The MAK Collection For Occupational Health and Safety - 2016 - Schneider - Solvent Mixtures Air Monitoring Methods 2014b

2139
Solvent mixtures
Method number 2
Application Air Analysis
Analytical principle Gas chromatography (activated charcoal/ternary
mixture) (Double capillary technique)
Completed in October 2013
Summary
This measurement method is suitable for monitoring the Occupational Exposure
Limits (OELs) of solvent components at workplaces. Sampling is performed by
drawing air through a tube containing activated charcoal using a suitable sampling
pump. Then the adsorbed solvents are extracted with a ternary mixture consisting
of dichloromethane, carbon disulphide and methanol. The sample solution is ana-
lysed by means of gas chromatography using two capillary columns of different po-
larity with the help of flame ionisation detectors (FID). Quantitative evaluation is
based on a multiple-point calibration with an internal standard.
Characteristics of the method

Precision: Standard deviation (rel.): s = 0.5 to 3.2%
Expanded uncertainty: U = 10 to 22%
in the concentration range of the respective limit of
quantification to twice the Occupational Exposure
Limits and for n = 6 determinations
Limit of quantification: 1 to 5 mg/m3
depending on the substance, for an air sample vo-
lume of 40 L, a desorption solution of 10 mL and an
injection volume of 1 μL
Recovery: 83 to 100%
Sampling recommendations: Air sample volume: 40 L
Flow rate: 20 L/h (0.333 L/min)
Authors: W. Schneider, D. Breuer
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA

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2140 Air Monitoring Methods
Solvent mixtures
Method number 2
Application Air Analysis
Analytical principle Gas chromatography (activated charcoal/ternary
mixture) (Double capillary technique)
Completed in October 2013
Contents
1 General principles 2141

2 Equipment, chemicals and solutions 2141
2.1 Equipment 2141
2.2 Chemicals 2141
2.3 Solutions 2142
2.4 Calibration standards 2142
3 Sampling and sample preparation 2145
3.1 Sampling 2145
3.2 Sample preparation 2145
4 Operating conditions for gas chromatography 2145
5 Analytical determination 2146
6 Calibration 2147
7 Calculation of the analytical result 2147
8 Reliability of the method 2147
8.1 Precision 2148
8.2 Recovery 2148
8.3 Limit of quantification 2148
8.4 Expanded uncertainty 2148
8.5 Storage stability 2148
8.6 Interferences 2149
Appendix 2149
References 2154
The MAK Collection for Occupational Health and Safety 2016, Vol 1, No 3
Solvent mixture Meth.-No. 2 2141
1 General principles
A defined air volume from the breathing zone is drawn through a charcoal tube (B
type) by a sampling pump. The solvent components occurring in a gaseous state in
the workplace air are adsorbed onto the activated charcoal layer. Then the adsorbed
solvents are extracted with a ternary mixture consisting of dichloromethane, carbon
disulphide and methanol. The sample solution is analysed by means of gas chroma-
tography using two capillary columns of different polarity with the help of flame
ionisation detectors (FID). Quantitative evaluation is based on a multiple-point
calibration with an internal standard.
2 Equipment, chemicals and solutions
2.1 Equipment
• Charcoal tubes type B, collection layer of 300 mg, control layer of 600 mg (e.g.
from Dräger Safety, 23558 Lübeck, Germany)
• Pump, suitable for a flow rate of 0.333 L/min (e.g. model LFS-113DC, Gilian Inc,
USA)
• Gas chromatograph with two flame ionisation detectors (FID), autosampler,
split/splitless injector and data evaluation system
• Non-polar capillary column (e.g. Rtx-5: 60 m, 0.25 μm film thickness and 0.25
mm ID, from Restek, 61348 Bad Homburg, Germany)
• Polar capillary column (e.g. HP-Innowax: 60 m, 0.25 μm film thickness and 0.25
mm ID, from Agilent, 76337 Waldbronn, Germany)
• Flow meter (e.g. GFM model, Analyt-MTC, 79379 Müllheim, Germany)
• Screw-capped vials with septum, nominal volume 20 mL
• Dispensette, 1 to 10 mL, adjustable in increments of 0.2 mL
• Volumetric flasks, nominal volume 2, 5, 10, 100 and 1 000 mL
• Microlitre syringes, 5, 10, 25, 50, 100, 250, 500 and 1 000 μL
• Disposable syringes made of polypropylene (PP), 2 mL
• Disposable filter (e.g. PTFE syringe filter, pore size 0.45 μm)
• Autosampler vials, 1.5 mL with PP screw caps and PTFE-coated butyl rubber septa
2.2 Chemicals
The substances to be determined should have the highest possible purity (see also
Table 5 in the Appendix).
• 1,2,3-Trimethylbenzene, p.a., purity ≥ 93.7% (e.g. Fluka)
• n-Propylbenzene, p.a., purity ≥ 99.8% (e.g. Fluka)

