CHEMICAL INTEGRITY IN THE GREAT LAKES
November 29-30, 2005
CONFERENCE PROCEEDINGS
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Table of Contents
INTRODUCTION 5
WhatisSOLEC? 5
What is Chemical Integrity? 5
Chemical Integrity Monograph 5
SUMMARY OF CHEMICAL INTEGRITY PLENARY PRESENTATIONS 5
What is chemical integrity? (Brian Eadie, National Oceanic and Atmospheric Administration, Great Lakes
Environmental Research Laboratory) 5
Naturally-occurring chemicals in the Great Lakes basin - Part 1 (Peter Richards, Heidelberg College) 6
Naturally-occurring chemicals in the Great Lakes basin - Part 2 (Joseph DePinto, LimnoTech Inc.) 6
Anthropogenic chemicals in the Great Lakes basin - Part 1 (Daniel Hryhorczuk, University of Illinois at Chicago) 6
Anthropogenic chemicals in the Great Lakes basin - Part 2 (Scott Brown, Environment Canada - National Water
Research Institute) 6
Assessing chemical integrity in the Great Lakes basin (Keith Solomon, University of Guelph) 6
CHEMICAL INTEGRITY BREAKOUT SESSIONS - DAY 1 7
Naturally-Occurring Chemicals - Sessions 1 & 2 7
Anthropogenic Chemicals - Session 1: What Do We Know? 10
Anthropogenic Chemicals - Session 2: What Do We Need to Learn? 11
CHEMICAL INTEGRITY BREAKOUT SESSIONS - DAY 2 13
Naturally-Occurring Chemicals - Session 3: Key Issues and the Path Forward 13
Anthropogenic Chemicals - Session 3: Key Issues and the Path Forward 15
Summary Thoughts (Murray Charlton) 19
Anthropogenic Chemicals 19
APPENDIX A - WORKSHOP AGENDA 21
APPENDIX B - SOLEC 2006 DRAFT AGENDA 25
APPENDIX C - WORKSHOP ATTENDEES 29
APPENDIX D - PLENARY PRESENTATIONS 33
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Please note: Many of the statements included in this summary are the opinions of the individual participants and are not
necessarily those of the federal governments of Canada and/or the United States of America.
INTRODUCTION
What is SOLEC?
The State of the Lakes Ecosystem Conferences (SOLEC) are hosted by the U.S. Environmental Protection Agency and
Environment Canada on behalf of the two countries. These conferences are held every two years in response to a reporting
requirement of the binational Great Lakes Water Quality Agreement (GLWQA). The conferences are intended to report
on the state of the Great Lakes ecosystem and the major factors impacting it, and to provide a forum for exchange of this
information amongst Great Lakes decision-makers. These conferences are not intended to discuss the status of programs
needed for protection and restoration of the Great Lakes basin, but to evaluate the effectiveness of these programs through
analysis of the state of the ecosystem. The goal of the conference is to provide information to people in all levels of
government, corporate, and not-for-profit sectors that make decisions that affect the Great Lakes and through this to
achieve the overall purpose of the GLWQA, "to restore and maintain the physical, chemical and biological integrity of
the Great Lakes Basin."
These conferences are a culmination of information gathered from a wide variety of sources and engage a variety of
organizations. In the year following each conference, the Governments prepare a report on the state of the Great Lakes
based in large part upon the conference process.
What is Chemical Integrity?
The following definition was proposed in the Chemical Integrity Workshop during SOLEC 2004:
"Chemical Integrity is Integrity is the capacity to support and maintain a balanced,
integrated and adaptive biological system having the full range of elements and processes
expected in a region's natural habitat. "
The purpose of this session was to facilitate planning for SOLEC 2006. This session considered the state of science on
chemical integrity, the relationship between chemical, physical and biological integrity, and the research that is currently
being performed or planned for the future.
Chemical Integrity Monograph
SOLEC organizers are in the initial stages of developing a monograph on the subject of Chemical Integrity. This book
will be comprised of a series of contributed papers. If possible, papers for each of the topic areas that were explored at the
Chemical Integrity Workshop will be included, as well as some topics for which there was not enough time for discussion.
Each paper would review the published literature and summarize our current state of knowledge, i.e. What do we know
about a specific chemical? What don't we know but would like to know? What are known or potential impacts from this
chemical on the environment in the Great Lakes basin? What known or potential impact does the chemical have on
human health in the basin? Each paper should also explore research and monitoring needs and management implications,
i.e. What are the messages to managers? What are the recommended actions? What should we do about the situation, if
anything? Draft papers may serve as reference information for SOLEC 2006, and they would be formally submitted for
publication following the conference.
Co-authors are desired for each paper, particularly from 2 or more sectors, e.g., industry, government, environmental
organizations, and academia, to help ensure a balanced presentation of status and issues. Consensus is not expected on all
topics, but all pertinent issues should be raised. Disagreement on a subject may be the message itself.
SUMMARY OF CHEMICAL INTEGRITY PLENARY PRESENTATIONS
Presentations are posted online at: http://www.epa.gov/glnpo/solec/solec 2006/presentations/index.html
What is chemical integrity? (Brian Eadie, National Oceanic and Atmospheric Administration, Great Lakes
Environmental Research Laboratory)
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Brian Eadie discussed issues related to chemical integrity, including: persistent bioaccumulative toxic chemicals (PBTs)
are declining but their presence still results in fish consumption restrictions/advisories; phosphorus is increasing in the
central basin of Lake Erie and nitrogen is increasing everywhere; and chemical contaminant concerns in Areas of Concern
(AOCs). Dr. Eadie provided suggestions for topics to cover regarding chemical integrity including, but not limited to:
impacts of pharmaceuticals and climate change, aging infrastructure of sewage and water treatment facilities, recruitment
and retention of younger Great Lakes scientists, constituent loads (including tributaries and global loads), and modeling.
He also suggested improving risk assessment tools and using satellite imagery to assist with better defining at chemical
integrity.
Naturally-occurring chemicals in the Great Lakes basin - Part 1 (Peter Richards, Heidelberg College)
Peter Richards discussed trends in water quality in Lake Erie's U.S. tributaries, e.g., general improvements for most
parameters in most rivers during 1975-1995; worsening conditions in total phosphorus, dissolved reactive phosphorus,
and total kjeldahl nitrogen since 1995 with an inflection point between 1993 and 2000; and mixed results for nitrate. He
also discussed the recent increases in the percentage of phosphorus that is dissolved, and the fact that total nitrogen, total
phosphorus, nitrate, and dissolved reactive phosphorus are decreasing or are at stable levels. He stated that the causes for
some of these trends could be changes in weather, population growth and exurbanization, concentrated animal agriculture,
and global climate.
Naturally-occurring chemicals in the Great Lakes basin - Part 2 (Joseph DePinto, LimnoTech Inc.)
Joseph DePinto discussed the chemical integrity of naturally-occurring substances in the Great Lakes. He explained that
ecological integrity cannot be achieved simply by managing chemical integrity, but that physical and biological integrity
have to be incorporated. He indicated that we cannot understand chemical integrity in an ecological vacuum, but instead
must understand the ecosystems' feedback mechanisms to define the boundaries of chemical integrity. Ecosystem
integrity cannot be achieved by managing single issues independently of understanding interactions with other
management issues, but instead requires coordinated modeling, monitoring, and research programs. He concluded with
saying that if we have learned anything over the last 30 years, it is that we need a Great Lakes Basin Ecosystem
Agreement.
Anthropogenic chemicals in the Great Lakes basin - Part 1 (Daniel Hryhorczuk, University of Illinois at Chicago)
Daniel Hryhorczuk discussed persistent toxic substances in the Great Lakes basin, including heavy metals and polycyclic
aromatic hydrocarbons, and chemicals of emerging concern, such as PBDEs. Key findings included elevated body
burdens of contaminants in persons who consume large quantities of Great Lakes fish; developmental deficits and
neurological problems in children of some fish-consuming parents, endocrine dysfunction among fish eaters; and
disturbances in reproductive parameters. Dr. Hryhorczuk summarized some recent human health studies regarding fish
consumption versus contaminant levels, children's growth and development, endocrine disruption, and reproductive
health. In one study, Windsor, Ontario, ranked the highest of 17 Canadian AOCs for selected health points. He ended his
talk with an overview of some of the known effects of emerging chemicals of concern, such as PBDEs.
Anthropogenic chemicals in the Great Lakes basin - Part 2 (Scott Brown, Environment Canada - National Water
Research Institute)
Scott Brown provided an overview of anthropogenic chemicals including a review of the history of beneficial use
impairments in AOCs. The good news is that many deleterious effects on wildlife and fish have been recognized in recent
decades and some have been mitigated, e.g. the return offish-eating birds populations to the Lake Ontario basin. Dr.
Brown reviewed the most recent data on wildlife and fish health effects in the AOCs, e.g., benthic and pelagic fish,
snapping turtles, herring gulls and mink, and found that health changes are detectable, with effects mostly found at sites
near AOCs. Early Mortality Syndrome (EMS) has been observed between hatch and first feeding in Great Lakes
salmonids. EMS is a symptom of degraded ecosystem and its presence emphasizes the need to maintain biodiversity.
Other effects include sporadic blue-green algae blooms and botulism outbreaks.
Assessing chemical integrity in the Great Lakes basin (Keith Solomon, University of Guelph)
The closing plenary presentation, given by Keith Solomon, explained how to assess chemical integrity in the Great Lakes
basin. He stated that in order to make this assessment, we must identify chemicals of concern as well as sources. We also
need to assess the effects above the level of the organism and assess the risks of chemicals of concern; we cannot simply
rely on traditional tests with traditional endpoints. He concluded by stating that dealing with mixtures is complex and
whole effluent testing offers advantages.
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CHEMICAL INTEGRITY BREAKOUT SESSIONS - DAY 1
Naturally-Occurring Chemicals - Sessions 1 & 2
Mercury
What Do We Know?
What Do We Need to Learn?
There are 3 forms in the environment; elemental,
methyl, oxidated
Sources are widespread
Smokestacks are a significant source of
atmospheric input
There is mercury in zebra mussel tissue
There are no wildlife consumption guidelines so we
don't know if anyone has looked at this
Mercury does trigger fish consumption advisories -
it's a human health issue
o
o
We need to make an assessment about what the
largest mercury contributors are and whether
addressing local issues will be enough. We need to
determine the amounts being deposited from
global, regional and local sources.
We need a better understanding of the mechanisms
of how mercury changes form in the environment.
We need to know how to lower fish consumption
advisories
What are the sources of bio-available mercury,
where are they, and can we remediate?
Can we look at changes in diatom communities
(this is difficult) in sediment cores to determine an
environmental baseline?
We need to keep looking for potential sources.
We need to research nearshore affects in addition to
open lake.
We need to research affects on fish behavior and
wildlife.
Phosphorus
What Do We Know?
What Do We Need to Learn?
We are able to control it.
We have made good decisions about controlling
loads and concentrations beginning in the 1970s,
but are they still good decisions?
We know the life histories of Great Lakes fish
depend on pulses in phosphorus levels. 80% of the
phosphorus loads to Lake Erie occur in 20% of the
year.
There is variability in phosphorus concentrations
by region, lake and season.
The season that the pulse occurs is significant. Late
summer fish production is determined by
phosphorus cycling.
Over the long term, phosphorus is a lake-specific
issue.
In Lake Erie, the sediments are closely coupled
with the water column. Because the Lake is
shallow, the phosphorus is redistributed more
quickly.
Residual phosphorus being recycled is a concern
and tied to tributary sources.
Residual phosphorus is lake specific.
Phosphorus is controlled from point but not non-
point sources.
Target loadings and endpoints
We don't know whether the decisions
made in the 1970s about acceptable levels
are valid today with a changed ecosystem.
