Extractable Petroleum Hydrocarbons Methodology August 2010 Ver 1_2 9 Aug 2010.pdf

Extractable Petroleum Hydrocarbons Methodology Page 1 of 42 Version 3.0 8/9/10

New Jersey Department of Environmental Protection Site Remediation Program

EXTRACTABLE PETROLEUM HYDROCARBONS METHODOLOGY

(Version 3.0)

New Jersey Department of Environmental Protection Office of Data Quality

Analytical Method

Title: Document #:

Analysis of Extractable Petroleum Hydrocarbon Compounds (EPH) in Aqueous and Soil/Sediment/Sludge Matrices

Prepared by: Greg Toffoli

Cleared for Issue by: Barry Frasco

Location: Master Set @ DEP/SRP/ODQ

NJDEP EPH 10/08

Date: August 2010 Revision: 3

1.0 SCOPE OF APPLICATION

1.1 Scope

This method utilizes a gas chromatograph (GC) fitted with a flame ionization detector (FID) to determine the collective concentrations of extractable aliphatic and aromatic petroleum hydrocarbons in water and soil/sediment matrices. A mass spectrometer (MS) may be used in lieu of a flame detector. However, the GC/MS must be operated in the scanning mode using the scan rate, scanning range and tuning criteria specified in USEPA Method SW-846 8270C or USEPA Method SW-846 8270D. Selected ion monitoring is not permitted. If GC/MS is used, then it should be used for both fractions.

1.1.1 This method can be used for the quantitative analysis of environmental samples (water, soil, sediment, and sludge) for residues from commercial petroleum products such as crude oil, diesel fuel, waste oil, fuel oil Nos. 2-6, lubricating oil, processed oil and bunker fuel.

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1.1.2 This method shall not be used for the quantitative analysis of gasoline, mineral spirits, petroleum naphtha and other petroleum products which contain a significant percentage of hydrocarbons lighter than C9 in water and soil/sediment/sludge matrices at contaminated sites.

1.2 Applicable Programs

Underground Storage Tanks (UST), New Jersey Spill Fund, Comprehensive Environmental Response Compensation and Liability Act (CERCLA), Industrial Site Recovery Act (ISRA), Sludge Residuals, and Resource Conservation and Recovery Act

(RCRA).

1.3 Method Advantages

1.3.1 This method replaces the Total Petroleum Hydrocarbons (TPH) method based on Freon 113 extraction and analysis by infrared spectroscopy (i.e., Method 418.1).

1.3.2 The FID response produces extractable petroleum hydrocarbon (EPH) chromatograms that can be used to calculate concentrations of specified carbon ranges for both aliphatic and aromatic fractions.

1.3.3 This method provides results for specific carbon number ranges in both aliphatic and aromatic fractions of EPH thereby providing a more accurate assessment of potential health risk at environmental sites.

1.3.4 This method provides an option where extracts from samples may be analyzed without having to be fractionated.

1.4 Method Limitations

1.4.1 Lower boiling hydrocarbons may co-elute with extraction solvents.

1.4.2 The EPH measured by this method is quantitatively restricted to the semi-volatile components as partial loss of volatiles (including those compounds lighter than C9) occurs during the extraction and/or concentration process.

1.4.3 The gas chromatographic conditions are not designed for samples containing

EPH with carbon numbers greater than C44.

1.5 Applicable Matrices

1.5.1 Surface water, ground water, and wastewater.

1.5.2 Soil, sediments or high solids sludge (>50%).

2.0 SUMMARY OF METHOD

2.1 This quantitative EPH method is adopted from the "Method for the Determination of Extractable Petroleum Hydrocarbons (EPH)," Massachusetts Department of Environmental Protection (1); the "Method for the Determination of Extractable Petroleum Hydrocarbons (EPH) Fractions," Washington State Department of Ecology (2); the "Leaking Underground Fuel Tanks Field Manual" of the California State Water Resources Control Board (3); "Test Methods for Evaluating Solid Waste" USEPA Method 8015B (4);

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"Method for the Determination of Total Petroleum Range Organics," Florida Department of Environmental Protection (5); and "Quantitation of Semi-Volatile Petroleum Products in Water, Soil, Sediment and Sludge," New Jersey Department of Environmental Protection

OQA-QAM-025-02/08 (6).

2.2 This method is adapted with modifications from ASTM Method D3328-82 and the US

Coast Guard Oil Spill Identification Procedure for Total Petroleum (7, 8).

2.3 Petroleum residues are extracted from sample matrices with methylene chloride, dried over sodium sulfate, solvent exchanged to hexane and concentrated in a Kuderna- Danish apparatus. However, if a non-aqueous sample is known to be contaminated with #2 fuel/diesel or the concentration of a non-#2 fuel/diesel petroleum product in a non-aqueous sample has been determined by this method to be below the number generated by the EPH calculator when it is assumed that 100% of the contamination is in the carbon range with the most conservative toxicity factor (as of June 1, 2010, the number is 1700 mg/Kg, subject to change), then solvent exchange and fractionation are not required.

Additionally, aqueous samples are not required to undergo solvent exchange and fractionation. Quantitation for non-fractionated samples is performed using the total area of all peaks present and dividing the chromatography into the eight carbon ranges is not required. For all other instances, the extracts are separated into aliphatic and aromatic fractions using silica gel columns, either commercially available or lab prepared. Each of the aliphatic and aromatic fractions are re-concentrated and subsequently analyzed separately by capillary column GC/FID. Each of the resultant chromatograms of the aliphatic and aromatic fractions are used to quantitate four distinct carbon number ranges. Each carbon number range is defined using equivalent carbon (EC) numbers.

