TPH in the Texas Risk Reduction Program (TRRP) · 2018-02-15 · nC6 - nC12 >nC8 – nC10 >nC12 – nC28 >nC12– nC16 . Is TPH Below Action Criteria? No Further Action. Yes No. Shell

Shell Global Solutions


TPH in the Texas Risk Reduction Program (TRRP)

Ileana Rhodes, PhDShell Global Solutions (US) Inc.

©2006 Shell Global Solutions (US) Inc. All rights reserved. Do not reproduce without the express written permission of copyright owner.


http://www.tceq.state.tx.us/comm_exec/forms_pubs/pubs/rg/rg-366_trrp_27.html

Texas Commission on Environmental Quality (TCEQ) Contact:

Ann Strahl [email protected]

Development of Human Health Protective Concentration Levels (PCLs) for Total Petroleum Hydrocarbon (TPH) Mixtures

TCEQ


Delineate & Characterize TPH Source Areas Using TCEQ Method 1005

• TPH is a method-defined parameter: Composition and concentration of TPH is determined by the procedures followed in the analytical method.

• TCEQ developed two analytical methods for TPH, TCEQ Methods 1005 and 1006which should be used for determining

• concentrations of TPH, • for establishing PCLs, and/or • determining the composition of TPH for PCL development.

• Analytical results from Method 1005 are primarily intended to be used to:• Determine the composition and concentration of the TPH • Identify source areas• Determine compliance with the established critical TPH PCLs.

• Additionally, the results from the method may also be used as a screening tool to determine whether or not the development PCLs for the TPH mixture is warranted.


TCEQ Method 1005http://www.tceq.state.tx.us/compliance/compliance_support/qa/rev03-NetEdit.html

Sample

Shake/VortexCentrifuge

Extract Analyze Process Data

GC-FIDTCEQ 1005

Conditions/Calibration

Reporting Limits: 5 ppm (water) & 50 ppm (soil)Single extraction with n-pentane, analysis using GC/FID: C6 to C28 (or 35)TPH reported in carbon ranges as follows:

nC6 to nC12>nC12 to nC28 or 35*

*report to nC35 (when applicable)

An n-C12 alkane and an n-C28 alkane are used as markers to aid the data user in evaluating the distribution of the hydrocarbons in the TPH based on the chromatographic profile.


Screen TCEQ Method 1005 ResultsScreen TCEQ Method 1005 ResultsCompare the concentration in each reported carbon range to the following Tier 1 PCLs:

Carbon range Tier 1 PCLs

nC6 to nC12 aromatics >nC8 – nC10>nC12 to nC28 or 35* aromatics >nC12 – nC16 *report to nC35 (when applicable)

Use TCEQ METHOD 1006 if Tier 1 PCLs exceeded for either carbon range

TIERED APPROACH

www.tceq.state.tx.us/assets/public/remediation/trrp/method1006.pdf


980.98>12-16 C aromatics (TPH)

980.98>8-10 C aromatics (TPH)

GWGWClass 3GWGWIng

(mg/L)GROUNDWATER*

5900059012000>12-16 C aromatics (TPH)

190001903900>8-10 C aromatics (TPH)

(mg/kg)COMMERICAL/INDUSTRIAL SOIL*

200002002300>12-16 C aromatics (TPH)

6500651600>8-10 C aromatics (TPH)

(mg/kg)RESIDENTIAL SOIL*

GWSoilClass 3GWSoilIng

TotSoilCombFor example:

TCEQ Method 1005TCEQ Method 1005TCEQ Method 1005Quantitate TPH

and BP Distribution

GC/FID for TPHExtract Sample with n-Pentane 1:1

Use TCEQ Method 1006 to fractionate

* When the air pathway is evaluated, compare to the most conservative aliphatic or

aromatic PCL in the ranges.

For each pathway compareTCEQ Method Tier 1 PCLs for 1005 results: aromatic range:nC6 - nC12 >nC8 – nC10

>nC12 – nC28 >nC12– nC16

IsTPH

Below Action Criteria?

No Further Action

Yes

No


TCEQ Method 1005

Extract Sample with n-Pentane 1:1 GC/FID for TPH

No further action

TPH Below Action Level Criteria?

Yes

No

Quantitate TPH and BP Distribution

Fractionate Representative Sample

Yes

Fractionate highest for each source

No

GC Fingerprint Similar for all

Samples?

TCEQ Method 1006


Compare Gas Chromatograms or “Fingerprints” to Determine if There are Different TPH Source Areas

For each TPH source with a distinctly different

composition, analyze a representative sample

using TCEQ Method 1006 to determine the

composition and mass fraction of each aliphatic

and aromatic boiling point range

Map site with sampling locations with chromatographic profiles from TCEQ Method 1005


TCEQ Method 1005Extract Sample with

n-Pentane 1:1 GC/FID for TPHQuantitate TPH and BP

Distribution

TPH Below Action Level

Criteria?

No Further Action

GC Fingerprint Similar for all

Samples?

Yes

Fractionate Representative Sample

Fractionate highest for each source

Yes

TCEQ Method 1006

Fractionate by Silica Column Separation

GC/FID of 1:1 methylene chloride eluate for

Aromatics

GC/FID of n-pentane eluate for

Aliphatics

Quantitate Aliphatic and

Aromatic Fractions

No

No


TCEQ Methods 1005 and 1006www.tceq.state.tx.us/assets/public/remediation/trrp/method1006.pdf

GC-FIDTCEQ 1005

Conditions/CalibrationSample

Shake/VortexCentrifuge

ExtractAnalyze

Process DataFractionate

Aliphatics

Aromatics

TCEQ Method 1006

Single extraction with n-pentaneFractionation with Silica Gel into aliphatic and aromatic fractions(based on EPA Method 3630C)

n-pentane - aliphaticsmethylene chloride - aromatics

Two analyses by GC-FID similar to EPA 8100/8015Data analyzed & processed: Boiling ranges/approximate

carbon numbers fraction


Assess and characterize the extent of environmental media affected with TPH and identify distinct TPH source areas TCEQ Method 1005

Fractionate the TPH Mixture

Establish PCLs for the TPH mixture and determine the critical PCL

Determine compliance with critical PCLs

TCEQ Method 1005

TCEQ Method 1006

CH3

CH3

nC6>nC6-nC8>nC8-nC10>nC10-nC12>nC12-nC16>nC16-nC21>nC21-nC35

Aliphatics>nC7-nC8 (TolueneToluene) >nC8-nC10>nC10-nC12>nC12-nC16>nC16-nC21>nC21-nC35

Aromatics

C-C-C-C-C-C-C

C-C-C-C-C=C


Summary of the Tiered Approach

• TCEQ Method 1005 is used to define the TPH source and to measure TPH across a site.

• If the TPH distributions patterns are similar in all chromatograms, i.e., only the concentration is changing from sample to sample, then the extract from the sample with highest Method 1005 concentration is fractionated using TPH Method 1006. If the TPH have different distribution patterns, (indicating more than one source of TPH) the extract with the highest Method 1005 TPH result from each source is fractionated.

• Once the TPH is fractionated into the aliphatic and aromatic ranges. The protective concentration levels (PCLs) for the TPH mixture are calculated using the mass fractions and the PCLs for each boiling point range.

The URL link to the Excel spreadsheet used to calculate the PCLsfor the TPH mixture is http://www.tceq.state.tx.us/remediation/analysis.html


Ability to obtain a TPH distribution by analysis of the n-pentane extract prior to fractionation - TIERED APPROACHProvides simple “fingerprint” of productTPH results can be correlated with existing methodologySingle extraction, one fractionation and one to three injectionsFractionation procedure based on EPA 3630C (silica gel)GC analysis similar to the one currently used for TPH-diesel range (based on EPA 8015 and EPA 8100)Method has been successfully implemented at commercial environmental laboratoriesFor TPH, the reporting limit for water is 5 ppm and for soil is 50 ppm For TPH with fractionation, the reporting limits for soil are ~5 to 50 ppm per fraction depending on the fraction

C6 to C35 Range

TCEQ Method 1005 and TCEQ Method 1006


The Methods are NOT …• Easy (Fractionation)• Perfect

The Methods ARE …• Adequate• Probably as accurate and precise as other TPH

methods in current use• The best tools available to characterize

petroleum contaminated media


Current Status According to Ann Strahl, TCEQ:

• The methods and the approach to calculating a PCL for the TPH mixture are working well in Texas.

• Very few site cleanups are driven by TPH.

• Analysis for BTEX and other petroleum target chemicals of concern is required regardless of TPH results. For release reporting, analysis for PAHs is required when hydrocarbons in the >nC12 boiling point range are detected in the TCEQ Method 1005 results.



Brief Overviews

- Petroleum Hydrocarbon Chemistry - Total Petroleum Hydrocarbon Criteria Working

Group (TPHCGW)

Ileana Rhodes, PhDShell Global Solutions (US) Inc.

©2006 Shell Global Solutions (US) Inc. All rights reserved. Do not reproduce without the express written permission of copyright owner.


Composition of Crude OilsComposition of Crude Oils

H — C — C — C — C

H|

H|

H|

H|

|H

|H

|H

|H

• HETEROATOM COMPOUNDS- sulfur (sulfides, thiophenes)- nitrogen (carbazoles)- oxygen (organic acids, phenols)

• INORGANIC SEDIMENTS

• METALS

• WATER

• HYDROCARBONS

H|C

H — C

C|H

H — C

H|C

C

C|H

C

C — H

C — H

aliphatics/paraffins/alkanes

naphthenes/cycloalkanes

arenes/aromatics/polyaromatichydrocarbons

— C — C — C — C — H

H|

H|

H|

H|

|H

|H

|H

|H

H — C — C — C — C

H|

H|

H|

H|

|H

|H

|H

|H

alkenes/olefins(not in crude)

Crude oils are highly complex mixtures of:


Refining Process...Refining Process...

Diesel Fuel C14-C18 (250oC - 325oC)

Gasoline C4-C10 (80oC - 150oC)

Kerosene/Jet Fuel C11-C13 (150oC - 250oC)

CrudeOil Heavy Gas Oil C19-C25 (325oC - 450oC)

Lubricating Oil C26-C40 (450oC - 500oC)

Residuum >C40 (> 500oC)

The various products are characterized by different complex mixtures of thehydrocarbons with differing boiling points, carbon numbers and compositions.


High Resolution Gas Chromatogram-South Louisiana Crude Oil

GASOLINE RANGE

DIESEL RANGE

RESIDUAL RANGE

Analys is : s a0737,31,1 P roject: hydrocarbons Ins trument: chanl_08 Method: ma0814

"hydrocarbons ,chanl_08.s a0737,31,1,1;"US 53 S outh Louis iana Crude

Acquis ition Time: 03 Oct 1997 at 04:24.37

Res pons e(mV)

Time(minutes )

20

30

40

50

60

70

80

90

100

110

120

130

140

150

160

170

180

190

0 5 10 15 20 25 30 35 40 45 50 55

OTP

AN

DR

OS

TAN

E10 15

20

25

30 35

Pr

Ph


Distribution of Hydrocarbon Types in

a Crude Oil

Boiling Point (oC)

WeightPercent

0

20

40

60

80

100100 200 300 400 500

GasolineC4 - C10

KeroseneC11 - C13

DieselC14-C18

HeavyGas OilC19 - C25

LubeOil

C26-40

Residuum>C40

NormalAlkanes

Iso-Alkanes

Cyclo-Alkanes

Aromatics

Naptheno-Aromatics

Resins &Related

Compounds

What portion of the crude oil can go directly into gasoline???

Octane 40-60 How to get octane up & get the heavier hydrocarbons into the gasoline pool???


SIMPLIFIED REFINERY FLOW CHARTSIMPLIFIED REFINERY FLOW CHART

OUTPUTRefinery Gas

Propane

Solvents

GASOLINES

Jet, Diesel

Heating Oil

Chemical Feeds

Lubricating Oils

Asphalt, Coke

ALKYLATION

REFORMING

HYDROCRACKING/TREATING

FLUID CAT CRACKING

COKING

DIS

TILL

ATI

ON

Gas

Napthas

Distillates

GasOils

Resid

CrudeOil

Refinery processes include:• Cracking big hydrocarbons ---> Increase gasoline yield/volume • Rearranging the structure of hydrocarbons ---> Increase gasoline “octane”


DIRECT INJECTION DIRECT INJECTION GC/FID or GC/MS GC/FID or GC/MS

METHODMETHODFOR FOR

CHARACTERIZATION CHARACTERIZATION OF PRODUCT TYPE... OF PRODUCT TYPE...

GC-FID = “Fingerprint”

Diesel

Jet A

Aviation Gasoline

Fresh Gasoline

New Motor Oil

Weathered Gasoline

2030405060708090100110120130140150160170180190

0 5 10 15 20 25 30 35 40 45 50 55

A Crude Oil


40+CC2 CC4 C C24C C10C C14C12 C18C16 C22C20 C30C28C26

69°C126°C 216°C 343°C 402°C

750°F

449°C

840°F156°F 258°F 421°F 649°F

Gasoline

JP-4

Diesel Fuel/ Middle Distillates

Lube Oil, Motor Oil, Grease

Fuel Oils

Stoddard Solvent

Naphthas

Jet Fuel/Kerosene

6 8

CARBON NUMBER NUMBER OF ISOMERS

NUMBER OF ISOMERIC PARAFFINS

123456789

101520253040

1112359

183575

4347366,319

36,797,5884,111,846,763

62,491,178,805,831

Large number of isomers!Large number of isomers!

Products overlap! Products overlap!

Approximate Carbon and Boiling Ranges of Petroleum Products

Cannot Identify Cannot Identify Individual Individual

CompoundsCompounds


GOALGOALDevelop scientifically defensible information for establishing

soil cleanup levels for TPH that are protective of human health at hydrocarbon contaminated sites.

TPH Working Group Series, Volumes 1-5

http://www.aehs.com/publications/catalog/tph.htm

Shell Global SolutionsBoiling Point (oC)-100 0 100 200 300 400 500 600

Equ

ival

ent C

arbo

n N

umbe

r

0

5

10

15

20

25

30

35

40

AliphaticsAromatics

EC = 4.12 + 0.02 (BP) + 6.5e-5 (BP)2

r2 = .99

Equivalent Carbon Number (EC)Related to the boiling point of a compound normalized to the boiling point of the n-alkanes or its retention time in a boiling point gas chromatographic column. Empirical correlation.

Equivalent Carbon Number:6 = hexane6.5 = benzene8 = octane


Equivalent Carbon (EC) Correlations for Aliphatic and Aromatic Hydrocarbons with Physical Properties

E qu iva len t C a rbon N um ber0 5 10 15 20 25 30 35 40

Solu

bilit

y (m

g/L)

1 0 -11

10 -10

10 -9

10 -8

10 -7

10 -6

10 -5

10 -4

10 -3

10 -2

10 -1

10 0

10 1

10 2

10 3

10 4

A rom atics :log 10S = -0 .21E C + 3 .7

r2 = .89

A lipha tics :log 10S = -0 .55E C + 4 .58

r2 = .94

Water Solubility

E q u iv a le n t C a rb o n N u m b e r0 5 1 0 1 5 2 0 2 5 3 0 3 5 4 0

log

Koc

(mg/

kg/m

g/L)

0

1

2

3

4

5

6

7

8

9

1 0

A lip h a tic s :lo g 1 0 K o c = 0 .4 5 E C + .4 3r2 = .9 4 A ro m a tic s :

lo g 1 0 K o c = 0 .1 0 E C + 2 .3r 2 = .8 1

A lip h a t ic sA ro m a tic s

Organic Carbon Partitioning

E qu iva len t C a rbon N um ber0 5 1 0 15 20 25 30 3 5 40

Hen

ry's

Law

Con

stan

t (cm

3 /cm

3 )

1 0 -11

10 -10

10 -9

10 -8

10 -7

10 -6

10 -5

10 -4

10 -3

10 -2

10 -1

10 0

10 1

10 2

10 3

10 4

A liph a tics :lo g 1 0H = 0 .0 2E C + 1 .56

r2 = .0 3

A rom a tics :lo g 1 0H = -0 .23 E C + 1 .66r2 = .8 4

A lip ha ticsA rom a tics

Henry’s Law Constant

Equivalent Carbon Num ber0 5 10 15 20 25 30 35

Vapo

r Pre

ssur

e (a

tm)

10 -14

10-13

10-12

10-11

10-10

10-9

10-8

10-7

10-6

10-5

10-4

10-3

10-2

10-1

100

101

EC > 12 and < 25log10VP =-0.36EC+.72r2 = .96

EC ≤ 12:log10VP = -0.50EC + 2.3r2 = .99

AliphaticsArom atics

Vapor Pressure


RETENTION TIMES AND BOILING POINTS OF SELECTED n-ALKANES

BP Retention Alkane°C Time (min) Marker

GasolineRange

69 4.79 nC698 6.96 nC7126 9.18 nC8174 13.25 nC10216 16.77 nC12287 22.58 nC16357 35.40 nC21431 48.96 nC28499 58.96 nC35

This information can be used as markers for the determination of the approximate boiling point distribution and approximate carbon number of hydrocarbons using gas chromatography

The retention times listed mustbe determined for a given set ofoperation parameters

Documents

TPH in the Texas Risk Reduction Program (TRRP) · 2018-02-15 · nC6 - nC12 >nC8 – nC10 >nC12 – nC28 >nC12– nC16 . Is TPH Below Action Criteria? No Further Action. Yes No. Shell