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- Welcome, everyone, to 
Wednesday Nite @ the Lab.

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I'm Tom Zinnen.

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I work here at the UW-Madison 
Biotechnology Center.

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I also work for UW Extension 
Cooperative Extension,

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and on behalf of those folks 
and our other co-organizers,

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Wisconsin Public Television,

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the Wisconsin 
Alumni Association,

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and the UW-Madison 
Science Alliance,

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thanks again for coming to 
Wednesday Nite @ the Lab.

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We do this every Wednesday 
night, 50 times a year.

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Tonight it's my pleasure

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to introduce to you 
Christy Remucal.

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She was born in 
Prescott, Arizona,

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and grew up in Taos, New Mexico.

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And then she went to MIT

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for her undergraduate in 
environmental engineering,

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went to Cal-Berkeley

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to get her PhD in 
environmental engineering,

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and then went to the Swiss 
Federal Institute for Technology

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in Zurich in Switzerland 
to do a post doc,

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and she's been here at 
UW-Madison since 2012.

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She's here to talk about one

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of our favorite 
things, lampreys.

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She's gonna talk about 
the environmental fate

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of lampricides in tributaries 
of the Great Lakes.

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This week is the run up 
to Earth week, Earth Day,

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excuse me, and I think it's a 
particularly interesting topic

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to think about what one of 
these special days sponsored

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and started largely by 
Gaylord Nelson of Wisconsin,

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how we look at things 
today compared to 1970

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when Earth Day first started.

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Please join me in 
welcoming Christy Remucal

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of Civil and 
Environmental Engineering

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to Wednesday Nite @ the Lab.

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Thank you. 
- Thank you.

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(audience applauds)

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All right, is the 
volume is okay?

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Well, thank you, Tom, for 
the invitation to be here,

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and thank you all.

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A really big thanks 
for coming out

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with the bad roads and weather.

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Like I said, I had 
low expectations,

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but it's really nice to 
see all you out here.

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Is it okay? 
All right.

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Right, so as Tom said,

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I'm gonna present 
some of our work

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looking at the fate 
of lampricides.

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Lampricides are pesticides

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which are used to 
kill the sea lamprey.

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So I'll sort of talk 
about why we use them

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and what happens to them

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once we put them out 
in the environment.

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I'm coming from the 
Department of Civil

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and Environmental Engineering

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and I'm also in the 
Environmental Chemistry

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and Technology Program 
here at UW Madison.

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And the project I'm 
gonna present is really

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near and dear to my heart.

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This is the first project I 
started when I came to Madison.

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So I've been 
working on this for,

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I guess, the last six years.

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So to give you an overview of 
what I'll be talking about,

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first I wanna set the stage 
and talk about lampricides,

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what they are, and they're 
used to kill the sea lamprey.

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So I'm actually gonna start

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by telling you a little 
bit about the sea lamprey.

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How many people have heard 
of the sea lamprey before?

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Most of you, yeah,

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they're, I don't know, 
gross, scary fish.

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So I'll show you some 
pictures of them.

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And then I'm an 
environmental chemist

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and so I really care 
about, you know,

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we put these chemicals 
in the environment

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and they do their job to kill

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this really nasty 
invasive species,

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and then I wanna find 
out what happens to them

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out in the environment.

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And so we'll start simple.

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We'll start with some 
experiments we did 
in the laboratory

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under very well-controlled 
conditions.

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And then I'll take you 
out into the field.

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Our group focuses on 
photo degradation.

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So that's how 
sunlight can naturally

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cause chemicals to break down,

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so this is a natural process.

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And that's what 
we're gonna focus on.

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And what we'll see 
is that even though

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in the lab we can look at the 
chemicals degrading by light,

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we can identify the products,

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the chemicals they turn into,

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and what I'll show you is 
that they can actually,

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they change from 
something that's toxic

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to something that's nontoxic, 
which is a really good thing.

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But when we move out into the 
field,

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sort of it is 
hindsight is 20/20.

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We picked our field 
sites pretty poorly.

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We didn't actually see 
much photo degradation out

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in the field of the 
sites that we picked.

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And we can explain it 
and talk about that,

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but part of this story is 
also some of the challenges

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when we go from our 
well-controlled conditions

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in the laboratory out 
into the environment

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and some of the other 
factors that come into play.

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So if we knew then 
when we know now,

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we might have picked 
sites differently,

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but it's still an interesting 
story to go through.

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And we do think that 
photo degradation,

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so this natural break 
down by sunlight,

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is gonna be important 
in some systems,

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and we can kind of calculate

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how important it is gonna be.

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I wanna start, I have a huge 
list of people to thank.

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This is really a team effort.

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The main person here 
is Megan McConville.

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She was my first PhD 
student in my lab.

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She's actually holding 
a sea lamprey there

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and looking very happy 
about it for some reason.

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And then Laura and 
Natan are undergrads

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who contributed to this project.

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We also did a lot 
of work with USGS,

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particularly Terry Hubert.

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He was a really big asset

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in helping us really 
understand the system.

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And then, for the field studies,

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the two in the middle on 
the bottom, Steve and Shawn.

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So US Fish & Wildlife is a group

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that actually goes and puts 
these chemicals in the water,

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and so we worked really closely

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with them on all the fieldwork,

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like in the middle of the night

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in the pouring down 
rain sampling with them,

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and we couldn't have done 
this work without them.

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And then Adam is a 
hydrologist who helped

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with some of the modeling 
that I'm gonna show.

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And then most of 
this work was funded

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by the Great Lakes 
Fishery Commission.

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This is the US and 
Canadian agency

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that actually oversees the 
sea lamprey control program.

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This fish is a problem in 
both the US and Canada,

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so it's really nice 
that they work together,

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and they've been really 
supportive of our work.

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And then we also got a 
little bit of funding

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from Sea Grant and then the 
National Science Foundation.

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So I wanna start, I guess,

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by introducing you to 
the villain in our story,

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which is of course 
the sea lamprey.

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And you've probably seen 
pictures like this before.

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So the sea lamprey is 
an invasive species.

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It's found in all 
of the Great Lakes.

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And there are a lot of invasive 
species in the Great Lakes.

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You hear a lot about 
different species.

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And the reason why 
the sea lamprey is

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such a big deal is 
because it's a parasite.

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And so it preys on large fish,

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like lake trout, walleye, 
catfish, and so on.

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And you can see in 
this first picture

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there's those like 
sucker-like fish,

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and they basically, you 
know, attach to fish.

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And you can see on 
this picture there are

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actually some wound marks from 
where the lamprey attached.

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And this obviously can be lethal 
in many cases for the fish.

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And this has been a really big 
deal for harming fisheries,

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and that's why 
it's real important

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to control the 
population of these fish.

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The sea lamprey have been 
around for a really long time.

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So they came in through 
shipping canals,

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so from the Atlantic Ocean.

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So they were first found in 
Lake Ontario in the 1800s,

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and then, as we opened up 
more and more shipping canals,

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they kind of made 
their way westward.

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And so they were found 
in Lake Eerie in 1921,

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and then they made 
their way westward.

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So they were found in 
Lake Superior by 1938.

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So they've been around 
for a really long time.

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And one of the reasons 
we care about this is

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because of their impact 
on the fisheries,

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especially the large 
commercial game fish.

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What I'm showing here is data

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that shows the commercial 
lake trout harvest with time,

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in Lake Superior on the top and 
Lake Michigan on the bottom.

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And you can see up until 
about the 1940s or 1950s

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there was a pretty 
nice, stable harvest,

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and then there was this 
big plummet that came down.

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The populations 
basically crashed.

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And so I marked here 
in red the years

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when the sea lamprey 
were first detected

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in each of these lakes, 
and then about a decade,

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10 to 15 years later 
there was this big crash.

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And I don't want you to think 
that the sea lamprey were

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the only thing that caused 
the crash of the fisheries.

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There were other 
chemical stressors

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and other issues 
going on as well,

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but the sea lamprey definitely 
contributed pretty heavily

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to the decline of the 
fisheries during this time.

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The good news, though, is 
that if you look further out

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with time, you can 
see the fisheries,

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I mean they're not 
back to where they were

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but they've definitely 
been steadily improving.

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And the sea lamprey control 
program has actually

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it's actually really effective 
at maintaining the population

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of the sea lamprey at sort of 
a low level as best they can.

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It's been really successful,

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and that's helped the 
fisheries to come back.

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So I'm gonna talk, I'm a chemist

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but I need to talk a little bit

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about the fish biology just 
because it's really important

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to know why they do 
the sea lamprey control

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the way that they do.

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And so this is, yeah, sort of 
the life cycle of the fish.

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And so they start out down 
here at the bottom as larvae.

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And this is a picture that we 
took up at USGS in La Crosse.

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And they're sort of these 
work-like little creatures.

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They live in the sediments.

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They start out their life 
and they're not parasitic,

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so that means they're not 
gonna attach to larger fish.

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After several years,

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they undergo a transformation 
or like a metamorphosis,

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and that's when they get 
like the big, scary teeth.

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And then, at that point, 
once they're parasitic,

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they go out into the Great Lakes

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where they feed on large fish.

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And then they're like salmon.

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They go, return to the 
tributaries to spawn.

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They're not picky.

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They're not like salmon 
in that they always

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go to the same place.

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They can go to any 
tributary they want to,

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which actually makes 
it kind of harder

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to control them in a way.

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But they do return back to 
the tributaries to reproduce.

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And so the tributaries 
I guess I should define.

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Those are all the rivers that 
feed into the Great Lakes.

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And they spend a lot of 
their life in those rivers.

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And so for that reason,

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all the efforts to control the 
population of the sea lamprey

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focus on the rivers, 
on the tributaries.

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And that's because they're sort 
of in a more contained area,

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and that's also where they 
spend when they're larvae.

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So that's when they're 
most vulnerable,

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at least for the 
chemical stressors.

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And so that's why the 
sea lamprey control

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really focuses on 
those tributaries.

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Now, to give you 
a sense of scale,

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how widespread these fish are,

245
00:09:50,600 --> 00:09:52,966
this is a nice map put 
together by Mike Siefkes,

246
00:09:53,066 --> 00:09:55,466
and every dot on this 
map shows a tributary

247
00:09:55,566 --> 00:09:58,000
with a known sea 
lamprey population.

248
00:09:58,100 --> 00:10:01,533
So you can see that it 
spans both the Great Lakes

249
00:10:01,633 --> 00:10:04,000
in the US and in Canada.

250
00:10:04,100 --> 00:10:06,800
There are total 
around 450 tributaries

251
00:10:06,900 --> 00:10:09,500
that have sea lamprey 
living in them.

252
00:10:09,600 --> 00:10:10,966
This is about,

253
00:10:11,066 --> 00:10:12,700
there are about 5,000 
tributaries all together,

254
00:10:12,800 --> 00:10:14,400
so this is about 
8% of the rivers

255
00:10:14,500 --> 00:10:17,433
around the Great Lakes have 
a sea lamprey infestation.

256
00:10:18,433 --> 00:10:20,666
So this gives you 
a sense of scale

257
00:10:20,766 --> 00:10:22,833
and why it's really 
important that both US

258
00:10:22,933 --> 00:10:25,100
and Canada work together 
to control these fish.

259
00:10:26,100 --> 00:10:28,000
As far as sea 
lamprey control goes,

260
00:10:28,100 --> 00:10:30,933
there are a bunch of different 
things that are used.

261
00:10:31,933 --> 00:10:34,233
First of all, you can put in 
barriers to prevent migration.

262
00:10:34,333 --> 00:10:35,966
So the fish, when 
they're gonna reproduce,

263
00:10:36,066 --> 00:10:37,300
they swim upstream.

264
00:10:37,400 --> 00:10:40,433
So if you put in a barrier 
and they can't go upstream,

265
00:10:40,533 --> 00:10:41,966
they can't go upstream 
and reproduce.

266
00:10:42,066 --> 00:10:44,000
Of course, this will 
prevent any native fish

267
00:10:44,100 --> 00:10:45,566
that also need to go upstream,

268
00:10:45,666 --> 00:10:47,666
so you have to be 
careful about that.

269
00:10:47,766 --> 00:10:48,833
And there's work done

270
00:10:48,933 --> 00:10:51,166
on like sort of how 
to be more selective

271
00:10:51,266 --> 00:10:52,733
about which fish 
can go upstream.

272
00:10:52,833 --> 00:10:55,066
You can actually go out 
and physically trap them,

273
00:10:55,166 --> 00:10:57,433
the larger fish, and 
catch them and kill them,

274
00:10:57,533 --> 00:10:59,900
so they do that 
in some instances.

275
00:11:00,000 --> 00:11:02,733
They also sometimes will 
release sterile males,

276
00:11:02,833 --> 00:11:05,033
so try to decrease fertility

277
00:11:05,133 --> 00:11:08,233
by putting out male fish 
that can't reproduce.

278
00:11:09,600 --> 00:11:10,733
There's some really 
interesting work

279
00:11:10,833 --> 00:11:12,433
going on now with pheromones.

280
00:11:12,533 --> 00:11:15,566
Pheromones are chemicals 
that the fish can smell,

281
00:11:15,666 --> 00:11:17,733
and they actually have 
identified pheromones

282
00:11:17,833 --> 00:11:19,766
that the fish really like

283
00:11:19,866 --> 00:11:21,166
and that the fish 
really don't like.

