United States       Region III     Region III      EPA 903-R-07-005
Environmental Protection   Chesapeake Bay   Water Protection    CBP/TRS 288/07
Agency          Program Office   Division       October 2007

In coordination with the Office of Water/Office of Science and Technology, Washington, D.C., and the states
of Delaware, Maryland, New York, Pennsylvania, Virginia and West Virginia and the District of Columbia
Ambient Water Quality
Criteria  for Dissolved
Oxygen, Water Clarity
and Chlorophyll a for
the Chesapeake Bay
and Its Tidal Tributaries
2007 Chlorophyll CritprAddendum
November 2007

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       Ambient Water Quality Criteria
    for Dissolved Oxygen, Water Clarity
and  Chlorophyll a for the Chesapeake Bay
            and  Its Tidal Tributaries
       2007 Chlorophyll Criteria Addendum
                     November 2007

              U.S. Environmental Protection Agency
                       Region III
                Chesapeake Bay Program Office
                   Annapolis, Maryland

                         and

                       Region III
                  Water Protection Division
                  Philadelphia, Pennsylvania

                    in coordination with

                      Office of Water
               Office of Science and Technology
                     Washington, D.C.

                         and

                      the states of
                Delaware, Maryland, New York,
                  Pennsylvania, Virginia, and
            West Virginia and the District of Columbia

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                                                                                      1
                         Contents
Acknowledgments 	   v

I. Introduction  	   1
      Literature Cited 	   2

II. Chlorophyll a Criteria	   3
   State Water Quality Standards	   3
   Deriving Scientifically Sound Numerical Chlorophyll a Criteria	   4
   Phytoplankton, Water Quality and Chlorophyll a	   4
      Chlorophyll a dynamics in the mainstem Chesapeake Bay  	   6
      Chlorophyll a dynamics in the tidal tributaries and embayments	   7
   Scientific Basis for Numerical Chlorophyll a Criteria	   7
       Historical chlorophyll a reference concentrations	   7
       Dissolved oxygen impairments  	   8
       Water clarity impairments  	   8
       Harmful algal bloom impairments	   8
   Literature Cited	   9

III. Historical Chlorophyll a Reference Concentrations  	  12
   Rationale for 1950s-1960s Reference Period	  13
   Reference Concentration Derivation Approach	  13
      Historical data sources and temporal coverage  	  14
      Modeling approach	  15
      Accounting for flow	  15
   Derivation of Reference Thresholds Based on Spatial and
      Temporal Variances 	  16
   Depth-Weighted Integrated Water-Column Chlorophyll a  	  19
   Historical Chlorophyll a Reference Concentrations	  21
   Literature Cited	  22

IV. Chlorophyll a Relationship to Dissolved Oxygen Impairments  .  24
   Literature Cited	  35
                                                                                Contents

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                 V. Chlorophyll a Contribution to Water
                   Clarity Impairments	  36
                    Determining Background TSS Concentrations	  38
                    Ecological Relationship Between Chlorophyll a and Water Clarity
                      Impairments 	  40
                    Regionalizing the Factors Contributing to Water Column Light
                      Attenuation 	  42
                    Water Clarity Impairment-Based Chlorophyll a Thresholds	  43
                    Literature Cited	  46

                 VI. Chlorophyll a Concentrations Characteristic of  Impairments by
                    Harmful Algal Blooms	  49
                    Deriving Numerical Chlorophyll Criteria  	  51
                      Microcystis cell densities/chlorophyll a relationship	  54
                      Literature-based toxin levels, cell counts and chlorophyll conversions . .  55
                      Chesapeake Bay Microcystis toxins comparison with thresholds	  56
                      CART analyses assessment of risk levels	  58
                    HAB Impairment-Based  Chlorophyll a Criteria	  59
                    Literature Cited	  60

                 VII. Chesapeake Bay Chlorophyll a Criteria and
                     Reference Concentrations	  63
                    Harmful Algal Bloom Impairment-Based Chlorophyll a Criterion ....  63
                    Historical Chlorophyll a Reference Concentrations 	  64
                    Dissolved Oxygen Impairment-Based Reference Concentrations	  64
                    Water Clarity Impairment-Based Chlorophyll a
                      Reference Concentrations  	  65
                    Other Chlorophyll a Concentration Thresholds, Criteria,
                      and Standards	  66
                    Literature Cited	  68

                 VIM. Chesapeake Bay Chlorophyll a Criteria
                     Recommended Attainment Assessment Procedures	  69
                    Harmful Algal Bloom Impairment Based Chlorophyll a Criteria
                      Assessment Procedures	  69
                      Sampling regime	  69
                      Time and space dimensions  	  69
                    Chlorophyll a Concentration-Based Criteria Assessment Procedures ...  70
                    Literature Cited	  72

                 Acronyms   	  73

                 Appendix A: Delaware, Maryland, Virginia and the District of Columbia's
                             Narrative Water Quality Standards Regulations Relevant
                             to Algal Related Impairments	A-l

                 Appendix B: Listing of Harmful Algal Species  in Chesapeake Bay	B-l

                 Appendix C: States Chlorophyll a Criteria and  Water Quality Standards . . . . C-l
Contents

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               Acknowledgments
This third addendum to the April 2003 Water Quality Criteria for Dissolved Oxygen,
Water Clarity and Chlorophyll a for Chesapeake Bay and Its Tidal Tributaries was
developed and documented through the collaborative efforts of the members of the
Chesapeake Bay Program's Chlorophyll Criteria Team, Criteria Assessment Protocol
Workgroup and Water Quality Steering Committee.

PRINCIPAL AND CONTRIBUTING AUTHORS

This document resulted  from the collaborative expertise and  talents of the
Chesapeake Bay Program's state agency, federal  agency and academic institutional
partners.  The principal (listed first) and contributing authors (listed in alphabetical
order) are listed here  by chapter.  Chapter 1:  Richard Batiuk; Chapter 2: Tom
Malone, Arthur Butt; Chapter 3: Larry Harding, Elgin Perry; Chapter 4: Tom Fisher,
Michael Williams; Chapter 5: Chuck Gallegos,  David Jasinski;  Chapter 6:  Peter
Tango, Jackie Johnson, Margie Mulholland and Hans Paerl; Chapter 7: Richard
Batiuk; Chapter 8: Peter Tango, Richard Batiuk and Elgin Perry.

CHLOROPHYLL CRITERIA TEAM

Tom Malone,  Chair, OceansUS; Richard Batiuk, U.S. Environmental Protection
Agency  Chesapeake Bay Program Office; Arthur Butt, Virginia  Department of
Environmental  Quality; William Dennison, University of Maryland Center for
Environmental  Science; Charles Gallegos, Smithsonian Environmental  Research
Center; Tom Fisher, University of Maryland Center  for Environmental Science;
Larry Haas, Virginia Institute of Marine Science; Larry Harding, University of
Maryland Center for Environmental Science/Maryland Sea Grant; Margie
Mulholland, Old Dominion University; Hans Paerl, University of North  Carolina;
Peter Tango, U.S. Geological Survey/Chesapeake Bay Program Office and Jonathan
Sharp, University of Delaware.

Chlorophyll Criteria Team data analysts: David Jasinski, University of Maryland
Center for Environmental Science/Chesapeake Bay Program Office; Jackie Johnson,
Interstate Commission of the Potomac River Basin/Chesapeake Bay Program Office;
and Michael Williams, University of Maryland Center for Environmental Science.

CRITERIA ASSESSMENT PROTOCOL WORKGROUP

Peter Tango, Chair, U.S. Geological Survey/Chesapeake Bay Program Office; Harry
Augustine, Virginia Department of Environmental Quality; Mark Barath, U.S.
                                                                          Acknowledgments

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                  Environmental Protection Agency Region III; Thomas  Barron,  Pennsylvania
                  Department  of Environment; Joe  Beaman,  Maryland  Department  of the
                  Environment;  Stephen Cioccia, Virginia Department of Environmental Quality;
                  Elleanore Daub, Virginia Department of Environmental Quality; Sherm Garrison,
                  Maryland Department of Natural Resources; Darryl Glover, Virginia Department of
                  Environmental Quality; John Hill, Maryland Department of the Environment; Rick
                  Hoffman, Virginia Department of Environmental Quality; Dave Jasinski, University
                  of Maryland Center for Environmental  Science/Chesapeake Bay Program Office;
                  Jim Keating, U.S. Environmental Protection Agency Office of Water; Rodney Kime,
                  Pennsylvania  State  Department  of the Environment;  Larry  Merrill,  U.S.
                  Environmental Protection Agency Region III; Bruce Michael, Maryland Department
                  of Natural Resources; Ken  Moore, Virginia Institute of Marine  Science;  Shah
                  Nawaz,  District of Columbia Department of  Health; Roland  Owens, Virginia
                  Department of Environmental Quality;  Jennifer Palmore, Virginia  Department of
                  Environmental Quality; Elgin Perry,  Statistics Consultant; Charley Poukish,
                  Maryland Department of the Environment; Matt Rowe, Maryland Department of the
                  Environment;  John Schneider, Delaware  Department of Natural Resources and
                  Environmental Control; Gary Shenk,  U.S.  Environmental Protection Agency
                  Chesapeake Bay Program Office;  Nicoline Shulterbrandt, District of  Columbia
                  Department of  Health; Donald  Smith, Virginia Department of  Environmental
                  Quality; Matt  Stover, Maryland Department of the Environment;  Robert Swanson,
                  Virginia  Department of Environmental Quality;  Bryant  Thomas,  Virginia
                  Department of Environmental Quality; Mark Trice, Maryland Department of Natural
                  Resources; Michael Williams,  University  of Maryland Center for  Environmental
                  Science; Dave Wolanski, Delaware Department of Natural Resources and Environ-
                  mental Control.

                  WATER QUALITY STEERING COMMITTEE

                  Diana Esher,  Chair,  U.S.  Environmental Protection Agency Chesapeake  Bay
                  Program Office; Richard Batiuk, U.S. Environmental Protection Agency Chesapeake
                  Bay Program Office; Sheila Besse, District of Columbia Department of Health; Bill
                  Brannon, West Virginia Department of Environmental Protection; Patricia Buckley,
                  Pennsylvania Department of Environmental Protection; Katherine Bunting-Howarth,
                  Delaware Department of Natural Resources and Environmental  Control; Jennifer
                  Capagnini, Delaware Department of Natural Resources and Environmental Control;
                  Moira Croghan, Virginia Department  of Conservation and Recreation; Frank
                  Dawson, Maryland Department of Natural Resources; Rusty Diamond, Department
                  of Environmental  Protection-South Central  Office;  Ron  Entringer, New  York
                  Department of Environmental Conservation; Richard Eskin, Maryland Department
                  of the Environment; Stuart Gansell, Pennsylvania Department of  Environmental
                  Protection; Dave Goshorn, Maryland Department of Natural Resources;  Carlton
                  Hay wood, Interstate Commission on the Potomac River Basin; Teresa Koon, West
                  Virginia Soil Conservation Association; Bruce Michael, Maryland  Department of
                  Natural Resources; Matt Monroe, West  Virginia Department of Agriculture;  Kenn
                  Pattison,  Pennsylvania Department of  Environmental Protection;  Alan Pollock,
                  Virginia  Department  of  Environmental  Quality;  John  Schneider,  Delaware
                  Department of  Natural Resources and Environmental Control; Rick Shertzer,
Acknowledgments

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                                                                                            vii
Pennsylvania State  Department  of Environmental Protection; Tom  Simpson,
University  of  Maryland;  Randolph Sovic,  West  Virginia  Department  of
Environmental Protection; Pat Stuntz, Chesapeake Bay Commission; Ann Swanson,
Chesapeake Bay Commission.

SCIENCE AND TECHNICAL ADVISORY COMMITTEE

The support and expert advice of all the members of the Chesapeake Bay Program's
Scientific and Technical Advisory Committee are hereby acknowledged, under the
leadership of Dr.  Carl Hershner, Virginia Institute  of Marine  Science, and the
Executive Secretarial  support  of Dr. Kevin Sellner,  Chesapeake  Research
Consortium.

The contributions  of the independent  scientific peer reviewers, selected and con-
vened  by the Chesapeake  Bay  Program's  Scientific  and Technical  Advisory
Committee based on their recognized national expertise and drawn from institutions
and agencies from across the country, are hereby acknowledged.

Without the efforts of the hundreds of colleagues involved in all aspects of field col-
lection, laboratory analysis, management and  interpretation of Chesapeake Bay
Monitoring Program data over the past two decades, these criteria could not have
been derived and the criteria attainment assessment procedures could not have been
developed.

The technical editing by Nina Fisher,  independent technical editor, and document
preparation by Jamie McNees, Chesapeake Research Consortium/Chesapeake Bay
Program Office is hereby acknowledged.
                                                                             Acknowledgments

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                              chapter  |

                        Introduction
In April 2003, the U.S. Environmental Protection Agency (EPA) published the Am-
bient Water Quality Criteria for Dissolved Oxygen, Water Clarity and Chlorophyll a
for the Chesapeake Bay and Its Tidal Tributaries (Regional Criteria Guidance) in
cooperation  with  and on behalf  of the  six watershed  states—New  York,
Pennsylvania, Maryland, Delaware, Virginia, and West Virginia—and the District of
Columbia. The culmination of three years of work, the criteria document resulted
directly from the collective contributions of hundreds of regional scientists, techni-
cal staff,  and agency managers as well as  the independent review by recognized
scientific  experts across the country (U.S. EPA 2003).
In October 2004, EPA published the first addendum to the 2003 Regional Criteria
Guidance (U.S. EPA 2004). The addendum provided additional guidance on: applying
the temperature-based open-water dissolved oxygen criteria required to protect the
endangered shortnose sturgeon; assessing attainment of the instantaneous  minimum
and 7-day mean dissolved oxygen criteria using monthly mean water quality monitor-
ing data; deriving site-specific dissolved oxygen criteria for tidal systems where the
extensive  adjacent  tidal  wetlands cause naturally  low  dissolved  oxygen levels;
delineating the upper and lower boundaries of the pycnocline; defining attainment of
the shallow-water bay grass designated use; and determining where numerical chloro-
phyll a criteria should apply to local Chesapeake Bay and tidal tributary waters.
From 2004 through early  2006, Delaware, Maryland, Virginia, and the District of
Columbia adopted: the EPA-published Chesapeake Bay water quality criteria for
dissolved oxygen,  water clarity,  and  chlorophyll a;  the EPA-recommended tidal
water designated uses; and the EPA-established criteria assessment procedures into
their respective state water quality standards regulations. All four jurisdictions1
promulgated  narrative chlorophyll a criteria in their standards regulations. Virginia
promulgated  numerical segment-  and season-specific chlorophyll a criteria for the
tidal James River.  The District of Columbia promulgated numerical chlorophyll a
criteria for its reach of the tidal Potomac River and its remaining tidal waters, hav-
^eferences throughout the text to "states" or "jurisdictions" means a collective reference to the states
 of Delaware and Maryland, the Commonwealth of Virginia, and the District of Columbia. All four have
 Chesapeake Bay tidal waters within their jurisdictional boundaries.
                                                                       chapter i  •  Introduction

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                  ing previously adopted numerical chlorophyll a criteria for protection of the tidal
                  Anacostia River.
                  In July 2007, EPA published a second addendum  to the 2003 Regional  Criteria
                  Guidance (U.S. EPA  2007).   This second  addendum documented the  revised,
                  refined, and new criteria assessment methods for the published Chesapeake Bay dis-
                  solved oxygen, water clarity, and chlorophyll a criteria.
                  This third addendum documents numerical Chesapeake Bay chlorophyll a criteria
                  and reference concentrations.
                     • Chapter 2 documents the scientific basis for numerical chlorophyll a  criteria.
                     • Chapter 3 documents historical chlorophyll a reference concentrations.
                     • Chapter 4 documents  the  chlorophyll a relationship to dissolved  oxygen
                       impairments.
                     • Chapter 5 documents the chlorophyll a contribution to  water clarity impair-
                       ments.
                     • Chapter 6 documents chlorophyll a concentrations characteristic of address-
                       ing impairments by harmful algal blooms.
                     • Chapter 7 documents the recommended Chesapeake Bay chlorophyll a  criteria.
                     • Chapter 8 documents the recommended procedures for assessing attainment
                       of numerical chlorophyll a criteria.
                  This document represents the third formal addendum to the 2003 Chesapeake Bay
                  water quality criteria document. As  such, readers should regard the sections in this
                  document as new or replacement chapters and appendices to the original published
                  report and two prior published addendums. The criteria attainment assessment pro-
                  cedures published in this  addendum replace and otherwise supercede similar criteria
                  assessment procedures originally published in the 2003 Regional Criteria Guidance
                  and the 2004 and 2007 addendums  (U.S. EPA 2003, 2004, 2007). Publication of
                  future addendums by EPA in coordination with and on behalf of the Chesapeake Bay
                  Program watershed jurisdictional partners is likely.   Continued scientific research
                  and management applications reveal new insights and knowledge that should  be
                  incorporated into revisions of state water quality standards regulations in upcoming
                  triennial reviews.
                                            LITERATURE CITED
                  U.S. Environmental Protection Agency. 2003. Ambient Water Quality Criteria for Dissolved
                  Oxygen, Water Clarity and Chlorophyll a for Chesapeake Bay and Its Tidal Tributaries. EPA
                  903-R-03-002. Region III Chesapeake Bay Program Office, Annapolis, MD.
                  U.S. Environmental Protection Agency. 2004. Ambient Water Quality Criteria for Dissolved
                  Oxygen, Water Clarity and Chlorophyll a for Chesapeake Bay and Its Tidal Tributaries -
                  2004 Addendum.  EPA  903-R-04-005. Region  III Chesapeake  Bay Program  Office,
                  Annapolis, MD.
                  U.S. Environmental Protection Agency. 2007. Ambient Water Quality Criteria for Dissolved
                  Oxygen, Water Clarity and Chlorophyll a for Chesapeake Bay and Its Tidal Tributaries -
                  2007 Addendum.  EPA  903-R-07-003. CBP/TRS  285/07.   Region  III Chesapeake Bay
                  Program Office, Annapolis, MD.
chapter i  •  Introduction

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                                                                                                1
                             chapter||

             Chlorophyll  a  Criteria
             STATE  WATER QUALITY STANDARDS

With publication of the April 2003 Ambient Water Quality Criteria for Dissolved
Oxygen, Water Clarity and Chlorophyll afar the Chesapeake Bay and Its Tidal Trib-
utaries, the U.S. Environmental Protection Agency (EPA) provided the states with
recommended narrative chlorophyll a criteria applicable to all Chesapeake Bay and
tidal tributary waters (Table II-l) (U.S. EPA 2003a). The four jurisdictions  that
include Chesapeake Bay tidal waters within their boundaries—Delaware, Maryland,
Virginia, and the District of Columbia—all have narrative water quality standards in
their existing regulations that require achievement and maintenance of a balanced,
non-nuisance phytoplankton community  (Appendix A). Individually and  collec-
tively,  these four jurisdictions'  existing  water quality standards regulations contain
clear narrative requirements that address the adverse human health and aquatic life
impairments caused by overabundant, nuisance algal production measured as chloro-
phyll a.  The absence of numerical chlorophyll a  criteria,  however, prevents the
jurisdictions from assessing whether their tidal waters are meeting their designated
uses. Beyond the tidal James  River and  the District's tidal waters, however, the
absence of a numerical interpretation of the narrative desired ecological condition
prevents the states from fully and properly applying the narrative sections of their
water quality standards regulations (as described in Appendix A).

From 2004  through  early  2006, Virginia and the District of Columbia adopted
numerical chlorophyll a criteria for the tidal James River (Virginia) and across all the
District's jurisdictional tidal waters. Both jurisdictions determined that algal-related
Table 11-1.  Chesapeake Bay narrative chlorophyll a criteria.

Concentrations of chlorophyll a in free-floating microscopic aquatic plants (algae) shall not exceed
levels that result in ecologically undesirable consequences—such as reduced water clarity, low
dissolved oxygen, food supply imbalances, proliferation of species deemed potentially harmful to
aquatic life or humans or aesthetically objectionable conditions—or otherwise render tidal waters
unsuitable for designated uses.

Source: U.S. EPA 2003a.
                                                               chapter ii  •  Chlorophyll a Criteria

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                  designated use impairments were likely to persist in these waters even after attain-
                  ment of the applicable dissolved oxygen and water clarity criteria. The water quality
                  standards regulations in Virginia and the District of Columbia now contain numer-
                  ical chlorophyll a criteria for the protection of aquatic life. The technical information
                  supporting both jurisdictions'  adoption of numerical chlorophyll a criteria was
                  published in the 2003 Chesapeake Bay water quality criteria document (U.S. EPA
                  2003a). Delaware, Maryland, Virginia and the District of Columbia all adopted
                  narrative chlorophyll a criteria into their states' water quality standards regulations
                  (Table II-1).
                        DERIVING SCIENTIFICALLY  SOUND  NUMERICAL
                                      CHLOROPHYLL a  CRITERIA

                  The EPA's published narrative criteria states that chlorophyll a "... not exceed levels
                  that result in ecologically undesirable consequences—such as reduced water clarity,
                  low dissolved oxygen, food supply imbalances, proliferation of species deemed
                  potentially harmful to  aquatic life or humans or aesthetically objectionable con-
                  ditions—or otherwise  render tidal  waters unsuitable for designated uses for
                  balanced aquatic plant life populations and against the overgrowth of nuisance,
                  potentially  harmful  algal  species" (U.S. EPA  2003a).  Quantifying undesirable
                  chlorophyll a levels in the water remains a challenge, however, because concentra-
                  tions  that cause "ecologically undesirable consequences" in one tidal tributary or in
                  one region of the Bay do not necessarily  cause problems  in other tidal tributaries
                  or regions.

                  This duality comes about for two primary reasons. First, as a measure of phytoplankton
                  biomass, chlorophyll a also becomes a measure of the amount of food available for
                  animals in the Bay.  Second, while chlorophyll a functions as an indicator of phyto-
                  plankton biomass as a whole, phytoplankton are a highly diverse group of microscopic
                  algal  (plant) species. Many constitute important sources of food for planktonic animals
                  (zooplankton), fish,  and shellfish while others are poor  quality food sources. Some
                  phytoplankton produce chemicals toxic to humans  and  other organisms. Thus,  the
                  Bay's "carrying capacity" or its ability to support productive and diverse populations
                  of flora and fauna, including highly valued species, depends largely on how well the
                  quantity and quality of phytoplankton meet the nutritional needs of animal consumers.
                  However, chlorophyll a is solely an index of quantity, not quality.
                                PHYTOPLANKTON, WATER  QUALITY,
                                         AND  CHLOROPHYLL a

                  Excessive accumulation of phytoplankton biomass due to nutrient over-enrichment
                  is one of the primary causes  of declining water quality in the nation's estuaries
                  (Howarth et  al. 2000), including the Chesapeake Bay (Neilson and Cronin 1981;
                  Boynton et al. 1982; Harding et al. 1986; Seliger et al. 1985; Fisher et al. 1988;
                  Malone 1992; Malone et al. 1996; Harding and Perry 1997; Kemp et al. 2005). High
                  and variable  nutrient inputs coming from freshwater runoff can destabilize coastal
chapter ii  •  Chlorophyll a Criteria

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ecosystems  when nutrient  loading  exceeds the  ecosystem's rate  compensating
capacity1  (Malone  et al.1996).  This situation has occurred  in Chesapeake Bay,
marked by increases in phytoplankton biomass, decreases in water clarity, and a shift
from demersal to pelagic food webs which began about 100 years ago (Cooper 1995;
Cooper and Brush 1993; Kemp et al. 2001; Kemp et al. 2005).

Variations in phytoplankton biomass  and water clarity  are the primary links between
nutrient loading and changes in  water quality (e.g., water clarity and bottom water
dissolved oxygen levels), submerged aquatic  vegetation  (SAV)  abundance, and
trophic dynamics in coastal marine and estuarine ecosystems (Kemp et al. 2005 and
references therein). Thus, nutrient over-enrichment2 causes  ecological symptoms in
Chesapeake Bay of impaired designated uses as defined by  the Clean Water Act.

Chlorophyll a concentration serves as an especially useful indicator of water quality
for two  important reasons.  First, as  concluded  by Harding and Perry  (1997),
"Chlorophyll a is a useful expression of phytoplankton biomass and is arguably the
single  most responsive indicator of N [nitrogen] and P [phosphorus]  enrichment in
this system [Chesapeake Bay]."  Second, measurements are routine and techniques
are now available to obtain them in near-real time. Relatively rapid methods evolved
over the years to measure  the  concentration of  chlorophyll a in discrete water
samples and in vivo (Flemer 1969). Methods have also been developed to measure
chlorophyll a using aerial surveillance techniques (remote sensing) based on passive
multispectral signals associated with  phytoplankton (Harding et al. 1992).

Improvement in water clarity is a major issue for the recovery of the Bay's shallow-
water underwater grasses.  Correcting the low dissolved oxygen problem that occurs
in the deeper waters of the mesohaline mainstem Chesapeake Bay, lower tidal tribu-
taries  and episodic  events  in shallow water has remained  a challenge  to  Bay
restoration for decades.  Increases in water clarity and dissolved oxygen occur when
excess phytoplankton biomass—measured  as chlorophyll a—is  substantially re-
duced  (National Research Council 2000). Water  clarity improves throughout the
water column when light attenuation by phytoplankton decreases. The extent  of
oxygen depletion in bottom waters (leading to hypoxia and anoxia) decreases when
the sedimentation of organic matter produced by phytoplankton into bottom waters
decreases. Thus, attaining the Chesapeake Bay dissolved oxygen and water clarity
criteria requires reductions in chlorophyll a concentrations by lessening nutrients to
limit the production of phytoplankton biomass  (in addition to reducing sediment
loading which also contributes to lower water clarity). For these reasons, the EPA
believes developing and adopting  numerical chlorophyll a criteria (in addition  to
water clarity and dissolved oxygen criteria) is necessary to protect  Chesapeake Bay
tidal waters.
]Rate compensating capacity is the capacity of a system to respond to nutrient inputs by increasing bio-
 mass-specific rates of nutrient assimilation into biomass (Caperon et al. 1971). This capacity is ex-
 ceeded when increases in the rate of nutrient assimilation can only be achieved through increases in
 biomass. An important assumption is that all of the nutrient input to the system from external sources
 is taken up within the system.

2 Nutrient over-enrichment in the case of Chesapeake Bay refers to both nitrogen and phosphorus since
 both must be controlled to manage nutrient impacts (D'Elia et al. 1986; Fisher et al. 1992, 1999).
                                                                                                  '
                                                                 chapter ii  •  Chlorophyll a Criteria

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                  While excessive chlorophyll a levels are often associated with low bottom-water
                  dissolved oxygen and the loss of SAV, such negative outcomes are not always the
                  result. Some regions of the Bay  and its tidal tributaries  experience excessive
                  accumulations of chlorophyll a without such impairments—especially shallow well-
                  mixed systems.  Conversely, harmful algal blooms may occur in the absence of other
                  water quality impairments. Consequently, the EPA recommends adoption of numer-
                  ical chlorophyll a criteria for protection of open-water designated uses for tidal
                  waters where algal-related impairments will likely  persist even after attainment of
                  the Chesapeake Bay dissolved oxygen and water clarity criteria.

                  CHLOROPHYLL a DYNAMICS IN THE MAIN STEM CHESAPEAKE BAY

                  Plots of the seasonal variation in chlorophyll a concentrations capture both episodic
                  (e.g.,  storm-induced) and month-to-month variations in nutrient loading. Chloro-
                  phyll a levels over time, therefore, offer a good indication of phytoplankton biomass
                  response to nutrient loading and the effects of phytoplankton on water quality and
                  benthic habitats. The seasonal asynchrony of the annual cycles of phytoplankton
                  chlorophyll a in the Chesapeake as well as phytoplankton productivity also indicate
                  that the rate compensating capacity of the Bay  has been exceeded (Caperon et al.
                  1971). The chlorophyll a content of the water column (chlorophyll a concentration
                  integrated from surface to bottom) rises in the Bay to a spring maximum (usually
                  from March to May) when grazing rates are low and nutrient loads are high. During
                  this period, chlorophyll a concentrations are elevated throughout the water column.
                  As the Bay transitions from the spring biomass maximum to the summer phyto-
                  plankton productivity maximum (May to June), bottom-water  chlorophyll  a
                  concentrations decline rapidly with high concentrations restricted to the surface
                  layer  throughout the summer. In contrast to the  annual cycle of phytoplankton
                  biomass, phytoplankton productivity (which is generally limited to the surface layer)
                  increases rapidly from a winter minimum to a summer maximum (usually from July
                  to August) as incident solar radiation increases (Malone et al. 1988; Malone 1991,
                  1992; Miller and Harding 2006).

                  The magnitudes of both the spring water-column-integrated chlorophyll a maximum
                  and the summer phytoplankton productivity maximum vary widely from year to
                  year, but no evidence exists for a secular trend over  the last two to three decades
                  (Harding and Perry 1997;  Harding et al. 2002; Miller  and Harding 2006).  Under
                  current  conditions (1980-present),  seasonal and interannual variations in phyto-
                  plankton productivity are primarily related to the  annual cycles of incident solar
                  radiation and temperature (Malone 1991,  1992; Harding et al. 2002). In contrast,
                  seasonal and interannual variations in chlorophyll a levels in the salt-intruded reach
                  of the mainstem Bay are caused primarily by variations in nitrate loading (using flow
                  of the Susquehanna River as a proxy) (Malone 1991; Malone et al. 1996).

