Seismic and Geochemical Research

in Chesapeake Bay, Maryland

Sandy Point State Park, Annapolis, Maryland

July 15 and 18, 1989

Field Trip Guidebook T23 1

Leaders:
Robert Cuthbertson
JeH Halka James Hill

American Geophysical Union, Washington, D.C.

 Leaders:

Robert Cuthbertson,
Jeff Halka, and James Hill
Maryland Geological Survey
2300 St. Paul Street
Baltimore, MD 21218

Copyright 1989 American Geophysical Union

2000 Florida Ave., N.W., Washin-gton, D.C. 20009

ISBN: 0-87590-569-2

Printed in the United States of America

COVER The research vessel Discovery.
 IGC FIELD TRIP 231: BOTTOM SEDIMENTS OF THE CHESAPEAKE BAY:
PHYSICAL AND GEOCHEMICAL CHARACTERISTICS
James M. Hill and Jeffrey P. Halka
Maryland Geological Survey, Baltimore, Maryland
Field Coordination: Robert H. Cuthbertson
INTRODUCTION
The Chesapeake Bay, the largest estuary
in the United States, is located in the
densely populated 'megalopolis' which
extends from the nation's capital,
Washington, D.C. northward to Boston,
Massachusetts and southward to Richmond,
Virginia (Figure 1). Some 13 million people
reside within its watershed, a number which
is projected to increase to nearly 16
million by the year 2000. As is the case
with most estuaries the Bay has served a
variety of functions related to man's needs
since European occupation of the continent
began nearly 4 centuries ago. Ample
supplies of both shellfish and finfish are
harvested from its waters with an annual
commercial value exceeding $100 million. The
Bay ranks third in the United States in
overall fisheries catch surpassed only by
U.S. landings from the Atlantic and Pacific
Oceans. It also serves as a significant
commercial waterway with major ports located
near the mouth at the Hampton Roads Complex,
in Virginia, and in Maryland at the Port of
Baltimore. More than 50,000 commercial
vessel trips are recorded annually from
these major and other minor ports in the
Bay. Besides the commercial aspect, the Bay
is becoming an increasingly important
recreation area. Maryland alone has more
than 125,000 pleasure boats registered.
The many human uses of the Chesapeake
Bay, combined with the high population
density and industrialized nature of the
drainage basin is applying stress on the
estuarine ecosystem. Sediments and water
which enter the Bay from its tributaries,
runoff, and the atmosphere contain a
loading of anthropogenic nutrients, trace
elements, organic compounds and radio-
nuclides. These materials are efficiently
trapped within the estuarine system and can
have a profound effect on the environmental
quality of the Bay. Developing an
understanding of the sources, routes, and
ultimate sites of deposition of sediments,
and the associated geochemical and
biological processes operating within them
once deposited, is important for developing
T231:
effective management strategies for the
future of the Bay.
OBJECTIVES
Research efforts in the Coastal and
Estuarine Geology Program of the Maryland
Geological Survey have focused on
understanding the recent biogeochemical
history of sediments accumulating in the
Chesapeake Bay, and the record of sediment
infilling which has occurred in the
Quaternary. Determining this history
requires an integration of sediment
chemistry, the early stages of diagenesis,
sediment textural characteristics, and the
activities of the benthic infauna. During
this field trip we will examine some
characteristics of modern fine grained
sediments accumulating in the northern
portion of the Chesapeake Bay. The
following sections will provide background
information on the physical and biogeochem-
ical structure of the Bay. This information
will be the basis for detailed discussions
at each of the sampling sites.
BACKGROUND
History and Basin Characteristics
The Chesapeake Bay is a classic coastal
plain estuary located on a trailing edge
continental margin. It is nearly 300 km
long and ranges from 8 to 48 km in width,
having a surface area of almost 6000 square
km. The modern Bay formed in response to
changing sea level during and following the
last major continental glaciation. At the
height of the glacial period, a time of
relative low sea level, the Susquehanna
River debouching from the Piedmont
physiographic province at the head of the
Bay eroded the gently dipping Tertiary age
strata of the coastal plain. The reSUlting
river valley was drowned by rising sea level
as the glaciers waned. This history of
formation is reflected in the bathymetry,
which is characterized by a deep axial
channel flanked by broad shallow benches,
and in the deeply dissected and invaginated
shoreline (Figure 2). Water depths exceed
 700W

EXPLANATION

[::J Adirondack Mtns.

