Rubbertown NGEM Demonstration Project Update Meeting #4, March 27-28, 2018 Eben Thoma, Rachelle Duvall, and Ingrid George (for the team) EPA Office of Research and Development, Durham, NC 27711

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Office of Research and Development NRMRL Fugitive and Area Source Group National Risk Management Research Laboratory, Air and Energy Management Division Source and Fenceline Measurements Methods and Technology Development Rubbertown NGEM Demonstration Project

Topics for Update Meeting #4:

(1) Status and next steps on NGEM project (Eben Thoma)

(2) Discussion of potential citizen science project (Rachelle Duvall)

(3) Questions and discussion

1 Rubbertown NGEM Demo Project Meetings - March, 2018 Rubbertown NGEM Demonstration Project Quick Background Review for Meeting #4

• What is NGEM? …..Next Generation Emission Measurements – Air quality sensors (mobile and fixed) – Lower cost gas chromatographs – Passive samplers and canisters – New source location modeling

• What do we want to do? –Work together to try new NGEM approaches and learn about air pollution sources in Louisville (research)

• Who is involved in this project? –EPA Office of Research and Development (ORD), EPA Region 4, Louisville Air Pollution Control District (APCD), and Jacobs Technology (EPA contractor) 2 Rubbertown NGEM Demo Project Meetings - March, 2018 Rubbertown NGEM Demonstration Project Quick Background Review for Meeting #4

• What is the project focus? –Prototype NGEM system near Rubbertown facilities –Select gas-phase air pollutants

• Is this a community health or exposure study? –No, this is a NGEM technology demonstration project that may inform some aspects of emissions in Rubbertown

• Is this an enforcement or compliance activity? –No, this is a voluntary research effort –We will provide information to facilities, communities, and publish results

3 Rubbertown NGEM Demo Project Meetings - March, 2018 Rubbertown NGEM Demonstration Project Status Update - March 2018:

• Passive samplers deployed by APCD since Sept., 2017 (ongoing)

• 20 second canister grab samples acquired by EPA, Jacobs, and APCD

• Prototype SPod fenceline sensors deployed at Site 01

• Two prototype field gas chromatographs (GCs) deployed at Site 01 (only one is working)

Today we will focus on the passive samplers and canisters

4 Rubbertown NGEM Demo Project Meetings - March, 2018 SPod 2 NGEM Demo Study Started Fall 2017 SPod 1 Firearms Training Center (Site 01)

Passive Sampler

EPA GC 2

Canister Grab Sample (20 sec)

Louisville Air Pollution Control District Shelter (Installed Fall 2017)

APCD GC EPA GC 1 inside shelter

5 5 Rubbertown NGEM Demo Project Meetings - March, 2018 Primary NGEM Project Sites Firearms Training Site Passive samplers all these sites MSD-MF Sensors and GCs at S01 (current) Marathon Sensors at S08 (future)

Carter Elem. School

PolyOne Zeon Lubrizol Carbide

DuPont Eckart Al

Rohm & Haas

ASRC

Citgo Cane Run Elem. School

Future EPA Sensor Site

Hexion Marathon

Rubbertown NGEM Demo Project Meetings - March, 2018 Passive Samplers at Sites 8, 9, and 10

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6 Rubbertown NGEM Demo Project Meetings - March, 2018 Rubbertown NGEM Demonstration Project Geospatially Deployed Passive Samplers

• Two-week Passive Samplers are pretty good for:

–Helping us understand spatial differences in concentrations

–Helping us understand chemical source signatures

• Two-week Passive sampler are not good for:

– Informing short-term concentrations or “emission events”

– Informing low absolute concentrations for some compounds (small uncertainties in tube background levels and variable uptake rates)

8 Rubbertown NGEM Demo Project Meetings - March, 2018 Passive Sampler Primary Compound List

*Benzene *Tetrachloroethene Freon 114 Dichlorotetrafluoroethane Chlorobenzene Freon 11 Trichlorofluoromethane *Ethylbenzene 1,1-Dichloroethene m,p-Xylene Some preliminary Freon 113 Trichlorotrifluoroethane *Styrene results are presented for these two 1,1-Dichloroethane o-Xylene compounds cis-1,2-Dichloroethene 4-Ethyltoluene 1,2-Dichloroethane 1,3,5-Trimethylbenzene 1,1,1-Trichloroethane m-Dichlorobenzene *Carbon Tetrachloride o-Dichlorobenzene *Indicates APCD 1,2-Dichloropropane p-Dichlorobenzene Target Compound *Trichloroethene *1,3-Butadiene *Toluene