• o-Xylene, p.a., purity ≥ 99% (e.g. Fluka)

• Toluene, p.a., purity ≥ 99.7% (e.g. Fluka)
• 2-Methylheptane, reference substance for the GC (e.g. Merck)
• n-Undecane, reference substance for the GC (e.g. Merck)
• Dichloromethane, p.a., purity > 99.9% (e.g. Merck)
• Carbon disulphide, p.a., free of benzene, purity ≥ 99.8% (e.g. LGC-Promochem)
• Methanol, p.a., purity > 99.9% (e.g. Merck)
Gases for operation of the gas chromatograph:
• Helium 5.0 (carrier gas)
• Nitrogen 5.0
• Synthetic air (free of hydrocarbons)
• Hydrogen 5.0
2.3 Solutions
Desorption solution: Ternary mixture: CH2Cl2/CS2/MeOH (60/35/5)
600 mL of dichloromethane, 350 mL of carbon disulphide and 50 mL of methanol

are mixed in a 1 000 mL volumetric flask.
The mixture containing carbon disulphide should be stored in the refrigerator at 4 °C

and protected from light, in order to prevent yellow colouration or turbidity of the
desorption solution due to the initiation of sulphur release. The desorption solution is
stable for one week at most.
Internal standard (ISTD): 2-Methylheptane/n-Undecane (50/50)
500 μL each of 2-methylheptane and n-undecane are mixed in a 1.5 mL autosam-

pler vial.
2.4 Calibration standards

Calibration standards are necessary for obtaining the required calibration functions.
These should cover the minimum measurement range (0.1 up to twice the respec-
tive Occupational Exposure Limits). Should this not be possible for reasons of line-
arity, then calibration is carried out in the linear range and the samples are subse-
quently diluted accordingly. Examples of the procedure for the determination of
toluene, n-propylbenzene, o-xylene and 1,2,3-trimethylbenzene is described below.
Solution 1 (stock solution) for the 6-point working calibration

Initially a stock solution is prepared from the substances to be determined. For this
purpose a 100 μL syringe is used to add the volumes listed in Table 1 of the respec-
Table 1 Dosing scheme for the preparation of solution 1 (stock solution)
Substance Volume Density Final volume Concentration

[μL] [g/mL] [mL] [μg/μL]
Toluene 80 0.87 2 34.8
n-Propylbenzene 80 0.86 2 34.4
o-Xylene 80 0.88 2 35.2
1,2,3-Trimethylbenzene* 80 0.89 2 33.4
* in the calculation of the concentration of 1,2,3-trimethylbenzene its purity of 93.7% was taken into account.
tive substances into a 2 mL volumetric flask, into which approx. 500 μL of de-
sorption solution have already been placed. The volumetric flask is then filled to
the mark with desorption solution and shaken.
Calibration standards for the 6-point working calibration

The calibration standards are prepared from the stock solution (solution 1) accord-
ing to Table 2. Approx. 7 mL of desorption solution are placed into 10 mL volu-
metric flasks and the volumes of the stock solution given in Table 2 are added in
each case. The volumetric flasks are then filled to the mark with desorption solu-
tion and shaken. Finally, 5 μL of the internal standard (ISTD) are added to each
calibration standard. Aliquots of the four prepared calibration standards are trans-
ferred into autosampler vials and analysed by gas chromatography.
Table 2 Dosing scheme for the preparation of the calibration standards of the 6-point working
calibration and corresponding air concentrations*
Calibration standard No. 1 2 3 4 5 6

