TOXIC SUBSTANCES IN THE CHESAPEAKE BAY ESTUARY
OWEN P. BRICKER*
ENVIRONMENTAL PROTECTION AGENCY
CHESAPEAKE BAY PROGRAM
ANNAPOLIS, MARYLAND
i
INTRODUCTION
The Chesapeake Bay"i~s "a "geologically young estuarine system, born less
than 10,000 years ago when the Atlantic Ocean, rising in response to • •>
r
meltwaters from receding Pleistocene glaciers, began to flood the valleys
of the rivers draining the east coast of the'. North American continent. ' By
approximately"3,000 years ago, ?tidal waters were beginning to encroach on
the present mouth of the Susquehanna'River at Havre de Grace, and the
*
estuarine geometry was probably quite similar to that which we observe
< t > . , * "" '
today. The flooding process did not -stop then, but the rate of sea level
' ''r '-" ' '
rise decreased. Even to'day, the flooding continues at approximately 1.6
mm/yr. in the Chesapeake Bay area (Nichols, 1972). This rate of sea level
rise is larger than the world-wide average and reflects a local tectonic
component in addition to that caused by the increase in volume of sea
waters from melting ice caps.
Estuaries form a buffer zone between fresh water rivers and the sea.
They behave as very efficient sediment traps for particulate material
carried by the rivers and by the inflow of saline marine bottom waters
through their mouths. The sediment that accumulates in estuaries is
commonly a mixture of river bourne terrestial debris derived from
*Current address: United States Department of the Interior, Geological
Survey, Water Resources Division, Reston, Va. 22092
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weathering and erosion of the tributary watersheds and coastal marine
sediment derived from the continental shelf (Mead, 1969; Hathaway, 1972).
From a geologic perspective, estuaries are very ephemeral features, quickly
filling with sediment from these sources. The lifespan of an estuary is a
function of the rate of change in sea level vs. the rate of accumulation of
sediment. In the Chesapeake Bay, the continuing rise of sea level
partially compensates for the rate of accumulation of sediments and the net
"effect is a prolongation cTf "the~ lifespan of the system. The estuary,
however, is a dynamic system, undergoing continuous evolutionary changes
which will ultimately lead to its destruction through infilling with
sediment.
The Chesapeake Bay began to experience impacts, in addition to those
caused by natural processes, from the time of first European settlement
along its shores. Clearing of land for agriculture and development has
greatly accelerated the rate of erosion in the adjacent land areas and
increased the amount of sediment delivered to the estuary by its tributary
rivers. Perhaps an even more serious impact is related to the tremendous
technological advances that have been made through the years. Man has been
exceedingly ingenious in synthesizing and producing a miriad of new
chemical compounds, and in finding uses for an increasing variety of metals
and, more recently, radionuclides. These substances enter the environment
through waste discharges and other disposal practices, (e.g., industrial
discharges, sewage effluents, land fills), by direct applications for
specific purposes (e.g., herbicides, pesticides, fertilizers) and via
atmospheric pathways (e.g., automotive exhausts, combustion of oil, coal
and wood, incineration of refuse, fugitive dusts from storage or disposal
sites, bomb testing). It is now clear that many of the substances that
were either purposely or inadvertently released to the environment are
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displaying unanticipated adverse affects on the biosphere. Historically,
estuaries have been favored localities for siting industries, power plants
and sewage treatment facilities. They provide an abundant supply of water
for industrial processes and for cooling power plants, they are a
convenient conduit for the disposal of a broad spectrum of wastes, and they
provide direct accessibility to marine transportation of raw materials and
finished products. As a consequence, estuaries have bourne the brunt of
man's activities." The"Chesapeake Bay is no exception.
Two classes of materials, toxic substances and sediment, pose the
greatest threat to the environmental well being of.the estuarine system.
These materials are intimately related in that many toxic substances,
inorganic and organic, associate strongly with sediment via
physico-chemical mechanisms. As a consequence, the sediment accumulating
on the bottom is the largest reservoir of toxic materials in the estuary
(Bricker and Troup, 1975).
Sediments
The sediments that accumulate in Chesapeake Bay are important for a
number of reasons. From a physical standpoint, sediments tend to fill in
channels and harbours and thus create a need for periodic dredging in order
to maintain these facilities for their intended purpose. Dredging, in
turn, requires disposal sites for placement of the material removed.
Appropriate handling techniques and disposal site characteristics depend
upon the chemical components and physical properties of the spoil.
