Analysing EDB, 123-TCP, and DBCP in Drinking Water

Numerous laboratories use USEPA Method 504.1 or USEPA 8011 to analyze 1,2-Dibromo-3-chloropropane (DBCP), 1,2,3-Trichloropropane (123-TCP), and 1,2-Dibromoethane (EDB) in drinking water.

These methods involve a micro-extraction step and analysis with dual column gas chromatography with dual electron capture detectors. USEPA Method 524.3 can also be applied to analyze these compounds using purge and trap sample concentration followed by gas chromatographic separation with selective ion monitoring (SIM) and mass spectrometric detection (GC/MS). This is a simpler approach as it removes the need for sample preparation and also provides the benefit of mass spec selectivity while producing equivalent, if not better reporting limits than the GC/ECD method.

Numerous laboratories use USEPA Method 504.1 or USEPA 8011 to analyze 1,2-Dibromo-3-chloropropane (DBCP), 1,2,3-Trichloropropane (123-TCP), and 1,2-Dibromoethane (EDB) in drinking water.

Methodology

Method 524.3 was followed using the conditions and instrumentation listed below. Next, a seven-point calibration from 20 ppt to 2000 ppt was run. Initial demonstrations of capability (IDC) were run by analyzing seven replicates of 100 ppt and 250 ppt standard. Seven replicates at 20 ppt were then examined to establish the half range for the prediction interval of results (HRPIR). All QC samples and standards were prepared using the maleic acid/ascorbic acid preservative needed by the method.

Table 1. Instrument Confi guration and Operating Conditions

Purge-and-Trap Eclipse 4760 P & T Sample Concentrator
Trap #10 trap; Tenax® / Silica gel / CMS
Purge Gas Zero grade Helium at 45 mL/min
Purge Time 10 min
Sparge Mount Temperature 45 °C
Sample Temperature (purge) 45 °C
Sample Temperature (bake) 45 °C
Desorb Time 0.5 min
Bake Time 4 min
OI #10 Trap Temperature Ambient during purge
180 °C during desorb pre-heat
190 °C during desorb
210 °C during bake
Water Management 120 °C during purge
Ambient during desorb
240 °C during bake
Transfer Line Temperature 140 °C
Six-port Valve Temperature 140 °C

Autosampler 4100 Water/Soil Sample Processor
System Gas Zero grade nitrogen
Purge Gas Zero grade helium
LV20 Pressure 8.0 psi
Loop-based Time Settings Default
Rinse Water 80 °C
Soil Sample Transfer 150 °C
Soil Oven 150 °C
Soil Lift Station 45 °C

4100 Sample Processor Methods
Sample Type Waters Only Blanks Only
Vial Cap Color Blue Green
Needle Rinses 1 0
SAM A (µL) 5 5
SAM B (µL) 0 0
SAM C (µL) 0 0
SAM D (µL) 0 0
Purge Time (min) 10.0 10.0
Desorb Time (min) 0.5 0.5
P&T Rinses 3 0
Rinse Water Hot Hot
Water Stir Time (min) 0.0
Water Settle Time (sec) 0
Soil Add Water to Vial (#loops)
Soil Pre-Heat Stir
Soil Pre-Heat/Purge Temp (°C)
Soil Stir During Purge

Gas Chromatograph Agilent 7890A
Column Restek Rtx-VMS
20 meter, 0.18 mm ID, 1.0 pm film
Carrier Gas Zero grade helium
Inlet Temperature 250 °C
Inlet Liner Agilent Ultra Inert, 1 mm straight taper
Column Flow Rate 0.6 mL/min
Split Ratio 30:1
Oven Program Hold at 40 °C for 1 min
18 °C/minute to 180 °C
40 °C/minute to 220 °C
Hold at 220 °C for 3 min
Total GC Run is 12.78 min

