Integrated
Atmospheric
Deposition
Network
Implementation
Plan
November 1990
.
Canada' ® Ontario
Canada-Ontario Agreement Respecting Great Lakes Water Quality
L'Accord Canada-Ontario relatif a la qualite de I'eau dans les Grand Lacs
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100R90118
Integrated Atmospheric Deposition Network Implementation Plan
prepared by
Canada/U.S. Coordinating Committee on Annex 15
March 6, 1990
presented to the Parties to the Great Lakes Water Quality Agreement
June 14, 1990
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Canada/U.S. Great Lakes Water Quality Agreement
Parties Policy Regarding Annex 15
The attached Implementation Plan for the Integrated Atmospheric Deposition Network is
hereby approved.
L. E
Valdas V. AdamKus
Date
/4tffr^
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Integrated Atmospheric Deposition Implementation Plan
Introduction
The Great Lakes Water Quality Agreement, first signed in 1972, has evolved over the
years. In 1987 new annexes were introduced into the 1978 version of the agreement. These
updates to the agreement recognized the importance of the complete Great Lakes eco-system. In
particular, Annex 15 was included to deal with the problem of airborne contaminants in the Great
Lakes Basin. The influence of airborne contaminants will be an important factor to consider
when developing Lake-Wide Management Plans for each of the Great Lakes. Annex 15 has four
main components: an enhancement of the measurement of the importance of the air pathway for
toxic substances through the establishment of an integrated monitoring network; improvements in
our understanding of the processes in the atmosphere that influence the fate of toxic substances
through an enhanced research program; identification of the human health aspects of the problem;
and the development of appropriate control strategies. The purpose of this document is to outline
an implementation plan for the establishment jointly by Canada and the United States of the
Integrated Atmospheric Deposition Network.
In July 1988, The International Joint Commission published the report to the Water
Quality Board prepared by the Atmospheric Deposition Monitoring Task Force of the Surveillance
Work Group. The report outlined a three phase plan for addressing the problem of airborne toxic
substances in the Great Lakes Basin. A key element of this plan was the establishment of an
Integrated Atmospheric Deposition Network for the Great Lakes Basin. This network would
consist of several Master (research grade) Stations augmented by a number of Satellite (routine)
stations. The objective of this network was to acquire sufficient, quality assured data to estimate
with a specified degree of confidence the loading to the Great Lakes Basin of selected toxic
substances. The relative importance of the atmospheric pathway could then be ascertained and
appropriate control strategies developed. The IJC report also identified many critical research
issues that must be addressed in order to understand and quantify the importance of the
atmospheric pathway for toxic substances.
Although resources were scarce, some efforts to address the airborne toxics issues
continued. A Canadian Master station was established at Point Petre (1988) providing a platform
for many agencies to take simultaneous measurements of a number of substances in a number of
ways. The United States established a Master station at Green Bay (1987) to monitor airborne
toxics and study their effect on the region.
On December 4 to 5, 1989 a U.S./Canada group of managers and scientists met in Detroit
to begin preparation of an implementation plan for the envisioned Integrated Atmospheric
Deposition Network. The implementation provides detail and specific direction over the next 6
years and follows directly from the more general IJC report. Research issues were not explicitly
addressed at the December meeting or in the document that follows, however, the importance of
on-going research in developing a clear understanding of atmospheric pathways and fate of toxic
substances should not be understated.
The following document considers various aspects of a workable implementation plan.
The problem was divided into three parts; 1) the choice of chemicals to be measured, 2) the siting
criteria and sampling methodology and 3) the Quality Assurance/Quality Control required. These
categories are somewhat arbitrary and the inter-relationships among them are many. However,
for planning purposes it is useful to maintain the distinction.
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Determination of Chemicals to be Measured
Several hundred toxic chemicals have been be detected in the Great Lakes Basin of which
many are thought to have a significant airborne component. In choosing appropriate chemicals to
measure in the Integrated Atmospheric Deposition Network a number of criteria are important.