Suspended sediment creates turbidity which decreases the depth of light
penetration and may also affect its spectral distribution. The decrease in
intensity and shift in spectral qualities may adversely affect aquatic
plants. Large concentrations of suspended sediment tend to clog the gills
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and filtering apparatus of filter feeders causing impairment or death.
Rapid sedimentation may cause burial and smothering of benthic fauna and
flora.
In the absence of sediments, however, the estuary would not be the
fertile and productive environment that it is. Sediments form a substrate
upon which rooted aquatic plants grow; they provide a habitat for burrowing
benthic organisms; they are a source of nutrients for benthic flora and
fauna. Sediments also carry with them metals derived from natural
weathering and erosional processes and those introduced by man. Many of
these metals are essential to maintain a healthy biota, 4>ut if present in
excess are toxic. In addition, sediments are a vehicle for the transport
and localization of a large number of the anthropogenic organic compounds
that enter the aquatic environment (Olsen, 1979). Both inorganic and
organic toxic substances have a great affinity for particulate matter of
small size and large surface area. Sites of accumulation of sediments
possessing these physical characteristics usually contain significantly
higher concentration of metals and organic compounds than sites of
accumulation of sediments of sand size or larger. Sediments thus play a
major role in the transport and distribution of toxic materials in the
estuary.
No systematic study of toxic materials in the Chesapeake Bay had been
attempted until the Environmental Protection Agency Chesapeake Bay Program
•was initiated in 1975. In planning that program, it was concluded that any
toxic substances discharged into the Bay and its tributaries could have
direct impact during their residence time dissolved in the water, however,
because of the rapid water movement and concomitant dilution, these effects
would be short lived. The most serious potential problems were identified
as those associated with toxic substances that accumulate in the sediment
and/or biota. These substances have a much longer residence time in the
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system and may also build up to very high concentrations through sediment
sorption mechanisms or bioaccumulation. For these reasons, knowledge of
the distribution, amount, and physical characteristics of the recent
sediments in the Bay is fundamental to understanding the behavior and fate
of toxic substances in the estuary. In addition to the physical
characteristics, the content of organic carbon and sulphur play an
important role in determining the oxidation/reduction state of the
sediments after deposition. The water content correlates with the
stability and ease of resuspension of the bottom and with the rate at which
dissolved substances diffuse through the sediment. The mineralogy of the
sediment provides information on the reactivity of the inorganic
particulate constituents. These parameters together form the framework
into which the chemical and biological pieces of the system fit.
The most basic data concerning sediments in the estuary are:
1. location in the system
2. morphology of deposits
3. physical characteristics
4. rate of addition to the system
5. sources
6. sites and rates of present accumulation
In Chesapeake Bay, geophysical methods have been used to examine the
thickness and morphology of the bottom sediment (Maryland Geological
Survey, Virginia Institute of Marine Science open file reports). These
methods also provide information on some other sediment properties in that
sand and shell layers can be differentiated from finer silty and muddy
sediments.
The physical characteristics of the surface sediments (particle size
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distribution, water content) have been determined for the entire Bay; on a
1 km grid in Maryland waters and on a 1.4 km grid in Virginia waters. In
addition, these same properties have been determined on a selected suite of
meter length cores collected between the Susquehanna River and the Virginia
capes. Sediment, on the basis of particle size, displays a relatively
systematic distribution pattern with sand occurring in the shallow
shoreline areas and mud in the deeper mid-Bay regions. Between, there
occurs a zone of mixing "of"these"two sediment types (Byrne, 1980; Kerhin,
1980). This sediment work provides a description of the state of the
system relative to sediments at the present time in history and it will
serve as a valuable baseline against which future changes can be measured.
Three major sources contribute sediment to Chesapeake Bay; tributary
rivers, shoreline erosion and marine inflow. The northern part of the Bay
is dominated by sediment carried via the Susquehanna River; the southern
Bay, by sediments transported by inflowing coastal marine waters; and the
mid-Bay region, by sediments derived from shoreline erosion.
Each of the tributary rivers, with exception of the Susquehanna, is
characterized by an estuarine segment in its lower reaches. A large part
of the sedimenf carried by these rivers is trapped in their lower estuarine
portions and never reaches the main Bay. As a consequence, infilling of
the middle portion of the Bay is occurring at a slower rate than to the
north or the south, with fine particle size sediment that escapes the
tributary estuaries collecting in the deeper areas and coarse sediment
derived from shoreline erosion accumulating in the shallow waters adjacent
to the shorelines. The Susquehanna River debouches directly into the upper
Bay and the bulk of the sediment it carries is deposited there. Sediments
from the continental shelf, carried into the Bay in the saline bottom
waters, dominate the southern segment of the Chesapeake Bay.