284
00:11:21,266 --> 00:11:22,933
I think they take 
like dead sea lamprey

285
00:11:23,033 --> 00:11:25,233
and it's like a dead sea 
lamprey extract, basically.

286
00:11:25,333 --> 00:11:28,033
But it's, you can think about 
you might put a chemical

287
00:11:28,133 --> 00:11:29,566
that they like in one stream

288
00:11:29,666 --> 00:11:32,133
and a chemical that they 
don't like in another stream

289
00:11:32,233 --> 00:11:34,666
and make them all go 
toward you know one spot

290
00:11:34,766 --> 00:11:37,233
and then you can trap 
them or do something else.

291
00:11:37,333 --> 00:11:39,266
And this is not really 
widely used yet,

292
00:11:39,366 --> 00:11:41,066
but it's sort of up and coming

293
00:11:41,166 --> 00:11:44,100
and like where a lot of the 
research is on new directions

294
00:11:44,200 --> 00:11:46,133
for sea lamprey control.

295
00:11:46,233 --> 00:11:47,600
And then, last but not least,

296
00:11:47,700 --> 00:11:49,600
is what I'm gonna talk about, 
which are the lampricides.

297
00:11:49,700 --> 00:11:51,300
These are the two 
chemical pesticides,

298
00:11:51,400 --> 00:11:53,033
and these are the 
most widely used.

299
00:11:53,133 --> 00:11:54,633
They've been used 
a really long time

300
00:11:54,733 --> 00:11:56,800
and they're used all 
around the Great Lakes

301
00:11:56,900 --> 00:11:58,500
and they've been 
really effective.

302
00:11:58,600 --> 00:12:01,033
So let me, 
I guess now that we know

303
00:12:01,133 --> 00:12:02,500
a little bit about the fish,

304
00:12:02,600 --> 00:12:04,800
I wanna show you a little bit 
about these two chemicals.

305
00:12:04,900 --> 00:12:06,333
And there are two of them.

306
00:12:06,433 --> 00:12:09,266
And so, like I said, 
adding a lampricide is

307
00:12:09,366 --> 00:12:11,800
the most common way to 
control the sea lamprey,

308
00:12:11,900 --> 00:12:13,466
and there are two.

309
00:12:13,566 --> 00:12:15,433
So the one that's in blue here,

310
00:12:15,533 --> 00:12:17,933
3-trifluoromethyl-4-nitrophenol,

311
00:12:18,033 --> 00:12:19,866
which I'll just 
call TFM for short

312
00:12:19,966 --> 00:12:22,133
because that's just easier

313
00:12:22,233 --> 00:12:23,333
This chemical is 
pretty interesting.

314
00:12:23,433 --> 00:12:26,500
We started using 
it in the 1950s.

315
00:12:26,600 --> 00:12:30,833
So it's been put in our 
waters for a really long time.

316
00:12:30,933 --> 00:12:34,266
And it's considered to be 
selective for the sea lamprey.

317
00:12:34,366 --> 00:12:35,633
So back in the 1950s,

318
00:12:35,733 --> 00:12:39,666
they tested thousands of 
chemicals on sea lamprey

319
00:12:39,766 --> 00:12:41,066
and also on native fish.

320
00:12:41,166 --> 00:12:43,500
And TFM they found was 
really good at killing

321
00:12:43,600 --> 00:12:48,100
the sea lamprey and less, 
not as toxic for native fish.

322
00:12:48,200 --> 00:12:50,033
And this has to do 
with the fact that,

323
00:12:50,133 --> 00:12:51,400
again I'm not a biologist,

324
00:12:51,500 --> 00:12:53,700
but the sea lamprey are 
really ancient species

325
00:12:53,800 --> 00:12:56,533
and they're not able to 
get rid of the chemical,

326
00:12:56,633 --> 00:12:58,966
and so it is able to kill 
them pretty effectively.

327
00:13:00,966 --> 00:13:04,733
So TFM is added pretty 
much at all streams

328
00:13:04,833 --> 00:13:06,700
where they're adding 
these chemicals.

329
00:13:06,800 --> 00:13:08,533
It's added all the 
time at a rate of

330
00:13:08,633 --> 00:13:10,533
about 50,000 kilograms 
per year, which is a lot.

331
00:13:10,633 --> 00:13:12,333
I'll show you some 
pictures here in a minute

332
00:13:12,433 --> 00:13:14,366
so you can kinda get 
a sense of the scale.

333
00:13:14,466 --> 00:13:18,166
In total, they treat about 
120 tributaries every year

334
00:13:18,266 --> 00:13:20,000
in the US and Canada.

335
00:13:20,100 --> 00:13:22,300
Usually on a three- 
to four-year cycle,

336
00:13:22,400 --> 00:13:24,466
and that's because of the 
life cycle of the fish.

337
00:13:24,566 --> 00:13:27,900
So they'll treat a river and 
then three or four years later

338
00:13:28,000 --> 00:13:30,833
they'll come back and 
treat it again, usually.

339
00:13:30,933 --> 00:13:32,366
So TFM is selective.

340
00:13:32,466 --> 00:13:33,900
It's used everywhere.

341
00:13:34,000 --> 00:13:36,066
And then in some tributaries 
they also add the chemical

342
00:13:36,166 --> 00:13:37,833
that's in orange, 
which is niclosamide.

343
00:13:37,933 --> 00:13:40,800
I'm not gonna bother with 
the whole chemical name

344
00:13:40,900 --> 00:13:42,100
'cause it's really long.

345
00:13:42,200 --> 00:13:44,733
Niclosamide is added as 
a percentage by weight.

346
00:13:44,833 --> 00:13:48,033
So about 1% by weight with 
TFM in some tributaries,

347
00:13:48,133 --> 00:13:50,333
usually in the really 
large river systems

348
00:13:50,433 --> 00:13:53,600
or in areas where the water 
is moving really slowly.

349
00:13:53,700 --> 00:13:55,600
So it's not added as often.

350
00:13:55,700 --> 00:13:57,566
It's added in a 
lower concentration,

351
00:13:57,666 --> 00:13:59,533
and that's probably a good thing

352
00:13:59,633 --> 00:14:01,900
because this chemical 
is an active ingredient

353
00:14:02,000 --> 00:14:04,200
in Bayluscide, which is 
for killing mollusks.

354
00:14:04,300 --> 00:14:07,133
So that kills other kinds 
of organisms as well.

355
00:14:07,233 --> 00:14:08,633
And so it's not gonna be as,

356
00:14:08,733 --> 00:14:11,200
it's gonna be more toxic 
to non-target organisms,

357
00:14:11,300 --> 00:14:13,000
things that they're 
not trying to harm.

358
00:14:13,100 --> 00:14:16,800
So I'll talk about both of them,

359
00:14:16,900 --> 00:14:18,033
but it's important to remember

360
00:14:18,133 --> 00:14:20,300
that TFM is the one 
that's used the most.

361
00:14:20,400 --> 00:14:22,033
It actually degrades 
the most quickly too,

362
00:14:22,133 --> 00:14:23,533
which is a good thing.

363
00:14:24,533 --> 00:14:26,166
So I wanna show 
you some pictures

364
00:14:26,266 --> 00:14:27,900
so you can kind 
of envision this.

365
00:14:28,000 --> 00:14:29,900
I really, before I 
started working on this,

366
00:14:30,000 --> 00:14:32,233
really didn't have a good 
appreciation of the scale

367
00:14:32,333 --> 00:14:34,100
of what one of these 
treatments looked like.

368
00:14:34,200 --> 00:14:35,433
It's really, really impressive,

369
00:14:35,533 --> 00:14:38,233
especially when you're 
out on a really big river.

370
00:14:38,333 --> 00:14:40,666
So, first of all, this 
is the kind of trailer

371
00:14:40,766 --> 00:14:42,366
that they carry the 
chemicals around in.

372
00:14:42,466 --> 00:14:44,566
And so you can just 
imagine like driving down

373
00:14:44,666 --> 00:14:46,033
the highway next 
to this trailer.

374
00:14:46,133 --> 00:14:47,200
It's pretty amazing.

375
00:14:47,300 --> 00:14:49,400
You know, they have 
their fish on the side,

376
00:14:49,500 --> 00:14:51,366
the lamprey on the 
side of a fish,

377
00:14:51,466 --> 00:14:53,833
and then all the big 
sucker mouths on the side.

378
00:14:53,933 --> 00:14:55,033
But these are the trailers

379
00:14:55,133 --> 00:14:57,033
that they haul 
chemicals around in.

380
00:14:57,133 --> 00:14:58,333
This is a huge operation.

381
00:14:58,433 --> 00:15:00,000
So this is from the 
Manistique River

382
00:15:00,100 --> 00:15:02,233
up in the upper 
peninsula of Michigan,

383
00:15:02,333 --> 00:15:04,333
I guess about a year 
and a half ago now.

384
00:15:05,333 --> 00:15:07,200
I'll show you a 
map a little later,

385
00:15:07,300 --> 00:15:08,600
but it's such a big operation.

386
00:15:08,700 --> 00:15:10,533
They pretty much filled 
up every hotel in town

387
00:15:10,633 --> 00:15:11,533
with people working on this.

388
00:15:11,633 --> 00:15:13,300
Like, it's a big deal.

389
00:15:14,766 --> 00:15:16,833
And this is kinda 
what it looks like.

390
00:15:16,933 --> 00:15:18,533
So these are toxic chemicals.

391
00:15:18,633 --> 00:15:21,333
You can see on the 
picture on the left,

392
00:15:21,433 --> 00:15:24,266
you know, it's a toxic 
chemical, it's a pesticide.

393
00:15:24,366 --> 00:15:27,300
It's labeled toxic with 
like a skull and crossbones.

394
00:15:27,400 --> 00:15:29,200
And then, the bigger picture,

395
00:15:29,300 --> 00:15:30,666
there's someone 
from Fish & Wildlife

396
00:15:30,766 --> 00:15:33,233
that's pumping those 
chemicals into the river.

397
00:15:33,333 --> 00:15:36,066
And I think at that site, this 
was just a small tributary,

398
00:15:36,166 --> 00:15:38,500
it was something like eight 
or nine of those cans an hour

399
00:15:38,600 --> 00:15:40,500
being pumped into the river,

400
00:15:40,600 --> 00:15:42,400
which is pretty 
impressive to see.

401
00:15:42,500 --> 00:15:43,600
And then in some cases,

402
00:15:43,700 --> 00:15:45,200
you can actually 
see it in the river.

403
00:15:45,300 --> 00:15:47,000
It's maybe a little 
hard to see in here,

404
00:15:47,100 --> 00:15:49,666
but you can see there's like 
the little bit of yellow splash

405
00:15:49,766 --> 00:15:51,600
where the chemical 
is being mixed in.

406
00:15:52,600 --> 00:15:54,600
And then, yeah, it goes 
and does its thing.

407
00:15:54,700 --> 00:15:56,000
And the way that they add it

408
00:15:56,100 --> 00:15:57,500
they're trying to 
get acute toxicity,

409
00:15:57,600 --> 00:16:01,033
which means they wanna 
kill the fish right away.

410
00:16:01,133 --> 00:16:03,266
And so they add the chemical

411
00:16:03,366 --> 00:16:04,966
in like an eight 
or nine hour block,

412
00:16:05,066 --> 00:16:07,200
and they try to make sure 
the chemical concentration is

413
00:16:07,300 --> 00:16:08,633
the same for eight or nine hours

414
00:16:08,733 --> 00:16:10,200
and then they turn 
off the switch

415
00:16:10,300 --> 00:16:12,200
and they'll come back 
three or four years later

416
00:16:12,300 --> 00:16:13,933
is kinda how it works.

417
00:16:14,033 --> 00:16:16,600
And if you can imagine like 
a really big river system,

418
00:16:16,700 --> 00:16:18,900
like maybe if you have two 
rivers coming together,

419
00:16:19,000 --> 00:16:21,333
they'll add the chemical and 
they have it all worked out

420
00:16:21,433 --> 00:16:24,433
so the chemicals come 
together at the same time.

421
00:16:24,533 --> 00:16:26,133
It's, like I said, a really 
impressive operation,

422
00:16:26,233 --> 00:16:28,133
and they're actually 
out there in the field

423
00:16:28,233 --> 00:16:30,000
in real time measuring 
the concentrations,

424
00:16:30,100 --> 00:16:31,300
the amounts in the water,

425
00:16:31,400 --> 00:16:34,333
to make sure it's 
the right amount.

426
00:16:34,433 --> 00:16:36,700
So they're adding what they 
need to achieve toxicity

427
00:16:36,800 --> 00:16:40,433
but not too much that they 
harm native, other fish.

428
00:16:40,533 --> 00:16:42,066
So, like I said, it's 
really impressive

429
00:16:42,166 --> 00:16:44,133
and I really didn't 
appreciate it

430
00:16:44,233 --> 00:16:47,266
till I got to go out and see it.

431
00:16:47,366 --> 00:16:51,066
So as a chemist and now 
as an environmental engineer,

432
00:16:51,166 --> 00:16:52,466
you know we put 
these chemicals in,

433
00:16:52,566 --> 00:16:53,900
there's obviously 
trade-offs of doing that.

434
00:16:54,000 --> 00:16:56,366
The sea lamprey are 
a really, you know,

435
00:16:56,466 --> 00:16:58,233
big deal and 
important to control.