Criteria for Selection of Target Atmospheric Pollutants
• The substances are listed in List 1 of Annex 1 of the Great Lakes Water Quality
Agreement. This list includes substances believed to be toxic and believed to be present in
the Great Lakes.
• The substance is currently an established or perceived water quality problem. The
toxicology of the substance may indicate a potential serious problem; the substance may
bio-accumulate or be persistent. The loading to the eco-system can then become
significant. The human health concerns could be a factor.
• The substance is now on the Water Quality Board's list of critical pollutants.
• Evidence exists that the chemical is present in the atmosphere (rain, snow, aerosol) and/or
has an important atmospheric pathway (volatilization; occurrence in remote lake/peat
sediments).
• The chemical should be feasible to measure in a routine monitoring network. Routine in
this sense means a sequence of collection, transport, processing and analysis procedures
can be performed in a prescribed manner.
The Selection of Phase I Substances
Phase one is considered to be the first two years of the program. Naturally in this phase a
significant emphasis will be on research. Evidence is required to establish whether any toxic
chemical can be routinely monitored in ambient air or in wet deposition samples. The dry
deposition will be estimated using air concentrations. Therefore, the toxic chemicals measured in
Phase I should be selected to demonstrate feasibility and efficacy of the methodology, namely:
1. PCBs: Total PCBs and major congeners
2. HCHs: a , -7 isomers
3. PAHs: B[a]P (goal)1
4. Pb
The selection of specific compounds within families will be established by regular
consultation.
As a second priority, methodologies will be developed and applied for the following
compounds:
The PAH B[a]P is among the most difficult of all the PAHs to determine. Sampling is
particularly difficult as this PAH is chemically very reactive with ambient oxidants and is
subject to UV degradation. Other less reactive PAHs will be sampled along with B[a]P. There
is no doubt that B[a]P is an important substance and work should continue on an appropriate
sampling procedure.
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• Cl-pesticides such as DDT plus metabolites; chlordane; nonachlor;
heptachlorepoxide; methoxychlor; dieldrin; HCB; endrin
• Trace Metals - Arsenic, Selenium, Cadmium, Mercury
Substances Requiring Extensive Methodology Development
A number of other chemicals are known or suspected of having an important atmospheric
pathway. However, the following chemicals require extensive method development and/or
confirmation of their importance. The topics requiring attention include:
• Some chemicals, such as the Cl-benzenes, with an established atmospheric
component to their environmental cycling, may require methodology development
in order to take valid measurements.
• A wide range of PAHs are present in the Great Lakes eco-system. Although there
are currently very few measurements, PAHs have an important atmospheric
pathway. The measurement methodology for a broad range of PAHs requires
considerable improvement.
• Toxaphene is present in the Great Lakes eco-system and has been shown to be
transported by air from large distances. The analytical methodology requires
considerable improvement before extensive atmospheric sampling can be done.
• There are a variety of toxic substances which may have an atmospheric pathway
but as yet there is a lack of definitive data to establish the existence or importance
of this pathway. As well, routine analytical procedures generally do not exist for
these substances. For example, co-planar PCBs, dioxins and furans.
• New chemicals are being introduced each year into the Great Lakes Basin. The
significance of these chemicals is largely unknown. A range of modern
agrochemicals, such as Triazines, Alachlor/Metachlor, as well as, industrial
chemicals such as plasticizers, PCB substitutes, etc. may have to be studied.
Stations. Siting. Samplers, and Sampling Protocols
Each of the three phases of the Integrated Atmospheric Deposition Network Plan will last
for a period of two years, commencing with the implementation date of January 1990. This
section considers four aspects of the implementation:
• The number of stations in the network
« The siting criteria for those stations
• The sampling equipment to be used at those stations
• The sampling protocol for the acquisition of deposition data.
