Purpose :: Textile & Garment Industry Research & Development Center Quality Standard and Testing Laboratory Research Desk

TEXTILE & GARMENT INDUSTRY RESEARCH &
DEVELOPMENT CENTER
Quality Standard and Testing Laboratory Research Desk
SOP for Analysis of Chlorinated Organic Carriers By Revision No

GCMS
Issue Date
1. Purpose*:
1.1 This method describes a procedure for determining the chloro-organic carriers in textile
and leather samples.
1.2 This method coverage with three chloro-organic carriers families including
Chlorobenzene; Chlorotoluene and Chloroxylene
1.3 The sample is extracted with dichloromethane in a closed vessel using ultrasonic
bath and the extract is determined by gas chromatography with mass spectrometer
(GC-MS) after filtration.
2. Scope*:
2.1 This method which complies with DIN 54232: 2010-08 specifies an analysis
procedure for the determination of the content at chloro-organic carriers in textile and
leather products and components, e.g. Colonel off, inserts, fodder, zippers, buttons,
labels, yarns and applications
2.2 This procedure is valid for proportion of 0.1 mg/kg to 10 mg/kg for each single COC.
Higher and lower proportions can be determined, if the originally sample size is
reduced accordingly and/or corresponding dilutions is made.
2.3 1,2-Dichlorobenzene confirmation differentiate with 2 different lower GC inlet
temperatures, if detected. Upon approval from TCD, alternative GC program in Appendix
3 ZB-35 can be used for analysis of COCs.
2.4 COCs test is not appropriate with white color fabric unless upon request
3. Definitions:
3.1 Not Applicable
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Review By Document No
Initiated By Approved By
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4. Apparatus and Equipment:

4.1 Gas Chromatography with Mass Spectrum Detector (GC-MSD), Agilent HP 6890 &
MS5975 or equivalent
4.2 ZB-35, 15 m x 0.25 mm x 0.5 µm, Phenomenex or equivalent (For alternative GC
program in Appendix 3)
4.3 DB-35MS, 30 m x 250 µm x 0.25 µm J&W or equivalent
4.4 Ultrasonic bath
4.5 Vacuum rotary evaporator with water bath
4.6 100 µL and 1 mL Autopipette
4.7 Evaporating tube with 1 mL graduated mark
4.8 General laboratory apparatus
5. Reagents, and Consumables:
All chemicals and reagents shall be in analytical grade unless otherwise specified.
5.1 Standards
Item Compound CAS Purity Brand
5.1.1 2-Chlorotoluene 95-49-8 99.4 % Chemservice
5.1.2 3-Chlorotoluene 108 -41-8 99.0 % Dr. Ehrenstorfer
5.1.3 4-Chlorotoluene 106-43-4 98.2 % Chemservice
5.1.4 2,4-Dichlorotoluene 95-73-8 99.4 % Chemservice
5.1.5 2,5-Dichlorotoluene 19398-61-9 - Dr. Ehrenstorfer
5.1.6 2,6-Dichlorotoluene 118-69-4 99.5 % Dr. Ehrenstorfer
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5.1.7 2,3-Dichlorotoluene 32768-54-0 98.5 % Chemservice
5.1.8 3,4-Dichlorotoluene 95-75-0 99.0 % Dr. Ehrenstorfer
5.1.9 1,3-Dichlorobenzene 541-73-1 - Dr. Ehrenstorfer
5.1.10 1,4-Dichlorobenzene 106-46-7 - Dr. Ehrenstorfer
5.1.11 1,2,4,5-Tetrachlorobenzene 95-94-3 99.5 % Chemservice
5.1.13 2,3,6-Trichlorotoluene 2077-46-5 - -
5.1.14 2,4,5-Trichlorotoluene 6639-30-1 99.5 % Chemservice
5.1.15 Pentachlorotoluene 877-11-2 98.4 % Chemservice
5.1.16 1,2-Dichlorobenzene 95-50-1 99.3 % Chemservice
5.1.17 1,2,3-Trichlorobenzene 87-61-6 99.5 % Chemservice
5.1.21 Pentachlorobenzene 608-93-5 99.5 % Chemservice
5.1.22 Hexachlorobenzene 118-74-1 99.5 % Chemservice
5.1.23 α, α -Dichlorotoluene 98-87-3 98.9% Chemservice
5.1.24 3,5-Dichlorotoluene 25186-47-4 - -
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5.1.26 2,3,4,5-Tetrachlorotoluene 1006-32-2 - -
5.1.28 Chlorobenzene 108-90-7 99.5% Chemservice
5.1.29 α,α,α-Trichlorotoluene 98-07-7 98.5% Dr. Ehrenstorfer
5.1.30 α,2,6-Trichlorotoluene 2014-83-7 99.5% Chemservice
5.1.31 α,2,4-Trichlorotoluene 94-99-5 98.6% Acros
5.1.32 α,3,4-Trichlorotoluene 102-47-6 99.5% Acros
5.1.33 α,α,α-2-Tetrachlorotoluene 2136-89-2 99.0% Dr. Ehrenstorfer
5.1.34 α,α,α-4-Tetrachlorotoluene 5216-25-1 98.5% Dr. Ehrenstorfer
5.1.35 α,α,2,6-Tetrachlorotoluene 81-19-6 99.0% Dr. Ehrenstorfer
5.1.37 2-Chloro-1,4- 95-72-7 99.6% TCI

dimethylbenzene
5.1.38 4-chloro-1,2- 615-60-1 99.2% TCI

dimethylbenzene
5.1.39 4-methylbenzylchloride 104-82-5 99.8% TCI
5.1.40 1,2- 612-12-4 99.6% TCI

