ENVIRONMENTAL PRIORITY SERVICE, INC.

GROUNDWATER, SOIL & SOIL GAS

COLLECTION AND ON-SITE ANALYSIS

UTILIZING HEATED HEADSPACE METHOD

FIELD PROCEDURES MANUAL

April, 2015

GENERICHEADSPACESOPSPage 1

table of contents

Page No.

sampling equipment

EQUIPMENT...... 3

Probing Machine and related sampling equipment...... 3

Analytical Equipment...... 3

equipment specifications...... 3-4

Gas Chromatographs...... 3-4

Data Integrators...... 3-4

Megabore Column...... 4

preliminary Instrument operating conditions...... 4

sample collection & analysis

analytes of interest...... 5

sample collection procedures...... 5

Soil Gas Sampling Procedures...... 5

Soil Sampling Procedures...... 5-6

Groundwater Sampling Procedures...... 6

verification of reporting limits...... 6-7

Verification of Soil Gas Reporting Limit...... 6-7

Verification of Groundwater/Soil Reporting Limit...... 7

calibration of gas chromatograph...... 8-10

Calibration of Gas Chromatograph for Soil Gas Samples...... 8-9

Calibration of Gas Chromatograph for Groundwater/Soil Samples...... 9-10

field screening & analysis...... 10-12

Soil Gas Analysis...... 10

Soil Analysis...... 11

Groundwater Analysis...... 11-12

quality control/quality assurance...... 12-13

Calibration Check...... 12

Blank Samples...... 12

Duplicate Samples...... 13

GENERICHEADSPACESOPSPage 1

Field Procedures Manual

January, 2006Environmental Priority Service, Inc.

sampling equipment

equipment

Probing Machine and Related Sampling Equipment

  • Geoprobe 4200 & 5400 Series Hydraulic Probe Machines
  • Geoprobe 6620 Track Units
  • Geoprobe 54DT Track Unit
  • On-board vacuum/volume system for vapor extraction
  • Hardened alloy steel probe roads (1.25” x 3,4,5’ flights)
  • Larger diameter (2.125” & 3.25”) probe rods for mini-well installation and track unit use
  • Hollow Stem Augers for shallow (<30’) 2” conventional wells
  • Soil sampling tools: 4 & 5 ft. macros & 4 & 2 ft. discreet large-bore sampler
  • Groundwater sampling tools: 2 & 4’ mill-slotted, 4’ stainless steel screen
  • Groundwater screen implants
  • Expendable Drive Points
  • Polyethylene tubing for sampling
  • Soil Gas sampling tools: PRT system
  • Soil Electrical Conductivity System
  • Grout Pump
  • Generators
  • Water Tanks
  • Power Washers
  • Holding tanks

Analytical Equipment

  • Shimadzu model GC-14A laboratory grade gas chromatograph
  • Hewlett Packard model 5890A Series 2 computerized laboratory gas chromatograph
  • Shimadzu model CR-7A Chromatopac Data Processor for Chromatography
  • P/E Nelson model 970A chromatography signal interface
  • P/E Nelson Analytical Turbochrom 4.0 series integration software
  • Three detectors – Flame Ionization (FID), Electron Capture (ECD), & Photoionization (PID)
  • Temperature-controlled laboratory oven
  • Odyssey Spectrophotometer

equipment specifications

Gas Chromatograph (GC-14A)

  • Two temperature-controlled injector ports and three detectors (FID, ECD, & PID)
  • Temperature Range from -80C to +399C
  • Provides 5 Program Ramping Stages with a maximum temperature range of 40C/minute
  • Injection Port Range is 399C

Data Integrator (CR-7A)

  • Contains 2 imprint channels.
  • Maximum peak number for identification: 1000 peaks
  • Minimum peak width processed: 0.04 seconds (width at half-height)
  • Linearity: less than 0.1%
  • Dynamic Range: 10E6
  • Disk Drives: 3.5” hard disk drive (40 Mbyte), 3.5” floppy disk drive (1.6 Mbyte)

Gas Chromatograph (HP-5890 Series 2)

