July 4th Fireworks as an Unconventional Source of

Groundwater ContaminationUnreacted Perchlorate survives the show to impact groundwater

October 17, 2019Joel Henry & Alyssa Olson

This Photo by Unknown Author is licensed under CC BY

1) How much perchlorate survives?

2) What is the fate of unreacted perchlorate?

3) Fireworks, and other “one-time” events, need to be considered in Wellhead Protection Planning

GOALS

ClO4-

Perchlorate Ion

Perchlorate is an excess reagent in fireworks.

Perchlorate Refresher

Literature – Perchlorate & Fireworks

Evart Case Study

Conclusions

ClO4-

Perchlorate Ion

AGENDA

4

Chloro-Oxyanions

ClO4- ClO3

-

Perchlorate ChlorateClO2

-

ChloriteClO-

Hypochlorite

Cl+7 Cl+5 Cl+3 Cl+1

Decreasing oxidation state of chloride ion

5

Perchlorate – ClO4-

Phosphate – PO4-3

Sulfate – SO4-2 • HIGHLY SOLUBLE

• Naturally-occurring• Perchlorate is not nearly as

abundant or biologically-active

Tetrahedral Oxyanions

6

Regulatory – Drinking Water

• 56 µg/L - US EPA Drinking Water Criteria (proposed)

• 15 µg/L - US EPA Drinking Water Health Advisory Benchmark (non-enforceable)

• 6 µg/L - California

• 2 µg/L – Massachusetts

• 1 µg/L – California (Public Health Goal)

• Unregulated in Michigan

7

Health Effects

THYROID GLAND• Iodide Uptake Inhibitor

• Substitutes for iodine in thyroid • Slows thyroid function • Disrupt hormones needed for normal

growth

• Women and children most at risk

8

• Lightning – O3 + Cl-à perchlorate

• Accumulates in desert soils:• Chile – Atacama desert• Death Valley• West Texas / Eastern New Mexico

TexasNatural Sources

Michigan precipitation: 0.1 µg/L

Gu and Coates, 2006

NM

TX

~60-county highly-irrigated area around Lubbock, TX

Perchlorate concentrations 1-20 ug/L or higher in groundwater

9

• Aerospace / Military (90%)

• Sodium Hypochlorite Solution (~10 ppm)

• Imported Chilean fertilizer

• Fireworks

• 0 to 70% perchlorate

Texas“Unnatural” Sources

Solid rocket boosters about 70% NH3ClO4

This Photo by Unknown Author is licensed under CC BY-SA

10

Literature: Fireworks and Rain

Long Island, NY

• Baseline concentration ~0.1 µg/L

• Peak concentration of 2.5 µg/L

• Peaks immediately after July 4, multiple locations

Munster et al. 2008 (Water Air Soil Pollut v.198, 1, 149)

11

Literature: Fireworks and Groundwater

UMass-Dartmouth, 2007

• 10 years of fireworks from same location

• 30-60 µg/L in groundwater at shallow wells adjacent to launch area

12

Literature: Fireworks and Water Supply

Mount Rushmore

• Up to 38 µg/L in GW samples (200-500 ft wells)

• Up to 54 µg/L in SW samples (intermittent streams)

• Attributed to fireworks launched annually from above/behind monument

USGS Scientific Investigations Report 2016-5030

13

Unanswered Questions

Mass released varies by:• Type of fireworks (0-70% perchlorate)• Mass/number of fireworks in a show• Environmental variables

• Temperature, humidity, wind speed and direction• Transport mechanisms

• Paper wrappers; dust; vapors

14

Setting – Evart, Michigan

EVART

15

Setting - Twin Creek Wellfield – Evart MI

Good screen shot of Michigan, then show the LP

• 7 Municipal wells

• First well - 1930

• Unconfined aquifer

• Aquifer thickness 30-60 feet

• Depth to Water 10-20 feet

• Permitted rates: 290-500 GPM

• Average daily use: 500 GPM• Supplies about 1/2 to 2/3 of

municipal supply• Balance from 3 “Western”

wellfield production wells

7

5 6

3 2

1

4

16

Setting – Groundwater Flow Directions

Muskegon River

Study Area

To Lake Michigan, ~150 miles

17

Winter 2014 – Spring 2015

Seven production wells in City of Evart Twin Creek Wellfield

Good screen shot of Michigan, then show the LP 7.4

8.6

20

4.8

ND

ND

3

LAUNCH AREA

Osceola County Fairgrounds

18

Remedial ActionsPurge perchlorate out through existing production wells Three wells offline - highest concentrations – greatest mass flux One well to sanitary sewer NPDES permit, WET testing Two wells to surface water Move as much production as possible to Western wellfield (2 wells) Start constructing new 3rd well in Western wellfield MOVE NEXT YEAR’S FIREWORKS!!!