Bis(chloromethyl)benzene
5.1.41 1,4- 623-25-6 99.7% TCI
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5.1.46 2-Chloronaphthalene 91-58-7 99.5% Chemservice
5.1.47 Benzyl Chloride 100-44-7 99.5% Chemservice
5.2 Internal standard (Dr. Ehrenstorfer or equivalent)

5.2.1 2,4,5,6 Tetrachloro-m-xylene, CAS no. 877-09-8, 98.5%
5.3 Reagents and Solvents
5.3.1 Dichloromethane (DCM)
Remark: Suggest brand name: HPLC grade from Duksan (577-4L) and
PESTINORM® from VWR (83665.320)
5.4 Standard solutions
5.4.1 10000 mg/L individual standard stock solution (kept in freezer at 4 oC and storage
up to maximum 12 months)
5.4.1.1 Weigh to nearest 1 mg, 0.1 g of each standard (5.1) in a 10 mL beaker
respectively.
5.4.1.2 Dissolve the standard with small amount of dichloromethane
(5.3.1). (Ultrasonic if necessary)
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5.4.1.3 In each of the standard solution, transfer into a 10 mL volumetric flask

respectively; rinse the beaker twice with small amount of
dichloromethane (5.3.1). Combine the washings and make up to the
mark with dichloromethane (5.3.1).
5.4.2 ^ 100 mg/L of COCs mixed intermediate standard solution (2 set of grouping,
kept in freezer at 4 oC and storage up to maximum 6 months)
5.4.2.1 Group 1 (5.1.1 – 5.1.12, 5.1.14 – 5.1.23, 5.1.37 -- 5.1.41, 5.1.46 - 5.1.47)
5.4.2.1.1 For the item 5.1.1 – 5.1.6, pipette 33 uL of each of
10000 mg/L individual standard stock solution (5.4.1) into
10 mL volumetric flask
5.4.2.1.2 For the item 5.1.7 – 5.1.8 and 5.1.11 – 5.1.12, pipette 50 uL
of each of 10000 mg/L individual standard stock solution
(5.4.1) into above volumetric flask
5.4.2.1.3 For the others, pipette 100 uL of each of 10000 mg/L
individual standard stock solution (5.4.1) into above
volumetric flask
5.4.2.1.4 Make up to the volume with DCM (5.3.1).
Remarks: Lab can prepare no. of analyte depends on actual needs
5.4.2.2 ^ Group 2 (5.1.28 - 5.1.35)
5.4.2.2.1 pipette 100 uL of each of 10000 mg/L individual standard
stock solution (5.4.1) into a 10 mL volumetric flask
5.4.2.2.2 Make up to the volume with DCM (5.3.1).
Remarks: Lab can prepare no. of analyst depends on actual needs
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5.4.3 10 mg/L of COCs mixed working standard solutions (kept in freezer at 4

o
C and storage up to maximum a month)
5.4.3.1 Pipette 1 mL of each 100 mg/L of COCs mixed standard solutions (5.4.2.1
and 5.4.2.2) into
two 10 mL volumetric flask respectively for Group 1, Group 2^.
5.4.3.2 Make up with dichloromethane (5.3.1)
^ Remark:
- Inject the COC mixed standard solution into GC-MS for purity check before
use. If any impurity is found, discard the solution and re-prepare new
individual standard solution (5.4.1) and 100mg/L mixed standard solution
(5.4.2.2) respectively.
5.5 Internal standard solutions
5.5.1 100 mg/L of internal standard solution (kept in freezer at 4 oC and storage up to maximum 6
months)
5.5.1.1 Weigh to nearest 1 mg, 0.01 g of 2,4,5,6-tetrachloro-m-xylene (5.2.1) into a 10 mL beaker.
5.5.1.2 Dissolve the standard with small amount of dichloromethane (5.3.1).
(Ultrasonic if necessary).
5.5.1.3 Combine and transfer the standard solution in a 100 mL volumetric
flask; rinse the beaker twice with small amount of dichloromethane
(5.3.1). Combine the washings and make up to the mark with
dichloromethane (5.3.1).
5.5.2 1 mg/L of internal standard solution – for sample dilution (kept in freezer at 4
o
C and storage up to maximum a month)
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5.5.2.1 Pipette 1 mL of 100 mg/L internal standard solution (5.5.1) into a 100 mL
volumetric flask
5.5.2.2 Make up with dichloromethane (5.3.1)
5.5.3 Calibration standard solutions (a If anyone of Group 2 target (5.1.28 - 5.1.35) is
included, freshly prepare is needed. Otherwise, it can be kept in freezer at 4 oC and
storage up to maximum a month)According to Table 1, pipette a volume of 10
mg/L of COCs mixed standard solutions (5.4.3) into
three 10 mL volumetric flask respectively.
5.5.4 Pipette 0.1 mL of 100 mg/L of internal standard solution (5.5.1) in each flask.
Make up with dichloromethane (5.3.1) Table 1. Working standard solution
Vol. of 10 Vol. of 10 Final Final conc. Final conc.

mg/L of mix mg/L of mix conc. of of mix stds of mix stds
std. (5.4.3) std. (5.4.3), Istd, (Group 1), (Group 2),
(Group 1 ), mL (Group 2 a ), mg/L mg/L mg/L
mL
1 0.1 0.1 1 0.1 0.1
2 0.5 0.2 1 0.5 0.2
3 2 0.5 1 2 0.5
6. Quality Control:
6.1 QC, Spike ,Linearity
7. Interferences:
7.1 Not Applicable
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8. Safety and PPE Information:

8.1 All the organic waste should be disposed in halogenated wastes bottle.
8.2 Good laboratory practice should be followed. Use of fume hood, safety glasses,
laboratory coat and gloves are necessary.
9. Method*:
9.1 Sample preparation
9.1.1 Cut the textile and leather sample into small pieces of about 20mm x
20mm and mix homogeneously.
Note: No COCs test should be tested on white color fabric unless upon
request.
9.1.2 Weigh 1 g of sample into a reaction vial.
9.1.3 Add sufficient volume (at least 30 mL) of dichloromethane (5.3.1) into a vial,
which aim to total immerse of sample.
9.1.4 Screw cap and ultrasonic at room temperature for 30 minutes.
9.1.5 Squeeze / filter the sample extract into a flat bottom flask.
9.1.6 Concentrate the extract into 1-2 mL by vacuum rotary evaporator (4.5) at
approximate 480 mbar, 40
± 5oC. Avoid to dryness.
9.1.7 Transfer the concentrated extract into evaporating tube with graduated mark.
9.1.8 Rinse the flat bottom flask with dichloromethane and combine the washing into the
tube.
9.1.9 Concentrate into 1 mL with inert gas (argon gas or nitrogen gas) by general
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flow. (Do not blow the extract too vigorously or to dryness to prevent analyte
loss).
9.1.10 Pipette 0.01 mL of 100 mg/L of internal standard solution (5.5.1) into a flask
and make up to the mark with dichloromethane (5.3.1)
9.1.11 Transfer about 1 mL of extract into injection vial for GC-MS analysis
9.1.11.1 For default GC-MS setting, refer to 9.4.1 or 9.4.2.
9.1.11.2 Upon approval from TCD with alternative GC-MS setting, refer to
Appendix 3 (ZB-35).
9.2 Method blank
9.2.1 Without sample involved, perform a method blank following procedure 9.1.
9.3 Spike blank / Sample spike
9.3.1 For spike blank, without sample involved, spike 0.05 mL of 10 mg/L COCs
mix standard solution (5.4.3) into a reaction vial. Process the step 9.1
9.3.2 For spike sample, with 1 g sample involved, spike 0.05 mL of 10 mg/L COCs
mix standard solution (5.4.3) into a reaction vial. Process the step 9.1
9.3.3 Theoretical value of each COC is 0.5 mg/L in sample extract, which is
equivalent to 0.5 mg/kg in sample and assuming sample size is 1 g.
9.4 Instrumental setting
9.4.1 Default GC-MS setting for Chlorobenzene and Chlorotoluene families
GC: Agilent 6890
Injection Volume: 2.0 µL
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Plunger speed: Fast
Column: Agilent DB-35MS, 30 m x 0.25 mm x 0.5 µm,

Capillary column (Max. Temp.: 340 oC)
Carrier gas flow: 1.0 mL/min, He (Constant flow)
Injection Mode: Split
Inlet Temp.: 250 oC
Inlet Pressure: 7.3523 psi
Split ratio: 5:1
Split flow: 5 mL/min
Total Flow: 9 mL/min
Liner: Split / Splitless liner (ID: 4mm, single tap, with

glasswool)
Oven Temp.: Initial : 50C, hold 1 min

Ramp 1 : 50C to 280C (30C/min)
Total Run Time: 8.6 min
MSD Transfer Line Heater:
MSD Heater: 280 oC
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MS: MS 5975
Ionization mode: EI
Relative voltage 400 V

(offset):
Solvent delay: 2.5 min
Acquisition mode: SCAN / SIM
MS Quad: 150 oC (Max: 200 oC)
MS Source: 230 oC (Max: 250 oC)
Sampling Rate: 2
Threshold: 50
Scan Range: 50 amu – 400 amu
Group 1
Start time: 2.5 min
SIM parameters: Ion (Dwell) : 77 (20) 91 (20) 112 (20)
114 (20) 126 (20) 128 (20)
Group 2
Start time: 4.4 min
Ion (Dwell) : 65 (20) 91 (20) 111 (20)
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126 (20) 146 (20) 148 (20)
Group 3
Start time: 5.2 min
Ion (Dwell): 89 (20) 125 (20) 145 (20)
159 (20) 160 (20) 161 (20)
162 (20) 180 (50) 182 (50)
196 (20)
Group 4
Start time : 6.0 min
Ion (Dwell): 63 (20) 127 (20) 159 (20)
162 (20) 193 (20) 194 (20)
195 (20) 196 (20) 197 (20)
214 (20) 216 (20) 218 (20)
248 (20) 250 (20) 252 (20)
Group 5
Ion (Dwell) : 229 (20) 242 (20) 244 (20)
246 (20) 262 (20) 264 (20)
282 (20) 284 (20) 286 (20)
* Start time of each SIM group is just a reference and must be align when column cut
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Characteristic for GC-MS analysis for default setting
GC-MS
Substances RT, min Target ion, Reference ions. (m/z)
(m/z)
Chlorobenzene 3.43 112 114, 77
2-Chlorotoluene 91 126, 128
3-Chlorotoluene 4.12 91 126, 128
1,3-Dichlorobenzene 4.53 146 148, 111
Benzyl Chloride 4.71 91 126, 65

3

4
2,4-Dichlorotoluene 125 160, 162
2,5-Dichlorotoluene 5.236 125 160, 162
1,3,5-Trichlorobenzene 5.61 180 182, 145

3
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2,3-Dichlorotoluene 5.420 125 160, 162
α, α -Dichlorotoluene 5.46 125 160, 162

6
1,2,4-Trichlorobenzene 5.613 180 182, 145
1,2,3-Trichlorobenzene 5.852# 180 182, 145
α,α,α-Trichlorotoluene 5.861# 159 161, 89
2,4,5-Trichlorotoluene 6.197 159 196, 194
2,3,6-Trichlorotoluene 6.294 159 196, 194
1,2,4,5- 6.418 216 214, 218

