![Page 1: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/1.jpg)
MCHM/PPH in the Elk and Kanawha Rivers after the January 2014 Spill:
Lessons Learned
Jennifer Weidhaas, Karen Buzby Aubrey Harris, Paul Ziemkiewicz, Kung Wang
and Lance Lin
West Virginia UniversityApril 1, 2015
![Page 2: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/2.jpg)
Spill TimelineJan 8‐9 spill of 10,000 gal to Elk RiverJan 9WVDEP informed WVAmW, “do not use order” issuedJan 10 CDC says 1 ppm safeJan 13 ban lifted for 25,000 customersJan 15 CDC recommends pregnant women not drink the waterJan 17 Freedom Industries files for bankruptcyJan 18 ban lifted for remaining usersJan 21 WVDEP informed of PPH release
Feb 11 6 ppb MCHM in schools
Jan 11 prepared proposalJan 13 called NSF
Jan 15 conducted round 1 sampling (CEE Department $10,000)
Jan 22 conducted round 2 samplingJan 30 conducted round 3 samplingLaboratory studies
http://www.dhsem.wv.gov/Pages/WV‐American‐Water‐Emergency.aspx
![Page 3: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/3.jpg)
Freedom Industries
WV American WaterTreatment Plant
~1.6 miles
![Page 4: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/4.jpg)
Mixture constituentsCrude MCHM (88.5% of tank contents), PPH Stripped (7.3% of tank contents)
Assuming 10,000 gallons spilled
Eastman Chemical and DOW MSDS’s, 2014
Normalized gallons spilled into Elk River
After 10 minutes
4‐(methoxymethyl)cyclohexanemethanol
1151 gal
methyl 4‐methylcyclohexanecarboxylate
443 gal
Di‐PPh, 435 gal
PPH, 154 gal
water
MCHM6947 gal
![Page 5: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/5.jpg)
What was in the tanks?• Crude MCHM (89% of tank contents)
– 4‐methylcyclohexanemethanol (68 to 89 % of crude)SG = 0.9074log Kow = 2.35 (cis isomer, Dietrich et al, 2015)log Kow = 2.46 (tran isomer, Dietrich et al, 2015)Water solubility = 2,250 mg/L at 23 C (Dietrich et al., 2015)
= 1,585 mg/L at 23 C (He et al., 2015)Odor threshold concentration = 0.06 ppb‐v, tran‐isomer
= 120 ppb‐v, cis‐isomer (Gallagher et al., 2014)
Henry’s constant = ~6.4 * 10‐6 atmm3/mol (EPA Suite v4.11)
– 4‐(methoxymethyl)cyclohexanemethanol (4 to 22 % of crude)Unknown properties
Eastman Chemical and DOW MSDS’s, 2014
![Page 6: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/6.jpg)
What was in the tanks?• PPH stripped? PPH Basic? (7% of tank)
– Dipropylene glycol phenyl ether (<= 85% of PPH Basic)Henry’s constant = 4.7* 10‐10 atm m3/mol
– Propylene glycol phenyl ether (<= 20 % of PPH Basic)log Kow = 1.52 (calc); water solubility = 1.1 g/L Henry’s constant = 4.4* 10‐7 atm m3/mol
![Page 7: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/7.jpg)
NMR analysis of MCHMKung Wang, Chemistry
100
49.68
TCI America Analytical Standard1H‐NMR spectrum (600 MHz)
Eastman Chemical crude‐MCHM1H‐NMR spectrum (600 MHz)
100
54.26
![Page 8: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/8.jpg)
WVAmW: Influent and Effluent
Date
1/9/14 1/13/14 1/17/14 1/21/14 1/25/14 1/29/14
MC
HM
, mg
L-1
0
1
2
3
Raw waterFinished waterspillban lifted downtown
1/9/14 1/13/141/17/141/21/141/25/141/29/14
MC
HM
, mg
L-1
0.00
0.02
0.04
0.06
0.08
0.10
MDL
Jan 15 AM Jan 16 PMJan 14 AMJan 13 AM Jan 18 PMJan 14 PM Jan 17
Do not use order (Red) over time
![Page 9: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/9.jpg)
1. Open all hot water taps and run for 15 minutes
2. Open all cold water taps (inside) and run for 5 minutes, flush all toilets (once)
3. Flush all remain faucets and appliances
Estimate of odor threshold = 0.06 ppb‐v
CDC “safe” limit in water = 1000 ppb
![Page 10: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/10.jpg)
Downtown Charleston
House B
House C
House A
Elk River
Ohio River
Kanawha River
![Page 11: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/11.jpg)
Residential sampling resultspr
e-flu
shpo
st-fl
ush
1 w
eek
2 w
eek
MC
HM
, mg
L-1
0.000.050.100.150.200.250.300.350.400.45
pre-
flush
post
-flus
h1
wee
k2
wee
k
pre-
flush
post
-flus
h1
wee
k2
wee
k
pre-
flush
post
-flus
h1
wee
k2
wee
k
pre-
flush
post
-flus
h1
wee
k2
wee
k
pre-
flush
post
-flus
h1
wee
k2
wee
k
House A House B House CCold
WaterHot
WaterCold
WaterHot
WaterCold
WaterHot
Water
MDL
Water distribution system
![Page 12: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/12.jpg)
Chemical Attenuation and Barriersin Current Water Supply Infrastructure
• Mixing and dilution in the river
• Other mass transfer processes resulting in losses of the chemicals from the river water‐ sorption, volatilization, degradation, hydrolysis, etc.