                  In summary, the rate of nutrient assimilation by phytoplankton (per unit biomass) is
                  nutrient saturated during spring; therefore, increases in nutrient assimilation can
                  only occur when biomass increases  (Malone et al. 1996). The rate compensating
                  capacity of the Chesapeake Bay ecosystem is exceeded  and phytoplankton biomass
                  accumulates (i.e., the consumption of phytoplankton biomass by benthic and pelagic
                  consumers cannot keep pace with phytoplankton production on a baywide scale).
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This effect may have been exacerbated by the Bay's oyster population decline during
the 20th century (Newell 1988). In summer, nutrient assimilation and phytoplankton
growth rates are nutrient limited and the rate compensating capacity of the Bay is not
exceeded.

CHLOROPHYLL a DYNAMICS IN THE TIDAL TRIBUTARIES
AND EMBAYMENTS

Chlorophyll a concentrations that impair tidal-water designated uses, as defined by
the Clean Water Act, will differ among Chesapeake Bay's "subsystems" (the main-
stem Bay along with its tidal  tributaries and embayments) depending on salinity,
depth, flushing rate, and the degree of vertical stratification. For example, massive
blue-green  algae blooms occur primarily in the upper tidal-fresh Potomac River
(Jaworski 1990) while many small shallow-water (vertically  mixed)  embayments
have inordinately high chlorophyll a concentrations  associated with supersaturated
dissolved oxygen levels in the afternoon and hypoxic to anoxic conditions during the
hours before sunrise (D'Avanzo and Kremer 1994). In some parts of the Bay and its
tidal tributaries, reductions of nutrient and sediment loading to levels that meet the
deep-water  and deep-channel  dissolved oxygen  and shallow-water water clarity
criteria may not prevent development of harmful algal blooms nor ensure the return
of high-quality food to open-water habitats. Such areas include, but are not limited
to, waters that do not experience  oxygen depletion for hydrodynamic reasons (e.g.,
high mixing rates) and those in which reduced water clarity results primarily from
suspended sediment rather than algae (e.g., tidal James River).
                      SCIENTIFIC  BASIS  FOR
          NUMERICAL  CHLOROPHYLL a CRITERIA

HISTORICAL CHLOROPHYLL a REFERENCE CONCENTRATIONS

Seasonal accumulations of chlorophyll a in the Chesapeake Bay remain excessive.
Using changes in chlorophyll a to assess shifts in the Bay's condition due to human
activities requires: long-term  time series measurements of chlorophyll a  with
seasonal resolution along the salinity gradients of the mainstem Bay and its tribu-
taries; and a "baseline" annual  cycle of water column-integrated chlorophyll a with
seasonal resolution to assess changes in terms of positive and negative deviations
from the baseline.

Ideally, this baseline would be  the mean annual cycle based on monthly means and
standard errors for a range of climate conditions prior to European settlement of the
Chesapeake Bay watershed. However, data to calculate means and standard errors
are available only from about 1960 to the present. Even so, establishing secular
trends based on numerical deviations necessitates a quantitative reference. Given the
strong  seasonality  of chlorophyll  a concentrations,  a mean annual  cycle  with
seasonal  resolution is needed. Chapter 3, "Historical  Chlorophyll a  Reference
Concentrations", documents this approach for deriving  numerical chlorophyll a
concentrations protective against ecological impairments.
                                                             chapter ii  • Chlorophyll a Criteria

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                  DISSOLVED OXYGEN IMPAIRMENTS

                  Although bottom-water hypoxia has probably occurred in Chesapeake Bay for over
                  100 years (Cooper and Brush 1991), analysis of available data suggests that the time-
                  space extent of hypoxia began to increase with nutrient loading in the 1950s (Hagy
                  et al. 2004; Kemp et al. 2005) and continues to increase in some areas (e.g., Fisher
                  et al. 2006). A statistically significant relationship between nutrient loading and the
                  severity of oxygen depletion from 1950 to 2001, however, has not been established.

                  Seasonal accumulations of water column-integrated chlorophyll a during winter and
                  spring provide the fuel for oxygen depletion and summer hypoxia in the Chesapeake
                  mainstem and its tidal tributaries. The rate of decline of bottom-water oxygen shows
                  little interannual variability and is primarily a function of temperature (Malone 1992;
                  Hagy et al. 2004). In contrast, the time-space extent of bottom-water hypoxia varies
                  considerably  from year to year due primarily to interannual variations in vertical
                  stratification during  the summer and secondarily to variations in the spring  freshet's
                  magnitude  (Malone  1991, 1992; Hagy 2002). These observations suggest that the
                  aerobic capacity  of the Bay to assimilate the winter-spring accumulation of phyto-
                  plankton biomass has been exceeded for the last 20 to 30 years, explaining the lack
                  of correlation between nutrient loading and the severity of oxygen depletion. Given
                  the Bay's current eutrophic state, therefore,  relationships between chlorophyll a
                  concentrations and  oxygen depletion may  not necessarily yield useful numerical
                  chlorophyll a criteria. This hypothesis is tested in Chapter  4, "Chlorophyll a Rela-
                  tionship to Dissolved Oxygen Impairments."

                  WATER CLARITY IMPAIRMENTS

                  Clear water with sufficient penetration of solar radiation is essential for SAV growth
                  (Dennison et al.  1993; Kemp et al. 2004).  Chlorophyll a creates a major source of
                  light attenuation in the water column, along with suspended inorganic sediments and
                  colored dissolved organic material (CDOM).  In the 1700s  and 1800s, much of the
                  turbidity in the Chesapeake Bay resulted from anthropogenic sediment inputs. Land-
                  based inputs of sediments have declined over the last 50 to 60 years (Brush 1989),
                  however, and declines in water clarity during spring and summer are related prima-
                  rily to accumulations  of chlorophyll a (Gallegos and Jordan  2002). Increases in
                  chlorophyll a were already affecting underwater bay grass  distributions throughout
                  much of the  Chesapeake Bay by the early 1960s  (Orth and Moore  1983). If the
                  effects of sediments and CDOM can be accounted for, then the quantitative rela-
                  tionships between chlorophyll a concentration and diffuse  light attenuation should
                  provide the basis for numerical chlorophyll a criteria. Chapter 5, "Chlorophyll a
                  Contribution  to Water  Clarity Impairments", pursues this approach for  deriving
                  numerical chlorophyll a concentrations protective against water clarity impairments.

                  HARMFUL  ALGAL BLOOM IMPAIRMENTS

                  As defined in Harmful Algal Research and Response: A National  Environmental
                  Science Strategy 2005-2015, harmful algae are those algae that "cause harm to the
                  environment through the production of toxins ...  or through the accumulation of
chapter ii  • Chlorophyll a Criteria

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                                                                                                   '
biomass that, in turn, affects co-occurring organisms and alters food webs in nega-
tive ways" (HARRNESS 2005). The latter impairments are addressed in chapters 3
through 5. The focus of Chapter 6 is on algae that produce toxins harmful to humans
and/or living resources.

Not all toxic algae are pigmented and many toxic algae can cause human patholo-
gies at low cell densities. In addition, most variability in the time-space distributions
of chlorophyll a is not caused by pigmented toxic algae, especially  in the high-
salinity lower  reaches of the Chesapeake Bay mainstem and its higher salinity tidal
tributaries. Thus, chlorophyll a can be used as an indicator of toxic harmful algal
blooms (HABs)  under three special conditions:
   1. the toxic algal species must contain chlorophyll a;
   2. the health  risk to humans or aquatic life must be relatable to chlorophyll a
     concentration; and
   2. the toxic algal species must have known periods during the year as well as
     specific  places  (hot  spots) where it  dominates increases in  chlorophyll a
     concentrations.
Under these conditions, increases in chlorophyll a concentrations can  also be used
to trigger an adaptive sampling program to identify and enumerate the toxic species.
This approach is pursued in Chapter 6, "Chlorophyll a Concentrations Characteristic
of Impairments by Harmful Algal Blooms."
                          LITERATURE CITED
Boynton, W.R., W.M. Kemp, and C.W. Keefe. 1982. A comparative analysis of nutrients and
other factors influencing estuarine phytoplankton production. In: V.S. Kennedy (ed.). Estu-
arine Comparisons, pp 209-230, New York: Academic Press.
Brush, G.S. 1989.  Rates and patterns of estuarine sediment accumulation. Limnology and
Oceanography 34:1235-1246.
Caperon, J., S. Cattell,  and  G.  Krasnick.  1971. Phytoplankton  kinetics in a subtropical
estuary:  eutrophication. Limnology and Oceanography 16:599-607.
Cooper,  S.R. and G.S. Brush. 1991. Long-term history of Chesapeake Bay anoxia. Science
254:992-996.
Cooper,  S.R. and G.S. Brush. 1993. A 2,500-year history of anoxia and eutrophication in
Chesapeake Bay. Estuaries 16:617-626.
Cooper,  S.R. 1995. Chesapeake Bay watershed historical land use: impact on water quality
and diatom communities. Ecological Applications 5: 703-723.
D'Avanzo, C. and J.N. Kremer. 1994. Diel oxygen dynamics and anoxia in Waquoit Bay, a
eutrophic embayment on Cape Cod, MA. Estuaries  17:131-139.
D'Elia, C.F., J.G. Sanders and W.R. Boynton. 1986. Nutrient enrichment studies in a coastal
plain estuary: phytoplankton growth in large-scale,  continuous cultures.  Canadian Journal
Fisheries and Aquatic Science 43:397-406.
                                                                 chapter ii  •  Chlorophyll a Criteria

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10
                      Dennison, W.C., RJ. Orth, K.A. Moore, J.C. Stevenson, V. Carter, S. Kollar, P. Bergstrom,
                      and R.  Batiuk. 1993. Assessing water quality with submersed aquatic vegetation. Habitat
                      requirements as barometers of Chesapeake Bay health. Bioscience 43: 86-94.
                      Flemer, D.A. 1969. Continuous measurement of in vivo chlorophyll of a dinoflagellate bloom
                      in Chesapeake Bay. Chesapeake Science 10(2):99-103.
                      Fisher, T.R., L.W. Harding, D.W. Stanley, andL.G. Ward. 1988. Phytoplankton, nutrients and
                      turbidity in the Chesapeake,  Delaware and Hudson estuaries. Estuarine, Coastal and Shelf
                      Science 27:61-93.
                      Fisher, T.R.,  E.R. Peele, J.A. Ammerman and L.W. Harding. 1992. Nutrient limitation of
                      phytoplankton in Chesapeake Bay. Marine Ecological Progress Series 82:51-63.
                      Fisher, T.R., J.D. Hagy III, W.R. Boynton, and M.R. Williams. 2006. Cultural eutrophication
                      in the Choptank and Patuxent estuaries of Chesapeake Bay. Limnology and Oceanography
                      51:435-447.
                      Gallegos, C.L. and T.E. Jordan. 2002. Impact of the spring 2000 phytoplankton bloom in
                      Chesapeake Bay on optical properties and light penetration in the Rhode River, Maryland.
                      Estuaries 25:508-518.
                      Hagy, J.D. 2002. Eutrophication, hypoxia and trophic transfer efficiency in Chesapeake Bay.
                      PhD dissertation, University of Maryland, College Park, MD.
                      Hagy, J.D., W.R. Boynton, C.W Wood, and K.V. Wood. 2004. Hypoxia in Chesapeake Bay,
                      1950 - 2001: long-term changes in relation to nutrient loading  and river flow. Estuaries
                      27:634-658.
                      Harding, L.W., Jr., B.W. Meeson, and T.R. Fisher. 1986. Phytoplankton production in two
                      East coast estuaries: photosynthesis-light functions and patterns  of carbon assimilation in
                      Chesapeake and Delaware Bays. Estuarine, Coastal and Shelf Science 23: 773-806.
                      Harding, L.W., Jr., E.G. Itsweire, and W.E.  Esaias. 1992. Determination of phytoplankton
                      chlorophyll  concentrations in the Chesapeake Bay with aircraft remote  sensing. Remote
                      Sensing of the Environment 40:79-100.
                      Harding, L.W, Jr. and E.S. Perry 1997. Long-term increase of phytoplankton biomass in
                      Chesapeake Bay, 1950-1994. Marine Ecological Progress Series 157:39-52.
                      Harding, L.W., Jr., M.E. Mallonee, and E.S. Perry. 2002. Toward a predictive understanding
                      of primary productivity in a temperate, partially stratified estuary. Estuarine, Coastal and
                      Shelf Science 55:437^63.
                      HARRNESS. 2005. Harmful Algal Research and Response: A National Environmental
                      Response Strategy 2005 - 2025. J.S.  Ramsdell, D.M. Anderson, and  P.M. Gilbert (eds.).
                      Washington D.C.: Ecological Society of America.
                      Howarth, R.W, D. Anderson, J. Cloern, C. Elfring, C. Hopkinson, B. Lapointe, T. Malone,
                      N. Marcus, K. McGlahery, A. Sharpley, and D. Walker. 2000. Nutrient pollution of coastal
                      rivers, bays and seas. Ecology 7:15.
                      Jaworski, N. 1990. Retrospective of the water quality issues of the upper Potomac estuary.
                      Aquatic Science 3:11-40.
                      Kemp, W.M., M.T. Brooks, and R.R. Hood. 2001. Nutrient enrichment, habitat variability
                      and trophic transfer efficiency in  simple models of pelagic ecosystems.  Marine Ecology
                      Progress Series 223:73-87.
                      Kemp, W.M., R. Batiuk, R. Bartleson, P. Bergstrom, V. Carter, G. Gallegos, W  Hunley, L.
                      Karrh, E. Koch, J. Landwehr, K. Moore, L. Murray, M. Naylor, N. Rybicki, J.C. Stevenson,
  chapter ii  •  Chlorophyll a Criteria

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                                                                                                       "
and D. Wilcox. 2004. Habitat requirements for submerged aquatic vegetation in Chesapeake
Bay: Water quality, light regime, and physical-chemical factors. Estuaries 27:263-377
Kemp, W.M, W.R. Boynton, J.E. Adolf, D.F. Boesch, W.C. Boicourt, G. Brush, J.C. Corn-
well, T.R. Fisher,  P.M. Gilbert, L.W. Harding, Jr., E.D. Houde, D.G. Kimmel, W.D. Miller,
R.I.E. Newell, M.R. Roman, E.M. Smith, and J.C. Stevenson. 2005. Eutrophication of Chesa-
peake Bay: Historical trends  and ecological interactions. Marine Ecology Progress Series,
303:1-29.
Malone, T.C., L.H. Crocker, S.E. Pike, and B.W. Wendler. 1988. Influences of river flow on
the dynamics of phytoplankton production in a partially stratified estuary. Marine Ecology
Progress Series 48: 235-249.
Malone, T.C. 1991. River flow, phytoplankton production and oxygen depletion in Chesa-
peake Bay. In Tyson, R.V. and T.H. Pearson (eds.). Modern and Ancient Continental Shelf
Anoxia No. 58, pp. 83-93. The Geological Society. Special Publication.
Malone, T.C. 1992. Effects of water column processes on dissolved oxygen, nutrients, phyto-
plankton and zooplankton. In: D. Smith, M. Leffler, G. Mackiernan (eds.). Oxygen Dynamics
in Chesapeake Bay: A Synthesis of Research, pp. 61-112. University of Maryland Sea Grant,
College Park, MD.
Malone, T.C., D.J. Conley, T.R. Fisher, P.M. Gilbert, and L.W. Harding, Jr. 1996. Scales of
nutrient limited phytoplankton productivity in Chesapeake Bay. Estuaries 19:371-385.
Miller, W.D. and L.W. Harding, Jr. 2007. Climate forcing of the spring bloom in Chesapeake
Bay. Marine Ecology Progress Series 331:11-12.
National Research Council. 2000. Assessing the TMDL Approach to Water Quality Manage-
ment. Committee to Assess the Scientific Basis of the Total Maximum Daily Load Approach
to Water Pollution Reduction, Water Science and Technology Board, Division on Earth and
Life Studies. Washington, D.C.: National Academy Press.
Neilson,  B.J.  and L.E.  Cronin.  1981.  Estuaries  and Nutrients. North  Carolina:  The
HUMANA Press.
Newell, R.E. 1988. Ecological changes in Chesapeake Bay: Are  they the result of overhar-
vesting the Eastern oyster (Crassostrea virginica)! In: M.P. Lynch and E.G.  Krome (eds.).
Understanding the Estuary: Advances in Chesapeake Bay Research, pp. 536-546. Gloucester
Point, VA: Chesapeake Research Consortium Publication 129 (CBP/TRS  24/88).
Orth, RJ. and K.A. Moore. 1983. Chesapeake Bay: An unprecedented decline in submerged
aquatic vegetation. Science 222:51-53.
Seliger, H.H., J.A. Boggs, and W.H. Biggley. 1985. Catastrophic anoxia  in the Chesapeake
Bay in 1984. Science 228:70-73.
U.S. Environmental Protection Agency. 2003a. Ambient Water Quality Criteria for Dissolved
Oxygen, Water Clarity and Chlorophyll a for the Chesapeake Bay and Its Tidal Tributaries.
EPA 903-R-03-002. Region III Chesapeake Bay  Program Office, Annapolis, MD.
                                                                    chapter ii  •  Chlorophyll a Criteria

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    12
                                              chapter|||

                               Historical  Chlorophyll  a
                             Reference Concentrations
                     Chlorophyll a constitutes an important
                     indicator of water quality in estuaries
                     such as the Chesapeake  Bay where
                     chlorophyll a has increased signifi-
                     cantly  since World  War II  (Figure
                     III-l).  Chlorophyll a increases have
                     coincided with a doubling or  more of
                     nitrogen loadings (Boynton et  al.
                     1995),  particularly in the Bay's lower
                     polyhaline regions. Long-term data on
                     chlorophyll a for the  Chesapeake Bay
                     extend  back more than 50 years to
                     provide a historical context for the more
                     recent observations from the extensive
                     ongoing Chesapeake Bay water quality
                     monitoring program (Chesapeake Bay
                     Program 1989). The focus on historical
                     reference concentrations to set concen-
                     trations protective against ecological
                     impairments is based on the conclusion
                     that chlorophyll a levels in the 1950s
                     and 1960s  were lower than contempo-
                     rary  levels documented by  Harding
                     1994 and  Harding and Perry  1997.
                     While  not characteristic of "pristine"
                     conditions, data  from these earlier
                     decades provide "baseline" concentra-
                     tions for a less-stressed ecosystem prior
                     to severe  eutrophication  with  wide-
                     spread  hypoxia, loss of submerged
                     aquatic vegetation,   and  declines in
                     productive fisheries (Kemp et al. 2005).
                                                 (a) oligohaline
                                                (c) polyhaline
                                                            Year
                                          Figure 111-1. Historical changes in surface
                                          chlorophyll a concentrations from 1950
                                          to 2003.
                                          Sources: Harding 1994; Harding and Perry 1997,
                                          updated in Kemp etal. 2005.
chapter
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                                                                                              •
                RATIONALE  FOR  THE  1950S TO
                   1960S  REFERENCE  PERIOD

The extensive review paper, "Eutrophication of Chesapeake Bay: historical trends
and ecological interactions" by Kemp et al. (2005), chronicles significant changes in
the Chesapeake Bay ecosystem over the past  five decades, noting degradation of
water quality that accelerated from the 1950s through the 1960s. The 18 estuarine
scientists who contributed to this paper provide a systematic account of the eutroph-
ication record in Chesapeake Bay and its ecological implications.  Evidence from
dated sediment cores revealed organic enrichment in -200-year-old strata, while
signs of increased phytoplankton biomass and decreased water clarity first appeared
about 100 years ago. Kemp et al. (2005) summarize changes from the most recent
50 years against a backdrop of long-term changes  spanning the period since colo-
nization. Two manifestations of water quality degradation evident since the 1950s
and 1960s are recurring deep-water hypoxia (Officer et al. 1984) and the loss of
submerged aquatic vegetation (Kemp et al. 1983; Orth and Moore 1983). This degra-
dation coincides with a significant increase in the use of commercial fertilizers after
the 1950s along with a ~2.5-fold increase in total nitrogen loadings from the Susque-
hanna River from  1945 to 1990 (Boynton et al. 1995).

The sediment record also reveals a major shift in phytoplankton community compo-
sition within the  same  50-year  period, exemplified by a shift in the  ratio of
planktonic to benthic diatoms. This shift indicates decreased water clarity, which led
to the suppression of benthic algal production (Cooper and Brush  1991,  1993).
Consistent with this shift was a sharp increase of bacterial carbon burial beginning
in the mid-20th century (Zimmerman and Canuel 2000), paralleled by increases in
the ratio of bacterial carbon to biogenic silica that suggests a decline in the efficiency
at which diatom production transfers to upper trophic levels (e.g., Kemp et al. 2001).

Direct measurements of the macroinvertebrate benthic community were not avail-
able prior to 1950. However, shifts in dominant macrofaunal species occurred in the
early 1960s in the York River (Boesch and Rosenberg  1981) and in the early 1970s
in the mainstem Chesapeake Bay (Holland et al. 1987). Finally, the authors suggest
that eutrophication also affects higher trophic levels, noting that the shifts in primary
producers (that accompanied  fundamental changes of ecological structure) have
altered fisheries production (Kemp et al. 2005).
REFERENCE CONCENTRATION DERIVATION APPROACH

The  reference concentration derivation  approach began with the acquisition of
historical through present-day (1950-2004) chlorophyll a data from archival hold-
ings  (1950-1983) and the  Chesapeake  Bay Water Quality Monitoring Program
(1984-2004). All data used comes from the Chesapeake Bay Program website's data
hub (www.chesapeakebay.net/data). These data holdings consisted of surface chloro-
phyll a and vertical chlorophyll a profiles from various sources (Table III-l).
                                     chapter iii  •  Historical Chlorophyll a Reference Concentrations

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14
                    These data were analyzed and modeled to develop reference chlorophyll a concen-
                    trations  for  the  Chesapeake Bay.  Models  of  surface  chlorophyll  a and
                    depth-weighted average chlorophyll a from profiles were devised for the complete
                    historical time series to generate predictions for specific periods and flow conditions.
                    This process allowed selection of a time period (e.g., a decade) to function as a refer-
                    ence restoration target.  The  approach follows the logic that chlorophyll  a
                    concentrations have increased significantly between the 1950s and 1980s (Harding
                    and Perry 1997) (Figure III-1). It also accounted for strong climate forcing of chloro-
                    phyll a concentrations (past and present) by establishing regional seasonal reference
                    chlorophyll a concentrations (based on mean chlorophyll a concentrations) and
                    factoring in spatial and temporal variances for wet, dry, and average conditions.
                    HISTORICAL DATA SOURCES AND TEMPORAL COVERAGE

                    The analysis presented here extends the earlier published analyses of Harding (1994)
                    and Harding and Perry (1997) which only used data from the Chesapeake Bay Insti-
                    tute (1950-1982) and the first 8 years  of data from the Chesapeake Bay Water
                    Quality Monitoring Program (1985-1992) to quantify trends in surface chlorophyll
                    a during the post-World War II period. To derive chlorophyll a reference concentra-
                    tions, additional data were identified in the archived data holdings (Table III-l).
                    Table 111-1. Sources of historical 1950-1983
                    Chesapeake Bay chlorophyll a concentration
                    data used in the derivation of historical
                    chlorophyll reference concentrations.
Source
AFO-MAINBAY
AFOLIGHT
CBI-AESOP
CBI-PROCON
CBIBAY
CBITRIB
FLEMER-BIGGS
HEINLE-WILSON
MARYLAND 106
NUTRIENT
STORET
TAFT
VIMS
WHALEY-CARPENTER
Period
1979
1979
1969-1971
1975-1976
1950-1980
1950-1980
1965-1967
1966-1971
1969-1981
1977-1978
1978-1980
1980
1975-1979
1964-1966
                                             The  field collection and laboratory
                                             analytical methods used in the 1950s,
                                             1960s, and 1970s were carefully eval-
                                             uated to ascertain comparability with
                                             current field and  analytical methods
                                             in terms  of: (a) filter type  used to
                                             collect   suspended  material;  (b)
                                             solvent used to extract phytoplankton
                                             pigments;  (c)   spectrophotometric
                                             approach (monochromatic,  trichro-
                                             matic); and (d) calibration approach
                                             (use of pure chlorophyll a to develop
                                             standards for spectrophotometric  and
                                             fluorometric  measurements).  The
                                             historical data  archives  were also
                                             queried  for vertical chlorophyll  a
                                             profile data to determine if the spatial
                                             and  temporal  coverage  remained
                                             adequate  to compute integrated-water
                                             column chlorophyll  a prior to 1984.
                                             The geo-locations of all stations were
                                             examined to assure  that they were
                                             located within  the mainstem  Chesa-
                                             peake  Bay  and  not in the tidal
                                             tributaries. A parallel set of queries
                                             was  conducted  using chlorophyll  a
                                             data from the Chesapeake Bay Water
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                                                                                               •
Quality Monitoring Program (1984-2004) for mainstem stations, including both
surface and water column measurements.

MODELING APPROACH

The  surface chlorophyll a (chla)  model for  historical data consists of a General
Linear Model (GLM) in SAS with Iog10 (chlorophyll a)  as the dependent variable
and a set of eight independent categorical variables: decade, salinity zone, season,
month (season), decade*salinity zone, decade*season, decade*month (season), and
salinity zone*season.  In addition,  four  continuous variables—salinity,  salin-
ity*month (season), water temperature, and total depth—were used. The model used
three salinity zones (oligohaline (OH), mesohaline (MH), and polyhaline (PH)) as
well as five complete decades (1950s through 1990s) along with 2000 to 2004 data.
Each year was divided into five seasons: winter (January, February, March), spring
(April,  May), transition (June),  summer  (July, August,  September),  and fall
(October, November, December).

ACCOUNTING FOR FLOW

Climate forcing  of phytoplankton dynamics in  Chesapeake Bay is  strongly ex-
pressed by the seasonal to interannual variability of chlorophyll a in aircraft remote
sensing data (aggregated for "wet," "long-term average," and "dry" conditions) from
1989 to 2004 (Figure III-2).  Statistical methods to incorporate flow as an in-
dependent variable in historical chlorophyll a models have met with mixed success.
The unequal experimental designs in the temporal dimension limit specification of
the correct flow-lag and flow-averaging window since the historical dataset compiles
many different tidal-water data collection and field research projects  with distinct
goals and designs. In contrast, salinity nested within a  salinity zone was a very
successful independent variable. Nesting salinity within a salinity zone is important
so that the salinity term models the effect of high or low flow, rather than the along-
axis  spatial distribution of chlorophyll a in the Chesapeake Bay.

To equate salinity to flow, the model assumed a direct correspondence between these
two variables. For spring and summer seasons of each decade, the 10th percentile,
median, and 90th percentile of  the monthly  mean salinity were  computed. A
synthetic prediction data set with Iog10 (chlorophyll a) set to "missing" was created
with one observation for each decade, month, salinity zone, and salinity value. Water
temperature was computed as the seasonal average with station depth set to the
salinity zone average. Using GLM, the predicted value of Iog10 (chlorophyll a) was
obtained for each of these synthetic observations. In plots and output, these predic-
tions are labeled as:
   GLM (10th salinity percentile) = high-flow prediction;
   GLM (median salinity) = mid-flow prediction;  and
   GLM (90th salinity percentile) = low-flow prediction.
                                      chapter iii  •  Historical Chlorophyll a Reference Concentrations

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16
                                  Warm/Wet
                                        LTA
   Cool/Dry
                          39.5
                          39.0
                          38.5
                       CD
                       T3
                       •I  38.0
                       CD
                          37.5
                          37.0
                               a)
                                  b)
c)
 Chi a
(mg m~3)
                                                                         P
                                                                                              14
                                                                                              12
                                                                             10
                                76.5    76.0    75.5  76.5    76.0   75.5  76.5    76.0   75.5
                                                   Longitude (°W)

                    Figure III-2. Climate forcing of phytoplankton biomass as chlorophyll a from aircraft
                    remote sensing data. Warm/wet, LTA, and cool/dry are predominant climatic conditions
                    for which LTA represents the long-term average (1989-2005).
                    Source: Miller and Harding 2006.
                     DERIVATION  OF REFERENCE  THRESHOLDS BASED  ON
                                SPATIAL  AND TEMPORAL  VARIANCES

                    To complete the definition of chlorophyll a concentrations of the 1960s and 1970s
                    as reference concentrations, establishing a criteria threshold for each season/salinity
                    zone combination to use for criteria attainment assessment proved necessary (U.S.
                    EPA 2003a). The criteria threshold for chlorophyll a is a concentration that should
                    rarely be exceeded by a "population" of chlorophyll a concentrations characterizing
                    healthy levels. When the population is unidimensional (e.g., the nutrient concentra-
                    tion in a wastewater treatment facility effluent),  then one can obtain an upper
                    threshold based on  the simple distribution of values in a "healthy  population"
                    (Figure III-3).

