2 Hexanal (72%)3 Acetic acid, butyl ester (64%)4 Tetrachloroethylene (94%)5 Benzene, 1,3-dimethyl- (94%)6 Heptanal (90%)7 Benzene, 1,3-dimethyl- (90%)8 Benzene, (1-methylethyl)- (50%)9 Benzaldehyde (93%)10 Benzeneacetaldehyde (50%)11 3-Pentanone, 2,2,4,4-tetramethyl- (90%)12 2-Heptanone, 4,6-dimethyl- (86%)13 Octanal (95%)14 1,2,4-Trimethylbenzene (90%)15 Decane (90%)16 1-Hexanol, 2-ethyl- (90%)17 Benzene, 1,2,3-trimethyl- (94%)18 Cyclohexanone, 3,3,5-trimethyl- (90%)19 Benzene, 1,1'-(1-ethenyl-1,3-propa (78%)

Abundance,counts

Time, min



15 20 25 300,0

2,0x10 6

4,0x10 6

6,0x10 6

1 2 34 5 6

7

8

9

10

11

1213

14

15

16

17

18

19

2021

22

23

24

25

26

2728

29

30

31

32

33

34

35

36

37

38

39

40

41

Sample no.5SHEEPSKIN EUROPEAN

WET BLUE - FOOTWEAR1 Ethanol, 2-butoxy- (59%)2 Nonane (90%)3 1,3-Cyclohexanedione, 5,5-dimethyl (46%)4 4-Heptanone, 2,6-dimethyl- (60%)5 Benzene, 1,3,5-trimethyl- (50%)6 Benzene, 1-ethyl-3-methyl- (64%)7 Cyclohexene, 1-ethyl- (35%)8 Benzene, 1,3,5-trimethyl- (90%)9 Decane (96%)10 Benzene, (1-methylpropyl)- (59%)11 Benzene, 1,3,5-trimethyl- (58%)12 Dodecane, 2,6,11-trimethyl- (46%)13 Tetradecane (46%)14 Cyclodecane (94%)15 Benzene, 1-methyl-3-propyl- (83%)16 Benzene, 1-ethyl-3,5-dimethyl- (87%)17 Benzene, 1,2-diethyl- (45%)18 Benzene, 1-methyl-3-propyl- (68%)19 Benzene, 2-ethyl-1,4-dimethyl- (91%)20 Benzene, methyl(1-methylethyl)- (91%)21 Benzene, 2-ethyl-1,3-dimethyl- (90%)22 Indan, 1-methyl- (72%)23 Cyclopentane, 1-ethyl-2-methyl-, c (55%)24 Undecane (94%)25 Benzene, 1-ethyl-2,4-dimethyl- (90%)26 Benzene, 1-methyl-4-(1-methylethyl (91%)27 Dodecane, 2,6,10-trimethyl- (53%)28 Benzene, 1-methyl-2-(1-methylethyl (64%)29 Benzene, (2-methyl-1-butenyl)- (38%)30 Benzene, 2-ethyl-1,4-dimethyl- (50%)31 Benzene, 1,2,3,4-tetramethyl- (90%)32 Benzene, 1-ethyl-2,3-dimethyl- (47%)33 Benzene, (1,1-dimethylpropyl)- (59%)34 Decane, 1,1'-oxybis- (90%)35 Naphthalene (94%)36 1H-Indene, 2,3-dihydro-1,2-dimethy (76%)37 Dodecane (96%)38 Benzene, 1,3-dimethyl-5-(1-methyle (76%)39 Undecane, 2,6-dimethyl- (96%)40 Benzene, pentamethyl- (81%)41 1H-Indene, 2,3-dihydro-1,3-dimethy (70%)