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It is important to know what changes have occurred in the system in the
past so that predictions can be made concerning future trends. In order to
understand how the system has changed from past to present, and to identify
•impacts related to man's activities, we must rely on information recorded
in the sediment. To interpret this record, we must first know the time
interval represented by the record. Three independent methods for
deciphering the time (rate) of sedimentation have been employed in the
.Chesapeake Bay: .._!.)..comparison ofhistorical bathymetric charts, 2) pollen
710
biostratigraphy, and 3) Pb geochronology. Parts of the Bay have been
surveyed bathytnetrically at irregular time intervals beginning in 1846.
Where these surveys overlap, the change in depth represents the amount of
deposition (or erosion) that has occurred during the time between surveys
(Maryland Geological Survey, Virginia Institute of Marine Science, open
file reports). A second technique is based on pollen biostratigraphy, that
is, the identification of specific time horizons in the sediment recognized
by pollen distribution. For instance, the time of disappearance of
American chestnut in the 1930's, in response to the chestnut blight, is
recorded by the absence of chestnut pollen in sediments deposited after
that time. Other identifiable horizons, both older and younger, have been
recognized in Chesapeake Bay sediments and are valuable time markers in
this system (Brush, 1980). A third technique employs the decay of a
210 238
radioactive isotope of lead. Pb , a member of the U series, is
continuously being added to the earth's surface environment. It adsorbs
strongly onto sediment particles and is deposited with them wherever they
accumulate. Once buried beneath the sediment-water interface, no
210
additional Pb can be added, and that contained in the sediment
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continues to decay at a constant rate (half life = 22.5 years). This
permits the dating of sediments back to approximately 100-125 years B.P.
A?
(5 x half life) (Setlock and Helz, 1980). Each of these methods provides
an estimate of the rate at which sediment has accumulated at the site
sampled. In areas of the Bay where sedimentation rates have been
determined by either two or all three of the above techniques, the
correspondence is usually quite good. Using this information the age of a
particular layer or bed-of-sediraent can-be dated by its depth beneath the
surface. If a change in the concentration of any toxic substance is
observed as a function of depth, the rate of loading of that substance can
be inferred and projections made about future concentration trends. The
time of introduction of various substances into the system can also be
documented. Data about sedimentation rates are directy useful in planning
dredge disposal sites, locating channels to provide minimum maintenance,
and estimating the frequency and volumes of material that will have to be
dredged in order to maintain harbours and channels in various parts of the
system.
Toxic Substances
Along with knowledge of the distribution and physical characteristics
of bottom sediments in the estuary, it is necessary to know the
concentrations of the toxic substances they contain if these materials are
to be effectively managed.
Two major classes of toxic materials are particularly important to the
estuarine environment; metals and anthropogenic organic compounds. Metals
are derived from natural weathering and erosion of the metalliferous
Piedmont rocks underlying the watersheds of many of the Bay tributaries,
and from man's activities. Most of the organic compounds of environmental
concern are strictly the product of man's chemical ingenuity. These sub-
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stances enter the system via direct discharges, in input from the
tributaries, in non point source runoff, and through atmospheric pathways.
The distribution of these materials in surface sediments (upper few
centimeters) is a result of recent deposition and accumulation in the
estuary. Dated cores provide information on how the concentrations of
these materials have changed with time in the sediment. Because metal
behavior is better understood and analytical methods for metals are more
straightforward and less expensive than"those for organic compounds, the
data for metals in the estuarine environment is much more detailed than
that for organic compounds. Emerging evidence over the past decade
suggests, however, that synthetic organic compounds may be of greater
concern than metals from the standpoint of environmental degradation of
aquatic systems.
The similarity in behavior between metals and many organic pollutants
with respect to sorption behavior on fine particle size sediment suggest
that metals may be used as surrogates for predicting the transport and
accumulation of many organic pollutants. A limited number of samples of
surface sediment from the main stem of the Chesapeake Bay have been
analyzed for organic compounds using glass capillary gas chromatography/
mass spectrometry and corroborate this hypothesis. Preliminary inspection
of both the metals data and the organics data show that the highest
concentrations of these substances occur in samples from tributary mouths,
suggesting that the tributaries act as sources of these materials to the
main Bay (Huggett, 1980). Not surprisingly, the highest concentrations
were observed at the mouths of the Susquehanna, Patapsco, and James Rivers.