Preliminary passive sampler results expressed in parts per billion by volume (ppbv or ppb) Average method detection limit (MDL) for 1,3 butadiene ≈ 0.04 ppb, tetrachloroethene ≈ 0.02 ppb

9 Rubbertown NGEM Demo Project Meetings - March, 2018 Draft* Passive Sampler Data Ten, ≈14-day sampling periods MSD-MF 9/13/17 to 1/31/18 Marathon (*Raw data, subject to adjustments ) ≈ 0.1 ppb ≈ 0.1 ppb

Carter Elem. School 1,3 Butadiene 10-period average PolyOne Zeon approximate (≈) Lubrizol concentrations Carbide ≈ 0.2 ppb

DuPont Eckart Al

Rohm & Haas

ASRC ≈ 0.1 ppb ≈ 0.2 ppb Citgo Cane Run Elem. School ≈ 0.1 ppb

Hexion Marathon

10 Rubbertown NGEM Demo Project Meetings - March, 2018 Draft* Passive Sampler Data Ten, ≈14-day sampling periods 9/13/17 to 1/31/18 (*Raw data, subject to adjustments )

Tetrachloroethene

Some sampling periods at S09 and S10 show slightly elevated readings ≈ 0.2 ppb indicating potential source to the south

Source?

11 Rubbertown NGEM Demo Project Meetings - March, 2018 Rubbertown NGEM Demonstration Project 20 second Canister Grab Samples

• Canister Grab Samples are pretty good for: – Understanding what is in the air at moment in time (snapshot) – Helping us study emission events (source signatures)

• Canister Grab Samples are not good for: – Informing long-term concentrations because there is a lot of variability in concentrations when close to a source (24-hour canisters are needed) We can’t draw strong conclusions from 20 second grab sample data but we can learn a few things

12 Rubbertown NGEM Demo Project Meetings - March, 2018 SPod VOC Plume Detection on 10/31/17 1400 This is why 20 second 1200 canister grab samples Canisters acquired aren’t good indicators at different times 1000 of long term can differ greatly concentrations 800

600 SPod (cts) SPod Signal

400

200

0

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Rubbertown NGEM Demo Project Meetings - March, 2018 Time (hr:min) Canister Grab Sample Compound List

Observed in all canisters (N = 59 canisters) Butane Heptane n-Decane 1,2,3-Trimethylbenzene Ethanol *1,3-Butadiene Carbon Disulfide 1,2-Diethylbenzene iso-Pentane Isoprene 1,2-Dichloropropane 1,1,2,2-Tetrachloroethane Propane Methylcyclopentane *Vinyl Chloride Methyl-t-Butyl-Ether n-Pentane 2,4-Dimethylpentane Vinyl Acetate *Bromoform Isobutane 2,3-Dimethylpentane Undecane 1,1,1-Trichloroethane Method Detection Propylene 1-Hexene *Trichloroethene cis-1,2-Dichloroethene Chloromethane Tert-Butanol Ethyl Tert-Butyl Ether trans-1,2-Dichloroethene Limit = MDL Dichlorodifluoromethane trans-2-pentene o-Ethyltoluene o-Cymene

