#208

Analysis of Volatile Organic Compounds

in Soil Sample by EPA Method 8260 using CDS 7000C
Dynamic Headspace Module

Application Note
Environmental

Author: Abstract
The CDS 7000C is the industry’s first Purge and Trap concentrator seamlessly
Xiaohui Xang integrated with the PAL system. This application note demonstrated the analytical
performance of the Dynamic Headspace Module as an option in the CDS 7000C
purge and trap system, by following the soil sample testing scheme defined in the
EPA Method 8260.

Introduction
Purge and Trap technique was first brought up in the 60s by Zlatkis et al in response
to the Clean Water Act. This technique still remains today as the most sensitive
method in extracting and concentrating volatile organic compounds (VOC) from
liquids and solids to Gas Chromatograph (GC). The modern Purge and Trap
process involves purging the sample with an inert gas in a sealed environment
(sparge vessel) at the appropriate temperature. The gas going through the sample
will establish thermal equilibrium with VOCs in the sample, therefore transferring
the VOCs from an aqueous state to a vapor. After eliminating the moisture through
the wet trap, the gas is then swept to an analytical trap that absorbs and retains the
VOCs, where they are transferred to the GC/MS for separation and quantification.

United States Environmental Protection Agency (USEPA) developed a series of

methods (500 family and 600 family), which focus on using the Purge and Trap
technique in VOC testing. These methods evolved and were integrated into a gen-
eral method 8260 to cover both water and soil samples. To accommodate the EPA
methods and automate the process, CDS Analytical launched the industry’s first
microprocessor-controlled Purge and Trap concentrator in 1980. The most recent
breakthrough is the highly efficient CDS 7000C concentrator that is integrated to the
PAL System. The previous application note demonstrated the 7000C’s analytical
performance in the water sample, where the CDS proprietary X type trap improved
the Relative Response Factor (RRF) by an average of 30%.

In this application note, we continue to demonstrate the analytical performance of

this setup in soil sample through the Dynamic Headspace Module, which is also
seamlessly integrated to the PAL system. Dynamic Headspace sampling was first
described by Teranishi et al, which has close tie to the Purge and Trap technique.
These two techniques are similar to each other, and work on the same physics
principle as direct thermal volatilization of analytes. The difference is where the
thermal equilibrium was established.
7000C Dynamic Headspace Module
Experimental Setup