The EC number is related to a compound's boiling point and retention time on a gas chromatography column normalized to the actual carbon numbers of n-alkanes. For example, the EC of acenaphthylene is 15.06 because its boiling point and GC retention time are halfway between those of n-tetradecane (a straight 14-carbon chain compound) and n-hexadecane (a straight 16-carbon chain compound). The EC numbers are used because they are more closely related to environmental mobility. The four EC number ranges for the aliphatic fractions are: EC9 to EC12, EC12 to EC16, EC16 to EC21 and EC21 to EC40. Similarly, the resultant chromatograms of the aromatic fractions are used to quantitate four distinct carbon number ranges. The four carbon number ranges for the aromatic fractions are: EC10 to EC12, EC12 to EC16, EC16 to EC21 and EC21 to EC36.

Surrogate compounds are added to all samples before extraction and their recoveries are monitored. Percent recoveries for the surrogates can be expected to be in the 50 - 90 % range. If fractionation is required, then fractionating surrogates are added to the hexane extract just prior to fractionation to monitor the efficiency of the fractionation process.

Percent recoveries for the fractionating surrogates should be between 40% – 140 %.

2.3.1 The EPH concentration is determined by integration of the FID chromatogram

(see section 11.2). Average calibration factors or response factors using the aliphatic standard mixture are used to calculate the concentration of each carbon range. Average calibration factors or response factors using the aromatic standard mixture are used to calculate the concentration of each carbon range. Concentrations of each carbon range from both fractions are summed for a total EPH concentration.

2.3.2 For extracts not undergoing fractionation, the concentration is determined by integration of the FID chromatogram (see section 11.3). Average calibration factors or response factors using the standard mixture are used to calculate the concentrations.

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2.3.3 The sensitivity of the method may be dependent on the level of interference rather than on instrumental limitations. The quantitation limit for each carbon range in soil is approximately 10 mg/kg and in water 100 ug/L.

2.3.4 Approximate Dynamic Range

2.3.4.1 EPH, both Fractionated and Non-fractionated Samples

Soil 80 -16000 mg/kg Aqueous 0.8 - 160 mg/L

2.3.4.2 Individual Carbon Ranges

Soil 10 - 2000 mg/kg Aqueous 0.10 - 20 mg/L

2.4 Compounds

2.4.1 Aliphatic Hydrocarbon Standard

Aliphatic Hydrocarbon (EC #) n-Nonane (C9) n-Decane (C10) n-Dodecane (C12) n-Tetradecane (C14) n-Hexadecane (C16) n-Octadecane (C18) n-Eicosane (C20) n-Heneicosane (C21) n-Docosane (C22) n-Tetracosane (C24) n-Hexacosane (C26) n-Octacosane (C28) n-Triacontane (C30) n-Dotriacontane (C32) n-Tetratriacontane (C34) n-Hexatriacontane (C36) n-Octatriacontane (C38) n-Tetracontane (C40)

2.4.2 Aromatic Hydrocarbon Standard

Aromatic Hydrocarbon (EC #) Acenaphthene (C15.5) Acenaphthylene (C15.06) Anthracene (C19.43) Benzo[a]anthracene (C26.37) Benzo[a]pyrene (C31.34) Benzo[b]fluoranthene (C30.14) Benzo[g,h,i]perylene (C34.01) Benzo[k]fluoranthene (C30.14) Chrysene (C27.41) Dibenz[a,h]anthracene (C30.36) Fluoranthene (C21.85) Fluorene (C16.55) Indeno[1,2,3-cd]pyrene (C35.01) 2-Methylnaphthalene (C12.89)

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Naphthalene (C11.7) Phenanthrene (C19.36) Pyrene (C20.8) 1,2,3-Trimethylbenzene (C10.1)

2.5 #2 Diesel Fuel Standard

The standard used for the LCS for #2 Fuel/Diesel analyses is #2 Diesel Fuel (available from Restek (item 31233), Supelco and NSI Solutions)

3.0 INTERFERENCES

3.1 Method interferences are reduced by washing all glassware and then rinsing with tap water, distilled water, methanol, and methylene chloride.

3.2 High purity reagents such as Burdick and Jackson GC2 methylene chloride, Baker capillary grade methylene chloride or equivalent must be used to minimize interference problems.

3.3 Before processing any sample, the analyst shall demonstrate daily, through the analysis of a method blank, that the entire system is interference-free.

3.4 Matrix interferences may be caused by contaminants that are co-extracted from the sample. The extent of matrix interference will vary considerably from source to source (e.g., fatty acids, biogenic materials, oxidized biodegradation products), depending upon the nature and diversity of the site being sampled. The silica gel cleanup procedure, USEPA SW-846 Method 3630B, can be used to overcome many of these interferences but unique samples may require additional cleanup approaches such as SW-846 Methods 3610B, 3620B and 3660B to achieve the necessary analytical sensitivity.

3.5 Naturally occurring alkanes may be detected by this method and may interfere with product identification. Naturally occurring plant waxes include predominantly odd carbon number alkanes from n-C25 through n-C35, and exhibit a dominant odd/even chain length distribution.

4.0 SAFETY

4.1 The toxicity or carcinogenicity of each reagent used in this method has not been defined precisely. Each chemical compound should be treated as a potential health hazard.

Exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of Occupational Safety and Health Administration (OSHA) regulations regarding the safe handling of the chemicals specified in this method. A reference file of material safety data sheets (MSDS) should also be made available to all personnel involved in the chemical analysis. Additional references to laboratory safety are available and have been identified for use by the analyst (9, 10).

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5.0 APPARATUS AND EQUIPMENT

5.1 Sampling Containers

5.1.1 Prior to use, wash bottles and cap liners with aqueous detergent solutions and rinse with tap water, distilled water, and methylene chloride. Allow the bottles and containers to air dry at room temperature, place in a 105oC (minimum temperature) oven for one hour, then remove and allow them to cool in an area known to be free of organic analytes.