Trichlorofluoromethane 2-Methylheptane n-Propylbenzene Vinyl Bromide anyin sample MDL > present Not *Methylene Chloride Isooctane Cumene 3-Chloro-1-Propene Average MDL = 0.01 CFC 113 2,3-Dimethylbutane Hexachlorobutadiene Tert Amyl Methyl Ether Acetone *Ethylbenzene *Ethyl Acetate 1,4-Dioxane ppbv (except *Carbon Tetrachloride Cyclopentane Naphthalene cis-1,3-Dichloropropene methylene chloride = 3-Methylpentane cis-2-pentene 1,1-Dichloroethene trans-1,3-Dichloropropene 2-Methylhexane Octane 1,2,4-Trimethylbenzene 1,1,2-Trichloroethane 0.019 ppbv) n-Hexane *Acrylonitrile Acetonitrile 2-Hexanone 3-methylhexane p-Xylene 2-Chloroprene Dibromochloromethane *Benzene Tetrahydrofuran Dodecane 1,2-Dibromoethane *Chloroform Dichlorotetrafluoroethane 1-Ethyl-4-Methyl Benzene 1,1,1,2-Tetrachloroethane 2-Butanone 2,2-Dimethylbutane 1,3,5-Trimethylbenzene Chlorobenzene *Toluene m-Xylene Bromomethane Tert-Butyl Benzene Methylcyclohexane o-Xylene Chloroethane 1,3-Dichlorobenzene *Indicates APCD 1-Butene 2,3,4-Trimethylpentane Bromodichloromethane *1,4-Dichlorobenzene 2-Methylpentane 1-Pentene 1,2-Dichloroethane Sec-Butyl Benzene Target Compound Isopropyl Alcohol 1,2,4-Trichlorobenzene 1,1-Dichloroethane 1,2-Dichlorobenzene trans-2-butene Nonane *Methyl Methacrylate 1,3-Diethylbenzene Acrolein m-Ethyltoluene *Styrene n-Butyl Benzene Cyclohexane *Tetrachloroethene Diisopropyl ether cis-2-butene 3-Methylheptane *4-Methy-2-Pentanone 14 Listed in order of frequency of occurrence above MDL for sites 1, 5, 7, 8, 10 Rubbertown NGEM Demo Project Meetings - March, 2018 110 Methylene Chloride Canister Grab Samples 100 What is in the air near the facilities? Benzene 90 Chloroform Toluene What compounds are above detection limit? 46 canisters at sites 1, 5, 7, 8, 9, 10 80 Blue Bar Indicates APCD Target compound 70

60 1,3 Butadiene

50 Ethylbenzene Acrylonitrile 40

30 Percentage Above Detection Limit (%) 20

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Percentage of SamplesWhere Compound Percentage Detected was 0 Butane Octane Ethanol CFC 113 Toluene Acrolein Acetone Propane Benzene Heptane p-Xylene Isoprene 1-Butene n-Hexane 1-Hexene Isooctane Isobutane Propylene n-Pentane Chloroform 2-Butanone iso-Pentane Acrylonitrile cis-2-butene Cyclohexane Tert-Butanol Ethylbenzene Cyclopentane cis-2-pentene 1,3-Butadiene trans-2-butene Chloromethane trans-2-pentene 3-methylhexane 2-Methylhexane Tetrahydrofuran Isopropyl Alcohol 3-Methylpentane 2-Methylpentane 2-Methylheptane Methylcyclohexane Methylene Chloride Methylene 2,3-Dimethylbutane 2,2-Dimethylbutane Methylcyclopentane Carbon Tetrachloride Carbon 15 2,4-Dimethylpentane 2,3-Dimethylpentane

15 Trichlorofluoromethane Dichlorodifluoromethane Dichlorotetrafluoroethane

*Average MDL = 0.01 ppbv (except methylene chloride = 0.019 ppbv) Rubbertown NGEM Demo Project Meetings - March, 2018 Canister Grab Samples Near Facilities (N= 46) 16.0 Butane Preliminary Draft Data Ranked average values of 46 canister grab samples 14.0 taken near facilites (9/13/17-1/31/18) Ethanol Not indicative of long term average concentrations Sites represented (1, 5, 7, 8, 9, 10) 12.0 iso-Pentane Values < MDL set to zero, Error bars = +/- 1 Stdev Acetone 10.0 Chloromethane Isopropyl Alcohol Propane 8.0 n-Pentane Propylene Isobutane 6.0 Cyclohexane 1,3-Butadiene

Concentration (ppbv) Concentration Acrylonitrile 4.0 Toluene 2-Methylpentane 2.0

0.0 0 2 4 6 8 10 12 14 16 16 Compound Rank

*Average MDL = 0.01 ppbv (except methylene chloride = 0.019 ppbv) Canister Grab Samples at Carter and Cane Run Elementary Schools (N= 6) 16.0 Preliminary Draft Data Average values of 6 canister grab samples taken at 14.0 School sites (9/13/17-1/31/18) Not indicative of long term average concentrations Sites represented (4, 6) 12.0 Values < MDL set to zero, Error bars = +/- 1 Stdev Ethanol