436
00:16:58,333 --> 00:17:00,633
But the chemist in me and 
the engineer in me is like,

437
00:17:00,733 --> 00:17:02,133
okay, so what happens 
to the chemicals

438
00:17:02,233 --> 00:17:04,533
after they've done their thing?

439
00:17:04,633 --> 00:17:06,233
Where do they go?

440
00:17:07,233 --> 00:17:10,133
And so what we knew when 
we started this project,

441
00:17:10,233 --> 00:17:12,200
I mean they've been 
used for a long time

442
00:17:12,300 --> 00:17:14,200
and there's been a lot 
of work done on them,

443
00:17:14,300 --> 00:17:16,233
so we knew some things to start.

444
00:17:16,333 --> 00:17:19,200
First of all, neither 
chemical undergoes hydrolysis.

445
00:17:19,300 --> 00:17:22,300
This is a transformation 
process that happens

446
00:17:22,400 --> 00:17:24,166
when the chemicals 
react with water.

447
00:17:24,266 --> 00:17:25,466
A lot of pesticides do this.

448
00:17:25,566 --> 00:17:26,900
These chemicals don't.

449
00:17:27,000 --> 00:17:28,833
So they're not gonna 
spontaneously break down.

450
00:17:28,933 --> 00:17:30,533
They're gonna be pretty stable.

451
00:17:30,633 --> 00:17:31,900
Neither chemical is volatile,

452
00:17:32,000 --> 00:17:33,966
which means it's not 
gonna go into the air.

453
00:17:34,066 --> 00:17:35,833
It's gonna stay in the water.

454
00:17:35,933 --> 00:17:38,033
Or it can go into the sediment,

455
00:17:38,133 --> 00:17:39,500
so into the soil.

456
00:17:39,600 --> 00:17:41,133
For niclosamide, 
the one in orange,

457
00:17:41,233 --> 00:17:42,733
it's a little bit of 
a bigger chemical,

458
00:17:42,833 --> 00:17:44,000
so it's gonna be more sticky.

459
00:17:44,100 --> 00:17:47,533
It's gonna associate 
with the sediment more.

460
00:17:47,633 --> 00:17:50,533
Whereas, TFM is gonna pretty 
much stay in the water.

461
00:17:50,633 --> 00:17:52,166
So we're gonna add 
it to the water

462
00:17:52,266 --> 00:17:53,900
and it's gonna 
stay in the water.

463
00:17:55,033 --> 00:17:57,533
They do undergo 
biological degradation.

464
00:17:57,633 --> 00:18:00,766
So some types of bacteria 
can make them break down

465
00:18:00,866 --> 00:18:02,200
under some conditions.

466
00:18:02,300 --> 00:18:04,300
And there's some 
work still being done

467
00:18:04,400 --> 00:18:06,366
to learn more 
about that process.

468
00:18:06,466 --> 00:18:07,766
And then when we 
started this project,

469
00:18:07,866 --> 00:18:10,633
we saw that there were a 
couple papers suggesting

470
00:18:10,733 --> 00:18:12,166
that degradation by sunlight

471
00:18:12,266 --> 00:18:15,000
or photo degradation 
was important.

472
00:18:15,100 --> 00:18:16,233
And, again, this is, yeah,

473
00:18:16,333 --> 00:18:19,033
sunlight causing the 
chemicals to break down.

474
00:18:19,133 --> 00:18:21,900
And so to tell you a little 
bit more about that process,

475
00:18:22,000 --> 00:18:25,200
this is my photo chemistry 101.

476
00:18:25,300 --> 00:18:26,633
Pretty simple, this 
is the Manistique

477
00:18:26,733 --> 00:18:28,600
on the one day it was sunny,

478
00:18:28,700 --> 00:18:30,000
which was one of the reasons

479
00:18:30,100 --> 00:18:32,333
why we didn't see much photo 
degradation there it turns out.

480
00:18:32,433 --> 00:18:35,800
But the idea here is 
that we have our sun,

481
00:18:35,900 --> 00:18:37,666
the chemicals absorb light.

482
00:18:38,833 --> 00:18:40,400
I'll show you their 
spectrum in a minute.

483
00:18:40,500 --> 00:18:42,000
They overlap with 
the solar spectrum,

484
00:18:42,100 --> 00:18:44,766
and it's possible that 
they can fall apart

485
00:18:44,866 --> 00:18:47,000
into chemicals that, you know,

486
00:18:47,100 --> 00:18:48,233
we actually characterize those

487
00:18:48,333 --> 00:18:49,666
and we found out 
that they're ones

488
00:18:49,766 --> 00:18:52,166
that are not gonna be as 
toxic, which is a good thing.

489
00:18:52,266 --> 00:18:53,833
And so, I guess, let me show you

490
00:18:53,933 --> 00:18:55,933
a little bit more about 
what they look like.

491
00:18:56,033 --> 00:18:58,266
So this figure here,

492
00:18:58,366 --> 00:19:00,833
let me walk you through 
it, is important.

493
00:19:00,933 --> 00:19:03,533
So the dark blue line 
shows the solar spectrum.

494
00:19:03,633 --> 00:19:05,033
This is the wavelengths of light

495
00:19:05,133 --> 00:19:06,300
that are coming into the Earth.

496
00:19:06,400 --> 00:19:08,400
And so what you can 
see is that starting

497
00:19:08,500 --> 00:19:10,333
at about 300 nanometers and up,

498
00:19:10,433 --> 00:19:11,566
those are the 
wavelengths of light

499
00:19:11,666 --> 00:19:13,733
that the sunlight 
that hits our Earth.

500
00:19:15,100 --> 00:19:16,666
The lines in orange and blue are

501
00:19:16,766 --> 00:19:19,900
the absorbent spectra 
of TFM and niclosamide.

502
00:19:20,000 --> 00:19:21,200
These are the 
wavelengths of light

503
00:19:21,300 --> 00:19:23,200
that those chemicals absorb.

504
00:19:23,300 --> 00:19:25,300
And the main point here 
is that there's a lot

505
00:19:25,400 --> 00:19:27,466
of overlap between the chemicals

506
00:19:27,566 --> 00:19:30,133
UV-vis spectra and 
the solar spectrum.

507
00:19:30,233 --> 00:19:31,700
And so to put that another way,

508
00:19:31,800 --> 00:19:33,900
that means they overlap 
with the incoming light

509
00:19:34,000 --> 00:19:36,166
so they can absorb light

510
00:19:36,266 --> 00:19:38,366
and they can break 
down, potentially.

511
00:19:39,366 --> 00:19:41,266
That's sort of the first 
rule of photo chemistry.

512
00:19:41,366 --> 00:19:42,900
If those two curves 
didn't overlap,

513
00:19:43,000 --> 00:19:44,100
there'd be no possible way

514
00:19:44,200 --> 00:19:46,633
of having photo 
degradation at all.

515
00:19:46,733 --> 00:19:50,700
So we knew this sort of coming 
in that they do absorb light.

516
00:19:50,800 --> 00:19:52,700
And we also knew 
a little bit more

517
00:19:52,800 --> 00:19:56,033
about their behavior 
from some older studies,

518
00:19:56,133 --> 00:19:59,400
so one from 1981 
and one from 2004.

519
00:19:59,500 --> 00:20:01,866
And so here what we 
knew from these works,

520
00:20:01,966 --> 00:20:03,266
again there's sort of my cartoon

521
00:20:03,366 --> 00:20:04,833
where we have sunlight reacting

522
00:20:04,933 --> 00:20:07,533
with our two chemicals 
causing them to break down.

523
00:20:07,633 --> 00:20:10,233
We knew that this process 
depends on the pH,

524
00:20:10,333 --> 00:20:14,700
so that's like the 
acidity of your water.

525
00:20:14,800 --> 00:20:18,500
Most waters, rivers are 
gonna be around a pH

526
00:20:18,600 --> 00:20:22,233
between six and eight, usually 
more like seven or eight,

527
00:20:22,333 --> 00:20:24,233
so that's like neutral pH.

528
00:20:24,333 --> 00:20:27,433
But if you had the pH higher 
or pH lower, how quickly

529
00:20:27,533 --> 00:20:30,300
these chemicals are gonna 
break down is gonna change.

530
00:20:30,400 --> 00:20:33,533
We also knew something 
about their half-lives

531
00:20:33,633 --> 00:20:35,766
And this is a term I'm 
gonna use quite a bit.

532
00:20:35,866 --> 00:20:38,733
And so a half-life 
is the time it takes

533
00:20:38,833 --> 00:20:40,600
for half of the 
chemical to go away.

534
00:20:40,700 --> 00:20:41,966
And so if you have something

535
00:20:42,066 --> 00:20:43,400
that has a half-life 
of a minute,

536
00:20:43,500 --> 00:20:45,700
that means it's gonna 
go away really quickly,

537
00:20:45,800 --> 00:20:49,400
and if it's something with 
a half-life of five days,

538
00:20:49,500 --> 00:20:50,966
that's gonna take 
a really long time.

539
00:20:51,066 --> 00:20:52,400
So I'm gonna use 
half-life, again,

540
00:20:52,500 --> 00:20:53,800
as sort of a way to measure

541
00:20:53,900 --> 00:20:56,166
how quickly these chemicals 
are breaking down.

542
00:20:56,266 --> 00:20:59,066
And so we knew, this is 
actually from the 1981 study,

543
00:20:59,166 --> 00:21:00,666
that that half-life of TFM,

544
00:21:00,766 --> 00:21:04,133
and again that's the 
chemical that's more specific

545
00:21:04,233 --> 00:21:07,700
for the sea lamprey, it's 
used in higher concentrations.

546
00:21:07,800 --> 00:21:09,433
These researchers 
thought it would go away

547
00:21:09,533 --> 00:21:11,333
on the order of a few days,

548
00:21:12,466 --> 00:21:15,100
so that's kind of a long time.

549
00:21:15,200 --> 00:21:17,833
Whereas niclosamide, the one 
that isn't used as often,

550
00:21:17,933 --> 00:21:19,366
they said it was gonna go away

551
00:21:19,466 --> 00:21:21,833
on the order of 
seven to 30 hours,

552
00:21:21,933 --> 00:21:24,066
and that was under their 
experimental conditions.

553
00:21:24,166 --> 00:21:25,633
So you can think back,

554
00:21:25,733 --> 00:21:28,300
we know when we go from the 
lab out to real conditions,

555
00:21:28,400 --> 00:21:30,500
things are different, 
and we actually found

556
00:21:30,600 --> 00:21:32,766
that this was quite 
different in practice.

557
00:21:33,766 --> 00:21:34,866
So we knew a little bit.

558
00:21:34,966 --> 00:21:36,266
We know enough to 
say like, okay,

559
00:21:36,366 --> 00:21:37,433
this is probably important.

560
00:21:37,533 --> 00:21:38,766
We didn't know much about

561
00:21:38,866 --> 00:21:41,133
what the transformation 
products were,

562
00:21:41,233 --> 00:21:42,766
so what they break down into.

563
00:21:42,866 --> 00:21:44,166
And this is important 
to understand

564
00:21:44,266 --> 00:21:46,466
because there aren't 
very many examples

565
00:21:46,566 --> 00:21:48,566
but there are some 
where a chemical

566
00:21:48,666 --> 00:21:50,000
undergoes photo degradation

567
00:21:50,100 --> 00:21:51,900
and it actually forms 
something that's more toxic

568
00:21:52,000 --> 00:21:53,700
than what you started with,

569
00:21:53,800 --> 00:21:55,766
so that would not be good.

570
00:21:55,866 --> 00:21:58,000
So we wanna make sure that 
once it does break down,

571
00:21:58,100 --> 00:22:00,500
it's forming things that 
aren't gonna be harmful.

572
00:22:00,600 --> 00:22:02,133
So we didn't know that,

573
00:22:02,233 --> 00:22:04,133
and no one had ever looked 
at these two chemicals

574
00:22:04,233 --> 00:22:06,266
under the same 
conditions before.

575
00:22:06,366 --> 00:22:10,266
And there were some room for 
adding a little bit more here.

576
00:22:10,366 --> 00:22:12,500
And we actually learned a lot.

577
00:22:12,600 --> 00:22:15,633
So, I mean, you know, you 
all live in Wisconsin,

578
00:22:15,733 --> 00:22:17,100
you know what it's like,

579
00:22:17,200 --> 00:22:19,433
and so we do our experiments 
in the lab for starters.

580
00:22:19,533 --> 00:22:22,833
And this is a picture of our 
merry-go-round photo reactor,

581
00:22:22,933 --> 00:22:24,300
so it's like a little 
merry-go-round.

582
00:22:24,400 --> 00:22:26,333
You can see in the middle,

583
00:22:26,433 --> 00:22:28,633
you can see these are 
all test tubes in here

584
00:22:28,733 --> 00:22:30,533
and that the little 
thing spins around.

585
00:22:30,633 --> 00:22:32,833
So that's why it's 
called a merry-go-round.

586
00:22:32,933 --> 00:22:35,900
And on the outside we have 
all different light bulbs.

587
00:22:36,000 --> 00:22:38,866
In this case, we're using 
light at 365 nanometers,

588
00:22:38,966 --> 00:22:41,000
which is in part of 
the solar spectrum.

589
00:22:41,100 --> 00:22:43,500
And it's fun 
'cause it's a black light,

590
00:22:43,600 --> 00:22:45,333
so that's pretty 
much what it is,

591
00:22:45,433 --> 00:22:46,633
so that's kind of fun too.