Tetrachlorobenzene
1,2,3,5- 216 214, 218

Tetrachlorobenzene
α,2,4-Trichlorotoluene 6.571 159 196, 194
α,α,α-4-Tetrachlorotoluene 6.709 193 195, 197
1,2,3,4- 6.723 216 214, 218

Tetrachlorobenzene
2-Chloronaphthalene 6.806 162 127, 63
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α,α,α-2-Tetrachlorotoluene 7.041 193 195, 197
α,α,2,6-Tetrachlorotoluene 7.179 195 193, 197
Pentachlorobenzene 7.359 250 248, 252
Pentachlorotoluene 8.028 229 264, 262
Hexachlorobenzene 8.200 284 286, 282
Internal standard
2,4,5,6-Tetrachloro-m- 7.728 244 246, 242

xylene
Remark: #details refer with section 9.4.5.6.3

9.4.2 Default GC-MS setting for Chlorobenzene, Chlorotoluene and Chloroxylene
families
GC: Agilent 6890
Injection volume: 2.0 µL
Plunger speed: Fast
Column: Agilent DB-35MS, 30 m x 0.25 mm x 0.5 µm,

Capillary column (Max. Temp.: 340 oC)
Injection mode: Split
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Inlet temp.: 250 oC
Inlet pressure: 7.3523 psi
Split ratio: 5:1
Split flow: 4.88 mL/min
Total flow: 8.85mL/min
Liner: Split / Split less liner (ID: 4mm, single tap, with glass
wool)
Oven temp.: Initial : 60C, hold 3 min

Ramp 1 : 60C to 180C
(5C/min) Ramp 2 : 180C to
280C (30C/min)
Total run time: 30.333 min
Post time: 2 min
Post time 290 oC

temperature:
MSD Heater: 280 oC
MS: MS 5975
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Ionization mode: EI
EMV mode: Relative
Sampling Rate: 2
Threshold: 50
Group 1
Start time: 2.5 min
Ion (Dwell) : 65 (50) 77 (50) 91 (50)
105 (50) 111 (50) 112 (50)
114 (50) 125 (50) 126 (50)
128 (50) 140 (50) 146 (50)
148 (50)
Group 2
Start time: 10.0 min
Ion (Dwell) : 89 (50) 105 (50) 125 (50)
140 (50) 145 (50) 159 (50)
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160 (50) 161 (50) 162 (50)

180 (50) 182 (50) 194 (50)
196 (50)
Group 3
Ion (Dwell) : 63 (50) 103 (50) 127 (50)
SIM parameters: 139 (50) 159 (50) 162 (50)
174 (50) 193 (50) 194 (50)
195 (50) 196 (50) 197 (50)
214 (50) 216 (50) 218 (50)
Group 4
Ion (Dwell) : 103 (30) 139 (30) 159 (30)
174 (30) 193 (30) 194 (30)
195 (30) 196 (30) 197 (30)
229 (30) 242 (30) 244 (30)
246 (30) 248 (30) 250 (30)
252 (30) 262 (30) 264 (30)
282 (30) 284 (30) 286 (30)
* Start time of each SIM group is just a reference and must be

align when column cut Characteristic for GC-MS analysis for
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default setting 9.4.2
GC-MS
Substances RT, min Target Reference ions.
ion, (m/z) (m/z)
Chlorobenzene ~4.145 112 114, 77
3-Chlorotoluene ~6.65* 91 126, 128
1,3-Dichlorobenzene ~8.449 146 148, 111
Benzyl Chloride ~9.421 91 126, 65
2-Chloro-1,4- ~9.729 105 125, 140

dimethylbenzene
4-Chloro-1,2- ~10.955 105 125, 140

dimethylbenzene
2,4-Dichlorotoluene ~11.99* 125 160, 162
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1,3,5-Trichlorobenzene ~12.219 180 182, 145
4-Methylbenzylchloride ~12.580 105 125, 140
2,3-Dichlorotoluene ~13.01* 125 160, 162
3,5-Dichlorotoluene Screening 125 160, 162
α, α -Dichlorotoluene ~13.379 125 160, 162
α,α,α-Trichlorotoluene ~15.391 159 161, 89
2,4,5-Trichlorotoluene ~17.319 159 196, 194
2,3,6-Trichlorotoluene ~17.731 159 196, 194
2,3,4-Trichlorotoluene Screening 159 196, 194
1,2,4,5- ~18.47* 216 214, 218

Tetrachlorobenzene
1,2,3,5- 216 214, 218

Tetrachlorobenzene
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α,2,4-Trichlorotoluene ~19.455@ 159 161, 194
1,2- ~19.455@ 139 103,174

α,2,6-Trichlorotoluene ~19.791 159 161, 194
1,2,3,4- ~20.073 216 214, 218

Tetrachlorobenzene
α,α,α-4-Tetrachlorotoluene ~20.171 193 195, 197
2-Chloronaphthalene ~20.460 162 127, 63
1,4- ~21.303 139 103, 174

α,α,α-2-Tetrachlorotoluene ~21.881 193 195, 197
α,α,2,6-Tetrachlorotoluene ~22.674 195 193, 197
2,3,4,5-Tetrachlorotoluene Screening 195 193, 194, 230,

228
2,3,4,6,- Screening 195 193, 194, 230,

Tetrachlorotoluene 228
2,3,5,6-tetrachlorotoluene Screening 195 193, 194, 230,

228
Pentachlorobenzene ~23.648 250 248, 252
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Pentachlorotoluene ~27.331 229 264, 262
Hexachlorobenzene ~27.943 284 286, 282
Internal standard
2,4,5,6-Tetrachloro-m- ~25.713 244 246, 242

xylene
Remark: *details refer with section 9.4.9

@details refer with section 9.4.5.6.2
9.4.3 Instrumental setting for confirmation of 1,2-dichlorobenzene analysis

only (inlet at 200°C): Refer to Section 9.4.1 or 9.4.2, except setting
below inlet temperature
Inlet Temp.: 200 oC
9.4.4 Instrumental setting for confirmation of 1,2-dichlorobenzene analysis

only (inlet at 150°C): Refer to Section 9.4.1 or 9.4.2, except setting
below inlet temperature
Inlet Temp.: 150 oC
9.4.5 Qualitative and quantitative analysis