Volume of solution 1 [μL] 1.0 50 150 250 350 450
Toluene mg/10 mL 0.035 1.74 5.22 8.70 12.2 15.7
[mg/m3]* 0.87 43.5 131 218 305 392
n-Propylbenzene mg/10 mL 0.034 1.72 5.16 8.60 12.0 15.5
[mg/m3]* 0.86 43.0 129 215 301 387
o-Xylene mg/10 mL 0.035 1.76 5.28 8.80 12.3 15.8
[mg/m3]* 0.88 44.0 132 220 308 396
1,2,3-Trimethylbenzene mg/10 mL 0.033 1.67 5.00 8.34 11.7 15.0
[mg/m3]* 0.83 41.7 125 208 292 375
* The data is based on a desorption volume of 10 mL and an air sample volume of 40 L.
Control solution for the 6-point working calibration

A control solution is used for the purpose of checking the calibration functions. Its
content of substances to be determined must lie at the lower end of the concentra-

tion range and it must have been prepared independently from the calibration solu-
tions described above.
Solution 2 for the equidistant 10-point calibration

Initially, a stock solution is prepared from the substances to be determined (see
Table 3). For this purpose a 10 μL syringe is used to add 5 μL of each of the sub-
stances to be determined into a 10 mL volumetric flask, into which approx. 7 μL of
desorption solution have already been placed. The volumetric flask is then filled to
the mark with desorption solution and shaken.
Table 3 Dosing scheme for the preparation of solution 2
Substance Volume Density Final volume Concentration

[μL] [g/mL] [mL] [μg/μL]
Toluene 5 0.87 10 0.435
n-Propylbenzene 5 0.86 10 0.430
o-Xylene 5 0.88 10 0.440
1,2,3-Trimethylbenzene* 5 0.89 10 0.417
*the purity of 93.7% was taken into account in the calculation of the concentration of 1,2,3-trimethylben-
zene.
Calibration standards for the equidistant 10-point calibration

The calibration standards are prepared from the stock solution (solution 2) accord-
ing to Table 4. Approx. 7 mL of desorption solution are placed into 10 mL volu-
metric flasks and the volumes of the stock solution given in Table 4 are added in
each case. The volumetric flasks are then filled to the mark with desorption solu-
tion and shaken. 5 μL of the internal standard are added to each calibration stan-
dard.
Table 4 Dosing scheme for the calibration standards of the equidistant 10-point working cali-
bration and corresponding air concentrations
Calibration standard No. 1 2 3 4 5 6 7 8 9 10

Volume of solution 2 [μL] 10 20 30 40 50 60 70 80 90 100
Toluene μg/10 mL 4.35 8.70 13.1 17.4 21.8 26.1 30.5 34.8 39.2 43.5
[mg/m3]* 0.11 0.22 0.33 0.44 0.54 0.65 0.76 0.87 0.98 1.09
n-Propylbenzene μg/10 mL 4.30 8.60 12.9 17.2 21.5 25.8 30.1 34.4 38.7 43.0
[mg/m3]* 0.11 0.22 0.32 0.43 0.54 0.65 0.75 0.86 0.97 1.08
o-Xylene μg/10 mL 4.40 8.80 13.2 17.6 22.0 26.4 30.8 35.2 39.6 44.0
[mg/m3]* 0.11 0.22 0.33 0.44 0.55 0.66 0.77 0.88 0.99 1.10
1,2,3-Trimethylbenzene μg/10 mL 4.17 8.34 12.5 16.7 20.8 25.0 29.2 33.4 37.5 41.7
[mg/m3]* 0.10 0.21 0.31 0.42 0.52 0.63 0.73 0.83 0.94 1.04
* The data is based on a desorption volume of 10 mL and an air sample volume of 40 L.
3 Sampling and sample preparation
3.1 Sampling
A charcoal tube (B type) is opened and connected to a flow-regulated pump for
sampling. Following this, workplace air is drawn through the charcoal tube at a flow
rate of 20 L/h (0.333 L/min). It must be ensured that an air sample volume of 40 L
is not exceeded. If the sampling is to be carried out over a longer time period (up to
8 h), then the flow rate must be adjusted accordingly. Sampling can be carried out
at a relative humidity of up to 75% without any limitations; in the case of a greater
relative humidity two tubes connected in series are to be used. After sampling, the
loaded charcoal tubes are sealed with the plastic caps that are supplied with them
and unambiguously labelled. No breakthrough at concentrations of up to twice the
Occupational Exposure Limits occurs, if compliance with these parameters is en-
sured.
3.2 Sample preparation