Are our decisions about target levels,
which were based on what we were
looking at then, still valid today?
What are appropriate loads by watershed?
How are we going to pick desired
endpoints?
Bioavailability of phosphorus
We don't know whether it is important to
look at proportions of soluble to total
phosphorus. The soluble portion has been
increasing recently.
We don't know about changes in
bioavailability.
We need to research total and soluble
phosphorus in this new environment.
Environmental fate and loadings
Naturally occurring pulses - do we know
about them? We don't know whether we
have changed the phosphorus pulses.
We need to look at phosphorus on a
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Phosphorus
What Do We Know?
What Do We Need to Learn?
Tributaries are the largest sources, whereas in the
past the largest sources were municipal.
In Lake Erie there has been a reduction in non-
point source loads.
In the Maumee River there are not enough point
sources upstream to account for the phosphorus
load. Some is from non-point sources.
We have good information on how hydrology of
the system affects phosphorus loads.
watershed by watershed basis because the
mechanisms making phosphorus available
to aquatic systems are unique to each.
How is the residual phosphorus in systems
recycled and then eventually sequestered?
No model now exists that deals with
nearshore vs. offshore loading.
Round out SOLEC reports so we
communicate the difference between
offshore and nearshore loads, including
tributaries.
Monitoring issues
We need to look at a finer scale to
determine whether phosphorus levels are in
balance.
Are we monitoring enough of the
watershed and the correct sites to get
accurate results?
Storm drainage, aging infrastructure, etc.,
are not monitored, and we need to
determine if they are contributors.
What is the accuracy of the monitoring
networks that are in place? Do we need to
change, increase frequency of monitoring,
etc.?
We need better phosphorus data from
Canada and Michigan. Concentrations in
tributaries may have been measured but
have not been made available.
We need to focus on regulations for non-point
sources.
Bio-toxins - Cyanobacteria
What Do We Know?
What Do We Need to Learn?
We know that we are measuring high
concentrations that cause issues in drinking water
and wildlife.
Chlorophyll is one measure or part of the measure
of photosynthetic capacity but it doesn't give you
biomass.
Human ingestion of algal blooms promotes tumors
and affects the liver.
Less than 20% of water treatment plants remove
microcystins. This requires tertiary treatment.
Occurrence in the environment
We do not know which species is making
the toxins, and it is different in every
basin.
We don't know how it is getting into the
system or whether this is a natural
phenomena.
What is a bloom? There is no accepted
definition. What promotes an algal
bloom and what promotes toxin
production?
What are the factors of bloom formation
from one species to another?
Need to know the taxonomy of
algae/phytoplankton, not just
chlorophyll type and amount.
Monitoring and measurement
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Bio-toxins - Cyanobacteria
What Do We Know?
What Do We Need to Learn?
We need a finer scale analysis of the
problems and integrated monitoring.
There may be a bias in how we are
measuring the toxins.
A phosphorus level of 20 micrograms/liter
and increasing precedes a bloom. We
need an early warning indicator. There
is no predictive measure right now.
Human health effects
We need human health, epidemiological
studies about acute and chronic toxicity.
We may not have established a maximum
acceptable contaminant level in the US for
microcystins. There are questions about
exposure for humans. Do we know
exposure levels
What are the effects of small exposures for
long periods of time
We need to establish basic understanding
of exposure routes.
Nitrates
What Do We Know?
What Do We Need to Learn?
o Once it is in the system, it is there for good.
Prevention is preferred.
o At most environmental levels it is not toxic, but it
is soluble.
o 75-80% of total nitrogen is nitrates in tributaries
o It does present problems in groundwater. It is
being monitored in Ontario and maybe in
Michigan, but not regularly in the US
o Municipalities test for it in drinking water
o 10 mg per liter is the guideline for nitrates and 1
mg for nitrites in the US for drinking water
o Nitrate concentrations are going up in all the lakes.
o Lake Superior paper from 1970 sites an increase
over the last century.
o Loading is increasing since phosphorus is
decreasing.
o The sources of nitrates are acid rain, Concentrated
Animal Feeding Operations (CAFOs), sewage
treatment plants, (correlations exist between nitrate
increases and the amount of it sold for fertilizers.
The Lake Superior basin is not predominantly
agricultural, so the source of the increase in Lake
Superior might be acid rain.)
o Management tradeoff between phosphorus in
sediments and nitrates
Presence, fate and transport in the environment
We do not fully know the nitrogen
transformations in the system, i.e., the
nitrogen cycle.
We do not know why concentrations are
changing. Is it still an issue?
We need to know where the main inputs
are and how much is coming in before it
gets diluted.
What is the extent of internal loading
through nitrification of sediment? What is
the ratio of nitrate to nitrogen gas?
Is agriculture a major source? (Corn and
soybean production have increased in the
basin)
Effects on human health
Our knowledge of human health dietary
impacts are incomplete.
Environmental effects
Are nitrates affecting the hatchability of
fish eggs close to storm sewer outlets?
What effects are there on certain species?
What effects are occurring at wetland (or
other systems) vegetative margins? Could
increases in nitrates be explaining
population shifts of some species?
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Ammonia
What Do We Know?
What Do We Need to Learn?
o This form of fixed nitrogen is released by biota in a
nitrogen cycle.
o Fish are sensitive to un-iodized ammonia.
o There have been Green Bay beach closures because
of toxic ammonia levels.
o In most areas, concentrations in the water are at or
near detection limits.
o Concentrations are not high in tributaries unless
there is a local point source
o There are still incidences of where ammonia may
affect algal growth.
o Where are the major sources of ammonia in the
watershed, e.g. sewage treatment plants?
Chloride
What Do We Know?
What Do We Need to Learn?
o
o
This is an indicator of anthropogenic impact on the
ecosystem
It naturally existed at 1 mg per liter, but now
concentrations are much higher
There is an argument that an increase in chloride
concentrations may provide a friendlier
environment for [marine] species to acclimate to
fresh water.
There has been a decrease in chloride
concentrations in the Lower Lakes.
The last studies were from the 1970s.
750 stormwater ponds are sequestering brackish
water. Late-1990s Toronto studies are raising
concerns because brackish water is coming into
sensitive areas
True marine organisms would not survive with
these levels, only brackish creatures.
What are the ecological impacts of increased
chloride concentrations?
We don't know what the cumulative impacts might
be basinwide. We need to revisit because the data
are 30 years old.
We should look at loading issues and salt chloride
relationships.
Are there issues of cross contamination in aquifers
of brine?
Is sodium a limiting nutrient for blue-green algae?
Anthropogenic Chemicals - Session 1: What Do We Know?
Presence of anthropogenic chemicals in the Great Lakes basin
o Discussion included the definition of what we mean by "what do we know?" Full certainty is not possible, but we
have strong evidence about certain classes of chemicals.
o We need to be discussing actual constituents of all of these chemicals; and not just the classes of chemicals.
o Sources of Contaminants
Waste water effluent is a source of emerging contaminants and we have not typically looked at waste
water for legacy contaminants.
There are data about emerging compounds that we can consult from studies conducted outside the basin.
Groundwater contains radon and arsenic
We know some sources of contaminants (for example, mercury) are long-range. Regulatory action
outside of the Great Lakes basin is needed.
"New" sources of chemicals are not being monitored
o Regarding the "dirty dozen" (legacy chemicals)
See Binational Toxics Strategy documentation for more information. A lot of research has been done on
these contaminants.
We have the data to show downward trends but they are still present in the environment, even after events
such as the banning of DDT.
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Are the current regulations sufficient? If consensus is that they are sufficient, then why are we still
addressing issues associated with these contaminants in the environment?
Regulation does not equal virtual elimination.
o Modeling
We can predict/model contaminant presence and trends before we measure them in the environment (this
is true for some, not all)
We need better models and the data to input into the models.
Observed or potential impacts on Great Lakes ecosystem health
o The highest priority contaminant class to be focused on in terms of input and quantity should be PBDEs
Their toxicology is unknown
Sediment cores show exponential increases in the 1990s
Are we lacking data about trends of contaminants in the sediment?
o Observed feminization in fish and amphibians. Fish are functioning differently but complete feminization is not
evident. Are there ecosystem effects though? No effects have been documented on Great Lakes function.
o Perfluorinated Compounds (PFCs) are persistent in the water column.
Is this a worse problem than persistence in the sediments?
o Wildlife are recovering from known legacy contaminants since environmental concentrations of POPs have
decreased.
o It is unknown as to whether wildlife are recovering from chemicals of emerging concern. One theory is that the
"new" chemicals are not as "bad" as the legacy contaminants.
Observed or Potential Impacts on Human Health
o We know that a healthy ecosystem is important to maintain healthy people.
o It is harder to detect trends in human health because concentrations of some toxic chemicals are decreasing in the
environment (see Daniel Hryhorczuk's talk). Therefore, should we now focus studies on fetal exposure AND
specific times during people's lives when they are more sensitive to exposure, i.e. study PCB levels of people
born in the 1950s or teenagers going through puberty? There are many potential confounding factors. (A study
would need archived cord blood or archived breast milk samples to be rigorous.) Current exposure might not be
the important exposure to focus on and larger populations need to be surveyed in the future.
o Some members of the discussion group claimed we know little about direct exposures of mercury on human
health in the Great Lakes basin; others claimed that we do know that there are direct effects of mercury exposure
(via consumption of Great Lakes fish) on human health when a certain does is ingested. This statement was
challenged by some members who stated we do not have data to support this claim. It was agreed that we think
we know that there is some sort of problem from eating Great Lakes fish and that the government is using the
advisories in an attempt to inform the public about the situation and potential impacts. The existence offish
consumption advisories does not mean that exceeding the advice will result in an impact. Some believe that most
people don't eat Great Lakes fish (as most fish purchased in supermarkets comes from other locations) and
therefore the contamination is not from these fish but from air emissions.
o The health of the general population in the Great Lakes basin is based on life expectancy. Since life expectancy in
the Great Lakes basin has increased over the years, it can be inferred that the health of Great Lakes basin residents
is also improving/increasing. However, we know very little about actual chemical exposure from the Great Lakes
and the health impact on basin residents.
This trend could also be due to better health care.
To make this claim, we need to separate fish ingestion from exposure to other media.
Overall population health is not a good indicator for certain at-risk populations that consume a lot of fish.
Studying subsets of populations is the key. We can't generalize across the Great Lakes basin regarding
exposure.
The Great Lakes basin is contaminated from a lot of different sources. Accumulation of contaminants [in
humans] does not occur primarily via fish consumption.
Anthropogenic Chemicals - Session 2: What Do We Need to Learn?
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o There is a need to determine what is in the lakes in terms of chemicals, what the effects of these chemicals are and
what are the risk assessment paradigms with respect to these chemicals working synergistically. There is a
difference between documenting the presence of chemicals and risk assessment.
o The trends, sources, loads, etc for each chemical is important information that needs to be determined.
o We need to know more about the "mixture" or synergistic effects of these chemicals and the impacts on the
ecosystem and human health.
o Need to develop a priority list of chemicals that need to be addressed. We cannot look at every chemical being
used, but we can develop a list of priority chemicals to look at and research.
o The list of chemicals [presented to the workshop] is not accurate as it stands now.
o Need to learn how to categorize these chemicals. For example, in Canada the Domestic Substance List is under
review. PBT properties, risk assessments, management action required and data gaps for these chemicals are
being identified. Chemicals with unknown information are also being included on this list.
o Endpoints. SOLEC was never given the charge to determine and set endpoints. Endpoints help to determine
whether management action or programs are working or need to be modified. Since the Great Lakes Water
Quality Agreement will be under review, the issue of a lack of endpoints for the Great Lakes indicators should be
brought forward as a discussion item that needs to be addressed during this review process.
o Need timeframe to meet endpoints.