9.4.5.1 Quantification by SIM mode and Qualification by SCAN mode.
9.4.5.2 3,5-Dichlorotoluene, 2,3,4-Trichlorotoluene, 2,3,4,5-Tetrachlorotoluene,
2,3,4,6- Tetrachlorotoluene, 2,3,5,6-Tetrachlorotoluene only for
screening purpose by semi- quantitation. (9.4.7 & 9.4.8).
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9.4.5.3 Calibrate the standard with GC-MS prepared from 5.6.

9.4.5.4 Analyze the method blank, spike blank / spike sample and sample.
9.4.5.5 Qualify each COC by GCMS comparing the retention time and
characteristic masses in standard and sample. The characteristic
masses of each COC are shown in 9.4.1 (chlorobenzene and
chlorotoluene) and 9.4.2 (chlorobenzene, chlorotoluene and
chloroxylenes).
9.4.5.6 Confirm the result if following analytes is detected.
9.4.5.6.1 1,2-Dichlorobenzene, refer to Section 9.4.6
9.4.5.6.2 For any positive finding of α,2,4-Trichlorotoluene and / or 1,2-
Bis(chloromethyl)benzene, prepare the individual calibration
standards for verification as both analyte retention time merge
each other on GCMS program 9.4.2.
9.4.5.6.3 For 1,2,3-Trichlorobenzene and α,α,α-Trichlorotoluene,
9.4.5.6.4 If either one of analyte is detected by GCMS program 9.4.1,
identify the suspected peak by comparing the mass spectra of
the suspected peak with target analyte in NIST library.
9.4.5.6.5 If both of analytes are detected, confirm and quantify by GCMS
program 9.4.2, as both analyte retention time merge each other
on GCMS program 9.4.1.
9.4.5.7 Dilute the sample with 1 mg/L internal standard working solution (5.5.2)
if the concentration is out of the calibration range.
9.4.6 Confirmation of 1,2-dichlorobenzene ONLY for any positive finding of 1,2-
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dichlorobenzene in Section 9.4.5

9.4.6.1 Inject “Sample extract”, “Method blank”, “Spike blank/Sample spike”
and “Calibration curve” again by BOTH GCMS setting in 9.4.3 and
9.4.4.
- If 3 results are deviated from their average less than 30%, report
result at 250oC GC inlet.
- If 3 results are deviated from their average more than 30% AND
the result of 250°C inlet > result of 200oC inlet > result 150oC inlet,
1,2-dichlorobenzene may originated from degradation of other
chemicals (i.e. dye). Report “Not Detected”.
Remark: refer to Appendix 2 for structure of dye that may degrade in GC
inlet to give 1,2- dichlorobenzene resulting in false positive result.
9.4.7 Semi-quantitation of 2,3,4,5-Tetrachlorotoluene,
2,3,4,6-Tetrachlorotoluene and
2,3,5,6- Tetrachlorotoluene
9.4.7.1 Screen the target masses (m/z 195, 193, 194, 230 and 228) for any
suspected peak.
9.4.7.2 Compare the mass spectra of the suspected peaks with the mass
spectrum of any tetrachlorotoluene in NIST library. The matching score
should be over 80 for positive finding. Inject a series of working
standards (5.6) including α,α,α-2-Tetrachlorotoluene, α,α,α-4-
Tetrachlorotoluene and α,α,2,6-Tetrachlorotoluene into GC-MS for
confirmation of retention time.
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9.4.7.3 Compare the retention time (with reference to internal standard) of the
suspected peaks with that of α,α,α-2-Tetrachlorotoluene, α,α,α-4-
Tetrachlorotoluene and α,α,2,6- Tetrachlorotoluene. If they share the
same retention time, identify and quantify as these analytes. Otherwise,
semi-quantitate the suspected peaks by α,α,2,6-Tetrachlorotoluene.
9.4.7.4 If there are more than one such unidentified peak, integrate and semi-
quantitate the peaks separately by α,α,2,6-Tetrachlorotoluene. Sum up
the concentrations read from the calibration curve of α,α,2,6-
Tetrachlorotoluene and calculate the tetrachlorotoluenes (total mix)
content in sample (9.5.1).
9.4.8 Semi-quantitation of 3,5-Dichlorotoluene, 2,3,4-Trichlorotoluene, 2,4,6-
Trichlorotoluene,and 3,4,5- Trichlorotoluene
9.4.8.1 Screen the target masses (m/z 125, 160, 162 for 3,5-Dichlorotoluene;
m/z 159, 196 and 194 for 2,3,4-Trichlorotoluene, 2,4,6-
Trichlorotoluene,and 3,4,5-Trichlorotoluene) for any suspected peak.
9.4.8.2 Inject working standard (5.6) and compare the retention time (with
reference to internal standard) of the suspected peaks with the known
dichlorotoluenes and trichlorotoluenes. If they share the same retention
time, identify and quantify as these isomers.
9.4.8.3 Search in NIST library to compare the spectrum of the suspected peak
with the library. For positive finding, the matching score shall be over
80. Otherwise report as “Not Detected”.
9.4.8.4 Semi-quantitate 3,5-Dichlorotoluene by 2,3-/3,4-Dichlorotoluene
calibration curve; semi- quantitate 2,3,4-Trichlorotoluene, 2,4,6-
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Trichlorotoluene,and 3,4,5-Trichlorotoluene by 2,3,6-Trichlorotoluene