Mass Spectrometer Agilent 5975C
Mode SIM 100 msec dwell time
SIM Compounds
Group 1 1,2-Dibromoethane m/z 107,109
Group 2 Chlorobenzene-d5 m/z 82,117,119
Group 3 4-Bromofl uorobenzene m/z 95,174,176
Group 4 1,2-3-Trichloropropane m/z 75,77,100
Group 5 1,4-Dichlorobenzene-d4 m/z 115,150,152
Group 6 1,2-Dichlorbenzene-d4 m/z 115,150,152
Group 7 1,2-Dibromo-3-Chloropropane m/z 75,155,157
Scans/Second 5.19
Solvent Delay 1.4 min
Transfer Line Temperature 250 °C
Source Temperature 300 °C
Quadrupole Temperature 200 °C
Draw Out Plate 6 mm

Results and Discussion

Table 2 through 6 show the calibration data and the USEPA Method 524.3 Quality Control data. It is essential to validate the calibration by determining the analytes concentration for each of the points used to create the curve using the regression equations.

Table 2. Calibration Data

Analyte Compound Avg RF % RSD
1 Chlorobenzene-d5 (IS) N/A N/A
2 1,2-Dibromoethane 0.340 4.15
3 1,4-Dichlorobenzene-d4 (IS) N/A N/A
4 4-Bromofl uorobenzene (SS) 0.796 1.82
5 1,2,3-Trichloropropane 0.783 4.02
6 1,2-Dichlorobenzene-d4 (SS) 1.011 3.19
7 1,2-Dibromo-3-chloropropane 0.210 15.62

Table 3. Calibration Acceptance and Validation - 5 mL of 524.3 Standard

[Results Signal 1] 20 ppt
Std
20 ppt
% Rec
50 ppt
Std
50 ppt
% Rec
100 ppt
Std
100 ppt
% Rec
250 ppt
Std
250 ppt
% Rec
500 ppt
Std
500 ppt
Std
1000 ppt
Std
1000 ppt
% Rec
2000 ppt
Std
2000 ppt
% Rec
Chlorobenzene-d5 (IS) 500 100% 500 100% 500 100% 500 100% 500 100% 500 100% 500 100%
1,2-Dibromo-ethane 22.12 111% 55.36 111% 106.70 106% 272.89 109% 523.82 105% 1027.31 103% 1976.83 99%
1,4-Dichloro-benzene-d4 (IS) 500 100% 500 100% 500 100% 500 100% 500 100% 500 100% 500 100%
4-Bromofl uoro-benzene (SS) 498.29 100% 495.99 99% 492.50 99% 493 99% 494.24 99% 513.75 103% 512.23 102%
1,2,3-Trichloro-propane 21.91 110% 55.88 112% 104.63 105% 270.33 108% 515.01 103% 1022.98 102% 1981.82 99%
1,2-Dichloro-benzene-d4 (SS) 507.62 102% 497.94 100% 493.47 99% 498.87 100% 501.48 100% 500.97 100% 499.64 100%
1,2-Dibromo-3-chloropropane 21.61 108% 60.02 120% 106.29 106% 271.18 108% 517.04 103% 1029.68 103% 1977.67 99%

Table 4. Initial Demonstration of Capability at 100 ppt

100 ppt IDC 1 IDC 2 IDC 3 IDC 4 IDC 5 IDC 6 IDC 7 Precision
% RSD
<= 20%
Accuracy
% Recovery
+ - 20%
Chlorobenzene-d5 (IS) 500 500 500 500 500 500 500 N/A 100.00
1,2-Dibromoethane 101.99 107.32 104.85 105.05 104.78 103.67 106.75 1.71 104.92
1,4-Dichlorobenzene-d4 (IS) 500 500 500 500 500 500 500 N/A 100.00
4-Bromofl uorobenzene (SS) 504.76 495.08 499.53 496.20 496.45 501.74 501.78 0.72 99.87
1,2,3-Trichloropropane 101.32 106.91 105.83 106.21 106.04 105.8 107.82 1.95 105.70
1,2-Dichlorobenzene-d4 (SS) 496.66 505.69 508.38 506.60 515.47 512.23 510.79 1.19 101.59
1,2-Dibromo-3-chloropropane 111.68 106.24 103.11 100.32 100.82 97.36 98.10 4.91 102.52

