Former Alpena Hide and Leather
Project Status – February 2019
Janice Adams, MDEQ Project Manager: [email protected]
Len Mankowski, Wood Geologist: [email protected]
Sesha Kallakuri, DHHS Toxicologist: [email protected]
OverviewAlpena 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
Post Tannery (to 2005)
Warehousing
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)
NEC
Bulk Fuel
Tannery
AHL – Site Activities2008 – 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
Hydrophobic(repels
water) and oleophobic
(repels oil, fat, grease)
5,000+ compounds
F F F F F F FF
F
F F F F F F F F
C
C C
C
C
C
C
C
O
O O-
S
PFOA - perfluorooctanoic acid
PFOS - perfluorooctanesulfonic acid
7
PFAS Uses
Chemicals and
PharmaceuticalsElectronicsAerospace Apparel
Building and
Construction
Aqueous Film
Forming FoamSemiconductorsOil & Gas Energy
Healthcare and
Hospitals
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
Where are we now? EPA expected to list as
Hazardous Waste in 2019
22 States with some form of water criteria (70% in last 2 years; MI - Jan 2018)
Over half have adopted current EPA lifetime advisory (70 ng/L)
Ten states have adopted criteria for other PFAS PFHxS - Perfluorohexanesulfonic acid
Federal
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
Arizona (AZ) DW 0.07 0.07
California (CA) DW 0.014 0.013
Colorado (CO) DW 0.07 0.07
GW 0.07 0.07
Connecticut (CT) DW/GW 0.07 0.07
Delaware (DE) GW 0.07 0.07
Iowa (IA) GW 0.07 0.07
DW 0.07 0.07
GW 0.13 0.56
RW 0.05 1.2
Massachusetts (MA) DW 0.07 0.07
SW 0.42 0.011
DW/GW 0.07 0.07
Minnesota (MN) DW/GW 0.035 0.027
Nevada (NV) DW 0.667 0.667
New Hampshire (NH) GW 0.07 0.07
New Jersey (NJ) DW 0.014 0.013
North Carolina (NC) GW 2 NA
Oregon (OR) SW 24 300
Pennsylvania (PA) GW 0.07 0.07
Rhode Island DW/GW 0.07 0.07
Texas (TX) GW 0.29 0.56
Vermont (VT) DW/GW 0.02 0.02
West Virginia (WV) DW 0.07 0.07
Maine (ME)
Michigan (MI)
PFOA PFOS
MPARTMichigan 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
Alpena Hide and Leather
DEQ Testing 40+ PFAS sites
identified
Municipal water
River, Lakes &
Streams
Biosolids
Landfill leachate
Fish & Deer
Public Water Supply Testing
14
• 1,119 community water
supplies sampled
• 461 Schools sampled
• 168 Daycares/Head start
facilities sampled
Michigan PFOS / PFAS groundwater
standard established in 2018:
70 nanograms per liter (ng/L)
Statewide Municipal Drinking Water
Testing Program
Surface Water Investigation
15
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
AHL – Current Understanding
Tannery-Related Operations
16
▪ Soil Exposure
- Arsenic
- Residual petroleum
- Residual hides
▪ Groundwater
- Arsenic Plume
- Other Metals
- Cyanide
Former
Bulk Fuel
Area
Arsenic
in Soil
2017 Hide
Removal
PFAS – Source (Soil)
17
▪ 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
PFAS - Groundwater
18
▪ 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
PFAS – Seasonality in Groundwater
19
▪ Source Area
- PFHxS & PFOS >> PFOA
- Correlation of PFHxS to
Groundwater Elevation
598.0
598.5
599.0
599.5
600.0
0
500
1,000
1,500
2,000
2,500
3,000
3,500
4,000
4,500
Jun-17 Sep-17 Dec-17 Apr-18 Jul-18 Oct-18 Feb-19
Gro
undw
ate
r E
levation (
feet am
sl)
PF
AS
(ng/L
)
MW-5 (Source Area)
PFHxS PFOA PFOS GWE Top of Screen
593.0
594.4
595.8
0
100
200
300
400
500
600
700
Jun-17 Sep-17 Dec-17 Apr-18 Jul-18 Oct-18 Feb-19
Gro
undw
ate
r E
elv
ation (
feet am
sl)
PF
AS
(ng/L
)
MW-19 (Downgradient)
PFHxS PFOA PFOS GWE Top of Screen
▪ Downgradient
- PFOA > PFOS
- PFOA & PFHxS Correlation
to Groundwater Elevation
PFAS – Surface & Storm Water
20
▪ 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)
PFAS – Surface Water/Foam
21
▪ Foam - April, 2018
▪ Surface water/foam samples
collected at four locations
Location 3rd Ave. & Carter 9th Ave Culvert S
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
T-PFOA 8.74 1.38 JJ 3.62 JJ 1.91 JJ
T-PFOS 490 3.93 U 4.53 0.830 JJ
Location Island BridgeIsland Bridge Right
Bank
Date 4/24/18 11/15/18 4/24/18 11/15/18
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
PFAS – Conceptual Site Model
22
PFAS – Treatment Approaches?
23
▪ PFAS/Site-Related Challenges:
- Thin aquifer
- Shallow depth to water
- PFAS impacts below water table
- Solid Waste?
- Lack of in-situ destruction
technologies (C-F Bond)
▪ Immobilization Approach:
- Carbon - tested ex-situ
- Largely untested in-situ
- Delivery - Inject or Mix?
- Long-term - sorptive capacity?
Injection Area
Soil Mixing Area
December 2018 Pilot Tests
2018 PFAS – Injection Pilot Test
24
▪ Advantages:
- Ability to work in
“developed” areas
- No solid waste
- Relatively cost effective
▪ Disadvantages:
- Treats saturated soil only
- Uniform distribution?
- Liquid waste
- Potential short circuiting
EW-2 (~7ft)
PZ-1 (~4ft)
MW-5 (~9ft)
2018 PFAS – Soil Mixing Pilot Test
25
▪ Advantages:
- Treat unsaturated and
saturated soil
- More uniform mixing/contact
- No liquid waste
- Ability to remove material
- Non-hazardous disposal?
▪ Disadvantages:
- Slower / more costly
- Requires complete access
- Compaction/build-ability?
Soil Mixing
Area
(10’x10’x8’)
Arsenic – Next Steps
26
▪ What Levels are Safe?
- In Vitro Bioaccessibility
(IVBA) Study Underway
- Determine Site Specific
Safe Levels
▪ Excavation / Restoration
- Arsenic impacted soil
- Residual hides
▪ Groundwater
- Source removal
Arsenic
in Soil
2017 Hide
Removal
Hide
Removal
Surface Water Pathway
27
▪ Former Bulk Fuel
- Residual petroleum impacts
- Site Drainage to RCCB-1
during high water table
conditions
▪ Storm Water
- High Water Drainage to
SFCB-2
- Unmapped Systems?
- Thunder Bay River Outfall?
- Groundwater / Storm Water
Interactions?
Former
Bulk Fuel
Area
RCCB-1
Old
Storm?
SFCB-2
?
?
www.Michigan.gov/PFASresponse
Janice Adams, MDEQ Project Manager: [email protected]
989-705-3434www.michigan.gov/deq
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