                    The 90th percentile of this distribution might be chosen as the "criterion threshold"
                    to allow 10 percent noncompliance due to the expectation of a low level of naturally
                    occurring exceedances even in a healthy population (U.S. EPA 2003). A standard
                    technique to estimate distribution percentiles is assuming a mathematical form for
                    the distribution (e.g., a normal  distribution for logarithm-transformed chlorophyll a)
                    and estimating the percentile as some number of standard deviations above the mean.
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               0.61
               o.s;
               o.4;
               0.2:
               0.1;
                                                                                                  "
                                 10      15
                                     Chlorophyll
                                                20
                                                        25
                                                               30
 Figure III-3. Hypothetical log-normal distribution typical of chlorophyll a concentrations,
 illustrating the relationship of the geometric mean and  the criterion threshold set at the
 90th percentile.
The 90th  percentile of the normal distribution is 1.2815 standard deviations above
the mean.

When regulating "populations" distributed in both space  and time, this simple
concept for assessing non-attainment must be extended to account for variability in
each dimension. This extension adds some complexity to the mathematics, but the
fundamental  concept remains  the same: to set  the criterion threshold a certain
distance  above the  mean concentration  such that exceedance of that threshold
remains rare in a healthy population. In this case, the distance by which the threshold
must exceed the mean is a function of both the spatial and temporal variance compo-
nents, as described below.

To establish these criteria thresholds, one could assume the simple model:

     Xy = u + 34 + by                                               Equation 1

where:
  u is the desired mean level of chlorophyll a (in log space);
  &i is a random term for variation over time with variance 2a;
  by  is a random term for variation over space with variance 2b; and
  Xy  is a Iog10 chlorophyll a at time i and location].
The variance of xy- is 2a
                                    (Equation 2). The standard deviation of xy is
sqrt(2) =  (Equation 3). It is common to allow an overall 10 percent exceedance
rate without declaring an assessment unit out of compliance (U.S. EPA 2003). Ten
percent of the xy- is expected to fall above u + 1 .2815*0, for which 1.2815 is the 10th
percentile of the standard normal distribution. Assuming normality, a population
with spatial  and temporal variances  characterized by  2a and 2b with a mean
                                       chapter iii  •  Historical Chlorophyll a Reference Concentrations

-------
                   1.2815* below the threshold criterion will have an exceedance rate of 10 percent
                   over space and time. To illustrate this process, thresholds were computed for spring
                   and summer for three salinity zones using 1960s and 1970s mid-flow surface chloro-
                   phyll a concentrations as the "desirable" levels to attain (Tables III-2 and III-3).

                   The spatial and temporal variances from the ongoing Chesapeake Bay Water Quality
                   Monitoring Program data (1985-2004) were used to determine thresholds to apply
                   to the historical means. The 1960s and  1970s  historical data were too limited in
                   spatial and temporal coverage to support these variance computations. The 1985 to
                   2004 monitoring program data, on the other hand, are more synoptic in design; each
                   field sampling cruise is completed in just a few days.  Moreover, they are the prin-
                   cipal data that will be used to assess attainment of the chlorophyll a criteria.

                   The temporal  and spatial variance terms in Tables III-2 and III-3 were completed
                   from mean square terms of the decadal  model fitted  to 1985-2004  chlorophyll a
                   concentration data from the Chesapeake Bay Water Quality Monitoring Program. In
Table 111-2. Surface chlorophyll a (chla) reference concentrations (/jg-liter"1) derived by computing an upper
threshold based on predicted surface mean Iog10 (chlorophyll a) for the 1960s at mid-flow conditions.
Season
Spring
Summer
Spring
Summer
Spring
Summer
Salinity Mean log
zone chla
OH
OH
MH
MH
PH
PH
0.768
1.17
0.414
0.863
0.139
0.218
Geometric
mean chla
5.87
14.8
2.59
7.29
1.38
1.65
Table III-3. Surface chlorophyll a (chla) reference
threshold based on predicted surface mean Iog10
Season
Spring
Summer
Spring
Summer
Spring
Summer
Salinity Mean log
zone chla
OH
OH
MH
MH
PH
PH
1.06
1.24
0.948
0.955
0.658
0.734
Geometric
mean chla
11.4
17.4
8.87
9.01
4.55
5.42
Temporal
variance
0.0233
0.0233
0.0233
0.0233
0.0233
0.0233
concentrations
(chlorophyll a)
Temporal
variance
0.0233
0.0233
0.0233
0.0233
0.0233
0.0233
Spatial
variance
0.0658
0.0658
0.0658
0.0658
0.0658
0.0658
Standard
deviation
log chla
0.2985
0.2985
0.2985
0.2985
0.2985
0.2985
Threshold
criterion
log chla
1.26
1.66
0.905
1.35
0.630
0.709
(jug-liter ~1) derived by computing an
for the 1970s at mid-flow conditions
Spatial
variance
0.0658
0.0658
0.0658
0.0658
0.0658
0.0658
Standard
deviation
log chla
0.2985
0.2985
0.2985
0.2985
0.2985
0.2985
Threshold
criterion
log chla
1.55
1.73
1.44
1.45
1.15
1.23
Threshold
criterion
chla
18.2
45.7
8.03
22.6
4.26
5.12
upper
Threshold
criterion
chla
35.3
53.8
27.5
27.9
14.1
16.8
chapter iii  •  Historical Chlorophyll a Reference Concentrations

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                                                                                               "
this model, the Chesapeake Bay Program segment (U.S. EPA 2004, 2005) replaced
salinity zone while cruise replaced month relative to the model for the historical data.
The spatial variance term was taken directly from the mean square error (MS(error))
term and the temporal variance term computed from the cruise(season) mean square
term. The expected mean square obtained using the RANDOM statement of the GLM
program is:

  EMS[CRUISE(season)] = Var(Error) + 38.505 Var[CRUISE(season)]  Equation 4

The estimate of temporal variance is:

  $2a = MS[month(season)] - MS(error)/38.505                      Equation 5
    DEPTH-WEIGHTED INTEGRATED  WATER COLUMN
                          CHLOROPHYLL a

The analysis of historical chlorophyll a data included vertical chlorophyll a profiles,
supporting the use of integrated water column chlorophyll a as a measure of phyto-
plankton biomass. The rationale for  this approach is the strong link of nutrient
loading to phytoplankton biomass that develops during the spring bloom of diatoms
(Malone  1992; Malone et al.  1996). The prevailing view is that the winter-spring
diatom bloom sequesters nutrients from freshwater rivers and other sources, and that
the timing, position, and magnitude of the bloom are sensitive to the variability of
freshwater flow that relates closely to climate (Adolf et al. 2006; Miller  and Harding
2006). Surface chlorophyll a data, collected using aircraft remote sensing and aggre-
gated by climatic conditions, illustrate the strong role of climate (see Figure III-2).
The vertical chlorophyll a concentration profiles reveal strong seasonality, reflecting
the accumulation of diatom biomass in spring and subsequent sedimentation below
the pycnocline. The resultant below pycnocline phytoplankton biomass ultimately
brings about hypoxia (Malone 1992).

Sufficient historical data containing vertical chlorophyll a profiles were available to
conduct an analysis similar to the study of surface chlorophyll a above. As the Bay's
bathymetry strongly  affects integral-water column chlorophyll a computed from
these profiles within a major salinity region, the integrated-water column chlorophyll
a were normalized to water column depth for each sampling site to take account of
the effect on the  integral. This approach  generated depth-weighted average chloro-
phyll a values for the  same seasons and regions used to develop the criteria in Tables
III-2 and III-3 for surface chlorophyll a.  Spatial and temporal variances for depth-
weighted average  chlorophyll a  were  computed using Chesapeake Bay Water
Quality Monitoring Program data from  1985 to 2004. Tables III-4  and III-5 give
depth-weighted  chlorophyll  a means  in  logarithmic space,  back-transformed
geometric means, variances, and threshold concentrations for the 1960s and 1970s
for mid-flow conditions. Separate solutions for low- and high-flow conditions were
also  calculated,  as for surface chlorophyll  a.  Thresholds computed  from depth-
weighted average chlorophyll a were  typically lower than those in Tables III-2 and
III-3. The polyhaline  Chesapeake Bay proved the exception, partly due to the lower
                                      chapter iii  •  Historical Chlorophyll a Reference Concentrations

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20
 Table 111-4. Depth-weighted average chlorophyll a (dwachl) reference concentrations (jug-liter1) derived by
 computing an upper threshold based on predicted means for mid-flow 1960s data.
Season
Spring
Summer
Spring
Summer
Spring
Summer
Table III-5.
computing
Season
Spring
Summer
Spring
Summer
Spring
Summer
Salinity Mean log
zone dwachl
OH
OH
MH
MH
PH
PH
0.551
0.906
0.299
0.617
0.222
0.492
Geometric
mean
dwachl
3.56
8.05
1.99
4.14
1.67
3.10
Temporal
variance
0.0251
0.0251
0.0251
0.0251
0.0251
0.0251
Spatial
variance
0.0404
0.0404
0.0404
0.0404
0.0404
0.0404
Standard
deviation
log dwachl
0.2559
0.2559
0.2559
0.2559
0.2559
0.2559
Depth-weighted average chlorophyll a (dwachl) reference concentrations (jug
an upper threshold based on predicted means for mid-flow 1970s data.
Salinity Mean log
zone dwachl
OH
OH
MH
MH
PH
PH
0.980
1.043
1.081
0.689
0.873
0.650
Geometric
mean
dwachl
9.54
11.0
12.1
4.89
7.46
4.47
Temporal
variance
0.0251
0.0251
0.0251
0.0251
0.0251
0.0251
Spatial
variance
0.0404
0.0404
0.0404
0.0404
0.0404
0.0404
Standard
deviation
log dwachl
0.2559
0.2559
0.2559
0.2559
0.2559
0.2559
Threshold Threshold
criterion criterion
log dwachl dwachl
0.9723
1.3270
0.7202
1.0384
0.6430
0.9124
•liter1) derived
9.38
21.2
5.25
10.9
4.40
8.17
by
Threshold Threshold
criterion criterion
log dwachl dwachl
1.40
1.46
1.50
1.11
1.29
1.07
25.2
29.1
31.8
12.9
19.7
11.8
                     spatial variance of the depth-weighted average compared to the spatial variance for
                     surface chlorophyll a.

                     Figure II-4 provides  a graphical summary and comparison of model outputs for
                     surface chlorophyll a and depth-weighted average chlorophyll a from the historical
                     analysis for the three major salinity regions. The plots indicate that the 1960s and
                     1970s had lower surface chlorophyll a and depth-weighted average chlorophyll a in the
                     polyhaline Bay—the region most sensitive to nutrient loading variability (Harding et al.
                     2005).  The 1960s showed the strong effect of prolonged low-flow conditions as a less-
                     ening of light limitation in the upper oligohaline  Bay  and  as  heightened nutrient
                     limitation in the lower polyhaline Chesapeake Bay. The 1970s highlighted the strong
                     effects  of prolonged high-flow conditions (superimposed on historical increases of
                     chlorophyll a) as higher surface chlorophyll a and depth-weighted average chlorophyll
                     a in all salinity regions. The strong seasonality of both chlorophyll a measures supports
                     separate spring and summer chlorophyll a reference concentrations.
  chapter iii  •  Historical Chlorophyll a Reference Concentrations

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                                                                                                  "
                      Spring
                                                       Summer

            1950  1960  1970  1980  1990  2000
                                             1950  1960  1970   1980  1990  2000
            1950  1960  1970  1980  1990  2000
                                             1950  1960  1970   1980  1990  2000
                                      Decade
Figure III-4. Geometric means of surface and depth-weighted chlorophyll a by the
oligohaline (OH), mesohaline (MH) and polyhaline (PH) salinity zones and decade
(1950s-2000s) for mid-flow conditions.
         HISTORICAL  CHLOROPHYLL a REFERENCE
                          CONCENTRATIONS

These historical analyses were undertaken to offer a spatial and temporal context for
developing numerical  chlorophyll a  criteria for Chesapeake Bay. The described
analyses drew upon extensive data spanning nearly six decades to quantify seasonal
regionally based chlorophyll  a reference concentrations. Few coastal ecosystems in
the world, if any, have the data to support such analyses. The trajectory over time of
chlorophyll a concentrations in Chesapeake Bay signifies increased nutrient loading,
making chlorophyll a an invaluable indicator. This indicator, however, is strongly
affected by climate. The challenge is to separate climatically induced variability
from long-term trends related to increased nutrient loading. This challenge was met
here using  nearly six decades of data  along with statistical modeling. The resultant
surface chlorophyll a  and depth-weighted average chlorophyll a concentrations
based on 1960s thresholds represent chlorophyll a reference concentrations charac-
teristic of a more balanced Chesapeake Bay ecosystem.
                                       chapter
Historical Chlorophyll a Reference Concentrations

-------
22
                                                LITERATURE  CITED

                     Adolf, J.E., C.L. Yeager, W.D. Miller, M.E. Mallonee, and L.W. Harding, Jr. 2006. Environ-
                     mental forcing of phytoplankton floral composition, biomass, and primary productivity in
                     Chesapeake Bay, USA. Estiiarine Coastal and Shelf Science, 67:108-122.

                     Boesch, D.F. and R. Rosenberg. 1981. Response to stress in marine benthic communities. In:
                     G.W. Barrett and R. Rosenberg (eds.). Stress Effects on Natural Ecosystems, pp 179-200.
                     New York: John Wiley and Sons.

                     Boynton, W.R., J.H. Garber, R. Summers, and W.M. Kemp. 1995. Inputs, transformations,
                     and transport of nitrogen and phosphorus in Chesapeake Bay and selected tributaries. Estu-
                     aries 18:285-314.

                     Chesapeake Bay Program. 1989. Chesapeake Bay Monitoring  Program Atlas. Volume 1.
                     Water Quality and Other Physiochemical Monitoring Programs.  CBP/TRS 34/89. Chesa-
                     peake Bay Program Office, Annapolis, MD.

                     Cooper, S.R.  and G.S. Brush.  1991. Long-term history of Chesapeake Bay anoxia. Science
                     254:992-996.

                     Cooper, S.R. and G.S.  Brush. 1993. A 2,500-year history of anoxia and eutrophication in
                     Chesapeake Bay. Estuaries 16:617-626.

                     Harding, L.W., Jr. 1994. Long-term trends in the distribution of phytoplankton in Chesapeake
                     Bay: roles of light, nutrients and stream flow. Marine Ecology Progress Series, 104:267-291.

                     Harding, L.W., Jr. and E.S. Perry 1997. Long-term increase of phytoplankton biomass in
                     Chesapeake Bay, 1950-1994. Marine Ecological Progress Series 157:39-52.

                     Harding, L.W., Jr., A. Magnuson, and M.E. Mallonee. 2005. SeaWiFS retrievals of chloro-
                     phyll in Chesapeake Bay and the mid-Atlantic bight. Estuarine,  Coastal and Shelf Science,
                     62:75-94.

                     Holland, A.F., A.T. Shaughnessy, and M.H. Hiegel.  1987. Long-term variation in mesohaline
                     Chesapeake Bay macrobenthos: Spatial and temporal patterns. Estuaries 10:227-245.

                     Kemp, W.M., W.R. Boynton, J.C.  Stevenson, R.R. Twilley, and J.C.  Means. 1983. The
                     decline of submerged vascular plants  in  upper  Chesapeake Bay:  Summary of results
                     concerning possible causes. Marine Technological Society Journal 17:78-89.

                     Kemp, W.M., M.T. Brooks, and R.R.  Hood. 2001. Nutrient enrichment, habitat variability
                     and trophic transfer efficiency in simple models of pelagic ecosystems.  Marine Ecology
                     Progress Series 223:73-87.

                     Kemp, W.M,  W.R. Boynton, J.E. Adolf, D.F. Boesch, W.C. Boicourt, G. Brush, J.C. Corn-
                     well, T.R. Fisher, P.M. Glibert, L.W. Harding, Jr., E.D. Houde, D.G. Kimmel, W.D. Miller,
                     R.I.E. Newell, M.R. Roman, E.M.  Smith, and J.C. Stevenson. 2005. Eutrophication of Chesa-
                     peake Bay: Historical  trends and  ecological interactions. Marine Ecology Progress Series,
                     303:1-29.

                     Malone, T.C.  1992. Effects of water column processes on dissolved oxygen, nutrients, phyto-
                     plankton and zooplankton. In: D. Smith, M. Leffler, G. Mackiernan (eds.). Oxygen Dynamics
                     in Chesapeake Bay: A Synthesis of Research, pp. 61-112. University of Maryland Sea Grant,
                     College Park, MD.
  chapter iii  •  Historical Chlorophyll a Reference Concentrations

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                                                                                                     11
Malone, T.C., DJ. Conley, T.R. Fisher, P.M. Gilbert, and L.W. Harding, Jr. 1996. Scales of
nutrient limited phytoplankton productivity in Chesapeake Bay. Estuaries 19:371-385.

Miller, W.D. and L.W. Harding, Jr. 2007. Climate forcing of the spring bloom in Chesapeake
Bay. Marine Ecology Progress Series 331:11-12.

Officer, C.B. R.B. Biggs, J.L. Taft, L.E. Cronin, M.A. Tyler, and W.R. Boynton. 1984. Chesa-
peake Bay anoxia: Origin, development and significance. Science 223:22-27.

Orth, RJ. and K.A. Moore.  1983. Chesapeake Bay: An unprecedented decline in submerged
aquatic vegetation. Science 222:51-53.

U.S. Environmental Protection Agency. 2003. Ambient Water Quality Criteria for Dissolved
Oxygen, Water Clarity and Chlorophyll a for the Chesapeake Bay and Its Tidal Tributaries.
EPA 903-R-03-002. Region III Chesapeake Bay Program Office, Annapolis, MD.

U.S. Environmental Protection Agency. 2004. Chesapeake Bay Program Analytical Segmen-
tation Scheme:  Revisions,  Decisions and  Rationales  1983-2003.  EPA  903-R-04-008.
CBP/TRS 268/04. Region III Chesapeake Bay Program Office, Annapolis, MD.

U.S. Environmental Protection Agency. 2005. Chesapeake Bay Program Analytical Segmen-
tation Scheme: Revisions, Decisions and Rationales 1983: 2003-2005 Addendum. EPA
903-R-05-004. CBP/TRS 278-06. Region  III Chesapeake Bay Program Office, Annapolis,
MD.

Zimmerman, A.R. and E.A.  Canuel. 2000. A  geochemical record of eutrophication and
anoxia in Chesapeake Bay sediments: anthropogenic influence on organic matter composi-
tion. Marine Chemistry 69:117-137.
                                        chapter iii  •  Historical Chlorophyll a Reference Concentrations

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    24
                                            chapter
                           Chlorophyll  a  Relationship
                                 to  Dissolved  Oxygen
                                         Impairments
                     Scientists have long recognized the ecological relationships between various water
                     quality parameters, such as chlorophyll a in surface waters and dissolved oxygen in
                     bottom waters. These relationships were initially recognized in freshwater lakes
                     where eutrophication problems developed because of the lakes' proximity to anthro-
                     pogenic nutrient sources. Taken from a textbook on water quality (Novotny and Olem
                     1994), Table IV-1 summarizes water quality studies in fresh waters, including their
                     classification in terms of trophic status. Shallower Secchi readings, along with higher
                     total phosphorous (TP), chlorophyll a, and primary production, are all associated with
                     increasing eutrophication and lower dissolved  oxygen in bottom (hypolimnetic)
                     waters. In terms of the water quality parameters documented in Table IV-1, the current
                     conditions in Chesapeake Bay are equivalent to those of eutrophic lakes.

                     Analyses focused on several key systems to determine whether significant quantita-
                     tive relationships between chlorophyll a and dissolved oxygen concentrations in
                     Chesapeake Bay could prove  useful in developing chlorophyll a criteria. For
                     instance,  data from the  tidal Choptank River were analyzed  to determine if such
     Table IV-1. Trophic status of lakes and characteristic water quality parameter values.
Water quality parameter
TP, ug liter1
chlorophyll a, ug liter1
Secchi depth, m
hypolimnetic O2, % sat.
phytoplankton productivity g C m"2 d"1
Oligotrophic
<10
<4
>4
>80
7-25
Mesotrophic
10-20
4-10
2-4
10-80
75 - 250
Eutrophic
>20
>10
<2
<10
350 - 700
Source: Novotny and Olem 1994, p. 784.
chapter iv  • Chlorophyll a Relationship to Dissolved Oxygen Impairments

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                                                                                                  •
relationships exist since this well-studied system is representative of many rural tidal
tributaries on the Eastern Shore Coastal Plain with low human population density
and significant agriculture. Similarly, the tidal Patuxent River was included because
this tidal tributary, although smaller than many of the other major tidal tributaries on
the western shore, represents the more urbanized western shore tributaries that rest
on Piedmont  and Coastal Plain lands with  high population densities and large
sewage inputs. These analyses also included fixed-station water quality monitoring
data from all major tidal tributaries and the mainstem Chesapeake Bay to identify
overarching relationship  patterns between chlorophyll a  and dissolved  oxygen
concentrations.

Chlorophyll a—the universal algal pigment indicative of phytoplankton biomass—
varies  on interannual, seasonal, and shorter  time scales based on phytoplankton
dynamics.  Interannually,  chlorophyll a varies least  with no consistent trends in
annual average chlorophyll a concentrations baywide or in the tidal fresh, oligoha-
line, mesohaline, and polyhaline zones  of the  Bay (Figure IV-1). Seasonally, larger
variations in chlorophyll a occur, typically with a cool-season minimum and warm-
season maximum in biomass (Figure IV-2).  Chlorophyll a production in tidal fresh
regions is typically light-limited during times other than summer due to high turbidi-
ties and short residence times. Large increases in chlorophyll a occur  in July and
August (Fisher et al.  1999) under  conditions of low freshwater flow and high light
intensity. In contrast, mesohaline and  polyhaline regions  have  damped  seasonal
cycles  driven primarily by river-borne nutrient inputs.

The long-term means for early and late growing season in the Patuxent River estuary
show these interacting influences on the  time and space distributions of chlorophyll a
(Figures IV-3  and IV-4). The normal spatial pattern in the tidal Patuxent River is a
             1985    1987   1989   1991   1993   1995    1997   1999   2001   2003
                                        Year
Figure IV-1. Interannual variations in average surface chlorophyll a concentrations for the
tidal fresh (TF), oligohaline (OH), mesohaline (MH), and polyhaline (PH) zones of the
Chesapeake Bay and its tidal tributaries (1985-2004).
Source: Chesapeake Bay Water Quality Monitoring Program (www.chesapeakebay.net/data)
                             chapter iv  •  Chlorophyll a Relationship to Dissolved Oxygen Impairments

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26
                                  Jan   Feb   Mar   Apr   May   Jun   Jul   Aug   Sep   Oct  Nov   Dec
                                                                  Month
                      Figure IV-2. Mean monthly surface chlorophyll a concentrations for the tidal fresh (TF),
                      oligohaline (OH), mesohaline (MH) and polyhaline (PH) salinity zones of the Chesapeake
                      Bay (1985-2004) with standard error bars.
                      Source: Chesapeake Bay Water Quality Monitoring Program (www.chesapeakebay.net/data)


^^_^
IB 's_
— 0)
>* —
.c T
°§?
o -•-
1 §
g.1
2 ^
s> 8
^ §
o




















-*-4 985-2005 (Apr-Jun)
— »-2001 (low flow)
— - 2003 (high flow)




^


1 \

1 \
1 \

1 \
1 \
I \
1 \
1 \
1 LE1.1 \

TF14/X*\\ T^^L
Tidal Fresh
.y— ^ '

*-/ X*""~*^^;^RET1.1 ^'
^.-^

100 80 60 40
Lower Estuary

- 140
- 120

- 100




- 60
- 40




20 0
Tidal River Kilometer
                      Figure IV-3. Average surface chlorophyll a in the tidal Patuxent River during the early
                      growing season (April-June, 1985-2005) by Chesapeake Bay Water Quality Monitoring
                      Program station with high- and low-flow years. Standard error bars are shown for the
                      long-term average.
                      Source: Chesapeake Bay Water Quality Monitoring Program (www.chesapeakebay.net/data)
  chapter iv •  Chlorophyll a Relationship to Dissolved Oxygen Impairments

-------
                                                                                                  "
     O CC
     0) J=
     05 C
     2 8
     0> C
     >. o
     -2001 (low flow)
                                                        "2003 (high flow)
        //'    '
Tidal Fresh/   '  ./
                                         TF1.7
                                                            Lower Estuary
                                                                       60
         100
                      80
                                  60          40

                                Tidal River Kilometer
                                                         20
Figure IV-4. Average surface chlorophyll a concentrations in the tidal Patuxent River
during the late growing season (July-October from 1985-2005) by Chesapeake Bay
Water Quality Monitoring Program station with high- and low-flow years. Standard error
bars are shown for the long-term average.
Source: Chesapeake Bay Water Quality Monitoring Program (www.chesapeakebay.net/data)
chlorophyll a maximum in tidal fresh waters at -60 km from the river mouth, with
lower concentrations downstream. The chlorophyll a maximum represents initial
consumption of the local terrestrial nutrient supply, with recycling and processing of
this material downstream (Fisher et al. 1988). This spatial pattern is accentuated at
low flows, whereas higher flows push the chlorophyll  a maximum downstream into
the lower estuary. This pattern also occurs in the mainstem Chesapeake Bay in near-
synoptic data, with higher temperatures focusing the chlorophyll a maximum in the
upper Bay (Figure IV-5).

At issue is whether surface chlorophyll a represents total integrated water column
chlorophyll a—especially important in the spring when chlorophyll a accumulates
both above and below the pycnocline until the hypoxia onset (Malone et al. 1988).
At mainstem water quality monitoring stations in the Bay, the annual average surface
chlorophyll a (|ig chla-liter -1) correlated strongly with the annual, average,  inte-
grated water column chlorophyll a  (mg chla-nr2)  (Figure  IV-6).  The spring
accumulations of chlorophyll a in bottom waters, therefore, do not significantly in-
fluence annual  averages of surface chlorophyll  a, which can be used to estimate
annual average  phytoplankton accumulation in the water.

In most tidal tributaries, chlorophyll a is usually related to nutrient loading on an
annual time scale. For instance, at the tidal Choptank River water quality monitoring
station ET5.2,  stream discharge from the Greensboro, Maryland stream  gauging
station is a proxy for nutrient loading. Annual average chlorophyll a increases to
>20  jig-liter1 with increasing annual discharge (Figure IV-7). The year 2003 had
                             chapter iv  •  Chlorophyll a Relationship to Dissolved Oxygen Impairments

-------
28
                               35-,


                               30 -


                               25 -
                                           March 1982
                                           temp = 4°C
                                           Sus. Rflow = 53760 cfs
                                           June 1982
                                           temp = 4°C
                                           Sus. Rflow =75680 cfs
                      Figure IV-5. The distribution of surface chlorophyll a concentrations in the Chesapeake
                      Bay mainstem in March and June 1982 showing the distinct chlorophyll a maximum in
                      the upper Bay (lower salinities) during warmer months and the more diffuse chlorophyll
                      maximum in the mid to lower Bay (higher salinities) during cooler months.
                      Source: Fisher et al. 1988.
                                 600
                                 500-
                              0
                              O

                              §  400-
                              CD
                              2  300-
                              ^
                              o
                              T3

                              2  200-
                              D)
                              CD
                              f
                              CD
                              Q
100
                                                      r2 = 0.76
                                                 8    10    12    14    16    18    20
                                                 Surface chlorophyll a concentration (ug-liter"1)
                                                                                          22
                                                                                                24
                      Figure IV-6. Relationship between surface chlorophyll a and depth-integrated chlorophyll a
                      concentrations for select water quality monitoring stations in the mainstem Chesapeake
                      Bay (March-June, 1985-2004).
                      Source: Chesapeake Bay Water Quality Monitoring Program (www.chesapeakebay.net/data)
  chapter iv  •  Chlorophyll a Relationship to Dissolved Oxygen Impairments

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                                                                                                  "
                 25
                 20
•§.
Q
_0
6
                 15
                 10
               c
               0)
               OT

               I
                     chla=  39.8* dis  r2 = 0.62"
                          9.5 + dis
              o
                                                            10
                        Average Annual River Discharge (m -s )
Figure IV-7. Average annual river discharge versus average annual surface chlorophyll a
concentration for the tidal Choptank River water quality monitoring station ET5.2
(1985-2003).
Source: Chesapeake Bay Water Quality Monitoring Program (www.chesapeakebay.net/data);
U.S. Geological Survey Stream Gage Network (www.usgs.gov)
record rainfall and was also one of the highest discharge years in the U.S. Geolog-
ical Survey's 50-year record. The relationship is hyperbolic, much like a saturation
function. Under high loading (high river flows), the chlorophyll a maximum is likely
displaced downstream from station ET5.2 or is suppressed by the high turbidity
accompanying the high freshwater flows.
Higher chlorophyll  a concentrations at the tidal Choptank River station ET5.2 are
linked to lower bottom dissolved oxygen (Figure IV-8, top panel). Both the annual
average and the January-to-August average chlorophyll a concentrations at station
ET5.2 are inversely correlated with the summer (June,  July, August) bottom dis-
solved oxygen concentrations in the tidal Choptank River at the same station (r2 =
0.40 and 0.33, respectively). Figure IV-8 shows the somewhat weaker relationship
between summer bottom dissolved oxygen and January-to-August chlorophyll a
because it is more logically  consistent  with, although statistically weaker than,
annual average chlorophyll a concentration. These relationships are caused by sedi-
mentation of organic matter  from the water column to the river bottom, where
microbial and metazoan benthos consume the matter and deplete oxygen in the near-
bottom waters. Annual and January-to-August average chlorophyll a concentrations
over 10 to 15 jig-liter"1 are  consistently associated with summer bottom dissolved
oxygen concentrations under 5 mg-liter1.
                             chapter iv  •  Chlorophyll a Relationship to Dissolved Oxygen  Impairments

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30
                     Summer average bottom dissolved oxygen is also inversely correlated with stratifi-
                     cation in  the  water column (Figure IV-8, bottom panel). Here stratification is
                     characterized as the difference in salinity from top to bottom (DS) during summer
                     (June-August). This relationship is stronger than the one between chlorophyll a
                     concentration and summer average bottom dissolved oxygen concentration (r2 = 0.67
                                0           5          10          15          20          25

                                   Average January-August Chlorophyll a Concentration (ug-liter1)
                         CU

                         5?
                             i
                         o  c
                         c/> £
                         •-  c
                         0  o
                           '
                         O  CU
                         DO  O
                         ,_  c
                         en  O
                         E"
                         E
                         D
                         w
                                                                             r2 = 0.67
                                  I  I  I  I  I  I  I  I  I  I  I
0.0        0.5        1.0        1.5       2.0       2.5
             Summer Top to Bottom Salinity Difference
                                                                                           3.0
               Figure IV-8. Top panel: Summer bottom dissolved oxygen concentration vs. average January-to-
               August surface chlorophyll a concentration for the Choptank River water quality monitoring station
               ET5.2 (1985-2004). Bottom panel: Summer bottom dissolved oxygen concentration vs. summer
               top-to-bottom salinity difference (AS) (1984-2004).
               Source: Chesapeake Bay Water Quality Monitoring Program (www.chesapeakebay.net/data)
  chapter iv  •  Chlorophyll a Relationship to Dissolved Oxygen Impairments

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                                                                                                "
and  0.33, respectively).  A  multiple linear regression between summer bottom
dissolved oxygen and summer DS with January-through-August chlorophyll a (Jan
Aug Chla) is dominated by DS. Substituting annual average chlorophyll a gives a
similar result with a nearly identical r2. All terms in both equations are significant,
with an r2 of 0.73:

   Summer average bottom dissolved oxygen =
   6.51 - 1.22*DS - 0.0361 *JanAugChla                            Equation 6

This statistical relationship may be viewed as an initial value of dissolved oxygen
slightly below saturation, which is weakly diminished by increasing chlorophyll a
(the organic matter source) and strongly diminished by increasing stratification (the
isolating  mechanism). Indeed, Malone  (1992) found a strong inverse relationship
between stratification and summer average bottom dissolved oxygen concentration
in the Chesapeake Bay mainstem between stations CB4.2 and 4.3, indicating that the
relationship of dissolved oxygen concentration to stratification strength is a ubiqui-
tous phenomenon in the Chesapeake Bay.

