Former Alpena Hide and Leather Project Status – February 2019 Janice Adams, MDEQ Project Manager: ADAMSJ1@michigan.gov Len Mankowski, Wood Geologist: leonard.mankowski@woodplc.com Sesha Kallakuri, DHHS Toxicologist: KallakuriS@Michigan.gov
Overview Alpena Hide and Leather (AHL) History and Land Use Preliminary Findings Per- and Polyfluorinated Alkyl Substances (PFAS) What are PFAS? Why are they a Concern? DEQ Statewide Initiative AHL – Current Understanding Non-PFAS Tannery Impacts PFAS Nature and Extent AHL – Next Steps (2018-2019) PFAS Pilot Tests – Immobilization Arsenic Surface Water
Alpena Hide & Leather (AHL) Tannery ~1895-1952 Northern Extract Company (NEC) Sinclair Bulk Fuel Terminal Tannery NEC Post Tannery (to 2005) Warehousing Bulk Fuel Insulation Manufacturing Metal recycling (Alro Steel) Excavation Company (North) Post Fire (October 2005) Thunder Bay Self Storage Austin Brothers Brewery (North) Treatment Facility (South) Soccer Fields (East)
AHL – Site Activities 2008 – Environmental Site Assessments Tannery Property (2008-2013) Austin Brothers Property (2014-2015) 2015/2016 – Remedial Investigation (DEQ) Electromagnetic Survey 130 Soil Borings 21 Monitoirng Wells Installed Mar. 2017 – Interim Response Buried Hides (5200 tons) Metals Fuel-related chemicals Cyanide and Chloride Aug. 2017 – PFAS Tested & Detected
What are PFAS? Per and Poly-fluoroalkyl substances Generic family (over 5000) of chemicals Man-made and do not occur naturally Developed in 1940’s Used to make products that resist heat, oils, grease, stains and water Most prevalent/researched: PFOS & PFOA
Per-and polyfluoroalkyl substances (PFAS) Strong carbon- fluorine bonds Surfactants PFOA - perfluorooctanoic acid Hydrophobic(repels O F F F F F O - F F F water) and oleophobic S C C C C (repels oil, fat, grease) C C C F C O 5,000+ compounds F F F F F F F F PFOS - perfluorooctanesulfonic acid
PFAS Uses Building and Chemicals and Apparel Aerospace Electronics Construction Pharmaceuticals 7 Healthcare and Aqueous Film Energy Oil & Gas Semiconductors Hospitals Forming Foam
Why the Concern? Pervasive Persistent Bioaccumulative Associated with adverse health effects Scarcity of information in scientific literature Lack of sufficient standards In water, we analyze for PFAS at the parts per trillion level
What is a Part per Trillion? Units; nano- (10 -9 ): Liquid - nanograms per liter (ng/L) Solid - nanogram per kilogram (ng/Kg) often reported in parts per billion or nanograms per gram (ng/g) Conceptual: One drop in 500,000 barrels of water 6-Inches in the 93 million mile journey to the sun A square foot of floor tile on a floor as big as Indiana Challenges: Laboratory (measurement / analyses) Sample collection procedures and checks Potential introduction of PFAS into samples
Mobility Highly mobile Unconventional Affected by organic carbon, pH, clay content Low volatility (especially longer chains) Persistent Current models lacking
Federal PFOA PFOS Where are we now? USEPA DW 0.07 0.07 USEPA GW 0.4 0.4 US States Alabama (AL) DW 0.07 0.07 Alaska (AK) GW 0.40 0.40 EPA expected to list as Arizona (AZ) DW 0.07 0.07 California (CA) DW 0.014 0.013 Hazardous Waste in 2019 Colorado (CO) DW 0.07 0.07 GW 0.07 0.07 22 States with some form of Connecticut (CT) DW/GW 0.07 0.07 Delaware (DE) GW 0.07 0.07 water criteria (70% in last 2 Iowa (IA) GW 0.07 0.07 DW 0.07 0.07 years; MI - Jan 2018 ) Maine (ME) GW 0.13 0.56 RW 0.05 1.2 Over half have adopted Massachusetts (MA) DW 0.07 0.07 SW 0.42 0.011 Michigan (MI) current EPA lifetime DW/GW 0.07 0.07 Minnesota (MN) DW/GW 0.035 0.027 advisory (70 ng/L) Nevada (NV) DW 0.667 0.667 New Hampshire (NH) GW 0.07 0.07 New Jersey (NJ) DW 0.014 0.013 Ten states have adopted North Carolina (NC) GW 2 NA criteria for other PFAS Oregon (OR) SW 24 300 Pennsylvania (PA) GW 0.07 0.07 Rhode Island DW/GW 0.07 0.07 PFHxS - Perfluorohexanesulfonic acid Texas (TX) GW 0.29 0.56 Vermont (VT) DW/GW 0.02 0.02 West Virginia (WV) DW 0.07 0.07
MPART Michigan PFAS Action Response Team Governor Snyder signed ED 2017-4 on November 13, 2017 Statewide cooperation and collaboration to strategically and proactively address this emerging contaminant. 12
DEQ Testing Alpena Hide and Leather 40+ PFAS sites identified Municipal water River, Lakes & Streams Biosolids Landfill leachate Fish & Deer