Number of Stations in the Network
The final design of the network will be based on the knowledge gained during the phased
approach of the implementation. As such, the final number of stations is still open to
determination based on criteria associated with spatial homogeneity of the deposition fields,
temporal scales of the deposition variation, and the importance of local physical variables of
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deposition, many of which can be identified but currently are not quantified. The first priority of
the network will be to determine the deposition of toxic chemicals to the Great Lakes from the air
in terms of annual averages, but to the extent possible, the network will address source region
attribution questions. While the deposition processes are governed by very short time scales,
annual average deposition can be determined with much longer scale sampling times. Although
sampling should occur at the shortest temporal scale which can be accommodated by data quality,
logistics and cost, the smallest scales will be below network resolution. It is felt that the design of
the IJC Plan is basically correct for the objective of determining longer scale loadings to the Great
Lakes Basin; that is, there is a requirement for five research grade Master Stations throughout the
Great Lakes basin and up to twenty-two routine measurement or satellite stations within the basin.
During Phase I of the Plan, the Parties will initiate sampling at one Master Station site
each. Master Stations will be designed with sufficient space and infrastructure to accommodate
temporary, intensive research efforts. Canada has chosen Point Petre on Lake Ontario as its initial
Master Station site. The U.S. has operated a Master Station grade site at Green Bay from April
1987 to the present. It is planned that during Phase I, a more regionally representative site will be
established on the south shore of Lake Superior during the summer of 1990. The Green Bay site
will continue to operate at least until the end of the Green Bay Mass Balance Study.
By April 1991, Canada will initiate construction of the third Master Station on Lake
Huron. Two U. S. Master Stations will be sited: one on the southeastern shore of Lake Erie and
one on Lake Michigan. The Lake Erie site will be implemented at the beginning of Phase II and
the Lake Michigan site during Phase II. Phase II under this plan will be initiated in January 1992
and will run through December 1993. During 1992, five satellite stations in Canada and six
satellite sites in the U.S. will be chosen and implemented. The intent is that one satellite station
will be added to each side of each of the four international lakes, two U. S. stations to Lake
Michigan and one Canadian station northwest of the Great Lakes basin.
Analysis of data from the five Master Stations and eleven satellite sites for Phases I and II
will be completed by June 1994. At that time the Parties will determine the need for, and the
necessary sites for, up to an additional eleven satellite stations. .The intent is to have one station
added on each side of each international lake, two U.S. stations on Lake Michigan and an
additional station northeast of the Great Lakes basin in Canada.
Siting Criteria
It is desirable to place each station physically as close to the Lakes as is logistically
possible. Although the impact of urban sources on deposition to the lakes and of land/lake breeze
circulation was considered, these effects will be difficult to discern, in a statistical sense, from the
general noise in the annual average deposition data and thus should be ignored initially. Research
to quantify the level of the smaller scale impacts must take place within Phases I and II. To this
end, use of a ship or offshore platform for collection of samples downwind of urban centres is
recommended as an effective research approach especially when coupled with model studies.
A siting criteria document will be produced by May 1990. The document will consider the
general principles of future station siting and give optimal guidelines to be followed by the
Parties. When no appropriate site can be found meeting all criteria, it is agreed that the Parties
may deviate from the guidelines provided there is reasonable justification and mutual
consultation.
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Sampling Equipment
There are currently variations in the types of samplers being used to measure air and
precipitation concentrations of organics and trace metals in the Great Lakes. It is not
recommended at this time that a formal decision be taken on the types of samplers to be used in
the network but rather that Phase I be used to evaluate the sampler methodologies used by the
agencies involved in Great Lakes sampling. To that extent, reference is made to Tables 4 and 5 of
the IJC plan. The initial Master Station complement will consist of:
• 1 precipitation sampler to measure nutrients and inorganic chemicals in wet
deposition in order to compare with existing networks.
