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January 30, 2018, 1:30 pm (Eastern)
TPH – A Simple Concept?
Bryce Stearns,
Corporate Technical
Director, TestAmerica
Ask The Expert Webinar Series
Thank you for joining today’s webinar.
Any comments or questions may be
submitted via the GoToWebinar question
panel and a Question & Answer session
will immediately follow the presentation.
Today’s Presenter:
1
Overview
• What is ‘TPH’
• How can TPH be described
• How is TPH measured
• TPH Analytical Methods
3
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?
Crude Oil Components
Chemical Breakdown:
8
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
9
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
10
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
13
Methods – 1664A & 9071B
• Gravimetric
• “Gross” value for HEM (~TPH)
• Clean-ups (1664A)
• ~C7-C40+
• Loss of lighter VOA analytes
16
Methods – 1664A & 9071B
• Very non-specific
• Higher RLs
• Requires clean-ups to
remove interferences
• No individual analytes
• Single value
• Widely supported
• Fewer technical
challenges
17
Gas Chromatography
Gas Chromatography or “GC”
Most widely used analytical technique
Separation and detection
Capillary Column
Detectors
Output
https://www.chromatographer.com
18
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
19
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
20
Method – 8015 GRO
• Purge and Trap GC/FID
• Waters and soils
• Common Carbon Range
• C6-C10
• Non-specific detector
21
Method – 8015 GRO
• Pattern evaluation may be
important
• Can be impacted by non-
petroleum analytes
22
Method – 8015 DRO
• Extractable GC/FID
• Widely used
• Common Carbon Ranges
• C10-C28
• Non-specific detector
23
Side Note:
Fractions - Fractionation
Fractions:
Aliphatic Aromatic
Hexane Naphthalene
Fractionation:
• Process of differentiating between Aliphatic and
Aromatic portion (TPH)
• Instrumentally
• Chemically
27
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
29
EPH Analytical Process
Extractable Petroleum Hydrocarbons
Sample Homogenization*
Extraction
Concentration
Fractionation
Concentration
Analysis
31
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
32
Method - 8260
• Volatile Method
• Purge and Trap GC/MS
• Wide range of Compounds
• Positive Compound ID (BTEX)
• Non Routine for TPH
33
Method - 8270
• Semi-Volatile Method
• Extractable GC/MS
• Wide range of Compounds
• Positive Compound ID
• Not Routine for TPH
• Commonly used for PAHs
34
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
35
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
37
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
38
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
39
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
40
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
43
Things to think about
Identification of patterns
Identification of non-petroleum interferences
Complex Chromatograms require accurate peak
assignment and integration
Analyst Experience!
44
Conclusion:
TPH - far from simple
Often defined by the method
Understanding analytical method application
Method Choice is important
45
Ask The Expert Webinar Series
Thank you for attending
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To view a recording of this webinar session, please contact:
TPH – A Simple Concept?
http://www.testamericainc.com/services-we-offer/ask-the-expert/bryce-stearns/