Instrument

The 7000C Dynamic Headspace Module has a maximum temperature of 300 °C

with user settable needle height. A sample stirring mechanism could be activated
at user-selectable speed in compliance with 8260 soil method. The soil sample
is stored in a 20 mL headspace vial with a pre-loaded magnetic bar and then
able 1: Purge and Trap Method Parameters (Soil Mode)
Purge and Trap Model 7000C-Headspace-CTC PAL transferred to the Dynamic Headspace Module by the PAL’s
RTC magnetic dilutor tool. The sample is then filled with fixed amount
Trap Type X
Purge Gas (He or N2) He
(10 mL) of distilled water and heated to setting temperature. After
Headspace Parameters: the thermal equilibrium is reached, the purging step begins to
Valve Oven Temperature 180 °C bring VOC from the sample matric to the 7000C concentrator as
Transfer Line Temperature 180 °C
Vial Station Temperature 40 °C
shown in Figure 1. The 7000C parameters for this application are
Stirrer Power Output 40% shown in Table 1, For the separation and detection stage, a Shi-
Purge Parameters: madzu 2010/ QP 2010 GCMS was used. The GCMS parameters
Valve Oven Temperature 130 °C
Transfer Line Temperature 130 °C
are shown in Table 2.
Pre-purge warmup 1 min
Standby Flow 10 mL/min Internal Standard
Trap Ready Temperature 35 °C
Wet Trap Ready Temperature 45 °C
Purge Time 11 min The internal standard was prepared from a 3 component 8260
Purge Flow 40 mL/min internal standard stock mix (Supelco #CRM861183), and further
Purge Temperature 40 °C
Dry Purge Time 2 min diluted to 125 mg/L concentration. Around 5 mL of such diluted
Dry Purge Flow 200 mL/min internal standard was added to the Internal Standard Module of
Dry purge Temperature 35 °C 7000C. In the soil mode, each sample vial has 5 mL of deion-
Foam Sensor On
Desorb Parameters: ized water to simulate the sample. The internal standard was
Over Flow Sensor On first loaded with a fixed volume of 2 μL to a high precision valve
Desorb Preheat Temperature 245 °C groove. Then 5 mL of deionized water flushed the groove to bring
GC Start Signal Desorb
Desorb Time 6 min all the 2 μL internal standard into the sample vial. This procedure
Desorb Drain Flow 250 mL/min is compliant with EPA Method 5035. The final concentration of
Desorb Temperature 250 °C the internal standard in the sample is 25 μg/L and the final vol-
Bake Parameters:
Bake Time 4 min ume of the sample reached 10 mL.
Bake and Vessel Flow @MFC 300 mL/min
Trap Bake Temperature 260 °C Automated Calibration
Wet Trap Bake Temperature 260 °C
Table 1. Purge and Trap Method Parameters (Soil Mode). The 7000C system featured automated calibration with external
calibration standard diluted by a preset method, where two stock
Table 2: GC/MS Conditions
solutions at different concentration were diluted into 6 external
Gas Chromatograph: Shimadzu GC 2010 calibration standards, ranging from 1 to 200 μg/L as shown in
Analytical Column: Rtx-VMS (30 m x 0.25 mm x 1.40 µm)
Injector Temperature: 135 °C
Table 3.
Carrier Gas: Helium @ 1.0 mL/min
Split Ratio: 40:1
Oven Program: Rate Temperature Hold Time The external calibration standard was prepared from a 50 com-
5 °C/min
35 °C
90 °C
4 min
0
ponent 8260 calibration mix (Supelco #500607) and a 6 com-
12 °C/min 150 °C 0 ponent 502.2 calibration gas mix (Supelco #47408). Two stock
30 °C/min 220 °C 2.67 min
Mass Spectrometer: Shimadzu GCMS-QP 2010 external standards were diluted to 400 μg/L and 20 μg/L respec-
GC Transfer Line Temperature:
Ion Source Temperature:
220 °C
200 °C
tively and added to two separate 20 mL headspace vials.
Function Type: Full Scan
Solvent Delay: 1.0 min
Scan Range: m/z 35-260
Scan Time: 0.3 sec VOC to the 7000C
Scan Speed: 833 concentrator

Table 2. GC/MS Conditions. Inert gas flow to

purge the sample

Table 3: Automated External Calibration Standard Preparation

Calibration Level Concentration
(µg/L)
1 1.0
2 3.0
3 10.0
4 20.0
5 60.0
6 200.0
Preparation Method
Auto dilution from 20 μg/L stock standard Heating block
Auto dilution from 20 μg/L stock standard Magnetic
Auto dilution from 20 μg/L stock standard
Auto dilution from 400 μg/L stock standard
Stirrer
Auto dilution from 400 μg/L stock standard
Auto dilution from 400 μg/L stock standard