calibration curve.
9.4.9 Result interpretation for 2-Chlorotoluene, 3-Chlorotoluene and 4-
Chlorotoluene; 2,4-Dichlorotoluene, 2,5-Dichlorotoluene and 2,6-
Dichlorotoluene; 2,3-Dichlorotoluene and 3,4-Dichlorotoluene; 1,2,3,5-
Tetrachlorotoluene and 1,2,4,5-Tetrachlorotoluene in GCMS setting 9.4.2
- Integrate 2-Chlorotoluene, 3-Chlorotoluene and 4-Chlorotoluene as ONE peak;
- Integrate 2,4-Dichlorotoluene, 2,5-Dichlorotoluene and 2,6-Dichlorotoluene as
ONE peak;
- Integrate 2,3-Dichlorotoluene and 3,4-Dichlorotoluene as ONE peak;
- Integrate 1,2,3,5-Tetrachlorotoluene and 1,2,4,5-Tetrachlorotoluene as ONE
peak as the calibration curve prepared on 9.4.1 by grouping with above targets.
Note: Upon request, the above targets (except 2,3-Dichlorotoluene and
3,4-Dichlorotoluene) can be reported individually by a new set of
calibration standards preparation refer to preparation method in section
5.4.2 for group 2.
9.5 Calculation
CxVxDF
Each COC in sample, mg/kg =
W
Where, C = Concentration of substances read from instrument, mg/L
V = Final Volume, 1 mL
D.F. = Dilution factor
W = Sample weight, 1 g
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9.5.1 Calculation of tetrachlorotoluenes content

(for 2,3,4,5-Tetrachlorotoluene, 2,3,4,6- Tetrachlorotoluene and
2,3,5,6-Tetrachlorotoluene)
CTeCT(total) = CTeCT1 + CTeCT2 + CTeCT3 +……
Where,
CTeCT(total) = Concentration of tetrachlorotoluenes in solution, mg/L
CTeCTn = Individual concentration of unidentified tetrachlorotoluene read from
calibration
curve of α,α,2,6-Tetrachlorotoluene (mg/L),
where n represents the number of unidentified tetrachlorotoluenes
CTeCT(total) x V
Tetrachlorotoluenes in sample, mg/kg = X D.F.
W
Where,
CTeCT = Concentration of tetrachlorotoluenes in

(total) solution, mg/L
V = Final Volume,1 mL
D.F. = Dilution factor
W = Sample weight, 1 g
10 Reporting Criteria*:
10.1 Laboratory reporting limit (According to DIN 54232:2010-08)
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Substanc Laboratory Reporting

es Limit, mg/kg
2-Chlorotoluene
3-Chlorotoluene 0.1 (mix total)
4-Chlorotoluene
2,3-Dichlorotoluene 0.1 (mix total)
3,4-Dichlorotoluene
2,4-Dichlorotoluene
2,5-Dichlorotoluene 0.1 (mix total)
2,6-Dichlorotoluene
2,3,6-Trichlorotoluene 0.
1
2,4,5-Trichlorotoluene 0.
1
Pentachlorotoluene 0.1
1,2-Dichlorobenzene 0.1
1,2,3-Trichlorobenzene 0.1
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1,2,3,4-Tetrachlorobenzene 0.1
1,2,4,5-Tetrachlorobenzene 0.1 (mix total)
1,2,3,5-Tetrachlorobenzene
Pentachlorobenzene 0.1
Hexachlorobenzene 0.1
10.2 Laboratory reporting limit for other analytes (expanded scope)
Substances Laboratory Reporting

Limit, mg/kg
Chlorobenzene 0.1
α,α,α-Trichlorotoluene 0.1
α,α,α-2-Tetrachlorotoluene 0.1
α,α,α-4-Tetrachlorotoluene 0.1
α,α,2,6-Tetrachlorotoluene 0.1
3,5-Dichlorotoluene @ 0.1
2,3,4-Trichlorotoluene #
2,4,6-Trichlorotoluene # 0.1(mix total)
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3,4,5-Trichlorotoluene #
2,3,4,5-Tetrachlorotoluene *
2,3,4,6-Tetrachlorotoluene * 0.1 (mix total)
2,3,5,6-Tetrachlorotoluene *
2-Chloro-1,4-dimethylbenzene 0.1
4-Chloro-1,2-dimethylbenzene 0.1
4-methylbenzylchloride 0.1
1,2-Bis(chloromethyl)benzene 0.1
1,4-Bis(chloromethyl)benzene 0.1
α,2,6-Trichlorotoluene 0.1
Benzyl Chloride 0.1
2-Chloronaphthalene 0.1
α, α -Dichlorotoluene 0.1
@
Semi-quantitate by 2,3-/3,4 Dichlorotoluene
# Semi-quantitate by 2,3,6 Trichlorotoluene
*Semi-quantitate by α,α,2,6-Tetrachlorotoluene
10.3 Method Detection Limit (MDL):
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0.1 mg/kg of each COCs except the following combination:
2-chlorotoluene; 3-chlorotoluene & 4-chlorotoluene – report 0.1 mg/kg mix total;

