SAP Addendum for Subsurface Soil Boring Activities DO 5084

SAP Addendum Specific to Field Sampling Plan for Subsurface Soil Boring Activities at AOC-65 and AOC-67 under AETC DO 5084

Appendix A - Examples of Field Log Forms

There are no new forms for activities described in this Sampling and Analysis Plan Addendum.

Appendix B - Analytical Methods

Approved By: Scott Schroeder, Laboratory Manager	Date:___________
Approved By: John DuPont, Quality Assurance Manager	Date:___________

__________________________________________________________

Record of Review/Revision

Review Codes

0 - REVIEW - No change required

1 - REVIEW - With revisions

2 - Modification of SOP - With approvals

Scope and Applications

1.1

Method 8021B is modified by DHL Analytical's mobile laboratory to determine aromatic and halogenated volatile organic compounds in soil vapor matrix.

1.2

This method is limited to use as a screening method only.

Summary

2.1

This method is used for the determination of gaseous aromatic and halogenated volatile compound including BTEX (Benzene, Toluene, Ethylbenzene, Xylenes) and halogenated VOCs (Tetrachloroethene, Trichloroethene, cis-1,2-Dichloroethene, trans-1,2-Dichloroethene, and Vinyl Chloride) in soil vapor samples. A Purge and Trap connected to a gas chromatograph equipped with a photo-ionization detector (PID) and a Hall Electrolytic Conductivity Detector (HECD) in series is used to analyze samples. A Tekmar 2000 purge and trap concentrator is used to enrich these compounds to achieve low detection limits.

2.2

Samples and gas standards shall be at the same temperature when analyzed to avoid results differing due to temperature change. All standards and samples are warmed to slightly above ambient temperatures (40 � 5� C) in an oven. This prevents surface adsorption of xylenes and ethylbenzene and maintains equal air density for standards and samples.

2.3

The PID detector is always considered the "primary" detector and the HECD detector is considered the "secondary" detector. The QC must pass for all compounds on the PID detector. The QC criteria in this SOP do no apply to the HECD detector. The HECD detector is used to confirm the presence of halogenated VOCs above the reporting limit. No confirmation is performed for BTEX. If the HECD detector does not confirm the presence of a halogenated compound which the PID detector identified, then the compound identification by the PID is considered faulty and the compound is reported as not detected.

Interferences

3.1

Interference due to carryover contamination can occur whenever high-concentration and low-concentration samples are sequentially analyzed. To reduce carryover, the sample syringe must be triple-cleaned between samples with zero air. Whenever an unusually concentrated sample is encountered (such as super saturated peaks), it should be followed by the analysis of zero air to check for any possible cross contamination.

3.2

The change of ambient temperature in the mobile lab can adversely affect the surface adsorption, particularly for higher boiling point compounds such as PCE, ethylbenzene, and xylenes. Therefore, to minimize these effects, it is necessary to maintain both the samples and the un-pressurized gaseous standards at a constant temperature. The minimization of contacting cold surfaces is important. Therefore, the use of an unheated Tekmar 2016 is not recommended for this method.

Apparatus and Materials

4.1

Gas Chromatograph System:

4.1.1

Gas Chromatograph: Shimadzu GC-14A

4.1.2

Primary Column: DB-624 (3 um), 75 meters, 0.53 mm id megabore (No secondary column is used.)

4.1.3

Detector: HNU PID detector with 10.2 eV lamp.

4.1.4

Detector: Hall Electrolytic Conductivity detector.

4.1.5

Purge and Trap Concentrator: A Tekmar 2000 purge and trap concentrator equipped with a 2-way valve for sample introduction

4.1.6

Calibrated 1-liter dilution bottles (Supelco)

4.1.7

Oven (maintained @ 40� C�5� C)

4.2

Syringes: 10.0 ul and 100 uL Hamilton syringes and SGE 2.5 ml and 10.0 ml gas-tight syringe with luer-lok tips and Teflon plungers.

4.3

Concentrator Trap: K trap (Supelco)

4.4

Reagants: All chemicals should be stored away from possible contamination sources.

4.4.1

Gas: Ultra High Purity (UHP) grade Hydrogen and zero-air.

4.4.2

Methanol: Purge and Trap Grade

4.4.3

Standards: All neat liquid standards are obtained from Chem Services. The vinyl chloride gaseous standard (1000 ppmV, or 2,550ug/L) is obtained from Scott Specialty Gases.