Presence in the Great Lakes watershed
o SOLEC reports on a small percentage of compounds - consider expanding the list.
o Chemicals that are or should be added to the list are below. The comments related to each chemical can often
apply to one or more classes of chemicals in the list.
Pharmaceuticals (including SSRIs)
Other countries have conducted risk assessment studies on pharmaceuticals. No harmful effects
were detected.
No studies showed health impacts by pharmaceuticals.
USGS conducted a study regarding pharmaceutical products in water supply.
Non-prescription drugs (use is completely unknown)
Legacy contaminants
Mercury - global transport and in basin sources are both sources of mercury
PBDEs
More exploratory work is needed, more analytical methods are needed.
Fish consumption in the Great Lakes is not the main route of exposure for PBDEs in humans
(currently).
There are data showing PBDEs are increasing exponentially in rainbow smelt.
The longer we continue to use PBDEs, this risk could increase.
We need to prevent PBDEs from entering the food chain.
Pesticides - global and in-basin sources are both sources of pesticides.
Polymers (brominated) - breakdown rate in the environment is unknown
Agricultural chemicals (registered and veterinarian drugs) - screening needed in agricultural and urban
areas as there is a time lag between emissions and absorption by fish. Temporal trends are needed. Need
tissue samples and archives to determine temporal trends.
Nanomaterials - not easy to monitor, ubiquitous, non-biodegradable, pass through membranes,
bioconcentrate
Perfluoride compounds - breakdown rate in the environment is unknown
Leachate from landfills
Surfactants (alkyl phenols)
Metabolites of hormones, pharmaceuticals, mirex, atrazine, etc.
Water effluent
Metals - naturally occurring but when chemical reactions occur, they can change their structure and
speciation - free metal ions (Ca and Mg)
Personal Care Products (PCPs)
Antibacterial surfactants in PCPs are causing bacterial resistance.
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These bacteria might not survive in the environment (studies show survival in the lab but not in
the field).
Endocrine disrupters - Many chemicals comprise this group; "endocrine disrupters" are an endpoint
classification
Androgenic and estrogenic-mimicking compounds
These compounds can cause the effects attributed to endocrine disrupters.
Estrogen sources can be from farm animals, agriculture, chemicals, etc.
Musks
Carcinogens and mutagens
Road salt (anti-slip agents)
Impacts on Great Lakes basin ecosystem function
o A contaminant concentration that may not be high enough to pose risks to humans could cause risk to aquatic
biota. Do we know or not know this?
o General statements about ecosystem function
We know that at high concentrations and exposures of certain chemicals, there are toxicity impacts on
ecosystem health and function and effects on organism reproduction. Inhibition of lake trout reproduction
(in the past) is an example.
"Critter level" impacts apply to populations, not individuals.
Ecosystem effects definition needs to include the spatial scale and area affected.
If you don't know if there is an impact, can you say that there is ^.potential impact?
Keep in mind that just because there is a risk, it doesn't mean that there is a problem.
There are regulations in other nations for some of these chemicals. We might not need to reinvent the
wheel.
o How do we move into risk management? What is the expectation of where we are going?
Summary of what we need to learn
o Need to be vigilant because we have done a lot of work on chemicals to get where we are today. Learn from this
process and react quicker next time. For example, human population growth and vehicle miles traveled are
important indicators of an increase in the release of PBDEs, therefore the trends in usage/emissions need to be
considered.
o If we aren't finding problems, then do we assume that the issues do not exist or do we need to look harder?
o We have improved methods to detect chemicals, but still need to determine endpoints so that progress towards a
goal can be measured..
o Need more money so research can continue, especially long-term monitoring.
o Need to expand the list of compounds being reported on.
CHEMICAL INTEGRITY BREAKOUT SESSIONS - DAY 2
Naturally-Occurring Chemicals - Session 3: Key Issues and the Path Forward
Need studies/research about the systems/parameters.
o The nearshore is the center of most problems.
o We need to assess loadings into the lakes by tributary.
o What are the interactions of nutrients in ecosystem function? We need to assess functional approaches,
productivity, biomass, growth rates within systems.
o We need accurate information about primary production
Need risk assessments and cost benefit analyses to prioritize what to study further and monitordecisions need to be
based on agreement by scientists and managers.
Need long term monitoring of parameters that have been prioritized.
o In general, we need long term monitoring on all naturally occurring chemicals.
o We need monitoring on radon/arsenic/nutrients.
o Restore long term monitoring to tributaries.
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o Expertise is lost when you lose monitoring years. Then there is no message.
o We need more atmospheric deposition monitoring, especially for mercury.
o Measure the right things. Take into account "Type 3" questions (what are we really looking for?).
o Increase replication not duplication.
o We don't know what the future is, therefore long term monitoring is essential.
o Long term monitoring is undervalued by agencies.
o Long term monitoring needs to be better coordinated between Environment Canada and EPA. If methods differ
but results are similar, that is ideal.
o Data can be shared through the monitoring inventory on binational.net.
o Unrealistic expectations about binational monitoring coordination may actually provide a check and balance in the
long term.
o Monitoring can be opportunistic, e.g., vessels on the lakes can measure more than one thing at a time.
o Nearshore monitoring is expensive but necessary.
o We need indicators for mass balance and rate of accumulation of phosphorus (e.g., lawn care, fertilizers, urban
areas, groundwater, inland lake eutrophication, feed lots).
Need to inhabit appropriate models with data from the studies and monitoring
o We need data on all naturally occurring chemicals for the models.
o We need models that are hypothesis driven.
o We need to be able to parameterize the models.
o Previous models aren't appropriate today due to invasive species and loadings.
o Models need to be holistic enough to include the entire food web.
o We need wetlands and riverine modeling.
Need to determine bounded endpoints based on science for those parameters that are important or prioritized.
Manage systems based on the studies, monitoring, and models. This requires communication.
o Laws exist for arsenic but not for phosphorus, which is just as important.
o Monitoring is useless unless it becomes information and is shared.
o Coordination and management needs dollars and people. Funding requirements need to be well stated and
directed at the appropriate agency. A contingency fund for unexpected problems needs to be included in cost
estimates.
o Agricultural systems are primarily voluntary. Therefore, we need a watershed approach and additional
information for managers regarding best management practices.
o Managers need to understand the importance of letting researchers meet and talk.
o Researchers need to talk frequently with environmental managers about problems and needs (e.g., Lake Erie
Millennium).
o We need to inform managers about connection between groundwater, nearshore, and open lake.
o We need to get information out there on a constant basis. We need to be more articulate.
o NEMO (non-point education for municipal officials) is a model we should look at.
This is a continuing process requiring vigilance.
o It will be necessary to continue long term studies, modeling, and monitoring, because while we will solve some
problems, new ones will emerge.
o Each Lake needs to have an equivalent of the Lake Erie Millennium group.
Summary
o Long term assessment programs need to be maintained.
o Old models need to be revamped because of changes in the system. We need models to integrate what we are
learning, so we better understand the system. How serious is this for decision making?
o Researchers need to be funded to share information and to keep flinders' concerns in mind.
Make better use ofbinational.net.
There is a need for researchers to talk. Establish a Millennium-like equivalent for each lake.
Maintain adequate and consistent funding.
Translate information and present it to managers.
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Anthropogenic Chemicals - Session 3: Key Issues and the Path Forward
Priority Chemicals List
o Find a process to identify and prioritize these chemicals and processes. This could be a useful piece for the
replacement of Annex 1 in the GLWQA. Current Annex is static and needs to be updated and revised.
o We need to identify the chemicals that we have consensus on and get the funding.
o Set aside chemicals that are not problematic. Perhaps we are including chemicals in the list that don't need to be
researched. However, it is a waste of resources looking at a very specific suite of chemicals just because they are
easy to measure.
o As we prioritize the list, we can remove chemicals during this process as well. Don't get caught up in making
lists. Don't be afraid to de-list. The removal of chemicals may show progress.
o Economic analyses: cost effectiveness / cost benefit analyses to be included in these prioritization approaches.
o Use the Domestic Substance List to identify existing chemical compounds and to assist with the development of
the priority chemical list for the Great Lakes.
Human Health Issues
o Finish the job on legacy contaminants. As long as there are fish consumption advisories, there is the perception
that there is a problem. Is there a reference or an endpoint?
o We need to be better at developing messages for the public. The public is very confused, for example, about
pesticide bylaws and advisories and whether or not they should use pesticides or eat fish from the Great Lakes.
Clear and concise messaging is needed.
o Trends in cancer rates are leveling out (incidences) except for lung and skin cancer. Refer to the Center for
Disease Control (CDC) website. There is a causal relationship between skin cancer and the sun and lung cancer
and smoking. If our drinking water was causing these things, we would see it.
o There are increased incidences of cancer rates in young people, increased cancer rates in non-smoking people,
etc., that are a result of multiple causes.
o We are dealing with a chemical soup in the environment. Epidemiology is associated with statistics that cannot
determine causality. We should not be encouraged to be able to identify one chemical that is hurtful from
epidemiological studies when exposure is to many chemicals.
o Epidemiological language may not be the best to use, but rather human health effects in response to chemicals,
not based on cancer endpoints, but rather neuro, renal results, etc.
o Studies in recent years show that thallium acts like methyl mercury. Sediment core studies from Switzerland show
neurotoxin issues similar to methyl mercury.
Ecosystem Health Issues
o There seems to be reduced interest in ecosystem health. Much money is going into human health, but not
ecosystem health.
o We need to legitimize the importance of ecosystem health and science.
o We should move towards a sustainable environment.
Remediation and Environmental Control
o Try to pull in economical analysis when determining priorities for Great Lakes remediation or other management
actions. Any prioritization that is done needs an economical assessment.
o There is a whole range of things [chemicals and issues] in the environment and we can't look at them all on the
same level. We need to focus on things now that can be addressed in the future. Managers want to get the most
"bang for their buck".
o We need to look at the things that need to be done (based on the priority chemicals list), evaluate the cost
effectiveness of different approaches, and then show the benefits of the most efficient approaches.
o Governments are spending millions on restoring the ecosystem. Sixty million dollars spent on sediment
remediation. Did it work? Governments need to go back and evaluate effectiveness.
o A timeline for Area of Concern (AOC) cleanup is needed.
Indicators and Endpoints
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o Legacy contaminants require endpoints and a timeframe for reading these endpoints.
o What are the human health indicators that we should be reporting on? What is it that you would like to see done
with the existing information?
o Reference toxicity values are not agreed to, i.e., no consensus, but if you look at metadata, you can look at trends
and see that things are happening.
o We have to worry about too high of levels [of chemicals], but also too low of levels. Does this come into play
with endpoints?
o The assessment of biological health is an indicator of chemical impairments. Linkage is needed with biological
and chemical integrity. Biological health can serve as a warning of chemical problems.
o When is clean, too clean?
Research Issues
o Research priorities need to be reviewed. Is the list in Annex 17 of the GLWQA still relevant? Where is the
research on climate change, energy sources, etc? Through the process of defining chemical integrity, there is an
opportunity to look at research agendas, and this could happen with the review of Annex 17. Use the messages
that are coming out of SOLEC (i.e. chemical integrity) and consider them very seriously in the review of the
GLWQA.
o There is a lot of tension when we talk about the effects on humans related to chemicals. Research is unclear, but
what is this tension conveying to managers? Epidemiological research is needed that is designed to be conclusive,
i.e., the right cohorts, right exposure. Ecosystem and human health work is not an epidemiological study. Health
effects are unclear, and scientists disagree. Federal governments have a responsibility to get this research done.
o Where do we need research? We should not use a fear approach because it is not sustainable. If we identify
unknowns that we are all trying to research, we may have more leverage to receive funding.
o Rather than referring to "environmental research," we should revise our lexicon to help focus more towards
"sustainability."
o Let us caution against "Type 3" errors, i.e., we think we know what we are looking for, but we are trying to
answer the wrong question. Are there ways to help recognize this error?
o We need more research on chemical mixtures (additive or synergistic effects)
o More university involvement in research occurring in the Great Lakes is needed.