5.1.2 Screw cap bottle - 40 mL PTFE-faced silicone cap liners.

5.1.3 Narrow mouth bottles - 1 liter, amber, PTFE faced silicone cap liners.

5.1.4 Wide-mouth glass jar-four ounce, amber, PTFE faced silicone cap liners.

5.2 Glassware

5.2.1 Serum bottles - 100 mL, 10 mL, 2 mL crimp-top, PTFE-faced silicone cap liners.

5.2.2 Pasteur pipettes.

5.2.3 Screw-cap Erlenmeyer flasks - 250 mL, with PTFE faced silicone cap liners.

5.2.4 Volumetric flasks - 10 mL, 25 mL, 100 mL.

5.2.5 Kuderna-Danish apparatus (KD), 500 mL flask.

5.2.6 Separatory funnels - 2 L Pyrex, Teflon stopcock.

5.2.7 Soxhlet Extractor with 500 mL flask.

5.2.8 1 cm I.D. by 10 to 20 cm long glass column with glass or Teflon stopcock.

5.3 Apparatus

5.3.1 Analytical balance capable of accurately weighing 0.0001 g.

5.3.2 A gas chromatograph with split/splitless injector, equipped with a capillary column, capable of temperature programming. The analytical column chosen must adequately resolve the n-C9 to n-C40 aliphatic standard compounds and the aromatic standard compounds listed in 6.8.1 and 6.8.2 below. The recommended column is:

5.3.2.1 Column - 30m long x 0.32mm I.D., 0.25um film thickness, 95% dimethyl-5% diphenyl polysiloxane (Restek RTX-5 or equivalent).

Recommended Conditions:

Oven Temperature: 60oC; hold for 1 minute; 8o/minute to 290oC, hold for 7 minutes Injection size: 1 - 4 uL Gas Flow Rates: Carrier Gas - Helium @ 2 -3 mL/minute;

Oxidizer - Air @ 400 mL/minute;

Fuel - Hydrogen @ 35 mL/minute;

Make up - Air @ 30 mL/minute.

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Injection Port Temperature: 285oC Column Inlet Pressure 15 p.s.i.

Detector Temperature: FID @ 315oC Linear Velocity: 50 cm/sec

5.3.2.2 Detector - Flame Ionization Detector is required.

5.3.3 An autosampler is recommended.

5.3.4 Boiling chips (Teflon® preferred) - Solvent extracted approximately 10/40 mesh.

5.3.5 Water bath - Top, with concentric ring cover, capable of temperature control.

The bath should be used in a hood.

5.3.6 Gas-tight syringe - One milliliter (mL) with chromatographic needles.

5.3.7 Microsyringes - l0uL, 100uL, 200uL.

5.3.8 Magnetic stirrer and 2-inch Teflon coated stirring bars.

5.3.9 Nitrogen concentration system composed of a precleaned pasteur pipette, with a small plug of glass wool (previously washed with solvent and dried) loaded at the tip end, and filled with approximately 1-2 cm of precleaned alumina. The top of the pipette is attached to a hydrocarbon free nitrogen gas source using precleaned Teflon tubing. This concentration step should be performed at room temperature or lower to retain light end compounds.

6.0 REAGENTS

6.1 Purity of Reagents - Reagents are to be of the highest quality appropriate and shall conform to all pertinent specifications of the American Chemical Society.

6.2 Reagent water - Reagent water is defined as a water in which an interference is not observed at the MDL of each parameter of interest (ASTM Specification D1193, Type ii).

6.3 Methylene chloride, methanol, carbon disulfide and hexane - pesticide grade, Burdick and Jackson GC2, Baker Capillary Grade or equivalent.

6.4 Sodium sulfate - (ACS) granular, anhydrous. Purify by heating at 400oC for four hours in a shallow tray, cool in a desiccator and store in a sealed glass bottle.

6.5 Silica gel desiccant (for fractionation) - 100/200 mesh (Davison Chemical Grade 923 or equivalent). Before use, activate for at least 16 hours at 130oC in a shallow glass tray that is loosely covered in foil. Cool and store as in section 6.4. Commercially available Solid Phase Extraction (SPE) cartridges (20 ml tube volume/5 g bed weight) may be used (Restek - Massachusetts TPH Specialty SPE Cartridge or equivalent). (Please note:

Silica gel is hygroscopic. Unused cartridges must be stored in properly maintained desiccators prior to use to prevent absorption of moisture from air.)

6.6 Ottawa and/or masonry sand, free from extractable petroleum products, may be used in lieu of sodium sulfate where applicable (such as for sections 9.2.1 and 9.2.2.2)

6.7 Hydrochloric acid, 1:1 - Mix equal volumes of (ACS grade) concentrated HCl and distilled water.

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6.8 Standard Solutions

6.8.1 Aliphatic Hydrocarbon Stock Standard - Prepare a hexane solution containing at a minimum the aliphatic compounds listed in Section 2.4.1, naphthalene, 2-methylnaphthalene and the surrogates (1-chlorooctadecane and ortho-terphenyl) each at a concentration of 1 mg/ml. (Naphthalene and 2-methylnaphthalene are added to the aliphatic standard as their presence in the laboratory control sample and/or laboratory control sample duplicate is used to determine if fractionation for a batch is acceptable. Ortho-terphenyl is added to allow for surrogate recovery calculations from those extracts not undergoing fractionation.) For those extracts undergoing fractionation, the area from the surrogate ortho-terphenyl is not used in aliphatic calculations. Aliphatic mixtures are available from Supelco, Restek (Cat. # 31266), NSI Solutions and Ultrex. (Note: Due to the commercial availability of standards, it may be necessary to combine two commercially available standard mixtures which may result in the addition of compounds such as n-Nonane (C9) and n- Nonadecane (C19) to the aliphatic hydrocarbon standard.)