I~:~:~:;:;~ Great Lakes Lowland
• Appalachian Plateau
a Valley and Ridge
~ Blue Ridge
1::::<:1 Piedmont Plateau
D Coastal Plain

: : : : : : : -:- Savannah

"

80 0 W
o 200 400KM. o /5KM.
I I I L...L.....L...J

FIGURE 1 Location map for the Chesapeake Bay showing its relation to the
major physiographic provinces of the eastern United States, and the major
tributary rivers which flow into the Bay. The field trip will depart from
Sandy Point State Park.

T231: 2
30 m in the deep channel but overall the Bay
is quite shallow with an average depth of 8 BATHYMETRY
m. Contour Intervals
4 meters - Depths < 20 meters
The drainage basin encompasses 167,000 10meters -Depths >20 meters
square km with the Susquehanna River, being -Dredged
the primary source of fresh water
discharging at the head of the Bay. The Bay
is a microtidal system with a tide range of
one meter at the mouth, decreasing
progressively up-bay to a minimum of less
than 30 centimeters in the vicinity of
Baltimore, and then increasing to nearly 60
centimeters at the more constricted head of
the Bay (Hicks, 1964). Due to the extreme
shallowness relative to its length the tidal
wave takes 13.75 hours to progress from the
mouth to the head. Consequently, the Bay is
able to contain one complete semidiurnal
tide wave at all times. The tidal influence
is sufficiently large relative to the fresh
water discharge to produce a partially mixed
estuary (Pritchard, 1971). Mixing between
the relatively fresh surface water and the
denser, more saline bottom water occurs
throughout the system. The Susquehanna
River provides 60% of the total freshwater
input to the Bay, with an average long-term
discharge of 9.698x10 5 liters/sec (Lang and
Grason, 1980). The other major tributaries
are the Potomac River (3.225x10 5 liters/sec)
and the James River (1.995x10 5 liters/sec).
Residence time of freshwater in the Bay is
approximately one year, assuming complete
mixing and neglecting saltwater throughput.
The circulation of water in the Bay is
controlled by freshwater inflow, density
stratification, basin morphology, tidal
forcing and the Coriolis force. Southward
flowing freshwater travels predominantly
along the western side of the basin. Saline
water entrained in this southward flow, by
mixing, is removed from the Bay to the
Atlantic Ocean. The lost volume is replaced
by the inflow of seawater which enters the
system as bottom water at the mouth of the
Bay. The more saline water travels
northward along the eastern side of the
basin where the flow eventually becomes
trapped and directed by the main axial
channel. The turbidity maximum, located
slightly downstream of the landward limit of
saline water intrusion, is generally found
30 km from the mouth of the Susquehanna
River, although its location varies
seasonally with the river discharge.
Current velocities are characteristically
low in the mainstem of the Bay. Typical
maximum velocities in the water column due
to tidal forcing average less than 0.5
m/sec. In physically constricted areas and
in the northernmost reaches velocities FIGURE 2 Bathymetric map of the Chesapeake
occasionally approach 1.2 m/sec. Near Bay.