Monitoring
o Continuing long-term data sets is important. We can't put all of the money into PCB research, but it is still
important to be able to look at PCB trends.
o The foundation for all of this [evaluating chemical integrity] is monitoring. It is our way of measuring our
successes and determining where problems are.
o The Council of Great Lakes Research Managers is trying to develop a monitoring strategy to compete for research
money.
o We can use many different approaches to additional research that is necessary, but we need to continue
monitoring. If all stakeholders communicate that we need to continue monitoring, then the chance of funding is
higher.
o There are issues concerning archiving environmental samples
We must create an archive tool for fish tissue and/or sediment NOW! There are chemicals that we don't
know about now that we will need to test for in the future.
The 30 year old archive offish tissue in Canada is threatened.
The fish archive in U.S. is held by U.S. Geological Survey, and every year the question is raised about
whether money is available to keep the freezers running.
We don't have a good mammal archive in Canada. We don't routinely store air, water and sediment
extracts.
Funding
o In terms of funding and research, we know what we need to do, but we need to identify who is doing this
research, i.e., we need a common research strategy and an overall funding program.
o There is no [centralized] fund in the Great Lakes to which researchers can apply for funding. There should be a
source for basin-wide, competitive, research funding. For example, IADN is run by a university contractor.
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o There are very large amounts of money being put into [Great Lakes research] that has nothing to do with
human/public health. Very little money is put into research to identify relationships between chemicals in the
environment and public health.
o Prevention is a very wise way of spending money. We have intervention programs that have been successful and
can translate into human health improvements and remediation. Perhaps we have not seen the human health
improvements because of time lags.
o An underlying theme for these points is the lack of money. Eco-evaluation is going on internationally. You
should care for the organisms because they need it, but money is one of the considerations that is looked at when
determining research.
o If this were your last chance to get funding for the future, what would you convey to managers?
o What does it mean when we say that 98% of our samples have "x" in it, but it may not be something that causes
harm. We can't use scare tactics to get research grants.
o There are many examples of a shortage of funding for Great Lakes research:
In many cases, research and monitoring budgets are either static or declining. The continuation of the
Canadian fish monitoring program is questionable.
Why are Diporeia declining? We came up with some good ideas, but where is the money going to come
from to determine why they are declining? Millions of dollars are needed for research.
Unless you have dead bodies, there is no political motivation to get funding for research.
A lot of environmental research has been "crying wolf for a long time. Now we need to show ways of
cost savings to get funding money.
Great Lakes Governance
o Taxpayers and politicians are overwhelmed and don't know what to pay attention to. We [stakeholders] may be
passionate about some issue, but it is not always an issue for government. How do you convey this message?
o Build in for SOLEC participants, how the governments are dealing with issues related to chemical sources that are
affecting the Great Lakes. There are mechanisms, but they are not well understood.
o Cost benefit analysis does not capture everything. We need adaptive management tools to take the cost benefit
analysis and make it relevant in the ecosystem.
o We have been successful with POPs (Persistent Organic Pollutants), because we ultimately came to a near
consensus decision that all stakeholders needed to work towards the same goal.
o A multi-stakeholder approach is needed, as well as being aware of public perception.
o The main messages from the U.S. Great Lakes Regional Collaboration included:
We need to finish the job related to existing problems (still need to reduce legacy contaminants) and be
aware of chemicals (grandfathered chemicals) that need to be tracked and reported
We need funding. We have a big job ahead of us to reduce existing chemicals in the environment.
o Specific agency challenges that lie ahead include:
U.S. EPA - GLNPO is sub-optimizing its monitoring program. Funding has been constant for years. To
monitor new chemicals requires trade-offs within the existing program to stay within budget.
Beginning in 2006, Environment Canada will be charged to use the LIMNOS, which they had used for
free in the past. No one has this cost included in their budgets.
Many Great Lakes scientists within Environment Canada are retiring, which will affect not only
Environment Canada but other Great Lakes institutions as well.
Communications and Reporting
o Defining Chemical Integrity
We need one definition of chemical integrity in the Great Lakes basin so everyone can work towards this
one definition. We want to make sure that there is a consistent message about what chemical integrity
means.
o Improving Communications with the Public
Things are getting better in the Great Lakes for the compounds that we are measuring. Where is this
information being provided to the public? Maybe those things aren't so bad, but what other things do we
need to be worried about? We need to do a better job of communicating the science.
We need to better communicate the status of certain chemicals in the Great Lakes which isn't going to
change quickly because of retention time. We still need to monitor those chemicals, but maybe our focus
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should change. How much effort do we put into tracking and reporting on these slowly-changing
chemicals ?-
How do you convey the message regarding human health issues? In the 1950s-1960s, the exposure to
anthropogenic chemicals was higher, but now the general population is living longer and leading healthier
lives. How do you compel the public to see that there is a health issue? Some of the chemicals that we
talking about in the system are also the drugs that are helping people live longer.
It is also important to communicate to the public about what contaminants we are NOT finding through
our monitoring programs.
We need to better report on the implications of trends of contaminants
o Getting press release attention from the Media
When we have a success, it should be blasted out to the public. Lack of media interest should not waylay
communicating good news to the public.
Success is a tough term. SOLEC can demonstrate where there have been successes, but what newspaper
will carry the message that a 98% reduction of loadings to the Niagara River has occurred? Someone else
needs to commend the government(s) for doing a good job, e.g., the Sierra Club might announce that the
government did a good thing.
You get media attention by putting key words in a press release, e.g., "DEAD ZONE" in Lake Erie.
SOLEC-related Comments from Workshop Participants
o What are the future trends? SOLEC is an opportunity to get some big issues into the arena in a multi-stakeholder
forum. For example, what is going to happen when we run out of oil? Will major restructuring be occurring?
What about climate change? Forecast the trends.
o SOLEC should not marginalize issues.
o As you think about SOLEC 2006 messaging, ensure that ecosystem function assessments are included.
Prioritization of issues such as lumps and bumps versus Diporeia is important.
o SOLEC is a process to evaluate the effectiveness of the programs. Therefore you need to monitor the effects of
the interventions. What has been spent on the Great Lakes in terms of monitoring to track improvements? You
may find that the money spent on monitoring is nothing compared to the money spent on remediation.
o For SOLEC Success Stories, try to identify local, state/provincial, and regional levels that have done something
successful. No one has recognized what the governments have done that has benefited industry, etc.
o The Binational Toxics Strategy group produced a good report on how reductions are happening. Maybe we need
to find a better way of reporting.
o If we believe that governments need to invest more money, then maybe SOLEC should invite keynote message-
givers who are not government staff, but are industrial representatives, ENGOs, etc.
o The public perceives that there is a strong link between the Great Lakes and human health impacts. SOLEC could
help focus the message around this strong perception, including research that is being conducted and the scientific
results that are available.
Summary of Main Messages to Relay to Decision Makers in the Great Lakes Basin
o Monitoring: long-term monitoring is essential. It is cheaper to monitor then remediate. Monitor ecosystem
function, not just human health impacts.
o Prioritization of chemicals is needed. We need consensus on the chemicals to monitor.
o Funding for research is needed.
o Endpoints are required for the Great Lakes indicators in order to see progress and successes.
o Messaging is important. We need to better communicate messages to the public, including success stories.
o Sustainability is a goal that we should be aiming towards.
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A summary flow chart of the components that are involved with assessing the state of the Great Lakes.
f
;,, ... CC OnOn-'C
Summary Thoughts (Murray Charlton)
Naturally-occurring Chemicals
o Nitrate and chloride loadings are out of control. Road salt is now a toxic chemical! Nitrate concentrations in
groundwater are now an issue.
o Phosphorus loading estimates have not been confirmed. Non-point loads may be increasing, but around the lakes
the monitoring data are sparse.
o Don't put too much effort into studying and explaining the annual variability of the "dead zone" in Lake Erie. It
may very well be reflecting variations in meteorological events.
o Mercury in the Great Lakes ecosystem needs further assessment, especially perspectives on global sources. What
further actions can be taken?
o Cyanotoxins are an issue. Blue-green algae occur where total phosphorus concentrations are greater than 20
micrograms/liter. This concentration creates an aesthetic problem and a potential human health issue.
o We may need renewed attention to nearshore effects. Shoreline algae are a problem in some areas again, and
there may be a nearshore shunt of nutrients due to zebra and quagga mussels. We may need to lower phosphorus
loads and pay attention to urban runoff and lawn fertilizers.
o We need an indicator of whether nutrients are accumulating in the basin. Data for the Lake Erie watershed show
that phosphorus may be accumulating in the soils.
Anthropogenic Chemicals
o Assessing the presence, transport, fate and effects of chemicals in the Great Lakes ecosystem is a capacity issue.
It takes people, equipment and money.
o A stable, credible, long-term science effort is needed, and it needs to be sustained.
o We have had considerable success reducing the quantity of anthropogenic chemicals in the Great Lakes basin
ecosystem. But remember that PCBs were not banned, just their production was, and the in-use stock is still a
threat.
o There needs to be biological monitoring to indicate integrated effects of exposures to toxic chemicals. For
example, reproduction impairments can signal a chemical cause.
o Restricted areas such as AOCs may represent important biological production resources. EDCs and
Pharmaceuticals, etc., may be their most destructive in these areas.
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o New and emerging chemicals need to be monitored. We need to assess the degree of their threats. Their sources
may be ubiquitous. They may be less toxic than the legacy chemicals, but we need to check to see if an
assessment about emerging chemicals of concern can be made.
o Regarding contaminants in fish, we need to bring into the discussion the numbers of people affected by fish
consumption. What is the source of contamination for the majority?
General Observations
o Environmental models are out of date. More work is needed to understand the effects of new non-native species
and to integrate physics, hydrodynamics and hydrology.
o Is there a chance for early warning monitoring? How would that be done?
o We need to market and articulate science needs to Great Lakes management.
o Don't rule out problems by thinking that they are already solved.
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APPENDIX A - WORKSHOP AGENDA
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SOLEC Chemical Integrity Workshop
November 29-30, 2005
Windsor, ON
Tuesday November 29, 2005
9:00 Welcomes and Overview of Workshop
Paul Bertram, U.S. Environmental Protection Agency
Douglas Dodge - StreamBenders (Workshop Master of Ceremonies)
9:15 What is chemical integrity? (Includes a summary of the Chemical Integrity workshop held at SOLEC 2004, the
working definition of chemical integrity and the relative importance of chemical balance and integrity vs. physical
and biological integrity with respect to maintaining ecosystem integrity)
Brian Eadie - NOAA/GLERL
9:40 Naturally-occurring chemicals in the Great Lakes basin - Part 1 (Includes trends in loadings of naturally
occurring chemicals (phosphorus and nitrogen) as measured over the last thirty years in Lake Erie tributaries)
Peter Richards - Heildelberg College.
10:05 Naturally-occurring chemicals in the Great Lakes basin - Part 2 (Includes environmental health effects resulting
from loadings of naturally occurring chemicals, based on expected outcomes from ecosystem models)
Joe DePinto - LimnoTech Inc.