• 1 precipitation sampler to measure trace metals in wet deposition
• replicated precipitation samplers to measure toxic organics in wet deposition (2 or
more)
• replicated high volume air samplers with filter/adsorbent combinations to measure
gaseous and paniculate toxic organics in air (2 or more)
• 1 high volume sampler to measure total suspended particulate mass loading in air
and total organic carbon
• 1 sampler for trace metals in air
• A set of meteorological instruments to measure rain and snow intensity and
amount, temperature, relative humidity, wind velocity and solar radiation.
• dichotomous Hi-Vol samplers2
The initial satellite stations will have one sampler for the measurement of each of:
trace metals in precipitation
trace metals in air
toxic organics in precipitation
toxic organics in air
Total suspended particles
plus meteorological instruments to measure rain and snow intensity and amount,
temperature, relative humidity, and wind velocity.
During Phase I, differing sampling methodologies will be examined and not precluded
between the Parties. The QA/QC programme will address the significance of the difference
between the sampling methodologies. Subsequently, after the Critical Network Design Review
(June 1992), the Co-ordinating Committee will make recommendations to the Parties for sampling
methodologies for the Master and Satellite stations.
High-volume and low-volume dichotomous air samplers will be installed at a single Master
Station early in Phase I in order to evaluate their performance side-by-side with existing air
samplers. Before the beginning of Phase II, a decision will be made on whether dichotomous
samplers will be chosen for air sampling at all Master sites and Satellite sites.
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Sampling Protocols/Analysis Protocols
It is recognized that current sampling and analysis protocols differ-between the Parties due
to a number of factors including sample handling capacity, sampling protocols which agree with
other sampling networks, expected need for valid sample volumes, and tested sampling
procedures. During Phase I such disagreements between protocols will be accepted but
comparability should be established by the time of the Critical Network Design Review during
Phase II (June 1992). Each agency will document their current sampling and analysis protocols for
exchange under the QA/QC programme before June 1990.
It is recognized that the requirement of the network to deliver estimates, with a specified
degree of confidence, of annual deposition to the Great Lakes is not necessarily the same
requirement as to deliver information on source identification information for input to remedial
action strategies. Source identification information can be delivered by specific research
programmes in cooperation between the Parties for intensive periods at the Master Stations or
other appropriate sites.
Quality Assurance and Quality Control
The Integrated Atmospheric Deposition Network will consist of individual stations, run by
different US and Canadian agencies. To be useful, the data generated by each of the agencies will
need to be combined into one data set. Thus the data from each individual project will need to be
demonstrated to be of comparable quality. Generation of comparable data by the individual
agencies will only be accomplished if each of the agencies adheres to a thorough, Program-wide
QA/QC Plan.
The work will begin immediately on the design and development of a Quality Assurance
Program Plan for the overall monitoring network. This plan will address the following issues:
• Quality assurance objectives
• Procedures for demonstrating and assessing performance
Quality Assurance Objectives
A clear definition will be provided of relevant QA components, which will be used to
assess the performance of a monitoring agency, and ultimately determine the acceptance/ non-
acceptance of a data-set.
It is agreed that clear data quality objectives be set for each chemical (or group of
chemicals) to be monitored on a routine or research basis. For each contaminant, these objectives
will be based upon the estimated amount entering the Great Lakes and the significance of the
atmospheric components.
The data quality objectives will govern all aspects of the measurement process, i.e.
sampling, analysis, data reduction/reporting. The data quality objectives will be used as the basis
for the final acceptance of data from a given agency.
It will be the responsibility of each agency to document compliance/attainment of the data
quality objectives. The program plan will also provide clear guidelines as to the procedures by
which this attainment should be assessed.
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Procedures For Demonstrating and Assessing Performance
For each of the specified quality assurance components included in the data quality
objectives, procedures will be defined for individual agencies to demonstrate attainment. For
instance, precision of analysis for a given target species should be assessed by the approaches of
duplicate sampling in the field. Replicate analyses in the laboratory will provide another measure
of precision.