T231: 3
bottom currents, however, only rarely exceed
30-40 cm/sec. Wind events can have a
significant impact on the current velocities
by augmenting or suppressing the tidal
flows. These events can add or subtract as
much as 0.3 m/sec to the underlying
semidiurnal driven currents depending upon
the direction and speed of the wind.
The salinity of the Bay varies
seasonally, in response to the freshwater
inputs. Typically, the lowest salinities
occur in the spring and the highest
salinities occur in the fall. The dissolved
load is a source of chemical species to the
sediments. Of particular interest are
diss~lved oxidants (such as 02' N0 -, and
3 blanket in deeper waters (Byrne et al.,
8°4 2 ) which strongly influence the
geochemical environments of the sediment.
Figure 3 shows the conservative mixing
behavior found in the Chesapeake Bay. In
this figure, the independent variable CI- is
used as an indicator of conservative mixing.
The dependent variables are the ratio of the
major seawater ions to CI-, a measure of the
relative composition, and the total
dissolved solids, an indicator of the
absolute concentration. There are two
principal features to note:
1) In the shallow Northern Bay region
the relative composition is strongly
influenced by fluvial inputs, shown by the
marked variation of the major ion ratios to
CI-. This behavior is in contrast to the
rest of the Bay, where seawater is the
dominant influence (shown by the horizontal
lines in the major ratios), and;
2) The Northern Bay shows the widest
range of concentration variability. The
total dissolved solids load varies over two
orders of magnitude in the Northern Bay,
while the total range of variation through
the rest of the Bay is only a factor of two.
Non-conservative processes strongly
influence the geochemical environment of the
water column. The most significant of these
is the occurrence of hypoxic/anoxic water.
These events occur during the warm, low flow
summer months, and are confined primarily to
water depths >10 m (i.e. the main axial
channel). During severe anoxic events
sulfide species are measurable in the water
column.
Textural Characteristics of Bottom Sediments
Ever since the reconnaissance survey of
Ryan (1953) the bottom sediments of the
Chesapeake Bay have been considered to
consist largely of fine grained muds. This
view prevailed, in part, due to the
recognition that the Bay is a microtidal
system, has limited fetch inhibiting the
T231:
formation of large storm waves, and receives
a large suspended sediment load from upland
drainage sources. In fact, one often
encounters direct references to the muddy
nature of the Bay's sediments in the
literature (e.g. "Most of the Bay is
blanketed with mud. Sand is predominant
only ••• [in limited areas]"; Schubel and
Carter, 1977; p. 49). While this concept is
certainly true to a first approximation
recent more detailed surficial sediment
sampling has shown that a considerable sand
sized component is present in the Bay bottom
sediments and, furthermore, that muddy
sediments do not necessarily form a uniform
1982; Kerhin et al., 1988).
The surficial sediments can be most
readily characterized by using the
classification scheme of Shepard (1954) with
the sand, silt, and clay sized components
comprising the end members of a ternary
diagram. In the entire Bay all ten
classifications of this system are
represented albeit some more heavily than
others (Figure 4 and Table 1). A summary of
the areal extent of each sediment type
occurring on the Bay floor is provided in
Table 1. The sands, covering 57% of the Bay
floor, dominate the bottom sediments in the
mainstem of the Bay as was visually apparent
on Figure 5. The fine grained silty clays
(17.9%) and clayey silts (8.12%) together
cover more than one quarter of the Bay
floor. Together these three sediment
textural classes account for nearly 83% of
the Bay bottom with the remaining seven
classes making up the remaining 17%.
In regard to the distribution of the data
there are two dominant textural types in the
Bay as exhibited on Figure 4. Sands in the
lower left corner of the diagram and fine
grained muds which occur primarily as silty
clays with some overlap into the clayey
silts and clays. A broad swath of
intermixed sediment types falls across the
center of the diagram, although these mixed
sediment types are not numerically dominant.
The general pattern reflects a differen-
tiation in bottom energy conditions which
occurs in the Bay. In areas with relatively
high energy conditions, due to either waves
or high current velocities, sandy bottom
sediments are dominant with the finer
materials removed from the bottom and
incorporated in the suspended sediment load
of the water column. The suspended detrital
sediments derived from reworking of the
bottom, shoreline erosion and fluvial inputs
settle from the water column into deeper
waters of the Bay in those areas where tidal
currents are also low. Bottom sediments in
4
 TABLE 1 Area of the Bay floor characterized
i ! by sediments of each of the ten textural
i Middle! classes.
Northern Bay - - _ . i-and-'~
•Southern:
Boy
-/00
Sediment Area (sq km) Percent
::::
~ Classification
~
5
\I) Sand 3912.77 56.69
e~ Silty Sand 560.27 8.12
15:
-/0 ()
\I)
Clayey Sand 72.14 1.05
\I)
1-:
<to Q
~:
<t:
~:
~
..."
Silt 1.92 0.03
UP
~ Sandy Silt 96.79 1.40
Clayey Silt 577.04 8.36
-/.0
Clay 74.49 1.08
Sandy Clay 3.10 0.04
Silty Clay 1235.67 17.90