6.8.2 Aromatic Hydrocarbon Stock Standard - Prepare a methylene chloride solution containing the aromatic compounds listed in Section 2.4.2, the surrogate compound (ortho-terphenyl) and the fractionating surrogate compounds (2- Bromonaphthalene and 2-Fluorobiphenyl) each at a concentration of 1 mg/ml.

(Aromatic mixtures are available from Supelco, Restek (Cat. # 31469), NSI Solutions and Ultrex.)

6.8.3 Surrogate - The surrogate ortho-terphenyl (OTP) is prepared by weighing

0.0100 g of pure material in a 10 mL volumetric flask. Dissolve the material to volume in methylene chloride. The surrogate 1-chlorooctadecane (COD) is prepared by carefully weighing 0.0100 g of pure material in a 10 mL volumetric flask. Dissolve the material to volume with hexane. (Surrogate solutions are available from Restek Inc. [11].)

6.8.4 Surrogate Spiking Solution - Prepare a surrogate spiking solution containing

OTP and COD at a concentration of 100 ng/uL each in acetone. Each sample, blank, and matrix spike is fortified with 1.0 ml of the surrogate spiking solution.

Alternative concentrations are permissible and, in instances when spiking highly contaminated samples, the use of higher concentrations is advisable.

6.8.5 Laboratory Control Sample (LCS) (Blank Spike) Solution - The LCS solution is the same as the matrix spiking solution described in 6.8.6 below. 1 mL is used to fortify either reagent water or clean sand (or sodium sulfate).

6.8.6 Matrix spiking solution (MSS) - Prepare the MSS containing all the compounds in sections 2.4.1 and 2.4.2 in pentane each at a concentration of 100 ng/uL.

The source of the standards shall be different than those from which the calibration standards are made. A 1 mL aliquot is added to the sample designated as the matrix spike. Alternative concentrations are permissible and, in instances when spiking highly contaminated samples, the use of higher concentrations is advisable. (Matrix spiking solutions are available from Restek.)

6.8.7 Fractionating Surrogates: The fractionating surrogates (2-Bromonaphthalene and 2-Fluorobiphenyl) are prepared by weighing 0.0100 g of pure material in a 10-ml volumetric flask and dissolving the material in Methylene Chloride.

(Surrogates are available from Restek Inc.)

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6.8.8 Fractionating Surrogate Spiking Solution - Prepare the solution containing 2-

Bromonaphthalene and 2-Fluorobiphenyl at concentrations of 100 ng/ul each in hexane. An aliquot of 1 ml of the fractionating surrogate spiking solution is added to the 1 ml EPH sample extract prepared in accordance with sections

10.1 and 10.2 just prior to fraction separation with silica gel. Alternative concentrations are permissible and, in instances when spiking highly contaminated samples, the use of higher concentrations is advisable.

6.8.9 Fractionating Check Solution - This solution is used to monitor the fractionation efficiency of the silica gel cartridge/column and establish the optimum hexane volume required to efficiently elute the aliphatic fraction without significant aromatic breakthrough.

Prepare the solution containing 200 ng/uL of all the compounds listed in the aliphatic hydrocarbon standard and 200 ng/uL of all the compounds listed in the aromatic hydrocarbon standard cited in sections 6.8.1 and 6.8.2 respectively, in hexane.

6.8.10 #2 Fuel/Diesel Laboratory Control Sample (LCS) (Blank Spike) Solution –

Prepare a #2 Diesel fuel (purchased from an analytical standards provider such as Supelco, cat. # 31233) in methylene chloride at a recommended concentration of 250 ng/uL) 1 mL is used to fortify either reagent water or clean sand (or sodium sulfate).

6.8.11 #2 Diesel Fuel Standard (Optional). Prepare in methylene chloride a standard of # 2 Diesel fuel at a recommended concentration of 250 ng/uL and OTP and COD at concentrations of 100 ng/uL. This standard may be used to determine the recoveries of the #2 Fuel/Diesel LCS and LCSDs in lieu of using the Aliphatic Hydrocarbon Standard.

7.0 SAMPLE COLLECTION, PRESERVATION AND STORAGE

7.1 Aqueous Matrix

7.1.1 Collect a representative water sample in a 1 L narrow mouth bottle. A delay between sampling and analysis of greater than four hours requires sample preservation by the addition of 5 ml HCl (see section 6.7). Confirmation of a pH < 2 must be obtained in the field.

7.1.2 Sample must be chilled to 4±2oC at the time of collection and stored at 4±2oC until received at the laboratory.

7.1.3 The laboratory must determine the pH of all water samples as soon as possible after sample receipt and prior to extraction. Any sample found to contain a pH 2 must be noted in a laboratory notebook and the pH must be adjusted as soon as possible. Samples are to be stored at 4±2oC until extraction.

7.1.4 Samples must be extracted within fourteen days from the time of collection.

Extracts must be analyzed within 40 days of extraction.

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7.2 Solid Matrix

7.2.1 Collect a representative soil-sediment sample in a four-ounce, wide-mouth jar with a minimum of air space.

7.2.2 Samples must be chilled at 4±2oC at the time of collection and stored at 4±2oC until analyzed.

7.2.3 Samples must be extracted within fourteen days from the time of collection.

Extracts must be analyzed within 40 days of extraction.

8.0 CALIBRATION

8.1 Initial Calibration for samples undergoing fractionation

8.1.1 Retention time windows

8.1.1.1 Before establishing windows, make sure the GC system is within optimum operating conditions. Make three injections of the Aromatic Hydrocarbon and Aliphatic Hydrocarbon standard mixtures. Serial injections over less than a 72 hr period result in retention time windows that are too restrictive.

8.1.1.2 Calculate the mean and the standard deviation of the three retention times (use any function of retention time including absolute retention time or relative retention time) for each individual compound in the aromatic standard, each individual compound in the aliphatic standard and all surrogates.