The loaded charcoal tube is opened in the laboratory and the contents are trans-
ferred into a 20 mL screw-capped vial. Then the loaded charcoal is covered with 10
mL of the desorption solution using a dispensette. The vial is sealed and allowed to
stand for approx. 30 minutes at room temperature. Then 5 μL of the internal stan-
dard are added using a 10 μL syringe and the vial is shaken. After this an aliquot of
the sample solution is taken from the supernatant, filtered into an autosampler vial
using a disposable filter and analysed. In order to ensure that the desorption solu-
tion and the loaded charcoal used do not contain any interfering impurities, an un-
used charcoal tube from the same batch as the ones used is analysed.
4 Operating conditions for gas chromatography
Each sample is analysed in parallel on two capillary columns of different polarity. 2-

Methylheptane is used as internal standard for the non-polar column and n-unde-
cane for the polar column. No overlaps occur with the substances listed in Table 7
when these standards and the temperature program are used.
Apparatus: Agilent 6890 series gas chromatograph with autosampler,

split/splitless injector, column flow splitter and two flame
ionisation detectors
Double capillary technique; both the capillary columns are
connected in parallel with the injector by means of a col-
umn flow splitter

Separation columns Fused silica capillaries:

1st column: stationary phase Rtx-5 (95% methylsiloxane,
5% phenylsiloxane) length 60 m, ID
0.25 mm, film thickness 0.25 μm
2nd column: stationary phase HP INNOWAX (polyethy-
lene glycol) length 60 m, ID 0.25 mm, film
thickness 0.25 μm
Temperatures: Injector: 250 °C
Detector: 250 °C
Temperature program: 11 min at 50 °C, with 4 °C per minute up to 150 °C
Injector: Split injection, split ratio 20:1
Injection volume: 1 μL
Column flow: 5 min of 1.2 mL/min, then 0.6 mL per minute up to
1.8 mL/min
Carrier gas: Helium 5.0
Detector gases: Hydrogen 5.0 (40 mL/min)
Synthetic air (400 mL/min)
Make-up gas: Nitrogen 5.0 (25 mL/min)
5 Analytical determination
1 μL of the sample solution is injected into the gas chromatograph in each case
using the autosampler, and split onto two columns of different polarity. The mean
value of the measurement data from both columns is used for the evaluation in
each case. If the deviation of the data from both separation columns is less than
20%, the mean value is used for the evaluation. In the case of a greator deviation, it
must be determined on the basis of different criteria, which value should be used
for the evaluation, e.g.:
• If the signal in a chromatogram of a substance to be determined is overlapped by
that of another substance, then the result from the other chromatogram is used
for the evaluation.
• If the signal of the internal standard in a chromatogram is overlapped by that of
another substance, then the results from the other chromatogram are used for
the evaluation.
If the measured concentrations are above the calibration range, then a suitable dilu-
tion must be prepared and the analysis must be carried out again.
6 Calibration
The calibration solutions described in Section 2.4 are used to obtain a calibration
function. The internal standard method is used for calibration. Each calibration
standard is injected into the gas chromatograph three times and analysed in the
same manner as the sample solution (determination in triplicate). The calibration
must be performed anew if the analytical conditions change or the quality control
results indicate that this is necessary.
7 Calculation of the analytical result
Based on the peak areas obtained the corresponding mass X in μg is obtained from
the calibration curve. The corresponding mass concentration (ρ) of a component is
calculated according to Equation (1) as follows:
X
ρ¼ ð1Þ
V $η
Equation (2) enables calculation of the value at 20 °C and 1013 hPa:
273 þ ta 1013
ρ0 ¼ ρ $ $ ð2Þ
293 pa
where:
ρ is the mass concentration of a solvent component in mg/m3
ρ0 is the mass concentration of the component in mg/m3 at 20 °C and 1013 hPa
X is the mass of the component in the analytical sample in μg
V is the air sample volume in litres
η is the recovery
ta is the temperature during sampling in °C
pa is the air pressure during sampling in hPa
8 Reliability of the method
The characteristics of the method were calculated as stipulated in EN 482 [1] and
EN 1076 [2]. Test gases were produced on a dynamic test gas facility in a concen-
tration range of the respective limits of quantification up to twice the Occupational
Exposure Limits. These test gases were humidified to give a relative humidity from
30 to 75%. Samples were taken from each of these concentrations at room tempera-

