January 30, 2018, 1:30 pm (Eastern)

TPH – A Simple Concept?

Bryce Stearns,

Corporate Technical

Director, TestAmerica

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Today’s Presenter:

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TPH – A Simple Concept?

Presented By:

Bryce Stearns – Corporate Technical Director

Overview

• What is ‘TPH’

• How can TPH be described

• How is TPH measured

• TPH Analytical Methods

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Total Petroleum Hydrocarbons

Quantitative value representing the

amount of petroleum related material in

a sample.

Often defined by the analytical method

and not all definitions are the same

What is TPH?

What is TPH

Origin:

Crude Oil

Refined products

Properties

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Petroleum Refining

http://wiki.chemprime.chemeddl.org/

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Key Petroleum Products

Gasoline

Diesel

Motor Oil

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Crude Oil Components

Chemical Breakdown:

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Aliphatics

Aromatics

Hexane Naphthalene

cyclohexane

Benzo(e)Pyrene

Crude Oil Components

Characterized as:

Compound Classes Aliphatic Aromatic volatile semi-volatile

Boiling Point 60 C to >500 C

Carbon Range* e.g., C5-C40

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How do all these relate?

Carbon Ranges - Boiling Points - Classes

Analytical Implications

VOA

Aliphatics and

Aromatics

C5-C12

bp 60-170 C

SVOA

Aliphatics and

Aromatics

C10-C40

bp 170-520 C

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Key Petroleum Products

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Others Petroleum Products

Mineral Spirits

Kerosene

Hydraulic Fluids

Lubricating Fluids

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Analytical Methods

VOA

Primarily GC Purge

and Trap

Methods Covered:

8015 GRO

VPH

8260

Select State Methods

SVOA

Extractable

GC Analysis

Methods Covered:

8015 DRO

EPH

8270

Select State Methods

Gravimetric

Oil and Grease

Methods Covered:

1664A

9071B

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Analytical Methods

8260/8270

VPH/EPH

GRO/DRO

O&G

Specificity:

High

Low

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Analytical Methods

VOA

Purge

and Trap

SVOA

Extractable

Procedure

Gravimetric

Weighing

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Methods – 1664A & 9071B

• Gravimetric

• “Gross” value for HEM (~TPH)

• Clean-ups (1664A)

• ~C7-C40+

• Loss of lighter VOA analytes

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Methods – 1664A & 9071B

• Very non-specific

• Higher RLs

• Requires clean-ups to

remove interferences

• No individual analytes

• Single value

• Widely supported

• Fewer technical

challenges

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Gas Chromatography

Gas Chromatography or “GC”

Most widely used analytical technique

Separation and detection

Capillary Column

Detectors

Output

https://www.chromatographer.com

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VOA - Purge and Trap

Sample concentration

technique for volatile

compounds

Sample constituents are

purged

And trapped on a solid sorbent

material.

Subsequently desorbed off and

introduced to the GC

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SVOA - Sample Extraction

• Sample constituents are isolated and

concentrated prior to analysis

• Sample extracted with an organic solvent

• Solvent extract is dried

• Solvent extract may be “cleaned-up”

• Finally, solvent extract is concentrated

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Method – 8015 GRO

• Purge and Trap GC/FID

• Waters and soils

• Common Carbon Range

• C6-C10

• Non-specific detector

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Method – 8015 GRO

• Pattern evaluation may be

important

• Can be impacted by non-

petroleum analytes

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Method – 8015 DRO

• Extractable GC/FID

• Widely used

• Common Carbon Ranges

• C10-C28

• Non-specific detector

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Method – 8015 DRO

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• non-petroleum

related

analytes

Method – 8015 DRO

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• non-petroleum

related

analytes

Method – 8015 DRO

• Impacts from

other

petroleum

types

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Side Note:

Fractions - Fractionation

Fractions:

Aliphatic Aromatic

Hexane Naphthalene

Fractionation:

• Process of differentiating between Aliphatic and

Aromatic portion (TPH)

• Instrumentally

• Chemically

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Method – VPH

• Similar to 8015 GRO

• Purge and Trap GC/FID

• Additional detector - PID

• Supports Aliphatic and Aromatic Ranges

• Approximate Carbon Ranges

• Aliphatic C5-C12

• Aromatic C9-C10

• Can provide for BTEX 28

Method – VPH

• Pattern matching may be required

• Can be impacted by non-petroleum

analytes

• More specific then 8015 GRO

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VPH Analytical Process

Volatile Petroleum Hydrocarbons

VPH Methods (MADEP)