8.1.1.3 Plus or minus three times the standard deviation of the mean retention times for each compound in the aromatic and aliphatic standards will be used to define the retention time window;

however, the experience of the analyst should weigh heavily in the interpretation of chromatograms. The default value for the retention time shall be a minimum of ± 0.1 minutes, if the standard deviation is zero or close to zero.

8.1.1.4 Establish the midpoint of the retention time window for each surrogate by using the absolute retention for each surrogate from the mid-concentration standard of the initial calibration. The absolute retention time window equals the midpoint + 3 SD, where the standard deviation is determined as described in section 8.1.1.2.

8.1.1.5 The laboratory must calculate retention time windows for each aromatic standard compound, each aliphatic standard compound and each surrogate on each GC column and whenever a new GC column is installed. The data must be retained by the laboratory.

8.1.2 FID External Standard Calibration for Quantitation of EPH. - Calibrate the GC-

FID with an initial five-point calibration. The recommended standard concentrations of each individual component are 20 ng/uL, 100 ng/ul, 250 ng/uL, 500 ng/uL and 1000 ng/uL. Separate calibrations are to be conducted for each fraction (see sections 6.8.1 and 6.8.2). The highest concentration

Extractable Petroleum Hydrocarbons Methodology Page 11 of 42 point should be twice the expected sample concentration and within the linear range of the instrument. To maintain the standards in solution, a 10% carbon disulfide / 90% methylene chloride solvent may be required. Standards with concentrations greater than 20 mg/L may need to be equilibrated to room temperature prior to analysis. Prepare the calibration standards to contain the surrogates at the same concentrations as the individual components. The surrogate OTP and the fractionating surrogates are included in the Aromatic Hydrocarbon Standard. The surrogates COD and OTP are included in the Aliphatic Hydrocarbon Standard.

A calibration factor (CF) must be established for each individual component.

Also, a separate calibration factor (CF) must be established for each carbon range of interest. Calculate CFs for the C9-C12, C12-C16, C16-C-21 and C21- C40 Aliphatic Hydrocarbon carbon ranges from the appropriate aliphatic analysis chromatogram. Calculate CFs for C10-C12, C12-C16, C16-C-21 and C21-C36 Aromatic Hydrocarbon carbon ranges from the appropriate aromatic analysis chromatogram.

For the aliphatic fraction, use the following compounds as carbon range markers:

Range Compound EC C9-C12 n-Nonane 9.0 n-Dodecane 12.0 C12-C16 n-Dodecane + 0.1 min n-Hexadecane 16.0 C16-C21 n-Hexadecane + 0.1 min n-Heneicosane 21.0 C21-C40 n-Heneicosane + 0.1min n-Tetracontane 40.0

For the aromatic fraction, use the following compounds as carbon range markers:

Range Compound EC C10-C12 1,2,3-Trimethylbenzene 10.1

Naphthalene 11.7 C12-C16 Naphthalene + 0.1 min

Acenaphthene 15.5 C16-C21 Acenaphthene + 0.1 min

Pyrene 20.8 C21-C36 Pyrene + 0.1min

Benzo(g,h,i)perylene + 1.0 minute 34.01

(Please note: The "+ 0.1 minutes" noted above in both the aromatic and aliphatic fractions are maximums. The laboratory should use less than the "compound + 0.1 minute" as the carbon range marker if peak shape and chromatographic resolution are favorable.)

The Calibration Factor (CF) is defined as the ratio of the peak area to the concentration injected.

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For individual compounds, the calibration factors are determined by the following equation.

)/( uLngInjectedionConcentrat

PeakofArea

CF

For the carbon ranges, tabulate the summation of the peak areas of all the compounds in each carbon range against the total concentration injected for that carbon range. The Calibration Factor (CF), defined as the ratio of the summed peak area to the concentration injected, is calculated for each carbon range using the following equation:

)uL/ng(InjectedionConcentratTotal theRangeinPeaksofAreaSummed CFRangeCarbon

Note that the areas for the surrogates must be subtracted out from the area summation of the range in which they elute. Also, any areas associated with naphthalene and 2-methylnaphthalene in the aliphatic fraction must be subtracted out from the appropriate carbon range.

The percent relative standard deviation (%RSD) of the calibration factors for each compound and surrogate must be 25% over the working calibration range.

CFsofMean

CFs5ofDeviationStandard

RSD

each carbon range for the compounds and surrogates must be 25% over the working calibration range.

CFsRange5ofMean

CFsRange5ofDeviationdardtanS

RSD%

If any %RSD is 25%, the source of the problem should be identified and the problem resolved.

8.2 Daily Calibration for samples undergoing fractionation

8.2.1 At a minimum, the working calibration factors must be verified on each working day, after every 20 samples or every 24 hours (whichever is more frequent) and at the end of the analytical sequence by the injection of the mid-level calibration standards (both aliphatic and aromatic). Calculate the percent differences (D %) between the continuing calibration factors and the average calibration factors from the initial calibrations for each compound, for each carbon range for each fraction and for the surrogates. If the %D of any carbon range is 25% (30% for any single compound in a range) then a new calibration curve has to be generated for that range. Any sample associated with a non-compliant calibration shall be reanalyzed.

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AVG

ccAVG

CF

CFCF

D%

Where:

CFAVG = Average Calibration Factor calculated from initial calibration CFCC = Calibration Factor calculated from continuing calibration standard

8.2.2 The retention times of surrogates in the calibration verification standard analyzed at the beginning of the analytical shift must fall within the absolute retention time windows calculated in Sec. 8.1.1.2. The purpose of this check is to ensure that retention times do not continually drift further from those used to establish the widths of the retention time windows. If the retention time of any surrogate at the beginning of the analytical shift does not fall within the ± 3 SD window (minimum ±0.10 min.), then a new initial calibration is necessary.