ture (air sample volume 40 mL), prepared according to the Sections 3.2, 4 and 5
and analysed.
8.1 Precision
Six charcoal tubes for each of the three different concentrations were loaded at a
relative humidity of approx. 50% for the purpose of determining the precision. The
resulting relative standard deviations are shown in Table 5 (Appendix).
8.2 Recovery
The recoveries of the selected solvent components were determined for concentra-
tions from 0.5 to twice the Occupational Exposure Limits using a dynamic test gas
facility. The values were determined for six sample tubes in each case at a relative
humidity of approx. 50%. In contrast, determination of the recoveries and relative
standard deviations close to the limits of quantification was carried out by direct
application of the substances onto the charcoal tubes (liquid spiking). Then 40 L of
air were drawn through the tubes at a flow rate of approx. 20 L/h (0.333 L/min).
The samples were prepared and analysed as described in the Sections 3.2, 4 and 5.
The results are shown in Table 6 (Appendix).
8.3 Limit of quantification

The limits of quantification for the selected substances were determined from 10-
point calibrations with equidistant values in the lower working range by one deci-
mal power (see Section 2.4) according to DIN 32645 [3]. The results are shown in
Table 6 (Appendix).
8.4 Expanded uncertainty

The expanded uncertainties for the determination of the investigated substances
were estimated taking all relevant influencing factors into consideration as stipu-
lated in EN 482 [1] and EN 1076 [2] and calculated according to [4]. The expanded
uncertainties were between 10 and 22% for the substances described. The indivi-
dual results are shown in Table 5.
8.5 Storage stability

Tests on storage stability of the loaded sample tubes were carried out over a period
of two weeks. For this purpose charcoal tubes were loaded on a test gas facility at a
relative humidity from 75 to 80% with concentrations of half and twice the Occupa-
tional Exposure Limits of the selected substances and sealed with plastic caps. After
a storage period of 7 and 14 days at room temperature six sample tubes were ana-
lysed in each case. During the investigation period no significant losses could be
detected.
8.6 Interferences
Interferences from overlapping signals should be corrected by the use of two se-
paration columns arranged in parallel of different polarity. Experience of using this
equipment has shown that, apart from a few exceptions, at least one chromatogram
without signal interference is obtained and can be evaluated. Table 7 lists the reten-
tion times of the investigated substances for the columns used (for chromato-
graphic conditions see Section 4).
Appendix
Characteristics of the investigated substances
Table 5 Characteristics of the investigated substances for n = 6 determinations
Substance Concentration Standard deviation Expanded