Table 3. Automated External Calibration Standard Preparation. Figure 1. Sample purged in vial station of the 7000C Dynamic
Headspace Module.
 Benzene, 1,2,4-trimethyl- 0.124 3.70 2.839 9.41 0.11
Sec-Butylbenzene 0.189 5.79 3.407 9.86 0.10
p-Isopropyltoluene 0.168 5.30 2.707 10.08 0.15
Benzene, 1,3-dichloro- 0.214 6.37 1.601 7.71 0.11
1,4-Dichlorobenzene-d4 (IS) - - - - -
Results and Discussion
Benzene, 1,4-dichloro- 0.201 5.56 1.644 8.21 0.12
Benzene, butyl- 0.173 5.46 2.375 8.97 0.28 The Total Ion Chromatogram (TIC) of a 20 μg/L external cali-
Benzene, 1,2-dichloro- 0.158 4.62 1.484 6.45 0.09 bration standard mixed with internal standard and surrogates is
Propane, 1,2-dibromo-3- shown in Figure 2. From the chromatogram, all the analytes are
chloro- 0.221 6.68 0.190 7.17 0.36
Hexachlorobutadiene 0.149 5.53 0.386 12.29 0.68
adequately resolved.
Benzene, 1,2,4-trichloro- 0.146 5.18 0.888 10.29 0.32
Naphthalene 0.053 1.83 2.721 6.93 0.24 The Internal Standard Module delivered 2 µL of the pre-mixed
Benzene, 1,2,3-trichloro- 0.152 5.40 0.827 9.53 0.26 internal standard solution to each soil sample along with 5 mL
of deionized water. The reproducibility data are summarized in
Table 4. The RDS ≤ 3.0% in soil mode is observed. Figure 3 is
Figure
FigureFigure 2. TIC2.
3. Overlap TIC
of of of 1,4-Dichlorobenzene-d4
theeight the
external external
calibration standardcalibration
(20 μg/L)runs standard
mixedfrom (20
the internal
with surrogates μg/L)
standard
and internal module.the
standards Thetime-shifted
retention overlap of 8 1,4-Dichlorobenzene-d4 runs using
time of each peak has been shifted 1.2 seconds to show the consistency of the peak shape. the internal standard module.
mixed with surrogates and internal standards.

Table 5 shows the results for Method Detection Limits (MDL),

Table 4: Internal Standard Module Reproducibility (n=8) Percent Relative Standard Deviation (% RSD) of the initial cal-
Internal Standard Benzene, fluoro- Chlorobenzene-d5 1 ,4-Dichlorobenzene-d4 ibration, Average Relative Response Factors (Avg RRF), along
RSD (%) 1.889 2.868 3.027
with RRF % RSD and Carryover. All analytes exceed the EPA
8260C method requirements. MDL were determined by analyz-
ing eleven replicate samples at a concentration of 1.0 μg/L. Most
target compounds had carryover <0.4%

Conclusion
Figure 3.ofOverlap
Figure 2. TIC of eightstandard
the external calibration 1,4-Dichlorobenzene-d4 runs
(20 μg/L) mixed with surrogates and from
internal the
standards
internal standard module. The retention time of each peak has The analytical performance of the 7000C Dynamic Headspace
been shifted 1.2 seconds to show the consistency of the peak Module easily meets and exceeds the EPA Method 8260C in soil
shape. sample over a concentration range from 1 μg/L to 200 μg/L with
Table 4: Internal Standard Module Reproducibility (n=8) excellent MDLs. The high sample capacity and fully automated
Internal Standard Benzene, fluoro- Chlorobenzene-d5 1 ,4-Dichlorobenzene-d4 calibration method provides a valuable tool for high throughput
RSD (%) 1.889 2.868 3.027
studies. The CDS proprietary Type X trap proves to be the opti-
Table 4. Internal Standard Module Reproducibility (n=8). mal choice to achieve excellent analytical performance.