The  tidal Patuxent River has a  somewhat similar  relationship between annual
average chlorophyll a and summer average bottom dissolved oxygen concentrations
(Figure IV-9). The tidal Patuxent River consistently experiences low summer bottom
dissolved oxygen concentrations and somewhat higher annual average chlorophyll a
concentrations. However, the morphological features of the tidal Patuxent River—a
small deep estuary with a large basin/estuary ratio—increases the sensitivity of the
relationship between these parameters in the tidal Patuxent River compared to the
tidal Choptank River—a broad shallow  estuary with a small basin/estuary ratio
(Fisher et al. 2006).

Combining data for the tidal Patuxent and Choptank rivers, an envelope of concen-
trations indicate a tendency for summer average dissolved oxygen to decline by
0.15-1.1 mg-O2 per jig chlorophyll a. This amount of variation in summer bottom
dissolved oxygen sensitivity to increasing annual average chlorophyll a concentra-
tion is caused by differences in physical properties (morphology, stratification) and
by differences in nutrient inputs (agriculture, sewage, rainfall).

Despite the  variability, the relationship  is still useful. Chlorophyll a concentrations
of 7 to 28 jig-liter1 are associated with violations of the 30-day, open-water dissolved
oxygen criterion;  annual average chlorophyll a values greater than 20 jig-liter"1 are
consistently associated with summer average  bottom dissolved  oxygen concentra-
tions under 4 mg-liter1 in two important tidal tributaries of the Bay.

To broaden the basis of the chlorophyll a/dissolved oxygen relationship, data were
examined from additional portions of the Chesapeake Bay and its tidal tributaries.
Four time domains (calendar year, water year, January-August, and May-August)
were examined (Table IV-2). Although some of the r2 values reported below are
small (indicating  only small fractions of the variance explained), the large sample
size (number of stations x 20-year time periods) enables detection of significant rela-
tionships. Figure IV-10 shows an example of one of these relationships.
                             chapter iv  •  Chlorophyll a Relationship to Dissolved Oxygen Impairments

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32
                                              5          10          15         20          25

                                            Average Annual Chlorophyll a Concentration (|jg-liter"1)
30
                       Figure IV-9. Comparison of the annual average surface chlorophyll a (chla) concentration
                       versus summer average bottom dissolved oxygen (DO) concentration relationships for the
                       tidal Choptank and Patuxent rivers.
                       Choptank River relationship:       DO = 5.9 - 0.11 * chla       r2 = 0.37 **
                       Patuxent River relationship:       DO = 2.4 - 0.057 * chla      r2 = 0.26 *
                       All data relationship:            DO = 5.6 - 1.9 * chla        r2 = 0.36 **
                       Source: Chesapeake Bay Water Quality Monitoring Program (www.chesapeakebay.net/data)
  Table IV-2. Summary of statistical relationships between summer average bottom dissolved oxygen (mg-liter1)
  and average surface chlorophyll a (jug-liter1) at several time scales. The r2 is the percent of the variance in
  summer average bottom dissolved oxygen explained by average surface chlorophyll a at each time scale,
  and the symbols represent the significance level.

Chesapeake
Bay
Mainstem
Tidal
Tributaries
Time scale
o
r
Slope
r2
Slope
Calendar Year
0.23 **
-0.123 ±
0.020
0.12 **
-0.105 ±
0.025
Water Year
0.23 **
-0.127±
0.021
0.11 **
-0.082 ±
0.021
January-
August
0.23 **
-0.098 ±
0.016
0.11 **
-0.076 ±
0.020
May —
August
0.27 **
-0.076±
0.011
0.07*
-0.046 ±
0.015
  r2 = percent of the variance in summer average bottom dissolved oxygen explained by average surface chlorophyll a at each time scale
  * = p < 0.05
  **=p<0.01
  Slope = change in summer average bottom dissolved oxygen per unit chlorophyll a (mg-O2 [ug-chla]"1 ± standard error).
  chapter iv  •  Chlorophyll a Relationship to Dissolved Oxygen Impairments

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                                                                                                 •
Figure IV-10 illustrates the relationship between summer (with a one-month delay of
May to August) average chlorophyll a concentrations and summer (June-August)
average bottom dissolved oxygen concentrations. The relationship is similar to the
others in Table IV-2, but with a more pronounced shift to low bottom dissolved
oxygen when May-to-August chlorophyll a averages >15 jig-liter"1. No paired obser-
vation at any Chesapeake Bay Water Quality Monitoring Program station within the
Chesapeake Bay has a May-to-August  chlorophyll a that exceeds 15  jig-liter1 with
a summer average bottom dissolved  oxygen value  (June-August) that exceeds
3 mg-liter1. Variations in physical morphology, nutrient loading, and stratification
among stations result in the scatter shown in Figure IV-10. Clearly, however, May-
to-August average surface chlorophyll a concentrations >15 jig-liter"1 are associated
with summer average dissolved oxygen values <3 ing-liter1 in the bottom waters.

An inverse relationship between chlorophyll a and dissolved oxygen is also apparent
in the high-frequency monitoring data collected by the Maryland Department of
Natural Resources. In Figure IV-11, inverse relationships occur between long-term
average dissolved oxygen,  chlorophyll a, dissolved  inorganic phosphorous, and
dissolved  inorganic nitrogen concentrations at the high-frequency water quality
monitoring stations in the tidal Magothy and Severn rivers. In this  shallow-water
              25
            CD

           I20
            CD
             . 15
            o
           _c
           O
              10
            CD
            O)
               0
                   chla =  39.8'dis   r2 = 0.62"
                        9.5 + dis
                 0                      5                     10
                     Average Annual River Discharge (m3-s"1)
Figure IV-10. Average chlorophyll a (May-August) concentration versus summer average
(June-August) bottom dissolved oxygen concentration for various Chesapeake Bay mainstem
water quality monitoring program stations identified by their respective Chesapeake Bay
Program segment (CB3 MH, CB4 MH, CB5 MH, and  CB6 PH).
Source: Chesapeake Bay Water Quality Monitoring Program (www.chesapeakebay.net/data)
                             chapter iv  •  Chlorophyll a Relationship to Dissolved Oxygen Impairments

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34
        10
    S.-C  8
    >i CJ
   o ^
                                                          10
o ^
o E,  6
!.|
« -S
                                                                                        Cattail Creek
          0     10    20     30     40     50    60

            Average Chlorophyll a Concentration (|jg-liter~1)
      0
      0.00         0.01          0.02         0.03

       Average Orthophosphorus Concentration (mg-liter"1)
                                   10
                                            Q Sloninglon
                                                        DO = 9.9-22* DIN
                                                            r2= 0.89
                                                                   Cattail Creek
                                    0.0
                                              0.1
                                                       0.2
                                                                0.3
                                                                          0.4
                                          Average Dissolved Inorganic Nitrogen
                                               Concentration (mg-liter~1)
  Figure IV-11. Significant relationships among average concentrations of the continuous monitoring surface
  chlorophyll a, orthophosphorous, and dissolved inorganic nitrogen data versus dissolved oxygen concentrations
  for the tidal Magothy and Severn rivers.
  Source: Fisher and Gustafson 2005.
                     case, average surface concentrations of chlorophyll a less than 30 jig-liter1 are asso-
                     ciated with depressed dissolved oxygen concentrations in surface waters, further
                     strengthening the link between nutrient loading, phytoplankton abundance, and low
                     dissolved oxygen.

                     A simple conceptual model can be derived from these observations. The sequence of
                     events leading to low dissolved oxygen conditions in the Chesapeake and its tidal
                     tributaries can be viewed as follows: high nutrient inputs lead to high chlorophyll a
                     in excess of the needs of local phytoplankton-consuming organisms. Excess organic
                     matter settles to  the bottom, where it is  microbially degraded and results in low
                     bottom dissolved oxygen.  This conceptual model applies to deep waters separated
                     from the upper mixed layer by a pycnocline via sedimentation at lower concentra-
                     tions of average surface chlorophyll a (10-15 jag-liter1, Figures IV-8 through IV-10)
                     or directly in the surface layer of shallow waters at higher concentrations of average
                     chlorophyll a (>30 jag-liter1, Figure IV-11) due to the greater access to atmospheric
  chapter iv  •  Chlorophyll a Relationship to Dissolved Oxygen  Impairments

-------
                                                                                                     •
O2 in the upper  mixed layer. These relationships provide quantitative linkages
between the amount of chlorophyll a in surface waters and dissolved oxygen impair-
ment of bottom waters.
                           LITERATURE CITED

Fisher, T.R., L.W. Harding, D.W. Stanley, andL.G. Ward. 1988. Phytoplankton, nutrients and
turbidity in the Chesapeake, Delaware and Hudson estuaries. Estuarine, Coastal and Shelf
Science 27:61-93.

Fisher, T.R., A.B. Gustafson, K. Sellner, R. Lacouture, L.W. Haas, R. Magnien, R. Karrh. and
B. Michael. 1999. Spatial and temporal variation in resource limitation in Chesapeake Bay.
Marine Biology 133:763-778.

Fisher, T.R. and A.B. Gustafson. 2005. December 2005 Report to the Maryland Department
of Natural Resources, Annapolis, MD.

Malone, T.C., L.H. Crocker, S.E. Pike, and B.W. Wendler. 1988. Influences of river flow on
the dynamics of phytoplankton production in a partially stratified estuary. Marine Ecology
Progress Series 48: 235-249.

Malone, T.C. 1992. Effects of water column processes on dissolved oxygen, nutrients, phyto-
plankton and zooplankton. In: D. Smith, M. Leffler, G. Mackiernan (eds.). Oxygen Dynamics
in Chesapeake Bay: A Synthesis of Research, pp. 61-112. University of Maryland Sea Grant,
College Park, MD.

Novotny, V. and H. Olem. 1994. Water Quality: prevention, identification, and management
of diffuse pollution. New York, NY: Van Nostrand Reinhold.
                              chapter iv  •  Chlorophyll a Relationship to Dissolved Oxygen Impairments

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    36
                                                chapter
                            Chlorophyll a  Contributions
                          to  Water Clarity  Impairments
                      Deterioration of water clarity is widely believed to be the principal cause of the cata-
                      strophic decline in submerged aquatic vegetation (SAV) that occurred throughout
                      most of the Chesapeake Bay during the 1960s to  1980s (Orth and Moore 1983).
                      Compared to other plants, SAV requires strong light—about 22 percent of surface
                      light for polyhaline and mesohaline communities and about 13 percent for oligoha-
                      line and tidal-fresh communities (Dennison et al. 1993). The  light requirement for
                      SAV, together with the depth to which the plants can potentially grow, places an
                      upper limit on the diffuse attenuation coefficient (Kd) for photosynthetically active
                      radiation (PAR) that permits maintenance or restoration of SAV (Kemp et al. 2004).
                      Phytoplankton chlorophyll is one of three constituents that increase the light attenu-
                      ation above that due to water alone. On average, the contribution of chlorophyll to
                      diffuse attenuation can be  calculated from a bio-optical model incorporating the
                      effects of phytoplankton chlorophyll  on  the absorption and  scattering  of light
                      (Gallegos 2001). The upper limit of chlorophyll that will permit SAV growth in a
                      particular location can also be calculated, but the precise value depends on the
                      concentrations and optical properties of other attenuating substances.

                      The two constituents in addition to chlorophyll a that contribute to light attenuation
                      are colored dissolved  organic matter (CDOM)  and suspended particulate matter
                      (quantified by  the concentration  of total  suspended solids, TSS). The  general
                      approach to establishing chlorophyll a concentrations which will not impair water
                      clarity, therefore, requires  determination  of  the characteristic concentrations of
                      CDOM and TSS and their  effect on light  attenuation for a particular system. The
                      approach then determines the allowable chlorophyll a concentration that permits
                      (when combined with the characteristic  CDOM  and TSS concentrations) the
                      required level of light to penetrate to the appropriate application depth as established
                      on a segment-specific basis  in the 2003 EPA Regional Criteria Guidance and Desig-
                      nated Uses Technical Support Document (U.S. EPA 2003a, 2003b).

                      Figure V-l illustrates this concept. Bio-optical modeling can be used to determine
                      the threshold concentrations of light-attenuating water quality parameters that allow
                      some  surface light (13 or 22 percent, depending on salinity zone) to penetrate to a
chapter v  •  Chlorophyll a Contribution to Water Clarity Impairments

-------
              Insufficient light
              forSAV
	 Original
  • •  Elevated CDOM
 	Smaller Particles
^B  Algal Solids
                 Chlorophyll a (mg-m"3)
                                                                                                 "
                       Figure V-1. Chlorophyll thresh-
                       olds and TSS for SAV survival
                       depend on other parameters.
                       Increases in CDOM (dashed line)
                       or in the absorption and scatter-
                       ing per unit mass  of TSS (dotted
                       line) move thresholds toward the
                       origin (i.e., make the system more
                       sensitive to the deterioration of
                       water quality).
given application depth. The figure uses two-dimensional plots for clarity of illus-
tration with chlorophyll a and TSS concentrations as x-axis and y-axis, respectively
(Figure V-1). Changes in the concentration of CDOM (solid line), or optical proper-
ties of the particulate matter (largely determined by particle-size distribution, dotted
line), and application depth  determine the thresholds. Chlorophyll  a adds to the
particulate matter concentration of any sample; the  gray shaded region denotes the
approximate contribution of chlorophyll a to TSS. Systems with median concentra-
tions of chlorophyll a and TSS that fall closer to the origin than the threshold line
have water quality conditions that will provide sufficient light  for SAV, while
systems with concentrations that fall beyond the threshold line will not (Figure V-1).

The chlorophyll a concentration that will support  SAV  light requirements (e.g.,
water clarity criteria) clearly depends on the concentration  of other  attenuators
(CDOM and TSS). Colored dissolved organic matter comes from decaying plants,
which includes phytoplankton but mostly emanates  from terrestrial sources in estu-
arine waters. It  absorbs light strongly  in the blue  portion  of the  spectrum.
Concentrations of CDOM can be  very high in some systems, such as the tidal
Pocomoke River on the Eastern Shore of Chesapeake Bay, which drains low-lying
coastal wetlands. While some slight reduction in CDOM may accompany reductions
in chlorophyll  a concentrations,  CDOM is considered a fixed  characteristic  of a
particular tidal tributary or Bay region in deriving chlorophyll a criteria.

Due to the unique hydrodynamics, morphology, and basin characteristics of each
tributary,  Sanford (personal communication 25 October 2005) has suggested that
each tidal tributary may have some natural or "background" concentration of TSS
that represents a dynamic balance between settling and resuspension,  and persists in
the absence of immediate riverine inputs. Management may be  able to lower TSS
concentrations only to "background" concentrations; therefore,  identifying the back-
ground level for each tributary will prove critical (see below).
                                 chapter v •  Chlorophyll a Contribution to Water Clarity Impairments

-------
38
                    Figure V-2 illustrates the determination of light-based chlorophyll a concentration
                    thresholds. The concentration of CDOM and optical properties, along with the desig-
                    nated application depth for a segment, determines the threshold concentrations of
                    chlorophyll a and TSS that will  support SAV (Figure V-2, outer dark blue edge). The
                    medium blue region denotes an  adjusted threshold obtained by subtracting the back-
                    ground TSS concentration characteristic of that waterbody. The point at which this
                    adjusted threshold intersects the algal contribution to TSS represents the maximum
                    allowable chlorophyll a that will meet the SAV requirements at the application depth
                    (for the given CDOM and background TSS concentrations for that Chesapeake Bay
                    Program segment (Figure V-2).
                      £
                      5
                      w
                                                       • 22% Light Contour
                                                       • Adj. for bkg. TSS
                                                         Algal solids
                                                        • Limit
                                   10      20      30      40

                                      Chlorophyll (mg-m"3)
                                                                50
Figure V-2.
Determination of
maximum allowable
CHLA that will meet
light requirements
of SAV, adjusting for
"background"
concentration of TSS.
                     DETERMINING  BACKGROUND  TSS  CONCENTRATIONS

                    This analysis made several general assumptions: a background TSS concentration
                    could be determined for each Chesapeake Bay Program segment; this concentration
                    would vary from month to month; and the median value of the TSS concentration
                    distribution for each month would represent this concentration after removing outlier
                    concentration values (Sanford, personal communication). Identifying and removing
                    outlier  TSS values is important because high-flow or wind events can elevate
                    concentrations above the  background range. Based on these assumptions, a SAS
                    program was developed to estimate the monthly background TSS concentration for
                    each monitoring segment  using surface TSS concentration data from 1985 through
                    2004 from the Chesapeake Bay water quality monitoring program.

                    The monitored TSS  concentrations were first converted to non-algal  suspended
                    solids (NASS). The formula for this conversion is:
                       NASS = TSS - 0.1333[CHLA]
          Equation 7
  chapter v •  Chlorophyll a Contribution to Water Clarity Impairments

-------
The 0.1333 coefficient is based on a carbon to chlorophyll ratio of 40 mg C per mg
chlorophyll a and the Redfield algal composition (Gallegos 2001). The resultant
NASS concentration data were grouped by segment, year, and month. Mean NASS
concentration was then determined.

Figure V-3 shows an example of the output from this step for Chesapeake Bay
Program segment CB2OH. This graph is generally representative of the distribution
of monthly NASS levels for the majority of segments. Mean NASS concentrations
tended to cluster at lower levels with the means for some years well above these clus-
ters. These outliers, as discussed, most likely represent NASS concentrations during
high-flow  or wind events. The next step identifies these outliers for each month in
the 78 Chesapeake Bay Program segments, removing them before calculating back-
ground TSS concentrations.

Mean NASS concentrations for each  month and segment were sorted in descending
order and the difference between each mean concentration and the mean concentra-
tion just above it was determined. The mean difference for each month and  segment
was then calculated and the individual differences expressed as a percentage of this
mean. Since the objective was to identify high-concentration outliers, individual
means below the monthly median were not included in the outlier search. From the
remaining numbers, if the individual  difference was greater than 250 percent of the
mean difference, the data point was also identified as an outlier.
                                                                                           .
      80 -i
      70 -
      60 -
  =   50
  O
  CO
  73
  CD
  73
  £Z
  CD
  CL
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  CO
  "CD
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40 -
30 -
20 -
      10 -
       0 -
            Segment CB2OH
                Mean NASS
*     $
                                   i
                                                             ii
!     *
       I
                                               6

                                              Month
                                                                          10
                                                                                 11     12
Figure V-3. Segment mean non-algal suspended solids (NASS) levels calculated for each month of each year
(1985-2003) for monitoring segment CB20H. NASS was calculated from TSS as NASS = TSS-0.13*CHLA.
Source: Chesapeake Bay Water Quality Monitoring Program (www.chesapeakebay.net/data)
                               chapter v •  Chlorophyll a Contribution to Water Clarity Impairments

-------
  40
                 The outliers for each month and segment were then grouped with the minimum value
                 tagged as the breakpoint for values outside the typical distribution of monthly means.
                 For each month, the mean NASS concentrations that matched this breakpoint were
                 identified (more than one concentration was possible for each month). The next
                 lowest mean NASS concentration was identified as the upper end of background
                 distribution NASS levels (since more than one  concentration for each month is
                 possible, the mean is used). Figure V-4 provides an example of these upper end
                 thresholds for segment CB2OH.

                 The median of all monthly mean NASS concentrations less than or equal to these
                 upper end values is then selected as the background TSS concentration (Figure V-5).
                 In cases with no outlier concentration values, the median became the background
                 TSS concentration for that segment.
   in
  73
  ~o
  CO
  73
   CD
  73
   C
   CD
   CL
   in
   12
  CO
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  CD
80 -,

70 -

60 -

50 -

40 -

30 -




10 -

 0 -
            Segment CB2OH
                 Mean NASS
                •Upper Threshold
 »   *   -f-  -r.
ttitmm

                                                            10
                                                                  11
                                                                       12
                                        Month
Figure V-4. Segment mean TSS levels calculated for each month of each year (1985-2003) for monitoring segment
CB20H. Black bars represent the upper level of the "background" distribution of means for each month.
Source: Chesapeake Bay Water Quality Monitoring Program (www.chesapeakebay.net/data)
                          ECOLOGICAL  RELATIONSHIP BETWEEN
                  CHLOROPHYLL a AND WATER CLARITY IMPAIRMENTS

                 Phytoplankton are pigment-bearing photoautotrophs; they require light and absorb
                 light. This basic fact drives the  ecological connection between chlorophyll a and
                 water clarity impairments. The relatively simple exponential decrease of PAR with
                 depth, along with the contribution of phytoplankton chlorophyll to light attenuation,
   chapter v • Chlorophyll a Contribution to Water Clarity Impairments

-------
                                                                                    .
   in
  73
  ~o
  CO
  73
   CD
  73
   C
   CD
   CL
   in
   13
  CO
  "CD
  _D)
   CD
80 -,

70 -

60 -

50 -

40 -

30 -

20 -
              Segment CB2OH
                •  Mean MASS
                	 Upper Threshold
                •  Background TSS
 *     *   -f-  -4-
If   jtiTHH
                                                                                   •
                                                                      1 0
                                                                             11
                                                                                   12
Figure V-5. Segment mean MASS levels calculated for each month and each year for segment CB20H (blue
diamonds), along with upper thresholds for "normal" conditions (horizontal black lines) and "background TSS"
calculated as the median of values less than or equal to the threshold.
provided the basis for previous models of environmental controls on phytoplankton
production (Tailing  1957; Ryther and Yentsch 1957). Wofsy (1983) derived equa-
tions for the maximum phytoplankton standing crop that can be supported in a
nutrient-saturated mixed layer based on self shading. His treatment explicitly
accounted for  the attenuation of light  by water and other substances (notably
suspended sediments). Figure 5a in his publication bears strong resemblance to
Figure V-2 here, except that his treatment offers concentration limits for phyto-
plankton growth rather than SAV.

The direct connection between chlorophyll a concentration and water clarity-based
impairments was inherent in Carlson's (1977) Trophic State Index. Each increase of
ten units for the index represented a doubling in algal biomass. Carlson showed that
values calculated from Secchi depth readings were roughly equivalent to those esti-
mated from chlorophyll a  measurements for temperate lakes.  He recognized,
however, that Secchi depth measurements in lakes with large amounts of non-algal
particulate matter might prove erroneous.

The practice of partitioning the diffuse attenuation coefficient into components due
to water, dissolved color, phytoplankton, and other particulates has had both propo-
nents (Lorenzen 1972; Smith 1982, Verduin 1982; Xu et al. 2005) and critics (Morel
and Bricaud 1981; Stavn 1988;  Kirk  1994; Gallegos 2001). The  approach is
appealing because it ostensibly permits calculation of each component's relative
attenuation (as a percent of the total) (Xu et al. 2005). One problem with using partial
                             chapter v •  Chlorophyll a Contribution to Water Clarity Impairments

-------
42
                    attenuation coefficients, however, is that the linearity of the diffuse attenuation coeffi-
                    cient with water quality concentrations only pertains to small variations in concentration
                    (Kirk 1994). The partial attenuation coefficient of a component estimated from field
                    data will be smaller at higher concentrations of the component. For chlorophyll a, this
                    means that the percentage of attenuation attributed to chlorophyll a will be underesti-
                    mated in eutrophic systems, when the partial attenuation of chlorophyll a is estimated
                    from a regression of field data on Kj against water quality measurements.

                    An alternative approach partitions the inherent optical properties—namely absorp-
                    tion and scattering coefficients—into  contributions due to water, dissolved color,
                    chlorophyll, and other particulates. Inherent optical properties, unlike Kj, are truly
                    additive and proportional to the concentration of the causal component (Kirk 1994).
                    Radiative transfer modeling provides the link between the inherent optical proper-
                    ties, and apparent optical properties such as Kj (Kirk 1994; Mobley et al. 1993).
                    Gallegos (1994, 2001) used this approach to calculate the threshold concentrations
                    of optically active water quality constituents that would permit SAV growth in the
                    Rhode River, a mesohaline tidal tributary of Chesapeake Bay. Figure V-2 is based on
                    that approach, modified to allow for a background concentration of TSS.
                        REGIONALIZING  THE FACTORS CONTRIBUTING TO
                                WATER COLUMN  LIGHT ATTENUATION

                    Although linearity between Kj and water quality is not assumed when determining the
                    threshold boundaries that determine the water clarity-based chlorophyll a threshold
                    concentrations, the boundaries are very nearly linear and can be represented as such for
                    algebraic convenience. Figure V-l indicates that the threshold boundaries depend on
                    CDOM concentrations and the optical properties of the particulate matter. Hence, the
                    slopes  and intercepts of the threshold lines vary regionally, as for "background" TSS
                    concentration, and this variability needs to be incorporated into the procedure for deter-
                    mining water clarity-based chlorophyll a concentration thresholds.

                    The bio-optical modeling approach represents the absorption and scattering spectra as
                    functions of water quality concentrations (Gallegos and Bergstrom 2005). Several coef-
                    ficients are required to  relate light  absorption and  scattering to  water  quality
                    concentrations. The absorption at wavelength A [a(A)] can be expressed as the sum due
                    to water, [aw(A)], CDOM, chlorophyll a, and TSS (Gallegos and Bergstrom 2005)

                     a(A) = aw (A)+a/440)g(A)+a^(675)[a/LA]0(A)+ a^ (44G)[TSS]p$)    Equation 8
                    in which g(A), 0(A), andp(A) are spectral shapes of absorption due to CDOM, chloro-
                    phyll a, and TSS, respectively, a^(440) is the absorption by CDOM at 440 nm, and
                    a/(675) and a/,.^*(440) are specific-absorption coefficients for chlorophyll and TSS
                    at reference wavelengths 675 and 440 nm, respectively.

                    Scattering is due to particulate matter, therefore:

                               bp (A) = b'fi (555lTSS})n (A)                             Equation 9



  chapter v  • Chlorophyll a Contribution to Water Clarity Impairments

-------
                                                                                             .
in which bp(K) = particulate scattering spectrum, bp*(555) is the specific-scattering
coefficient at 555 nm, and £>„(!) is the spectral shape of scattering.