2,3-diclorotoloene and 3,4-dichlorotoluene – report 0.1 mg/kg mix total;
2,4-dichlorotoluene; 2,5-dichlorotoluene & 2,6-dichlorotoluene – report 0.1 mg/kg mix total;
1,2,4,5-tetrachlorobenzene & 1,2,3,5-tetrachlorobenzene – report 0.1 mg/kg mix total
2,3,4-Trichlorotoluene, 2,4,6-Trichlorotoluene & 3,4,5-Trichlorotoluene – report 0.1 mg/kg mix total (semi-
quantitation by 2,3,6-Trichlorotoluene)
2,3,4,5-Tetrachlorotoluene, 2,3,4,6-Tetrachlorotoluene & 2,3,5,6-Tetrachlorotoluene – report 0.1 mg/kg mix
total (semi-quantitation by α,α,2,6-Tetrachlorotoluene)
10.4 Datasheet
10.1.1 The data sheet shall include the followings:
1. Unique reference no., e.g., application no., sample no., report no., etc.
2. Standard/ procedure performed
3. Sample ID
4. Sample description
5. Material, e.g. textile, polyester, leather, etc.
6. Sample weight
7. GC-MS raw data
8. Total contents in sample
9. Identity of equipment used including: balance, GC-MS, etc.
10. Identity of personnel performing the specific task and date:
i. Sample preparation
ii. Sample extraction
iii. Instrumental analysis
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iv. Calculation
v. Result checking
11 Measurement Uncertainty:
11.1 Measurement uncertainty needs to be calculated by locations themselves if necessary
12 Literature References:
12.1 DIN 54232: 2010 – Textile – Determination of the content of bonds based on
chlorobenzene and chlorotoluene
13 Modifications from Standard:
13.1 Sample size reduced to 1 g and pre-concentrate the extract into 1 mL
13.2 GC-MS program modified
13.3 More COC targets are included in DIN 54232: 2010-08 modification method (refer to
section 2.1)
14 Associated Documents:
14.1 Appendix
Appendix 1
14.2 Chromatogram of all COCs GC-MS spectrum by default program on section 9.4.1
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EIC of 2-Chlorotouluene / 3-Chlorotouluene / 4-Chlorotouluene
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EIC of 2,4-DCT / 2,5-DCT / 2,6-DCT
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EIC of 1,2,3,5-TeCB / 1,2,4,5-TeCB
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TIC of default program on section
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EIC of 2,3-/ 3,4 –Dichlorochlorotoluene
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EIC of 1.2,4,5-/ 1,2,3,5-Tetrachlorohlorotoluene
Integrate as one peak
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Appendix 2
Alternaitve GCMS program using ZB-35 column (Upon TCD approval)
(Below instrument conditions are for reference only and should be used as a guide.)
GC: Agilent 6890
Injection Volume: 1.0 µL
Plunger speed: Fast
Column: Phenomenex ZB-35, 15 m x 0.25 mm x 0.5

µm, Capillary column (Max. Temp.: 340
o
C)
Injection Mode: Split
Inlet Temp.: 250 oC
Inlet Pressure: 1.32 psi
Split ratio: 5:1
Split flow: 5.1 mL/min
Total Flow: 8.8 mL/min
Liner: Split / Splitless liner (ID: 4mm, single tap, with

glasswool)
Oven Temp.: Initial : 50C, hold 1 min
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Ramp 1 : 50C to 260C (30C/min)
Total Run Time: 8.0 min
Post temperature: 290C
Post run flow: 0.9 mL/min
Post time: 2.5 min
MSD Heater: 280 oC
MS: MS 5975
Ionization mode: EI
Relative voltage 400 V

(offset):
Sampling Rate: 2
Threshold: 50
Group 1
Start time: 1.9 min
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Ion (Dwell) : 51 (20) 63 (20) 77 (20)

91 (20) 112 (20) 114 (20)
126 (20) 128 (20)
Group 2
Start time: 3.1 min
Ion (Dwell) : 75 (20) 111 (20) 146 (20)
148 (20)
Group 3
Start time: 3.75 min
SIM parameters: Ion (Dwell): 89 (20) 125 (20) 145 (20)
159 (20) 160 (20) 161 (20)
162 (20) 180 (50) 182 (50)
196 (20)
Group 4
Ion (Dwell): 123 (20) 159 (20) 161 (20)
179 (20) 193 (20) 194 (20)
195 (20) 196 (20) 197 (20)
214 (20) 215 (20) 216 (20)
218 (20) 248 (20) 250 (20)
252 (20)
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Group 5
Ion (Dwell) : 171 (20) 191 (20) 209 (20)
229 (20) 242 (20) 244 (20)
246 (20) 249 (20) 262 (20)
264 (20) 282 (20) 284 (20)
286 (20)
Characteristics for GC-MS analysis
GC-
Substances RT, min MS
Target Reference ions.

ion, (m/z)
(m/z)
Chlorobenzene ~ 2.453 112 114, 77
3-Chlorotoluene ~ 3.128 91 126, 128
1,3-Dichlorobenzene ~ 3.498 146 148, 111
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2,5-Dichlorotoluene ~ 4.129 125 160, 162
1,3,5-Trichlorobenzene ~ 4.186 180 182, 145
2,3-Dichlorotoluene ~ 4.374 125 160, 162
α,α,α-Trichlorotoluene ~ 4.813 159 161, 89
2,4,5-Trichlorotoluene ~ 5.093 159 196, 194
2,3,6-Trichlorotoluene ~ 5.184 159 196, 194
1,2,4,5- ~ 5.272 216 214, 218

Tetrachlorobenzene
1,2,3,5- 216 214, 218

Tetrachlorobenzene
1,2,3,4- ~ 5.602 216 214, 218
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Tetrachlorobenzene
α,α,α-4-Tetrachlorotoluene ~ 5.593 193 195, 197
α,α,α-2-Tetrachlorotoluene ~ 5.947 193 195, 197
α,α,2,6-Tetrachlorotoluene ~ 6.082 195 193, 197
Pentachlorobenzene ~ 6.206 250 248, 252
Pentachlorotoluene ~ 6.850 229 264, 262
Hexachlorobenzene ~ 7.007 284 286, 282
Internal standard
2,4,5,6-Tetrachloro-m- ~6.564 244 246, 242

xylene
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Total ion chromatogram for using ZB-35 column
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Appendix 3
Flow Chart
Sample
Cut sample in to 5mm pices and

transfer to Reaction vial
Add methylene Di Chloride as

10-20 ml
Sonicate for 30 min
filter layer and inject in GC
Analyse the sample and

release the report
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TEXTILE & GARMENT INDUSTRY RESEARCH &