Average RRF
MDL Replicate Carryover
Compound RRF RSD
(μg/L) RSD (%) (%)
(1-200 μg/L) (%)
Dichlorodifluoromethane 0.273 5.85 0.172 7.39 0.16
Methane, chloro- 0.153 3.17 0.357 7.22 0.08
Vinyl chloride 0.149 3.44 0.336 7.08 0.08
Methane, bromo- 0.114 5.40 0.096 13.16 0.00
Ethyl Chloride 0.286 6.24 0.240 6.23 0.00
Trichloromonofluoromethane 0.185 3.98 0.296 10.73 0.00
Ethene, 1,1-dichloro- 0.180 6.42 0.186 13.56 0.00
Methylene Chloride 0.159 4.51 0.253 5.69 0.00
Ethene, 1,2-dichloro-, (trans)- 0.176 6.33 0.237 13.95 0.00
Ethane, 1,1-dichloro- 0.130 4.65 0.311 16.65 0.00
Ethene, 1,2-dichloro-, (cis)- 0.084 2.77 0.253 15.95 0.00
Propane, 2,2-dichloro- 0.093 4.01 0.187 16.39 0.00
Methane, bromochloro- 0.191 5.54 0.172 4.18 0.00
Trichloromethane 0.180 5.71 0.322 7.45 0.03
Carbon Tetrachloride
Table 5. MDL, initial calibration,0.153 4.84results (continued
and carryover 0.155 on the12.54 0.00
following page).
Ethane, 1,1,1-trichloro- 0.224 7.73 0.228 13.55 0.00
Dibromofluoromethane (Surr) 0.263 7.93 0.150 5.97 -
1-Propene, 1,1-dichloro- 0.139 4.37 0.252 12.39 0.00
 Ethane, 1,1-dichloro- 0.130 4.65 0.311 16.65 0.00
Ethene, 1,2-dichloro-, (cis)- 0.084 2.77 0.253 15.95 0.00
Propane, 2,2-dichloro- 0.093 4.01 0.187
Average 16.39
RRF 0.00
MDL Replicate Carryover
Methane,Compound
bromochloro- 0.191 5.54 0.172
RRF 4.18
RSD 0.00
(μg/L) RSD (%) (%)
Trichloromethane 0.180 5.71 (1-200 μg/L)
0.322 (%)
7.45 0.03
Dichlorodifluoromethane
Carbon Tetrachloride 0.273
0.153 5.85
4.84 0.172
0.155 7.39
12.54 0.16
0.00
Methane,
Ethane, chloro-
1,1,1-trichloro- 0.153
0.224 3.17
7.73 0.357
0.228 7.22
13.55 0.08
0.00
Vinyl chloride
Dibromofluoromethane (Surr) 0.149
0.263 3.44
7.93 0.336
0.150 7.08
5.97 0.08
-
Methane, bromo-
1-Propene, 1,1-dichloro- 0.114
0.139 5.40
4.37 0.096
0.252 13.16
12.39 0.00
Ethyl Chloride
Benzene 0.286
0.151 6.24
4.38 0.240
0.904 6.23
7.33 0.00
Trichloromonofluoromethane
1,2-Dichloroethane-d4 (Surr) 0.185
0.246 3.98
6.85 0.296
0.147 10.73
3.11 0.00
-
Ethene, 1,2-dichloro-
Ethane, 1,1-dichloro- 0.180
0.112 6.42
3.41 0.186
0.210 13.56
5.09 0.00
Methylenefluoro-
Benzene, Chloride
(IS) 0.159
- 4.51
- 0.253
- 5.69
- 0.00
-
Ethene, 1,2-dichloro-, (trans)-
Trichloroethylene 0.176
0.196 6.33
6.06 0.237
0.239 13.95
9.10 0.00
Ethane, 1,1-dichloro-
Methane, dibromo- 0.130
0.127 4.65
3.92 0.311
0.110 16.65
4.40 0.00
0.34
Ethene, 1,2-dichloro-,
Propane, 1,2-dichloro-(cis)- 0.084
0.177 2.77
5.90 0.253
0.222 15.95
5.81 0.00
Propane,
Methane,2,2-dichloro-
bromodichloro- 0.093
0.237 4.01
8.14 0.187
0.227 16.39
6.58 0.00
Methane,
Toluene-D8 bromochloro-
(Surr) 0.191
0.212 5.54
6.18 0.172
1.032 4.18
9.20 0.00
-
Trichloromethane
Toluene 0.180
0.106 5.71
3.00 0.322
1.430 7.45
8.90 0.03
0.00
m,p-Xylene 0.185 5.22 2.431 10.54 0.00
Carbon Tetrachloride
