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

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: ADAMSJ1@michigan.gov

989-705-3434www.michigan.gov/deq

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