tph in the texas risk reduction program (trrp) · 2018-02-15 · nc6 - nc12 >nc8 – nc10...
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Shell Global Solutions
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.
Shell Global Solutions
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 astrahl@tceq.state.tx.us
Development of Human Health Protective Concentration Levels (PCLs) for Total Petroleum Hydrocarbon (TPH) Mixtures
TCEQ
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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.
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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.
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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
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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
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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
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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
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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
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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
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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
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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
Shell Global Solutions
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
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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
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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.
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Shell Global Solutions
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.
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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:
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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.
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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
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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???
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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”
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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
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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
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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
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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
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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
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