Table 5. Initial Demonstration of Capability at 250 ppt

250 ppt IDC 1 IDC 2 IDC 3 IDC 4 IDC 5 IDC 6 IDC 7 Precision
% RSD
<= 20%
Accuracy
% Recovery
+ - 20%
Chlorobenzene-d5 (IS) 500 500 500 500 500 500 500 N/A 100.00
1,2-Dibromoethane 270.31 273.31 279.05 277.28 274.09 270.32 268 1.46 109.28
1,4-Dichlorobenzene-d4 (IS) 500 500 500 500 500 500 500 N/A 100.00
4-Bromofl uorobenzene (SS) 494.02 499.7 496.26 495.66 504.14 496.54 501.51 0.73 99.65
1,2,3-Trichloropropane 270.27 276.10 282.09 276.90 281.39 271.80 273.69 1.64 110.41
1,2-Dichlorobenzene-d4 (SS) 517.41 511.79 517.66 513.69 522.48 522.66 522.64 0.86 103.67
1,2-Dibromo-3-chloropropane 263.33 260.60 279.67 261.18 268.73 265.01 253.61 3.06 105.84

Table 6. Minimum Reporting Level (MRL) Confirmation

20 ppt PIR 1 PIR 2 PIR 3 PIR 4 PIR 5 PIR 6 PIR 7 Mean STD DEV HRPIR (4.0 ppt = True Value)
Upper PIR Limit
<= 150%
Lower PIR Limit
>= 50%
Chlorobenzene-d5 (IS) 500 500 500 500 500 500 500 N/A N/A N/A N/A N/A
1,2-Dibromoethane 22.87 22.51 22.10 22.22 22.20 21.95 22.86 22.39 0.37 1.45 119.21 104.66
1,4-Dichlorobenzene-d4 (IS) 500 500 500 500 500 500 500 N/A N/A N/A N/A N/A
4-Bromofl uorobenzene (SS) 509.84 498.94 504.58 498.39 502.51 511.53 505.63 504.49 5.02 19.91 104.88 96.92
1,2,3-Trichloropropane 21.63 21.88 21.81 21.90 22.28 22.33 21.59 21.92 0.29 1.15 115.33 103.84
1,2-Dichlorobenzene-d4 (SS) 481.10 496.06 506.4 498.39 511 510.32 497.02 500.04 10.43 41.33 108.27 91.74
1,2-Dibromo-3-chloropropane 23.19 22.28 20.81 21.01 20.98 21.14 23.53 21.85 1.14 4.53 131.91 86.58

250 ppt Standard

Figure 1. 250 ppt Standard

Conclusions

Analysis of EDB, 123-TCP, and DBCP by Method 524.3 using GC/MS SIM provides a rapid, accurate alternative to Method 8011 and 504.1 and also meets the low reporting levels easily. Since the preservative for this method can accumulate in the purge and trap, care should be taken to run cleaning blanks, rinsing the sparger between samples, and intermittently washing the sample pathway.

References

USEPA Method 524.3 Measurement of Purgeable Organic Compounds in Water by Capillary Column Gas Chromatography/Mass Spectrometry, Version 1.0 June 2009

USEPA Method 504.1 1,2-Dibromoethane (EDB), 1,2-Dibromo-3-chloro-propane (DBCP), and 1,2,3-Trichloropropane (123TCP) in Water by Microextraction and Gas Chromatography, Revision 1.1 Edited 1995

USEPA Method 8011 1,2-Dibromoethane and 1,2-Dibromo-3-Chloropropane by Microextraction and Gas Chromatography, Revision 0 July 1992

This information has been sourced, reviewed and adapted from materials provided by OI Analytical.

For more information on this source, please visit OI Analytical.

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