In addition, the retention times of all surrogates in the subsequent calibration verification standards analyzed during the analytical shift must fall within the absolute retention time windows established in Sec. 8.1.1.4.

8.2.3 Surrogate Standards (SS) - The SS responses and retention times in the calibration check standard must be evaluated during or immediately after data acquisition. If the retention time(s) for the SS is outside the determined RT window, the chromatographic system must be inspected for malfunctions and corrections must be made. If the area(s) for the SS changes by ±50% from the last daily calibration standard check, the GC must be inspected for malfunctions and corrections must be made.

8.3 Initial Calibration for samples not requiring fractionation

8.3.1 Retention time windows

The same retention time window criteria described in 8.1.1 are used to satisfy the requirements of this section. It is only necessary to address the aliphatic components of the section.

8.3.2 FID External Standard Calibration for Quantitation of pre-fractionated extract analyses

The same calibration standards analyzed pursuant to Section 8.1.2 above are used to determine concentrations found in the extracts that have not undergone fractionation. Only the aliphatic fraction is used for the calibration standards for extracts that have not undergone fractionation. However, the aliphatic calibration standards are to include both surrogates OTP and COD.

Additionally, for extracts from samples known to be contaminated with #2 Fuel/Diesel, the gas chromatographic analyses may be stopped after C28 elutes, providing no peaks in the sample analysis elute after the peak represented by C28.

As noted above in 8.1.2, a calibration factor (CF) must be established for each individual component. The calibration factors established in section 8.1.2 above are used. Additionally, a separate calibration factor (CF) must be established for the total range from those compounds listed in section 2.4.1 including the first and last eluting compounds in the series (i.e., C-9 through and including C-40). For extracts from samples known to be contaminated

Extractable Petroleum Hydrocarbons Methodology Page 14 of 42 with #2 Fuel/Diesel, the total range calibration factor is determined using the areas from the C9 through and including the C28 peaks.

The Calibration Factor (CF) is defined as the ratio of the peak area to the concentration injected.

For individual compounds, the calibration factors are determined by the following equation.

)/( uLngInjectedionConcentrat

PeakofArea

For the total range, tabulate the summation of the peak areas of all the compounds against the total concentration injected. The Calibration Factor (CF), defined as the ratio of the summed peak area to the concentration injected, is calculated for the total range using the following equation:

uLngInjectedionConcentratTotal

CFRangeTotal

Note that the areas for the surrogates must be subtracted out from the area summation of the range.

each compound and surrogate must be 25% over the working calibration

CFsofMean

CFs5ofDeviationStandard

RSD

the total range for the compounds must be 25% over the working calibration

CFsRange Total ofMean

CFsRange Total5ofDeviationStandard

RSD

If any %RSD is 25%, the source of the problem should be identified and the problem resolved.

8.4 Daily Calibration for samples not requiring fractionation

8.4.1 The same calibration standards analyzed pursuant to Section 8.2.1 above are used to determine the concentrations found in the extracts that have not undergone fractionation. At a minimum, the working calibration factors must be verified on each working day, after every 20 samples or every 24 hours (whichever is more frequent) and at the end of the analytical sequence by the injection of the mid-level calibration standards. It is only necessary to calculate the percent differences (%D) between the continuing calibration factors and the average calibration factors from the initial calibrations for each compound, for the total range for aliphatic compounds and for the surrogates. If the %D of the total range is 25% (30% for any single compound) then a new calibration

Extractable Petroleum Hydrocarbons Methodology Page 15 of 42 curve has to be generated. Any sample associated with a non-compliant calibration shall be reanalyzed.

AVG

ccAVG

CF

CFCF

D%

CFAVG = Average Calibration Factor calculated from initial calibration CFCC = Calibration Factor calculated from continuing calibration standard

8.4.2 The retention times of surrogates in the calibration verification standard analyzed at the beginning of the analytical shift must fall within the absolute retention time windows calculated in Sec. 8.3.1. The purpose of this check is to ensure that retention times do not continually drift further from those used to establish the widths of the retention time windows. If the retention time of any surrogate at the beginning of the analytical shift does not fall within the ± 3 SD window (minimum ±0.10 min.), then a new initial calibration is necessary.

In addition, the retention times of all surrogates in the subsequent calibration verification standards analyzed during the analytical shift must fall within the absolute retention time windows established in Sec. 8.3.1.4.

8.4.3 Surrogate Standards (SS) - The SS responses and retention times in the calibration check standard must be evaluated during or immediately after data acquisition. If the retention time(s) for the SS is outside the determined RT window, the chromatographic system must be inspected for malfunctions and corrections must be made. If the area(s) for the SS changes by ±50% from the last daily calibration standard check, the GC must be inspected for malfunctions and corrections must be made.

8.5 #2 Diesel Fuel Standard (optional) – This standard may be used for calculations associated with the #2 Fuel/Diesel LCS calculations only. Linearity of the gas chromatography system is demonstrated through the analyses of the individual standards noted in previous sections. As such, it is not required to generate an additional calibration curve for the #2 diesel fuel standard. The calibration factor used to calculate the LCS data is determined by the following equation

(ng/uL)InjectedionConcentratTotal

CFFuel Diesel #2

8.6 Mass Discrimination Check

8.6.1 Mass discrimination can take place in the injection port of the gas chromatograph. The higher boiling point molecules may not enter the column with the same efficiency as the lower boiling point molecules with a resulting bias toward the lower boiling molecules. This phenomenon must be checked and if present corrected prior to calibrating and analyzing samples.

8.6.2 Mass discrimination is minimized by placing a small plug of silanized glass wool one centimeter from the base of the glass injection liner. The end of the capillary column is placed just below the glass wool. The capillary column should be placed flush with the surface of the gold seal. A full range alkane standard should be run to test the degree of mass discrimination before

Extractable Petroleum Hydrocarbons Methodology Page 16 of 42 performing any actual sample analyses. For non-#2 Fuel/Diesel analyses, the response ratio of C30/C20 shall be ≥ 0.8. . For #2 Fuel/Diesel analyses, if the chromatography range ends at C28, then the response ratio of C28/C20 shall be ≥ 0.8. If the response ratio is less than 0.8, the column should be repositioned until the mass discrimination is minimized.