Tetrachloroethylene 0.153
0.179 4.84
5.21 0.155
0.318 12.54
11.33 0.00
o-Xylene 0.142 4.17 1.208 9.57 0.04
1,1,1-trichloro-
Ethane, 1,1,2-trichloro- 0.224
0.213 7.73
6.48 0.228
0.277 13.55
4.85 0.00
Bromoform 0.206 8.51 0.154 7.65 0.00
Dibromofluoromethane
Methane, dibromochloro-(Surr) 0.263
0.179 7.93
6.30 0.150
0.251 5.97
6.67 -
0.00
Styrene 0.148 4.94 0.926 10.89 0.11
1-Propene,
Propane, 1,1-dichloro-
1,3-dichloro- 0.139
0.096 4.37
2.90 0.252
0.488 12.39
5.02 0.00
Cumene 0.138 4.20 1.508 11.44 0.09
Benzene
Ethane, 1,2-dibromo-
Benzene, 1-bromo-4-fluoro- 0.151
0.125 4.38
4.05 0.904
0.256 7.33
5.71 0.00
1,2-Dichloroethane-d4
Chlorobenzene-d5 (IS) (Surr)
(Surr) 0.246
-
0.140 6.85
-
3.91 0.147
-
0.891 3.11
-
7.04 --
Ethane, 1,2-dichloro-
Benzene, chloro-
bromo- 0.112
0.175
0.196 3.41
5.43
5.76 0.210
0.974
1.293 5.09
7.60
7.09 0.00
0.06
0.00
Benzene, fluoro- (IS)
Ethylbenzene
Benzene, propyl- -
0.148
0.134 -
4.30
4.03 -
1.516
3.757 -
10.34
9.51 -
0.02
0.11
Trichloroethylene
1,1,1,2-Tetrachloroethane
Ethane, 1,1,2,2-tetrachloro- 0.196
0.209
0.123 6.06
7.27
3.87 0.239
0.295
0.850 9.10
7.11
4.58 0.00
0.00
Methane, dibromo-
2-Chlorotoluene 0.127
0.164 3.92
4.72 0.110
2.316 4.40
7.07 0.34
0.11
Propane, 1,2-dichloro-
1,2,3-Trichloropropane 0.177
0.116 5.90
3.37 0.222
0.661 5.81
5.80 0.00
0.00
Methane,1,3,5-trimethyl-
Benzene, bromodichloro- 0.237
0.173 8.14
5.17 0.227
2.855 6.58
9.64 0.00
0.11
Toluene-D8 (Surr)
4-Chlorotoluene 0.212
0.181 6.18
5.36 1.032
2.379 9.20
7.80 -
0.12
Toluene tert-butyl-
Benzene, 0.106
0.187 3.00
5.89 1.430
2.309 8.90
9.32 0.00
0.06
Tetrachloroethylene
Benzene, 1,2,4-trimethyl- 0.179
0.124 5.21
3.70 0.318
2.839 11.33
9.41 0.00
0.11
Ethane, 1,1,2-trichloro-
Sec-Butylbenzene 0.213
0.189 6.48
5.79 0.277
3.407 4.85
9.86 0.00
0.10
Methane, dibromochloro-
p-Isopropyltoluene 0.179
0.168 6.30
5.30 0.251
2.707 6.67
10.08 0.00
0.15
Propane, 1,3-dichloro-
Benzene, 1,3-dichloro- 0.096
0.214 2.90
6.37 0.488
1.601 5.02
7.71 0.00
0.11
Ethane, 1,2-dibromo- (IS)
1,4-Dichlorobenzene-d4 0.125
- 4.05
- 0.256
- 5.71
- 0.00
-
Chlorobenzene-d5
Benzene, (IS)
1,4-dichloro- -
0.201 -
5.56 -
1.644 -
8.21 -
0.12
Benzene, butyl-
Benzene, chloro- 0.175
0.173 5.43
5.46 0.974
2.375 7.60
8.97 0.06
0.28
Ethylbenzene
Benzene, 1,2-dichloro- 0.148
0.158 4.30
4.62 1.516
1.484 10.34
6.45 0.02
0.09
1,1,1,2-Tetrachloroethane
Propane, 1,2-dibromo-3- 0.209 7.27 0.295 7.11 0.00
chloro- 0.221 6.68 0.190 7.17 0.36
Hexachlorobutadiene 0.149 5.53 0.386 12.29 0.68
Benzene, 1,2,4-trichloro- 0.146 5.18 0.888 10.29 0.32
Naphthalene 0.053 1.83 2.721 6.93 0.24
Benzene, 1,2,3-trichloro- 0.152 5.40 0.827 9.53 0.26
Table 5. MDL, initial calibration, and carryover results, cont’d.

Figure 3. Overlap of eight 1,4-Dichlorobenzene-d4 runs from the internal standard module. The retention