4.4.4

A mixed neat liquid standard containing trans-1,2-DCE, cis-1,2-DCE, TCE, PCE, and BTEX is prepared as follows using a 100uL syringe:

Compounds Amount used (uL)

Trans-1,2-DCE 80

Cis-1,2-DCE 78

TCE 68

PCE 60

Benzene 114

Toluene 115

Ethylbenzene 115

m-Xylene 114

o-Xylene 114

4.4.4.1

The syringe is thoroughly rinsed with methanol in between standards.

4.4.4.2

P-Xylene is not used because it has the same retention time as m-Xylene.

4.4.4.3

This mixture is assigned a DHL Lot# (VAyymmdd) in the LIMS (laboratory information management system) for future reference.

4.4.4.4

This mixture will give equal weight ratio for each compound within a unit volume (for example, 8.6uL of this mixture will contain 1000 ug of each compound).

4.4.4.5

This mixture is further certified by GC/MS analysis (comparison to a purchased standard mix). The results must be within �15% of the true value.

4.4.4.6

This standard is prepared in a 1-mlvialwith mininert valve to prevent vapor losses. It is stored in the mobile lab freezer. This standard shall be re-certified monthly by GC/MS analysis.

4.4.5

The 1000 ppmV gaseous Vinyl chloride standard is also certified by GC/MS analysis and the acceptance criteria is �15% of the true value. The standard is assigned a DHL LOT# (VAyymmdd).

4.4.6

The documentation for all standard verification is kept in the mobile lab and in the QA department of the fixed lab for reference.

Sample Handling and Preservation

5.1

Soil vapor samples must be collected in 1-liter tedlar bags. Upon receipt at the mobile laboratory each sample is checked for sample name, date of collection, time of collection, and other miscellaneous information such as depth and sample location. This information is then verified on the Chain of Custody and each sample is assigned a unique laboratory identification number. Once sample check-in is completed, the samples are first stored in the 40�C oven to reach temperature equilibrium (15 � 20 minutes) and then processed for analysis. When analysis is completed samples are stored at room temperature until the results are qualified by the first tier review (see 13.1). If further analysis is required, the sample will again be equilibrated to 40�C. The sample holding time is 72 hours from the time of collection.

Instrument Parameters

6.1

Setting Up the Instrument

The carrier gas, Hydrogen, should be approximately 10 ml/min. for the column. Power on the following instruments: HECD detector, PID detector, GC, Tekmar 2000. The instrument parameters follow:

The GC parameters are:

Initial Oven Temp: 60^o C

Initial Time: 5 min

Program Rate: 10^o C

Final Temp: 120^o C

Final Time: 3.0 min

Backflush: Event 92 at 7.50 min., Event -92 at 15 min.

Note: The event times are different for each system and must be determined by the analyst

* Back flush is used to prevent higher boiling point compounds other than target compounds from entering the chromatographic system.

The Tekmar 2000 purge-and-trap parameters are as follows:

Standby Temp: 38^o

Purge: 5:00 min

Dry Purge: 1.00 min

Desorb Preheat: 245^o C (K Trap)

Desorb: 250^o C for 0.5 min (K Trap)

Bake: 260^oC for 0.5 min (K Trap)

All lines and valves 120^oC (Mount 120^oC)

Purge Flow: 30 ml/min

Trap pressure control: 6 psi

The HECD detector parameters are as follows:

Solvent flow: approximately 1.5 ml/min (setting of 41)

Reactor Temperature: 890^oC

The PID detector parameters are as follows:

Detector Temperature: 120^oC

6.2

Setting Up the Date System

6.2.1

Using ChromPerfect Direct (integration and chromatography data handling), establish a method, calibration, and ReportWrite Plus file to be used for this calibration or analytical run. For initial calibration, set all parameters (i.e. events, retention times, run, and plot times) by running a standard and evaluating the bestset of conditions for optimum results.

Preparation of Standards

7.1

Stock gaseous standard mix (1000 ug/L): Using a 10.0 uL syringe, transfer 8.6 uL of mixed neat liquid standard (4.4.3) into a pre-cleaned (purge with at least 3 volumes of zero air) 1-Liter dilution glass bottle. Place this container in the oven @ 40^oC and allow it to equilibrate for 1-hour.