The procedures can be roughly divided into
• Internal procedures
• External procedures
Internal procedures can be defined as those methods that can be employed by a given
agency to confirm data quality, e.g., regular calibrations, complete documentation, internal audits.
External procedures are defined as those methods which will require intervention by an
outside party, e.g., external audits, laboratory inter-comparisons, co-location of samplers
employing different approaches, etc.
Preparation of the Plan
The QA Program Plan will be developed by October 1990. Development of the network
QA Program will be undertaken by a contractor under the management of the QA/QC Working
Group. To assist in the development of the Program Plan, each agency will provide copies of
existing approved QA Project Plans to the co-chairs of the QA/QC Working Group by the end of
May 1990.
Implementation of the Plan
To ensure the effective implementation of the QA Plan, the following actions are required.
• The appointment of a QA Manager to oversee the whole program is strongly
recommended. Failing that, the appointment of QA officers by each of the parties
will be required.
• To assure compliance with the QA/QC Program Plan and to demonstrate the
production of comparable data, the QA Manager will be responsible for the
organization and execution of external performance evaluation studies. This aspect
needs to be implemented as soon as possible, since a considerable amount of data
has already been collected by the various groups involved. The QA Manager will
co-ordinate a series of sample exchanges/inter-comparison studies during early
1991 (or earlier if feasible).
• Individual Agencies will be required to demonstrate compliance with the data
quality objectives in the QA Plan by October 1991. The supporting documentation
that must be submitted to the QA Manager at that time will include:
• QA Project Plans
• QA Manuals
• Performance Assessment Results
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At this point, the QA Manager will decide upon the overall suitability of data
being generated by a given agency.
The QA Manager will have ultimate responsibility for acceptance of final data sets
from approved agency monitoring networks.
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Milestones for Implementation of the Integrated Atmospheric Deposition Network
(/M
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I
• •M
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PHASE I
PHASE II
PHASE III
January 1990*
- QA/QC
- Exchange QA Project Plans
(May '90)
- Coordinate Agency QA Plans
(e.g. Intercomparison/Round
Robin) (1990)
- Contract IADN QA Manager
- Develop IADN Program Plan
(October '90)
- Siting Criteria (May '90)
- Select/Construct Master Sites
(1990)
- Pt. Petre (CAN; Lake Ontario)
- Keweenau Peninsula
(U.S.; Lake Superior)
- Co-location of CAN/US Sampling
Equipment (1990), Pt. Petre
- Select Chemicals for Monitoring
(Jan. '90)
- Meeting CAN/U.S. Coordinating
Committee (2 x per year)
- Initiate Research Activities
- Select/Construct CAN Master Site
(April -91) (Lake Huron)
*each phase is 2 years in length
January 1992
- Update Estimates of
Atmospheric Deposition
(Jan.'92 thereafter annually;
CAN/US Coord.Comm.)
- Review IADN and research activities
(Jan.'92; CAN/US Coord.Comm.)
- Project Complilance with IADN
Program Plan (QA) (IADN QA Manager)
- Review and modify chemical list
for IADH
- Select/Construct US Master Site(s)
- Lake Erie site (May '92)
- Lake Michigan (east, side) (May '93)
- Select/Construct Satellite Stations
(1992)
- 1 per international lake (U.S.)
- 1 per international lake (CAN)
- 2 sites on Lake Michigan (U.S.)
- 1 site upwind of GL's (ELA) (CAN)
- Continue research activities
January 1994
- Update estimates of
atmospheric deposition
(Jan. '94; annually;
CAN/US Coord.Comm.)
- Review IADN and research
activities
(Jan. '94; CAN/US Coord.Comm.)
- Review/modify chemical list
- Select/Construct Satellite Station
number and location to be determin
- Continue research activities
- Network Implementation
(Dec. '95)
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