SOP for Analysis of Chlorinated Organic Carriers By Revision No

SOP for Analysis of Chlorinated Organic Carriers By Revision No

4. Apparatus and Equipment:

Item Compound CAS Purity Brand

5.1.1 2-Chlorotoluene 95-49-8 99.4 % Chemservice

5.1.2 3-Chlorotoluene 108 -41-8 99.0 % Dr. Ehrenstorfer

5.1.3 4-Chlorotoluene 106-43-4 98.2 % Chemservice

5.1.4 2,4-Dichlorotoluene 95-73-8 99.4 % Chemservice

5.1.5 2,5-Dichlorotoluene 19398-61-9 - Dr. Ehrenstorfer

5.1.6 2,6-Dichlorotoluene 118-69-4 99.5 % Dr. Ehrenstorfer

SOP for Analysis of Chlorinated Organic Carriers By Revision No

5.1.7 2,3-Dichlorotoluene 32768-54-0 98.5 % Chemservice

5.1.8 3,4-Dichlorotoluene 95-75-0 99.0 % Dr. Ehrenstorfer

5.1.9 1,3-Dichlorobenzene 541-73-1 - Dr. Ehrenstorfer

5.1.10 1,4-Dichlorobenzene 106-46-7 - Dr. Ehrenstorfer

5.1.11 1,2,4,5-Tetrachlorobenzene 95-94-3 99.5 % Chemservice

5.1.12 1,2,3,5-Tetrachlorobenzene 634-90-2 99.1 % Chemservice

5.1.13 2,3,6-Trichlorotoluene 2077-46-5 - -

5.1.14 2,4,5-Trichlorotoluene 6639-30-1 99.5 % Chemservice

5.1.15 Pentachlorotoluene 877-11-2 98.4 % Chemservice

5.1.16 1,2-Dichlorobenzene 95-50-1 99.3 % Chemservice

5.1.17 1,2,3-Trichlorobenzene 87-61-6 99.5 % Chemservice

5.1.18 1,2,4-Trichlorobenzene 120-82-1 99.5 % Chemservice

5.1.19 1,3,5-Trichlorobenzene 108-70-3 99.5 % Chemservice

5.1.20 1,2,3,4-Tetrachlorobenzene 634-66-2 99.8 % Chemservice

5.1.21 Pentachlorobenzene 608-93-5 99.5 % Chemservice

5.1.22 Hexachlorobenzene 118-74-1 99.5 % Chemservice

5.1.23 α, α -Dichlorotoluene 98-87-3 98.9% Chemservice

5.1.24 3,5-Dichlorotoluene 25186-47-4 - -

SOP for Analysis of Chlorinated Organic Carriers By Revision No

5.1.25 2,3,4-Trichlorotoluene 7359-72-0 - -

5.1.26 2,3,4,5-Tetrachlorotoluene 1006-32-2 - -

5.1.27 2,3,4,6-Tetrachlorotoluene 875-40-1 - -

5.1.28 Chlorobenzene 108-90-7 99.5% Chemservice

5.1.29 α,α,α-Trichlorotoluene 98-07-7 98.5% Dr. Ehrenstorfer

5.1.30 α,2,6-Trichlorotoluene 2014-83-7 99.5% Chemservice

5.1.31 α,2,4-Trichlorotoluene 94-99-5 98.6% Acros

5.1.32 α,3,4-Trichlorotoluene 102-47-6 99.5% Acros

5.1.33 α,α,α-2-Tetrachlorotoluene 2136-89-2 99.0% Dr. Ehrenstorfer

5.1.34 α,α,α-4-Tetrachlorotoluene 5216-25-1 98.5% Dr. Ehrenstorfer

5.1.35 α,α,2,6-Tetrachlorotoluene 81-19-6 99.0% Dr. Ehrenstorfer

5.1.36 2,3,5,6-Tetrachlorotoluene 1006-31-1 - -

5.1.37 2-Chloro-1,4- 95-72-7 99.6% TCI

5.1.38 4-chloro-1,2- 615-60-1 99.2% TCI

5.1.39 4-methylbenzylchloride 104-82-5 99.8% TCI

5.1.40 1,2- 612-12-4 99.6% TCI

5.1.41 1,4- 623-25-6 99.7% TCI

SOP for Analysis of Chlorinated Organic Carriers By Revision No

5.1.42 2,4,6-Trichlorotoluene 23749-65-7 - -

5.1.43 3,4,5-Trichlorotoluene 21472-86-6 - -

5.1.44 2,3,4,5-Tetrachlorotoluene 76057-12-0 - -

5.1.45 2,3,5,6-Tetrachlorotoluene 29733-70-8 - -

5.1.46 2-Chloronaphthalene 91-58-7 99.5% Chemservice

5.1.47 Benzyl Chloride 100-44-7 99.5% Chemservice

5.2 Internal standard (Dr. Ehrenstorfer or equivalent)

SOP for Analysis of Chlorinated Organic Carriers By Revision No

5.4.1.3 In each of the standard solution, transfer into a 10 mL volumetric flask

SOP for Analysis of Chlorinated Organic Carriers By Revision No

5.4.3 10 mg/L of COCs mixed working standard solutions (kept in freezer at 4

SOP for Analysis of Chlorinated Organic Carriers By Revision No

Vol. of 10 Vol. of 10 Final Final conc. Final conc.

1 0.1 0.1 1 0.1 0.1