Statewide Municipal Drinking Water Testing Program Michigan PFOS / PFAS groundwater standard established in 2018: 70 nanograms per liter (ng/L) Public Water • 1,119 community water Supply Testing supplies sampled • 461 Schools sampled • 168 Daycares/Head start facilities sampled 14
Surface Water Investigation Sources: - Public owned treatment works ▪ Industrial pretreatment program ▪ Biosolids - Industrial direct dischargers Pathway : Storm Water At the Receptor: - Ambient monitoring - Surface Water Foam - Fish and Wildlife 15
AHL – Current Understanding Tannery-Related Operations ▪ Soil Exposure - Arsenic Arsenic - Residual petroleum in Soil - Residual hides ▪ Groundwater - Arsenic Plume - Other Metals 2017 Hide - Cyanide Removal Former Bulk Fuel Area 16
PFAS – Source (Soil) ▪ Screening Levels (ng/g) - PFOS > 0.24 - PFOS + PFOA > 1.4 - PFOS or PFOA > 25,000 ▪ Detected PFAS (84 of 110) - 14 different PFAS detected - PFOS - 69 detections (63%) Max = 264 ng/g (> 0.24 ng/g) - PFHxS - 62 detections (56%) Max = 43 ng/g - PFOA - 10 detections (9%) Max = 5.4 ng/g 17
PFAS - Groundwater ▪ Screening Levels (ng/L) - PFOS > 12 - PFOA > 12,000 - PFOS + PFOA > 70 ▪ Detected PFAS (125 of 130) - 16 different PFAS detected - PFOS - 94 detections (72%) Max = 5,420 ng/L (76 > 12 ng/L) - PFHxS - 105 detections (81%) Max = 10,800 ng/L - PFOA - 110 detections (85%) Max = 710 ng/L PFOS+PFOA > 70 ng/L in 60 samples 18
PFAS – Seasonality in Groundwater ▪ Source Area MW-5 (Source Area) 4,500 - PFHxS & PFOS >> PFOA 4,000 600.0 Groundwater Elevation (feet amsl) 3,500 - Correlation of PFHxS to 3,000 599.5 PFAS (ng/L) 2,500 Groundwater Elevation 2,000 599.0 MW-19 (Downgradient) 1,500 1,000 598.5 700 500 Groundwater Eelvation (feet amsl) 600 595.8 0 598.0 Jun-17 Sep-17 Dec-17 Apr-18 Jul-18 Oct-18 Feb-19 500 PFAS (ng/L) PFHxS PFOA PFOS GWE Top of Screen 400 ▪ Downgradient 300 594.4 200 PFOA > PFOS - 100 PFOA & PFHxS Correlation - 0 593.0 Jun-17 Sep-17 Dec-17 Apr-18 Jul-18 Oct-18 Feb-19 to Groundwater Elevation PFHxS PFOA PFOS GWE Top of Screen 19
PFAS – Surface & Storm Water ▪ Screening Levels (ng/L) - PFOS > 12 - PFOA > 12,000 ▪ Detected PFAS in river (33 of 33; perfluorobutanoic acid-PFBA) - 11 different PFAS detected - PFOS - 5 detections (15%) Max= 10.5 ng/L (Storm=175 ng/L) - PFHxS - 9 detections (27%) Max= 44.2 ng/L (Storm = 626 ng/L) - PFOA - 8 detections (24%) Max= 9.93 ng/L (Storm = 51 ng/L) 20
PFAS – Surface Water/Foam ▪ Foam - April, 2018 ▪ Surface water/foam samples collected at four locations 3rd Ave. & Carter 9th Ave Culvert S Location Date 4/25/18 5/8/18 4/24/18 5/8/18 L-PFBA 4.22 JJ 7.39 5.51 7.32 T-PFHxS 4.57 U 3.93 U 16.1 2.51 JJ 8.74 T-PFOA 1.38 JJ 3.62 JJ 1.91 JJ T-PFOS 490 3.93 U 4.53 0.830 JJ Island Bridge Right Island Bridge Location Bank 4/24/18 11/15/18 4/24/18 11/15/18 Date L-PFBA 3.68 JJ 1.99 JJ 3.53 JJ 2.17 JJ T-PFHxS 4.06 U 4.21 U 3.97 U 4.22 U T-PFOA 1.19 JJ 4.21 U 0.863 JJ 4.22 U T-PFOS 12.8 4.21 U 3.97 U 4.22 U 21
PFAS – Conceptual Site Model 22
PFAS – Treatment Approaches? ▪ PFAS/Site-Related Challenges: Thin aquifer - Shallow depth to water - Injection Area PFAS impacts below water table - Solid Waste? - Lack of in-situ destruction - Soil Mixing Area technologies (C-F Bond) ▪ Immobilization Approach: Carbon - tested ex-situ - Largely untested in-situ - Delivery - Inject or Mix? - December 2018 Pilot Tests Long-term - sorptive capacity? - 23
2018 PFAS – Injection Pilot Test ▪ Advantages: EW-2 (~7ft) Ability to work in - “developed” areas No solid waste - MW-5 (~9ft) Relatively cost effective - PZ-1 (~4ft) ▪ Disadvantages: Treats saturated soil only - Uniform distribution? - Liquid waste - Potential short circuiting - 24
2018 PFAS – Soil Mixing Pilot Test ▪ Advantages: Soil Mixing Treat unsaturated and - Area saturated soil (10’x10’x8’) More uniform mixing/contact - No liquid waste - Ability to remove material - Non-hazardous disposal? - ▪ Disadvantages: Slower / more costly - Requires complete access - Compaction/build-ability? - 25
Arsenic – Next Steps ▪ What Levels are Safe? - In Vitro Bioaccessibility (IVBA) Study Underway Hide Removal - Determine Site Specific Safe Levels Arsenic in Soil ▪ Excavation / Restoration - Arsenic impacted soil 2017 Hide - Residual hides Removal ▪ Groundwater - Source removal 26
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