Monitor, monitor, monitor Bi-weekly sampling of all production wells Monthly average ClO4 x monthly pumping volume = mass flux

19

Monitoring

• Every 2 weeks – Sample municipal wells and water towers

• Obtain monthly pumping records from City

• Calculate monthly mass flux

Concentration of perchlorate (m/v) X

Withdrawal rate of production wells (v/t)

= Flux of perchlorate (m/t)

This Photo by Unknown Author is licensed under CC BY-NC-ND

20

3 Months (June 2015)

0

5

10

15

20

25

30

Apr-

15M

ay-1

5Ju

n-15

Jul-1

5Au

g-15

Sep-

15O

ct-1

5N

ov-1

5De

c-15

Jan-

16Fe

b-16

Mar

-16

Apr-

16M

ay-1

6Ju

n-16

Jul-1

6Au

g-16

Sep-

16O

ct-1

6N

ov-1

6De

c-16

Jan-

17Fe

b-17

Mar

-17

Apr-

17M

ay-1

7Ju

n-17

Jul-1

7Au

g-17

Sep-

17O

ct-1

7N

ov-1

7De

c-17

Jan-

18

Aver

age

Mon

thly

Con

cent

ratio

n (u

g/L)

Well 2 Well 3

84 grams/month

18 µg/L

8 µg/L

Well 3: 55 GPM average rate

Well 2: 62 GPM average rate

All 6 wells combined = 500 grams per month

162 grams/month

21

Possible SourcesWhat accounts for a pound of perchlorate each month?

Bleach / Cleaning Products at Fairgrounds

1 pound/month of perchlorate would require 155 drums

Roads; dust control brines, flares

Hypochlorite Solution

• By-product of manufacturing, age

• 14 mg/L (14,000 µg/L)

22

Twin Creek Wellfield – Evart, MI

Seven production wells in City of Evart Twin Creek Wellfield

Good screen shot of Michigan, then show the LP LAUNCH

AREA

Osceola County Fairgrounds

1000’ 3 21300’

23

June 2015 – What we didn’t know

• Were perchlorate concentrations rising or falling in groundwater?

• How high would concentrations go, and for how long?

• How much perchlorate was in the aquifer, or in the unsaturated soils?

• How much per show?

• Where and how was the perchlorate deposited – wind dispersal, unreacted powder, used wrappers, launch area?

24

• Sandy glacial outwash

• High recharge rates (12-16 in/yr)

• Groundwater velocity ~3 ft/day

• Removing ~1 pound per month

• Assuming that fireworks are the primary source of perchlorate

• Another fireworks show coming up on July 4, 2015

June 2015 – What we did know

25

Evart Community Fireworks EventJuly 4th 2015

July 4, 2015• Warm, humid, light breeze• Half-hour of fireworks• July 5, 2015 – picked up wrappers & litter

Rain Events• July 7 – 0.5 inch of rain

• July 14 – 0.5 inch of rain• Aug 3 - 1.5 inches of rain

26

Source Area Investigation

3-4 soil samples per boring

1-2 water samples per boring

Uns

atur

ated

Aqui

fer

Debris Area

27

Source Area Results- November 2015

SOILS• Less than ½ pound perchlorate

WATERHighest concentrations were at water table

• Maximum: 240 µg/L• <0.05 µg/L within a few feet of

the water table

perchlorate < 0.05 µg/L

~2 feet of elevated perchlorate

18-20 feet: unsaturated soils

<200 g

GW Flow

28

Setting - Twin Creek Wellfield – Evart MI

Good screen shot of Michigan, then show the LP

7

5 6

3 2

1

4

29

3 Months (June 2015)

0

5

10

15

20

25

30

Apr-

15M

ay-1

5Ju

n-15

Jul-1

5Au

g-15

Sep-

15O

ct-1

5N

ov-1

5De

c-15

Jan-

16Fe

b-16

Mar

-16

Apr-

16M

ay-1

6Ju

n-16

Jul-1

6Au

g-16

Sep-

16O

ct-1

6N

ov-1

6De

c-16

Jan-

17Fe

b-17

Mar

-17

Apr-

17M

ay-1

7Ju

n-17

Jul-1

7Au

g-17

Sep-

17O

ct-1

7N

ov-1

7De

c-17

Jan-

18

Aver

age

Mon

thly

Con

cent

ratio

n (u

g/L)