10.0 Propane iso-Pentane Propylene 8.0 Isobutane Chloromethane Acetone 6.0 n-Pentane 1,3-Butadiene Cyclohexane Isopropyl Alcohol Concentration (ppbv) Concentration 4.0 Butane 2-Methylpentane Toluene

2.0 Acrylonitrile

0.0 0 2 4 6 8 10 12 14 17 17 Compound Rank

*Average MDL = 0.01 ppbv (except methylene chloride = 0.019 ppbv) “Chemical Sweet” Odor in South Rubbertown 9/27/17, 5:31 am

Tetrachloroethene, Other, 24% 19%

Lee’s Lane Landfill Hexion Chloroform, 16%

Carbon Tetrachloride, 13% 18 Canister Grab Sample

Rubbertown NGEM Demo Project Meetings - March, 2018 “Strong Bio Odor” near Morris Forman 9/27/17, 6:14 am Likely odor compounds not part of analysis MSD-MF

Other, 19%

Butane, 30%

iso-Pentane & Acetone, 29%

19 Canister Grab Sample Rubbertown NGEM Demo Project Meetings - March, 2018 “sweet plastic chemical” Odor in South Rubbertown 9/27/17, 8:02 am

Lubrizol Zeon

ASRC iso-Pentane & Acetone, 14%

Other, 38% Ethanol, 10%

Butane, 10%

Isopropyl Alcohol, 9% 1,3- Propane, Butadiene, 20 19 Canister Grab Sample 7% 8% Rubbertown NGEM Demo Project Meetings - March, 2018 2020

Carbon Threecanister grab samples acquired early on 9/27/17(draft data) Chloroform (5.4 ppb) Tetrachloroethene Tetrachloride 1515 (6.5 ppb) (4.3 ppb)

1010 5:31 am, chemical odor S11 5 Percentage of Analysis by Volume (%) Volume by Analysis of Percentage

0 20 Butane Ethanol Toluene Acrolein Acetone Propane Benzene Heptane Isoprene 1-Butene m-Xylene n-Hexane Isooctane Isobutane Propylene n-Pentane Chloroform 2-Butanone iso-Pentane Acrylonitrile cis-2-butene Cyclohexane Tert-Butanol Ethylbenzene 20 Cyclopentane Vinyl Chloride Vinyl 1,3-Butadiene trans-2-butene Chloromethane Trichloroethene trans-2-pentene

30 3-methylhexane 2-Methylhexane Isopropyl Alcohol 3-Methylpentane 2-Methylpentane Tetrachloroethene 1,1-Dichloroethene Methylcyclohexane 2,3-Dimethylbutane 2,2-Dimethylbutane Methylcyclopentane 1,2-Dichloropropane Carbon Tetrachloride Carbon 2,4-Dimethylpentane 2,3-Dimethylpentane Hexachlorobutadiene Trichlorofluoromethane Dichlorodifluoromethane 15 6:14 am, strong bio odor, S01 near Morris Forman (likely odor compound not part of analysis) 10

5 Percentage of Analysis by Volume (%) Volume by Analysis of Percentage canister canister (%)Analysis byVolume -

0 20 Butane Ethanol Toluene Acrolein Acetone Propane Benzene Heptane Isoprene 1-Butene m-Xylene n-Hexane Isooctane Isobutane Propylene n-Pentane Chloroform 2-Butanone iso-Pentane Acrylonitrile cis-2-butene Cyclohexane Tert-Butanol Ethylbenzene Cyclopentane Vinyl Chloride Vinyl 20 1,3-Butadiene trans-2-butene Chloromethane Trichloroethene trans-2-pentene 3-methylhexane 2-Methylhexane Isopropyl Alcohol 3-Methylpentane 2-Methylpentane Tetrachloroethene 1,1-Dichloroethene Methylcyclohexane 2,3-Dimethylbutane 2,2-Dimethylbutane Methylcyclopentane 1,2-Dichloropropane Carbon Tetrachloride Carbon 2,4-Dimethylpentane 2,3-Dimethylpentane Hexachlorobutadiene Trichlorofluoromethane 8:02 am, chemicalDichlorodifluoromethane odor near S05 15 1,3 Butadiene Vinyl Chloride (3.9 ppb) (0.4 ppb) Acrylonitrile 10 (2.0 ppb)