592
00:22:46,733 --> 00:22:48,633
But yeah, this is how 
we do our experiments

593
00:22:48,733 --> 00:22:51,066
'cause we can put a whole 
bunch of test tubes in there,

594
00:22:51,166 --> 00:22:52,700
and test a lot of 
different conditions,

595
00:22:52,800 --> 00:22:54,033
do a lot of 
different replicates,

596
00:22:54,133 --> 00:22:55,766
and like it's the 
same every day.

597
00:22:55,866 --> 00:22:57,833
So we can do these experiments

598
00:22:57,933 --> 00:23:00,200
when the weather 
is like it is today

599
00:23:00,300 --> 00:23:01,733
or in the summer, any time.

600
00:23:02,733 --> 00:23:04,833
So we did this and the 
first thing we looked at

601
00:23:04,933 --> 00:23:07,533
was just when we shine this 
light on these two chemicals,

602
00:23:07,633 --> 00:23:09,433
how fast do they go away?

603
00:23:09,533 --> 00:23:10,866
Just, as a first cut,

604
00:23:10,966 --> 00:23:13,533
wanting to verify what was 
already known in the literature.

605
00:23:15,466 --> 00:23:19,600
And so, yeah, this is 
what this figure shows.

606
00:23:19,700 --> 00:23:24,600
And so, on the x or y-axis, 
this is a rate constant,

607
00:23:24,700 --> 00:23:27,133
so this is how quickly 
it goes away.

608
00:23:27,233 --> 00:23:28,433
So things that are higher up,

609
00:23:28,533 --> 00:23:30,033
they're going away quickly,

610
00:23:30,133 --> 00:23:31,800
and things that are lower down,

611
00:23:31,900 --> 00:23:33,033
they're going away more slowly.

612
00:23:33,133 --> 00:23:35,133
And so we can see 
a couple things.

613
00:23:35,233 --> 00:23:39,100
First, with TFM, and this 
is all plotted versus pH,

614
00:23:39,200 --> 00:23:40,633
so the acidity of our water.

615
00:23:40,733 --> 00:23:44,066
And, again, most waters are 
gonna be around pH seven.

616
00:23:44,166 --> 00:23:46,600
With TFM, as the pH goes up,

617
00:23:46,700 --> 00:23:48,933
the chemical degrades 
more quickly.

618
00:23:49,033 --> 00:23:52,566
And it changes a lot 
depending on the pH.

619
00:23:52,666 --> 00:23:55,300
And niclosamide had 
the opposite trend.

620
00:23:55,400 --> 00:23:57,166
So their behavior is 
gonna be different.

621
00:23:57,266 --> 00:24:00,733
So as the pH goes up, TFM is 
gonna degrade more quickly,

622
00:24:00,833 --> 00:24:03,666
whereas niclosamide is 
gonna actually slow down.

623
00:24:03,766 --> 00:24:06,266
So that was one thing that 
we knew or we learned.

624
00:24:06,366 --> 00:24:07,700
And the other thing was that,

625
00:24:07,800 --> 00:24:10,566
like I said, no one had ever 
looked at these two chemicals

626
00:24:10,666 --> 00:24:11,733
under the same 
conditions before,

627
00:24:11,833 --> 00:24:13,066
even though they're 
added together

628
00:24:13,166 --> 00:24:15,800
so you'd think it would be 
good to look at them together.

629
00:24:15,900 --> 00:24:17,933
And we can see there's 
a really big gap

630
00:24:18,033 --> 00:24:20,033
between those two curves.

631
00:24:20,133 --> 00:24:22,666
And what this means 
is that TFM is gonna

632
00:24:22,766 --> 00:24:25,533
go away much more 
quickly then niclosamide.

633
00:24:26,933 --> 00:24:30,666
And TFM is the one that's 
used in higher concentrations,

634
00:24:30,766 --> 00:24:32,133
it's more selective 
for the sea lamprey,

635
00:24:32,233 --> 00:24:34,366
and so it goes away 
much more quickly.

636
00:24:34,466 --> 00:24:38,066
Whereas niclosamide, which 
is harmful to other organisms

637
00:24:38,166 --> 00:24:40,400
like mollusks, is gonna 
go away much more slowly.

638
00:24:40,500 --> 00:24:43,466
And this sort of contradicted 
the earlier study.

639
00:24:43,566 --> 00:24:47,600
And that was a big of a 
surprise, but I think, yeah,

640
00:24:47,700 --> 00:24:48,966
we learned a lot from this.

641
00:24:49,066 --> 00:24:50,666
This was really 
valuable to find out

642
00:24:50,766 --> 00:24:52,033
how quickly they go away.

643
00:24:53,033 --> 00:24:55,533
These are our lab conditions.

644
00:24:55,633 --> 00:24:58,366
And, you know, those black 
lights are obviously not

645
00:24:58,466 --> 00:24:59,533
what sunlight looks like,

646
00:24:59,633 --> 00:25:01,600
but we can do the math 
and kind of calculate

647
00:25:01,700 --> 00:25:02,866
how quickly these will go away

648
00:25:02,966 --> 00:25:04,600
under actual 
sunlight conditions.

649
00:25:05,600 --> 00:25:08,366
And so I apologize 
for showing a table,

650
00:25:08,466 --> 00:25:10,066
but it kind of gets 
the point across.

651
00:25:10,166 --> 00:25:12,566
So what I'm showing 
here is the half-life.

652
00:25:12,666 --> 00:25:14,700
So, again, a smaller 
number is better.

653
00:25:14,800 --> 00:25:16,400
We wanna have a 
half-life being short

654
00:25:16,500 --> 00:25:18,400
'cause we want it to go away.

655
00:25:18,500 --> 00:25:21,333
For TFM, looking just at 
the surface of the water,

656
00:25:21,433 --> 00:25:23,333
like if you're looking 
at the very top

657
00:25:23,433 --> 00:25:24,766
that's getting 
the most sunlight,

658
00:25:24,866 --> 00:25:27,833
it's gonna go away on the 
order of a couple hours.

659
00:25:27,933 --> 00:25:30,333
Whereas niclosamide, even at 
the very surface of the water,

660
00:25:30,433 --> 00:25:34,300
it's gonna go away on the 
order of a day or longer.

661
00:25:34,400 --> 00:25:35,500
And this is assuming

662
00:25:35,600 --> 00:25:38,200
that the sun is on 
at noon all the time,

663
00:25:38,300 --> 00:25:39,900
which is obviously not accurate.

664
00:25:40,900 --> 00:25:42,200
As you can imagine, though,

665
00:25:42,300 --> 00:25:44,200
this is looking at the 
surface of the water,

666
00:25:44,300 --> 00:25:46,700
and as you go deeper in the 
water, obviously it gets darker.

667
00:25:46,800 --> 00:25:48,033
And it turns out the light

668
00:25:48,133 --> 00:25:50,233
actually drops off 
really quickly.

669
00:25:50,333 --> 00:25:54,300
And so if we do the 
same calculation over,

670
00:25:54,400 --> 00:25:56,266
like, 55 centimeters,

671
00:25:56,366 --> 00:25:58,300
now we can see TFM 
is gonna go away

672
00:25:58,400 --> 00:26:02,066
on the order of 20 hours, 
or something like that,

673
00:26:02,166 --> 00:26:04,733
and niclosamide we're 
talking hundreds of days,

674
00:26:06,166 --> 00:26:08,633
which is, you know, obviously 
the water is not gonna stay

675
00:26:08,733 --> 00:26:10,033
in the river for 
hundreds of days

676
00:26:10,133 --> 00:26:12,300
so that's not very practical.

677
00:26:12,400 --> 00:26:13,966
So what we learned from this,

678
00:26:14,066 --> 00:26:15,533
and I'll show you the data,

679
00:26:15,633 --> 00:26:16,966
a little more data 
on niclosamide,

680
00:26:17,066 --> 00:26:18,300
but we basically learned that

681
00:26:18,400 --> 00:26:20,700
from a photo chemical 
degradation perspective

682
00:26:20,800 --> 00:26:24,300
that's really probably only 
gonna be important for TFM.

683
00:26:24,400 --> 00:26:27,100
And that's the one 
that's more selective,

684
00:26:27,200 --> 00:26:30,500
it's less persistent, and it's 
added pretty much everywhere.

685
00:26:30,600 --> 00:26:34,866
Whereas niclosamide, 
which is less selective,

686
00:26:34,966 --> 00:26:37,600
it's gonna stick around a 
lot longer in the rivers.

687
00:26:39,633 --> 00:26:41,766
So we know about the rates,

688
00:26:41,866 --> 00:26:43,433
and we can make 
good calculations

689
00:26:43,533 --> 00:26:45,433
about how quickly 
they're gonna go away.

690
00:26:45,533 --> 00:26:48,433
The other question is to figure 
out what they degrade into.

691
00:26:48,533 --> 00:26:49,900
For both of them,

692
00:26:50,000 --> 00:26:52,166
we found that they're 
gonna degrade into things

693
00:26:52,266 --> 00:26:53,633
that are gonna be less harmful,

694
00:26:53,733 --> 00:26:54,966
which is a really good thing

695
00:26:55,066 --> 00:26:57,233
and that was really 
good to learn.

696
00:26:57,333 --> 00:27:02,100
And so, believe it or not, I 
did try to simplify this a lot

697
00:27:02,200 --> 00:27:03,966
'cause it's really complicated,

698
00:27:04,066 --> 00:27:06,433
but the basic idea 
is we start with TFM.

699
00:27:06,533 --> 00:27:10,733
The main product is this 
chemical called gentisic acid.

700
00:27:12,166 --> 00:27:16,033
And there, I think we 
detected, we quantified,

701
00:27:16,133 --> 00:27:17,966
I don't know, maybe four 
or five other chemicals,

702
00:27:18,066 --> 00:27:19,966
and we identified a 
lot of other chemicals.

703
00:27:20,066 --> 00:27:22,966
It basically makes a whole 
soup of different things.

704
00:27:23,066 --> 00:27:26,800
But what's important is 
that if we look at TFM,

705
00:27:26,900 --> 00:27:30,733
it has this fluorine 
in it, that's the F,

706
00:27:30,833 --> 00:27:33,166
and this NO2 group, 
the nitro group.

707
00:27:33,266 --> 00:27:34,400
Those are both signs

708
00:27:34,500 --> 00:27:36,000
that a chemical is gonna 
be really persistent.

709
00:27:36,100 --> 00:27:37,800
And I'll show you in 
a minute that things

710
00:27:37,900 --> 00:27:39,933
that have fluorine or chlorine 
on them are really common

711
00:27:40,033 --> 00:27:42,400
in a lot of contaminants 
that we worry about.

712
00:27:42,500 --> 00:27:44,266
So the fact that we're 
losing those chemicals

713
00:27:44,366 --> 00:27:45,533
is a really good thing.

714
00:27:46,766 --> 00:27:48,433
And to show you some more data

715
00:27:48,533 --> 00:27:50,600
what this actually 
looks like in practice,

716
00:27:50,700 --> 00:27:52,066
we did a bunch of modeling

717
00:27:52,166 --> 00:27:54,966
and we could see that the blue 
is showing TFM going away.

718
00:27:55,066 --> 00:27:58,633
We could see 
gentisic acid forms,

719
00:27:58,733 --> 00:28:00,100
and it goes away as well

720
00:28:00,200 --> 00:28:02,333
'cause it also undergoes 
photo degradation.

721
00:28:02,433 --> 00:28:03,833
And that's part of what makes

722
00:28:03,933 --> 00:28:06,766
understanding the chemical 
mechanism really complicated is

723
00:28:06,866 --> 00:28:09,633
because all of the products 
also photo degrade,

724
00:28:09,733 --> 00:28:11,633
so they form and 
then they go away.

725
00:28:11,733 --> 00:28:13,700
And so we have a whole 
bunch at the bottom

726
00:28:13,800 --> 00:28:15,066
that are really 
low concentrations

727
00:28:15,166 --> 00:28:17,466
because they form and 
they go away so quickly.

728
00:28:18,633 --> 00:28:20,533
And then what I think 
is really important

729
00:28:20,633 --> 00:28:24,033
and that I wanna emphasize 
is that we do form fluoride.

730
00:28:24,133 --> 00:28:25,266
So that's like just a salt,

731
00:28:25,366 --> 00:28:27,033
that's not harmful at all.

732
00:28:27,133 --> 00:28:28,400
But we're losing our fluoride

733
00:28:28,500 --> 00:28:31,233
from our floral 
methyl group here.

734
00:28:31,333 --> 00:28:34,766
And we can actually 
see production of 
fluoride coming in,

735
00:28:34,866 --> 00:28:36,433
which is really a good thing.

736
00:28:37,566 --> 00:28:39,266
Niclosamide, I'm not 
even gonna show you any

737
00:28:39,366 --> 00:28:41,566
of the organic products 
'cause it's like a mess.

738
00:28:41,666 --> 00:28:42,833
We quantified, I think,

739
00:28:42,933 --> 00:28:44,066
something like nine 
different chemicals

740
00:28:44,166 --> 00:28:46,866
and then identified 
the molecular ways

741
00:28:46,966 --> 00:28:48,266
of something like 30 more.

742
00:28:48,366 --> 00:28:50,433
It basically, the 
chemical falls apart right

743
00:28:50,533 --> 00:28:51,866
in the middle of the chemical

744
00:28:51,966 --> 00:28:53,933
and it makes a whole 
bunch of different things,

745
00:28:54,033 --> 00:28:55,466
but, again, it's 
losing the chlorines,

746
00:28:55,566 --> 00:28:57,566
which I circled in red up there.