In their effect on Kd, variations in the spectral-shape functions are of third-order
importance behind variations in water quality concentrations and specific-absorption
and specific-scattering coefficients. The literature offers information on spectral
shape functions (Gallegos 1994, Magnuson et al. 2004). Absorption by CDOM has
been  measured in Chesapeake Bay  segments for about one-and-a-half  years.
Magnuson et  al. (2004) characterized seasonal variations in a^*(675) for mainstem
Chesapeake Bay. A few studies (Gallegos 2001) have measured specific-absorption
and specific-scattering coefficients for TSS, but for most segments estimates for
a/,.^*(440) and bp*(555) relied on an inverse procedure described by Gallegos and
Bergstrom (2005).
            WATER CLARITY  IMPAIRMENT-BASED
    CHLOROPHYLL  a  CONCENTRATION THRESHOLDS

Segment-specific chlorophyll a concentration thresholds—the maximum allowable
concentration protective of SAV minimum light requirements (state-adopted water
clarity criteria)  assuming achievement of background TSS concentrations—vary
widely among the segments. The concentration thresholds range from "no chloro-
phyll a concentration could be determined" (due to high background TSS preventing
achievement of the  SAV minimum light requirement at the selected application
depth) to "greater than 150 jig-liter1" (Table V-l).

Several reasons exist for some of the inordinately high (e.g., greater than 80 lag-liter1
chlorophyll a) concentrations.  In several cases, the EPA-published water clarity
criteria application depths  (U.S. EPA 2003b) seem too low for the given water
quality conditions, especially in some mainstem Chesapeake Bay segments (e.g.,
CB2OH (0.5 m), CB3MH  (0.5 m), CB6PH (1 m) and CB8PH (0.5 m)).  The low
application depths may be appropriate given that the SAV restoration goals  for these
segments were set based on factors other than water clarity (e.g., historical distribu-
tions  or limitations  by physical factors)  (U.S. EPA 2003b). In other segments
(ANATF, JMSTF, and CHOTF), the background TSS concentrations appear too low
for the salinity zone represented. In another segment (BSHOH), the specific-absorp-
tion  and  specific-scattering  coefficients may be too low. Finally, segments
designated entirely as SAV  no-grow zones (WBEMH, SBEMH, EBEMH, LAFMH,
ELIPH, CHOTF, NANTF, and POCTF) were omitted from Table V-l and  from the
analyses used to generate Table V-2 (U.S. EPA 2007).

Aggregation of segment-specific results  (listed in Table V-2 by the EPA-published
water clarity  criteria application depths (U.S. EPA 2003b) and the  four salinity
regimes) provides water clarity-based chlorophyll a concentration thresholds that are
intuitively more reasonable than those for individual segments.  These aggregates
should meet SAV minimum light requirements (Table V-2). Summarized in this way,
the chlorophyll a concentration thresholds range from 2.7 jig-liter1 for mesohaline
and polyhaline zones with 2-meter application depths to 43 lag-liter1 for tidal fresh
and oligohaline zones with  0.5-meter application depths (Table V-2).
                               chapter v  •  Chlorophyll a Contribution to Water Clarity Impairments

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44
  Table V-1.  Segment-specific chlorophyll a (CHLA) (jug-liter1) concentration thresholds determined by inversion
  of a bio-optical model for the given colored dissolved organic matter (CDOM) (jug-liter1) and non-algal suspend-
  ed solids (MASS) (jug-liter1) concentrations. Concentration thresholds were calculated for all three water clarity
  criteria application depths (0.5, 1, and 2 meters). Bold values represent assigned application depths. The text
  describes the methods for determining CDOM. Segments designated entirely as SAV no-grow zones were
  omitted from the  analysis based on U.S. EPA 2007.
Water Clarity
Chesapeake Criteria
Bay Program Application
Segment Depth
ANATF
APPTF
BACOH
BOHOH
BSHOH
C&DOH
CB2OH
CB3MH
CB8PH
CHKOH
CHOOH
CHSOH
CHSTF
ELIPH
FSBMH
JMSMH
JMSOH
JMSTF
LYNPH
MPNOH
MPNTF
NANMH
NANOH
NANTF
NORTF
PAXOH
PAXTF
PMKOH
PMKTF
RPPTF
WBRTF
WICMH
POCOH
RHDMH
RPPOH
WSTMH
YRKMH
CB6PH
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
1
Salinity Zone
TF
TF
OH
OH
OH
OH
OH
MH
PH
OH
OH
OH
TF
PH
MH
MH
OH
TF
PH
OH
TF
MH
OH
TF
TF
OH
TF
OH
TF
TF
TF
MH
OH
MH
OH
MH
MH
PH
CDOM
0.94
1.50
3.79
0.78
0.91
0.84
0.47
0.39
0.23
0.79
1.22
1.56
1.36
1.17
4.50
0.54
0.73
1.44
0.80
2.75
3.12
1.62
4.85
1.98
1.06
0.81
1.07
1.55
1.92
1.41
1.10
1.46
6.34
0.51
0.78
0.41
0.77
0.27
NASS
7.87
22.74
16.31
22.62
22.56
18.70
7.88
5.88
5.80
17.15
22.08
42.04
41.94
8.95
21.05
12.30
21.27
13.94
7.36
27.81
6.21
30.20
30.20
17.94
11.43
26.45
18.44
41.83
12.01
19.59
9.85
21.31
17.22
8.57
21.15
10.05
25.28
6.68
CHLA-
0.5m
85.6
61.5
50.5
21.7
81.5
78.8
124.8
91.6
141.4
52.9
20.6
38.6
U
53.9
17.4
56.8
57.5
89.2
N/A
24.1
37.6
U
N/A
35.2
60.5
9.6
48.9
12.5
42.8
69.0
55.2
11.4
68.6
65.1
14.8
59.7
10.0
131.9
CHLA-
1.0m
17.9
U
U
U
U
U
39.5
27.9
55.3
U
U
U
U
U
U
U
U
8.3
N/A
U
U
U
N/A
U
U
U
U
U
U
U
U
U
U
8.4
U
3.0
U
48.8
CHLA-
2.0m
U
U
U
U
U
U
U
U
13.4
U
U
U
U
U
U
U
U
U
N/A
U
U
U
N/A
U
U
U
U
U
U
U
U
U
U
U
U
U
U
8.4
Notes
2



3

1
1
1








2



















1
  chapter v  •  Chlorophyll a Contribution to Water Clarity Impairments

-------
Table V-1.  (continued)
                                                                                                                     .
Water Clarity
Chesapeake Criteria
Bay Program Application
Segment Depth
CHOMH2
CHSMH
CRRMH
JMSPH
MAGMH
MATTF
PATMH
PAXMH
POCMH
POTMH
RPPMH
SASOH
SEVMH
SOUMH
YRKPH
BIGMH
CB1TF
CB4MH
CB5MH
CB7PH
CHOMH1
EASMH
ELKOH
GUNOH
HNGMH
LCHMH
MANMH
MIDOH
MOBPH
PIAMH
PISTF
POTOH
POTTF
TANMH
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
Salinity Zone
MH
MH
MH
PH
MH
TF
MH
MH
MH
MH
MH
OH
MH
MH
PH
MH
TF
MH
MH
PH
MH
MH
OH
OH
MH
MH
MH
OH
PH
MH
TF
OH
TF
MH
CDOM
0.39
1.56
0.48
0.37
0.68
1.22
0.82
0.54
0.55
0.85
0.49
0.64
0.55
0.50
0.58
0.82
0.63
0.32
0.32
0.28
0.55
0.67
0.85
0.84
0.60
0.39
2.58
0.54
0.47
0.46
1.36
0.64
1.13
0.60
NASS
11.74
6.71
4.50
9.17
3.89
12.27
7.45
8.28
16.27
6.61
13.37
12.53
4.59
4.62
7.08
14.73
8.85
4.02
5.35
7.05
6.87
4.24
13.56
14.68
14.68
7.36
19.34
10.07
8.56
6.64
11.11
14.32
13.31
10.27
CHLA-
0.5m
47.1
59.6
53.2
89.2
52.5
91.8
30.5
35.1
82.7
100.4
77.3
38.1
76.9
66.6
91.4
88.9
73.0
97.5
99.1
122.3
107.2
100.2
90.7
108.8
N/A
108.5
52.2
89.0
109.4
97.7
59.5
73.7
85.5
107.7
CHLA-
1.0m
U
6.4
10.4
21.1
11.2
12.8
U
U
8.7
29.8
8.7
U
22.1
16.9
24.9
13.2
9.7
34.5
33.0
43.0
34.2
34.3
10.4
19.3
N/A
34.8
U
16.1
33.1
29.7
U
0.1
7.8
30.0
CHLA-
2.0 m Notes
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
3.7
0.8
4.4
U
1.8
U
U
N/A
U
U
U
U
U
U
U
U
U
TF = tidal fresh (0 - <0.5 ppt)                                               Notes.
OH = oligohaljne (18 ppt)                                                            f         j,,™,,            J
CDOM = soluble absorption at 440 nm                                       2. Suspect  background  TSS.
NASS = Non-algal suspended solids or "background TSS" - 0.133*CHLA           3. Suspect particulate optical properties.
U = "Unattainable" (for reasons described in text)
N/A = insufficient data

Sources: U.S.  EPA 2004, 2005 (Chesapeake Bay Program segments); U.S. EPA 2003b (water clarity criteria application depths)
                                        chapter v  •  Chlorophyll a Contribution to Water Clarity Impairments

-------
46
                     Table V-2.  Surface chlorophyll a concentration thresholds determined by inversion of bio-
                     optical model as protective of SAV minimum light requirements, averaged by salinity zone
                     and water clarity criteria application depth. Averages were calculated over all segments
                     with sufficient data (see Table V-1). Segments flagged with concentration thresholds too
                     high due to one of three identifiable reasons (see Table V-1, notes) were excluded from
                     the below salinity/application depth-based averages.
Salinity zone
TF/OH
TF/OH*
MH/PH
MH/PH
MH/PH
Water clarity
criteria
application
depth (m)
0.5
1.0
0.5
1
2
Number of
segments included
in average
20
7
7
10
4
Chlorophyll a
concentration
threshold
(ing-liter"1)
43
10.9
39.2
16.0
2.7
Standard error
(ing-liter"1)
4.6
2.3
9.4
2.6
0.8





                      TF = tidal fresh (0 - <0.5 ppt)
                      OH = oligohaline (0.5 - <5 ppt)
                      MH = mesohaline (5-18 ppt)
                      PH = polyhaline (>18 ppt)

                      *Includes six segments with assigned water clarity criteria application depths of 2 meters.
                      Interestingly, the water clarity-based chlorophyll a concentration thresholds for tidal-
                      fresh/oligohaline segments with 0.5-meter application depths falls  close to that for
                      mesohaline/polyhaline  segments  with  0.5-meter application  depths despite  the
                      different minimum light requirements (Table V-2). Also noteworthy, the water clarity-
                      based chlorophyll a concentration thresholds for mesohaline/polyhaline segments with
                      1-meter application depths fell close to the 15 jig-liter1 chlorophyll a habitat require-
                      ment listed in the first Chesapeake Bay SAV technical synthesis (Table V-2) (Batiuk et
                      al. 1992;  Dennison et al. 1993). The water clarity-based chlorophyll a concentration
                      thresholds for mesohaline/polyhaline segments with a 2-meter application depth came
                      close to the  1960s average surface chlorophyll a concentration for the lower Chesa-
                      peake Bay (see Table III-2) (Harding and Perry 1997).

                      Given the variability in  segment-specific  chlorophyll a concentration thresholds
                      within  fixed application depths  and  salinity zones,  this  procedure should  not
                      presently be used for determining and  applying water clarity-based chlorophyll a
                      criteria on a segment-specific basis. The variability is due largely to the fluctuation
                      in calculated background TSS concentrations and to the considerable uncertainty in
                      segment-specific  CDOM concentrations and particulate optical properties (due to
                      the lack of local CDOM and optical properties data in all tidal waters). At this time,
                      the segment-specific chlorophyll a concentration thresholds in Table V-1 should be
                      used only to derive the numerical chlorophyll a criteria averaged by salinity zone and
                      water clarity criteria application depth (Table V-2).
  chapter v  • Chlorophyll a Contribution to Water Clarity Impairments

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                                                                                                      .
                           LITERATURE  CITED

Batiuk, R.A., R.J. Orth, K.A. Moore, W.C. Dennison, J.C. Stevenson, L. Staver, V.
Carter, N. Rybicki, R.E. Hickman, S. Kollar, S. Bieber, P. Heasly, and P. Bergstrom. 1992.
Chesapeake Bay Submerged Aquatic Vegetation Habitat Requirements and Restoration
Goals: A Technical Synthesis. CBP/TRS  83/92. U.S. EPA  Chesapeake Bay Program,
Annapolis, MD.

Carlson,  R.E. 1977. A trophic  state index for lakes. Limnology and Oceanography
22:361-369.

Dennison, W.C., RJ. Orth, K.A. Moore, J.C. Stevenson, V. Carter, S. Kollar, P. Bergstrom,
and R. Batiuk. 1993. Assessing water quality with submersed aquatic vegetation. Habitat
requirements as barometers of Chesapeake Bay health. Bioscience 43: 86-94.

Gallegos, C.L. 1994. Refining habitat requirements of submersed aquatic vegetation: role of
optical models. Estuaries 17:198-219.

Gallegos,  C.L.  2001.  Calculating optical  water quality targets to restore  and protect
submersed aquatic vegetation: Overcoming problems in partitioning the diffuse attenuation
coefficient for photosynthetically active radiation. Estuaries 24:381-397.

Gallegos,  C.L. and P.W. Bergstrom. 2005. Effects of a Prorocentrum minimum bloom on
light availability for and potential impacts on submersed aquatic vegetation in upper Chesa-
peake Bay. Harmful Algae 4:553-574.

Harding, L.W., Jr. and E.S. Perry  1997. Long-term increase of phytoplankton biomass in
Chesapeake Bay, 1950-1994. Marine Ecological Progress Series 157:39-52.

Kemp, W.M., R. Batiuk, R. Bartleson, P. Bergstrom, V. Carter, G. Gallegos, W. Hunley, L.
Karrh, E. Koch, J. Landwehr, K. Moore, L. Murray, M. Naylor, N. Rybicki, J.C. Stevenson,
and D. Wilcox. 2004. Habitat requirements for submerged aquatic vegetation in Chesapeake
Bay: Water quality, light regime, and physical-chemical factors. Estuaries 27:263-377

Kirk, J.T.O. 1994. Light and photosynthesis in aquatic ecosystems, Cambridge University
Press: Cambridge.

Lorenzen, C.J. 1972. Extinction of light in the ocean by phytoplankton. Journal du Conseil,
Conseil International pour I'Exploration de  la Mer 34:262-267

Magnuson, A., L.W. Harding, Jr.,  M.E. Mallonee, and J.E. Adolf.  2004. Bio-optical model
for Chesapeake Bay and the Middle Atlantic Bight. Estuaries, Coastal and Shelf Science
61:403-424.

Mobley, C.D., B. Gentili, H.R. Gordon, Z. Jin, G.W. Kattawar, A. Morel, P. Reinersman, K.
Stamnes, and R.H. Stavn. 1993. Comparison of numerical models for computing underwater
light fields. Applied Optics 32:1-21.

Morel, A. and A. Bricaud.  1981. Theoretical results concerning light absorption in a discrete
medium, and application to specific absorption of phytoplankton. Deep-Sea Research
28:1375-1393.

Orth, RJ. and K.A. Moore. 1983. Chesapeake Bay: An unprecedented decline in submerged
aquatic vegetation. Science 222:51-53.

Ryther, J.H. and C.S. Yentsch. 1957. The estimation of phytoplankton production in the
ocean from chlorophyll and light data. Limnology and Oceanography 2:281-286.
                                   chapter v  •  Chlorophyll a Contribution to Water Clarity Impairments

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48
                      Sanford, L. 2005. Personal Communication October 25,  2005.  University of Maryland
                      Center for Environmental Science, Horn Point Laboratory, Cambridge, MD.

                      Smith, W.O. Jr. 1982. The relative importance of chlorophyll, dissolved and particulate mate-
                      rial, and seawater to the vertical extinction of light. Estuaries, Coastal and Shelf Science
                      15:459^65.

                      Stavn, R.H. 1988. Lambert-Beer law in ocean waters: optical properties of water and of
                      dissolved/suspended material, optical energy budgets. Applied Optics 27:222-231.

                      Tailing, J.F. 1957. The phytoplankton population as a compound photosynthetic system. New
                      Phytologist 56:133-149.

                      U.S. Environmental Protection Agency. 2003a. Ambient Water Quality Criteria for Dissolved
                      Oxygen, Water Clarity and Chlorophyll a for the Chesapeake Bay and Its Tidal Tributaries.
                      EPA 903-R-03-002. Region III Chesapeake Bay Program Office, Annapolis, MD.

                      U.S. Environmental Protection Agency. 2003b. Technical Support Document for Chesapeake
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                      U.S. Environmental Protection Agency. 2004. Chesapeake Bay Program Analytical Segmen-
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                      CBP/TRS 268/04. Region III Chesapeake Bay Program Office, Annapolis, MD.

                      U.S. Environmental Protection Agency. 2005. Chesapeake Bay Program Analytical Segmen-
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                      903-R-05-004. CBP/TRS 278-06. Region III Chesapeake Bay Program Office, Annapolis,
                      MD.

                      U.S. Environmental Protection Agency. 2007. Ambient Water Quality Criteria for Dissolved
                      Oxygen, Water Clarity and Chlorophyll a for the Chesapeake Bay and Its Tidal Tributaries
                      2007 Addendum. EPA  903-R-07-007.  CBP/TRS  285-07. Region III Chesapeake Bay
                      Program Office, Annapolis, MD.

                      Verduin, J. 1982. Components contributing to light extinction in natural waters: Method of
                      isolation. Archiv fuer Hydrobiologie 93:303-312.

                      Wofsy,  S.C.  1983. A simple model to  predict extinction  coefficients and phytoplankton
                      biomass in eutrophic waters. Limnology and Oceanography 28:1144-1155.

                      Xu, J., R.R. Hood, and S.Y. Chao. 2005. A simple empirical optical model for simulating
                      light attenuation variability in a partially mixed estuary. Estuaries 48:572-580.
  chapter v  •  Chlorophyll a Contribution to Water Clarity Impairments

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                                                                                  49
                       chapter
    Chlorophyll  a  Concentrations
   Characteristic  of  Impairments
        by Harmful  Algal   Blooms
Harmful algal blooms (HABs) appear to be increasing in coastal waters around the
world due to cultural eutrophication (CENR 2000, HARRNESS 2005). Since the
1910s, there is a growing recognition and  appreciation for HAB-producing  taxa
occurring in Chesapeake Bay (Marshall and Alden 1997, Marshall 1996, Marshall et
al. 2005). While diatoms dominate production in the Chesapeake Bay mainstem,
dinoflagellate blooms  are frequent  in higher salinity waters and cyanobacteria
blooms  are increasingly common in the tidal-fresh and low-salinity habitats of the
Chesapeake Bay as well as its tidal tributaries and embayments. Because many (but
not all) HABs are frequently associated with high chlorophyll a concentrations in the
environment, a logical and relevant goal of numerical chlorophyll a criteria (applied
as a state water quality standard) is prevention of harmful algal bloom outbreaks.

Harmful effects of HABs include dissolved oxygen impairments, shading of  sub-
merged  aquatic vegetation, adverse ecosystem trophic and biogeochemical effects
caused by shifts in community structure, and the release of toxins (HARRNESS
2005). Globally, over 50 countries have reported toxic algal blooms with increased
frequency  in recent decades (Graham et al. 2006). Long-term Chesapeake  Bay
phytoplankton  monitoring programs have  identified  over 1,450 phytoplankton
species; 43 of these species are toxigenic (Marshall et al. 2005) (Appendix B). Toxi-
genic taxa include raphidophytes, diatoms, and dinoflagellates in more saline waters
along with  cyanobacteria in tidal fresh and low-salinity waters. The production of
microcystins by  a marine picoplankton,  Synechococcus, is a recent finding
(Carmichael and Li 2006) that may extend the range of habitats.

Such toxins and their effects can be found in Chesapeake Bay. Animal mortality and
human illness related to cyanobacterial toxin exposure have been well documented
in the United States (Yoo et al. 1995).  Researchers have noted socioeconomic and
living resource effects for dinoflagellate taxa in Chesapeake Bay (e.g., Luckenbach
et al. 1993, Lipton 1999, Gilbert and Magnien 2004, Tango et. al. 2005). Table VI-1
lists living  resource effects and human health risk events documented within the
Chesapeake Bay basin and linked with cyanobacteria.
      chapter vi  • Chlorophyll a Concentrations Characteristic of Impairments by Harmful Algal Blooms

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50
  Table VI-1.  Timeline of toxic cyanobacteria events in the Chesapeake Bay basin.
  Year
Events
Source
  1930 to 1931       Tisdale and Veldee describe a regional epidemic of
                    waterborne gastroenteritis in 1930 to 1931, related to
                    "a chemical irritant" in the water and associated with algae
                    blooms, including the Potomac River drainage near
                    Washington, D.C. The authors refer to the musty taste and
                    odors of the river waters, characteristics of cyanobacteria
                    bloom effects on water quality. Tisdale noted heavy blooms
                    were made up of "algae." In Tisdale's second paper (1931b),
                    algae referred to as blue-greens.
                                                       Tisdale (193la, b) and Veldee (1931)
  1975
Endotoxic shock of 23 dialysis patients in Washington,
D.C. attributed to a cyanobacterial bloom in a drinking
water reservoir in the Potomac River basin.
World Health Organization (2003)
  2000
In the Sassafras River, four samples from a cyanobacteria
bloom dominated by Microcystis show high concentrations
of the hepatoxin microcystin. Betterton Beach is closed for
the rest of the year.
Carmichael (2000)
  2001
Waterbird deaths linked with accumulation of microcystins.    Driscoll et al. (2002)
  2003
Summer cyanobacteria blooms in the Potomac River and
other Bay tributaries show diverse toxic activity with
positive results for microcystin, anatoxin-a, and
cyano-saxitoxin.
Maryland Department of
Natural Resources (2003):
www.dnr.state.md.us/bay/hab/index.html;
Carmichael (2003)
  2004
Beach closures on the tidal Potomac and Sassafras rivers
due to toxic cyanobacteria blooms.
Maryland Department of
Natural Resources (2004):
www.dnr.state.md.us/bay/hab/index.html;
Carmichael (2004); Boyer (2004)
  2005
Cautions issued for recreation on upper tidal
Transquaking and tidal Sassafras rivers when diverse
cyanobacteria blooms are encountered. Since 2000,
100 percent of cyanobacteria bloom samples submitted
by Maryland Department of Natural Resources from
Chesapeake Bay for toxin testing came back positive
for microcystins.
Maryland Department of
Natural Resources (2005):
www.dnr.state.md.us/bay/hab/index.html;
Carmichael (2005); Boyer (2005)
                       The challenges in deriving water quality criteria for chlorophyll  a based on HABs
                       include:

                       1) blooms of non-harmful species can also result in high chlorophyll a concentra-
                          tions;

                       2) chlorophyll a does not necessarily correlate with blooms of every HAB species due
                          to various factors  including migratory behavior or the inixotrophic life history  of
                          some species affecting potential spatial and temporal relationships of the parameters;

                       3) expression of toxic activity in HABs may not correlate to chlorophyll a measures;
  chapter vi  •   Chlorophyll a Concentrations Characteristic of Impairments by Harmful Algal Blooms

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                                                                                                "
4) spatial and temporal aspects of monitoring programs may not capture character-
   istics  of HAB  phenomena  accurately (e.g., magnitude, duration,  frequency,
   coverage, toxicity, etc.); and

5) natural variability of chlorophyll a in the environment.

One or more of these five listed issues has limited attempts to derive HAB-based
chlorophyll a  criteria for much of the Chesapeake Bay's higher salinity waters.
However, the record of cyanobacteria blooms in tidal fresh and oligohaline Chesa-
peake Bay habitats—their impacts, toxicity, and subsequent risk levels related to
human health guidance values in the global literature—provided the basis to derive
habitat-specific chlorophyll a criteria for Chesapeake Bay.

Since chlorophyll a is commonly considered one of the most direct  (and perhaps
best) indices of trophic  status in water bodies  (Auer  et al. 1996), the relationship
between toxin levels and chlorophyll a provides a sound basis for deriving HAB-
based water  quality criteria. Microcystin,  produced by multiple cyanobacteria
species including genera of Microcystis, Anabaena, and Oscillatoria,  is one of the
most common cyanotoxins found in various freshwater environments,  ranging from
oligotrophic alpine lakes to tropical reservoirs (Graham et al. 2006). Microcystin has
been detected in 100 percent of cyanobacteria bloom  samples  collected  between
2003 and 2005 in Chesapeake  Bay tidal-fresh and oligohaline waters  (Maryland
Department of Natural  Resources, unpublished data). No federal guidelines for
cyanobacteria or their toxins exist at this time in the United States, but state and local
guidelines have been implemented (Burns 2005).

While toxin expression in HABs is notably variable in space and time, Giani et al.
(2005) and Kotak and Zurawell (2006) note a possible link between microcystin-LR
and nutrients (total nitrogen  and phosphorus). They also suggest a strong  relation-
ship with toxin-producing cyanobacteria and the trophic status of a water body
leading to higher incidence of toxic species and toxin concentrations as the trophic
status degrades. In developing these HAB-based chlorophyll a criteria,  therefore, the
data analyses focused on tidal-fresh and low-salinity habitats where human health
risks have been most prevalent and the likelihood of success in reducing the impacts
of HABs is high.
     DERIVING  NUMERICAL  CHLOROPHYLL CRITERIA

A literature review was used to develop a gradient of management action thresholds
that focused on human health risks, but also included living resource impacts and
coincident chlorophyll a concentrations associated with the condition (Table VI-2).
Cyanobacteria toxins, principally the hepatotoxin microcystin, formed the basis of
human health thresholds. Conversions were developed between toxin concentration,
cell counts related to toxin levels, and chlorophyll a as a function of cell counts.

These values were then available for use in:

1) Assessing the chlorophyll  a levels expected based on literature-derived human
   health risks associated with cyanobacteria blooms;
       chapter vi •  Chlorophyll a Concentrations Characteristic of Impairments by Harmful Algal Blooms

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52
 Table VI-2.  Literature-derived management action levels relative to human health and living resource risk
 levels and their relationship to cyanobacteria cell counts and chlorophyll a concentrations.
 Chlorophyll a    Cells per
 concentrations   milliliter
 (jig-liter"1)     cyano-bacteria
                  Risk level
                                                             Background and Source
 0-2.5
<5,000
No effects.
NHMRC 2005 "Green level" for recreational
health protection. Based on cell count
threshold converted to chlorophyll a based on
Chorus and Bartram's (1999) proposed rela-
tionship—100,000 cells per milliliter give
-50 jig-liter1 of chlorophyll a (p. 167). Also
by conversion, this level should meet the
World Health Organization drinking water
standard of 1 jig-liter1 microcystin.
 2.5-25        5,000-50,000      Guidance protective of
                                 children in recreational setting.
                                                             NHMRC (2005) "Amber alert," protects
                                                             against levels of microcystin >10 jig-liter"1,
                                                             the level of concern for human health.
                                                             Computations are based on the lowest
                                                             observable effects level for microcystin-LR
                                                             for 100 jig per kg body weight derived from a
                                                             44-day study of pigs. Cell number is derived
                                                             from NHMRC/NRMMC (2004) assumption
                                                             of 2xlO'7 jag total microcystins/cell. Pilotto  et
                                                             al. (1997) showed participants exposed to
                                                             cells densities >5,000 cells per milliliter for
                                                             >1 hour had significantly higher levels of
                                                             health symptoms than those unexposed.
 10
20,000
Protects against irritative or allergenic
effects from cyanobacterial compounds.
World Health Organization guidance
published in Chorus and Bartram (1999). Still
used by some states (e.g., California).
 25
Estimated at
equivalent to
50,000
Australia revision to World Health
Organization criteria. Red Alert
= >25 jig -liter1 with cyanobacteria
dominance.
Requires the local government authorities
and health departments to warn the
public that the waters are unsuitable for
recreational use (NHMRC 2005).
 25
                  Risk of cyanobacteria dominance
                  >50 percent.
                                           Estimated point from graphic in Downing
                                           et al. (2001) in which risk of cyanobacteria
                                           dominance relative to chlorophyll a in study
                                           lakes transitions to >50 percent (n = 99 lakes).
 33
10,000
10,000 cells/ml was a level cited as
negatively impacting zooplankton
populations.
The 33 jig-liter1 chlorophyll a derived from
Maryland Department of Natural Resources
data on Microcystis cell concentration versus
chlorophyll a levels (U.S. EPA 2003).
 40
Cyanobacteria
dominant
(qualitatively)
Germany lakes: promotes microcystin
analyses of water samples.
If microcystin >10 jig-liter"1, publish
warnings and recommend temporary
closures of waters for bathing. Chorus
(2005), p. 62.
 50
100,000           Moderate health risks expected
                  (e.g., fever, nausea, vomiting,
                  gastroenteritis).
                                           World Health Organization guidance
                                           published in Chorus and Bartram (1999).
                                           Moderate health alert, but considers a child
                                           could be exposed to ten times the Tolerable
                                           Daily Intake under this condition. Risk of scum
                                           formation (high-risk condition) is high. Poten-
                                           tial for long-term illness effects and short-term
                                           adverse effects. A management threshold still
                                           used in some states (e.g., California).
  chapter vi  •   Chlorophyll a Concentrations Characteristic of Impairments by Harmful Algal  Blooms

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                                                                                                51
2) Assigning risk categories based on cell counts to determine whether previously
   described management action thresholds in the literature made sense with Chesa-
   peake Bay data; and

3) Evaluating Chesapeake Bay cyanobacteria toxins data to gauge if the published
   risk levels are applicable to Chesapeake Bay were being exceeded and, if so, how
   frequently and in accordance with what observed ambient chlorophyll a concen-
   trations.