10:30 Break
11:00 Anthropogenic chemicals in the Great Lakes basin - Part 1 (Includes relationships to chemical integrity; observed
and potential impacts; environmental concentrations and trends; factors which impact risk (toxicity and exposure);
sources, loadings, transport, fate with a focus on human health)
Daniel Hryhorczuk - University of Illinois at Chicago
11:25 Anthropogenic chemicals in the Great Lakes basin - Part 2 (Includes relationships to chemical integrity; observed
and potential impacts; environmental concentrations and trends; factors which impact risk (toxicity and exposure);
sources, loadings, transport, fate with a focus on ecosystem health)
Scott Brown - National Water Research Institute
11:50 Assessing chemical integrity in the Great Lakes basin (Includes a discussion on information needs defined
through LaMPs, GLBTS, other plans; status of current monitoring and Great Lakes indicators; factoring in risk
assessment; integrating chemical integrity with overall Great Lakes basin ecosystem assessment)
Keith Soloman - University of Guelph
12:15 Charge to Participants
Doug Dodge
12:30 Lunch
1:30 Breakout sessions I- Themes, Issues and Conclusions: What Do We Know?
3:00 Break
3:30 Breakout sessions II Themes, Issues and Conclusions: What Do We Need to Learn?
5:00 Adj ourn for the day
Wednesday November 30, 2005
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8:30 Summary of Day 1
Doug Dodge
9:00 Breakout sessions III - Key Issues and the Path Forward for Assessing Chemical Integrity
10:30 Break
11:00 Plenary Discussion - Key issues, management questions, suggested actions
Moderated by Doug Dodge
12:15 Workshop Wrap-Up - An overall perspective of what was heard at the workshop, summary of what messages we
need to take into SOLEC 2006
Murray Charlton - National Water Research Institute
12:30 Workshop Adj ourns
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APPENDIX B - SOLEC 2006 DRAFT AGENDA
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SOLEC 2006 Conference Agenda
(DraftAugust 2005)
Day 1State of the Great Lakes
MorningPlenary
9:00-9:30 Welcomes & Introductions [Responsibility of the SOLEC Steering and Executive Committees]
9:30-10:45 State of the Great Lakes [Responsibility of the SOLEC Steering and Executive Committees with input
from LaMP Managers}
Condition of Great Lakes human health, land use-land cover, contamination, biotic communities
including fisheries, invasive species, aquatic habitats, coastal zones, resource utilization, and climate
change based on indicators. To the extent possible, the presentations will report conditions at a Lake level
as well as convey the overall basinwide status.
10:45-11:15 Break
11:15-12:30 Management implications for the Lakes, the St. Clair-Detroit ecosystem, and the St. Lawrence River
[Responsibility of the LaMP Managers in coordination with the SOLEC Executive Committee}
Lake by Lake management implications resulting from the state of the Great Lakes based on the condition
reports and supplemental information.
12:30-2:00 Lunch
12:30-2:00 Networking - for all attendees
1:30-2:00 Introduction to Indicators session - for all attendees [Responsibility of the SOLEC
Steering and Executive Committees}
AfternoonBreakout Sessions
2:00-4:30 Lake by Lake sessions to discuss the next steps needed to address condition and management
implications. [Responsibility of the LaMP Managers with assistance from the SOLEC Executive
Committee}
EveningDinner/Reception
6:00-8:30 Success Story presentations will take place from 8:00-8:30, after the dinner. [Responsibility of the SOLEC
Steering and Executive Committees}
Day 2Chemical Integrity
MorningPlenary
9:00-9:15 Highlights from Day 1 [Responsibility of the SOLEC Steering and Executive Committees}
9:15-9:30 Chemical Integrity overview. [Responsibility of the SOLEC Steering and Executive Committees with input
from the Chemical Integrity Working Group and the LaMP Managers}
The following six presentations [Responsibility of the Chemical Integrity Working Group with assistance from the SOLEC
Executive Committee} will attempt to include Lake-specific examples:
9:30-9:50 TOXICS Impacts and Issues
9:50-10:10 TOXICS - Sources, Loads and Transport
10:10-10:30 TOXICS - Management Response/Actions and Environmental Changes
10:30-11:00 Break
11:00-11:20 NON-TOXICS - Impacts and Issues
11:20-11:40 NON-TOXICS - Sources, Loads and Transport
11:40-12:00 NON-TOXICS - Management Response/Actions and Environmental Changes
12:00-1:30 Lunch
1:00-1:30 Keynote addressinvited speaker
AfternoonChemical Integrity Workshops
1:30-4:30 Workshops will include additional presentations and discussions of specific issues including: municipal
sector issues (pesticides, pharmaceuticals, groundwater contamination, ecological footprint, and cycling
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of contaminants among others (topics will be determined by the experts attending the November 2005
workshop). [Responsibility of the Chemical Integrity Working Group}
Day 3Cross-Cutting Issues
9:00-12:00 Ideas include: beaches, groundwater, forestry, brownfields, eco-footprint, climate change, GLWQA,
societal values, land use/zoning. Sessions will be determined by the SOLEC Steering Committee.
[Responsibility of the SOLEC Steering and Executive Committees}
12:00 Adjourn
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APPENDIX C - WORKSHOP ATTENDEES
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Chemical Integrity Workshop Attendees
NAME
Jackie Adams
Doug Alley
Bill Alsop
Frank Anscombe
Paul Bertram
Giselle Bouchard
Scott Brown
George Bullerjahn
Murray Charlton
Stacey Cherwaty
Jan Ciborowski
David Culver
Sarah Da Silva
Marcia Damato
Nicole Davidson
Joe DePinto
Jon Dettling
Miriam Diamond
Doug Dodge
Jack Dutra
Brian Eadie
David Flakne
Diana Graham
Beth Hinchey-Malloy
Paul Horvatin
Daniel Hryhorczuk
Matt Hudson
Melissa Hulting
Allan Jones
Rimi Kalinauskas
Bruce Kirschner
Paul Klawunn
Gail Krantzberg
Edwina Lopes
Jianmin Ma
John Marsden
Gerald Matisoff
Ann McConnell
Michael McKay
Derek Muir
Beth Murphy
Melanie Neilson
Todd Nettesheim
Jerry Niemi
Carolyn O'Neill
Dan O'Riordan
AFFILIATION
U.S. Environmental Protection Agency - GLNPO
International Joint Commission
AMEC Earth and Environmental Consulting
U.S. Environmental Protection Agency - GLNPO
U.S. Environmental Protection Agency - GLNPO
Environment Canada
National Water Research Institute
Boiling Green University
Environment Canada
Environment Canada
University of Windsor
Ohio State University
Environment Canada
U.S. Environmental Protection Agency - GLNPO
Environment Canada
LimnoTech Inc.
Great Lakes Commission
University of Toronto
Streambenders
Industry Task Force
National Oceanic and Atmospheric Administration
Syngenta Crop Protection
Contractor to Syngenta Crop Protection
U.S. Environmental Protection Agency - GLNPO
U.S. Environmental Protection Agency - GLNPO
University of Illinois at Chicago - School of Public Health
Great Lakes Indian Fish and Wildlife Commission
U.S. Environmental Protection Agency - GLNPO
Canadian Chlorine Coordinating Committee
Environment Canada
International Joint Commission
Environment Canada
McMaster University
Environment Canada
Meteorological Service Canada
Environment Canada
Case Western Reserve
Proctor & Gamble Canada
Bowling Green State University
Environment Canada
U.S. Environmental Protection Agency - GLNPO
Environment Canada
U.S. Environmental Protection Agency - GLNPO
National Regulatory Research Institute
Environment Canada
U.S. Environmental Protection Agency - GLNPO
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NAME
Dale Phenicie
Lou Pocalujka
Peter Richards
David Rockwell
Karen Rodriguez
Dan Salvito
Hans Sanderson
Barbara Scudder
Ted Smith
Keith Solomon
Dee Ann Staats
Nancy Stadler-Salt
Jay Unwin
Srinivasan Venkatesh
Donald Versteeg
Jennifer Vincent
Alan Waffle
AFFILIATION
Council of Great Lakes Industries
Consumers Energy
Heidelberg College
U.S. Environmental Protection Agency - GLNPO
U.S. Environmental Protection Agency - GLNPO
Research Institute for Fragrance Materials
The Soap and Detergent Association
U.S. Geological Survey
U.S. Environmental Protection Agency - GLNPO
University of Guelph
Crop Life America
Environment Canada
National Council for Air and Stream Improvement, Inc.
Environment Canada
Proctor & Gamble U.S.
Environment Canada
Environment Canada
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APPENDIX D - PLENARY PRESENTATIONS
(Note: Plenary Presentations are also available online at:
http://www.epa.gov/glnpo/solec/solec 2006/presentations/index.html)
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'Chemical Integrity' of the
Great Lakes?
Brian J. Eadie
NOAA - GLERL
Summary of the 2004 Chemical
Integrity Workshop in Toronto
Chemical Integrity is the capacity to support and maintain a
balanced, integrated and adaptive biological system having
the full range of elements and processes expected in a
region's natural habitat.
Is Chemical Integrity the capacity to maintain Biological
Integrity?
* What about the capacity to maintain the sustainability of
human uses of the habitat?
What Items should be included in
Chemical Integrity?
The current suite of chemicals of concern are
declining
Toxicology information is needed, not just
concentrations
- Very weak information on the toxicology of mixtures
Focus on assessment not monitoring
How well do we find new chemicals of potential
concern ?
~ Perturbations (e.g.,Invasives, Climate, Land use)
What Items should be included in Chemical Integrity?
* Nature of the chemical
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What Chemicals are of Concern cont.
Taste/Odor
HABs (e.g., microcystins)
Pharmaceuticals
Road Salt
Caffeine / other WWTP discharges
Biohazards (viruses)
Medical wastes
Seasonal HABs
High concentrations of toxins
microcystin > l(jg/l
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Summarv - Issues relating to Chemical Inte^ritv
PBTs have declined, but some still result in restrictions
P increasing in the central t
N is increasing everywhere
Pharmaceuticals low levels detected Impacts ?
Impact of Climate Change
Aging infrastructure
Sewage and water treatment facilities
Recruitment and retention of younger Great L;
Summarv - Issues relating to Chemical Integrity - contuied
Areas of Concern
Constituent loads
Local (Tributary P, pharmaceuticals)
Regional (Combustion products)
Global (Hg, DDT)
Processes " Ecosystem Models
Improving Risk Assessment Tools
Algorithm improvements for satellite imagery
Development of automated obsei
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Trends in Water Quality in Lake
Erie Tributaries, 1975-2004
R. Peter Richards
National Center for Water Quality Research
Heidelberg College
Tiffin, Ohio 44883
November :
Outline
"death" and rehabilitation of Lake Erie
«>Trends in nutrient loads
^Causes?
What's wrong with Lake Erie?
Lampreys
Alewives
Cladophora
Overfishing
Blue Pike
Walleye
ated Harbors
!
tienols
Iron and other metals
PAHs
PCBs
Contaminated Open Lake and Fish
Mercury
PCBs No more mayflies..
DDT, DDE
Strategy for reducing hypoxia
/&»Reduce phosphorus
Sewage Treatment Plant upgrades
Phosphorus detergent ban
Non-point source programs, especially aimed at
agriculture
Nutrient management
Reduced tillage
Tributary Loading Studies
fy>Army Corps Wastewater Management Study
^Heidelberg Tributary Sampling Program
Major Lake Erie Tribs
Sandusky 1974
Maumee 1975
Cuyahoga 1982
Raisin 1982
Grand 1986
Autosamplers at "integrator" stations, 3 samples/day
. USDA-LEASEQ Trend Analysis 1975-1995 (Mau, Sand)
. USDA-CEAP Trend Analysis 1975-2004
-------
Trends in Water Quality, 1975-1995
Percent
Change
TP DRP NO3
**p<0.01 ***p<0.001
Trends in phosphorus mass balance
... substantial decrease, but always input>output
: Total input
Total output
Trends in soil fertility
... nearly doubled between 1975 and 1995
Soil Test Phosphorus (mg kg-1)
LEASEQ Conclusions
«^>Water quality trends are toward improved
conditions (except nitrate)
^Water quality trends result from intentional
changes in use of the land
<^»A major victory for environmental science
and management
Trends 1995-2004:
«>How do trends in the last 10 years compare
with trends in the previous 20 years?