The technical complexity and expense of analyzing estuarine samples for
organic compounds led to the development of a strategy for maximizing the
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output of data of the type that would be most useful to identify potential
problems with these compounds. Instead of trying to identify each peak
(compound) on GC/MS traces, the complete GC/MS output from each sample is
stored on the computer. Subsequent sampling at the same localities using
the same analytical procedures disclose changes in peak height
(concentration) for the organic compounds. If there has been a significant
increase in any peak from one sampling period to the next, the compound
represented by that peak-can be-identified and evaluated with respect to
its toxicity and potential impact on the system. Possible sources of the
compound can be identified by concentration gradients provided by a more
detailed sampling grid in that particular area of the Bay, and appropriate
regulatory measure instituted. The chances of associating a particular
compound with its source are increased by performing identical analytical
work on industrial, municipal sewage treatment plant and power plant
discharges into the Bay (Monsanto Research Corporation, 1980). By
periodically analyzing effluent discharges, it may be possible to stop a
potential toxic problem at a very early stage before the substance has been
discharged into the environment in large quantities. The frequency of
sampling, however, must be appropriate to correspond to changes in process
or treatment in the plants. One serious drawback is that the direct
discharge analysis may not detect some toxic substances present in very
v.
small concentrations, yet if these substances are strongly sorbed by
sediment or bioaccumulated by organisms, they may build up to dangerously
high levels in the environment. By emphasizing the sediment and biota
sampling in the estuary, and supplementing this with periodic sampling of
effluent discharges, it may be possible to manage toxic substances from
point sources in a much more effective manner than is presently being done.
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An up-to-date inventory of raw materials, processes and finished products
from all dischargers into the estuary would aid greatly in assessing the
loading of toxic materials in the Bay system.
Coupling the data on toxic subtances in the sediment with the
compositions and volumes of industrial discharges and the type of inventory
data described above, it will be possible to identify those substances that
accumulate in the environment and permit estimates of mass-balance budgets
for specific toxic sub's tarices" of "concern. Combining this information with
the distribution and physical characteristics of the sediment will disclose
specific toxic substance-sediment associations. Extending this type of
work to dated core samples will provide estimates of changes in loading of
toxic substances with time.
Perhaps as important as knowledge of the identities and spatial
distribution of toxic substances in the estuary is an understanding of how
these substances behave in the environment. After deposition and burial in
the bottom, sediments and associated toxic substances are exposed to an
anoxic reducing environment. This leads to changes in speciation,
desorption, dissolution and remobilization of many elements (Elderfield and
Hepworth, 1975). Three major mechanisms lead to the re-introduction of
these materials at the sediment surface and to the water column: 1)
transport in the dissolved state in the interstitial water via diffusion
and/or advection, 2) physical transport of sediment and interstitial water
by benthic infauna (bioturbation, irrigation, ventilation), and 3) physical
disturbance of the sediment by storms and by man's activities (dredging,
propeller wash, etc.). Investigation of the metal and organic content of
the sediment areally and with depth provides information which permits
prediction of the chemical impacts of re-exposure of sediments at the
surface. Sampling and analysis of interstitial waters provides a data base
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from which flux of metals and nutrients into the water column can be
calculated. Available data disclose that the sediment behaves as an
important source of nutrients to the estuary (Maryland Geological Survey,
open file reports). At certain times of the year, a significant flux of
dissolved manganese and iron into the deep bottom waters is also observed.
Data for other metals is not yet available. In addition to nutrient and
metals flux calculations, the interstitial water chemistry provides
critical information on the reactions that occur within the sediment and
the composition of the aqueous environment in which the benthic infauna
live.
Examination of the benthic fauna, particularly the infauna, is ~
providing a picture of the distribution of organisms in the estuary as a
function of salinity, sediment type, and depth beneath the sediment-water
interface (Maryland Geological Survey, Virginia Institute of Marine
Science, open file reports). These studies document the effects of the
benthic communities on the disturbance and mixing of the sediment
(bioturbation), the stabilization-destabilization of the bottom sediments
relative to erosion and resuspension, and the role of burrows and other
biogenic structures on physical and-chemical processes occurring in the
sediments. Benthic organisms are restricted in their mobility and
therefore must adapt to any changes that occur in the local environment.
For this reason, benthic organisms may be good early warning indicators of
environmental degradation. Investigations in the main Bay have disclosed
cycles of colonization and extermination of benthic fauna in the deep
trough along the Eastern Shore, apparently in response to the yearly summer
development of anoxia in the bottom waters (Reinharz and Diaz, 1980).