Perchlorate Concentration (ug/L)

Well 2 Well 3

2 µg/L

18

8

Fireworks July 2015

30

6 Months (September 2015)

0

5

10

15

20

25

30

Apr-

15M

ay-1

5Ju

n-15

Jul-1

5Au

g-15

Sep-

15O

ct-1

5N

ov-1

5De

c-15

Jan-

16Fe

b-16

Mar

-16

Apr-

16M

ay-1

6Ju

n-16

Jul-1

6Au

g-16

Sep-

16O

ct-1

6N

ov-1

6De

c-16

Jan-

17Fe

b-17

Mar

-17

Apr-

17M

ay-1

7Ju

n-17

Jul-1

7Au

g-17

Sep-

17O

ct-1

7N

ov-1

7De

c-17

Jan-

18

Aver

age

Mon

thly

Con

cent

ratio

n (u

g/L)

Perchlorate Concentration (ug/L)

Well 2 Well 3

1413

2 µg/L

Fireworks July 2015

31

9 Months (December 2015)

0

5

10

15

20

25

30

Apr-

15M

ay-1

5Ju

n-15

Jul-1

5Au

g-15

Sep-

15O

ct-1

5N

ov-1

5De

c-15

Jan-

16Fe

b-16

Mar

-16

Apr-

16M

ay-1

6Ju

n-16

Jul-1

6Au

g-16

Sep-

16O

ct-1

6N

ov-1

6De

c-16

Jan-

17Fe

b-17

Mar

-17

Apr-

17M

ay-1

7Ju

n-17

Jul-1

7Au

g-17

Sep-

17O

ct-1

7N

ov-1

7De

c-17

Jan-

18

Aver

age

Mon

thly

Con

cent

ratio

n (u

g/L)

Perchlorate Concentration (ug/L)

Well 2 Well 3

8

4 2 µg/L

Fireworks July 2015

32

12 Months (March 2016)

0

5

10

15

20

25

30

Apr-

15M

ay-1

5Ju

n-15

Jul-1

5Au

g-15

Sep-

15O

ct-1

5N

ov-1

5De

c-15

Jan-

16Fe

b-16

Mar

-16

Apr-

16M

ay-1

6Ju

n-16

Jul-1

6Au

g-16

Sep-

16O

ct-1

6N

ov-1

6De

c-16

Jan-

17Fe

b-17

Mar

-17

Apr-

17M

ay-1

7Ju

n-17

Jul-1

7Au

g-17

Sep-

17O

ct-1

7N

ov-1

7De

c-17

Jan-

18

Aver

age

Mon

thly

Con

cent

ratio

n (u

g/L)

Perchlorate Concentration (ug/L)

Well 2 Well 3

86

2 µg/L

Fireworks July 2015

33

15 Months (June 2016)

0

5

10

15

20

25

30

Apr-

15M

ay-1

5Ju

n-15

Jul-1

5Au

g-15

Sep-

15O

ct-1

5N

ov-1

5De

c-15

Jan-

16Fe

b-16

Mar

-16

Apr-

16M

ay-1

6Ju

n-16

Jul-1

6Au

g-16

Sep-

16O

ct-1

6N

ov-1

6De

c-16

Jan-

17Fe

b-17

Mar

-17

Apr-

17M

ay-1

7Ju

n-17

Jul-1

7Au

g-17

Sep-

17O

ct-1

7N

ov-1

7De

c-17

Jan-

18

Aver

age

Mon

thly

Con

cent

ratio

n (u

g/L)

Perchlorate Concentration (ug/L)

Well 2 Well 3

25

15

2 µg/L

Fireworks July 2015

34

18 Months (September 2016)

0

5

10

15

20

25

30

35

40

Apr-

15M

ay-1

5Ju

n-15

Jul-1

5Au

g-15

Sep-

15O

ct-1

5N

ov-1

5De

c-15

Jan-

16Fe

b-16

Mar

-16

Apr-

16M

ay-1

6Ju

n-16

Jul-1

6Au

g-16

Sep-

16O

ct-1

6N

ov-1

6De

c-16

Jan-

17Fe

b-17

Mar

-17

Apr-

17M

ay-1

7Ju

n-17

Jul-1

7Au

g-17

Sep-

17O

ct-1

7N

ov-1

7De

c-17

Jan-

18

Aver

age

Mon

thly

Con

cent

ratio

n (u

g/L)