7.2

Calibration Working Standard #1 (51 ug/L Vinyl Chloride and 20 ug/L of other compounds) used for making Cal Level #4 and #5 (Section 9.1):

7.2.1

Prepare for Vinyl Chloride: Use the cleaned 10.0 ml gas tight syringe withdraw 10.0 ml from the pressurized Vinyl chloride bottle (this is achieved by quickly opening and closing the valve on top of the pressurized bottle, the pressurized gaseous standard stay in the syringe adapter will fill the syringe when the on-off valve on the syringe is open), and transfer this portion to a cleaned 1-Liter glass dilution bottle. Repeat this procedure one more time (adding a total of 20 ml of standard) and clean the syringe with zero-air.

7.2.2

Prepare for other compounds: Using the same syringe withdraw 10.0 ml from the gaseous standard prepared in 7.1 and transfer it to the 1-Liter glass bottle described in 7.2.1. Repeat this procedure one more time (adding a total of 20 ml of standard) and clean the syringe with zero-air.

7.3

Calibration Working Standard #2 (5.1 ug/L Vinyl Chloride and 2.0 ug/L of other compounds) used for daily ICV and CCV, and preparing Cal Level #1, #2 and #3 (Section 9.1):

7.3.1

Prepare for Vinyl Chloride: Use the cleaned 2.0 ml gas tight syringe withdraw 2.0 ml from the pressurized Vinyl chloride bottle (follow the same technique described in section 7.2.1), and transfer this portion to a cleaned 1-Liter glass dilution bottle. Clean the syringe with zero air.

7.3.2

Prepare for other compounds: Using the same syringe withdraw 2.0 ml from the gaseous standard prepared in 7.1 and transfer it to the 1-Liter glass bottle described in 7.3.1. Clean the syringe with zero air.

7.3.3

A second source standard is not analyzed for this screening method.

7.4

All standards referenced in sections 7.1, 7.2, and 7.3 shall be stored in the 40^oC for at least 1 hour prior to use. These standards will be prepared fresh weekly.

Sample Preparation

8.1

Soil vapor samples are prepared by withdrawing 10 ml from the Tedlar bag after the temperature equilibration stage and transferring the entire 10-ml into the Tekmar 2000 through the luerlok connection on the 2-way valve. IMPORTANT - Sample transferring shall be deliberate and steady, a quick or forceful pushing the plunger will result in poor injection through forced leaks in the valve.

8.2

Dilutions above 20 times will be made in a cleaned glass dilution bottle. Samples diluted 20 times or less will be made by using a smaller volume of sample. The dilution factor shall be recorded on the sequence file. A dilution is required for any compound that has a response that exceeds the highest calibration point (i.e. 20 ug/L). All dilutions must be within the linear range of the calibration curve.

Calibration

9.1

Initial Calibration: A five-calibration level will be used for the initial calibration. The calibration levels are:

CAL Level #1: 0.51ug/L (Vinyl chloride)/0.2 ug/L (other VOCs) by injecting 2.5 syringe (zero air containing 1.0 ml 7.3 standard)

CAL Level #2: 2.55ug/L (Vinyl chloride)/1.0 ug/L (other VOCs) by injecting 10.0 ml (zero air containing 5.0 ml 7.3 standard)

CAL Level #3: 5.1ug/L (Vinyl chloride)/2.0 ug/L (other VOCs) by injecting 10.0 ml 73 standard

CAL Level #4: 25.5ug/L (Vinyl chloride)/10.0 ug/L (other VOCs) by injecting 10.0 ml (zero air containing 5.0 ml 7.2 standard)

CAL Level #5: 51.0ug/L (Vinyl chloride)/20.0 ug/L (other VOCs) by injecting 10.0 ml 7.2 standard

9.2

The acceptance criteria for the initial calibration is R² > 0.995

9.3

Initial Calibration Verification (ICV) and Continuing Calibration (CCV) - Each day before sample analysis, a mid-point continuing calibration verification (CAL Level #3) is analyzed and evaluated before any sample analysis is performed. The ICV/CCV standard is prepared and analyzed as described in Section 7.3. CCVs are analyzed after each sample batch or at a minimum rate of 10%, whichever is more frequent. The percent recovery (%R) of the ICV/CCV must fall within the limits of 75-125%. If the %R is not within these limits, corrective actions as outlined in Section 12.6 must be taken.

9.4

Retention Time Windows

9.4.1

Retention time windows are established once the optimum operating conditions for the chromatographic system have been established. Three aliquots of CCV standards containing all target compounds analyzed over the course of a 72-hour period. The standard deviation of the retention times for each analyte from the three analyses are determined.