[CAS No.] [mg/m3] (rel.) [%] uncertainty U [%]
1-Butanol 5.3 1.5 20
[71-36-3] 146.0 7.4 21
600.7 4.1 20
2-Butanol 5.3 1.3 19
[78-92-2] 145.4 6.3 20
598.4 4.2 19
2-Butoxyethanol 1.0 1.0 11
[111-76-2] 50.0 0.5 11
199.0 2.6 12
2-Butoxyethyl acetate 2.0 1.8 11
[112-07-2] 69.7 0.5 11
262.0 1.8 11
n-Butyl acetate 1.0 0.4 12
[123-86-4] 450.0 1.7 11
1860 1.7 11
Cumene (Isopropylbenzene) 1.0 3.4 17
[98-82-8] 124.0 0.3 16
485.0 0.6 16

Table 5 (Continued)

Cyclohexane 1.1 1.7 19
[110-82-7] 615.0 1.2 18
2020 1.9 17
Cyclohexanol 6.0 1.6 18
[108-93-0] 97.4 3.3 18
406.8 2.5 17
n-Decane 1.0 1.2 18
[124-18-5] 1093 0.9 17
4364 1.8 17
1,4-Dioxane 1.0 2.3 11
[123-91-1] 91.8 0.4 12
369.0 2.8 12
Ethanol 8.1 1.5 20
[64-17-5] 925.9 5.8 22
3806 5.2 20
Ethyl acetate 1.0 0.9 12
[141-78-6] 286.0 1.3 11
2781 2.6 11
Ethylbenzene 1.0 3.6 18
[100-41-4] 228.0 0.3 17
879.0 0.6 17
n-Heptane 1.0 1.6 19
[142-82-5] 1024 0.9 21
4021 1.0 19
n-Hexane 0.9 1.4 18
[110-54-3] 92.0 0.8 17
369.0 0.7 19
Isobutyl acetate 1.0 0.5 12
[110-19-0] 445.0 1.8 11
1839 2.8 11
Isopropyl acetate 1.0 0.3 12
[108-21-4] 359.8 1.6 11
1581 2.5 11
1-Methoxy-2-propanol 1.0 0.7 12
[107-98-2] 187.0 0.4 12
764.0 2.3 12
1-Methoxy-2-propyl acetate 2.0 1.3 11
[108-65-6] 136.0 0.3 11
555.0 1.8 11
Table 5 (Continued)

Methyl acetate 1.0 0.4 13
[79-20-9] 299.7 1.7 11
1198 0.9 12
Methylcyclohexane 1.1 1.3 17
[108-87-2] 1152 0.8 17
3949 1.4 17
2-Methyl-1-propanol 5.3 1.5 19
(Isobutanol) 144.8 5.8 20
[78-83-1] 595.4 4.7 19
n-Nonane 1.0 1.6 18
[111-84-2] 1074 0.9 17
4023 1.0 17
n-Octane 1.0 2.1 17
[111-65-9] 1305 1.4 17
4068 3.4 17
n-Pentane 0.9 1.5 17
[109-66-0] 1455 1.2 16
3037 2.2 17
1-Propanol 5.0 1.5 17
[71-23-8] 406.6 4.0 17
1698 2.4 17
2-Propanol 4.9 0.9 17
[67-63-0] 397.3 3.7 17
1659 2.3 17
Propyl acetate 1.0 0.5 13
[109-60-4] 101.2 1.5 11
1635 1.2 12
n-Propylbenzene 1.0 3.4 17
[103-65-1] 227.0 0.4 16
858.0 0.5 16
Tetrahydrofuran 1.0 0.8 11
[109-99-9] 296.0 0.3 11
1167 2.6 12
Toluene 1.0 2.8 19
[108-88-3] 97.2 0.5 18
377.1 0.7 18
1,2,3-Trimethylbenzene 1.0 2.8 22
[526-73-8] 232.0 0.4 22
880.0 0.5 22

Table 5 (Continued)

[95-63-6] 230.0 0.4 17
872.0 0.4 17
[108-67-8] 227.0 0.3 17
860.0 0.4 17
m-Xylene 1.0 3.0 18
[108-38-3] 227.0 0.3 17
877.0 0.7 18
o-Xylene 1.0 4.1 17
[95-47-6] 231.0 0.4 17
876.0 1.4 17
p-Xylene 1.0 4.0 18
[106-42-3] 226.0 0.3 17
873.0 0.7 17
Table 6 Recoveries, rel. standard deviations, and limits of quantification for n = 6 determina-
tions
Substance Recovery Standard deviation Limit of quantification