Abundance,counts

Time, min



15 20 25 300,0

2,0x10 6

4,0x10 6

6,0x10 6

12

3

4 5

67

8

9

10

11

12

13

14

15

16

17

18 1920 212223

24

25

26

27

28

2930

31

32

33

34

35


CRUST - FOOTWEAR1 2-Propanol, 1-methoxy- (90%)2 Toluene (90%)3 Hexanal (89%)4 Acetic acid, butyl ester (72%)5 Ethylbenzene (58%)6 Benzene, 1,3-dimethyl- (94%)7 Heptanal (94%)8 Ethanol, 2-butoxy- (64%)9 Benzaldehyde (94%)10 Benzene, propyl- (64%)11 3-Pentanone, 2,2,4,4-tetramethyl- (94%)12 Benzene, 1,3,5-trimethyl- (64%)13 2-Heptanone, 4,6-dimethyl- (90%)14 4-Heptanol, 2,6-dimethyl- (86%)15 Benzene, 1,2,4-trimethyl- (87%)16 Decane (91%)17 1-Hexanol, 2-ethyl- (90%)18 Benzene, 1-ethyl-2-methyl- (90%)19 Cyclohexanone, 3,3,5-trimethyl- (94%)20 Cyclohexene, 1-methyl-4-(1-methyle (96%)21 Cyclohexane, 1-methyl-2-propyl- (64%)22 Cyclobutanone, 3,3-dimethyl- (64%)23 Benzene, 1-ethyl-3,5-dimethyl- (80%)24 2-Butoxyethyl acetate (72%)25 Benzene, 1-ethyl-3,5-dimethyl- (72%)26 Nonanal (64%)27 Undecane (93%)28 2-Cyclohexen-1-one, 3,5,5-trimethy (91%)29 Cyclopentane, ethyl- (43%)30 Cyclohexane, 1,2-dimethyl-, trans- (72%)31 Acetic acid, 2-ethylhexyl ester (90%)32 Camphor (97%)33 3,4-Dihydroxymandelic acid, ethyl (59%)34 Naphthalene (64%)35 Dodecane (95%)

Abundance,counts

Time, min



15 20 25 300,0

2,0x106

4,0x106

6,0x106

8,0x106

1 2 3 4

5

6

7

8

9

10

11

12

13

14

15

16

17181920

212223

24 25

26

27

28

29

30

3132

33 34

35


FINISHED - FOOTWEAR1 Toluene (90%)2 Hexanal (53%)3 Acetic acid, butyl ester (78%)4 Ethylbenzene (91%)5 Benzene, 1,3-dimethyl- (91%)6 Heptanal (94%)7 Ethanol, 2-butoxy- (78%)8 Benzaldehyde (94%)9 Benzene, propyl- (46%)10 4-Heptanone, 2,6-dimethyl- (93%)11 Benzene, 1,3,5-trimethyl- (86%)12 2-Heptanone, 4,6-dimethyl- (90%)13 4-Heptanol, 2,6-dimethyl- (74%)14 Cyclotetrasiloxane, octamethyl- (56%)15 Decane (95%)16 1-Hexanol, 2-ethyl- (78%)17 Benzene, 1-ethyl-3-methyl- (86%)18 Cyclohexanone, 3,3,5-trimethyl- (95%)19 Benzene, 2-propenyl- (64%)20 Cycloheptane (60%)21 1-Hexene, 5-methyl- (62%)22 Benzene, 1-ethyl-2,3-dimethyl- (80%)23 Pentane, 2,4-dimethyl- (50%)24 Benzene, 1-methyl-2-propyl- (50%)25 Benzene, 2-ethyl-1,4-dimethyl- (90%)26 Nonanal (72%)27 Undecane (95%)28 2-Cyclohexen-1-one, 3,5,5-trimethy (94%)29 Benzene, 1,2,3,5-tetramethyl- (58%)30 Cyclopentane, 1,2,3-trimethyl-, (1 (70%)31 Camphor (97%)32 Cyclopentasiloxane, decamethyl- (90%)33 Benzene, 1-methyl-4-(2-methylpropy (59%)34 Azulene (81%)35 Dodecane (97%)

Abundance,counts

Time, min



10 15 20 25 30 35

0

500000

1000000

1500000

2000000

1 2

3

4 5

6

7

8 910

11

1213

14

15

161718

1920

21 22

23

24

25 26

27

28

29

3031

Sample no.8BOVINE

CRUST - FOOTWEAR

16 Decane (83%)17 1-Hexanol, 2-ethyl- (59%)18 Benzene, 1,3,5-trimethyl- (87%)19 2-Octenal, (E)- (87%)20 Benzene, 1-ethyl-2,3-dimethyl- (86%)21 2-Butoxyethyl acetate (64%)22 Benzene, 1-ethyl-3,5-dimethyl- (86%)23 Nonanal (91%)24 Heptane, 2,4-dimethyl- (72%)25 2-Cyclohexen-1-one, 3,5,5-trimethy (74%)26 Benzene, 1,2,3,4-tetramethyl- (80%)27 Cyclopentane, 1,2,3-trimethyl-, (1 (72%)28 2-Nonenal, (E)- (97%)29 Silane, [[4-[1,2-bis[ (trimethylsil (43%) )))))30 Azulene (76%)31 Dodecane (74%)

