PVI Risk Pathway: Sampling Considerations

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PVI Risk Pathway: Sampling Considerations AEHS PVI Workshop March 2015 Blayne Hartman Ph.D. 858-204-6170 www.hartmaneg.com

PVI VI Pathway Made Simple Start Exclusion Criteria Exist? yes no Collect Clean Soil Data clean dirty Done Do PVI Assessment

Exclusion Criteria: A PVI Pathway Game Changer Step 1: Can Site Be Screened Out? Based upon concentration & depth to source In CA if site is an active fueling station No field work Step 2: Can Screen-Out Data be Collected? Step 3: Do PVI Assessment Makes PVI Assessments Much Simpler & Less Expensive

CA-LTCP VI Exclusion Criteria Site Screens Out from VI Pathway if: If 30 of Biozone, NAPL screens out Vertically & horizontally If 10 of Biozone, benzene up to 1000 ug/l If 5 of Biozone, benzene up to 100 ug/l Bioattenuation zone: TPH-soil < 100 mg/kg

NJDEP Gasoline Exclusion Criteria VI Investigation is not required when: 10 ft between water table and foundation and benzene in GW is 1,000 μg/l; or 5 ft between seasonal high water table and foundation, oxygen levels measured at 2% (v/v), and benzene in shallow GW is 1,000 μg/l. O 2 Drops Separation Distance from 10 to 5 6

Step 2: Collect Screen-Out Data Soil Phase TPH Oxygen in Vadose Zone CA & NJ for sure Soil Headspace PID Data (<100 ppmv) Soil Gas VOC Data not required at this step

Clean Soil Model for HC Vapors Bio-barrier Reaction Zone

O 2 Profiling - Approach 18 Locations Throughout Neighborhood Vertically Every Foot Down to 8-10 bgs Used direct-push (not PRT) Oxygen by portable meter (& CO2 & CH4) Soil Samples at 1 & 5 bgs (backup) Did All Locations in 11 Hours!

Low-Threat Closure Policy The Power of Oxygen If oxygen in soil gas >4%: Separation distance drops from 10 to 5 for benzene up to 1,000 ug/l Soil gas SLs increase by 1000x! TPH-soil required for all scenarios but O2 not

Methods to Assess VI Indoor Air Sampling Groundwater Sampling Soil Phase Sampling Predictive Modeling Measure Flux Directly Soil Gas Sampling Supplemental Tools/Data

Approach Generalizations Indoor Air Always find something Multiple sampling rounds: Groundwater Data Typically over-predicts risk Soil Phase Data Typically not allowed; over-predicts risk for HCs Soil Gas Data Transfer rate unknown Sub-slab intrusive

Step 3: PVI Specific Sampling Issues Soil Gas VOC Analysis Benzene, ethylbenzene & naphthalene TPH?? Might Need to Sample <5 bgs If samples >5 bgs exceed allowable levels How to know? On-site analysis best If not, collect samples anyway Always Collect Oxygen Data

Soil Gas Temporal Study EPA-ORD Probe A3 (TCE - Normalize d) 2 1.8 1.6 15 bgs 1.4 Normalized Concentration 1.2 1 0.8 0.6 8 bgs P P 0.4 0.2 0 13:50:09 10:50:26 7:50:44 4:51:04 1:51:43 22:53:46 5:43:29 2:43:47 23:44:04 20:44:22 17:44:39 14:44:57 11:45:15 8:45:32 16:02:01 13:02:18 10:02:36 7:02:55 4:03:12 1:43:56 22:44:15 7:06:41 4:06:59 1:07:19 22:07:58 19:11:25 P 3 bgs Time (3/16/07 to 4/10/07)

Sub-slab Soil Gas Data 20 SSP-2 PCE 19 18 17 16 15 Sub-Slab Variations do NOT Occur Over Short Time Periods (days) 14 13 12 11 10 9 8 7 6 5 4 3 2 1 1 day PC 0 0 50 100 150 200 250 300 350 400 450 500 550 600 650 2/2012 1/2013 2/2013 3/2013

Ingredients for Effective VI Assessments Investigatory Approach Determine Correct Screening Levels Sample & Analyze Properly Know & Use Supplemental Tools Demonstrating Bioattenuation

The Most Important Ingredient Experience: Consultant Collector done soil gas before? Lab certified for methods? Regulator Public YOU! What level person is going in the field?

Most Common VI Bloopers Unit Confusion Assuming ug/l equivalent to ppbv Assuming ug/m3 equivalent to ppbv Screening Levels Comparing to generic screening levels Not calculating correct levels Sampling & Analysis Errors Program design: soil gas? GW? SS? IA? Using wrong hardware Using wrong analysis

It Won t Happen To Me Incorrect Units Wrong Screening Values Uncertifed Lab RLs Not Low Enough Units: ppmv

It Won t Happen To Me #2 All final vacuums at 0 All deployed & retrieved at exact same minute!

VI Assessment Point #1: Long Term IA Samples Maximize Your Chances to Fail the VI Pathway

Passive IA Collectors Longer Collection Times: Increases Odds of False Positives

Got A Life? Longer Collection Times = False Positives

Odor Eliminating & Odor Producing

Scented Ethylbenzene EthylBenzene: 3400 ug/m3 TPH: 390,000 ug/m3

VI Assessment Point #4: Is Sub-Slab Sampling for the Birds?

Why Not Sub-Slab? Large Spatial Variation Under Slabs What Value to Use? Poor Correlation with Indoor Air SS SLs Can Be < Ambient Air SS Data Are Poor Predictors of IA!!

Indoor Air & Sub-slab Vapor -- TCE 100 1:1 10:1 100:1 TCE Indoor Air Concentration (mcg/m3) 10 1 0.1 100*C bkgd 0.01 0.01 0.1 1 10 100 1000 10000 TCE Sub-slab Vapor Concentration (mcg/m3)

TPH Compounds Typical BTEX (BE only risk drivers) Methane Naphthalene (risk about same as benzene) Some States: Aliphatics (C5-C8 & C9-C18) Aromatics (C6-C8 & C9-C16) 1-2 dichloroethane (EDC) & 1-2 dibromoethane (EDB) TO-17 gets PVOCs, TPHg, TPHd in same run!!

TPH Analysis Considerations Laboratory Issues Has does the lab calibrate? Do they subtract out non-hcs? What volume of sample do they need? FID Based Methods (TO-3, 8015) Can t distinquish non-hcs from HCs Will over-report Certified? Best to Use a Mass Spec Method (8260, TO-15, TO-17)

Practical Strategies (Things to Do) Get Enough Data Consider Less Expensive Methods (8260) CL-HCs: Vertical Profiles Around Structure HCs: Shallower Samples Use Radon for Slab-Specific Alpha Measure Ventilation Rate Have Competent Subs Check Your Units!

Previews of the PVI Future PVI Less Likely at UST Sites PVI More Likely if Shallow Contamination EPA OUST Guidance Coming Out? ASTM Standard Increase # of Sites

Forthcoming VI Events 2-Day VI Course Knoxville March 31, 2015 2-Day VI Course Chicago May 28 & 29, 2015 At Argonne Nat l Lab Fall 2015: Texas (Dallas or Austin) Go to www.hartmaneg.com

Blayne Hartman, Ph.D. blayne@hartmaneg.com www.hartmaneg.com