9.4.2

The retention time window is defined as plus or minus three times the standard deviation of the retention time for each analyte. Retention time window information is kept on-file in the laboratory. Retention time windows must be calculated for each GC column and are re-calculated whenever a new column is installed.

9.4.3

Daily retention time windows are determined before the analyses of samples begins each day. The retention time for each analyte in the ICV analysis (Sec. 9.3) is set at the midpoint of the window � three times the standard deviation determined in Section 9.4.1.

9.4.4

Analyst experience is of paramount importance in interpreting chromatograms, particularly in the case of samples with degradation and weathering of target compounds.

9.5

Method Detection Limits (MDL) studies: Analyze seven replicates standard at the CAL Level #1 concentration (section 9.1). The results of these analyses are subjected to the MDL calculations. The MDL is defined as 3.1.4* STDEV (standard deviation) of these seven replicates results. A new MDL study must be conducted if this SOP is significantly changed or the instrumentation has changed. Otherwise, a new MDL shall be conducted once every 12 months.

9.6

Reporting Limits (RL): The RL is defined as the lowest calibration level (CAL Level #1) from the valid curve.

Sample Analysis

10.1

The sample preparation process and the entire chromatographic system must be contamination-free and this must verified before the analyses of every sample batch. The cleanliness of the sample preparation process and the entire analytical system is verified by the analysis of a Method Blank. Method Blanks are prepared by drawing 10.0 ml of zero air and analyzed at the beginning of the day and at the rate of one per matrix per sample batch (maximum 20 samples / batch). Detection of target analytes in the Method Blank must be less than the Method Detection Limit (MDL). If contamination above the MDL is noted in the method blank, corrective actions as outlined in Section 12.1.2.1 mustbe taken.

10.2

Make sure all maintenance records are kept up-to-date and analysis run-logs completed. The run logs and any corrective actions should be copied and placed in the project folder. Check for the correct sample ID and dilution factor included in the run logs.

Data Interpretation

11.1

Qualitative Analysis

11.1.1

Chromatography peaks should be examined carefully to ensure proper identification. This includes checking retention times to insure they are within established retention windows.

11.1.2

The HECD detector further confirms halogenated VOCs (Vinyl chloride, trans-1,2 DCE, cis-1,2-DCE, TCE, and PCE). Halogenated compounds detected above the RL must be confirmed on both detectors.

11.2

Quantitative analysis

11.2.1

Once qualitative analysis is confirmed the analyst must ensure that the baseline does not need to be redrawn and that the concentration does not exceed the linear range of the initial calibration. Any manual integration must be documented and the reason stated (such as baseline adjustment, etc.) Refer to the Admin-QA/QC-02 (Date Reporting) SOP for manual integration procedures.

11.3

Analyst experience is of paramount importance in interpreting chromatograms and monitoring the analytical system performance for items such as carry over, false positives or negative peaks.

QA/QC and Corrective Actions

12.1

All QC requirements apply to the PID detector only.

12.2

Prior to analysis of any samples, the analyst must show that the entire chromatographic system is contamination-free. This is accomplished by the analysis of the Method Blank.

12.2.1

The Method Blank consists of zero air treated as a sample and carried through the entire sample preparation process. The Method Blank indicates any contamination present in the chromatographic system, glassware, sample preparation, and analytical process. A Method Blank must be analyzed in each batch.

12.2.2

The concentration of target analytes in the Method Blank must be less than the method detection limit. If contamination above the method detection limitation is detected in a blank, the contamination must be evaluated and the following corrective actions must be taken:

Inspect instrument for signs of compound carry-over or contaminant build-up within the system. If carry-over is noted, a series of method blank must be run to clean out the chromatographic system. Document such measure in the instrument maintenance logbook.

12.3

The GC system must meet the Initial Calibration Verification (ICV) and Continuing Calibration Verification (CCV) criteria each day before sample analyses may begin. If any ICV/CCV %Recovery is outside of the range of 75-125%, corrective actions must be taken as specified in Section 12.6 below. ICV and CCVs that are within control limits must bracket all samples.

12.4

A probe blank will be analyzed if the laboratory receives one.

12.5

At the end of each batch, a CCV will be analyzed.