  • Two temperature-controlled injector ports and three detectors (FID, ECD, & PID)
  • Temperature Range from -80C to +450C
  • Connected in-line with Tekmar Purge and Trap
  • Provides 3 Program Ramping Stages with a maximum temperature range of 40C/minute
  • Injection Port Range is 0-399C

Signal Interface/Chromatography Integrator (Nelson model 970A)

  • Contains 2 imprint channels.
  • Maximum peak number for identification: 1000 peaks
  • Minimum peak width processed: 0.04 seconds (width at half-height)
  • Linearity: less than 0.1%

Megabore Column

  • Maximum temperature: 260C
  • Type of Column: J&W DB-624
  • Length of Column: 30 meters
  • Outer Diameter: 0.543 mm

preliminary Instrument operating conditions

The Hewlett Packard 5890A Series 2 Gas Chromatograph or the Shimadzu Gas Chromatograph 14-A (GC), each equipped with a photo-ionization detector (PID) and an electron capture detector (ECD) in series, will be utilized to analyze the samples. The GC column temperature will run isothermally for 3 minutes at 50 C, then temperature ramp at 10C/min to 170C, while the injector temperature is at 180 C and the detectors are at 225 C.

It should be noted that the instrument operating conditions noted above are preliminary. The conditions will be modified in the field, as necessary, to optimize instrument performance.

* * * * *

sample collection & analysis

analytes of interest

Soil gas, soil and groundwater samples will be collected from the sites of interest. Target compounds typically analyzed for during this type of project are anticipated to include; Carbon Tetrachloride (CCL4), Chloroform (CFM), Cis-1,2 Dichloroethene (DCE), Trichloroethene (TCE) and Tetrachloroethene (PCE), as well as Benzene, Toluene, Ethylbenzene and Xylenes (BTEX). For optimum detection of the analytes of interest, the gas chromatograph (GC) will be equipped with photoionization detector (PID) and an electron capture detector (ECD) in series.

sample collection procedures

To minimize cross-contamination of samples, each test hole is probed with pre-cleaned sampling rods. Pre-cleaning consists of steam-cleaning, washing with Alconox soap, and rinsing with deionized water. Enough probe rods are available so that they are used only once between decon periods. In addition, disposable gloves, polyethylene tubing, and syringes are used for sample collection and analysis to minimize cross-contamination. All disposable equipment is used only once.

Procedures specific to the collection of soil gas, soil and groundwater are detailed in the following paragraphs:

Soil Gas Sampling Procedure

Soil gas sampling procedures include advancing 1.25-inch outer diameter (O.D.) probe rods with a threaded point holder and disposable point to the desired sampling depth on each test hole. Polyethylene tubing (1/4” dia.) is then lowered down the inner diameter of the probe rods and threaded onto the threaded point holder. An o-ring is utilized to ensure a tight seal surrounding this threaded fitting. The probe unit is then used to retract the rods approximately 2- to 4-inches, thereby disengaging the disposable drive point attached to the threaded point holder. Once a space or void has been made for soil gas extraction, the tubing is purged, utilizing the on-board vacuum system, to remove any extraneous air present in the polyethylene tubing.

Once purged, a soil gas sample is collected using a disposable syringe. The soil gas sample is collected by first pinching off the upper sample tubing, puncturing the tubing directly above the upper probe rod with the syringe, and evacuating 0.50 cc of soil gas from within the tubing into the syringe. The sample, 0.50 cc of soil gas, is then immediately injected into the GC for analysis.

Soil Sampling Procedure

Soil sampling procedures include vertically profiling the soils to the desired sampling depths or probe refusal. Continuous profiling procedures include attaching a 4-ft. in length Geoprobe macro-core soil sampler to the leading probe rod, and advancing the sampler in 4-ft. increments from the ground surface to the desired sampling depths. Discreet profiling procedures include attaching a closed piston-assembled 4-ft. in length Geoprobe macro-core soil sampler to the leading probe rod, and advancing the sampler in 4-ft. increments from the ground surface to the desired sampling depth. Once at depth, small diameter (1/8”) extension rods are lowered down the I.D. of the probe rods until they make contact with the piston rod and the reverse-threaded, piston rod stop pin. The stop pin is unthreaded freeing up the inner piston rod and driving point. The 4-ft. sampler is then advanced filling the sample tube with the discreet sample. The sampler is equipped with an inner PVC, transparent liner, useful for logging purposes. The filled liners are placed on visqueen and placed on the ground surface for visual observation. Soil samples are then collected and logged by Client personnel. Once a selected sample has been determined, EPS will conduct the on-site analysis of the soil samples. Selected duplicate samples will be sent from the Client to a certified laboratory for analysis.