Data in the following analyses come from Chesapeake Bay water quality and phyto-
plankton monitoring programs from 1984 to 2006. The source data sets and related
data documentation files can be accessed through the Chesapeake Bay Program's
website at www.chesapeakebay.net. The Maryland Department of Natural Resources
houses additional data from phytoplankton and toxin surveys.

Summer data (July, August, and September) from tidal-fresh and oligohaline stations
(salinity 0-5 ppt) were compiled for the above-pycnocline layer of the water column
for the classification and regression tree (CART) analyses. Time  series  of Micro-
cystis  concentrations were developed  from  Maryland  Department of Natural
Resources annual data; habitat conditions associated with blooms generally occurred
when water temperatures were greater than or equal to 15°C.

Specific HAB sampling of the mainstem Chesapeake Bay and tidal tributaries from
2000 to  2006 illustrated the distribution and abundance  of cyanobacteria  HAB
species and their toxins. Cell abundance and level-of-toxin data from these algal
bloom investigations were compared with literature recommendations  regarding
recreational and living resource thresholds of human health and aquatic life concern.
These comparisons illustrated the applicability of such thresholds to Chesapeake
Bay tidal waters.

Graphical analyses illustrate the behavior of chlorophyll a concentration in relation
to cyanobacteria and toxin monitoring. Linear regression, correlations, and CART
analyses  complement the literature-derived thresholds for living resource (> 10,000
cells-mi"1 Microcystis) and human health (50,000 cells-mi"1 related to 10 jig-liter1
microcystin as the concentration threshold that protects children exposed to recre-
ational waters) to support and further validate applicable chlorophyll a concentration
thresholds.

The current world literature does  not provide adequate guidance values specific to
the cyanobacteria-derived neurotoxins. In sufficiently high doses, cyanotoxins  are
lethal. In recreational settings, however, there are reports of illness but  no confirmed
deaths. Detection of the neurotoxin  anatoxin-a has been common  in  Maryland
surveys (Carmichael 2000, 2003, 2004, 2005; Boyer 2004, 2005); one detection of
saxitoxin in blooms containing microcystins also occurred.

Fitzgeorge et al. (1994) demonstrated that microcystin toxicity is cumulative and
gave evidence for disruption of nasal tissues by microcystin-LR. The  membrane
damage by microcystin enhanced the toxicity of anatoxin-a in this  animal  study
(Fitzgeorge et al. 1994). Considering the relative lack of predictive capability  for
toxin levels and the dearth of information on cyanotoxin interaction effects, the synergy
of multiple toxins could enhance risks associated with aquatic sports recreation and
       chapter vi • Chlorophyll a Concentrations Characteristic of Impairments by Harmful Algal  Blooms

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54
                    cyanoblooms (NHMRC 2005). The possibility of synergistic effects (given the multiple
                    toxins detected in Chesapeake  Bay  waters) stresses the  need for  supporting,  at a
                    minimum, either the criterion recommended below or one that is more conservative.

                    MICROCYSITIS CELL DENSITIES/CHLOROPHYLL A RELATIONSHIP

                    The Maryland Department of Natural Resources has a data set independent from the
                    Chesapeake Bay Phytoplankton Monitoring Program that  encompasses additional
                    monitoring stations, but also includes the traditional long-term stations with surface-
                    water sampling (Figure VI-1). The data show that Microcystis blooms  greater
                    than 10,000  cells-mi"1 (considered the  threshold that impacts  the  food web) and
                    50,000 cells-mi"1 (a recommended threshold of risk for recreational waters and chil-
                    dren) are a nearly annual feature of Maryland's  Chesapeake Bay tidal-fresh and
                    low-salinity waters.

                    Tests for log normality of the tributary data showed six of eight tidal tributaries were
                    significant for log normally distributed chlorophyll a measures (Table VI-3).

                    A significant and increasing linear regression was found in the baywide assessment
                    between log chlorophyll a concentrations  and log Microcystis cell counts using the
                    Chesapeake Bay long-term water quality and phytoplankton monitoring programs'
                    data (P < 0.001; Figure VI-2). Subestuary  level analyses illustrated significant posi-
                    tive relationships for Maryland waters except for the small data set for the Patapsco
                    River (n = 7). The tidal Virginia Rivers—Rappahannock and York—tended not to
                    demonstrate the relationship except for the tidal James River (Table VI-3).

Whole Bay
Log_chl = -0.4371 +0.2472 logjnicro







^
iG(CHLA|jg/
u





2.25-

2.00 -


1.75-

1.50-
1.25-
1.00-
0.75-
0.50-
0.25-
0.00-

+
+4- +

-H- + ^ "++^ ^ -didst- +
4+ +iyit*?£t¥£t ++ '"~'
+ H+ +++ "l' + "t-^ -f^-i--V ^" jjr *~~'~~
++ +?+t ^+^^* aw^r"+ +
' ;
.>ri^*t|v^- +
,----'*''* + + ++ "t"t" "^ * *"+i:"1' + + """++ "*"
„;,--""' A+474 4 ^+^+ "+ +
+ + -+

N
584
Rsq
0.2879
Ad] Rsq
0.2867
RMSE
0.302





3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0
Log (Microcystis Cell/Liter)
                     Figure VI-1. Log-log regression of Microcystis concentrations against chlorophyll a
                     concentrations illustrating the positive relationship found in the water quality and
                     phytoplankton monitoring data for Chesapeake Bay tidal-fresh and oligohaline habitats
                     from 1984 to  2004.
                     Source: Chesapeake Bay Water Quality and Phytoplankton Monitoring Programs
                     http://www.chesapeakebay.net/data; Maryland Department of Natural Resources, unpublished data.
  chapter vi  •  Chlorophyll a Concentrations Characteristic of Impairments by Harmful Algal Blooms

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                                                                                               •
Table VI-3. Chesapeake Bay mainstem and tidal tributary regressions of log Microcystis
cells-l/1 (X) against log chlorophyll a mg-L"1 (Y) from 1984 to 2004.
Subestuary
Upper Bay
Choptank River
Patapsco River
Patuxent River
Potomac River
James River
N
102
95
7
107
148
85
Rappahannock River 44
York River
27
Regression r2
Y = 0.186X- 0.285 0.20
Y = 0.138X + 0.192 0.24
Y = 0.211X- 1.133 0.27
Y = 0.230X - 0.044 0.19
Y = 0.304X - 0.913 0.54
Y = 0.125X + 0.520 0.09
Y = 0.072X + 0.731 0.04
Y = 0.080X + 0.362 0.06
Pr>F
<0.0001*
<0.0001*
0.2353
<0.0001*
<0.0001*
0.0143*
0.231
0.280
*= significant at P < 0.05.
Source: Chesapeake Bay Water Quality and Phytoplankton Monitoring Programs
http://www.chesapeakebay.net/data.
10000000 ^
1 OOOOOO
100000
-5 i nnnn
"c
D ^ nnn
o
100
1 n
4



* ^
,
i 1
*> t
5S
* *

7- 6- 6- 6- 6-
Jan- Jan- Jan- Jan- Jan-
84 85 86 87 88
J'^'-Jihti*
\ hpljfli'
1 *' * 'f+, */+£* *
«• 4»*»«» •* «••«•• * * •

5- 5- 5- 5- 4- 4- 4- 4- 3- 3- 3- 3- 2-
Jan- Jan- Jan- Jan- Jan- Jan- Jan- Jan- Jan- Jan- Jan- Jan- Jan-
89 90 91 92 93 94 95 96 97 98 99 00 01
Time
t 1 ^
*: l\
" u
* /
»*
2- 2- 2- 1-
Jan- Jan- Jan- Jan-
02 03 04 05
Figure VI-2. Maryland Department of Natural Resources independent Microcystis data set
with cell densities (cells-mi"1) measured for surface water only from 1984 to 2004.
Source: Maryland Department of Natural Resources Phytoplankton Monitoring Program,
unpublished data.
LITERATURE-BASED TOXIN LEVELS, CELL COUNTS
AND CHLOROPHYLL CONVERSIONS

Originally, water quality management guidance values for chlorophyll a in the pres-
ence of cyanobacteria were published during the late 1990s through the World
Health Organization. The World Health Organization then provided two thresholds
of interest for risks associated with cyanotoxins:
• 10 jig-liter1 chlorophyll a and  20,000 cells-mi"1 cyanobacteria protects against
  irritative or allergenic effects from cyanobacterial compounds; and
       chapter vi  •  Chlorophyll a Concentrations Characteristic of Impairments by Harmful Algal Blooms

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56
                    •  50 jig-liter1 chlorophyll a and 100,000 cells-mi"1 cyanobacteria, resulting  in
                       moderate health risks.

                    In the most  recent reassessment of world literature (NHMRC 2005), Australian
                    authorities suggested guideline values for cyanobacterial exposure in recreational
                    waters based on the Lowest Observable Effects Level (LOAEL) for microcystin-LR
                    of 100  jig-kg"1 body  weight per day derived  from a 44-day study in pigs. These
                    values are 10 jig-liter"1 total microcystins for children and 44 jig-liter1 total micro-
                    cystins for adults (NHMRC 2005).

                    To derive a cell count that is equivalent to this toxin hazard, a toxin cell quota of
                    2 x 10~7 jig total microcystins per cell is assumed (NHMRC/NRMMC 2004). Toler-
                    able concentration limits for child and adult during recreational activities, therefore,
                    are suggested by the  following conversions. A LOAEL of 10 jig-liter"1 of toxin for
                    children converts to 50,000 cells-mi"1 Microcystis based on:
                    10 jig toxin-liter1  * 0.001 (Liter-mi"1)/ 2xlO"7 mg microcystins per cell    Equation 10

                    Protection at this level would likewise safeguard adults in a recreational setting.

                    Chorus and Bartram (1999, p.  167) defined a conversion between cell concentration and
                    chlorophyll a when cyanobacteria are in abundance. A density of 100,000 cells-mi"1 is
                    equivalent to  -50 jig-liter1 chlorophyll a if cyanobacteria dominate or 2,000 cells-mi"1
                    ~1 jig-liter1 chlorophyll a. Therefore, 50,000 cells-mi"1 is estimated at 25 jig-liter1
                    chlorophyll a—a concentration comparable to the above-cited recreational risk
                    threshold protective of children at 10 jig-liter1  total microcystins.

                    The  Australian revision to the World Health Organization criteria (NHMRC 2005)
                    uses three levels  and is more protective than the original two-tiered World Health
                    Organization approach:
                       Green Level: No effects level at less than 5,000 cells-mi"1 or less than 2.5 jig-liter1
                       chlorophyll a based on a cell:chlorophyll a translation.
                       Amber Alert: Increased monitoring intensity to assess risk at a chlorophyll a
                       concentration range of 2.5-25 jig-liter1.
                       Red Alert: Requires local  government authorities and health departments to warn
                       the public that the waters are unsuitable for recreational use at chlorophyll a concen-
                       trations greater than or equal to 25 jig-liter1 with cyanobacteria dominance.

                    Based on the extensive literature review, Table VI-2 summarizes a gradient of risk
                    thresholds for chlorophyll a concentrations associated with the presence of cyano-
                    bacteria blooms.  The chlorophyll a concentrations in Table VI-2 were based on the
                    toxin concentration to cell count conversion as well as the  cell count to chlorophyll a
                    conversion described and cited above.

                    CHESAPEAKE  BAY MICROCYSTIS TOXINS
                    COMPARISON WITH THRESHOLDS

                    In September 2000, a cyanobacteria bloom dominated by Microcystis aeruginosa
                    was  identified on the tidal Sassafras River with four samples collected and analyzed
  chapter vi  •  Chlorophyll a Concentrations Characteristic of Impairments by Harmful Algal Blooms

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                                                                                                 •
for microcystin toxin.  Analyses  showed  levels  approaching acute toxicity  for
consumption (Carmichael 2000).

Toxins data collected during cyanobacteria bloom investigations in tidal waters of
Chesapeake Bay from 2002 to 2006 show significant exceedances of suggested
human health risk thresholds for  microcystins (Tango and Butler 2007). Among
samples tested (n=70), 71% and 31% of results exceeded WHO drinking water guid-
ance (1 jig-liter1 in  Chorus and Bartram 1999) and NHMRC (2005) recreational
safety thresholds for children (10 jig-liter1) respectively (Figure VI-3). All areas
where cyanobacteria blooms have been identified have  demonstrated microcystin
toxin production in excess of 10 lag-liter1 (Tango and Butler 2007) and such events
were documented each year.

Coincident activity of additional  cyanotoxins—neurotoxins anatoxin-a and PSP-
toxin—were  also  noted.  Fitzgeorge et al.  (1994) noted  synergistic interactions
between microcystin and anatoxin-a exposures in mice that could lower the guidance
thresholds for the two toxins when found together in the  environment. Extensive
work with toxin interactions is in its infancy and no firm guidance taking account of
the simultaneous presence of multiple toxins is available at this time.

Microcystin toxin relationship to chlorophyll a

Falconer et al.  (1999) indicate a  cyanobacterial density of 100,000 cells-mi"1 is
expected to be equivalent to 50 jig-liter1 chlorophyll a.  Coincidently these condi-
tions are expected to have at least  20 jig-liter1 microcystin. This relationship gives
us an expected ratio of 1  jig-liter1 microcystin: 2.5  jig-liter1 chlorophyll a: 5,000
cells-mi"1 cyanobacteria.
      45
      40 -

    1 35

    I 3°
    S 25-
    Q.
    jg 20
    Q_
    I 15
      10 -

       5-

       0 -
                         0.1 to<1
                                      1 to<10
                                  Microcystin (|jg/L)
                                                 10to<100
                                                                >100
Figure VI-3. Frequency distribution of microcystin results from bloom sample investiga-
tions in Maryland (n=70, 2003-2006). 71% of results exceed 1 jug-liter1 while 31% of
results exceed 10 jug-liter1.

Source: Adapted from Tango and Butler 2007.
       chapter vi  •  Chlorophyll a Concentrations Characteristic of Impairments by Harmful Algal Blooms

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58
                    For Chesapeake  Bay  monitoring data, Microcystis aeruginosa concentrations
                    showed a significant increasing relationship with chlorophyll a concentration on
                    Bay-wide scale as well as for tributary specific relationships. Chlorophyll a concen-
                    trations represent one indicator level to the potential for cyanotoxin blooms. Species
                    taxonomy  and abundance, however,  will be required to understand if there is  a
                    heightened risk situation that may involve elevated levels of toxins.

                    Microcystin concentrations have been shown to increase with increasing levels of
                    Microcystis aeruginosa (Figure VI-4, adapted from Tango and Butler 2007). With
                    species identification and abundance data  available, an initial risk level can be
                    provided. Chlorophyll a concentrations, species identification and cell counts alone
                    cannot define the impairment.  Toxin  results  will  be  needed to  confirm any
                    exceedance of human health risk thresholds since there are 2-3 orders of magnitude
                    of variation in toxin concentration surrounding the regression relationship.
                         1000
                          100 -
                           10 -
                           1  -
                          0.1
                           1.E+02
                                   1.E+03    1.E+04
                                                   1.E+05    1.E+06
                                                                   1.E+07
                                         Microcystis cells-mi"
Figure VI-4. Microcystin
toxin relationship with
Microcystis aeruginosa
concentrations for
Chesapeake Bay
monitoring data.
Source: Adapted from
Tango and Butler 2007.
                     CART ANALYSES ASSESSMENT OF RISK LEVELS

                     Recently, classification and regression tree (CART) has proven useful in environ-
                     mental data analysis (Verbyla 1987). The water quality parameters for this analysis
                     included salinity, Secchi depth, orthophosphate, dissolved inorganic nitrogen (i.e.,
                     NH4, NO2, and NO3), chlorophyll a, pheophytin, dissolved organic carbon, paniculate
                     carbon, and water temperature as they relate to human- and ecosystem-health risk cate-
                     gories developed for zooplankton effects and Microcystis concentrations. Buchanan et
                     al. (2005) offers additional details on the protocol for compilation of data.

                     In CART analysis, values of a dependent parameter are being predicted from one or
                     more independent predictor parameters. One of CART's strengths is that it is a non-
                     parametric technique. There are no underlying assumptions about the distributions
                     of either the dependent or independent variables are normal or even known. This
  chapter vi  •  Chlorophyll a Concentrations Characteristic of Impairments by Harmful Algal Blooms

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                                                                                                ,
technique also does not require a linear relationship between dependent and inde-
pendent variables.

Exploratory CART analyses were  conducted to determine those  chlorophyll a
concentration thresholds that would prevent toxic Microcystis bloom events. The
CART analysis for this application used the tree algorithms in the Insightful SPLUS
7.0.6  software (SPLUS 2005). Microcystis abundance was the response variable,
with three categories of risk based on cell count. Individual CART analyses were run
for each of the major tidal tributaries and the upper Chesapeake Bay as well as for
all data combined.

Most  results show that average above-pycnocline chlorophyll a or surface chloro-
phyll  a concentrations  were the most significant  factors related to Microcystis risk
(seven of eight analyses). In the one exception—the above-pycnocline Choptank
River analysis—chlorophyll a concentration was  the second-most significant factor
after dissolved inorganic nitrogen concentration. The average chlorophyll a concen-
tration thresholds separating high-risk water  quality condition from middle- and
low-risk  water quality conditions  for  the surface and above-pycnocline water
samplings were 28.96 and 29.17  jig-liter"1, respectively.
 HAB IMPAIRMENT  BASED CHLOROPHYLL a CRITERIA

The analyses presented here illustrate the positive relationship between cyanobac-
teria levels  (which have inherent human health risks  seen in  Chesapeake  Bay
tidal-fresh and oligohaline waters based on cyanobacteria toxin surveys), cyanotoxin
levels and measured chlorophyll a concentrations. The management action threshold
gradient illustrated in Table VI-2 shows 25 jig-liter1 chlorophyll a as the first level
that generates water closures protective of human health. The World Health Organi-
zation previously  considered 50 jig-liter1 a level for moderate  health effects;
however, concentrations at which scum formation and significant human health risks
are possible (particularly for children) have been documented at lower chlorophyll a
concentrations. CART analyses of Chesapeake Bay data that provide an average of
subestuary  surface water chlorophyll  a values separating high human health risk
(>25 jig-liter"1 chlorophyll a) from lower risk levels was nearly the same (28.96 and
29.17 jig-liter1 chlorophyll a for surface and above pycnocline water's respectively).

As the CART assessment thresholds  analysis derived  a slightly higher threshold
chlorophyll  a concentration after factoring in data and conditions specific to  the
Chesapeake ecosystem, the most recent child-protective toxin threshold converted to
chlorophyll  a (25  jig-liter1) and the CART-derived threshold  (29 jig-liter"1) were
averaged to reach a criterion threshold value of 27.5 jig-liter1 chlorophyll a. This
value is characteristic of the expected cell counts and toxin concentrations for toxi-
genic cyanobacteria protective against human health impairments, as demonstrated
in the above analyses, respecting the variability in those related measures. Tidal trib-
utaries throughout  the  northern  Chesapeake Bay (e.g.,  Transquaking,  Chester,
Sassafras, Elk, Bush, Middle, Magothy, and Potomac rivers), the open waters of the
northern Chesapeake Bay, and the upper tidal James River (Virginia Department of
Environmental  Quality 2005) have  demonstrated the capacity to support blooms,
       chapter vi • Chlorophyll a Concentrations Characteristic of Impairments by Harmful Algal Blooms

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60
                     making the criteria broadly applicable to tidal fresh and oligohaline waters. Regres-
                     sion analyses  showed local variation  in  relationships with  chlorophyll a  and
                     Microcystis suggesting local  tailoring of trigger values for analyses could be imple-
                     mented.  Protecting against criteria exceedances  also safeguards against associated
                     risks of harmful cyanobacteria blooms and their potential impacts.
                     Chlorophyll a concentration data across the Chesapeake Bay and its tidal tributaries
                     and embayments demonstrate log normally distributed behavior. To attain the HAB-
                     based chlorophyll a criterion, there should be a limited  number, e.g. less than 10
                     percent, of ambient concentrations observed above 27.5|ig-liter1 with rare observa-
                     tions of large values that would be indicative of high human and living resource
                     health risk. Measures of central tendency for log normally distributed populations of
                     chlorophyll a exceeding  the criterion concentration by less than 10 percent are
                     similar  to historical chlorophyll a  concentrations  (i.e.,  1960s) documented in
                     Table 111-2 for low-salinity habitats.
                                               LITERATURE  CITED
                     Auer, M.T., S.W. Effler, M.L. Storey, S.D. Connors, P. Sze, C.A. Siegfried, N.A. Auer, J.D.
                     Madsen, R.M. Smart, L.W. Eichler, C.W. Boylen, J.W. Sutherland, J.A. Bloomfield, B.A.
                     Wagner, R. Danehy, N.A. Ringler, C.  Gandino,  P. Hirethota,  P. Tango,  M.A. Arrigo, C.
                     Morgan, C. Millar, M. Murphy,  R.  J.  Sloan, S.L. Niehaus, and K.A. Whitehead. 1996.
                     Chapter 6. Biology. In S.W. Effler (ed.).  Limnological and engineering analysis of a polluted
                     urban lake: prelude to  environmental management of Onondaga Lake, New York. pp.
                     384-522. New York, NY: Springer-Verlag.
                     Boyer,  G. 2004. Toxin Analysis  Reports to Maryland Department of Natural Resources.
                     Unpublished data.
                     Boyer,  G. 2005. Toxin Analysis  Reports to Maryland Department of Natural Resources.
                     Unpublished data.
                     Buchanan, C., R.V. Lacouture, H.G. Marshall, M. Olson,  and J. Johnson.  2005. Phyto-
                     plankton  reference communities  for Chesapeake Bay and its tidal tributaries. Estuaries
                     28(1):138-159.
                     Burns,  J.W. 2005. United States  of America: Cyanobacteria and the status  of regulatory
                     approaches. In I. Chorus (ed.) Current Approaches to Cyanotoxin Risk Assessment, Risk
                     Management and Regulations in Different Countries, pp. 111-117.
                     Carmichael, W 2000. Wright State University Report to the Maryland Department of the
                     Environment, Oct.  27, 2000, Baltimore, MD.
                     Carmichael, W. 2003. Toxin Analysis Reports to Maryland Department of Natural Resources.
                     Unpublished data.
                     Carmichael, W. 2004. Toxin Analysis Reports to Maryland Department of Natural Resources.
                     Unpublished data.
                     Carmichael, W. 2005. Toxin Analysis Reports to Maryland Department of Natural Resources.
                     Unpublished data.
                     Carmichael, WW and R.H. Li. 2006. Cyanotoxins in the Salton Sea. Saline Systems. 2:5.
  chapter vi  •  Chlorophyll a Concentrations Characteristic of Impairments by Harmful Algal Blooms

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                                                                                                     „
CENR 2000. A National Assessment of Harmful Algal Blooms in U.S. Waters. National
Science and Technology Council Committee on Environment and Natural Resources, Wash-
ington, DC.
Chorus, I. and J. Bartram. 1999. Toxic Cyanobacteria in Water: A Guide to Their Public
Health Consequences, Monitoring and Management. World Health Organization, London,
Routledge E&FN Spon.
Chorus, I. (ed.). 2005. Current approaches to cyanotoxin risk assessment, risk management
and  regulations  in  different  countries:  WaBoLu  Heft  02/05,  Umweltbudesamt.
www.umweltdaten.de/publikationen/fpdf-l/2910.pdf.
Downing, J.A., S.B. Watson, and E. McCauley. 2001. Predicting cyanobacteria dominance in
lakes. Canadian Journal of Fisheries and Aquatic Sciences 58(10):1905-1908.
Driscoll, C.P., PC. McGowan, E.A. Miller, and WW Carmichael. 2002. Case Report: Great
blue heron (Ardea herodias) morbidity and mortality investigation in Maryland's Chesapeake
Bay. Proceedings of the Southeast Fish and Wildlife Conference, Baltimore, MD Oct. 24,
2002 (Poster).
Falconer, I., J. Bartram, I Chorus, T.  Kuiper-Goodman, H. Utkilen, M. Burch ad G.A. Codd.
1999. Safe levels and safe practices. Pp. 155-178 in Chorus, I. and J. Bartram (eds.) Toxic
cyanobacteria in water - a  guide  to their public health consequences, monitoring  and
management. E.F. Spon. Published on behalf of the World Health Organization. 416pp.
Fitzgeorge, R.B., S.A. Clark, and C.W. Kevil. 1994. Routes of intoxication In G.A. Codd,
T.M. Jeffries, C.W. Keevil, and E. Potter (eds.). Detection methods for cyanobacterial toxins.
pp. 69-74. Cambridge, UK: The Royal Society of Chemistry.
Giani, A., D.F. Bird, Y.T. Prarie, and  J.F. Lawrence. 2005. Empirical study of cyanobacterial
toxicity along  a trophic gradient of lakes.  Canadian Journal of Fisheries and Aquatic
Sciences 62:2100-2109.
Gilbert, P.M. and R.E. Magnien.  2004. Harmful algal blooms in the Chesapeake Bay, USA:
Common species, relationships to nutrient loading, management approaches,  successes and
challenges. In S. Hall, S. Etheridge,  D. Anderson, J. Kleindinst, M. Zhu, and Y. Zou (eds.).
Harmful Algae Mitigation and Management, pp. 48-55. Asia-Pacific Economic Cooperation
(Singapore): APEC Publication #204-MR-04.2.
Graham, J.L., J.R. Jones, and S.B. Jones. 2006. Microcystin in Midwestern Lakes. Lakeline
26:32-35.
HARRNESS. 2005. Harmful Algal Research and Response: A National Environmental
Response Strategy 2005 - 2025. J.S. Ramsdell, D.M. Anderson, and P.M. Gilbert (eds.).
Washington D.C.: Ecological Society of America.
Kotak, E.G., A.K.Y. Lam, E.E. Prepas, S.L. Kenefick, and S.E. Hrudey. 1995. Variability of
the hepatoxin microcystin-LR in hypereutrophic drinking water lakes. Journal ofPhycology
31:248-263.
Kotak, E.G. and R.W Zurawell. 2006. Cyanotoxins in Canadian waters. Lakeline 26:24-28.
Lipton, D.W. 1999. Pfiesteria's economic impact on seafood industry sales and recreational
fishing. Proceedings of the Conference, Economics of Policy  Options for Nutrient Manage-
ment and Pfiesteria. B.L. Gardner and L. Koch (eds.).  Center for Agricultural and  Natural
Resource Policy, University of Maryland, College Park. pp. 35-38.
Luckenbach, M.W., K.G. Sellner, S.E. Shumway, and K. Greene. 1993. Effects of two bloom
forming dinoflagellates, Prorocentrum minimum and Gyrodinium uncatenum, on the growth
       chapter vi  •  Chlorophyll a Concentrations Characteristic of Impairments by Harmful Algal Blooms

-------
62
                      and survival of the Eastern Oyster, Crassostrea virginica (Gmelin 1791). Journal of Shellfish
                      Research 12(2):411-415.
                      Marshall, H. 1996. Toxin producing phytoplankton in Chesapeake Bay. Virginia Journal of
                      Science 47(l):29-38.
                      Marshall, H.G. and R.W. Alden.  1997. The influence of flow patterns  on phytoplankton
                      trends in the Chesapeake Bay. Oceanology Acta 20:109-117.
                      Marshall, H.G., L. Burchardt, and R. Lacouture. 2005. A review of phytoplankton composi-
                      tion within Chesapeake Bay and its tidal estuaries. Journal of Plankton Research_27:
                      1083-1102.
                      NHMRC. 2004. Australian drinking water guidelines.
                      www.nhmrc.gov.au/publications/synopses/ehl9syn.htm
                      NHMRC. 2005. Guidelines for managing risk in recreational waters. Australian Government
                      National Health and Medical Research Council, Canberra, Australia. 207 pp.
                      Pilotto, L., P. Hobson, M.D. Burch, G. Ranmuthugala, R. Attewell, and W. Weightman. 2004.
                      Acute skin irritant  effects  of  cyanobacteria (blue-green algae)  in  healthy  volunteers.
                      Australian and New Zealand Journal of Public Health. 28:220-224.
                      SPLUS 7.0.6 for Windows. 2005. Seattle, Washington: Insightful Corporation.
                      Tango, P., R. Magnien, W. Butler, R. Lacouture, M. Luckenbach, C. Poukish, and C. Luckett.
                      2005a. Characterization of impacts and potential effects due to Prorocentrum minimum
                      blooms in Chesapeake Bay. Harmful Algae 4:525-531.
                      Tango, P., W. Butler, B. Michael. 2005b. Cyanotoxins in the tidewaters of Maryland's Chesa-
                      peake Bay: The Maryland experience. 2 pp. Proceedings of the International Symposium on
                      Cyanobacterial Harmful Algal Blooms. Research Triangle Park, Raleigh, North Carolina.
                      Springer Press.
                      Tango, P. and W. Butler. 2007. Cyanotoxins in tidal waters of Chesapeake Bay. Northeast
                      Naturalist - Accepted for publication.
                      Tisdale, E.S. 1931b. The 1930-31 drought and its effect upon public water supply. American
                      Journal of Public Health 21:1208-1218.
                      U.S. Environmental Protection Agency. 2003. Ambient Water Quality Criteria for Dissolved
                      Oxygen,  Water Clarity and Chlorophyll a for Chesapeake Bay and Its Tidal Tributaries. EPA
                      903-R-03-002. Region III Chesapeake Bay Program Office, Annapolis,  MD.
                      Veldee M.V. 1931. An epidemiological study of suspected water-borne gastroenteritis. Amer-
                      ican Journal of Public Health. 21:1227-1235.
                      Verbyla, D.L. 1987.  Classification trees:  a new discrimination tool. Canadian Journal of
                      Forest Research 17:1150-1152.
                      Virginia Department of Environmental Quality. 2005. Virginia Department of Environmental
                      Quality Technical Report: Chlorophyll a Numerical Criteria for the Tidal James River. Rich-
                      mond, VA.
                      Yoo,  R.S. et al. 1995. Cyanobacterial (Blue-green algal) toxins: A resource guide. AWWA
                      Research Foundation and American Water Works Association.  Denver, CO.
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                                                                                    .
                       chapter \/||
   Chesapeake  Bay Chlorophyll  a
           Criteria  and  Reference
                  Concentrations
These Chesapeake Bay numerical chlorophyll a criteria and reference concentrations
were derived to address specific water quality, human,  and aquatic life impairments
when applied in specific seasons and to specific salinity-based tidal habitats (Tables
VII-1 and VII-2).  These criteria and reference concentrations protect the open-water
fish and shellfish designated use to "support the survival, growth and propagation of
balanced, indigenous population of ecologically, recreationally and  commercially
important fish and shellfish species inhabiting open-water habitats" (U.S. EPA 2003b).

