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Edward P. Kolodziej, Zhenyu Tian, Katherine Peter, Nina Zhao, Ximin Hu, Mike Dodd, Jen McIntyre
+ lots of collaboration with U. Toronto, WSU-Puyallup, NOAA-NMFS, U.S. Fish and Wildlife
-Urban stormwater runoff kills coho salmon in 2-24 hrs: “Urban Runoff Mortality Syndrome”, or URMS
-URMS cause unknown: not pathogens, metals, pesticides, PAHs, ammonia, basic water quality parameters, etc.
-Coho more sensitive, no mortality in cutthroat trout or chum salmon
Scholz et al. 2011
Which chemicals and sources are most important?
Agilent 6530 UPLC-QTOF
High Resolution Mass Spectrometry (HRMS):
-Identify novel compounds, holistic screening -Detect it “all”, then figure out what’s there. -More unbiased, fewer assumptions about what is going on
Coupled together HRMS and toxicology exposures in an “Effects Directed Analysis” framework
Tire Rubber Leachate
chum ch
um
Jen McIntyre (WSU-Puyallup) and NOAA studies
~320 mg/L tire rubber (HRMS: more like 100 mg/L)Leaching: 24 h at 8-10 ºC
Exposure: 24 hRepeated 4X (64 fish total)
16 of 16 exposed coho salmon died,16 of 16 exposed chum salmon lived
chum
control
chum
leachateJen McIntyre (WSU-Puyallup) and NOAA
studies
Leach tire particles into water, then fractionate & expose juvenile coho
Toxic
Are these still toxic?
What chemicals
were removed?
5 juvenile coho in 15-30 L, 24 h
+Control: TWP leachate, 27 exposures, 135 coho, 98.5% mortality-Control: Solvent and Exposure water blanks, 125 coho, 0% mortality
22161355
659
225
26
4
1
10
100
1000
EtOH
EA
H2O
CEX XAD-2 Silica gel
HPLCC18
Toxicant Fractionation Scheme
UPL
C-H
RM
S ES
I+ D
etec
tions
(#)
TWPleachate
HPLCPFP HPLC
Phenyl
SafeLethal
1:2
3:0
2:1
0:3
Hex : DCM
5-6
10-11
14-15
.
RT (min)
..
..
..
RT (min)
14-15
5-6
10-11
..
..
..
.
5-6
8-9
RT (min)
14-15
..
..
..
.
H2O : EtOH
H2O : EtOH
H2O : EtOH
(Tian et al. 2020 SCI)
C18H22N2O2 NOT found in literature/databases for environment or tire rubber chemicals “True Unknown”
-Assumed transformation product, held C and N constant.. Looked for matches. → C18H24N2 (“6PPD”) in EPA Crumb Rubber report
Lattimer et al., 1983Rubber. Chem. Technol.
C18H22N2O2“dinitrone”
-Used industrial grade (96%) 6PPD, protocol built from Lattimer et al. 1983, worked with Mike Dodd (UW CEE)
500 mL/min, 20 min, 6.9% (v/v) O3(g)
Ozonation Products form..
6PPD
(Tian et al. 2020 SCI)
-Andre Simpson, U. Toronto NMR Analysis: Identical structures, O3 synthesized ~98% pure
5x10
0123456
C18 H22 N2 O2, ESI+
11.004
Retention Time (min)1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
Tire leachate 6PPD ozonation11.010
Abu
ndan
ce
3x10
0.20.40.60.8
11.21.41.6
3x10
00.20.40.60.81
1.21.4 C18 H22 N2 O2, ESI+, CID 10, 20, 40 eV
241.0970187.0874
84.9601
104.0500 170.0603
m/z60 80 100 120 140 160 180 200 220 240 260 280 300 320
215.0815
256.1231
104.0515 170.0603
187.0854241.0949
256.1219
299.1775
299.1769215.0832
77.0394200.0717
200.0699
Abu
ndan
ce
(Tian et al. 2020 SCI)
6PPD
NH
HN
O3
NH
HN
O
O
NH
HN
O3
H2O2
1O2
OH
“6PPD-quinone”
~20 ug/L* 6PPD-quinone
Symptomatic cohoin 90 minutes,
All dead in 5 hrs
~20 ug/L* O3 mixture
All dead in 24 hrs
~450 ug/L* 6PPD
1 dead, 1 symptomatic
at 24 hrs
~30 ug/L* 6PPD
0 dead, at 24 hrs
(Figure S2 Tian et al)(*Nominal concentrations)
Products can be more toxic than parent chemicals…
Dilutions of multilane roadway runoff and TWP leachate
N = 365 coho, error bars reflect 3X replicates of 8 fish
Controlled Exposures: 6PPD-quinone ~98% purity
Each exposure: N = 80 coho, 2 replicates
(160 fish total)
6PPD-quinone:“Primary causal toxicant”
(Tian et al. 2020 SCI)
6PPD-quinone formation is expected for any location containing tire rubber residuals, including recycled materials
(Tian et al. 2020 SCI)
Los Angeles
Receiving Water
SeattleSite 1
SeattleSite 2
San Francisco
Seattle
Roadway Runoff
LC50
250 mg/L TWP leachate
1000 mg/L TWP leachate
6PPD
-qui
none
con
cent
ratio
ns (μ
g/L)
0
5
10
15
20
• Detected in 18/18 roadway runoff, all above LC50
• Detected in 6/7 creeks sampled during URMS events, concentrations near or above LC50
• Detected in Seattle, Los Angeles, San Francisco samples
October 21, 2017Lower Duwamish R.(Puget Soundkeeper)
February 17, 2020WSU-Puyallup
(Kolodziej video)
-Tire rubber residuals are sources of complex mixtures of emerging organiccontaminants and water quality impairment. Coho salmon are highlysensitive to these mixtures.
-6PPD: Toxic + designed reactive. Surprised? We should not be surprised when products of toxic compounds also are toxic.
-For California: Coho salmon are telling us to pay special attention when busyroads intersect with sensitive habitats/species.
-Habitat restoration includes chemical habitat (water quality) in addition tophysical habitat. Sensitive species restoration will likely teach us newthings about chemical habitat quality.
The big picture: How can fish and people coexist? What will we need to change in our lives and products to reduce our toxicity? Can we make
“salmon safe” tires?
The CUW Research Team!
Alex, Allan, Zhenyu, Rachel H., Rui, Ting, Nina, Melissa, Rachel L., and Kathy
+Kathy Peter
• Collaborators, Funders, & Citizen Science Teams– NOAA NWFSC – Nat Scholz, James Cameron,
Jessica Lundin (and many others)– WSU-Puyallup Stormwater Center – Jen McInty
John Stark (and many others)– Andre Simpson et al. (U. Toronto)– Suquamish and Puyallup Tribes– US Fish & Wildlife Service – Jay Davis, Ken Kin– WSDOT – Alex Nguyen, Jana Crawford– FHWA – Cindy Callahan– National Science Foundation– EPA-National Estuary Program– WA Department of Ecology– Miller Walker Community Salmon Investigation, Puget
Soundkeeper, Thornton Creek Alliance
re,
g
7th International Conference on Emerging ContaminantsVirtual Event, September 13-14, 2021
Will have lots of content on roadway runoff, microplastics, PFAS, other emerging contaminants, ecotoxicology
Host E.P.K., email [email protected]
https://cvent.me/7kvWG9