Groundwater Sampling Procedure

Once it has been determined that depth to groundwater is within sampling range of the hydraulic probe and that sufficient water is available for sampling, groundwater samples will be collected for analysis. A 1-inch by 2-foot length of mill-slotted groundwater sampling tool, which is attached to the leading probe rod, is advanced in 3-foot sections to the desired sampling depth at each test hole. A larger diameter (1.5-inch) pre-probe point is connected to the bottom end of the mill-slotted tool. This pre-probe point is used to prevent the mill-slots from plugging with sediment as the rods are advanced to depth. If conditions do not warrant mill-slot usage due to the presence of too much clay or too small fines, then a Geoprobe SP-15 Screen Point Sampler will be used. This sampler is equipped with an inner 4-foot length of mesh-wire screen. Once the rods and SP-15 sampler are advanced to depth, the rods are retracted approximately 4 feet, which exposes the inner screen. Once groundwater has infiltrated the sampler, a groundwater sample can be collected.

Prior to sample collection, a groundwater depth measurement will be taken using a Solinst water level indicator. Static water levels are taken by lowering the water level indicator inside the probe rods until contact with water occurs. The water level is then measured to within 1/100th of an inch.

Temporary 1 inch and 2 inch PVC wells may also be utilized to facilitate groundwater collection in some settings where insufficient groundwater volume is available for immediate sampling. Groundwater collection procedures from probe rods or pvc are as follows:

To collect the groundwater sample, the on board vacuum/volume system, a peristaltic pump, or a ball-and-seat check valve system is used. Whichever system is utilized, depending on hydrologic conditions, 3/8” polyethylene tubing will be used to collect the groundwater samples. The 3/8” tubing is lowered down the inside of the probe rod until it reaches the bottom of the screened section or SP-15 sampler. An up-down motion of the tubing allows groundwater to infiltrate up through the tubing to the ground surface if the ball-and-seat check valve system is used. Utilizing the vacuum/volume system, groundwater is extracted through the tubing by using a vacuum of no more than 21 inches of mercury. Once a sufficient amount of the groundwater has been purged from the sampling string, the tubing is pinched off at the ground surface and pulled from the probe rods. Groundwater is then immediately transferred from the lower end of the tubing directly into 40-ml vials. The vials are filled to minimize the headspace, and the samples are placed on ice and set aside awaiting analysis. Depending upon groundwater availability, a minimum of two 40-mL vials is typically collected at each sample location.

verification of reporting limits

The reporting limit for each compound is determined by the sensitivity of each detector that is utilized. Prior to field activities, the reporting limits will be verified as described in the following paragraphs.

Verification of Soil Gas Reporting Limits

The reporting Limits than can be met for this project are anticipated to be 2 ug/l for CCL4, CFM, DCE, TCE, PCE and BTEX. To verify the reporting limit, a standard is made for each analyte of interest, or a commercially prepared standard is utilized. The gas standard is made from stock solutions of the target compounds preserved in methanol. The distributor (Chem Service) guarantees the concentrations of the stock solutions are 100ug/ml plus or minus 5% in methanol. To produce a 5 ug/l gas standard, 50 microliters (l) of each stock solution is injected into a 1000-ml glass bulb. To produce a 50 ug/l gas standard, 500 l of the stock solution is injected into a 1000-ml glass bulb, and so on.

The verification of the reporting limit is made by analyzing three (3) injections of the standard prepared at or below the chosen reporting limit. If the instruments signal to noise ratio is 2.5 or greater, then the reporting limit has been verified. If this criterion is not met, then the reporting limit should be increased accordingly.