At a minimum, the EPA strongly encourages the states to adopt the harmful algal
bloom-based numerical chlorophyll a criteria for tidal fresh and oligohaline tidal
waters where algal-related impairments are expected to persist even after attainment
of the Chesapeake Bay dissolved oxygen and water clarity criteria. The states may
adopt the published Chesapeake Bay chlorophyll a reference concentrations as a
numeric criteria for the applicable salinity regimes and seasons. In addition,  the
states can use the scientific findings and data published here to derive tidal river,
embayment, and/or segment-specific numeric chlorophyll a criteria to account more
precisely for localized impairments and conditions.
     HARMFUL ALGAL BLOOM IMPAIRMENT-BASED
                CHLOROPHYLL a  CRITERION

The numeric chlorophyll a criterion that protects  against human and aquatic life
impairments from harmful algal blooms should only be applied to tidal-fresh and
oligohaline reaches of the Chesapeake Bay and its tidal tributaries and embayments
(Table VII-1). This criterion applies only to surface waters during the summer season
(June 1 through September 30). See Chapter VIII for the detailed criteria assessment
procedures. As documented previously, the scientific basis for establishing Chesapeake
Bay numerical chlorophyll a criteria that address  impairments for higher salinity
harmful algal bloom species and communities remains insufficient at this time.
                  chapter vii  • Chesapeake Bay Chlorophyll a Criteria and Reference Concentrations

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64
                     Table VIM. Chesapeake Bay harmful algal bloom impairment-based
                     chlorophyll a criterion.

                                                             Chlorophyll a Criterion Concentration3
                     Salinity Regime1               Season2                  (ing-liter"1)

                     Tidal Fresh-Oligohaline          Summer                    27.5

                     'Tidal fresh = 0 - <0.5 ppt salinity; oligohaline = 0.5 - <5 ppt salinity.
                     2Summer = June 1-September 30.
                     3The 27.5 ug-liter1 concentration is applied as a 90th percentile for log normal distribution of data coincident
                     with a mean chlorophyll a concentration of 14.7 ug-L for minimizing the risk of Microcystis concentrations
                     >50,000 cells-mi"1 and microcystin concentrations exceeding 10 ug-liter1.
                                       HISTORICAL  CHLOROPHYLL a
                                      REFERENCE  CONCENTRATIONS

                     The historic chlorophyll a reference concentrations based on 1960s Chesapeake Bay
                     mainstem concentrations under medium-flow conditions should only be used for the
                     applicable salinity regime within mainstem Bay tidal waters (Table VII-2).  These
                     reference concentrations specifically address the States' existing water quality stan-
                     dards' narrative requirements that: "concentrations of chlorophyll a in free-floating
                     microscopic aquatic plants (algae) shall not exceed levels that result in ecologically
                     undesirable  consequences." These reference concentrations should only be applied
                     to  mainstem Chesapeake Bay surface, open-water habitats only during the  spring
                     (March 1 through May 31) and summer (July 1 through September 30) seasons, the
                     most critical seasons for addressing algal-related impairments.
                              DISSOLVED  OXYGEN  IMPAIRMENT-BASED
                                      REFERENCE  CONCENTRATIONS

                     A set of chlorophyll a reference concentrations were determined to characterize water
                     column conditions having  suitable open-water,  summer averaged  bottom-water
                     dissolved oxygen conditions. These annual averaged chlorophyll a reference concen-
                     trations—10-15 jig-liter1 over deeper waters which routinely stratify and 30 jig-liter1
                     in  the  surface layer of shallow  waters—complement and support the  HAB-based
                     chlorophyll a criteria and the chlorophyll a reference concentrations that address other
                     water quality, human, and aquatic life impairments (Table VII-2). Evidence from the
                     multi-decadal record of Chesapeake Bay water quality monitoring supports the conclu-
                     sion that meeting these chlorophyll a reference  concentrations will contribute to the
                     achievement  of desired  dissolved oxygen  concentrations.   However,  these  low
                     dissolved oxygen impairment-based chlorophyll a reference concentrations should not
                     be adopted and applied as water quality criteria to protect against the adverse impacts
                     of low  dissolved oxygen. As described previously, many other factors must be consid-
                     ered in quantifying the relationship between excess phytoplankton biomass and the
                     onset and continuance of low dissolved oxygen  conditions. In the Chesapeake Bay's
                     current eutrophic state  ("supersaturated" with phytoplankton biomass), relationships
                     between the accumulation of chlorophyll a and oxygen depletion are not likely to yield
                     useful numeric chlorophyll a criteria.
  chapter vii  •  Chesapeake Bay Chlorophyll a Criteria and Reference Concentrations

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                                                                                                              .
Table VII-2.  Chesapeake Bay chlorophyll a reference concentrations.1

   Salinity Regime2/                          Water Clarity Criteria  Chlorophyll a Refer-
    Water Column                            Application Depth4    ence Concentration
       Location               Season3                 (m)                (ing-liter"1)

Historical Chlorophyll a Reference Concentrations5

Oligohaline                   Spring                   -6                   18

Mesohaline                   Spring                   -                     8

Polyhaline                    Spring                   -                     4

Oligohaline                   Summer                  -                    46

Mesohaline                   Summer                  -                    23

Polyhaline                    Summer                  -                     5


Dissolved Oxygen Impairment-Based Chlorophyll a Reference Concentrations

Deeper Waters Which Stratify   Annual                   -                   10-15

Shallow Waters                Annual                   -                    30


Water Clarity Impairment-Based Chlorophyll a Reference Concentrations

Tidal Fresh/Oligohaline         SAV                   0.5                   43

Tidal Fresh/Oligohaline         SAV                   1.0                   11

Mesohaline/Polyhaline           SAV                   0.5                   39

Mesohaline/Polyhaline           SAV                    1                    16

Mesohaline/Polyhaline           SAV                    2                     3


'All chlorophyll a reference concentrations apply as ug-liter1 across the surface waters of open-water
 designated-use segments for the applicable salinity regime and season.
2Tidal Fresh = 0 - <0.5 ppt salinity; Oligohaline = 0.5- <5 ppt salinity; mesohaline = 5-18 ppt salinity;
 polyhaline = >18 ppt salinity.
3Spring =  March 1-May 31; Summer = June 1-September 30; SAV or SAV growing season: for tidal-fresh,
 oligohaline, and mesohaline habitats = April 1-October 31; for polyhaline habitats = March 1-November 30
 (U.S. EPA 2003a).
4Water clarity criteria application depth for each Chesapeake Bay Program segment as published in U.S.
 EPA 2003b and as adopted into Delaware, Maryland, Virginia and the District of Columbia's water quality
 standards regulations.
'Reference concentrations  only apply to mainstem Chesapeake Bay segments.
6Not applicable.
WATER  CLARITY IMPAIRMENT-BASED  CHLOROPHYLL  a
                   REFERENCE  CONCENTRATIONS

The water clarity impairment-based chlorophyll a reference concentrations should
be  applied as threshold concentrations to surface waters  across open-water desig-
nated-use habitats by the applicable salinity regime. These reference concentrations
                        chapter vii  •  Chesapeake Bay Chlorophyll a Criteria and Reference Concentrations

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66
                     are for the applicable water clarity criteria application depth over the applicable SAV
                     growing season in those Chesapeake Bay Program segments with the shallow-water
                     bay grass designated use (Table VII-2). Given the degree of variability in segment-
                     specific  chlorophyll a reference  concentrations within specific  application depths
                     and salinity zones (see Table V-l), the procedure described previously should not be
                     used to determine and apply numeric water clarity-based chlorophyll a criteria on a
                     Chesapeake Bay Program segment-specific basis but only on a salinity regime basis.

                     These chlorophyll a reference concentrations complement and support (but do  not
                     replace) the EPA published water  clarity criteria and SAV restoration acreage criteria
                     already adopted by Delaware, Maryland, Virginia, and the District of Columbia into
                     their respective water quality standards regulations (U.S. EPA 2003a, 2003b). These
                     reference concentrations quantify the  chlorophyll a water  column  concentrations
                     required to allow sufficient penetration of surface light to attain the applicable water
                     clarity criteria at the established application depth given achievement  of background
                     concentrations of total suspended solids (TSS). The a priori  assumption of back-
                     ground TSS concentration achievement is critical. At ambient TSS  concentrations
                     higher than the  segment-specific background TSS concentration,  chlorophyll  a
                     concentrations lower than the salinity-regime/application-depth reference concentra-
                     tions in Table VII-2 are required to meet the applicable water clarity criteria.
                              OTHER CHLOROPHYLL a CONCENTRATION
                             THRESHOLDS,  CRITERIA, AND STANDARDS

                    In their comprehensive synthesis of the global scientific literature entitled A Literature
                    Review for Use in Nutrient Criteria Development for Freshwater Streams and Rivers in
                    Virginia, Walker et al. (2006) provided a concise summary of chlorophyll a concentra-
                    tions as  thresholds, criteria, and standards in  freshwater,  estuarine,  and marine
                    ecosystems around the world. Dodds et al. (1998) recommended a series of concentra-
                    tion ranges using benthic chlorophyll a, sestonic chlorophyll a, total nitrogen, and total
                    phosphorus for the trophic classification of streams based on cumulative frequency distri-
                    butions. The oligotrophic-mesotrophic boundary rested at  10 ing-liter1 chlorophyll a
                    with the mesotrophic-eutrophic boundary at 30 mg-liter1 chlorophyll a.

                    As reported by Walker et al (2006), Reckhow et al. (2005) used structural equation
                    modeling to identify the relationships between nutrient-related parameters and the
                    predictive use attainment for four water bodies  in the United States: Neuse River
                    estuary, San Francisco Bay, Lake Washington, and Lake Mendota. The authors found
                    that the existing North Carolina chlorophyll a water quality standard for the Neuse
                    River estuary had a 60 percent probability of attaining the designated uses supported by
                    a 5 ing-liter1 dissolved oxygen  standard. The authors reported that  their model
                    predicted that chlorophyll a concentrations under 10 mg-liter1  were necessary to
                    achieve dissolved oxygen concentrations of at least 5 mg-liter"1.

                    In the April 2003 publication Ambient Water Quality Criteria for Dissolved Oxygen,
                    Water Clarity and Chlorophyll a for the Chesapeake Bay and Its Tidal Tributaries,
                    U.S. EPA (2003a) documented the results of worldwide literature on aquatic system
                    trophic status as characterized by mean chlorophyll a concentrations  (see Table V-6
  chapter vii  •  Chesapeake Bay Chlorophyll a Criteria and Reference Concentrations

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                                                                                                 "
on page 112 in U.S. EPA 2003a). In freshwater aquatic systems, oligotrophic waters
were characterized by chlorophyll a concentrations ranging from 0.3 to 4 mg liter"1,
mesotrophic systems a range of 2 to 15 ing-liter1, and eutrophic systems a range of
greater than 10 to 31 mg-liter1 (Novotny and Olem 1994; Ryding and Rast 1989;
Smith 1998; Wetzel 2001). In marine ecosystems, oligotrophic systems were char-
acterized by chlorophyll a concentrations less than 2 mg-liter1, mesotrophic systems
a range of 1 to 7 mg-liter1, and eutrophic systems a range of 3 to greater than
7 mg-liter1 (Smith et al. 1999; Novotny and Olem 1994). U.S. EPA (2003a) provided
detailed narrative descriptions of the trophic  status, water quality, phytoplankton
community, and ecological function along a trophic continuum, defining  olig-
otrophic, mesotrophic, eutrophic, and highly eutrophic status as these terms apply to
the Chesapeake Bay ecosystem, both past and present (see Table V-2 on page 106 in
U.S. EPA 2003a).

In their paper on Chesapeake Bay phytoplankton reference communities and develop-
ment of an index of biotic integrity, Buchanan et al.  (2005) quantified the habitat
conditions supporting these communities. They reported maximum spring and summer
chlorophyll a concentrations (in ^g-liter1), respectively, for tidal fresh (13.5, 15.9),
oligohaline (24.6, 24.4), mesohaline (23.8,  13.5), and polyhaline (6.4, 9.2).

In its report to the Virginia Department of Environmental Quality, the Academic
Advisory Committee (2005 a) recommend April to October median  chlorophyll a
concentrations of 4 jig-liter1 for cold-water habitats designated for trout, 10 jig-liter1 for
other  cold-water habitats,  and 25  |ig-liter1 for  warm-water aquatic habitats to
"accommodate fishery recreation and protect aquatic life." In an addendum to their
original report, the Academic Advisory Committee (2005b)  recommended chloro-
phyll  a criteria derivation using a regression approach and application of  90th
percentile chlorophyll a concentrations to protect fishery recreation and aquatic life.
The recommended April to October,  90th percentile chlorophyll  a concentrations
were: 8 jig-liter1 for cold-water habitats designated for trout, 20 jig-liter1 for other
cold-water habitats, and 50 jig-liter1 for warm-water aquatic habitats. The authors
recommended "the regression approach uses the mathematical relationship between
chl-a median (chl-a  med) and the 90th percentile (chl-a  90)  to translate candidate
criteria  expressed as  medians to a  90th percentile  basis" (Academic  Advisory
Committee 2005b).

Although the EPA has not published  national chlorophyll a water quality criteria,
efforts are underway to derive and publish eco-region-based chlorophyll a criteria.
At least  eight states  across the country,  along with Virginia and the District of
Columbia, have adopted numerical chlorophyll a criteria into their water quality
standards regulations (U.S.  EPA 2003c; Walker  et al. 2006). Although  the exact
concentrations range widely given the variable needs in protecting Hawaii's coastal
oceans to Alabama's  reservoirs, most of these state's chlorophyll a water quality
standards, stated as  seasonal averages,  tend  to  fall within  15  to  27  jig-liter1
(Appendix  C),  closely matching the  concentration range of the Chesapeake  Bay
chlorophyll a criteria and reference concentrations (Tables VII-1 and VII-2). Many
of these states' adopted chlorophyll a criteria are water body- and/or habitat-specific
water quality standards or are used as part of an overall trophic index.
                     chapter vii  •  Chesapeake Bay Chlorophyll a Criteria and Reference Concentrations

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68
                                                 LITERATURE  CITED
                      Academic Advisory Committee. 2005a. January 2005 Report of the Academic Advisory
                      Committee to Virginia Department of Environmental Quality: Freshwater Nutrient Criteria.
                      Virginia Water Resources Research Center, Virginia Polytechnic Institute and State Univer-
                      sity, Blacksburg, VA.

                      Academic Advisory Committee. 2005b. Report of the Academic Advisory  Committee to
                      Virginia Department of Environmental Quality: Freshwater Nutrient Criteria -Addendum to
                      the January 2005 Report. Virginia Water Resources Research Center, Virginia Polytechnic
                      Institute and State University, Blacksburg, VA.

                      Buchanan, C.,  R.V Lacouture, H.G.  Marshall, M. Olson,  and J. Johnson. 2005. Phyto-
                      plankton reference communities for Chesapeake Bay  and  its tidal  tributaries. Estuaries
                      28(1):138-159.

                      Dodds, W.K., J.R. Jones, and E.B. Welch. 1998. Suggested classification of stream trophic
                      state: Distributions of temperature stream types by chlorophyll, total nitrogen,  and phos-
                      phorus. Water Resources 32(5): 1455-1462.

                      Novotny, V and H. Olem. 1994. Water Quality: prevention, identification, and management
                      of diffuse pollution. New York, NY: Van Nostrand Reinhold.

                      Reckhow, K.H., G.B. Arhonditsis, M.A. Kenny, L. Hauser, J.  Tribo, C. Wu, K.J. Elcock, L.J.
                      Steinberg, C.A. Stow,  and  S.J. McBride. 2005. A predictive approach to nutrient criteria.
                      Environmental Science and Technology. 39(9): 2913-2919.

                      Ryding, S.O. and W. Rast. 1989. The control of eutrophication of lakes and reservoirs. Man
                      and the Biosphere Series. Volume 1. Park Ridge, NJ: Parthenon Publication Group.

                      Smith, VH.1998. Cultural eutrophication of inland, estuarine and coastal waters. In: Pace,
                      M.L. and P.M. Groffman (eds). Successes, Limitation and Frontiers in Ecosystem Science.
                      Springer-Verlag. New York, New York. Pp. 7-49.

                      U.S. Environmental Protection Agency. 2003a. Ambient Water Quality Criteria for Dissolved
                      Oxygen, Water Clarity and  Chlorophyll a for the Chesapeake Bay and Its Tidal Tributaries.
                      EPA 903-R-03-002. Region III Chesapeake Bay Program Office, Annapolis, MD.

                      U.S. Environmental Protection Agency. 2003b. Technical Support Document for Chesapeake
                      Bay Designated Uses  and  Attainability. EPA 903-R-03-004. Region III Chesapeake Bay
                      Program Office Annapolis, MD.

                      U.S. Environmental Protection Agency. 2003c. Survey of  States, Tribes and  Territories
                      Nutrient Standards. Washington, D.C.

                      Walker,  J., C. Zipper,  L. Shabman, and T. Younos. 2006. A Literature Review for Use in
                      Nutrient  Criteria Development for  Freshwater Streams and Rivers in Virginia. VWRRC
                      Special Report SR28-2006. Virginia Water Resources Research  Center, Virginia Polytechnic
                      Institute and State University, Blacksburg, VA.

                      Wetzel, R. G. 2001. Limnology: Lake and River Ecosystems. Academic Press, San Diego,
                      CA. 1006 pp.
  chapter vii  •  Chesapeake Bay Chlorophyll a Criteria and Reference Concentrations

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                                                                               "
                     chapter\/l||
                Chesapeake Bay
           Chlorophyll a  Criteria
     Recommended Attainment
         Assessment  Procedures
There are two sets of procedures recommended for assessing attainment of the
numeric chlorophyll a criteria. The first set of procedures, described below, are for
assessing the  harmful  algal  bloom  impairment-based chlorophyll a criterion
published within this document. The second set of procedures, also described below
and originally published in the July 2007 addendum to the original 2003 Chesapeake
Bay water quality criteria document (see pages 61-62 in U.S. EPA 2007), apply to
the state adopted numerical chlorophyll a concentration-based criteria.
     HARMFUL ALGAL BLOOM  IMPAIRMENT-BASED
        CHLOROPHYLL a CRITERIA ASSESSMENT
                        PROCEDURES

A structured tiered sample collection, analysis and assessment procedure is recom-
mended for determining exceedance of the harmful-algal bloom based chlorophyll a
criterion. Note that while the criterion has its foundation in human health risk-related
science, the sampling and assessment program is not specifically intended for use as
a short-term recreational health risk evaluation procedure. This criterion and assess-
ment procedure considers a seasonal time scale and focuses on Chesapeake Bay
Program segment assessments. Risk evaluation and management may be triggered
by information gleaned in these assessments but require other time (daily to within
weekly) and space (beach focus or other significant recreational unit) assessments
without regard for the segment boundaries.

SAMPLING REGIME

The previously described chlorophyll a concentration threshold of 27.5 jig-liter1 is
used as the generalized trigger value for initiating sampling and enumeration of
cyanobacteria species composition-related samples.  The value was based on a
significant regression relationship using a composite of tidal tributary and mainstem
Chesapeake  Bay data. Tributary-specific chlorophyll a-Microcystis relationships,

 chapter viii  • Chesapeake Bay Chlorophyll a Criteria Recommended Attainment Assessment Procedures

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70
                    such as those expressed in Chapter VI, could, however, be used to justify an adjust-
                    ment of the  27.5  jig-liter1 sampling  trigger  threshold concentration.  Significant
                    area-specific  regressions  relating  chlorophyll  a measures to 50,000 cells-mi"1
                    Microcystis should be thoroughly documented to support  such a decision. Alterna-
                    tively, the presence of visible surficial algal  scum can also be used as sampling
                    trigger to evaluate for toxin without chlorophyll a data. For water quality conditions
                    represented by chlorophyll a concentrations below  27.5 jig-liter1, sampling  for
                    cyanobacteria determination would not be required.

                    Water quality monitoring in Chesapeake Bay segments presently involves multiple
                    approaches for chlorophyll a assessments: vertical fluorescence profiles, horizontal
                    fluorescence, dataflow mapping and calibration sites, in-situ continuous monitoring,
                    and emergency rapid response sampling due to anomalous water quality conditions,
                    fish or human health related events. Triggered by the above 27.5 jig-liter1 chloro-
                    phyll a concentration threshold, an extra water sample would be collected at 5-6 sites
                    separated by 1-2 miles within the appropriate  season,  defined by temperatures
                    greater than 15 °C and a segment characterized by less than 5 ppt salinity. The popu-
                    lation of Microcystis should be enumerated in each of these extra samples. If
                    Microcystis bloom conditions (> 50,000 cells per milliliter) are observed in any
                    single sample, all the collected extra samples  (n = 5 to 6) from the segment being
                    assessed would be processed for microcystin toxin analysis. If no Microcystis bloom
                    conditions were evident in the collected samples, the samples would be discarded.

                    TIME AND SPACE DIMENSIONS

                    In the most recent evaluation conducted by the Australian  Government National
                    Health and Medical Research Council (2006), the basis for the 10 jig-liter^micro-
                    cystin toxin threshold is conventional toxicological calculations used to  derive a
                    short term (14 day) exposure, in this case to children. The  guideline is derived from
                    a study based on lowest observable adverse effect levels considered the most suitable
                    for deriving the short-term exposure threshold. Dataflow assessments during the crit-
                    ical bloom season are conducted at monthly intervals, therefore, the time dimension
                    for determining criteria exceedance is  defined by encountering Microcystis blooms
                    conditions and observing toxin concentrations exceeding 10 jig-liter1 microcystin in
                    two successive sampling events bracketing a minimum of a two week period. Viola-
                    tions  need to be captured in at least two  successive sampling events providing
                    evidence of continuity in bloom persistence representative of extended risk con-
                    ditions in the Chesapeake Bay segment.

                    The recommended spatial dimension for defining criterion exceedance is based on
                    the fact that surface blooms shift with tides and winds. Tidal currents are highly vari-
                    able on the Bay. The Potomac River at Point Lookout for early June 2007 shows a
                    typical maximum flood or ebb tide average approximately  0.3 knots with time
                    between slack water  periods  approximately  7 hours  (http://tidesandcurrents.
                    noaa.gov/ for Point Lookout June 2007). A single bloom point could move linearly
                    in one direction approximately 1 nautical mile (1.15 miles or 1.8 km) at this current
                    speed. However, current speed up near the Chesapeake and Delaware Canal can have
                    a maximum current of over 2 knots, and a parcel of water could travel over 7 nautical
                    miles (approximately 8 miles  or 12.8 km) in half a tidal cycle.
  chapter viii  •  Chesapeake Bay Chlorophyll a Criteria Recommended Attainment Assessment Procedures

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                                                                                               "
A single data point is not necessarily suggestive of a large bloom. Two or more data
points from water quality monitoring sites, generally spaced 1-2 miles (1.6-3.2 km)
apart in small to medium sized  segments, achieving > 50,000 cells per milliliter
Microcystis and subsequently measuring > 10 ug/L microcystin toxin would suggest
an extensive  bloom and significant impairment status due to human health risks.
There is a significant risk due to tides and winds that can shift the bloom throughout
a large  area  of the  segment over a  relatively short period of time. Therefore,
combining space and time parameters, it is recommended that the exceedance of the
harmful algal bloom-based chlorophyll a criterion is defined by two or more samples
from separate fixed water quality monitoring and/or Dataflow calibration stations
within a Chesapeake Bay Program segment collected during each of two or more
consecutive sampling events (timed two weeks or more apart) with > 10 jig-liter1
microcystin toxin concentrations  observed.

Please note, from a human  health risk management perspective, identifying tidal
waters in a single sampling event with > 27.5 jig-liter1 chlorophyll a, > 50,000 cells
per milliliter Microcystis and microcystin toxin levels > 10 ug/L would be suitable
grounds for issuing a caution for recreational activity on affected waters, specifically
swimming and other water contact sports. Samples with fewer than 50,000 cells per
milliliter Microcystis in a cyanobacteria-dominated community can still pose a human
health risk though the probability of exceeding the microcystin toxin threshold tends
to decline with decreasing Microcystis abundance in  Chesapeake Bay tidal waters
(Tango and Butler 2007). However, it is  up to the individual jurisdictions and their
respective state and local environmental health departments to make such decisions
regarding  issuing advisories  dependent on  taxonomic assessments, cell counts  and
toxin results.  These assessments  should recognize that other cyanobacteria species
may be present and producing different toxins independently and coincidently. Phyto-
plankton community composition and toxin assessments beyond those for microcystin
should be  considered in making their advisory assessments.
  CHLOROPHYLL a  CONCENTRATION-BASED  CRITERIA
                   ASSESSMENT  PROCEDURES

To assess attainment of the State adopted numerical chlorophyll a concentration-
based criteria, it was necessary to establish a reference curve for use in the CFD
criteria attainment assessment process (U.S. EPA 2003, 2007). In the case of chloro-
phyll a  criteria where  a biologically-based reference curve is  not available, EPA
recommends  the  states use of the default reference curve originally described in
Chapter 2, Figure II-4 and Equation 1 in U.S. EPA 2007.

A criterion threshold is a concentration that should rarely be exceeded by a "popu-
lation"  of concentration  data  exhibiting healthy levels. The  state-adopted
concentration-based chlorophyll a criteria values are threshold  concentrations that
should only be exceeded infrequently (e.g., <10%) since a low number of naturally
occurring exceedances  occur  even  in a healthy phytoplankton population. The
assessment of chlorophyll a criteria attainment, therefore, should use the CFD-based
assessment method described in U.S. EPA 2007 (Chapter 2) that applies the default
  chapter viii  • Chesapeake Bay Chlorophyll a Criteria Recommended Attainment Assessment Procedures

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72
                     reference curve. These concentration-based Chesapeake Bay chlorophyll a criteria
                     apply only to those seasons and salinity-based habitats for which they were defined
                     to  protect against applicable  human health and  aquatic life  impairments. Each
                     season—spring (March 1-May 31) and summer (July  1-September 30)—should be
                     assessed separately to evaluate chlorophyll a criteria attainment.

                     Assessments  of seasonal mean chlorophyll a criteria  should be based on seasonal
                     averages of interpolated data sets. To calculate the seasonal averages, each interpo-
                     lated  cruise  within  a season should be averaged on a point-by-point  basis in
                     matching interpolator grid cells. Spatial violation rates should be calculated for each
                     seasonally aggregated interpolation in an assessment period.  For example, for  a
                     summer open-water seasonal chlorophyll  a criteria assessment of a three-year
                     assessment period, three seasonal  average interpolations representing each season
                     (Year 1 Summer, Year 2 summer, Year 3 summer) should be used.
                                              LITERATURE  CITED

                     Australian Government National Health and Medical Research Council. 2006. Guidelines for
                     managing risks  in recreational water. 219 pp.  http://www.nhrnrc.gov.au/consult/_files/
                     ACF227.pdf

                     Tango, P. and W. Butler. 2007. Cyanotoxins in tidal waters of Chesapeake Bay. Northeast
                     Naturalist - Accepted for publication.

                     U.S. Environmental Protection Agency. 2003. Ambient Water Quality Criteria for Dissolved
                     Oxygen, Water Clarity and Chlorophyll a for the Chesapeake Bay and Its Tidal Tributaries.
                     EPA 903-R-03-002. Region III Chesapeake Bay Program Office, Annapolis, MD.