(rel.) [%] [mg/m3]*
1-Butanol 0.95 1.2 5
2-Butanol 0.95 1.1 5
2-Butoxyethanol 0.97 1.4 2
2-Butoxyethyl acetate 1.0 1.3 2
n-Butyl acetate 1.0 0.5 1
Cumene (Isopropylbenzene) 0.95 1.3 1
Cyclohexane 0.96 1.0 1
Cyclohexanol 0.98 1.2 5
n-Decane 0.94 0.7 1
1,4-Dioxane 0.99 0.8 1
Ethanol 0.93 1.4 5
Ethyl acetate 1.0 0.7 1
Ethylbenzene 0.93 1.8 1
n-Heptane 0.95 0.6 1
n-Hexane 0.95 1.0 1
Isobutyl acetate 1.0 0.5 1
Isopropyl acetate 1.0 0.5 1
1-Methoxy-2-propyl acetate 1.0 1.2 2
Methyl acetate 1.0 0.8 1
Table 6 (Continued)
Substance Recovery Standard deviation Limit of quantification

(rel.) [%] [mg/m3]*
Methylcyclohexane 0.94 0.7 1
n-Nonane 0.94 1.0 1
n-Octane 0.96 0.7 1
n-Pentane 0.97 1.1 1
1-Propanol 0.97 0.6 3
2-Propanol 0.97 0.9 2
Propyl acetate 1.0 0.5 1
n-Propylbenzene 0.93 1.8 1
Tetrahydrofuran 0.99 1.3 1
Toluene 0.91 3.2 1
m-Xylene 0.91 2.9 1
o-Xylene 0.85 2.0 1
p-Xylene 0.90 2.7 1
* The data is based on a desorption volume of 10 mL and air sample volume of 40 L.
Table 7 Retention times (RT) of the investigated solvents on the polar (HP-INNOWAX) and
non-polar (Rtx-5) separation column
Rtx-5 HP-INNOWAX
RT [min] Substance RT [min] Substance
6.00 Ethanol* 4.70 n-Pentane
6.60 2-Propanol 5.00 n-Hexane
6.72 n-Pentane 5.60 n-Heptane
7.90 1-Propanol 5.93 Cyclohexane
9.43 n-Hexane 6.18 2-Methylheptane
9.43 2-Butanol 6.44 Methylcyclohexane
9.93 Ethyl acetate 6.70 n-Octane
10.67 2-Methoxy-1-propanol 7.33 Methyl acetate
(isobutanol)
10.88 Tetrahydrofuran 8.11 Tetrahydrofuran
12.55 Isopropyl acetate 8.79 Ethyl acetate
12.69 1-Butanol 9.00 n-Nonane
13.13 Cyclohexane 9.17 Isopropyl acetate
13.31 1-Methoxy-2-propanol 10.00 2-Propanol
15.00 n-Heptane 10.30 Propyl acetate