12.6

If the daily ICV/CCV standard recoveries are outside the acceptance limits, the following corrective actions must be taken before further analyses are performed. Unacceptable recoveries can be due to: (1) leaking in the glass bottle containing the daily CCV (due to damaged septum, loosen stopcock valve, etc.), (2) contaminated glass bottle, (3) leaking syringe, (4) leaking 2-way valve, (5) improper sample introduction to the analytical system, or (6) improper preparation of daily standard. The corrective measures are:

12.6.1.1

Inspect all containers, syringes and valves for leakage or obvious physical damage and replace or restore them as appropriate.

12.6.1.2

Re-analyze the standard to see if the results are reproducible. If the standard still fails, re-prepare the standard making sure the glass bottle is properly cleaned. Then analyze the newly prepared standard.

12.6.1.3

If the above corrective actions do not alleviate the poor performance and no other instrument malfunction is detected, a new initial calibration must be performed following the procedures outlined in sections 9.1, 9.2, and 9.3.

12.6.1.4

All samples that are affected (those analyzed after last passing CCV) must be re-analyzed against the new initial calibration.

12.7

Sample Duplicate: One sample per batch of 20 will be selected for duplicate analysis. Any compounds detected at or above 5 times the RL shall have an RPD within + 30%. If the RPD is not met, the duplicate sample will be reanalyzed and the values reported. The results will be discussed in the case narrative.

12.8

Analysis of mixed neat standard: The mixed neat standard and the certified vinyl chloride gas standard are analyzed by GC/MS. The results must be within 15% of the true value. On a monthly basis the mixed neat standard is analyzed to verify that no degradation has occurred. If outside the �15% range, the standard is reanalyzed. If still out, the standard is re-prepared.

Data Reporting

13.1

Daily Field Data (1st Tier QA reviewed) - This data is reviewed by the field chemist only. This data only consists of the analytical data for the true field samples in the EXCEL format. QA summary and case narrative will not be included. All positive hits above the RL will be reported. All positive hits that are between the RL and the established MDL will be reported with a "J" flag. Any data that is below the established MDL will be reported as "ND".

13.2

Final Data (2nd & 3rd Tier QA reviewed) - This data will be reviewed by the QA department (2nd Tier) and approved by the DHL QA manager (3rd Tier). The report will follow DHL report style with case narrative, proper data flagging, and QA summaries.

13.3

Results for each analyte are reported as mg/L.

Instrument Maintenance

14.1

Traps can go bad with time and may need to be replaced. A new trap's performance must be verified by analyzing CAL LEVEL #1, CAL Level #3, and CAL Level #5. If the recoveries are not within 25% for each level, a new calibration curve must be constructed.

14.2

It is advised that septa on the glass dilution bottle shall be changed regularly to prevent leaking. Whenever a new standard is prepared, the septum shall be replaced.

Health, Safety, and Waste Disposal

15.1

All waste disposal procedures must comply with federal and local regulations. Refer to DHL HAZCOM / Hazardous Waste Management Manual.

1.1	Method 8021B is modified by DHL Analytical's mobile laboratory to determine aromatic and halogenated volatile organic compounds in soil vapor matrix.
1.2	This method is limited to use as a screening method only.

2.1	This method is used for the determination of gaseous aromatic and halogenated volatile compound including BTEX (Benzene, Toluene, Ethylbenzene, Xylenes) and halogenated VOCs (Tetrachloroethene, Trichloroethene, cis-1,2-Dichloroethene, trans-1,2-Dichloroethene, and Vinyl Chloride) in soil vapor samples. A Purge and Trap connected to a gas chromatograph equipped with a photo-ionization detector (PID) and a Hall Electrolytic Conductivity Detector (HECD) in series is used to analyze samples. A Tekmar 2000 purge and trap concentrator is used to enrich these compounds to achieve low detection limits.
2.2	Samples and gas standards shall be at the same temperature when analyzed to avoid results differing due to temperature change. All standards and samples are warmed to slightly above ambient temperatures (40 � 5� C) in an oven. This prevents surface adsorption of xylenes and ethylbenzene and maintains equal air density for standards and samples.
2.3	The PID detector is always considered the "primary" detector and the HECD detector is considered the "secondary" detector. The QC must pass for all compounds on the PID detector. The QC criteria in this SOP do no apply to the HECD detector. The HECD detector is used to confirm the presence of halogenated VOCs above the reporting limit. No confirmation is performed for BTEX. If the HECD detector does not confirm the presence of a halogenated compound which the PID detector identified, then the compound identification by the PID is considered faulty and the compound is reported as not detected.