                     U.S. Environmental Protection Agency. 2007. Ambient Water Quality Criteria for Dissolved
                     Oxygen, Water Clarity and Chlorophyll a for the Chesapeake Bay and Its Tidal Tributaries—
                     2007 Addendum. EPA 903-R-07-007. CBP TRS 285/07. Region III Chesapeake Bay Program
                     Office, Annapolis, MD.
  chapter viii  •  Chesapeake Bay Chlorophyll a Criteria Recommended Attainment Assessment Procedures

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                                                                                           •
                                     Acronyms
°c
CART
CBP

CDOM
CFD
cfs
cells-mi"1
Chla
Chla (mg-m-3)

dwachl
DIN
DO
g-C-nr2 -d-1

GLM
g-nr3
HAB
LOAEL
km
LOAEL
m
m
degrees Celsius
classification and regression tree
Chesapeake Bay Program

colored dissolved organic matter
cumulative frequency diagram
cubic feet per second
cells per milliliter
chlorophyll a
milligrams of chlorophyll a
per meter cubed
depth-weighted average chlorophyll a
dissolved inorganic nitrogen
dissolved oxygen
grams of carbon per meter
squared per day
general linear model
grams per meter cubed
harmful algal bloom
Lowest Observable Effects Level
kilometers
lowest observable acute effects level
meter
milligram
l-ig-kg"1      micrograms per kilogram
jig-liter1     micrograms per liter
mg-chla-m2  milligrams of chlorophyll a
            per meter squared
mg-liter1    milligrams per liter
MH         mesohaline
NASS       non-algal suspended solids
NH4        ammonium
NO2        nitrite
NO3        nitrate

O2          oxygen
OH         oligohaline
PAR        photosynthetically active radiation
PO4         dissolved inorganic phosphorous/
            orthophosphorous
ppt         parts per thousand
PSU        practical salinity unit
% sat       percent saturation
SAV        submerged aquatic vegetation
TP          total phosphorous
TF          tidal fresh
TSS         total suspended solids
U.S. EPA    United States Environmental
            Protection Agency
                                                                                   Acronyms

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                                                                           A-1
                     appendix
   Delaware,  Maryland, Virginia
  and the  District of Columbia's
         Narrative Water  Quality
 Standards  Regulations  Relevant
   to Algal-Related  Impairments
DELAWARE

In the definitions section of Delaware's water quality standards regulation, nuisance
species are defined as "any species of fish, other animal, or plant living in or near the
water, the presence of which causes unreasonable interference with the designated
uses of the waters or the uses of adjoining land areas. Nuisance species include but
are not limited to filamentous and blue green-algae".

Within the criteria to protect designated uses section of the regulation, Delaware
states that "all surface waters of  the state...shall meet the following minimum
criteria: 4.1.1.3. Any pollutants, including those of a thermal, toxic, corrosive, bacte-
riological, radiological, or other nature, that may interfere with attainment and
maintenance of designated uses of  the water, may impart undesirable odors, tastes.
or colors to waters or to aquatic life found therein, may endanger public health, or
may result in dominance of nuisance species.

MARYLAND

Upfront in Maryland's water quality standards regulation, the term 'balanced indige-
nous community' is  defined as "a biotic community typically characterized by
diversity, the capacity to sustain itself through cyclic seasonal changes, presence of
necessary food chain species,  and by a lack of domination by pollutant tolerant
species" (26.08.01.01).

Within the surface water quality protection section of Maryland water quality stan-
dards regulations, it is stated that "water quality standards shall provide water quality
for the designated uses of (a) water  contact recreation, (b) fishing, (c) propagation of
fish, other aquatic life and wildlife,  and (d) agricultural and industrial water supply."
               appendix a • DE, MD, VA and DC's Narrative Water Quality Standards Regulations

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A-2
                     Within the designated use section of the regulation, Maryland defines open-water
                     fish and shellfish designated use as including "waters of the Chesapeake Bay and its
                     tidal tributaries that have the potential for or are supporting the survival, growth and
                     propagation of balanced, indigenous populations of ecologically, recreationally and
                     commercially important fish and shellfish species inhabiting open-water habitats"
                     (26.08.02.02).

                     Within Maryland's General Water Quality Criteria: The waters of this State may not
                     be polluted by: (1) Substances attributable to sewage, industrial waste, or other waste
                     that will settle to form sludge deposits that: (a) Are unsightly, putrescent, or odorous.
                     and create a nuisance, or (b) Interfere directly or indirectly with designated uses; and
                     (2) Any  material, including  floating debris, oil, grease, scum, sludge, and other
                     floating materials attributable to sewage, industrial waste, or other waste in amounts
                     sufficient to: (a)  Be unsightly; (b) Produce taste or odor; (c) Change the existing
                     color to produce objectionable color for aesthetic purposes; (d) Create a nuisance; or
                     (e) Interfere directly or indirectly with designated uses. (26.08.02.03)

                     VIRGINIA

                     Virginia's surface water quality standards contain the  following text for ecological
                     conditions for the state's waters and protection of human health and aquatic life that
                     directly relate to ensuring balanced, non-nuisance phytoplankton communities.

                     Within the state's designation of uses section  of the regulation, "all State waters,
                     including wetlands,  are designated for the following  uses:  recreational uses, e.g.,
                     swimming and boating; the propagation and growth of a balanced, indigenous popu-
                     lation  of aquatic  life, including game fish, which might reasonably be expected to
                     inhabit them;  wildlife; and  the  production  of  edible and  marketable natural
                     resources, e.g., fish and shellfish. (9 VAC 25-260-10).

                     Under the general criteria section of Virginia's water  quality standards regulation,
                     "all State waters, including wetlands,  shall be  free from substances attributable to
                     sewage, industrial waste, or other waste in concentrations, amounts, or combinations
                     which contravene established standards or interfere directly or indirectly with desig-
                     nated uses of such water or which are  inimical or harmful to human, animal, plant.
                     or aquatic life" (9 VAC 25-260-20).

                     Further, this section  states that "specific substances to be controlled include, but are
                     not limited to: floating  debris, oil,  scum, and other  floating  materials; toxic
                     substances (including those which bioaccumulate); substances that produce color.
                     tastes, turbidity,  odors, or settle to form sludge  deposits;  and substances which
                     nourish undesirable or nuisance aquatic plant life (9 VAC 25-260-20).

                     Virginia's Water Quality Standards regulation (9 VAC  25-260-10) has been around
                     since the late  1960s.  It designates all  waters for "the propagation and growth of a
                     balanced, indigenous population of aquatic life, including game fish, which might
                     reasonably be  expected to inhabit them."   The intent of the use designation is to
                     maintain balanced populations of all aquatic life from the base of the food chain
                     (algae) up to commercial and recreational fishes.  This existing narrative criteria in
  appendix a  •  DE, MD, VA and DC's Narrative Water Quality Standards Regulations

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                                                                                                A-3
the Water Quality Standards further require that substances "which nourish undesir-
able or nuisance aquatic plant life" will be controlled (9 VAC 25-260-20).

To meet that requirement, Virginia adopted the Nutrient Enriched Waters (9 VAC 25-
260-330-350)  and Policy for Nutrient Enriched Waters (9 VAC 25-40) in  1988.
These adopted regulations recognized that nutrients were contributing to undesirable
growths of aquatic plant life,  classified waters as nutrient enriched and imposed
phosphorus limits on discharges to waters classified as such. The Chesapeake Bay
and its tidal tributaries were all classified as nutrient enriched under these same regu-
lations. Chlorophyll a was also recognized in the Nutrient Enriched Waters sections
of the regulation as an indicator of nutrient enrichment.

Despite these narrative criteria having been in place for years, the tidal James River
was listed as impaired in May 1999 under the Clean Water Act required 303(d) list.
It was  based on violations of the general  narrative criteria and nutrients. The tidal
James  River was later  characterized  by the  most  'unbalanced' phytoplankton
community compared to Virginia's other tidal waters with numerous observations of
over-abundances of 'undesirable' plant life.

Criteria for dissolved oxygen  and water  clarity were adopted in 2005 to address
water quality impairments in Virginia's two  northerly tributaries, namely York and
Rappahannock river and Virginia's  portion of the Chesapeake Bay mainstem.
However, this  was not the case in the tidal James River.  Nutrients loads from this
southern watershed did not significantly impact dissolved oxygen concentrations or
water clarity conditions in James River or other Bay waters. Unlike the other major
tributary systems, the tidal James River itself is relatively shallow and well mixed.
These physical characteristics allow enhanced diffusion of atmospheric oxygen into
the water column.  The proximity of the James to the Atlantic Ocean and its input of
relatively well  oxygenated waters tends to keep the dissolved oxygen in the tidal
James  comparatively good compared to  the other  systems exposed to excessive
nutrients and high chlorophyll a concentrations.

Therefore, it was determined that continuing with a narrative criteria approach to the
tidal James River ecosystem would not provide the technical basis for the imple-
menting the necessary nutrient loading reduction actions needed to restore balance
to  that ecosystem. Virginia's State Water Control Board  adopted numerical chloro-
phyll a water quality standards for the tidal James River.

DISTRICT OF COLUMBIA

The District of Columbia's water quality standards regulations sets forth five desig-
nated  uses  applicable to its  tidal  waters:  (A)  primary contact recreation,  (b)
secondary contract recreation, (C) protection and propagation of fish, shellfish and
wildlife. (D) protection of human health related to consumption of fish and shellfish,
and (E) navigation.

Within the standards section of the regulation, the District of Columbia states that
"within tidally influenced Class C waters, concentrations of chlorophyll a in free-
floating microscopic aquatic plants (algae)  shall not exceed levels that result in
ecologically undesirable consequences such as reduced water clarity, low dissolved
                    appendix a  • DE, MD, VA and DC's Narrative Water Quality Standards Regulations

-------
A-4
                     oxygen, food supply imbalances, proliferation of species deemed potentially harmful
                     to aquatic life or humans  or  aesthetically objectionable conditions or otherwise
                     render tidal water unsuitable for designated uses."


                     SOURCES

                     Delaware Department of Natural Resources and Environmental Control. 2004. State of Dela-
                     ware Surface Water Quality Standards as Amended July 11, 2004. Dover, Delaware.

                     District of Columbia Register Department of Health Title 21 of the District of Columbia
                     Municipal Regulations, Chapter 11,Water Quality Standards as amended October 28, 2005.
                     Washington, D.C.

                     Maryland COMAR Title 26, Subtitle 08 Water Pollution Chapter 02 Water Quality.

                     Virginia Water Quality Standards regulations: 9 VAC 25-260-10 and 9 VAC  25-260-20.
  appendix a  •  DE, MD, VA and DC's Narrative Water Quality Standards Regulations

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                                                                     B-1
                           appendix |t^
         Listing  of  Harmful Algae Species
                    in Chesapeake  Bay
   Latin Name
rr,   ^       TOXIC
Taxa Group   „„,. ,
        F   Effect
Notes
Synonyms
References
AkashlWO ,. a „ , nor, T-IT-
dmoflagellate PSP,BF
sangmnea
Amphidinium ,• ^ n ^ T.TOT,
, dmo flagellate NSP
opercuiatum
Amphora .. . __.
rr -r • diatoms ASP
cojjaeijormis
, ff. . cyanobacteria
Anabaena ajjinis Hr,r;>r
Anabaena circinalis HP,PSP
Anabaena flos 'aquae HP,PSP
A z, * cyanobacteria
Anabaena recta HP,PSP
Has been implicated
in some fish kills,
echanism of action
appears to be 30,12
physical congestion
of gills during dense
bloom conditions.
Compounds with
haemolytic and
antifungal Pouchetia .„
properties polyphemus
(amphidinols)
known.
A strain from
Canada was found , ,„ .„
to produce domoic ' '
acid.
Produces
Microcystin, „
Saxitoxins, and
Anatoxin
Produces
Microcystin,
Saxitoxins, and
Anatoxin
Produces
Microcystin,
Saxitoxins, and '
Anatoxin
Produces
Microcystin,
Saxitoxins, and
Anatoxin
Key to Toxic Effects:
ASP — Amnesic Shellfish Poison
BF — Fish killing and bloom forming
CFP — Ciguateric Fish Poison
DSP — Diarrheic Shellfish Poison
    NSP — Neurotoxic Shellfish Poison
    NTX — Neurotoxic, fish killing and bloom forming
    PSP — Paralytic Shellfish Poison
    HP — Known Hepatotoxin Producer
                         appendix b • Listing of Harmful Algae Species in Chesapeake Bay

-------
      B-2
Latin Name
Anabaena spiroides
Aphanizomenon
flosaquae
Aphanizomenon
issatschenkoi
Chattonella
subsalsa
Chattonella
verruculosa
Cylindrospermopsis
raciborskii
Cochlodinium
polykrikoides
Dinophysis
acuminata
Taxa Group
cyanobacteria
cyanobacteria
cyanobacteria
dinoflagellate
dinoflagellate
cyanobacteria
dinoflagellate
dinoflagellate
Toxic -T ,
„„,. , Notes
Effect
Produces
HP,PSP MiciDcystin,
baxitoxms, and
Anatoxin
p<-,p Produces Saxitoxins
and Anatoxin
p(;;p Produces Saxitoxins
and Anatoxin
Produces
-VJQP brevitoxins which
has been linked to
numerous fish kills.
Produces
•KJXJP brevitoxins which
has been linked to
numerous fish kills.
Produces
cylindrospermopsin,
associated with fish
HP kills, considered the
likely organism in
alligator kills in
Florida
Associated with
mortality offish.
Physical contact with
taxa and not a
released toxin, was
NSP the cause of oyster
larvae (Crassostrea
virginica) deforma-
tion and mortality
during a red tide in
the York River.
_Qp Producer of okadaic
-LJO-T . -,
acid
Synonyms





Anabaena
raciborskii
Cochlodinium
heterolobatum
Dinophysis
borealis,
Dinophysis
lachmanni,
Dinophysis boehmii
References
55
55
55
5,30,35,
36
2, 30, 35,
36,50
57
26,53
1,23,27
   Dinophysis acuta
                             Producer of okadaic
 dinoflagellate                  acid and dino-
                    DSP         physistoxin-1
                                (DTXl)ordino-
	physistoxin-2 (DTX2)
23,27
Key to Toxic Effects:
ASP — Amnesic Shellfish Poison
BF — Fish killing and bloom forming
CFP — Ciguateric Fish Poison
DSP — Diarrheic Shellfish Poison
        NSP — Neurotoxic Shellfish Poison
        NTX — Neurotoxic, fish killing and bloom forming
        PSP — Paralytic Shellfish Poison
        HP — Known Hepatotoxin Producer
        appendix b  •  Listing of Harmful Algae Species in Chesapeake Bay

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                                                                                                                   B-3
Latin Name
Dinophysis caudata
Dinophysis fortii
Dinophysis
norvegica
Dinophysis
rotundata
Dinophysis sacculus
Dinophysis tripos
Heterosigma
akashiwo
Karlodinium
micrum/
Karlodinium
veneficum
Lingulodinium
polyedra
Microcystis
aeruginosa
„, „ Toxic
1 axa Group „ -,. ,
F Effect
dinoflagellate DSP
dinoflagellate DSP
dinoflagellate p§p
dinoflagellate
DSP
dinoflagellate _Qp
-LJO-T
dinoflagellate Dsp
dinoflagellate _„
DC
dinoflagellate „„
r>r
dinoflagellate PSP
cyanobacteria HP,PSP
Notes
Producer of okadaic
acid, toxin
implicated in DSP.
Producer of
dinophysistoxin - 1
(DTX1) and
pectenotoxin-2
(PTX2)
Producer of
dinophysistoxin- 1
and okadaic acid.
Production of DTX-
1 demonstrated in
Japan. North
American strains
apparently non-toxic.
Producer of okadaic
acid, toxin
implicated in DSP.
Producer of
dinophysistoxin- 1
(DTX1), a toxin
implicated in DSP
Linked to mortality
offish
Linked to mortality
offish
Producer of
saxitoxin
Produces
Microcystin and
saxitoxins,
Synonyms References
16,24
27 47 51
Dinophysis laevis ' '
27
Phalacroma ,„ „„
rotundatum '
Dinophysis
pavillardi,
Dinophysis
reniformis, 1 , 1 „
Dinophysis '
ventrecta,
Dinophysis
phaseolus
Dinophysis „„
caudata tripos
Heterosigma
carter ae, 11, 21, 30,
Olisthodiscus 41
carterae
Gymnodinium
galatheanum ,
Gymnodinium 6,12,25,
micrum, 29, 30
Gyrodinium
galatheanum
1
Micraloa
aeruginosa, Poly- 15,22,30
cystis aeruginosa
Key to Toxic Effects:
ASP — Amnesic Shellfish Poison
BF — Fish killing and bloom forming
CFP — Ciguateric Fish Poison
DSP — Diarrheic Shellfish Poison
NSP — Neurotoxic Shellfish Poison
NTX — Neurotoxic, fish killing and bloom forming
PSP — Paralytic Shellfish Poison
HP — Known Hepatotoxin Producer

       appendix b  •  Listing  of  Harmful Algae Species in Chesapeake Bay

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    B-4
Latin Name
Microcystis firma
Microcystis viridis
Pfiesteria piscicida
Pfiesteria
shumwayae
Planktothrix
agardhii
Planktothrix
limnetica
Planktothrix
limnetica acicularis
Prorocentrum lima
Toxic
Taxa Group „„„ Notes Synonyms References
Produces
cyanobacteria HP,PSP Microcystin and 15,22,30
saxitoxins,
Produces
cyanobacteria HP,PSP Microcystin and 15,22,30
saxitoxins,
Known to cause
lesioning and ulcers
on fish resulting in
sometimes massive Nitzschia
,. „ „ x -KTT.V T-.T- fish kills. There are delicatissima, „ „ .,
dmoflagellate NTX, BF ,,, , ,. , . 8, 9, 45
cases of human Nitzschia
respiritory distress, actydrophila
and memory loss
associated with
Pfiesteria
Fish are killed by
Pfiesteria feeding on
,. ,- „ -Kyrpv DC them. Cells attach to 0 n 10 .c
dmoflagellate NTX, BF ,,-,,,-,, 8,9,18,45
& the skin of fish and
denude the fish of the
epidermis.
cyanobacteria Produces „ .„
, TOT, _„_ ... . , Oscillatona ,, ,r
NSP,PSP Microcystin and , „ .. 55,56
Agardhii
anatoxin
cyanobacteria Produces „ .„
xror, r,or, TV f <.- j (Jsciuatoria ,, .,
NSP,PSP Microcystin and ,. . 55, 56
/ . limnetica
anatoxms,
cyanobacteria Produces
NSP,PSP Microcystin and 55, 56
anatoxins,
Has been found to
produce the Diarrhetic
Shellfish Poisoning
(DSP) toxins: okadaic
acid (Murakami et al.
T^CDDU 1982), DTX-1 (Lee et „ . ,, ,. __ .. ._
DSP'BF al. 1989), DTX-2 (Hu /*"*??" ^a' 2?' 3.1' 48'
dmoflagellate et al. 1993), in ExuvieIIa mama 49
Addition to a proro-
centrolide (Torigoe et
all 988) and a Fast
Acting Toxin (FAT)
(Tindalletal. 1984).
Key to Toxic Effects:
ASP — Amnesic Shellfish Poison
BF — Fish killing and bloom forming
CFP — Ciguateric Fish Poison
DSP — Diarrheic Shellfish Poison
NSP — Neurotoxic Shellfish Poison
NTX — Neurotoxic, fish killing and bloom forming
PSP — Paralytic Shellfish Poison
HP — Known Hepatotoxin Producer
      appendix b  •   Listing of Harmful Algae Species in Chesapeake Bay

-------
                                                                                                   B-5
    Latin Name       Taxa Group    „„,.  ,
                                  F    Effect
                               Notes
    Synonyms
References
   Prorocentrum     dinoflagellate   NSP, BF
      minimum
                           Intra-peritoneal
                            injections of
                        methanol extracts are
                           toxic to mice.
                          Ingested cells can
                          cause detrimental
                         effects in molluscs.
                        Some strains excrete
                         substances toxic to
                          Artemia-nauplii.
                            Producer of
                          venerupin (heap-
                        totoxin) which caused
                         shellfish poisoning.
Exuviaella marina
       lima
                                                                                             19,30,44
  Pseudo-nitzsch ia
    delicatissima
                           A strain from
                          Canada and one
diatoms        ASP      from New Zealand
                         found to produce
                            domoic acid
  Prorocentrum
mariae-lebouriae,
  Prorocentrum
   triangulatum
 37, 42, 43
Pseudo-mtzschia ,. . _,_.
, . . diatoms ASP
multiseries
Pseudo-nitzsch ia
diatoms ASP
Pseudodelicatissima
Pseudo-nitzschia diatoms ACD
-/VO-T
pungens
Pseudo-nitzschia diatoms . Qp
-AO-T
senata
Pyrodinium ,. _ „
, , dinoflagellate PSP
bahamense
Snowella lacustris cyanobacteria HP,PSP
Domoic acid
producer
Domoic acid
producer
This species is usually
non-toxic. Toxic
clones have been
reported from New
Zealand and the West
Coast of the U.S.A.
Several clones of this
species have been
found to produce
domoic acid
Producer of
paralytic shellfish
poisoning toxins
Produces
Microcystin and
saxitoxins,
Nitzschia pungens
multiseries,
Pseudo-nitzschia
pungens
multiseries
Pseudo-
nitzschia calliantha
Nitzschia pungens
Nitzschia senata
Gonyaulax
schilleri,
Pyrodinium
schilleri

4, 14, 46
31,33
4,38
31
20,39
55
Key to Toxic Effects:
ASP — Amnesic Shellfish Poison
BF — Fish killing and bloom forming
CFP — Ciguateric Fish Poison
DSP — Diarrheic Shellfish Poison
    NSP — Neurotoxic Shellfish Poison
    NTX — Neurotoxic, fish killing and bloom forming
    PSP — Paralytic Shellfish Poison
    HP — Known Hepatotoxin Producer
                                   appendix b  •  Listing of Harmful Algae Species in Chesapeake Bay

-------
B-6
                      Current List of Harmful Algae species in Chesapeake Bay from:
                      Marshall, H.G., L. Burchardt and R. Lacouture. 2005. A review of phytoplankton composi-
                      tion within Chesapeake Bay and its tidal estuaries. Journal of Plankton Research 27:
                      1083-1102.
                      Taxonomic references from:
                      Faust, M.A. and R. A. Gulledge. 2002. Identifying Harmful Marine Dinoflagellates.
                      Smithsonian Contributions from the United States National Herbarium, Volume 42: 1-144.
                      Moestrup, 0. (Ed.): IOC Taxonomic Reference List of Toxic Algae. Intergovernmental
                      Oceanographic Commission of UNESCO; ioc.unesco.org/hab/data.htm, 2004.
                                                LITERATURE  CITED

                      Andersen P., B. Hald and H. Emsholm. 1996. Toxicity of Dinophysis acuminata in Danish
                      coastal waters. In: T. Yasumoto, Y. Oshima and Y Fukuyo (Eds.), Harmful and Toxic Algal
                      Blooms, pp. 281-284. IOC, UNESCO, Paris.

                      Baba T., K. Momoyama and M. Hiraoka. 1995. A harmful flagellated plankton increased in
                      Tokuyama Bay. Bull. Xamaguchi Prefectural Naikai Fisheries 24:121-122.

                      Bates S.S., CJ. Bird, A.S.W. de Freitas, R. Foxall, M.W. Gilgan, L.A. Hanic, G.E. Johnson,
                      A.W. McCulloch, P. Odense, R.G. Pocklington, M.A. Quilliam, P.O.  Sim, J. C. Smith, D.V.
                      Subba Rao, E.C.D.  Todd, J.A. Walter and J.L.C. Wright. 1989. Pennate diatom Nitzschia
                      pungens  as  the primary source of domoic acid, a toxin in shellfish from Eastern  Prince
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                      Bates S.S.,  D.L.  Garrison and R.A.  Horner. 1998. Bloom dynamics and physiology of
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                      Hallegraeff  (Eds.), Physiological Ecology of Harmful Algal Blooms pp.  267-292.  Berlin
                      Heidelberg: Springer Verlag.

                      Biecheler, B. 1936. Sur une Chloromonadine nouvelle d'eau saumatre. Chattonella subsalsa
                      gen., n. sp. Archives de Zoologie Experimentale &  Generate 78:79-83.

                      Braarud T. 1957. A Red Water Organism from Walvis Bay. Galathea  Reports 1:137-138.

                      Bruno, M., P.M.B. Gucci, E. Pierdominici, A. loppolo & L. Volterra 1990. Presence of saxi-
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                      Burkholder, J.M., H.B. Glasgow, Jr. and AJ.  Lewitus. 1998. Physiological ecology of
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                      Verlag.

                      Burkholder, J.M., E.J. Noga and  H.B.Glasgow.  1992. New  'phantom' dinoflagellate is the
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  appendix b  •  Listing of Harmful Algae Species in Chesapeake Bay

-------
                                                                                                     B-7
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-------
B-8
                      Harada T., Y. Oshima, H. Kamiya and T. Yasumoto. 1982. Confirmation of paralytic shellfish
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                      Jochimsen, E.M., W.W. Carmichael, J.S. An, D.M.  Cardo, S.T. Cookson, C.E.M. Holmes,
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                      Maranda L., R. Wang, K. Musauda and Y. Shimizu. 1990. Investigations of the  source of
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-------
                                                                                                     B-9
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                                     appendix b •  Listing of Harmful Algae Species in Chesapeake Bay

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B-10
                       Subba Rao D.V., J.L.C. Quilliam and R.G. Pocklington 1988. Domoic acid - a neurotoxic
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                       of summer (1975-1977) dinoflagellate blooms in the York River, Virginia (Chesapeake Bay
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                       Elsevier/North-Holland, New York: 279-286.
   appendix b  •  Listing of Harmful Algae Species in Chesapeake Bay

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                       appendix
    States  Chlorophyll  a  Criteria
   and  Water  Quality  Standards
                                                                                    C-1
Alabama            Lake and reservoir specific chlorophyll a criteria ranging
                   from 5-27 jig-liter"1.
Colorado
Single reservoir with a 15 jig-liter1 chlorophyll a criteria.
Connecticut
Lake Trophic Classification System (also includes TP,
TN, Secchi) Chlorophyll a Concentrations (jig-liter"1)
by Trophic Class:
   Oligotrophic = 0-2
   Mesotropic = 2-15
   Eutrophic = 15-30
   Highly Eutrophic = >30
District of Columbia  Seasonal July 1-September 30 segment average
                   chlorophyll a concentration of 25 jig-liter1 applied
                   to tidally influenced waters only.

Georgia            Lake and reservoir specific chlorophyll a criteria ranging
                   from 15-27 jig-liter"1.

Hawaii             Chlorophyll a criteria applying to different locations within
                   Lake Mead ranging from 5^5 jig-liter1.
Nevada
North Carolina
"Chlorophyll a (corrected): not greater than 40 jig-liter"1
for lakes, reservoirs and other waters subject to growths of
macroscopic or microscopic vegetation not designated as
trout waters, and not greater than 15 jig-liter1 for waters
subject to growths of macroscopic or microscopic vegeta-
tion designated as trout waters" (15ANCAC 02B.0211)

Freshwater class C waters and tidal saltwaters: For lakes
and reservoirs and other waters subject to growths of
macroscopic and microscopic vegetation not designated as
trout waters: <40  jig-liter"1. For lakes and reservoirs and
other waters subject to growths of macroscopic and micro-
scopic vegetation designated as trout waters: <15 jig-liter1.
                          appendix c •  States Chlorophyll a Criteria and Water Quality Standards

-------
C-2
                     Oregon
Chlorophyll a criteria for:
   • Natural lakes which don't thermally stratify:
     <10 mg-liter1
   • Natural lake which doesn't thermally stratify,
     reservoirs, rivers and estuaries: <15 jig-liter1
     (OAR340-041-0019)
                     Virginia
Site specific seasonal numerical chlorophyll a criteria
applicable March 1-May 31 and July 1-September 30 for
the tidal James River segments JMSTF2, JMSTF1,
JMSOH, JMSMH, JMSPH (9 VAC 25-260-310)
Designated
Use
Open-
Water
Chlorophyll a
10
15
15
12
12
15
23
22
10
10
Chesapeake
Bay Program
JMSTF2
JMSTF1
JMSOH
JMSMH
JMSPH
JMSTF2
JMSTF1
JMSOH
JMSMH
JMSPH
Temporal
Application
March 1-
May31
July 1-
September 30
                     Source: U.S. Environmental Protection Agency. 2003. Survey of States, Tribes and Territories Nutrients
                     Standards. Washington, D.C.
  appendix c  •  States Chlorophyll a Criteria and Water Quality Standards

-------
  U.S. Environmental Protection Agency
               Region III
    Chesapeake Bay Program Office
          Annapolis, Maryland
           1-800-YOUR-BAY

                 and
               Region III
       Water Protection Division
       Philadelphia, Pennsylvania

          in coordination with

            Office of Water
    Office of Science and Technology
           Washington, D.C.

                 and

             the states of
     Delaware,  Maryland, New York,
       Pennsylvania, Virginia  and
West Virginia and the District of Columbia

-------