747
00:28:57,666 --> 00:29:02,733
So we can see the 
formation of chloride here.

748
00:29:03,933 --> 00:29:05,566
So it's losing those 
two chlorine atoms.

749
00:29:05,666 --> 00:29:07,533
And then we can see the 
formation of nitrate

750
00:29:07,633 --> 00:29:09,933
which is coming from 
this nitro group here,

751
00:29:10,033 --> 00:29:11,366
and that's a really good thing.

752
00:29:11,466 --> 00:29:16,133
Those chemicals, the chlorine 
and fluorine are markers

753
00:29:17,133 --> 00:29:18,500
of really kind of 
persistent chemicals.

754
00:29:18,600 --> 00:29:20,500
I actually wanna take a 
little bit of an aside

755
00:29:20,600 --> 00:29:22,500
and kinda show you a 
little bit about that.

756
00:29:22,600 --> 00:29:26,666
So the halogen group 
is in the seventh group

757
00:29:26,766 --> 00:29:27,933
of the periodic table.

758
00:29:28,033 --> 00:29:29,733
It's the one I have 
circled in the box.

759
00:29:29,833 --> 00:29:32,333
So we start with fluorine, 
chlorine, bromine, iodine.

760
00:29:32,433 --> 00:29:35,266
These are really 
electronegative atoms,

761
00:29:35,366 --> 00:29:37,266
and they form 
really polar bonds.

762
00:29:37,366 --> 00:29:38,666
And it's really kind of hard

763
00:29:38,766 --> 00:29:41,166
to break those 
carbon halogen bonds.

764
00:29:41,266 --> 00:29:43,466
And we see these chemicals,

765
00:29:43,566 --> 00:29:47,233
these halogens in 
a lot of chemicals

766
00:29:47,333 --> 00:29:49,266
that are like kind of 
our classic contaminants

767
00:29:49,366 --> 00:29:51,533
or even newer contaminants.

768
00:29:51,633 --> 00:29:53,066
Whenever you see 
halogens in a chemical,

769
00:29:53,166 --> 00:29:54,733
you're like that's 
probably not a good thing.

770
00:29:54,833 --> 00:29:55,933
It's usually gonna be toxic.

771
00:29:56,033 --> 00:29:57,633
It's usually gonna 
be persistent.

772
00:29:57,733 --> 00:30:01,200
And so I can give you 
a few examples here.

773
00:30:01,300 --> 00:30:05,933
So there's a lot 
of good examples of 
chlorinated compounds.

774
00:30:06,033 --> 00:30:08,100
So a good one is DDT.

775
00:30:08,200 --> 00:30:10,100
Who's heard of DDT before?

776
00:30:10,200 --> 00:30:11,266
Probably everyone, right?

777
00:30:11,366 --> 00:30:13,033
So it was around a long time.

778
00:30:13,133 --> 00:30:15,133
We don't use it anymore, 
which is a good thing.

779
00:30:15,233 --> 00:30:16,933
But this is the insecticide

780
00:30:17,033 --> 00:30:19,266
that Rachel Carson wrote 
Silent Spring about.

781
00:30:19,366 --> 00:30:22,266
So Silent Spring, the 
title refers to a spring

782
00:30:22,366 --> 00:30:23,800
where there's no birds

783
00:30:23,900 --> 00:30:26,666
because this insecticide 
has killed all the birds.

784
00:30:26,766 --> 00:30:28,333
So this is a really harmful one.

785
00:30:29,766 --> 00:30:33,233
PCBs, polychlorinated biphenyls, 
these are used in coolants.

786
00:30:33,333 --> 00:30:35,633
They're also not used anymore 
but they're really persistent.

787
00:30:35,733 --> 00:30:38,200
You can still find them in the 
sediments of the Great Lakes

788
00:30:38,300 --> 00:30:41,466
because these really 
stick to the sediments.

789
00:30:41,566 --> 00:30:43,133
They're still around.

790
00:30:43,233 --> 00:30:45,433
They last a really long time.

791
00:30:45,533 --> 00:30:48,433
PCE, this is used 
in dry cleaning.

792
00:30:48,533 --> 00:30:52,066
A lot of times dry cleaning 
fluid leaks underground,

793
00:30:52,166 --> 00:30:54,000
so we find these 
chlorinated solvents

794
00:30:54,100 --> 00:30:55,233
in our groundwater frequently,

795
00:30:55,333 --> 00:30:56,766
and they're also 
really persistent.

796
00:30:56,866 --> 00:30:59,666
These chemicals are really 
common in the environment.

797
00:30:59,766 --> 00:31:00,966
But you know, you can see

798
00:31:01,066 --> 00:31:03,066
they all have those 
halogens in them.

799
00:31:03,166 --> 00:31:05,633
These are kind of what I 
call classic contaminants,

800
00:31:05,733 --> 00:31:08,633
and then they're also 
emerging contaminants.

801
00:31:08,733 --> 00:31:10,633
I don't know why we call 
them emerging contaminants.

802
00:31:10,733 --> 00:31:12,266
We've been studying 
them for a while now.

803
00:31:12,366 --> 00:31:14,733
But these are chemicals 
that we, people in my area

804
00:31:14,833 --> 00:31:17,700
are really interested 
in looking at right now.

805
00:31:17,800 --> 00:31:20,200
And so we can show examples 
of brominated compounds

806
00:31:20,300 --> 00:31:24,666
like this polybrominated 
diphenyl ether, PBDE.

807
00:31:24,766 --> 00:31:25,933
These are flame retardants.

808
00:31:26,033 --> 00:31:28,433
These are added to like 
couches and furniture

809
00:31:28,533 --> 00:31:29,700
and things like that

810
00:31:29,800 --> 00:31:31,700
at kind of shockingly 
high concentrations.

811
00:31:31,800 --> 00:31:33,300
I don't know, if 
you look at them

812
00:31:33,400 --> 00:31:34,700
it looks a lot like the PCBs

813
00:31:34,800 --> 00:31:36,500
except they have that 
oxygen there in the middle.

814
00:31:36,600 --> 00:31:39,100
But it's, I don't know why we 
thought this was a good idea

815
00:31:39,200 --> 00:31:41,366
I don't know because 
they're pretty toxic

816
00:31:41,466 --> 00:31:44,366
and they're really persistent 
and hard to break down.

817
00:31:44,466 --> 00:31:45,633
And the fluorinated compounds,

818
00:31:45,733 --> 00:31:48,266
I put up a couple, 
PFOS and PFOA.

819
00:31:48,366 --> 00:31:50,233
These are really interesting 
looking chemicals.

820
00:31:50,333 --> 00:31:52,166
These are used, or were used,

821
00:31:52,266 --> 00:31:54,833
they've just phased them 
out in like Scotchgard

822
00:31:54,933 --> 00:31:56,200
and things like that.

823
00:31:57,366 --> 00:32:00,833
They're also used in 
firefighting foams 
like at airports.

824
00:32:00,933 --> 00:32:03,266
And these are, you'll see, if 
you pay attention to these,

825
00:32:03,366 --> 00:32:05,000
you'll see these 
in the news a lot

826
00:32:05,100 --> 00:32:07,000
for contaminating 
groundwater recently.

827
00:32:07,100 --> 00:32:09,200
These are sort of a hot 
topic at the moment.

828
00:32:09,300 --> 00:32:11,533
But I wanted to just 
talk about this

829
00:32:11,633 --> 00:32:13,700
because if we think 
about the two chemicals

830
00:32:13,800 --> 00:32:16,733
that we've been spreading, 
these lampricides, you know,

831
00:32:16,833 --> 00:32:18,966
niclosamide has two 
chlorine atoms on it,

832
00:32:20,033 --> 00:32:22,833
TFM has three 
fluorine atoms on it,

833
00:32:22,933 --> 00:32:25,633
and the fact that those 
halogens are going away

834
00:32:25,733 --> 00:32:27,966
when the chemical does 
undergo photo degradation

835
00:32:28,066 --> 00:32:29,566
is a really good thing.

836
00:32:29,666 --> 00:32:32,366
The chemicals that it turns 
into are gonna be ones

837
00:32:32,466 --> 00:32:35,633
that are gonna be easy 
for bacteria to eat.

838
00:32:35,733 --> 00:32:37,566
They're basically 
food at that point.

839
00:32:37,666 --> 00:32:39,400
They look pretty 
tasty to bacteria.

840
00:32:39,500 --> 00:32:41,633
So once they lose 
these halogen groups,

841
00:32:41,733 --> 00:32:44,033
they're not gonna be things 
that we're worried about.

842
00:32:45,033 --> 00:32:46,933
So even though the rates, 
especially for niclosamide,

843
00:32:47,033 --> 00:32:48,800
are quite slow, once 
they do break down

844
00:32:48,900 --> 00:32:50,666
they're gonna form things that 
we're not concerned about.

845
00:32:50,766 --> 00:32:53,033
And so that was really 
good to learn that.

846
00:32:55,100 --> 00:32:59,066
Okay, so we did this work 
looking at what happens

847
00:32:59,166 --> 00:33:01,366
in the lab where things 
are very well behaved.

848
00:33:01,466 --> 00:33:05,533
And then we wanted to find out, 
does it happen in the field?

849
00:33:06,733 --> 00:33:08,600
And sort of like 
I said at the top,

850
00:33:08,700 --> 00:33:09,866
you know, hindsight is 20/20.

851
00:33:09,966 --> 00:33:11,100
We might have picked 
different sites

852
00:33:11,200 --> 00:33:13,100
if we'd done this again, 
but it was, you know,

853
00:33:13,200 --> 00:33:15,266
it's all sort of happening 
at the same time.

854
00:33:15,366 --> 00:33:17,933
And so we went to 
three different sites,

855
00:33:18,033 --> 00:33:22,100
two in 2015 and two in 2016.

856
00:33:22,200 --> 00:33:26,766
And so, in 2015, these 
were tributaries that are,

857
00:33:26,866 --> 00:33:28,933
they're actually, 
this bottom map shows

858
00:33:29,033 --> 00:33:30,600
all three sites 
on the same scale.

859
00:33:30,700 --> 00:33:32,733
So here are the first 
two that I'm gonna show.

860
00:33:32,833 --> 00:33:33,733
They're really tiny.

861
00:33:33,833 --> 00:33:35,233
They barely show 
up there at all.

862
00:33:35,333 --> 00:33:37,233
And then here's the 
Manistique, which is huge.

863
00:33:37,333 --> 00:33:39,400
And this is the one that I said

864
00:33:39,500 --> 00:33:41,566
they filled up like 
every hotel in town

865
00:33:41,666 --> 00:33:43,700
because there's so many 
people working on this.

866
00:33:43,800 --> 00:33:46,133
For these two small sites, 
these are really simple.

867
00:33:46,233 --> 00:33:48,566
Basically what they're 
doing up here at this upper,

868
00:33:48,666 --> 00:33:51,666
where that green dot is, 
they add the chemical once

869
00:33:51,766 --> 00:33:53,600
and then the chemical 
just goes downstream.

870
00:33:53,700 --> 00:33:55,433
So they just add it 
in and that's it.

871
00:33:55,533 --> 00:33:57,433
They just leave it alone.

872
00:33:57,533 --> 00:34:00,100
So what we did here 
on these two sites,

873
00:34:00,200 --> 00:34:02,366
we sampled just downstream

874
00:34:02,466 --> 00:34:03,900
This is our upstream site.

875
00:34:04,000 --> 00:34:05,900
We sampled just downstream of 
where they added the chemical.

876
00:34:06,000 --> 00:34:07,900
And then we sampled as 
close as we could get

877
00:34:08,000 --> 00:34:09,133
to the river mouth.

878
00:34:09,233 --> 00:34:12,000
And what we also did 
in parallel to this,

879
00:34:12,100 --> 00:34:16,266
we added sodium bromide, which 
is a salt, it's a tracer.

880
00:34:16,366 --> 00:34:19,133
And so this basically 
let's us quantify

881
00:34:19,233 --> 00:34:21,133
or measure how much water,

882
00:34:21,233 --> 00:34:23,166
where the water is 
going in this system.

883
00:34:23,266 --> 00:34:25,866
And so we measured 
the bromide at the top

884
00:34:25,966 --> 00:34:28,566
and the TFM at the top 
of the water, the reach,

885
00:34:28,666 --> 00:34:30,800
and then the bromide and 
the TFM at the bottom,

886
00:34:30,900 --> 00:34:33,333
and we could calculate 
how much was lost and see,

887
00:34:33,433 --> 00:34:35,833
like, do we see any loss 
due to photo degradation?

888
00:34:35,933 --> 00:34:38,866
And so we did that 
at these two sites.

889
00:34:38,966 --> 00:34:41,666
I'll say a little bit more 
about that in a minute.

890
00:34:41,766 --> 00:34:45,533
And then, in 2016, we went 
out on the Manistique River,

891
00:34:45,633 --> 00:34:47,366
and this is a huge river.

892
00:34:47,466 --> 00:34:49,366
Every one of these, 
I know it's a little small,

893
00:34:49,466 --> 00:34:51,466
but every one of these 
green points is a point

894
00:34:51,566 --> 00:34:53,266
where they're adding chemical.

