Fireworks as source of groundwater contamination · Apr-15 May-15 Jun-15 Jul-15 Aug-15 Sep-15...
Transcript of Fireworks as source of groundwater contamination · Apr-15 May-15 Jun-15 Jul-15 Aug-15 Sep-15...
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.