«>Also extend analysis to Cuyahoga and
Grand
Station Locations
-------
Trends in Water Quality, 1975-2004
^Methods: Formal Analysis
Adjust concentrations for flow effects, using LOWESS
smoother
Analyze trend in flow-corrected, log-transformed
concentrations using ANCOV A-based two slope model
. log(c)=fn[log(q), t, sin(2nt), cos(2nt), PrePost, PrePost*t]
Results expressed as % change over 10 years
fy°Today: LOWESS smooths of unmodified daily flows
and daily loads (bin width 20%)
«*LOWESS: LOcally WEighted Scatterplot Smoother
I. Loads vs. Concentrations, Sandusky
Illustrate similarities/differences in trends for
loads as opposed to concentrations
Illustrate magnitude of trends relative to day-to-
day fluctuations
Avoid trying to show you 100+ different trend
graphs!
Discharge
Suspended Sediment
Total Phosphorus
Conceni:..
Dissolved Reactive Phosphorus
Concern i.
-------
Total Kjeldahl Nitrogen
Patterns, Loads vs. Concentrations
<°&«Loads and concentrations for a given parameter
tend to have similar trends
^But there can be important differences as well
^SS and TP load trends track flow strongly, others
less so or not at all
^"Trends reflect "something real" and important,
but...
^"Generally the 30-year trends are small compared to
the short-term variability, especially for loads
4^(What does this imply for management?)
II. Loads, parameter by parameter
«>Flow, SS, nutrients, derivative parameters
f§»°LOWESS values are essentially locally
weighted averages, tend to be intermediate
between the median and the mean
Precipitation (cm/month)
Northwest Ohio
Maumee Flow
-------
Discharge (cubic feet/second)
CuyahogJ
SS Load (metric tons/day)
\
\
TP Load (metric tons/day)
DRP Load (metric tons/day)
\
Cuyahoga
Nitrate Load (metric tons/day)
Cuyahoga
TKN Load (metric tons/day)
Cuyahoga
Sandusky
-------
Chloride Load (metric tons/day)
'PP'VSS ratio (g/kg) (-PP-TP-DRP)
Cuyahoga
DRP/TP (%
\
TN/TP ratio
(Redfield Ratio ~ 7)
/\ sadatt
/ \/
NO3/DRP ratio
Cuyahoga
(Redfield Ratio ~ 7)
Sandusky
i
Summary
^General improvements (except nitrate)
during 1975-1995, most params/most rivers
«* Worsening in TP, DRP, TKN since then;
inflection point between 1993 and 2000
^Continued improvement in Maumee SS but
not in other rivers
<>Mixed results for NO3
-------
Summary
<>PP/SS ratio (sediment "richness")
improving recently, but perhaps for bad
reasons
«>Recent increases in %P that is dissolved
^TN/TP and NO3/DRP decreasing or no
longer increasing, but ratios are appropriate
for phosphorus limitation
Impacts?
<%»Renewed problems in Lake Erie
Increased in-lake phosphorus concentrations
Hypoxia in summer in Central Basin
Microcystis and other cyanobacteria
^Tributary inputs are not the sole cause, but are
likely contributors to these problems
Causes?
fy*Weather? More important for loads than cones?
^Population growth and exurbanization?
<^»No-till concentrates nutrients at surface?
^Concentrated animal agriculture?
«> Winter spreading of manures?
^Global climate change?
«^»Whew! It could be all of them...
THE END
-------
-------
Chemical Integrity in the Great Lakes
Pre-SOLEC workshop
Windsor, ON - November 29-30, 2005
Chemical Integrity of
rall}fopjccurring Substances
Jn, tjie Great Lakes
-Jft.- H^
Joseph V. DePinto
ic-Tech, Inc.
Acknowledgements
USE PA - Great Lakes National Program Office
- David Rockwell, other staff
Environment Canada - NWRI
- Murray Charlton
NOAA-GLERL
- Dave Schwab and Dmitry Beletsky
UW-Green Bay
- Dave Dolan
SUNY - CESF
- Greg Boyer, MERHAB-LGL PI
New York Sea Grant
- Helen Domske, NYSG specialist
Naturally-occurring Substances
Chemical Integrity Analysis Logic
How to manage phosphorus in a changed
Great Lakes ecosystem?
Are there undesirable trends in general
water chemistry?
What bio-toxins should we worry about?
Nutrients and eutrophication
- Macro-nutrients (P, N, Si)
- Micro-nutrients (Fe, Zn, etc.)
- Chlorophyll a
Dissolved oxygen
Metals (Pb, Cd, Hg, etc.)
General water chemistry
- Major ions/salinity/hardness
- pH - Alkalinity - DIG system
Taste/odor compounds (MIB, geosmin)
Biota-produced toxins
- Cyanotoxins
- Botulinum toxins
Sources of Naturally-occurring Substances
Naturally occur in earth's crust
- Leached and eroded from soil
Formed by natural chemical and biochemical
reactions in soil, water, sediments
Humans can accelerate cycling and entry into
the Great Lakes
- Mining and application of road salt
- Mining and manufacturing processes
- Application of fertilizers
- Creation of conditions that accelerate natural
chemical and biochemical reactions
What is Chemical Integrity?
Chemical Integrity of the Great Lakes
- The chemical composition of a lake ecosystem that
provides all of the chemical needs for that system to
maintain overall ecosystem integrity.
Chemical concentrations are bounded such that there
is not too much or too little relative to other
chemicals and relative to the ecosystem's needs for
maintaining its integrity.
Chemical integrity must be understood and
evaluated in terms of sources, loadings.
transport, fate, and ecological effects (humans
are part of the ecosystem).
-------
What is Ecosystem Integrity?
An aquatic ecosystem is judged to have integrity when its
physical, chemical, and biological structure is such that it is
functioning as a complete and healthy ecosystem.
"Complete" and "healthy" can only be determined in terms
of indicators of that ecosystem's performance relative to a
performance goal
Measures of ecosystem performance
- Biologically diverse/complexity
- Evolving toward a more stable system
- Resilience/Homeostasis
resistance to irreversible change in response to external perturbations
(stressors)
Multiple
Stressors
Ecosystem
Structure and
Function
Multiple
Responses
Feed backs/Horn eostasis
Programs and Policy
to Ameliorate Stress
Indicators of Ecosystem Performance
Ecosystem Indicator: A measurable feature, or one
derivable from measurements, which singly or in
combination provides managerially and
scientifically useful evidence of ecosystem
integrity, or reliable evidence of progress toward
one or more ecosystem objective.
- Indicator can be a physical, chemical, or biological
measurement that can be related in a meaningful and
understandable way to ecosystem performance.
- Indicator can be a stressor, a process, or a system state
variable
Ecosystem models are a tool for relating indicators
to ecosystem performance.
Indicator
Type
Model for Measuring and Understanding
Ecosystem Health
\Great Lakes Basin /
Ecosystem /
Ecosystem Int
(Desired Out'
Processes
and State
Physical
Integrity
Biological
Integrity
Nutrients and Eutrophication
Phosphorus is limiting nutrient and is
controlled in Great Lakes
Nitrogen (as N/P ratio) can impact algal
speciation
Phosphorus management in 1970's and '80s
was based on chlorophyll a targets
- Very successful outcome
Now other factors raised as issues in P control
- Fish production
- Invasive species impacts
- Still seeing water quality impacts in Lake Erie -
hypolimnion DO
-------
Environment Canada TP Data for Lake Erie
(Charlton, 2005)
1B4B 2MO if Pi
Phosphorus, a key nutrient tor algae growth
.3
1670 1974 1*BO IdtS 19*0 1»(i 2000 309S 1*70 117* 1*10 IMS 1HO IMS IOW 3
Nitrogen nutrient not controlled much in sewage, also in fertilizer
DiToro, et al. Lake Erie Eutrophication
Model (1976)
Segmentation for
1976 Lake Erie
Model
T ~f f
(nL^i TrrAiwJr^' lAwpr I*i
mwjus 'J!°"-'-iA mtU
-»M»
Lake Erie
Total Phosphorus Loadings
i -
Lake Erie Model
Post-audit (Chi a)
(DiToro, etal. 1987)
Annual Total Phosphoms Loac
DirectMunicipal Loads
-TP Target Load
- -
_ ' .AT :' +. y' ^ ^r' j/^y »y>-y'
-------
Lake Erie in vummcr strati fkalion
June
-v_fii
r The area of the
hypotimnion or "dead
zone" changes with
stratification depth
and date.
t.piiimaiun »«n»
xmocfide _^--
llvpolunnion \ '
LAKE ERIE LONGfTUDWAL CROSS SECTION
(from Charlton 2005)
Lake Erie Central Basin
Dissolved Oxygen Concentrations
1993
1997
1998
1999
2000
2001
O
o o
o o
" ,0
o
I
o o
o o
O0O
0°0
0 O
o o
0%§o|
Early June Late June Mid-July Early Aug.
O > 6 mg/l ^ 4-6 mg/l Q 2-4 mg/l Q 1-2 mg/l
Mid-Sept.
0-1 mg /I O No Data
HVOD rates for the Central Basin from 1991
to 2001 corrected for temperature, vertical
mixing and hypolimnion thickness.
y = -52 + 0.0276X R= 0.203 p = 0.55
1990 1991 1992 1993 1994 1995 1996 1997 1998 1998 2000 2001 2002
Year
Hypothesis
4There is always zebra mussels
4 Due to a de-coupling of the
phosphorus-chlorophyll a relationship
in Lake Erie caused by the Dreissena
invasion, the net loss rate of total
phosphorus from the water column
(i.e., net apparent phosphorus
deposition rate to sediments) has
decreased.
Model Sensitivity to Net Vs (WB)
Lake Erie - Western Basin
(Sensitivity to Vs)
1975 1980 1985 1990 1995 2000
ise Loads & Vs=10.1 m/y +10% Vs
25%Vs 25%Vs
-------
Model Sensitivity to Net Vs (CB)
Lake Erie - Central Basin
(sensitivity to Vs)
2005
GLNPO Spring TP Base Loads &Vs=33.6 mfy +10% Vs
-10% Vs +25%Vs 25%Vs
Model Sensitivity to Net Vs (EB)
Lake Erie - Eastern Basin
(sensitivity to Vs)
f\
1980 1985
1990
Year
1995 2000
2005
GLNPO Spring TP Base Loads & Vs=36.7 m/y +10%Vs
-10% Vs +25%Vs 25%Vs
Nutrient Control versus Sport Fishing -
Lake Ontario
Nutrient
Load
Reduction
rSeverei
CWinterJ
Algal
Growth
Decline
Increased
Predation
Reduced
Eutrophication
Effects
Reduced
Prey Fish
Production
Increased
Salmonid
Stocking
Reduced
Sport Fish
Size and
Biomass
-------
Conceptual Model of Simplified Lake
Ontario Ecosystem Model
2.000.000 4.000.000 6.000.000 8.000.000 10.000.000 12.000,000
-------
Cyanotoxins in the Lower Great Lakes
MERHAB-LGL Study
- PI: Greg Boyer, SUNY-ESF
Produced by cyanobacteria
(blue-green algae)
Four primary classes of
toxin compounds
- Microcystin
- Anatoxin-a
- PSP toxins
- Cynlindospermopsin
Neurotoxicity and
hepatotoxicity in
- Fuana coming in contact
with blooms
- Can exceed WHO limits in
drinking water intakes
MERHAB-LGL
Cyanobacterial blooms are becoming
commonplace in Lake Erie.