895
00:34:53,366 --> 00:34:55,133
And, again, think of that 
they're wanting to get

896
00:34:55,233 --> 00:34:57,733
all the chemical, by the time 
it makes its way to the mouth,

897
00:34:57,833 --> 00:34:59,933
all the chemical and all 
this side tributaries

898
00:35:00,033 --> 00:35:02,500
are wanting to come together 
at the exact same time

899
00:35:02,600 --> 00:35:03,700
in the exact same concentration.

900
00:35:03,800 --> 00:35:06,600
So it's an amazing operation.

901
00:35:06,700 --> 00:35:09,566
And then every white 
dot on the figure,

902
00:35:09,666 --> 00:35:11,466
that's where they're out and 
they're actually measuring

903
00:35:11,566 --> 00:35:14,700
the chemical concentration 
in real time.

904
00:35:14,800 --> 00:35:17,233
And if the chemical 
concentration is too low,

905
00:35:17,333 --> 00:35:19,366
they're gonna add a 
little bit more in

906
00:35:19,466 --> 00:35:22,433
to make sure the 
concentration stays the same.

907
00:35:22,533 --> 00:35:25,400
So this is a huge operation.

908
00:35:25,500 --> 00:35:27,600
And so for the first, the 
two smaller tributaries,

909
00:35:27,700 --> 00:35:29,166
they only added TFM.

910
00:35:29,266 --> 00:35:31,866
TFM is often added 
only by itself.

911
00:35:31,966 --> 00:35:33,366
And in this bigger system,

912
00:35:33,466 --> 00:35:36,733
they're adding both TFM 
and niclosamide together,

913
00:35:36,833 --> 00:35:39,033
so they're measuring 
both in the field.

914
00:35:39,133 --> 00:35:40,733
So I'm gonna show you the data

915
00:35:40,833 --> 00:35:43,633
from these first two 
smaller tributaries first.

916
00:35:44,800 --> 00:35:47,566
And, again, I'll show 
you some more pictures.

917
00:35:47,666 --> 00:35:49,400
This is someone 
from Fish & Wildlife

918
00:35:49,500 --> 00:35:51,200
who's actually setting up 
to put the chemical in.

919
00:35:51,300 --> 00:35:53,933
You can see this is a 
really small tributary.

920
00:35:54,033 --> 00:35:57,933
You can kind of see it's 
maybe a meter or so across.

921
00:35:58,033 --> 00:36:02,400
Down here on the bottom 
right there's this can of TFM

922
00:36:02,500 --> 00:36:04,733
and this toolbox that's 
basically a pump,

923
00:36:04,833 --> 00:36:06,433
and it's pumping 
the chemical out.

924
00:36:06,533 --> 00:36:09,133
He has like the 
little drip line.

925
00:36:09,233 --> 00:36:10,333
They sort of picked a reach

926
00:36:10,433 --> 00:36:11,733
where there's a little 
bit of turbulence

927
00:36:11,833 --> 00:36:13,133
to kind of mix up the chemical

928
00:36:13,233 --> 00:36:14,533
and get it distributed 
across the river,

929
00:36:14,633 --> 00:36:15,666
but that's pretty much it.

930
00:36:15,766 --> 00:36:16,800
He's gonna set this up,

931
00:36:16,900 --> 00:36:18,800
he's gonna let it run 
for about 10 hours,

932
00:36:18,900 --> 00:36:20,800
and then that's 
it for this site.

933
00:36:20,900 --> 00:36:22,000
We added, we actually went,

934
00:36:22,100 --> 00:36:23,800
we had to do it 
on a different day

935
00:36:23,900 --> 00:36:25,400
because they wouldn't 
let us add the bromide

936
00:36:25,500 --> 00:36:26,566
on the same day.

937
00:36:26,666 --> 00:36:27,966
We went back the next day.

938
00:36:28,066 --> 00:36:31,333
Here, that's, yeah, very 
fancy field equipment,

939
00:36:31,433 --> 00:36:33,666
a trash can which we 
filled up with this salt,

940
00:36:33,766 --> 00:36:36,466
this sodium bromide, mixed 
it up with a big stick,

941
00:36:36,566 --> 00:36:38,966
and then poured it in the 
river all at one shot.

942
00:36:40,333 --> 00:36:44,666
And then we had our 
poor students downstream

943
00:36:44,766 --> 00:36:47,766
rapidly collecting samples 
as quick as you could

944
00:36:47,866 --> 00:36:50,100
so we could really 
capture those chemicals

945
00:36:50,200 --> 00:36:51,966
and see what happened.

946
00:36:52,066 --> 00:36:55,466
And so this is what the data 
looks like.

947
00:36:55,566 --> 00:36:57,900
So on the top, this 
top panel shows

948
00:36:58,000 --> 00:37:01,766
the TFM concentration and 
the bottom shows bromide.

949
00:37:01,866 --> 00:37:03,233
So the lighter colored blue,

950
00:37:03,333 --> 00:37:06,366
this is the TFM concentration 
measured right downstream

951
00:37:06,466 --> 00:37:07,933
of where they 
added the chemical.

952
00:37:08,033 --> 00:37:09,433
And you can see, okay, 
nothing's happening.

953
00:37:09,533 --> 00:37:12,000
Well, I guess my students slept 
in a little late that day,

954
00:37:12,100 --> 00:37:13,400
they didn't get those 
first couple points.

955
00:37:13,500 --> 00:37:15,066
But you can imagine 
nothing's happening,

956
00:37:15,166 --> 00:37:16,766
and then they turn 
the chemical on,

957
00:37:16,866 --> 00:37:18,700
it's staying steady 
concentration,

958
00:37:18,800 --> 00:37:21,366
around 20 micromolar 
for about 10 hours,

959
00:37:21,466 --> 00:37:23,100
and then they stop 
pumping in the chemical,

960
00:37:23,200 --> 00:37:25,333
and then it drops off again.

961
00:37:25,433 --> 00:37:28,166
And then we went downstream 
as far as we can,

962
00:37:28,266 --> 00:37:29,633
and we measure the chemical.

963
00:37:29,733 --> 00:37:32,800
We can see it's starting to 
come up, concentration's lower.

964
00:37:32,900 --> 00:37:34,666
It lasts for about 
the same time.

965
00:37:34,766 --> 00:37:36,366
And then the chemical 
goes away again

966
00:37:36,466 --> 00:37:37,600
once they stop adding it.

967
00:37:37,700 --> 00:37:39,933
So then we did the same thing 
with bromide,

968
00:37:40,033 --> 00:37:41,366
and this is one that we, like,

969
00:37:41,466 --> 00:37:43,800
dumped the trashcan of 
chemical into the water.

970
00:37:44,800 --> 00:37:47,266
And this is a salt, it's 
just a harmless tracer.

971
00:37:47,366 --> 00:37:48,600
When we measured downstream,

972
00:37:48,700 --> 00:37:51,100
you can see we see a huge 
spike of the chemical

973
00:37:51,200 --> 00:37:53,333
from dumping in the 
whole big bucket.

974
00:37:53,433 --> 00:37:55,233
And that's, you know,

975
00:37:55,333 --> 00:37:59,666
reaching concentrations 
of around 700 micromolar.

976
00:37:59,766 --> 00:38:01,500
And then, looking 
downstream, you know,

977
00:38:01,600 --> 00:38:03,000
things sort of spread out.

978
00:38:03,100 --> 00:38:05,266
You know, things aren't moving 
down in a nice, neat block.

979
00:38:05,366 --> 00:38:06,766
Things diffuse a little bit.

980
00:38:06,866 --> 00:38:09,266
But we can measure the 
chemical at the bottom.

981
00:38:09,366 --> 00:38:11,500
And this is really 
useful to us actually

982
00:38:11,600 --> 00:38:14,300
to collect the data at 
the top and the bottom

983
00:38:14,400 --> 00:38:16,800
'cause we can do is 
basically calculate the area

984
00:38:16,900 --> 00:38:18,200
under that curve and calculate

985
00:38:18,300 --> 00:38:20,433
how much mass we had 
at the beginning.

986
00:38:20,533 --> 00:38:22,200
Like what was our 
total mass added

987
00:38:22,300 --> 00:38:24,933
versus our total mass that 
we're measuring at the bottom.

988
00:38:25,033 --> 00:38:26,600
And the reason we 
did the tracer is

989
00:38:26,700 --> 00:38:28,900
because the sodium 
bromide tracer we know

990
00:38:29,000 --> 00:38:30,933
isn't gonna undergo 
any chemical reactions.

991
00:38:31,033 --> 00:38:33,200
It's only gonna 
move with the water.

992
00:38:33,300 --> 00:38:37,566
And we know if you imagine 
water flowing downstream,

993
00:38:37,666 --> 00:38:40,100
some of it can actually 
go into the ground,

994
00:38:40,200 --> 00:38:43,266
into the hyporheic zone, and 
that's actually what we saw.

995
00:38:44,366 --> 00:38:45,833
So what we saw was about,

996
00:38:45,933 --> 00:38:48,100
looking at the tracer 
and comparing the areas

997
00:38:48,200 --> 00:38:50,766
under the curve, we lost 
about 30% of the mass

998
00:38:50,866 --> 00:38:53,966
that we added to this 
exchange with the groundwater.

999
00:38:55,233 --> 00:38:57,000
Looking at the areas 
under the TFM curve,

1000
00:38:57,100 --> 00:38:59,800
we saw we lost 34% of the TFM.

1001
00:38:59,900 --> 00:39:02,833
And with an error, those are 
pretty much the same number.

1002
00:39:02,933 --> 00:39:05,600
And so what this means is 
that any TFM that we lost,

1003
00:39:05,700 --> 00:39:07,733
any of the lampricide 
that we didn't measure

1004
00:39:07,833 --> 00:39:09,200
at the bottom that we added,

1005
00:39:09,300 --> 00:39:11,200
that's because it's also 
going into the groundwater,

1006
00:39:11,300 --> 00:39:14,533
the same as we saw with 
the sodium bromide salt.

1007
00:39:14,633 --> 00:39:16,866
And then, because we 
had done all the work

1008
00:39:16,966 --> 00:39:19,733
to identify all the possible 
degradation products,

1009
00:39:19,833 --> 00:39:23,400
we could look for them, 
and we didn't find any.

1010
00:39:23,500 --> 00:39:27,133
So both of those two things 
together told us, like, okay,

1011
00:39:27,233 --> 00:39:29,033
we didn't see any 
photo degradation.

1012
00:39:30,433 --> 00:39:33,233
Well, okay, but we're sure 
that we didn't see it.

1013
00:39:33,333 --> 00:39:36,200
We have those two ways 
of sort of telling that.

1014
00:39:36,300 --> 00:39:37,833
Looking at Sullivan Creek,

1015
00:39:37,933 --> 00:39:40,633
the other really small 
tributary is the same.

1016
00:39:40,733 --> 00:39:42,066
You can see what it looks like.

1017
00:39:42,166 --> 00:39:44,066
It's a little bit of a bigger,

1018
00:39:44,166 --> 00:39:45,933
a little bit bigger, but 
it's still pretty small,

1019
00:39:46,033 --> 00:39:49,366
really forested and really 
beautiful up there on the UP.

1020
00:39:50,366 --> 00:39:51,833
And the data is really similar

1021
00:39:51,933 --> 00:39:55,400
where we have the top panel 
that shows TFM, you know,

1022
00:39:55,500 --> 00:39:57,800
higher concentration 
of the upper stream,

1023
00:39:57,900 --> 00:40:00,500
and then it decreases 
on the lower stream.

1024
00:40:00,600 --> 00:40:04,133
And then we did our sodium 
bromide tracer test again here.

1025
00:40:04,233 --> 00:40:06,166
And I didn't put the percentages 
up there, but, again,

1026
00:40:06,266 --> 00:40:07,833
they were basically 
about the same

1027
00:40:07,933 --> 00:40:10,833
where the amount of salt that 
we lost in our tracer test

1028
00:40:10,933 --> 00:40:13,166
was the same as the 
amount of TFM that we lost

1029
00:40:13,266 --> 00:40:16,166
in the actual chemical 
application of lampricide.

1030
00:40:16,266 --> 00:40:19,000
And so, again, we didn't 
see any photo products here.

1031
00:40:20,166 --> 00:40:21,366
And so we're like, okay,

1032
00:40:21,466 --> 00:40:23,366
we didn't see any 
photo degradation.

1033
00:40:23,466 --> 00:40:26,633
At the same time we sort of 
worked out all of our, you know,

1034
00:40:26,733 --> 00:40:28,633
measurements in the lab, 
and we're all like, okay,

1035
00:40:28,733 --> 00:40:30,500
well, we probably 
should have known that

1036
00:40:30,600 --> 00:40:31,766
because the residence time,

1037
00:40:31,866 --> 00:40:33,400
so the amount of 
time that it takes

1038
00:40:33,500 --> 00:40:34,900
from when we add the chemical

1039
00:40:35,000 --> 00:40:37,466
to when it reaches the 
Great Lake, Lake Superior,

1040
00:40:37,566 --> 00:40:40,166
is about one to four hours,

1041
00:40:40,266 --> 00:40:42,366
depending on which river 
we're talking about.

1042
00:40:42,466 --> 00:40:44,566
And our half-life, so the time 
it takes for the chemical,

1043
00:40:44,666 --> 00:40:47,266
half of it to go 
away is 12 hours.

1044
00:40:47,366 --> 00:40:50,866
So in retrospect, that's 
not really a surprise.

1045
00:40:50,966 --> 00:40:52,566
We probably should 
have known that.

1046
00:40:52,666 --> 00:40:55,366
But, like I said, that's 
part of the challenge.

1047
00:40:55,466 --> 00:40:59,433
And so we're like okay, well, 
this river was really small.

1048
00:41:00,433 --> 00:41:02,266
We want something where 
the chemical is gonna be

1049
00:41:02,366 --> 00:41:03,966
in the river for a 
really long time.

1050
00:41:04,066 --> 00:41:07,966
And so we went to basically one 
of the biggest river systems

1051
00:41:08,066 --> 00:41:10,566
that they treat, which 
is the Manistique River.

1052
00:41:12,466 --> 00:41:14,533
And I showed you this 
map before, and, again,

1053
00:41:14,633 --> 00:41:16,233
with the Sullivan Creek 
and Carpenter Creek,

1054
00:41:16,333 --> 00:41:17,933
those two little 
rivers I showed you,

1055
00:41:18,033 --> 00:41:19,733
I guess creeks, they don't 
really count as rivers.

1056
00:41:19,833 --> 00:41:20,900
They're really small.

1057
00:41:21,000 --> 00:41:22,566
Those are up there 
on the same scale.

1058
00:41:22,666 --> 00:41:24,633
And then here's our 
Manistique River which is,

1059
00:41:24,733 --> 00:41:26,633
I mean it pretty much 
goes across the whole UP.

1060
00:41:26,733 --> 00:41:28,966
It's really big, and 
it's a really wide river.

1061
00:41:29,066 --> 00:41:30,800
It's not as shaded.

1062
00:41:30,900 --> 00:41:32,566
And the chemical from 
the time it's added

1063
00:41:32,666 --> 00:41:34,166
at the most furthest 
upstream point

1064
00:41:34,266 --> 00:41:37,966
to the time it makes it all the 
way down is over three days.

1065
00:41:38,066 --> 00:41:39,766
So we're like, okay, three days,

1066
00:41:39,866 --> 00:41:41,466
you know, we've done 
our math, you know,

1067
00:41:41,566 --> 00:41:43,300
we think you should 
see something here.

1068
00:41:43,400 --> 00:41:46,033
And so what we did here, we 
didn't sample the whole thing.

1069
00:41:46,133 --> 00:41:47,333
This was a huge operation.

1070
00:41:47,433 --> 00:41:50,000
We sampled it where all 
the blue triangles are.

1071
00:41:50,100 --> 00:41:51,833
And so we could basically 
follow the chemical block

1072
00:41:51,933 --> 00:41:53,733
as it was moving downstream.

1073
00:41:54,733 --> 00:41:56,300
And one thing to 
remember here is

1074
00:41:56,400 --> 00:41:58,166
that they're working really hard

1075
00:41:58,266 --> 00:41:59,766
to make sure the 
chemical concentration is

1076
00:41:59,866 --> 00:42:01,900
the same throughout 
the whole river.

1077
00:42:02,000 --> 00:42:03,133
Again, at all those white dots

1078
00:42:03,233 --> 00:42:05,833
they're actually out in 
the field measuring it

1079
00:42:05,933 --> 00:42:07,933
and then adding more 
chemical as needed.

1080
00:42:08,933 --> 00:42:10,333
So to show you 
some more pictures

1081
00:42:10,433 --> 00:42:13,100
of what this river looks like.

1082
00:42:13,200 --> 00:42:14,733
First we're gonna look 
at the Cookson Bridge,

1083
00:42:14,833 --> 00:42:16,733
which is the site we 
have labeled here M1.

1084
00:42:16,833 --> 00:42:20,666
This was the furthest 
upstream site that we sampled.

1085
00:42:20,766 --> 00:42:22,866
You can see this is a 
really, really wide river.

1086
00:42:22,966 --> 00:42:25,233
There's a whole 
bridge across this.

1087
00:42:25,333 --> 00:42:27,833
What they did, 
basically, at this site,

1088
00:42:27,933 --> 00:42:29,133
this was a boosting site.

1089
00:42:29,233 --> 00:42:30,700
So they were actually 
there measuring

1090
00:42:30,800 --> 00:42:32,366
the chemical concentration 
and saying like

1091
00:42:32,466 --> 00:42:33,966
okay, it's a little 
lower than we want.

1092
00:42:34,066 --> 00:42:35,633
So they're adding 
in a little bit more

1093
00:42:35,733 --> 00:42:38,066
to kind of bump it up.

1094
00:42:38,166 --> 00:42:40,600
So they had the chemicals 
here at the bottom.

1095
00:42:40,700 --> 00:42:43,400
There's a pump, and then they 
have this drip line that they,

1096
00:42:43,500 --> 00:42:45,500
I think the Fish & 
Wildlife actually

1097
00:42:45,600 --> 00:42:47,966
in this picture is trying 
to get this drip line

1098
00:42:48,066 --> 00:42:50,566
across the river, they 
could drip the chemical in.

1099
00:42:51,766 --> 00:42:53,766
So that's what they 
were doing there.

1100
00:42:53,866 --> 00:42:55,566
And then there's 
my student, Megan.

1101
00:42:55,666 --> 00:42:57,800
We were, you know, 
sampling over the bridge,

1102
00:42:57,900 --> 00:43:00,466
throwing in a can or a bucket 
and pulling up a sample.

1103
00:43:00,566 --> 00:43:01,800
And she's holding a big sonde,

1104
00:43:01,900 --> 00:43:03,733
which is this big instrument,

1105
00:43:03,833 --> 00:43:05,700
it has a bunch of 
measures, temperature, pH,

1106
00:43:05,800 --> 00:43:07,733
and a whole bunch of 
things in real time.

1107
00:43:07,833 --> 00:43:09,400
So we're doing a bunch 
of measurements there

1108
00:43:09,500 --> 00:43:11,533
off the side of the bridge.

1109
00:43:11,633 --> 00:43:13,733
And then this was 
like, so I'm a chemist.

1110
00:43:13,833 --> 00:43:15,200
I like to stay in the lab.

1111
00:43:15,300 --> 00:43:16,533
I don't like to do fieldwork.

1112
00:43:16,633 --> 00:43:17,733
But this was really 
nice fieldwork

1113
00:43:17,833 --> 00:43:19,633
because the lab 
kind of came to us.

1114
00:43:19,733 --> 00:43:24,300
And so this is a Fish & Wildlife 
mobile analysis trailer,

1115
00:43:24,400 --> 00:43:26,333
which was really nice 
'cause this was midnight

1116
00:43:26,433 --> 00:43:28,333
in the pouring down rain 
so it was really nice

1117
00:43:28,433 --> 00:43:30,433
to have a nice 
place to go inside.

1118
00:43:30,533 --> 00:43:31,900
But they have these, like,

1119
00:43:32,000 --> 00:43:33,366
trailers that are basically 
like mobile laboratories

1120
00:43:33,466 --> 00:43:35,266
that they take out on 
these big field sites,

1121
00:43:35,366 --> 00:43:37,733
and they're actually 
measuring these chemicals

1122
00:43:37,833 --> 00:43:39,833
like in real time.

1123
00:43:39,933 --> 00:43:42,833
This one, this instrument here, 
this is a UV spectrometer.

1124
00:43:42,933 --> 00:43:44,266
This is for measuring TFM.

1125
00:43:44,366 --> 00:43:46,466
It's in a higher concentration 
so they basically just,

1126
00:43:46,566 --> 00:43:47,833
it basically takes advantage

1127
00:43:47,933 --> 00:43:49,700
of that UV-vis spectra 
that I showed you.

1128
00:43:49,800 --> 00:43:52,333
They shine light on it, they 
can measure the concentration.

1129
00:43:52,433 --> 00:43:54,966
And then this is a more, 
a fancier instrument.

1130
00:43:55,066 --> 00:43:56,700
It's a high performance 
liquid chromatograph.

1131
00:43:56,800 --> 00:43:58,166
This is for measuring 
niclosamide.

1132
00:43:58,266 --> 00:43:59,333
And so Steve Lantz,

1133
00:43:59,433 --> 00:44:02,300
I showed you a picture 
of him at the beginning,

1134
00:44:02,400 --> 00:44:05,233
he was out there in 
the middle of the night

1135
00:44:05,333 --> 00:44:06,566
measuring the chemical 
concentration,

1136
00:44:06,666 --> 00:44:09,000
making sure that what they 
were adding was right,

1137
00:44:09,100 --> 00:44:11,633
and there was a couple 
poor guys in boats

1138
00:44:11,733 --> 00:44:13,000
in the pouring down 
rain downstream

1139
00:44:13,100 --> 00:44:14,566
collecting samples and 
bringing them back.

1140
00:44:14,666 --> 00:44:18,466
And you can just imagine it 
was a good bonding experience,

1141
00:44:18,566 --> 00:44:19,733
being out there for it.

1142
00:44:21,600 --> 00:44:24,266
But it was pretty 
interesting to see.

1143
00:44:24,366 --> 00:44:26,133
And this is what 
the data looks like.

1144
00:44:26,233 --> 00:44:28,333
So let me walk you through 
it.

1145
00:44:28,433 --> 00:44:30,833
The top is TFM, the 
bottom is niclosamide.

1146
00:44:31,966 --> 00:44:33,866
In this we're looking 
over several days.

1147
00:44:33,966 --> 00:44:36,400
Again, remember, this is a 
multi-day treatment process.

1148
00:44:36,500 --> 00:44:38,266
It lasts a really long time.

1149
00:44:38,366 --> 00:44:40,766
So we have, this 
is our first site.

1150
00:44:40,866 --> 00:44:42,133
We can measure the TFM,

1151
00:44:42,233 --> 00:44:44,400
and we're basically 
following that chemical block

1152
00:44:44,500 --> 00:44:47,666
kinda as it moves 
downstream what's going on.

1153
00:44:47,766 --> 00:44:50,466
And then niclosamide is 
at a lower concentration.

1154
00:44:50,566 --> 00:44:51,800
It's a lot messier and that's

1155
00:44:51,900 --> 00:44:53,300
because it sticks 
to the sediments

1156
00:44:53,400 --> 00:44:56,433
and so it's a little bit less 
behaved, less well behaved.

1157
00:44:56,533 --> 00:44:58,500
We can see it.

1158
00:44:58,600 --> 00:45:01,133
And then we wanted to 
look for photo products,

1159
00:45:01,233 --> 00:45:02,766
the transformation products,

1160
00:45:02,866 --> 00:45:05,966
and we didn't find any, 
which was a bummer.

1161
00:45:06,066 --> 00:45:09,133
My poor grad student was really 
sad when we got this result.

1162
00:45:09,233 --> 00:45:11,033
We didn't find any.

1163
00:45:11,133 --> 00:45:12,200
And the question was, why?

1164
00:45:12,300 --> 00:45:13,700
You know, we're 
thinking the half-life

1165
00:45:13,800 --> 00:45:16,933
is something like 20 hours and 
it was there for three days.

1166
00:45:17,033 --> 00:45:19,333
Well, the environment 
is a messy place,

1167
00:45:19,433 --> 00:45:21,533
it's a lot more complicated 
than we think it's gonna be,

1168
00:45:21,633 --> 00:45:23,533
and so we can actually 
adjust for it.

1169
00:45:23,633 --> 00:45:25,933
And so, well, you can see I'm 
gonna walk you through that.

1170
00:45:26,033 --> 00:45:27,200
And this half-life is gonna get

1171
00:45:27,300 --> 00:45:28,933
bigger and bigger 
and bigger as we go.

1172
00:45:29,033 --> 00:45:31,466
But our initial estimate 
was about 20 hours.

1173
00:45:31,566 --> 00:45:33,533
And we look and say, 
okay, well first of all

1174
00:45:33,633 --> 00:45:34,800
that's not really 
a good estimate

1175
00:45:34,900 --> 00:45:37,966
because this is assuming 
that the sun is on

1176
00:45:38,066 --> 00:45:39,600
like noontime 
conditions all the time,

1177
00:45:39,700 --> 00:45:43,600
which, obviously, the sun is 
not shining 24 hours a day.

1178
00:45:43,700 --> 00:45:45,900
And we're looking at a 
depth of 55 centimeters.

1179
00:45:46,000 --> 00:45:48,766
So actually the first thing 
we looked at was, well,

1180
00:45:48,866 --> 00:45:49,766
that's a really deep river.

1181
00:45:49,866 --> 00:45:51,366
It's about two meters deep.

1182
00:45:51,466 --> 00:45:54,066
So if we, and this 
figure shows like

1183
00:45:54,166 --> 00:45:55,933
how quickly light 
drops off with depth.

1184
00:45:56,033 --> 00:45:57,166
And so thinking about how deep

1185
00:45:57,266 --> 00:45:59,066
the water is is 
really important.

1186
00:45:59,166 --> 00:46:01,733
So if we go from 55 
centimeters to two meters,

1187
00:46:01,833 --> 00:46:03,233
that triples the half-life,

1188
00:46:03,333 --> 00:46:05,400
so the chemical just 
over in a deeper water

1189
00:46:05,500 --> 00:46:08,133
is gonna go away three 
times more slowly.

1190
00:46:09,366 --> 00:46:13,900
And then Madison is not 
Manistique and the UP.