• Water treatment plantVulnerability?
• Alternative water sources
![Page 13: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/13.jpg)
Toxics.usgs.gov
Fate of organic contaminants in rivers
?
?
???
?
![Page 14: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/14.jpg)
3‐D MCHM Fate and Transfer Modeling
![Page 15: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/15.jpg)
Elk River DimensionsAverage width: 68 mAverage depth: 3.5 mMean velocity: 550 m/hr
This information was collected with 5 cross sections from USGS survey of the reach, and then interpolated with HEC‐RAS to create 74 cross sections, each about 35 m apart.
![Page 16: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/16.jpg)
Spill Characteristics
• MCHM was spilled for approximately 20 hours at a rate of (8 gpm); mass loading of 1,485 kg/hr.
• It travelled 2,600 m (1.61 miles) before being intercepted by the American Water System, a water intake for Charleston, WV
![Page 17: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/17.jpg)
• Mixing characteristics: Within about 500 m the chemical becomes mixed across the lateral width and vertical depth.
• The implication is that even though the chemical is a lower‐density, non‐aqueous phase chemical, the surface water is not the only area impacted.
Areal view of spill dispersion at 10 hours
3‐D view of spill dispersion at 10 hours
![Page 18: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/18.jpg)
0
500
1000
1500
2000
2500
3000
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Distance from
intake (m
)
Hours since spill began
Plume front (0.1 ppm) distance from intake
surface plume
distance from intake z=0.5
distance from intake z=1
distance from intake z=2
![Page 19: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/19.jpg)
WA American Water treatment plant unit processes
![Page 20: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/20.jpg)
Unit Processes & Lab Studies1. River sediment sorption/desorption2. Permanganate oxidation3. Coagulation/flocculation with Alum
4. GAC adsorption5. HOCl‐, OCl‐ disinfection6. Testing household filters
13
45
2
![Page 21: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/21.jpg)
Permanganate oxidation
www.gunnook.com
http://www.myfoxtwincities.com
Experimental protocol‐Vary MCHM + PPH from 10 to 30 ppm‐De‐ionized water‐Room temperature ‐1 to 10 minute reaction‐0, 5, 10, 50 and 100 ppm KMnO4
Conclusion: Permanganate oxidation would not have degraded the MCHM to any great extent in the treatment plant
![Page 22: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/22.jpg)
Granular Activated Carbon Sorption?
13.21312.812.612.412.21211.811.611.411.21110.810.610.410.2109.89.69.49.298.88.68.4
36,000
34,000
32,000
30,000
28,000
26,000
24,000
22,000
20,000
18,000
16,000
14,000
12,000
10,000
8,000
6,000
4,000
2,000
0 RT [min]
GAC t0 and t244.DATAGAC t03.DATA
µV
Sand filters with GAC commonly used to polish drinking water before distribution
trans‐MCHM
cis‐MCHM
Red line = 45 ppm MCHM & 5 ppm PPH at 0 hourBlack line = 45 ppm MCHM & 5 ppm PPH at 24 hour
Limited removal of MCHM & PPH by GAC!
Retention time
GC‐FID sig
nal inten
sity, uV
PPH compounds
![Page 23: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/23.jpg)
Biodegradation of MCHM
• Water flushed to wastewater treatment plant– Was the MCHM removed before it went back to the river?
• Was MCHM degraded in the Elk and Kanawha River?
Treated wastewater
?? ??
![Page 24: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/24.jpg)
Biodegradation study
Media & Activated Sludge River water & sediments Controls (no biological activity)
Experimental protocol‐50, 10 and 1 ppm MCHM + PPH ‐Mon River water‐25‐27 degrees Celsius‐12 days of degradation‐GC‐FID analysis
Conclusions: 1) Anaerobic and aerobic biodegradation likely occurs2) MCHM would have degraded biologically in Kanawha and Ohio
![Page 25: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/25.jpg)
Related Work by Others• WV WRI – MCHM fate in coal beneficiation
• Virginia Tech—Chemical properties and fate parameters
• University of Southern Alabama—sorption to water pipe materials and desorption
• Ohio State University—social & behavioral responses for improving science communication
• USGS‐NWQL—river sampling
• USGS‐Shepherdstown—toxicity testing
• WVU‐Biology—toxicity testing
![Page 26: MCHM/PPH in the Elk and Kanawha Rivers after the January ... · 15/01/2016 · Rivers after the January 2014 Spill: Lessons Learned ... Jan 10 CDC says 1 ppm safe Jan 13 ban lifted](https://reader034.vdocument.in/reader034/viewer/2022042303/5ecf059e736fc27d4d7f0e09/html5/thumbnails/26.jpg)
Acknowledgements
• Bill Cooper, NSF Program Officer– CBET‐1422803
• WVU CEE Department
• WV Water Research Institute