Table 7 (Continued)
Rtx-5 HP-INNOWAX
RT [min] Substance RT [min] Substance
15.47 1,4-Dioxane 12.91 n-Decane
15.65 Propyl acetate 14.11 Isobutyl acetate
16.80 Methylcyclohexane 14.53 2-Butanol
18.80 2-Methylheptane (ISTD) 15.21 1-Propanol
19.08 Isobutyl acetate 15.54 Toluene
19.10 Toluene 16.54 1,4-Dioxane
20.65 n-Octane 16.96 n-Butyl acetate
21.18 n-Butyl acetate 17.58 2-Methoxy-1-propanol
(isobutanol)
23.58 1-Methoxy-2-propyl acetate 17.62 n-Undecane (ISTD)
23.95 Ethylbenzene 19.29 1-Methoxy-2-propanol
24.34 m-Xylene 19.47 Ethylbenzene
24.41 p-Xylene 19.80 p-Xylene
25.05 Cyclohexanol 19.90 1-Butanol
25.30 2-Butoxyethanol 20.07 m-Xylene
25.44 o-Xylene 21.37 Cumene
25.44 n-Nonane 21.86 o-Xylene
26.76 Cumene 22.76 n-Propylbenzene
28.04 n-Propylbenzene 23.12 1-Methoxy-2-propyl acetate
28.63 1,3,5-Trimethylbenzene 24.07 1,3,5-Trimethylbenzene
29.52 1,2,4-Trimethylbenzene 25.41 1,2,4-Trimethylbenzene
29.69 n-Decane 27.29 1,2,3-Trimethylbenzene
30.82 1,2,3-Trimethylbenzene 28.99 2-Butoxyethanol
32.42 2-Butoxyethyl acetate 29.01 Cyclohexanol
33.12 n-Undecane 30.53 2-Butoxyethyl acetate
*Ethanol can only be determined on the Rtx-5 column and methyl acetate only on the HP-Innowax column,
as they overlap with the extraction agent on the respective other column.
References
1 EN 482 (2012) Workplace atmospheres – General requirements for the performance of proce-
dures for the measurement of chemical agents. Beuth Verlag, Berlin, Germany
2 EN 1076 (2010) Workplace exposure – Procedures for measuring gases and vapours using
pumped samplers – Requirements and test methods. Beuth Verlag, Berlin, Germany
3 DIN 32645 (2008) Chemical analysis – Decision limit, detection limit and determination limit
under repeatability conditions – Terms, methods, evaluation. Beuth Verlag, Berlin, Germany
4 Heckmann P, Breuer D (2013) IFA method for calculating expanded measurement uncer-
tainty, http://www.dguv.de/ifa/index-2.jsp
Authors: W. Schneider, D. Breuer

The MAK Collection For Occupational Health and Safety - 2016 - Schneider - Solvent Mixtures Air Monitoring Methods 2014b

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2139

Characteristics of the method

Authors: W. Schneider, D. Breuer

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA

1 General principles 2141

2 Equipment, chemicals and solutions

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA

• o-Xylene, p.a., purity ≥ 99% (e.g. Fluka)

600 mL of dichloromethane, 350 mL of carbon disulphide and 50 mL of methanol

The mixture containing carbon disulphide should be stored in the refrigerator at 4 °C

Internal standard (ISTD): 2-Methylheptane/n-Undecane (50/50)

500 μL each of 2-methylheptane and n-undecane are mixed in a 1.5 mL autosam-

2.4 Calibration standards

Solution 1 (stock solution) for the 6-point working calibration

Table 1 Dosing scheme for the preparation of solution 1 (stock solution)

Substance Volume Density Final volume Concentration

Calibration standards for the 6-point working calibration

Calibration standard No. 1 2 3 4 5 6

Control solution for the 6-point working calibration

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA

Solution 2 for the equidistant 10-point calibration

Table 3 Dosing scheme for the preparation of solution 2

Substance Volume Density Final volume Concentration

Calibration standards for the equidistant 10-point calibration

Calibration standard No. 1 2 3 4 5 6 7 8 9 10

3 Sampling and sample preparation

3.2 Sample preparation

4 Operating conditions for gas chromatography

Each sample is analysed in parallel on two capillary columns of diﬀerent polarity. 2-

Apparatus: Agilent 6890 series gas chromatograph with autosampler,

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA

Separation columns Fused silica capillaries:

7 Calculation of the analytical result

Equation (2) enables calculation of the value at 20 °C and 1013 hPa:

8 Reliability of the method

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA

8.3 Limit of quantification

8.4 Expanded uncertainty

8.5 Storage stability

Characteristics of the investigated substances

Table 5 Characteristics of the investigated substances for n = 6 determinations

Substance Concentration Standard deviation Expanded

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA

Substance Concentration Standard deviation Expanded

Substance Concentration Standard deviation Expanded

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA

Substance Concentration Standard deviation Expanded

Substance Recovery Standard deviation Limit of quantification

Substance Recovery Standard deviation Limit of quantification

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA

Authors: W. Schneider, D. Breuer

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA

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