In order to meet data input requirements for the Shimadzu and P/E Nelson Analytical Data Processors, the average retention time and peak area is calculated for each analyte of interest during the verification process. The result of an internal 3-point calibration curve automatically determines a response factor, which enters into the Identification Table of the Data Processor. The response factor, as defined/required by the Data Processor, is determined by dividing the known concentration of each individual compound within the standard by its average peak area. Appropriate retention time windows are selected for the identification of each compound, based on degree of separation.

Verification of Groundwater/Soil Reporting Limits

To verify the 2 g/L reporting limit, a standard is made for each analyte of interest. The liquid standard is made from stock solutions of the target compounds preserved in methanol. The stock solutions contain concentrations of the stock solutions at 100ug/ml plus or minus 5% in methanol.

A 1:5 Working Standard is prepared using the stock solutions. Standards are prepared in a 50cc volumetric flask for each calibration level using this compound mixture. Three 40-ml vials are then prepared by transferring 20-ml of the Working Standard from the volumetric glassware. Standards may also be prepared by spiking a half full 40-ml vial with the compound mixture. The vials are placed in a temperature-controlled oven at approximately 90C for approximately 15 minutes. Once a vial has been thoroughly heated, 0.20 cc of headspace from within the vial is collected with a syringe and immediately injected into the GC for analysis.

The verification of the reporting limit is made by analyzing three (3) injections of a standard prepared at or below the chosen reporting limit. If the instruments signal to noise ratio is 2.5 or greater, then the reporting limit has been verified. If this criterion is not met, then the reporting limit should be increased accordingly.

In order to meet data input requirements for the Shimadzu and P/E Nelson Analytical Data Processors, the average retention time and peak area is calculated for each analyte of interest during the verification process. The result of an internal 3-point calibration curve automatically determines a response factor, which enters into the Identification Table of the Data Processor. The response factor, as defined/required by the Data Processor, is determined by dividing the known concentration of each individual compound within the standard by its average peak area. Appropriate retention time windows are selected for the identification of each compound, based on degree of separation.

calibration of gas chromatograph

Prior to the start of field activities, the GC will be calibrated using a 3-point calibration. Concentrations of 2ug/l will be utilized for the low level calibration and the other two levels will be determined based on expected contamination levels present within the soils. Broader calibration ranges may need to be utilized if high concentrations of the analytes of interest are detected within the field. This may be accomplished by a calibration check of a concentration range equivalent to the high concentration sample. It is anticipated that the initial calibration may be sufficient for the entirety of this field activity. Calibrations will be re-established if necessary. The stability of the calibration will be assessed during the field program through the use of calibration checks (see Page 12,13 Quality Control / Quality Assurance).

A chromatograph and area report is generated by the chromatography software for each standard that is analyzed. Analytical reports that are generated by the chromatography softwarecan be provided for an additional fee.

Calibration of Gas Chromatograph for Soil Gas Samples

Standards will be made at concentrations of 2, 25 and 50 ppb for each chlorinated analyte of interest. The gas standard is made from stock solutions of the target compounds preserved in methanol. Concentrations of the stock solutions are 100ug/ml plus or minus 5% in methanol. To produce each concentration of the gas standard, the appropriate volume of each stock solution is injected into a 1000-ml glass bulb.

Once the gas standard has been made, a known volume (typically 0.50 cc) of the gas standard is injected into the GC for each concentration. A calibration factor is calculated for each concentration of each target compound. The ratio of the detector response (peak area or peak height) to the concentration of analyte in the calibration standard is defined as the calibration factor. The CF is calculated as follows:

CF = Peak Area (or Peak Height) of the Compound in the Standard

Concentration of the Compound Injected (ppb or g/L)

To evaluate the linearity of the initial calibration, the P/E Nelson integration software calculates a correlation coefficient (CC) by linear regression, from three calibration injections using a straight-line fit. The mean CF, the standard deviation (SD), and the relative standard deviation (RSD) can be manually calculated as follows:




Note: In the preceding calculations n is the number of calibration standards and RSD is expressed as a percentage (%).

If the RSD of the calibration factors is less than or equal to 25% over the calibration range for each compound of interest, then linearity through the origin is assumed. The average calibration factor (mean CF) can then be used to determine sample concentrations by manual calculation.

If the RSD for any target analyte exceeds 25%, then one or more of the following corrective actions will be necessary and will be performed in the following order: