TPH IN THE TEXAS RISK REDUCTION PROGRAM TRRP

TPH IN THE TEXAS RISK REDUCTION PROGRAM (TRRP) Environmental Impact Ileana Rhodes, GSI Mark Maglitto, TCEQ Ann Strahl, TCEQ November 2017

TX - 3 REMEDIATION PROGRAMS Programs, governing rules, and application of TPH are: • Petroleum Storage Tank (PST) under 334 rule: – At every tank pull, BTEX and TCEQ 1005 TPH in soil and water are analyzed. The TPH data are only used qualitatively to determine if hydrocarbons greater than n. C 12 are present in the TPH. If present, then PAH analysis required. The TPH data are never used quantitatively, i. e. , the program does not regulate TPH, and no TCEQ 1006 analyses are done • Risk Reduction Standard (rule 335) for non-PST: – This rule has been superseded by TRRP. • Texas Risk Reduction Program (rule 350): – No requirement for analyzing TPH – Decision to analyze for TPH is made by the program area and/or the person responding to rule based on the activities conducted at the on-site property – If either the program area or the person determines TPH is a chemical of concern (COC), then 1005/1006 is run as described in presentations – TPH is not used to screen for the presence, absence, or excedance of specific COCs, e. g. , benzene. Chemical specific analyses are required in addition to TPH 2

TRRP GUIDANCE FOR TPH • Risk-based Surrogate Approach • Generally follows the Total Petroleum Hydrocarbon Criteria Work Group (TPHCWG) Process Topics • TPH Analytical Methods • TPH PCL Development Process (RG-366/TRRP-27) • TPH PCL Spreadsheet Objective: The process to establish PCLs for total petroleum hydrocarbon mixtures • Case Study Audience: Environmental Professionals and the Regulated Community Reference: Texas Administrative Code, Title 30, Part 1, Chapter 350 URL for rule: http: //texreg. sos. state. tx. us/public/readtac$ext. View. TAC? tac_view=4&ti=30&pt=1&ch=350 URL for guidance: https: //www. tceq. texas. gov/publications/rg/rg-366_trrp_27. html Texas Commission on Environmental Quality (TCEQ) Contact: Mark Maglitto Mark. maglitto@tceq. texas. gov 3

THE TIERED PROCESS TPH is a method-defined parameter: The regulatory limit is established based on the analytical procedures used to measure the parameter. TCEQ developed two analytical methods for TPH • TCEQ Method 1005 is used to analyze TPH in environmental samples to: o Determine the composition of TPH o Determine the concentration of TPH o Determine if protective concentration levels (PCLs) need to be developed for the site-specific TPH mixture o Assess the extent of TPH contamination • TCEQ Method 1006 is used to determine the concentrations of hydrocarbons in defined boiling point ranges in the aliphatic and aromatic fractions of the TPH mixture for use in calculating site-specific PCLs. 6

PROCEDURAL STEPS TO ESTABLISH PCLS FOR TPH MIXTURES 1. Sample the environmental medium using TCEQ 1005 2. Compare TCEQ 1005 results to the Tier 1 TPH, TX 1005 PCLs 3. If exceedance is found – Identify source area(s) by comparing the TCEQ 1005 chromatograms. The concentrations (i. e. , peak areas) may change, but if the distribution of the hydrocarbons changes, the TPH is from more than one source 4. For each source area, use TCEQ 1006 to fractionate the extract of the sample with the highest TPH concentration 5. Following the TRRP 27 guidance, use Tier 1 PCLs for the aliphatic and aromatic TPH boiling point ranges and the TCEQ 1006 mass fraction results for each range to calculate PCLs for the site-specific TPH mixture 6. Select the critical PCL 7. Compare TCEQ 1005 TPH concentration(s) to the critical PCL 8. Steps 5 & 6 can be performed using the TPH Calculator Spreadsheet 7

TCEQ ANALYSIS – TCEQ METHOD 1005 https: //www. tceq. texas. gov/assets/public/compliance_support/qa/1005_final. pdf Sample Shake/Vortex Centrifuge GC-FID TCEQ 1005 Conditions/Calibration Extract Analyze Process Data þ Single extraction with n-pentane, analysis using GC/FID: C 6 to C 28 (or 35) þ TPH reported in carbon ranges: n. C 6 to n. C 12 >n. C 12 to n. C 28 or 35* *report to n. C 35 (when applicable) n-C 12 alkane and n-C 28 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. 8

TCEQ METHOD 1005 SCREENING TO DETERMINE IF SITE-SPECIFIC PCL SHOULD BE DEVELOPED Extract Sample with n-Pentane 1: 1 GC/FID for TPH Tot. Soil For example: Comb GWSoil Ing GWSoil Quantitate TPH and Determine BP Distribution Class 3 RESIDENTIAL SOIL 1 in mg/kg TPH, TX 1005, n. C 6 - n. C 12 1600 65 6500 TPH, TX 1005, >C 12 – n. C 28* 2300 20000 TPH, TX 1005, n. C 6 - n. C 12 3900 19000 TPH, TX 1005, >C 12 – n. C 28* 12000 59000 COMMERICAL/INDUSTRIAL SOIL 1 in mg/kg GROUNDWATER 1 in mg/L 1 GWGW Ing GWGW Class 3 TPH, TX 1005, n. C 6 - n. C 12 0. 98 98 TPH, TX 1005, >C 12 – n. C 28* 0. 98 98 When the air pathway is evaluated, compare to the Tier 1 Air. Soil Inh-v For each pathway compare TCEQ 1005 to Tier 1 PCLs for results for: TPH, TX 1005: n. C 6 - n. C 12 n. C 6 – n. C 12 >n. C 12 – n. C 28* >n. C 12– n. C 28* No Is TPH Below Tier 1 PCLs? and Air. GW-Soil. Inh-v PCLs. Fractionate using TCEQ Method 1006 2 to establish PCLs 2 Yes Fractionate extract from sample with highest TCEQ 1005 TPH concentration No Further Action 10

DETERMINE THE NUMBER OF TPH SOURCES BY COMPARING THE GAS CHROMATOGRAMS OR “FINGERPRINTS” Map site with sampling locations with chromatographic profiles from TCEQ Method 1005 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 11

OVERVIEW OF USE OF TCEQ METHOD 1005 AND TCEQ METHOD 1006 Extract Sample with n-Pentane 1: 1 GC/FID for TPH TCEQ Method 1005 Quantitate TPH and Determine BP Distribution No Yes Is GC fingerprint similar for all samples? Select sample with highest 1005 concentration co No Select sample with highest 1005 concentration from each source area Fractionate each sample TCEQ Method by silica column separation. 1006 GC/FID of n-pentane eluate for aliphatics TPH Below Action Level Criteria? GC/FID of methylene chloride eluate for aromatics Yes No Further Action Use mass fractions of BP ranges in the aliphatic & aromatic fractions to calculate PCLs 12

1 3 TCEQ METHODS 1005 AND 1006 Extract Sample Analyze Shake/Vortex Centrifuge Process Data GC-FID Analysis using TCEQ 1005 Conditions/Calibration Aliphatics ð n-pentane - aliphatics ð methylene chloride - aromatics Aromatics Fractionate by TCEQ Method 1006 þSingle extraction with n-pentane þ Fractionation with Silica Gel into aliphatic and aromatic fractions (based on EPA Method 3630 C) ðn-pentane - aliphatics ðmethylene chloride - aromatics þ Two analyses by GC-FID similar to EPA 8100/8015 þ Data analyzed & processed: Boiling ranges/approximate carbon numbers fraction 13

ASSESS AND CHARACTERIZE EXTENT OF ENVIRONMENTAL MEDIA AFFECTED WITH TPH AND IDENTIFY DISTINCT TPH SOURCE AREAS Analyze all samples by TCEQ Method 1005 Fractionate the TPH Mixture Aliphatics n. C 6 >n. C 6 -n. C 8 >n. C 8 -n. C 10 >n. C 10 -n. C 12 >n. C 12 -n. C 16 >n. C 16 -n. C 21 >n. C 21 -n. C 35 Aromatics >n. C 7 -n. C 8 (Toluene) Toluene >n. C 8 -n. C 10 >n. C 10 -n. C 12 >n. C 12 -n. C 16 >n. C 16 -n. C 21 >n. C 21 -n. C 35 TCEQ Method 1006 Use TCEQ TPH PCL calculator to establish PCLs for the TPH mixture and determine the critical PCL Use 1005 results to determine compliance with critical PCLs TCEQ Method 1005 14

SUMMARY OF THE TIERED APPROACH • TCEQ Method 1005 is used to measure TPH across a site and define the TPH source(s) • If the TPH distribution 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 has different distribution patterns (indicating more than one source of TPH), the extract with the highest Method 1005 TPH result from each source is fractionated using Method 1006 into the aliphatic and aromatic boiling point ranges The protective concentration levels (PCLs) for the TPH mixture are calculated using the Method 1006 mass fractions and the Tier 1 PCLs for each TPH aliphatic and aromatic boiling point range and the critical PCL is established. • The TCEQ Method 1005 results are compared to the critical PCL. • If no exceedance, no further action. • The URL link to the Excel spreadsheet used to calculate the PCLs for the TPH mixture is http: //www. tceq. state. tx. us/remediation/analysis. html 16

TCEQ METHOD 1005 AND TCEQ METHOD 1006 þ Ability to obtain a TPH distribution by analysis of the n-pentane extract prior to fractionation - TIERED APPROACH C 6 to C 35 Range þ Provides simple “fingerprint” of product þ TPH results can be correlated with existing methodology þ Single extraction, one fractionation and one to three injections þ Fractionation procedure based on EPA 3630 C (silica gel) þ GC analysis similar to the one currently used for TPH-diesel range (based on EPA 8015 and EPA 8100) þ Method has been successfully implemented at commercial environmental laboratories þ For TPH, the reporting limit (RL) should be below the lowest PCL. For example, the lowest TPH-TX 1005 PCL is 0. 98 mg/L, therefore, the RL should be below or as near to the PCL as possible. 17

Considerations • • 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 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 18

QUESTIONS?

2 1 SHORTENED STEPS • Sample • Screen 1005 • Analyze highest 1005 using TCEQ Method 1006 • Use TPH Spreadsheet 21

2 2 CASE STUDY Field ID # SO-01 SO-02 SO-03 SO-04 SO-05 SO-06 SO-07 SO-08 SO-09 SO-10 SO-11 SO-12 SO-13 SO-14 TCEQ 1005 C 6 to C 35 results (mg/kg) total C 6 -C 12 7689 13441 >C 12 -C 35 5752 C 6 -C 12 5154 14899 >C 12 -C 35 9745 C 6 -C 12 7075 7278 >C 12 -C 35 203 C 6 -C 12 3231 4975 >C 12 -C 35 1744 C 6 -C 12 2582 4348 >C 12 -C 35 1767 C 6 -C 12 4760 8433 >C 12 -C 35 3673 C 6 -C 12 9845 14429 >C 12 -C 35 4584 C 6 -C 12 7737 16542 >C 12 -C 35 8805 C 6 -C 12 4518 4523 >C 12 -C 35 5 C 6 -C 12 60 477 >C 12 -C 35 117 C 6 -C 12 36 243 >C 12 -C 35 207 C 6 -C 12 40621 64444 >C 12 -C 35 23823 C 6 -C 12 44926 71756 >C 12 -C 35 26830 C 6 -C 12 20684 46854 >C 12 -C 35 26170 v v v v TPH Screen Using TX 1005 • Source area 0. 49 acres • Action levels are Tier 1 residential 0. 5 acre assessment levels • Class 1 GW • 20 samples collected from 0 to 6 inches analyzed by TCEQ Method 1005 • Site passed the Tier 1 Ecological Exclusion Criteria checklist • GW at 30 feet • Distance to nearest well used for domestic purpose is 0. 25 miles. • Not secure; children use for baseball field TRRP Tier 1 Residential PCLs for 0. 5 acre source area Tot. Soil GWSoil Air. Soil Comb Ing Class 3 Inh-V Chemical of CAS (mg/kg) Concern TPH, TX 1005, TPH 1600 65 C 6 -C 12 1005 -1 TPH, TX 1005, TPH 2300 200 >C 12 -C 28 1005 -2 TPH, TX 1005, TPH 2300 200 >C 12 -C 35 1005 -3 TPH, TX 1005, TPH 2300 200 >C 28 -C 35 1005 -4 (mg/kg) Air. GW- Soil. Inh-V (mg/kg) 6500 3100 120000 15000 1000000 All chromatograms indicate one source, i. e. , no significant difference seen in boiling point range distribution of hydrocarbons 22

CASE STUDY: SITE-SPECIFIC PCL DEVELOPMENT TCEQ 1006 Results for SO-13 C 6 Aliphatic >C 6 - C 8 Aliphatic >C 8 - C 10 Aliphatic >C 10 - C 12 Aliphatic >C 12 - C 16 Aliphatic >C 16 - C 21 Aliphatic >C 21 - C 35 Aliphatic >C 7 - C 8 Aromatic >C 8 - C 10 Aromatic >C 10 - C 12 Aromatic >C 12 - C 16 Aromatic >C 16 - C 21 Aromatic >C 21 - C 35 Aromatic mg/kg 3815 1693 9579 12629 573 6518 9062 1339 7989 9420 4562 2104 734 TCEQ TRRP Tier 1 TPH PCL Calculator (v 2. 0 - 12/2016 ) for TCEQ Method 1006 Data - Input Sheet ▼ INPUT ▼ TCEQ Method 1006 Boiling Point Range Concentrations in Soil TCEQ Method 1006 Boiling Point Range i Ci (mg/kg) C 6 Aliphatic 1 3, 815. 14 mg/kg >C 6 - C 8 Aliphatic 2 1, 692. 96 mg/kg >C 8 - C 10 Aliphatic 3 9, 579. 20 mg/kg >C 10 - C 12 Aliphatic 4 12, 628. 68 mg/kg >C 12 - C 16 Aliphatic 5 573. 02 mg/kg >C 16 - C 21 Aliphatic 6 6, 518. 15 mg/kg >C 21 - C 35 Aliphatic 7 9, 062. 00 mg/kg >C 7 - C 8 Aromatic >C 8 - C 10 Aromatic >C 10 - C 12 Aromatic >C 12 - C 16 Aromatic >C 16 - C 21 Aromatic >C 21 - C 35 Aromatic 8 9 10 11 12 13 1, 339. 04 mg/kg 7, 988. 58 mg/kg 9, 419. 90 mg/kg 4, 562. 22 mg/kg 2, 103. 95 mg/kg 733. 79 mg/kg Sum Aliphatic Fraction: Sum Aromatic Fraction Sum. Total TPH : : : 43, 869. 15 mg/kg 26, 147. 48 mg/kg 70, 016. 62 mg/kg 23 23

OUTPUT USING TCEQ 1006 RESULTS IN TPH PCL CALCULATOR Theoretical soil saturation limit EXCEEDED for one or more TPH fractions - Presence of TPH NAPL Present? : Mobile NAPL Present? : Tier 1 Tot. SOILComb NAPL indicated - See TRRP-32 for NAPL management guidance Presence of Mobile NAPL IS indicated - See TRRP-32 for guidance on the Mobile NAPL Trigger 0. 5 Acre Residential 30 Acre Residential 0. 5 Acre Comm/Ind 30 Acre Comm/Ind PCLTPH Mix = 14023. 35 mg/kg 9641. 05 mg/kg 34181 mg/kg 18405 mg/kg Hazard Index (HI) of 4. 18 3. 79 3. 17 3. 02 TPHMix = Tier 1 GWSOILIng 0. 5 Acre Residential 30 Acre Residential 0. 5 Acre Comm / Ind 30 Acre Comm / Ind HI<10; GW-Soil-Ing PCL HI<10; GW-Soil-Ing PCLTPH Mix = PCL not needed * PCL not needed * Hazard Index (HI) of 1. 15 2. 28 0. 39 0. 76 TPHMix = Tier 1 GWSOILClass 3 0. 5 Acre Residential 30 Acre Residential 0. 5 Acre Comm / Ind 30 Acre Comm / Ind HI<10; GW-Soil-Ing PCLTPH Mix = PCL not needed * PCL not needed * Hazard Index (HI) of 0. 01 0. 02 0 0. 01 TPHMix = Tier 1 Air. SOILInh-V 0. 5 Acre Residential 30 Acre Residential 0. 5 Acre Comm / Ind 28 Acre Comm / Ind PCLTPH Mix = 27170 mg/kg 14023 mg/kg 37687 mg/kg 19282 mg/kg Hazard Index (HI) of 2. 84 2. 86 2. 81 24 TPHMix 24 ?

DETERMINE IF ACTION IS NEEDED Site-specific critical PCL for the TPH mixture is the Tot. Soil. Comb PCL of: 14023 mg/kg total TPH i. e. , TCEQ 1005 TPH Action is needed in the areas of concern represented by soil samples SO-02, -07, -08, -12, -13, and -14. Field ID # SO-01 SO-02 SO-03 SO-04 SO-05 SO-06 SO-07 SO-08 SO-09 SO-10 SO-11 SO-12 SO-13 SO-14 TX 1005 C 6 to C 35 total 13441 14899 7278 4975 4348 8433 14429 16542 4523 477 243 64444 71756 46854 TCEQ 1005 C 6 to C 35 results (mg/kg) total C 6 -C 12 7689 13441 >C 12 -C 35 5752 C 6 -C 12 5154 14899 >C 12 -C 35 9745 C 6 -C 12 7075 7278 >C 12 -C 35 203 C 6 -C 12 3231 4975 >C 12 -C 35 1744 C 6 -C 12 2582 4348 >C 12 -C 35 1767 C 6 -C 12 4760 8433 >C 12 -C 35 3673 C 6 -C 12 9845 14429 >C 12 -C 35 4584 C 6 -C 12 7737 16542 >C 12 -C 35 8805 C 6 -C 12 4518 4523 >C 12 -C 35 5 C 6 -C 12 60 477 >C 12 -C 35 117 C 6 -C 12 36 243 >C 12 -C 35 207 C 6 -C 12 40621 64444 >C 12 -C 35 23823 C 6 -C 12 44926 71756 >C 12 -C 35 26830 C 6 -C 12 20684 46854 >C 12 -C 35 26170 Field ID # SO-01 SO-02 SO-03 SO-04 SO-05 SO-06 SO-07 SO-08 SO-09 SO-10 SO-11 SO-12 SO-13 SO-14 25

2 DECISION TREE FRAMEWORK FOR TPH PCL DEVELOPMENT PROCESS 6 26