9.0 QUALITY CONTROL

9.1 Each laboratory that uses this method is required to operate a formal quality control program which conforms to New Jersey Regulation N.J.A.C. 7:18-4.7 (12). The minimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of QC samples to evaluate and document data quality. The laboratory must maintain records to document the quality of data that is generated.

Ongoing data quality checks are compared with laboratory established performance criteria to determine if the results of analyses meet the performance characteristics of the method.

9.1.1 The analyst must make an initial, one-time demonstration of the ability to generate acceptable accuracy and precision with this method (see section 9.2).

9.1.2 In recognition of advances that are occurring in chromatography, the analyst is permitted to improve the separations by changing the GC conditions or column.

Each time such a modification is made to the method, the analyst is required to repeat and document the procedure in section 9.2.

9.1.3 Each day before calibration and after the calibration, the analyst shall analyze a reagent blank (instrument blank) to demonstrate that interferences from the analytical system are under control. Peaks should not be detected above the quantitation limit within the retention time window of any carbon range of interest. If so, re-extraction of all associated samples may be warranted.

9.1.4 With each sample batch, the analyst must analyze a method blank to demonstrate that interferences from sample extraction are under control.

Target compounds' concentrations in the blank should be no more than 5X MDL. If blank levels for any component are above 5X MDL and the sample concentrations present in the samples are greater than 10X then the samples may be quantified and qualified. If the blank concentration is greater than 5X MDL and the sample concentrations present in the samples are less than 10X the blank level, the affected samples should be re-extracted and re-analyzed.

If a sample cannot be re-extracted or re-analyzed, the data must be qualified as such.

9.1.5 Contamination by carryover may occur when high concentration samples are analyzed. When highly contaminated sample extracts are analyzed, it is recommended that a solvent blank be analyzed immediately following to check for cross contamination. If contamination is present, the system must be cleaned before continuing sample analysis. If a sample immediately analyzed after the highly contaminated sample is free from contamination then it is safe to make the assumption that carryover or cross contamination is not an issue.

However, if the sample(s) analyzed after the highly contaminated sample exhibits the same compounds and/or same chromatographic fingerprint and no system cleaning was implemented, then carryover or cross-contamination may be suspected and all affected samples may be required to be reanalyzed.

Extractable Petroleum Hydrocarbons Methodology Page 17 of 42

9.1.6 The laboratory must, on an ongoing basis, demonstrate through the analyses of a Laboratory Control Sample (LCS) and Laboratory Control Sample Duplicate (LCSD) that the operation of the measurement system is in control.

This procedure is described in sections 9.3 and 9.4. The frequency of the LCS/LCSD pair is one in every 20 samples of similar matrix.

9.1.7 The laboratory must spike all samples with the surrogates to monitor recovery.

This procedure is described in section 9.5.

9.1.8 For all samples undergoing fractionation, the laboratory must spike all extracts with fractionating surrogate compounds prior to the extract being separated into aliphatic and aromatic fractions. The fractionating procedure is described in section 10.3.

9.1.9 The laboratory must spike a minimum of five percent or one per batch, which ever is more frequent of all samples in each matrix, with the MSS (see section 6.8.6) to monitor and evaluate laboratory data quality. This procedure is described in section 9.7.

9.1.10 An auto sampler vial septum should be penetrated and extracted with methylene chloride to evaluate the potential alkane distribution that could occur in re-analyzed extracts. Vial septa should be changed after each analysis.

9.2 To initially establish the ability to generate acceptable precision and accuracy, the laboratory must perform the following operations.

9.2.1 Samples undergoing fractionation

Multiple extraction and analysis of the LCSs containing aliphatic and aromatic compounds described in section 6.8.6 is required. The LCS concentrates must be prepared by the laboratory using stock standards prepared from a second source (i.e., other than the source used for calibration). All the LCSs must be prepared, extracted, fractionated and analyzed exactly as a typical environmental sample submitted for analysis.

9.2.1.1 For Soil and Sediments, prepare seven 10 g aliquots of clean sand

(or sodium sulfate) spiked with 1.0 mL of MSS from section 6.8.6 and 1.0 mL of the Surrogate Spiking Solution from section 6.8.4.

Follow all extraction, fractionation and analytical procedures described in this method.

9.2.1.2 Calculate the mean recovery (Cmean) for each of the aliphatic and aromatic compounds using the seven results. The average percent recovery for each compound must be between ±40% of the true value.

9.2.1.3 Calculate the percent relative standard deviation (%RSD) of the seven replicate analyses using the following calculation:

mean n

C

S

RSD 1%

Where

Sn-1 = standard deviation (n-1) of the replicates

Extractable Petroleum Hydrocarbons Methodology Page 18 of 42

Cmean = mean of the concentration of a compound from the replicates

The %RSD for each compound must be less than or equal to 25%.

A higher %RSD is allowed for n-Nonane but the value must be documented.

9.2.1.4 The FID retention times of the surrogates must match those in the calibration standard as described in section 8.1.1.

9.2.2 #2 Fuel/Diesel

Multiple extraction and analysis of the LCSs containing the solution described in section 6.8.10 is required. LCSs must be prepared, extracted and analyzed exactly as a typical environmental sample submitted for analysis.

9.2.2.1 Aqueous

Prepare seven 1 L aliquots of the well-mixed reagent water spiked with 1.0 mL of LCS solutions from section 6.8.10. Follow all extraction and analytical procedures described in this method.