1191
00:46:14,000 --> 00:46:18,466
So the sun's, you know, the 
sun is at a different angle,

1192
00:46:18,566 --> 00:46:20,733
so we corrected for that.

1193
00:46:20,833 --> 00:46:23,300
So you can see this 
is our sunlight data.

1194
00:46:23,400 --> 00:46:24,533
This is what Madison is.

1195
00:46:24,633 --> 00:46:26,600
It's basically higher,

1196
00:46:26,700 --> 00:46:28,866
getting a little more light 
for that first calculation.

1197
00:46:28,966 --> 00:46:30,866
This is the Manistique 
in September.

1198
00:46:30,966 --> 00:46:32,766
It's getting less light.

1199
00:46:32,866 --> 00:46:35,400
That, again, is gonna 
make the chemical go away

1200
00:46:35,500 --> 00:46:38,633
about two times more slowly.

1201
00:46:38,733 --> 00:46:41,966
So the location is really 
important in this calculation.

1202
00:46:43,233 --> 00:46:46,833
This isn't clear water, 
it has some color to it.

1203
00:46:46,933 --> 00:46:48,033
So we can account for that.

1204
00:46:48,133 --> 00:46:50,533
That's gonna slow us 
down a little bit more.

1205
00:46:50,633 --> 00:46:52,866
And then what really 
gets us in trouble is

1206
00:46:52,966 --> 00:46:54,733
when we actually take 
into account the fact

1207
00:46:54,833 --> 00:46:57,866
that the sun is not on all 
the day, and we can see,

1208
00:46:57,966 --> 00:47:00,566
you know, we can model 
the sunlight and all that.

1209
00:47:00,666 --> 00:47:04,233
Now we're getting up to a 
half-life around 300 hours.

1210
00:47:04,333 --> 00:47:06,566
And then I showed 
you the one picture

1211
00:47:06,666 --> 00:47:08,100
from when it was nice and sunny.

1212
00:47:08,200 --> 00:47:10,100
That was the only time 
the sun was shining

1213
00:47:10,200 --> 00:47:11,666
the whole time we were up there.

1214
00:47:11,766 --> 00:47:13,866
And so if you take 
into cloud cover,

1215
00:47:13,966 --> 00:47:17,400
now we're at around 600 
hours of a half-life.

1216
00:47:17,500 --> 00:47:19,233
So it's gonna take 600 hours

1217
00:47:19,333 --> 00:47:21,766
for half of the chemical to 
go away, accounting for, like,

1218
00:47:21,866 --> 00:47:23,266
the daily variability 
in sunlight

1219
00:47:23,366 --> 00:47:25,233
and everything else 
we can think of.

1220
00:47:26,233 --> 00:47:27,766
And so we can take our lab data

1221
00:47:27,866 --> 00:47:30,300
and we can explain what 
we saw in the field.

1222
00:47:30,400 --> 00:47:31,766
But that sort of 
begs the question,

1223
00:47:31,866 --> 00:47:34,666
well, does TFM ever 
undergo photolysis?

1224
00:47:35,666 --> 00:47:37,633
And so what we did 
here, you know,

1225
00:47:37,733 --> 00:47:41,066
my poor student is finishing 
up her PhD, you know,

1226
00:47:41,166 --> 00:47:43,066
we're not gonna go out 
and sample every river,

1227
00:47:43,166 --> 00:47:45,466
so we turn to doing 
some calculations.

1228
00:47:45,566 --> 00:47:47,933
And so Fish & Wildlife 
helped us out a lot here.

1229
00:47:48,033 --> 00:47:53,033
We took data from 
all the tributaries 
they treated in 2015,

1230
00:47:54,200 --> 00:47:56,666
so 76 tributaries 
just in the US side.

1231
00:47:56,766 --> 00:47:59,333
And we took all 
the data from 2016,

1232
00:47:59,433 --> 00:48:01,233
so another 63 tributaries.

1233
00:48:02,666 --> 00:48:05,633
And we took into account 
how long the rivers were,

1234
00:48:05,733 --> 00:48:06,833
the time of the year,

1235
00:48:06,933 --> 00:48:08,933
all those factors that 
I just showed you,

1236
00:48:09,033 --> 00:48:11,033
to come up with half-lives.

1237
00:48:11,133 --> 00:48:12,833
And that's shown 
here in this figure.

1238
00:48:12,933 --> 00:48:16,333
And so we just, these 
are the two years.

1239
00:48:16,433 --> 00:48:19,266
And basically what we 
want is a higher number.

1240
00:48:19,366 --> 00:48:21,500
A higher number is more 
percent degradation.

1241
00:48:21,600 --> 00:48:25,900
And so what we did was, again 
for all these tributaries

1242
00:48:26,000 --> 00:48:27,133
that were treated 
in those years,

1243
00:48:27,233 --> 00:48:28,800
we took into account 
the stream depth,

1244
00:48:28,900 --> 00:48:31,833
we took into account how long 
the chemical was in the water,

1245
00:48:31,933 --> 00:48:34,700
and the site specific 
daily radiation.

1246
00:48:34,800 --> 00:48:37,200
Basically what we found was 
that for 70 tributaries,

1247
00:48:37,300 --> 00:48:38,733
they're below this 10% line.

1248
00:48:38,833 --> 00:48:41,166
They really wouldn't see any 
photo degradation at all.

1249
00:48:41,266 --> 00:48:44,066
And you can see our first 
two sites are right there.

1250
00:48:44,166 --> 00:48:46,266
So, again hindsight is 20/20,

1251
00:48:46,366 --> 00:48:48,266
those probably weren't 
the best choices.

1252
00:48:49,700 --> 00:48:52,833
58 tributaries we might see 
some moderate degradation.

1253
00:48:52,933 --> 00:48:54,466
And 11 tributaries,

1254
00:48:54,566 --> 00:48:55,900
which are basically 
turn out to be

1255
00:48:56,000 --> 00:48:57,633
longer and more 
shallow tributaries,

1256
00:48:57,733 --> 00:49:00,566
we can actually see 
significant degradation.

1257
00:49:00,666 --> 00:49:03,633
So if we're thinking just 
about the rivers themselves,

1258
00:49:03,733 --> 00:49:06,300
this, you know, it's gonna 
be about 10% of the rivers

1259
00:49:06,400 --> 00:49:09,733
we're gonna actually see 
significant photo degradation

1260
00:49:09,833 --> 00:49:11,566
during a treatment application.

1261
00:49:12,566 --> 00:49:14,500
So where do the chemicals go?

1262
00:49:15,500 --> 00:49:17,733
There's a couple things that 
I think are really important

1263
00:49:17,833 --> 00:49:20,033
that I'm really interested in.

1264
00:49:20,133 --> 00:49:22,166
First of all is the groundwater.

1265
00:49:22,266 --> 00:49:25,200
So I talked about this a little 
bit, this hyporheic zone.

1266
00:49:25,300 --> 00:49:27,166
Below every river there's 
the hyporheic zone

1267
00:49:27,266 --> 00:49:29,133
which is basically where 
we have rapid exchange

1268
00:49:29,233 --> 00:49:31,133
between the river 
and the groundwater.

1269
00:49:32,333 --> 00:49:33,833
We found in Sullivan 
and Carpenter Creek

1270
00:49:33,933 --> 00:49:37,200
that about 20% to 30% of the 
chemical ends up in this river,

1271
00:49:37,300 --> 00:49:38,900
in the hyporheic zone,

1272
00:49:40,133 --> 00:49:42,566
and then it comes back 
out again, slowly.

1273
00:49:42,666 --> 00:49:45,666
And so we think what happens 
in the hyporheic zone

1274
00:49:45,766 --> 00:49:47,366
biodegradation could 
be really important

1275
00:49:47,466 --> 00:49:49,633
because it's staying 
in the sediment longer.

1276
00:49:49,733 --> 00:49:51,300
There's a lot of bacteria there.

1277
00:49:51,400 --> 00:49:52,933
That could be really important.

1278
00:49:53,033 --> 00:49:54,366
And so this is something

1279
00:49:54,466 --> 00:49:57,200
that we're really interested 
in finding more about.

1280
00:49:57,300 --> 00:49:59,200
But at the end of the 
day, the chemical,

1281
00:49:59,300 --> 00:50:00,700
most of it is gonna come out

1282
00:50:00,800 --> 00:50:02,733
and it's gonna end up 
in the Great Lakes.

1283
00:50:02,833 --> 00:50:06,066
And even in the large systems, 
like the Manistique River,

1284
00:50:06,166 --> 00:50:08,433
they're adding chemical 
pretty much up to the mouth

1285
00:50:08,533 --> 00:50:10,566
of where the river 
hits the Great Lakes

1286
00:50:10,666 --> 00:50:12,733
'cause they wanna keep that 
concentration constant.

1287
00:50:12,833 --> 00:50:14,200
They wanna make sure

1288
00:50:14,300 --> 00:50:17,200
no sea lamprey like sneak 
up back in, basically.

1289
00:50:17,300 --> 00:50:19,866
So a lot of the chemical does 
end up in the Great Lakes.

1290
00:50:19,966 --> 00:50:20,866
And there, I think, actually,

1291
00:50:20,966 --> 00:50:23,000
photo degradation is important.

1292
00:50:23,100 --> 00:50:25,833
And there's a couple 
reasons for that.

1293
00:50:25,933 --> 00:50:29,266
First of all, the, well 
there's a bunch of reasons.

1294
00:50:29,366 --> 00:50:32,133
So if the lake is stratified 
and the chemical stays

1295
00:50:32,233 --> 00:50:35,700
in the top of the water, the 
water is much more clear.

1296
00:50:35,800 --> 00:50:37,933
So sunlight is gonna 
go a lot deeper.

1297
00:50:38,033 --> 00:50:39,033
And then the residence time,

1298
00:50:39,133 --> 00:50:40,266
so the amount of time water

1299
00:50:40,366 --> 00:50:42,266
stays in the Great Lakes 
is a really long time.

1300
00:50:42,366 --> 00:50:43,933
So they're gonna have 
a lot more chance

1301
00:50:44,033 --> 00:50:45,233
to be exposed to sunlight.

1302
00:50:45,333 --> 00:50:48,166
And so this is something 
I'd be really interested in.

1303
00:50:48,266 --> 00:50:49,400
I don't know the answer

1304
00:50:49,500 --> 00:50:51,800
and I would really like 
to go out and do this,

1305
00:50:51,900 --> 00:50:53,733
but I think that's probably 
gonna be really important

1306
00:50:53,833 --> 00:50:56,400
and I think what we learned as 
far as the degradation rates

1307
00:50:56,500 --> 00:50:57,933
and the transformation 
products are really important

1308
00:50:58,033 --> 00:50:59,266
for thinking about 
what actually happens

1309
00:50:59,366 --> 00:51:00,800
out in the Great Lakes.

1310
00:51:01,800 --> 00:51:03,533
And so I'm gonna wrap up there.

1311
00:51:03,633 --> 00:51:05,333
A very nice, wordy 
slide to sum it up.

1312
00:51:05,433 --> 00:51:08,700
But basically what we 
learned was that degradation

1313
00:51:08,800 --> 00:51:10,600
by sunlight to these two 
chemicals can be important

1314
00:51:10,700 --> 00:51:12,333
under some conditions.

1315
00:51:12,433 --> 00:51:15,400
We know a lot more about how 
water chemistry affects it,

1316
00:51:15,500 --> 00:51:16,633
and we found that pH,

1317
00:51:16,733 --> 00:51:19,133
the acidity of the water 
was really important.

1318
00:51:19,233 --> 00:51:20,833
We found that TFM goes away

1319
00:51:20,933 --> 00:51:23,200
much more quickly 
than niclosamide.

1320
00:51:23,300 --> 00:51:25,433
I wouldn't expect to see 
niclosamide photo degradation

1321
00:51:25,533 --> 00:51:27,300
in a tributary ever.

1322
00:51:27,400 --> 00:51:29,500
It's really gonna be very slow.

1323
00:51:29,600 --> 00:51:31,100
And then we also found out

1324
00:51:31,200 --> 00:51:33,300
that once the 
chemicals do degrade,

1325
00:51:33,400 --> 00:51:34,966
they form chemicals 
that are gonna be

1326
00:51:35,066 --> 00:51:36,300
less harmful for 
the environment,

1327
00:51:36,400 --> 00:51:39,066
which I think is a really 
important thing to consider.

1328
00:51:40,466 --> 00:51:43,266
Yeah, we relied a lot on 
modeling to sort of predict

1329
00:51:43,366 --> 00:51:46,433
how important this 
process is gonna be.

1330
00:51:46,533 --> 00:51:49,200
And then, thinking about 
hyporheic zone storage

1331
00:51:49,300 --> 00:51:51,533
as well as what happens in 
the Great Lakes themselves

1332
00:51:51,633 --> 00:51:54,566
is really important for 
looking out in the future.

1333
00:51:54,666 --> 00:51:56,733
And so I want to end 
with this picture.

1334
00:51:56,833 --> 00:51:59,266
I took this picture in one of 
the Fish & Wildlife trailers.

1335
00:51:59,366 --> 00:52:01,533
So that's the enemy, 
the sea lamprey.

1336
00:52:01,633 --> 00:52:03,533
And thank you all again 
for your attention.

1337
00:52:03,633 --> 00:52:05,466
I'm happy to take any questions.

1338
00:52:05,566 --> 00:52:06,633
Thank you.

1339
00:52:06,733 --> 00:52:09,500
(audience applauds)