Lake Erie, August 23, '04
% toxic Highest
>0.1 ppb value, ppb
August 2003
Classic Microcystis blooms
14 - 20 ug L
t \ 0.5 - 0.7 ug L"1 Microcystin-LR eqv.
Microcystis present but mcyA suggests that microcystin
produced by Planktothrix in Sandusky Harbor! Rinta.Kanto etai
e-Jrn ' cw* ' iror* ' <
Toxic Blooms in Lake Ontario
(not as severe as in Lake Erie)
Cruise date # sta Toxin ? (%) Highest values N
2000 (Aug)
(late July)
(late June)
(July, August)
0% MC: < 0.02 ng H
Eastern
end
2% (MC) MC: 0.15 ^g M
4% (ATX) ATX: 0.05 ^g I'1
7 0% (MC) MC: 0.007 ^g I'1
70% (ATX) ATX: 0.006 ^g H
80 >25% (MC) MC: 1.06 ^g I'1
63 0.5% (ATX) ATX: 0.01 ^g H
Whole lake
Henderson
Bay
Whole lake
+ Eastern
2004 81 17% (MC) MC:0.85^g|-1 Whole lake
(Aug-Sept) 16% (ATX) ATX: 0.02 ug H
Clostridium botulinum
Bacterium that produces botulism toxin
Anaerobic bacterium- it grows in the absence
of oxygen
Forms endospores- dormant structures that
remain viable for years
The endospores quite resistant to temperature
extremes and drying.
Where are the bacteria found?
Spores of both type C and type E Botulism are naturally
found in anaerobic habitats:
Soils
Aquatic Sediments
Intestinal tracts of live, healthy animals
In the absence of oxygen, with a suitable nutrient
source, and under favorable temperatures and pH,
spores can germinate and vegetative growth of bacterial
cells can occur. (Brand, et. al 1988).
Botulism toxin is only produced during vegetative
growth, not when the bacterium is in its spore stage.
-------
Is the outbreak caused by a new strain?
Do algae blooms (Cladophora) play a role?
Do Dreissenids play a role?
Why have fish die-offs decreased since 2003?
Is the decrease related to goby populations?
Botulism Outbreaks in Lower Lakes
Lake Ontario
1999-2002- Large
Outbreaks
Confined primarily to
Eastern Basin
Smaller Outbreak in 2003
Minimal reports of fish
mortality in 2004, but a
larger die off of birds in
November and December
during migrations.
Nov 3-15 (ongoing)
approximately 200
Common Loons found at
Long Point National
Wildlife Area, Ontario.
2003 - First small recorded
outbreaks
Outbreaks first confined
primarily to Western Basin -
some fish and birds
2004 - Outbreaks continued,
September 2004 - central
portion of Lake Ontario, over
500 double-crested cormorants
collected, tests were positive
October 2004 - several
hundred dead long- tailed
ducks along the
Hamilton/Burlington beaches
Summer 2005 - over 1,400
double-crested cormorants
collected on the islands along
the Central-Eastern shore in
Ontario.
Lessons
lanaging chemical integrity
Physical and biological integrity matter
- Scale matters
Cannot understand chemical integrity in an ecological
vacuum
- Ecosystems have many feedback mechanisms that provide
resilience; these must be understood in order to define
bounds of chemical integrity
Ecological integrity cannot be achieved by managing
single issues independently of understanding
interactions with other management issues
Require coordinated modeling, monitoring, and research
programs
If we have learned anything over the last 30 years, it is
that we need a Great Lakes Basin Ecosystem Agreement
-------
Anthropogenic Chemicals in the Great
Lakes Basin: Human Health Effects
Daniel Hryhorczuk, MD, MPH
Persistent Toxic Substances
in the Great Lakes Basin
Organochlorine compounds
- PCBs
- Hexachlorobenzene
- DDT and metabolites
- Dioxins and dibenzofurans
- Mirex
- Dieldrin
- Toxaphene
Persistent Toxic Substances
in the Great Lakes Basin
Heavy metals
- Alkylated lead
- Methylmercury
Polycyclic aromatic hydrocarbons
Emerging contaminants
- Polybrominated diphenyl ethers (PBDEs)
Key Findings
Elevated body burdens of contaminants in persons who
consume large amounts of Great Lakes fish
Developmental deficits and neurologic problems in
children of some fish-consuming parents
Endocrine dysfunction among fish eaters
Disturbances in reproductive parameters
At Risk Populations from
Contaminated Fish Consumption
Native Americans and other
indigenous peoples
Sports anglers
Subsistence fisherman
Pregnant women, fetuses
Nursing infants
Human Health Studies:
Fish consumption vs contaminant levels
Michigan Sport Fisherman Study (Humphrey, 1976, 1983,
1988; Tee et al, 2003)
- First demonstration of association between consumption of
contaminated Great Lakes sport fish and serum levels of PCBs
- Persons who annually consumed >_ 24 Ibs of fish had serum
PCB levels 4x higher than controls
- Monotonic decline in serum PCB levels among all participants
from mean of 24ppbin 1980 to 12 ppb in 1994 paralleled by
and 83% decrease in fish consumption
Wisconsin Fish Eater Study (Fiore et al, 1989)
- Serum levels of PCBs and DDE statistically correlated with
amount of Great Lakes fish consumed
-------
I
Human Health Studies:
Fish consumption vs contaminant levels
Great Lakes fish eaters, age 50 years and older (Schantz
etal, 1996)
- Those who consumed >_ 24 Ibs of sport fish for more than 15
years had higher levels of RGBs and 2x higher levels of DDE
and mercury
Great Lakes Consortium fish eaters (Turyk et al, 2005)
- Blood samples from fish eaters obtained in 1993-95
- Noncoplanar RGBs higher in fish eaters than in referent
population, associated with fish consumption, and varied by
lake
Human Health Studies:
Children's growth and development
Michigan Maternal and Infant Study (Fein et al 1983,
1984; Jacobson et al, 1983, 1984, 1988)
- Intrauterine exposures to diet of contaminated Lake Michigan
sport fish (RGBs) associated with:
Decreases in infants birth weight
Decreases in gestational age
Decreases in head circumference
Infants exhibited neurodevelopmental and behavioral
deficits on tests of visual recognition and memory at 7
months and 4 years of age
Poorer short- and long-term memory and lower IQ scores at
11 years of age
Human Health Studies:
Children's growth and development
Newborns of Great Lakes fish eaters (Lonky et al, 1996)
- Neurobehavioral deficits at 12-24 hours and 25-48 hours after
birth from mothers who consumed on average 2.3 fish meals
per month
New York State Angler Cohort Study (Buck et al, 2003)
- Absence of an adverse relation between Lake Ontario fish
consumption and reduced birth size as measured by weight,
length and head circumference
Michigan Anglers Study (Karmaus and Zhu, 2004)
- Maternal PCS concentration >_ 25 mcg/l associated with
reduced birth weight of offsrping
Human Health Effects:
Endocrine disruption
New York State Angler Cohort Study (Bloom M et al,
2003)
- Hexachlorobenzene inversely associated with T4
Great Lakes Consortium fish eaters study (Persky et al,
2001)
- Serum PCS levels and fish consumption inversely associated
with T4 and Free thyroxine index in women and T4 in men
- Among men, there were significant inverse associations of both
PCS and fish consumption with sex hormone-binding globulin
(SHBG)-bound testosterone, but no association with SHBG or
free testosterone
Human Health Studies:
Reproductive health
New York State Angler Cohort Study (Mendola et al, 1997;
Buck et al, 2000)
- Consuming more than one fish meal per month associated with
reduction in menstrual cycle length in women
- Maternal consumption of fish for 3-6 years associated with
reduced fecundability
Human Health Studies
Community Health Profile of Windsor
Windsor AOC ranked among the highest of 17 AOCs on
Canadian side of the Great Lakes for selected health end
points potentially related to pollution
Health outcomes data
- Mortality
- Hospitalizations
- Congenital malformations
Local industrial sources and transboundary air and water
pollution from Detroit
Gilbertson and Brophy, EHP 109:827,2001
-------
I
Human Health Studies
Fish consumption and breast cancer risk
Wisconsin population-based case control study
Relative risk for recently consumed sport-caught fish
- Overall: 1 (0.86-1.17)
- Postmenopausal: 0.78 (0.57-1.07)
- Premenopausal: 1.70 (1.16-2.50)
Frequency of and location of consumption not associated
with breast cancer risk
McElroy et al. EHP 112:156, 2004
Emerging Pollutants
While concentrations of most
organochlorines in fish in the
Great Lakes declined as first
order decay from 1983-1999,
the concentration of
polybrominated diphenyl
ethers (PBDEs) increased
exponentially (Chernyak et al,
2005)
PBDEs used as flame
retardants
Can bioconcentrate and
bioaccumulate
Emerging Pollutants
Toxicologic effects of PBDEs
- Thyroid hormone imbalance (reduction in T4)
- Developmental neurotoxicity
- Estrogen disrupters
Increased liver tumors
Great Lakes Centers
Environmental Profile of PCBs
Joyce Foundation
Canadian Environmental Law Foundation and GLC
www.uic.edu/sph/glakes
Great Lakes Centers
Environmental Profile of PCBs
Environmental Profile of
PCBs in the Great Lakes
-------
-------
Wildlife and Fish Health
Effects in Canadian AOCs
Scott Brown, National Water Research Institute
Joanne Parrott, Mark
Hewitt, Derek Mulr
National Water Research Institute
Alice Dam, Scott Painter, Me/en/e Nellson, John Stmger
KimFerme, Pamela Martin, Canadian Wildlife Service,
Environment Canada-Ontario Region
Glen Fox, LiardSnutt, C. Hebert, Canadian Wildlife
Service, National Wildlife Research Centre, Environment
Canada
Great Lakes Areas of Concern
In 1987, the International Joint Commission
designated 43 areas of concern in the Great
Lakes Basin
To qualify as an AOC, the area contained
one or more beneficial use impairment
Beneficial Use Impairments
restrictions on fish and wildlife consumption
degradation offish and wildlife populations
bird or animal deformities or reproduction problems
restrictions on dredging acti
drinking water restric
beach closings
degradation of aesthetics
added costs to agriculture or industry
loss offish and wildlife habitat
Areas of Concern in the Great Lakes
St. Lawronco Rivor Basin
» Ci»g< Itm
.
*- ,
* ' r'&ssL
. v ......
.. _ m «J3, tSSSZ
"
*?--
us.*
.
A .
In Fish-Eating Predators
In the 1960s, Great Lakes fish wer
implicated in a large number of die
related reproductive failures in
ranch mink
LOEL for mink kit survival
associated with maternal liver
PCBs=2.2 mg/kg
Past Effects
Reproduction in shore-line nesting
eagles and cormorants failed
Egg-shell thinning and hatching
failures associated with DDT/DDE
Congenital malformations/GLEMEDs in
fish-eating birds was associated with
exposure to persistent organic
contaminants such as dioxins and RGBs
-------
A combination of rectors led to the decline of lake trout such
that by 1960 they were extirpated from the Great Lakes; sea
lamprey, overexploltatlon, changes In forage base, pollution
From mid SO'ata mid 70'a, Blue-Sac from exposure to TCDD-
Ilke contaminants was sufficient account for 100% offspring
mortality In Lake Ontario (Cook et al. 2003)
Effects of POPs on wildlife
have been recognized and
I there has been action
taken to reduce exposure
Good NEWS!!!