Perchlorate Concentration (ug/L)

Well 2 Well 3

37

12

2 µg/L

Fireworks July 2015

35

21 Months (December 2016)

0

5

10

15

20

25

30

35

40

Apr-

15M

ay-1

5Ju

n-15

Jul-1

5Au

g-15

Sep-

15O

ct-1

5N

ov-1

5De

c-15

Jan-

16Fe

b-16

Mar

-16

Apr-

16M

ay-1

6Ju

n-16

Jul-1

6Au

g-16

Sep-

16O

ct-1

6N

ov-1

6De

c-16

Jan-

17Fe

b-17

Mar

-17

Apr-

17M

ay-1

7Ju

n-17

Jul-1

7Au

g-17

Sep-

17O

ct-1

7N

ov-1

7De

c-17

Jan-

18

Aver

age

Mon

thly

Con

cent

ratio

n (u

g/L)

Perchlorate Concentration (ug/L)

Well 2 Well 3

10

2

11 months1,000 feet

14 months1,300 feet

2 µg/L

36

24 Months (March 2017)

0

5

10

15

20

25

30

35

40

Apr-

15M

ay-1

5Ju

n-15

Jul-1

5Au

g-15

Sep-

15O

ct-1

5N

ov-1

5De

c-15

Jan-

16Fe

b-16

Mar

-16

Apr-

16M

ay-1

6Ju

n-16

Jul-1

6Au

g-16

Sep-

16O

ct-1

6N

ov-1

6De

c-16

Jan-

17Fe

b-17

Mar

-17

Apr-

17M

ay-1

7Ju

n-17

Jul-1

7Au

g-17

Sep-

17O

ct-1

7N

ov-1

7De

c-17

Jan-

18

Aver

age

Mon

thly

Con

cent

ratio

n (u

g/L)

Perchlorate Concentration (ug/L)

Well 2 Well 3

2

Fireworks July 2015

37

27 Months (June 2017)

0

5

10

15

20

25

30

35

40

Apr-

15M

ay-1

5Ju

n-15

Jul-1

5Au

g-15

Sep-

15O

ct-1

5N

ov-1

5De

c-15

Jan-

16Fe

b-16

Mar

-16

Apr-

16M

ay-1

6Ju

n-16

Jul-1

6Au

g-16

Sep-

16O

ct-1

6N

ov-1

6De

c-16

Jan-

17Fe

b-17

Mar

-17

Apr-

17M

ay-1

7Ju

n-17

Jul-1

7Au

g-17

Sep-

17O

ct-1

7N

ov-1

7De

c-17

Jan-

18

Aver

age

Mon

thly

Con

cent

ratio

n (u

g/L)

Perchlorate Concentration (ug/L)

Well 2 Well 3

2

Fireworks July 2015

No fireworks July 2016

38

30 Months (September 2017)

0

5

10

15

20

25

30

35

40

Apr-

15M

ay-1

5Ju

n-15

Jul-1

5Au

g-15

Sep-

15O

ct-1

5N

ov-1

5De

c-15

Jan-

16Fe

b-16

Mar

-16

Apr-

16M

ay-1

6Ju

n-16

Jul-1

6Au

g-16

Sep-

16O

ct-1

6N

ov-1

6De

c-16

Jan-

17Fe

b-17

Mar

-17

Apr-

17M

ay-1

7Ju

n-17

Jul-1

7Au

g-17

Sep-

17O

ct-1

7N

ov-1

7De

c-17

Jan-

18

Aver

age

Mon

thly

Con

cent

ratio

n (u

g/L)

Perchlorate Concentration (ug/L)