1 Pentanal (64%)2 Toluene (86%)3 Hexanal (93%)4 Acetic acid, butyl ester (78%)5 Ethylbenzene (56%)6 Benzene, 1,3-dimethyl- (95%)7 Heptanal (94%)8 p-Xylene (87%)9 Benzaldehyde (91%)10 Benzene, propyl- (64%)11 Benzene, 1-ethyl-2-methyl- (91%)12 Benzene, 1-ethyl-4-methyl- (86%)13 Benzene, 1,2,3-trimethyl- (80%)14 Octanal (87%)15 Benzene, 1,2,3-trimethyl- (83%)

Abundance,counts

Time, min



5 10 15 20 25 30 35 400,0

2,0x10 6

4,0x10 6

6,0x10 6

8,0x10 6

1,0x10 7

1

23 4

5

6

7

8910

11

12

13

14

15

1617

18

19

20

21 22 23

24

25

26

27

28

29 3031 32

Sample no.9BUFFALO

FINISHED - FURNISHINGS

1 Carbon dioxide (4%)2 Acetone (59%)3 Isopropyl Alcohol (78%)4 Methylene Chloride (93%)5 Silanol, trimethyl- (64%)6 Hexane (91%)7 1-Propanol, 2-methyl- (87%)8 1-Butanol (87%)9 1-Penten-3-ol (47%)10 Pentanal (43%)11 Toluene (91%)12 2-Heptene (55%)13 Acetic acid, butyl ester (90%)14 2-Hexenal, (E)- (93%)15 2-Butanone (35%)16 Ethylbenzene (91%)17 Benzene, 1,3-dimethyl- (91%)18 Cyclohexanone (95%)19 Heptanal (93%)20 Ethanol, 2-butoxy- (95%)21 Benzaldehyde (94%)22 Benzene, 1-ethyl-2-methyl- (91%)23 Benzene, 1-ethyl-2-methyl- (83%)24 2-Pentanone, 3-methyl- (9%)25 1-Hexanol, 2-ethyl- (90%)26 Heptane, 3-methyl- (43%)27 Nonanal (94%)28 Cyclopentane, 1,2,3-trimethyl-, (1 (72%)29 Cyclopentasiloxane, decamethyl- (74%)30 Naphthalene (74%)31 Tridecane (96%)32 Tetradecane (97%)

Abundance,counts

Time, min



10 15 20 25 30 35 40

0,0

2,0x10 5

4,0x10 5

6,0x10 5

8,0x10 5

1,0x10 6

12

3

4

5

6

7

8

9

1011

12

13

14

15

161718

19

20

21

22

23

24

25

26

27

28

29

30

31

32

3334

35

36

3738 39 40 41

42

43

44

45

46

47

Cam pione n.10CROSTA

ARTICOLO BY CAST

25 B enzene, 1-methyl-4-propyl- (90% )26 B enzene, 4-ethyl-1,2-dimethyl- (94% )27 B enzene, 1-ethyl-2,3-dimethyl- (94% )28 B enzene, 2-ethyl-1,3-dimethyl- (91% )29 B enzene, 1-ethyl-2,4-dimethyl- (95% )30 A cetic acid, 2-ethylhexyl ester (90% )31 1H -Indene, 2 ,3-dihydro-4-methyl- (91% )32 1H -Indene, 2 ,3-dihydro-5-methyl- (60% )33 B enzene, 1-methyl-2-(1-methylethyl (59% )34 B enzene, (1,1-dimethylpropyl)- (78% )35 A zulene (94% )36 D odecane (81% )37 B enzene, 1-ethyl-4-(1-methylethyl) (64% )38 1,2-B enzisothiazole-3-carboxylic a (78% )39 1H -Indene, 2 ,3-dihydro-4 ,7-dimethy (90% )40 1H -Indene, 2 ,3-dihydro-1 ,2-dimethy (87% )41 1H -Indene, 2 ,3-dihydro-1 ,6-dimethy (72% )42 Tridecane (93% )43 N aphthalene, 2-methyl- (91% )44 A cetic acid, [bis[(trimethylsilyl) (50% )45 B iphenyl (74% )46 Tetradecane (96% )47 N aphthalene, 1-ethyl- (45% )

1 H exane (90% )2 1-P ropanol, 2-methyl- (91% )3 1-B utanol (78% )4 Toluene (90% )5 H exanal (59% )6 A cetic acid, butyl ester (74% )7 2-B utanone (7% )8 E thylbenzene (91% )9 B enzene, 1,3-dimethyl- (90% )10 C yclohexanone (94% )11 H eptanal (72% )12 p-Xylene (91% )13 B enzaldehyde (94% )14 B enzene, propyl- (64% )15 B enzene, 1-ethyl-2-methyl- (91% )16 B enzene, 1,2 ,4-trimethyl- (87% )17 B enzene, 1-ethyl-4-methyl- (86% )18 Octanal (83% )19 B enzene, 1,3 ,5-trimethyl- (94% )20 1-H exanol, 2-ethyl- (80% )21 B enzene, 1-ethyl-3-methyl- (91% )22 B enzene, 2-propenyl- (72% )23 B enzene, 1-methyl-2-propyl- (91% )24 B enzene, 1-ethyl-3,5-dimethyl- (90% )