4.1	Gas Chromatograph System:
	4.1.1	Gas Chromatograph: Shimadzu GC-14A
	4.1.2	Primary Column: DB-624 (3 um), 75 meters, 0.53 mm id megabore (No secondary column is used.)
	4.1.3	Detector: HNU PID detector with 10.2 eV lamp.
	4.1.4	Detector: Hall Electrolytic Conductivity detector.
	4.1.5	Purge and Trap Concentrator: A Tekmar 2000 purge and trap concentrator equipped with a 2-way valve for sample introduction
	4.1.6	Calibrated 1-liter dilution bottles (Supelco)
	4.1.7	Oven (maintained @ 40� C�5� C)
4.2	Syringes: 10.0 ul and 100 uL Hamilton syringes and SGE 2.5 ml and 10.0 ml gas-tight syringe with luer-lok tips and Teflon plungers.
4.3	Concentrator Trap: K trap (Supelco)
4.4	Reagants: All chemicals should be stored away from possible contamination sources.
	4.4.1	Gas: Ultra High Purity (UHP) grade Hydrogen and zero-air.
	4.4.2	Methanol: Purge and Trap Grade
	4.4.3	Standards: All neat liquid standards are obtained from Chem Services. The vinyl chloride gaseous standard (1000 ppmV, or 2,550ug/L) is obtained from Scott Specialty Gases.
	4.4.4	A mixed neat liquid standard containing trans-1,2-DCE, cis-1,2-DCE, TCE, PCE, and BTEX is prepared as follows using a 100uL syringe: Compounds Amount used (uL) Trans-1,2-DCE 80 Cis-1,2-DCE 78 TCE 68 PCE 60 Benzene 114 Toluene 115 Ethylbenzene 115 m-Xylene 114 o-Xylene 114
		4.4.4.1	The syringe is thoroughly rinsed with methanol in between standards.
		4.4.4.2	P-Xylene is not used because it has the same retention time as m-Xylene.
		4.4.4.3	This mixture is assigned a DHL Lot# (VAyymmdd) in the LIMS (laboratory information management system) for future reference.
		4.4.4.4	This mixture will give equal weight ratio for each compound within a unit volume (for example, 8.6uL of this mixture will contain 1000 ug of each compound).
		4.4.4.5	This mixture is further certified by GC/MS analysis (comparison to a purchased standard mix). The results must be within �15% of the true value.
		4.4.4.6	This standard is prepared in a 1-mlvialwith mininert valve to prevent vapor losses. It is stored in the mobile lab freezer. This standard shall be re-certified monthly by GC/MS analysis.
	4.4.5	The 1000 ppmV gaseous Vinyl chloride standard is also certified by GC/MS analysis and the acceptance criteria is �15% of the true value. The standard is assigned a DHL LOT# (VAyymmdd).
	4.4.6	The documentation for all standard verification is kept in the mobile lab and in the QA department of the fixed lab for reference.

7.1	Stock gaseous standard mix (1000 ug/L): Using a 10.0 uL syringe, transfer 8.6 uL of mixed neat liquid standard (4.4.3) into a pre-cleaned (purge with at least 3 volumes of zero air) 1-Liter dilution glass bottle. Place this container in the oven @ 40^oC and allow it to equilibrate for 1-hour.
7.2	Calibration Working Standard #1 (51 ug/L Vinyl Chloride and 20 ug/L of other compounds) used for making Cal Level #4 and #5 (Section 9.1):
	7.2.1	Prepare for Vinyl Chloride: Use the cleaned 10.0 ml gas tight syringe withdraw 10.0 ml from the pressurized Vinyl chloride bottle (this is achieved by quickly opening and closing the valve on top of the pressurized bottle, the pressurized gaseous standard stay in the syringe adapter will fill the syringe when the on-off valve on the syringe is open), and transfer this portion to a cleaned 1-Liter glass dilution bottle. Repeat this procedure one more time (adding a total of 20 ml of standard) and clean the syringe with zero-air.
	7.2.2	Prepare for other compounds: Using the same syringe withdraw 10.0 ml from the gaseous standard prepared in 7.1 and transfer it to the 1-Liter glass bottle described in 7.2.1. Repeat this procedure one more time (adding a total of 20 ml of standard) and clean the syringe with zero-air.
7.3	Calibration Working Standard #2 (5.1 ug/L Vinyl Chloride and 2.0 ug/L of other compounds) used for daily ICV and CCV, and preparing Cal Level #1, #2 and #3 (Section 9.1):
	7.3.1	Prepare for Vinyl Chloride: Use the cleaned 2.0 ml gas tight syringe withdraw 2.0 ml from the pressurized Vinyl chloride bottle (follow the same technique described in section 7.2.1), and transfer this portion to a cleaned 1-Liter glass dilution bottle. Clean the syringe with zero air.
	7.3.2	Prepare for other compounds: Using the same syringe withdraw 2.0 ml from the gaseous standard prepared in 7.1 and transfer it to the 1-Liter glass bottle described in 7.3.1. Clean the syringe with zero air.
	7.3.3	A second source standard is not analyzed for this screening method.
7.4	All standards referenced in sections 7.1, 7.2, and 7.3 shall be stored in the 40^oC for at least 1 hour prior to use. These standards will be prepared fresh weekly.