Systematic examination of benthic communities Baywide, and particularly in
the tributaries, may identify areas subject to environmental stress. These
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areas would be prime targets for detailed investigations of the causes of
the stress. The response of organisms; distribution, abundance, species
diversity, histopathologic features, genetic effects and other biologic
effects could be used as indicators of the state of health of the
particular segment of the system in which the organisms live. The
foundation for developing an assessment strategy based on biologic criteria
is a thorough description of the estuarine benthic organism communities in"
conjunction with the physical and chemical characteristics of the
environment in which they live.
Present Status of Toxics in the Chesapeake Bay
The past decade has witnessed disturbing changes in the ecosystem of
the Chesapeake Bay. Among the more widely publicized of these have been
the decline and virtual disappearance of rooted aquatic plants from much of
the Bay, the steady decrease in the abundance of striped bass and oysters,
the cessation of the spring shad runs in the upper Bay, poor yields of
clams and fluctuating, but generally declining catches of crabs.
Individually, any one of these could be attributed to a biological cycle or
some other natural phenomenon. Taken together, however, the implications
are more ominous. It has been strongly suggested that toxic substances are
responsible for the observed changes. Over the years, however, the Bay has
been under increasing pressures from a variety of man's activities. The
harvesting of shellfish and finfish by commercial watermen and sports
fishermen has not been effectively regulated from the standpoint of
preserving the resource. An expanding population on the shores of the Bay
and in the watersheds of the Bay tributaries, has tremendously increased
the volume of sewage effluent delivered to the estuary. Increasing need
<•
for energy has led to the siting of conventional and nuclear power plants
on the shores of the Bay and along its tributary rivers. Continued indus-
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trial development in the Bay area has burdened the estuary with increased
volumes of chemically complex discharges. Clearing land for agriculture
and for development has greatly increased the loads of suspended sediment
carried to the estuary. Chemicals in runoff from agricultural areas and in
storm drainage from city streets, parking lots and highways ultimately end
up in the Bay. Only recently has it been recognized that many toxic
substances, including metals and organic compounds, are transported
atmospherically and enter ~the~ surface environment via precipitation and by
dry fallout. The sources of these pollutants are often far removed from
where they impact the earth's surface. Each of these insults takes its
toll on the finite assimilative capacity and resiliance of the estuarine
environment. Cumulatively, they appear to have reached the stage at which
they exceed the regenerative capacity of certain parts of the resource. In
turn, this has led to the decline and/or disappearance of some of the more
sensitive biota.
What can be done to halt the degradation and reverse these trends? The
tendency in the past has been to look for a single cause of the problem,
such as toxic substances or excess nutrients and, thus far, the search has
been less than successful. The estuarine sys.tem is very complex and each
of the diverse activities mentioned1above has an impact on the system; some
greater than others. We observe the net integrated effect of all of these
factors acting in concert, and it is thus not surprising that no simple
answers have been found. Only two areas of the Bay, the Elizabeth River
and Baltimore Harbor, show serious environmental degradation that can be
directly attributed to toxic substances (Villa and Johnson, 1974; Johnson
and Villa 1976; Chu-fa Tsai et al, 1979). Even in these localities it is
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not possible, at present, to identify the specific effects of individual
toxic elements or compounds. Over most of the Bay the effects are much
more subtle and no direct cause and effect relationships have yet been
demonstrated.
Effective management of toxic substances in the estuarine environment
requires regulation of the amount of each toxic substance delivered to the
system from all sources in order to keep environmental concentrations below
the level at which adverse—impacts occur. This regulation must be based on
a firm understanding of the behavior and fate of natural and anthropogenic
toxic substances introduced into the system; the effects of these toxic
substances on estuarine biota; the identification of the sources
contributing toxic substances; and quantification of the load of each
substance delivered by each source. At the present time, there is no
comprehensive inventory of loadings to the system and there is only
fragmentary information concerning the types and concentrations of toxic
substances already in the environment. There is a moderate body of
information relative to the behavior and fate of metals in the estuarine
environment; however, similar information about toxic organic compounds is
difficult or impossible to-find. Perhaps the largest gap is in our
understanding of the effects of toxic substances, both metals and organic
compounds, on the estuarine biota.
The Environmental Protection Agency Chesapeake Bay Program has
initiated a research effort to begin to address these questions; however,
this research must be intensified and expanded if it is to provide the data
necessary to develop an effective program for the management of toxic
substances in the estuarine environment.
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BRUSH, G. (1980) Report on Pollen Biostratigraphy to EPA/Chesapeake Bay
Program
BYRNE, R. (1980) Report on Sediment Distribution in Virginia Waters to EPA/
Chesapeake Bay Program
CHU-FA TSAI, Welch, J., KWEI-YANG CHANG, SHAEFFER, J., CRONIN, L.E., (1979)
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