Abb

onda

nza,

cou

nts

T em po, m in



15 20 25 30

0,0

2,0x105

4,0x105

6,0x105

8,0x105

1,0x106

1,2x106

1

2

3

45

6

7 8

9 1011

12

13

1415

16

17

1819

20

21

22

2324252627 28

29

30

31 323334

3536 37

383940

41

42

4344

23 Eicosanoic acid, 2-ethyl-2-methyl- (37%)24 Benzeneacetaldehyde, ,alpha,-methy (43%)25 Benzene, 1,2,3,5-tetramethyl- (80%)26 Heptane, 3-methyl- (50%)27 Heptadecane, 7-methyl- (38%)28 Benzene, 1-ethyl-2,3-dimethyl- (38%)29 Nonanal (90%)30 Dodecane (86%)31 2-Cyclohexen-1-one, 3,5,5-trimethy (59%)32 5H-5-Methyl-6,7-dihydrocyclopentap (53%)33 Benzene, 1,3-diethyl- (80%)34 Hexyl octyl ether (43%)35 Cyclopentane, 1,2,4-trimethyl-, (1 (58%)36 2-Nonenal, (E)- (58%)37 Cyclopentasiloxane, decamethyl- (42%)38 1-Hexene, 4,5-dimethyl- (47%)39 Dotriacontane (53%)40 Decane, 3-methyl- (53%)41 Decanal (64%)42 Dodecane (90%)43 Undecane, 2,6-dimethyl- (58%)44 2-Methoxyphenyl isothiocyanate (27%)

Sample no.11GOATSKIN

FOOTWEAR - FINISHED1 2-Oxetanone, 4,4-dimethyl- (50%)2 Toluene (91%)3 Hexanal (86%)4 Acetic acid, butyl ester (39%)5 Ethylbenzene (59%)6 Benzene, 1,3-dimethyl- (94%)7 Heptanal (81%)8 p-Xylene (81%)9 1-Decanol, 2-ethyl- (50%)10 Benzaldehyde (78%)11 1,3,5-Cycloheptatriene, 7-ethyl- (38%)12 Benzene, 1-ethyl-2-methyl- (91%)13 5-Hepten-2-one, 6-methyl- (46%)14 Cyclopentanol, 3-methyl- (50%)15 Benzene, 1-ethyl-2-methyl- (59%)16 Octanal (46%)17 Benzene, 1,2,3-trimethyl- (83%)18 Octane, 4-ethyl- (83%)19 3-Octene, (E)- (43%)20 Benzene, 1,2,3-trimethyl- (46%)21 Decane, 4-methyl- (72%)22 D-Limonene (95%)

Abundance,counts

Time, min


Bibliography

1 Rapporti gruppo Scientifico Italiano Studi e Ricerche (GSISR), Milano, 2004

2 B. Naviglio, M. Tomaselli, D. Naviglio, C. Raia, Caratterizzazione gas-cromatografica

delle componenti volatili di pelli e cuoi, CPMC Anno 78 – n.2 marzo/aprile 2002

3 Dr. S. Adams, Dr B. Wegner and Dr. P. Weyland, Fogging from finishes in car leather,

Leather January 2000

4 Dr. Amanda Long, Automotive Leather – Constituents of Fogging Materials Revelealed,

Meeting the Environmental Challenge, November 2001, Kenilworth UK

5 EPA Method 5035, Closed-System Purge-and-Trap and Extraction for Volatile Organics in

Soil and Waste Samples, rev. 0 December 1996.

6 EPA Method 8260B, Volatile Organic Compounds by Gas Chromatography/Mass

Spectrometry (GC/MS), rev. 2 December 1996

7 EPA Method 8270C, Semivolatile Organic Compounds by Gas Chromatography/Mass

Spectrometry (GC/MS), rev. 3 December 1996

(N.d.t.: non è stato possible sovrascrivere nella figura n.13. Vogliate apporre la seguente traduzione: CAMPIONE N.10 � SAMPLE No 10 CROSTA � SPLIT LEATHER ARTICOLO BY CAST � BY CAST ARTICLE ABBONDANZA, COUNTS � ABUNDANCE, COUNTS

the characterisation of volatile organic compounds · pdf filethe characterisation of volatile...

Documents