9.1	Initial Calibration: A five-calibration level will be used for the initial calibration. The calibration levels are: CAL Level #1: 0.51ug/L (Vinyl chloride)/0.2 ug/L (other VOCs) by injecting 2.5 syringe (zero air containing 1.0 ml 7.3 standard) CAL Level #2: 2.55ug/L (Vinyl chloride)/1.0 ug/L (other VOCs) by injecting 10.0 ml (zero air containing 5.0 ml 7.3 standard) CAL Level #3: 5.1ug/L (Vinyl chloride)/2.0 ug/L (other VOCs) by injecting 10.0 ml 73 standard CAL Level #4: 25.5ug/L (Vinyl chloride)/10.0 ug/L (other VOCs) by injecting 10.0 ml (zero air containing 5.0 ml 7.2 standard) CAL Level #5: 51.0ug/L (Vinyl chloride)/20.0 ug/L (other VOCs) by injecting 10.0 ml 7.2 standard
9.2	The acceptance criteria for the initial calibration is R² > 0.995
9.3	Initial Calibration Verification (ICV) and Continuing Calibration (CCV) - Each day before sample analysis, a mid-point continuing calibration verification (CAL Level #3) is analyzed and evaluated before any sample analysis is performed. The ICV/CCV standard is prepared and analyzed as described in Section 7.3. CCVs are analyzed after each sample batch or at a minimum rate of 10%, whichever is more frequent. The percent recovery (%R) of the ICV/CCV must fall within the limits of 75-125%. If the %R is not within these limits, corrective actions as outlined in Section 12.6 must be taken.
9.4	Retention Time Windows
	9.4.1	Retention time windows are established once the optimum operating conditions for the chromatographic system have been established. Three aliquots of CCV standards containing all target compounds analyzed over the course of a 72-hour period. The standard deviation of the retention times for each analyte from the three analyses are determined.
	9.4.2	The retention time window is defined as plus or minus three times the standard deviation of the retention time for each analyte. Retention time window information is kept on-file in the laboratory. Retention time windows must be calculated for each GC column and are re-calculated whenever a new column is installed.
	9.4.3	Daily retention time windows are determined before the analyses of samples begins each day. The retention time for each analyte in the ICV analysis (Sec. 9.3) is set at the midpoint of the window � three times the standard deviation determined in Section 9.4.1.
	9.4.4	Analyst experience is of paramount importance in interpreting chromatograms, particularly in the case of samples with degradation and weathering of target compounds.
9.5	Method Detection Limits (MDL) studies: Analyze seven replicates standard at the CAL Level #1 concentration (section 9.1). The results of these analyses are subjected to the MDL calculations. The MDL is defined as 3.1.4* STDEV (standard deviation) of these seven replicates results. A new MDL study must be conducted if this SOP is significantly changed or the instrumentation has changed. Otherwise, a new MDL shall be conducted once every 12 months.
9.6	Reporting Limits (RL): The RL is defined as the lowest calibration level (CAL Level #1) from the valid curve.

11.1	Qualitative Analysis
	11.1.1	Chromatography peaks should be examined carefully to ensure proper identification. This includes checking retention times to insure they are within established retention windows.
	11.1.2	The HECD detector further confirms halogenated VOCs (Vinyl chloride, trans-1,2 DCE, cis-1,2-DCE, TCE, and PCE). Halogenated compounds detected above the RL must be confirmed on both detectors.
11.2	Quantitative analysis
	11.2.1	Once qualitative analysis is confirmed the analyst must ensure that the baseline does not need to be redrawn and that the concentration does not exceed the linear range of the initial calibration. Any manual integration must be documented and the reason stated (such as baseline adjustment, etc.) Refer to the Admin-QA/QC-02 (Date Reporting) SOP for manual integration procedures.
11.3	Analyst experience is of paramount importance in interpreting chromatograms and monitoring the analytical system performance for items such as carry over, false positives or negative peaks.