No Blue-Sac, Return of Fish-Eating Bird
Populations
Concerns Leading to Recent
Studies
Health Canada Reports released in 2000
suggest some human health outcomes
were more prevalent in certain AOCs
What, if any, are the present Wildlife and
Fish Health Effects in AOCs?
- Last assessment summarizing known spatial
and temporal trends in environmental
contaminants and associated effects in fish
& wildlife in 1991 Toxic Chemicals in the
Great Lakes and Associated Effects"
| Fish and Wildlife Health Effects and Exposure Study |
| Objectives
Update understanding of the state offish and
wildlife health
Determine if effects are similar to those in human
population
Measure current concentrations of chemicals (old
and new) in aquatic environment and tissues that
could be associated with heath outcomes
| Phase I (2001-2005)
Canadian AOCs in the lower Great Lakes
Benthic and pelagic fish, Snapping Turtles, Herring
Gulls and mink
Laboratory analyses:
histology
enzyme activity
estrogenicity assays
immunotoxicity
hormone function
Field assessments:
sex ratios
embryonic viability
-------
Assessment of Effects in Wild Fish
Examination of gonad development,
egg size, fecundity, expression of
secondary sexual characteristics
Measurement of circulating Vg,
reproductive steroid hormone levels
and thyroid hormones
Determination of steroid and thyroid
biosynthetic capacity
Liver mixed-function oxidase (index of
exposure to dioxin-like
organochlorines)
Histology of endocrine and other
tissues (gonads, thyroid, liver, gills)
Deformities and other anomalies
External Abnormalities in Brown Bullheads
Stubbed Barbels Melanoma | Focal Discoloration
(T*
Surface lumps and bumps in Western
Lake Erie are more prevalent 2001
than in 1990.
Association between sediment
contaminants (e.g. PAHs & metals)
and higher incidence of external
abnormalities- particularly barbel
and raised growths.
Stephen Smith, USGS
Raised Growth -
Health Changes Are Detectable!
reproduction, physiology,
morphology;
all age stages, from embryos to
young to adu
likely not just a OC issue, effects
suggest impacts from other
contaminants like EDSs
effects mostly found at sites
nearest to the AOCs.
What has wildlife told
us about the current
Great Lakes
environment?
Assessment of Effects
Ecosystem Health Factors]
Alien species have
appeared at the rate of
one per year since
Dreissena invasion,
"controls" networking.
Assessment of effects of
alien species impeded
by lack of basic annual
data on distribution and
numbers.
[Overview of Great Lakes Salmonids
|Today
w
With exception of Lake Superior and parts of
Lake Huron still recruitment bottleneck for lake
trout
Early mortality syndrome in salmonids
Major prey species for salmonids
ale wife, rainbow smelt, and bloater chub
Thiamine deficiency is a major factor
Alien invasive species contain thiamine
degrading activity
alewife and rainbow smelt
-------
What is Early Mortality Syndrome (EMS)?
Observed between hatch and first feeding in
Great Lakes salmonids and is characterized by:
Loss of equilibrium
* Swimming in a spiral pattern
Lethargy
Hyperexcitability
Hemorrhage, etc.
Neurological
Symptoms
"It seems to me that no
better case for
ecosystem disruption
can be made than Its
predatory Inhabitants
are suffering varying
degrees of beriberi"
~~~ nod Horfieri Illinois Dnn
BUS to a symptom of a
degraded ecosystem and It's
need for maintaining
biodiversity
Great Lakes Food Web Effects
"Nearshore Shunt"
Harvesting of offshore waters by mussel
filtration nearshore may alter food web,
affect YOY fish survival, increase/decrease
export of nutrients and contaminants.
Food Quality Issues (nutrition)
Need to assess Impacts of drelssenlds and Bythotrephes
on production at higher trophic levels.
Since the mid 1990's Diporeia, normally about 70% of the
biomass on the bottom, has disappeared in parts of the
Great Lakes, except Superior, including all suitable habitat
in Lake Erie, and above 80 m depth in Lake Ontario, Lake
Michigan and southern Lake Huron.
Need to examine the flow of essential nutrients from the
base of the food web to key species.
Gizzard shad and gobies now major components.
20:5n-3 = EPA (Ecosapentaenoic acid)
Other Effects
Shoreline filamentous algae - research
largely dropped but problem has re-
occurred.
Sporadic blue-green algae blooms
sporadic - taste/odor compounds and
toxins produced.
Botulism outbreak: why now? linkage
with gobies, blue-green algae toxins?
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ASSESSING CHEMICAL
INTEGRITY IN THE GREAT
LAKES BASIN
Keith Solomon
University of Guelph
ksolomon@uoguelph.ca
OUTLINE
Identifying chemicals of concern
Identifying sources
Assessing effects
Assessing risks of chemicals of concern
Toxicity, hazard and risk
Dealing with mixtures
Conclusions
IDENTIFYING CHEMICALS OF
CONCERN
The chemical is in the system
- So what?
By analogy because the chemical is in
other systems
- Other systems are different?
Must avoid Type-3 errors
CORMORANTS IN THE GREAT
LAKES
10'
I 10'
c
O 103
I
102
10°
DDT use
ormorant persecution $'
Alewife abundant
1900 1920 1940 1960 1980 2000
Year
Data from Weseloh et al, 1995
RESIDUES IN ORGANISMS
Presence in the organism does not mean
that it is causing a problem.
- Canadian "Toxic Nation" report.
Presence in the matrix does not mean that
it is causing a problem.
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CAUSAL CRITERIA
FOR ASSESSING
ENDOCRINE
DISRUPTORS: A
PROPOSED
FRAMEWORK
IPCS. 2002. Global Assessment
of the State-of-the-Science of
Endocrine Disrupters. Geneva,
Switzerland: International
Programme on Chemical Safety
of the World Health Organization
Report No.
WHO/PCS/EDC/02.2. August
2002. http://www.who.int/pcs
GUIDELINES FOR CAUSALITY
Temporality
Strength of association
Consistency
Biological plausibility
Recovery
Hill
Koch R. 1882. Die Aetiologie der Tuberculose. In: Clark
DH, ed. Source Book of Medical Histoiy. Dover
Publications, Inc. p 392-406
Hill AB. 1965. The environment and disease: association
or causation? Proc. Roy. Sec. Med. 58:295-300
Koch
Doll
CAUSE FOR WORRY
The concentrations are increasing
- PBDEs
- PFOAandPFCs
- Pharmaceuticals
The substance biomagnifies
- PBDEs, nottetrabromobisphenol A
- PFOA/ long chain PFCs
The substance is persistent or pseudopersistent
- PBDEs
- PFCs
- Pharmaceuticals
IDENTIFYING SOURCES
Where is it coming from?
Can we do anything about it?
- Process changes
- Source mitigation
PULP MILL EFFLUENTS
EFFECTS IN FISH
MFO
M F
STEROIDS
Data from Robinson et al, 1994
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IDENTIFYING THE KEY
FRACTION
Supelco
ENVI-CARB (rev)
Graph it izecCarbon
SPE-2
Waste
Condensates
Filter (0.45 urn)
Foritifywith 2% v/v methanol
pH adjust to 4withHCI
SPE-2
Hewitt ML, Smyth SAM, Dube MG, Oilman Cl, Maclatchy DL. 2002. Isolation of compounds
from bleached kraft mill recovery condensates associated with reduced levels of testosterone
in mummichog (Fundutus fceferactfus). Environ Toxicol Chem 21:1359-1367.
AGRICULTURAL
PHARMACEUTICALS
iiifluml Siifl.-KB Wal«s (n*97)
ASSESSING RISKS OF
CHEMICALS OF CONCERN
Frameworks for risk assessment
RISK ASSESSMENT
Problem
and Hazai
n Formulation
rd Identification
i
ANALYSIS
Effect
characterization
Exposure
characterization
USEPA 1998
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TOXICITY, HAZARD, AND RISK
Toxicity is not Hazard is not Risk
Ranking of concerns in the absence of
exposure information
EFFECTS CHARACTERIZATION
Laboratory studies
Surrogate species with standard protocols
Mechanisms of action
Simple mixtures
ACUTE GROWTH INHIBITION
ASSAYS
10000
1000-
100-
10-
&
i i P. subcapitata
^m C. vulgaris
^m S. quadricauda
i i S. acutus 1 1
II
1
Fluoxetine Sertraline Fluvoxamine
Johnson 2004
CON 10jig/L 30ng/L 100ng/L 300jig/L 100<>ng/L
140
120
J
"100
80
60
40
20
0
Atorvastatin
-Chlorophyll a
Chlorophyll b
Carotenoids
Number of Fronds
-Wet Weight
10
100
Concentration (ftg/L)
1000
Brain et al. 2004
"All substances are
poisons: there is
none which is not a
poison. The right
dose differentiates a
poison and a remedy"
PARACELSUS,1493-1541
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Assessment of hazard based on a ratio of single deterministic
^oxicity values
HAZARD.
(LOG)
QUOTIENTS
EXPOSURE CONCENTRATION
EFFECT CONCENTRATION
CARL FRIEDRICH GAUB
30 April 1777-23 Feb 1855
1 681HA2
Assessment of risk based on likelihood of
exposure and/or toxicity
PROBABILITY OF EFFECT
99.9
1Cr2 1Cr1 10° 101 102
Concentration (ng/l)
103
DEALING WITH MIXTURES
Additive toxicity and using potency
addition (TE).
Whole effluent testing
TOTAL POTENCY AS TOXIC UNITS
99.9-
99-
103 102 10' 10° 101 irf 103 10" 1(f
Total potency as sulfamethoxazole equivalents (ng/litre)
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RISK ASSESSMENT
Problem Formulation
and Hazard Identification
ANALYSIS
Effect
characterization
Exposure
characterization
Special considerations
Chronic exposures from pseudopersistence
Non-traditional endpoints
Mixtures a reality and additivity likely
AQUATIC COSMS
EFFECT CHARACTERIZATION IN
COSMS
Community-down approach - rapidly identify
sensitive species in several trophic levels
Observation of direct and indirect effects
Structural and functional endpoints
More realistic stressor exposure
Range of concentrations - upper and lower
thresholds - multiple species - multiple
responses
Synthetic mixtures (Whole Effluent Test)
FATE OF TYLOSIN IN AQUATIC MICROCOSMS
10000
.E 1000:
to
_0
o
c
o
o
100
10
-*- 3000 jig/L
1000ng/L
0 20 40 60 80
Bra/net a/, 2oos Time (days post final treatment)
100
MIXTURE CONCENTRATIONS
70 -
50 -
30 -
-------
Zooplankton Community Response
Ciprofloxacin, Fluoxetine, Ibuprofen
Control Treatment
14 21 28
Time (days)
Richards et al. 2004 ET&C
Phytoplankton Community Response
Ciprofloxacin, Fluoxetine, Ibuprofen
Time (days)
lards et al. 2004 ET&C
RESPONSE OF MYRIOPHYLLUM SIBIRICUM
Tetracycline, oxytetracycline, chlortetracycline, and doxycycline
_ 100
S
8 80
°eo
20
0
Total Primary Root Length
10 20 30 40
Time (days)
Brain et al, 2005
RESPONSE OF PLANKTON
o
0> 80-j
Q 100 -i
I"
W/son et a/, 2004
21 28 35 42
Time (d)
CONCLUSIONS
Identifying chemicals of concern
- Need to consider causality
Identifying sources
- Not always easy
Assessing effects
- Need to consider effects above the level of the
organism
Assessing risks of chemicals of concern
- Cannot rely on traditional tests with traditional
endpoints
Toxicity, hazard and risk
- Probabilistic approaches are promising
Dealing with mixtures
- Complex but whole effluent testing offers advantages
THANK
YOU
ksolomon@uoguelph.ca
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