Well 2 Well 3

1

Fireworks July 2015 No fireworks

July 2016No fireworks

July 2017

39

33 Months (December 2017)

0

5

10

15

20

25

30

35

40

Apr-

15M

ay-1

5Ju

n-15

Jul-1

5Au

g-15

Sep-

15O

ct-1

5N

ov-1

5De

c-15

Jan-

16Fe

b-16

Mar

-16

Apr-

16M

ay-1

6Ju

n-16

Jul-1

6Au

g-16

Sep-

16O

ct-1

6N

ov-1

6De

c-16

Jan-

17Fe

b-17

Mar

-17

Apr-

17M

ay-1

7Ju

n-17

Jul-1

7Au

g-17

Sep-

17O

ct-1

7N

ov-1

7De

c-17

Jan-

18

Aver

age

Mon

thly

Con

cent

ratio

n (u

g/L)

Perchlorate Concentration (ug/L)

Well 2 Well 3

0.5

Fireworks July 2015 No fireworks

July 2016No fireworks

July 2017

40

0

5

10

15

20

25

30

35

40

Apr-

15M

ay-1

5Ju

n-15

Jul-1

5Au

g-15

Sep-

15O

ct-1

5N

ov-1

5De

c-15

Jan-

16Fe

b-16

Mar

-16

Apr-

16M

ay-1

6Ju

n-16

Jul-1

6Au

g-16

Sep-

16O

ct-1

6N

ov-1

6De

c-16

Jan-

17Fe

b-17

Mar

-17

Apr-

17M

ay-1

7Ju

n-17

Jul-1

7Au

g-17

Sep-

17O

ct-1

7N

ov-1

7De

c-17

Jan-

18Fe

b-18

Mar

-18

Apr-

18M

ay-1

8Ju

n-18

Jul-1

8Au

g-18

Sep-

18O

ct-1

8N

ov-1

8De

c-18

Jan-

19Fe

b-19

Mar

-19

Apr-

19M

ay-1

9Ju

n-19

Jul-1

9Au

g-19

Aver

age

Mon

thly

Con

cent

ratio

n (u

g/L)

Well 2 Well 3

52 Months (July 2019)Fireworks July 2015

No

firew

orks

20

16

No

firew

orks

201

7

No

firew

orks

201

8

No

firew

orks

201

9

41

0

0.5

1

1.5

2

2.5

3

Apr-1

5

May

-15

Jun-

15

Jul-1

5

Aug-

15

Sep-

15

Oct

-15

Nov

-15

Dec

-15

Jan-

16

Feb-

16

Mar

-16

Apr-1

6

May

-16

Jun-

16

Jul-1

6

Aug-

16

Sep-

16

Oct

-16

Nov

-16

Dec

-16

Jan-

17

Feb-

17

Mar

-17

Apr-1

7

May

-17

Jun-

17

Jul-1

7

Aug-

17

Sep-

17

Oct

-17

Nov

-17

Dec

-17

Jan-

18

Feb-

18

Mar

-18

Apr-1

8

May

-18

Jun-

18

Jul-1

8

Aug-

18

Sep-

18

Oct

-18

Nov

-18

Dec

-18

Jan-

19

Feb-

19

Mar

-19

Apr-1

9

May

-19

Jun-

19

Jul-1

9

Aug-

19

Perc

hlor

ate

Rem

oved

per

mon

th (l

bs)Mass Flux

POUNDS OF PERCHLORATE BEING REMOVED EACH MONTH

2015 (2014 show)10-11 pounds

2017 (no 2016 show)5 pounds

2018 (no 2017 show)1.3 pounds

Monitoring Only Purging through Wellfield

2016 (2015 show)17 pounds

July

201

5 sh

ow2019

~0.8 pounds

Purging through Wellfield

Purging through Wellfield

Purging through Wellfield

42

Small-Town Show – 30-40 minutes

• 400-500 shells, 4-5 kg each = 2,000 kg

• 2,000 kg fireworks, 40% perchlorate = ~800 kg perchlorate

• Recovered in wellfield = ~5-10 kg (10-20 lbs.)

• ~1% to groundwater

• Very little retained in soils (<1/2 lb.)

Case Study Conclusions

43

• 100 lbs fireworks

• If 40% perchlorate, and 1% is unreacted = ~200 grams

• Heavy rain – 1 inch over 1 acre = 100,000 Liters

• 200g/100,000 L = 2 mg/L (2,000 ug/L)

Backyard Scenario

Insideauburnhills.com

44

• Overall consumption is increasing, ~300 million pounds (US)

• 3,500 public shows per year in Michigan

• 10x more “consumer” fireworks than “display”

• Perchlorate regulations are coming

• Consider one-time events (such as fireworks) in wellhead protection

Future Considerations

45

Acknowledgements

Thank you.