12.1	All QC requirements apply to the PID detector only.
12.2	Prior to analysis of any samples, the analyst must show that the entire chromatographic system is contamination-free. This is accomplished by the analysis of the Method Blank.
	12.2.1	The Method Blank consists of zero air treated as a sample and carried through the entire sample preparation process. The Method Blank indicates any contamination present in the chromatographic system, glassware, sample preparation, and analytical process. A Method Blank must be analyzed in each batch.
	12.2.2	The concentration of target analytes in the Method Blank must be less than the method detection limit. If contamination above the method detection limitation is detected in a blank, the contamination must be evaluated and the following corrective actions must be taken: Inspect instrument for signs of compound carry-over or contaminant build-up within the system. If carry-over is noted, a series of method blank must be run to clean out the chromatographic system. Document such measure in the instrument maintenance logbook.
12.3	The GC system must meet the Initial Calibration Verification (ICV) and Continuing Calibration Verification (CCV) criteria each day before sample analyses may begin. If any ICV/CCV %Recovery is outside of the range of 75-125%, corrective actions must be taken as specified in Section 12.6 below. ICV and CCVs that are within control limits must bracket all samples.
12.4	A probe blank will be analyzed if the laboratory receives one.
12.5	At the end of each batch, a CCV will be analyzed.
12.6	If the daily ICV/CCV standard recoveries are outside the acceptance limits, the following corrective actions must be taken before further analyses are performed. Unacceptable recoveries can be due to: (1) leaking in the glass bottle containing the daily CCV (due to damaged septum, loosen stopcock valve, etc.), (2) contaminated glass bottle, (3) leaking syringe, (4) leaking 2-way valve, (5) improper sample introduction to the analytical system, or (6) improper preparation of daily standard. The corrective measures are:
	12.6.1.1	Inspect all containers, syringes and valves for leakage or obvious physical damage and replace or restore them as appropriate.
	12.6.1.2	Re-analyze the standard to see if the results are reproducible. If the standard still fails, re-prepare the standard making sure the glass bottle is properly cleaned. Then analyze the newly prepared standard.
	12.6.1.3	If the above corrective actions do not alleviate the poor performance and no other instrument malfunction is detected, a new initial calibration must be performed following the procedures outlined in sections 9.1, 9.2, and 9.3.
	12.6.1.4	All samples that are affected (those analyzed after last passing CCV) must be re-analyzed against the new initial calibration.
12.7	Sample Duplicate: One sample per batch of 20 will be selected for duplicate analysis. Any compounds detected at or above 5 times the RL shall have an RPD within + 30%. If the RPD is not met, the duplicate sample will be reanalyzed and the values reported. The results will be discussed in the case narrative.
12.8	Analysis of mixed neat standard: The mixed neat standard and the certified vinyl chloride gas standard are analyzed by GC/MS. The results must be within 15% of the true value. On a monthly basis the mixed neat standard is analyzed to verify that no degradation has occurred. If outside the �15% range, the standard is reanalyzed. If still out, the standard is re-prepared.

13.1	Daily Field Data (1st Tier QA reviewed) - This data is reviewed by the field chemist only. This data only consists of the analytical data for the true field samples in the EXCEL format. QA summary and case narrative will not be included. All positive hits above the RL will be reported. All positive hits that are between the RL and the established MDL will be reported with a "J" flag. Any data that is below the established MDL will be reported as "ND".
13.2	Final Data (2nd & 3rd Tier QA reviewed) - This data will be reviewed by the QA department (2nd Tier) and approved by the DHL QA manager (3rd Tier). The report will follow DHL report style with case narrative, proper data flagging, and QA summaries.
13.3	Results for each analyte are reported as mg/L.

14.1	Traps can go bad with time and may need to be replaced. A new trap's performance must be verified by analyzing CAL LEVEL #1, CAL Level #3, and CAL Level #5. If the recoveries are not within 25% for each level, a new calibration curve must be constructed.
14.2	It is advised that septa on the glass dilution bottle shall be changed regularly to prevent leaking. Whenever a new standard is prepared, the septum shall be replaced.