5 Percentage of Analysis by Volume (%) Volume by Analysis of Percentage

Percentage of Single of Percentage 0 Butane Ethanol Toluene Acrolein Acetone Propane Benzene Heptane Isoprene 1-Butene m-Xylene n-Hexane Isooctane Isobutane Propylene n-Pentane Chloroform 2-Butanone iso-Pentane Acrylonitrile cis-2-butene Cyclohexane Tert-Butanol Ethylbenzene Cyclopentane Vinyl Chloride Vinyl 1,3-Butadiene trans-2-butene Chloromethane Trichloroethene trans-2-pentene 3-methylhexane 2-Methylhexane Isopropyl Alcohol 3-Methylpentane 2-Methylpentane Tetrachloroethene 1,1-Dichloroethene Methylcyclohexane 2,3-Dimethylbutane 2,2-Dimethylbutane Methylcyclopentane 1,2-Dichloropropane Carbon Tetrachloride Carbon 2,4-Dimethylpentane 2,3-Dimethylpentane Hexachlorobutadiene Trichlorofluoromethane Dichlorodifluoromethane

21 VOC Emissions Tracker (VET) …… in development

SPod • SPod or other sensor – Fast, nonspecific concentrations – Wind field – Pressure, temp, R/H • Field GC (low cost) – Compound specific (10 minute) GC • Triggered canister grab sample – Optimal acquisition (in-plume) – Detailed Lab speciation Lab Sample

Combining 22 NGEM Tools

http://www.forestry-suppliers.com/product_pages/products.php?mi=21531 Rubbertown NGEM Demonstration Project Next Steps - March 2018:

• Keep deploying passive samplers (Thanks APCD!) • Investigate addition of a passive sampler to the south to look at potential tetrachloroethene source • Improve automated canister grab sample capability (SPod and VET)

• Help APCD with 24 hour canisters and FTC GC validation

• Stand-up EPA Sensor Site S08 across from ASRC

• Continue to test NGEM technologies

• Make linkages between odors and chemicals in the air

23 Rubbertown NGEM Demo Project Meetings - March, 2018 Rubbertown NGEM Demonstration Project

Potential Citizen Science Project • EPA is looking into internal funding options for a citizen science add-on project – Unfortunately, EPA budget is not certain and we anticipate cuts! • What would the project include? – Explore a phone/computer app that can be used by the local community to report odors – App would allow user to record information about the odor such as • Date/time • Type of odor (chemical, sewage, rotten eggs, etc.) Odor App • How long odor is present N • Intensity of odor (mild, moderate, severe) • Location/address • Outdoor conditions (temperature, wind speed, wind direction) 24 Rubbertown NGEM Demonstration Project collaboration on an odor wheel App

How would an odor app be used? Odor Wheel Example (Draft idea for discussion) Step 2: Citizen enters Step 1: Citizen smells odor information into an App 1Bio mix 1 Raw / processed sewer Natural gas Odor App 1 odorant Bio mix 2 Fecal, H2S source Rotten skunky N cabbage Sewer rotten egg

Alkanes Gasoline, Rancid, Aromatics N 1Bio mix 3 • What is your location? oily decay • What is the intensity of the odor? rendering • Sweet, Rubber, What odor do you smell? Burnt, fingernail Plastic (See ‘Odor Wheel’ to right) polish garlic, • How long did the odor last? pungent 2Chem mix 1 2Chem mix 3

2 Step 4: Pair the odor Chem mix 2 Step 3: Information collected observations with NGEM measurements

1Bio mixes contain various complex combinations of VOCs, organic and inorganic sulfur compounds, ammonia, mercaptans, amines, aldehydes, and volatile fatty acids. 25 2 Chemical mixes contain various subsets of compounds and will relate to Rubbertown sources (compounds to be determined). Number of chemical categories may increase Rubbertown NGEM Demonstration Project

Contact Information

Eben Thoma Rachelle Duvall EPA ORD Technical Lead EPA ORD Co-Technical Lead [email protected] [email protected]

Jane Spann Tiereny Bell EPA Region 4 Co-lead EPA Region 4 Co-lead [email protected] [email protected]

Billy DeWitt Sheryl Good LMAPCD Lead EPA Region 4 EJ Coordinator [email protected] [email protected]

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