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FID

PID

EPH Analytical Process

Extractable Petroleum Hydrocarbons

Sample Homogenization*

Extraction

Concentration

Fractionation

Concentration

Analysis

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Method – EPH

• Similar to 8015 DRO

• Extractable Method

• Supports Aliphatic and Aromatic Ranges

• Approximate Carbon Ranges

• Aliphatic C9-C36

• Aromatic C11-C22

• Can provide for PAHs

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Method - 8260

• Volatile Method

• Purge and Trap GC/MS

• Wide range of Compounds

• Positive Compound ID (BTEX)

• Non Routine for TPH

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Method - 8270

• Semi-Volatile Method

• Extractable GC/MS

• Wide range of Compounds

• Positive Compound ID

• Not Routine for TPH

• Commonly used for PAHs

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Analytical Methods

SW-846 - GRO DRO 8260 8270

Massachusetts - VPH and EPH

Alaska – AK101, 102, and 103

Texas - TX1005 and TX 1006

New Jersey - EPH

Florida - FLPRO

Oregon and Washington – NWTPH Gx, Dx, VPH, EPH

Many others

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TPH by State

Method MA CT NJ NY NH PA

EPA 1664 X X X X X

SM 5520B F X X

EPA 8440 X X

EPA 9071 X X

SW 8015 DRO X X X X X X

SW 8015 GRO X X X X X

FL PRO X X

CT ETPH X

NJ EPH X

NJ QAM X

ASTMD5739 X

AK101, 102, 103 X

TX1005, TX1006 X

MADEP EPH X

MADEP VPH X

SW 8260 X X X X X

SW 8270 X X X X X

State Analytical Methods

Alaska – AK101, 102, and 103

Texas - TX1005 and TX 1006

Massachusetts - VPH and EPH

Kansas DHE – LRH, MRH, and HRH

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Alaska AK 101, 102, and 103

AK101

“GRO” C6-C10 P&T GC/FID/PID as Gasoline

AK102

“DRO” C10-C25 GC/FID Extractable as Diesel

AK103

“RRO” C25-C36 GC/FID Extractable as Motor Oil

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Texas TX1005 and TX1006

TX1005

Extractable method using GC/FID

Covers the range of C6-C35

! Both VOA and SVOA ranges

TX1006

Same as TX1005 + fractionation into Aliphatic and

Aromatic fractions

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MADEP VPH and EPH

VPH Fraction

C5 -C8 Ali

C9-C12 Ali

C9-C10 Aro

EPH Fraction

C9-C18 Ali

C19-C36 Ali

C11-C22 Aro

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Kansas DHE LRH, MRH, &

HRH

LRH

Fraction

C5 -C8 Ali

MRH & HRH

Fraction

C9-C18 Ali

C19-C35 Ali

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Analytical Options

TA Laboratory

Method

EPA 1664 Buffalo Chicago Denver Pensacola Nashville

SM 5520B F St Louis

NEPA 9071 Pittsburgh Savannah StLouis Nashville

SW 8015 DRO Numerous

SW 8015 GRO Numerous

FL PRO Nashville Pensacola Tallahassee

CT ETPH Nashville Pensacola Savannah Buffalo Edison

NJ EPH Nashville Edison Burlington

NJ QAM Edison Burlington Nashville

AK101, 102, 103 Nashville Pensacola Sacramento Seattle

TX1005, TX1006 Corpus Houston Pensacola Nashville

MADEP EPH Nashville Buffalo Pensacola

MADEP VPH Nashville Buffalo Pensacola

SW 8260 Numerous

SW 8270 Numerous

Things to think about

Methods are not without issues:

Co-eluting analytes

overlapping ranges,

Chemical interference

Possible loss of material (either VOA or SVOA)

Non-petroleum hydrocarbons, oils, and waxes

Biodiesel?

Weathering losses. Pattern recognition

Chromatographic Integration

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Things to think about

Identification of patterns

Identification of non-petroleum interferences

Complex Chromatograms require accurate peak

assignment and integration

Analyst Experience!

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Conclusion:

TPH - far from simple

Often defined by the method

Understanding analytical method application

Method Choice is important

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Thank You!

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Questions?

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TPH – A Simple Concept?

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