9.2.2.2 Soil and Sediment

Prepare seven 10 g aliquots of clean sand (or sodium sulfate) spiked with 1.0 mL of LCS solution from section 6.8.10. Follow all extraction and analytical procedures described in this method.

9.2.2.3 For each matrix, calculate the mean recovery (Cmean) for #2 diesel fuel using the seven results. The average percent recovery for each compound must be between ±40% of the true value.

9.2.2.4 For each matrix calculate the percent relative standard deviation

(%RSD) of the seven replicate analyses using the following calculation:

mean

C

RSD 1%

Sn-1 = standard deviation (n-1) of the replicates Cmean = mean of the concentration of a compound from the replicates

The %RSD for each compound must be less than or equal to 25%.

9.2.2.5 For each matrix, the FID retention times of the surrogates must match those in the calibration standard as described in section 8.1.1.

9.2.3 Aqueous samples other than #2 Fuel/Diesel

Prepare seven 1 L aliquots of the well-mixed reagent water spiked with 1.0 mL of MSS from section 6.8.6 and 1.0 mL of the Surrogate Spiking Solution from

Extractable Petroleum Hydrocarbons Methodology Page 19 of 42 section 6.8.4. Follow all extraction and analytical procedures described in this

9.3 For each analytical batch (up to 20 samples of a similar matrix) the laboratory must analyze a LCS.

9.3.1 Samples undergoing fractionation

For each analytical batch (up to 20 samples of a similar matrix) the laboratory must analyze a LCS. The LCS shall be prepared by fortifying a clean sand (or sodium sulfate) blank with 1.0 mL of the matrix spiking solution (section 6.8.6).

The recoveries of each of the compounds in the LCS must be between 40% - 140%. Lower recoveries are permissible for n-Nonane but the recoveries must be greater than 25% and must be noted in the case narrative. In addition to the individual recoveries, the recoveries of each of the carbon ranges should be determined and reported. The FID retention times of the surrogates must match the previous calibration as described in section 8.1.1.

9.3.2 #2 Fuel/Diesel Samples must analyze a LCS. The LCS shall be prepared by fortifying a reagent water or clean sand (or sodium sulfate) blank with 1.0 mL of the LCS solution (section 6.8.10). The recovery of the #2 diesel fuel used for the LCS must be between 40% - 140%. The FID retention times of the surrogates must match the previous calibration as described in section 8.1.1.

9.3.3 Aqueous samples other than #2 Fuel/Diesel

must analyze a LCS. The LCS shall be prepared by fortifying a reagent water blank with 1.0 mL of the matrix spiking solution (section 6.8.6). The recoveries of each of the compounds in the LCS must be between 40% - 140%. Lower recoveries are permissible for n-Nonane but the recoveries must be greater than 25% and must be noted in the case narrative. The FID retention times of the surrogates must match the previous calibration as described in section 8.1.1.

9.4 For the same analytical batch described in section 9.3 above, (up to 20 samples of a similar matrix) the laboratory must analyze a LCSD. The LCSD is separately prepared, processed and analyzed in the same manner as the LCS.

9.4.1 Samples undergoing fractionation

The recoveries of each of the compounds in the LCSD must be between 40% - 140%. Lower recoveries are permissible for n-Nonane but the recoveries must be greater than 25% and must be noted in the case narrative. In addition to the individual recoveries, the recoveries of each of the carbon ranges should be determined and reported. The Analytical batch precision is determined from the Relative Percent Difference (RPD) of the concentrations (not the recoveries) of the LCS/LCSD pair. The RPDs for the aliphatic and aromatic carbon range concentrations (the sum of the individual compounds'

Extractable Petroleum Hydrocarbons Methodology Page 20 of 42 concentrations within a carbon range) must be 25%. The FID retention times of the surrogates must match the previous calibration as described in section 8.3.1.

9.4.2 #2 Fuel/Diesel Samples

The recovery of #2 Diesel Fuel used for the LCSD must be between 40% - 140%. The Analytical batch precision is determined from the Relative Percent Difference (RPD) of the concentrations (not the recoveries) of the LCS/LCSD pair. The RPDs for the #2 diesel fuel must be 25%. The FID retention times of the surrogates must match the previous calibration as described in section 8.3.1.

9.4.3 Aqueous samples other than #2 Fuel/Diesel

The recoveries of each of the compounds in the LCSD must be between 40% - 140%. Lower recoveries are permissible for n-Nonane but the recoveries must be greater than 25% and must be noted in the case narrative. The Analytical batch precision is determined from the Relative Percent Difference (RPD) of the concentrations (not the recoveries) of the LCS/LCSD pair. The RPDs for the concentrations must be 25%. The FID retention times of the surrogates must match the previous calibration as described in section 8.3.1.

9.5 As a quality control check, the laboratory must spike all samples with the surrogates in section 6.8.3 and calculate the percent recovery (%R) of the Surrogate based on the FID response.

100*% s x

A

A R

Ax = Area response of SS in check sample As = Average area response of SS in standard

9.5.1 For the surrogate standards, the laboratory must develop separate accuracy statements of laboratory performance for each matrix and for both fractionated and non-fractionated extract analyses. An accuracy statement for the method is defined as Percent Recovery ± Standard Deviation (R ± s). The accuracy statement should be developed by the analysis of four aliquots as described in section 9.2, followed by the calculation of R and s. Alternatively, the analyst may use four data points gathered through the requirement for continuing quality control in section 9.3. The accuracy statements should be updated regularly. The recovery must be within 40% - 140%.

9.5.2 Calculate upper and lower control limits for %R for the surrogate standard in each matrix.

Upper Control Limit (UCL) = R + 3s Lower Control Limit (LCL) = R - 3s

The UCL and LCL can be used to construct control charts that are useful in observing trends in performance.

9.5.3 The following corrective actions can be taken when the percent recovery of

OTP and/or COD are outside of the recovery ranges:

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