-0./
Sand-Silt-Clay 367.94 5.33

10 100 1000 10,000

100.00
CI- (ppm)
Total 6902.13

FIGURE 3 Conservative mixing behavior of the
major sea water ions.
CLAY
SANDY CLAY . extends further from shore in the vicinity
SAND ........_--~---- __L....-...
SILTY SAND
FIGURE 4 Ternary diagram of surficial
sediment texture for 5924 grab sample
stations. Samples are located according to
the relative proportions of the thrOee end
member grain sizes. The nomenclature for
the sediment descriptors used in the text is
indicated.
these areas consist primarily of silty clays
and clayey silts. Although covering a broad
area of the diagram only a relatively few
samples represent intermixed types falling
between these two dominant classes. This
suggests that areas with intermediate energy
conditions where mixed sediment types occur
are only locally present in the Chesapeake.
The map of the textural distributions
based upon Shepard's (1954) classification
demonstrates the greater extent of marginal
sands in the Chesapeake Bay (Figure 5). The
offshore margin of the sand field in most
cases roughly parallels the shoreline but
of headlands, peninsulas, and adjacent to
the low-lying islands which occur throughout
the Bay. This is a result of erosional
retreat of these features as sea level
rises. The sands are most apparent south of
the confluence with the Potomac River, where
they occur as a broad expanse to the east of
the Bay's central axis. In the vicinity of
the Bay mouth this eastern marginal sand
field coalesces with the western and
'--- ~ SILT
southern shore marginal fields to from a
SANDY SILT
wide nearly continuous area. In general, the
sand fields bordering the eastern shore of
the Bay are wider than their western shore
counterparts. They extend further offshore
from projecting headlands and exhibit a
tendency to increase in width in a southerly
direction. Also of note are relatively
small isolated pockets of sand that occur in
deep water and are completely surrounded by
finer grained sediments (compare Figures 2
and 5).

T231: 5
 The areal distribution of the fine
grained clayey silts, silty clays and clays
is complementary to that of sand north of SEDIMENT DISTRIBUTION
the confluence with the Rappahannock River,
occurring in the deeper sections of the
estuary offshore from the sands. The
generalized longitudinal pattern in the
distribution of fine grained sediment types
(Figure 5) is related to the major external
sources of sediment to the Bay, the
Susquehanna River and the Atlantic Ocean.
Proximal to the Susquehanna River a variety
of sediment types occurs, but the
sand-silt-clay mixture is dominant. This
quickly grades into clayey silts which are
dominant southward to approximately 45
kilometers from the river's mouth. The
southern boundary of this field is located
at the normal southern position of the Bay's
turbidity maximum (Schubel, 1972).
Southward, where the Bay broadens between
the Patapsco and Chester Rivers, fine
grained silty clays dominate the bottom
sediments. The silty clays remain the
characteristic sediment type of the deeper
portions of the Bay southward to just below
the confluence with the Potomac River.
However, throughout this portion of the Bay
a variety of other sediment types occurs
within the silty clay field. Offshore of
the Rappahannock River mouth the silty clays
again grade into clayey silts, which,
together with sand-silt-clays, form the
dominant fine grained sediment type in this
portion of the Bay. The pattern of gradual
coarsening of sediment continues to the
south with a limited area of sandy silts
separating the clayey silts from the silty
sands which are dominant in the deeper
portions of the Bay between the Rappahannock
and York Rivers. Finally the silty sands
give way to a nearly continuous sand field
which extends to the Bay mouth.
These overall gradients in the sediment
type suggest that the Susquehanna River
exerts a dominant influence on the bottom
sediment characteristics north of
approximately 39°N. Within this region
there is a transition from intermixed
sand-silt-clays through clayey silts to the
finer grained silty clays, a gradual
fractionation dependent upon grain size.
Similarly the Atlantic appears to be a major
source of sediment to the southern Bay as
suggested by the fining sequence of sands

FIGURE 5 Textural characteristics of KlLOME7CRS

surficial sediments based upon the o 5 10
0$10
15

classification scheme of Shepard (1954). MILES

Adapted from Byrne and others (1982) and

Kerhin and others (1988).

T231: 6
through silty sands, then sandy silts to
clayey silts until finally north of about
37°40'N, 80 kilometers from the mouth,
predominantly silty clays are deposited in
deeper waters. Within the large central
region of the Bay the fine grained silty
clays predominate. However, many patches of
coarser grained sediment types appear on the
floor of the deeper portions of the Bay
throughout the region, these represent
regions of non-deposition or extremely slow
deposition.

Sedimentation Rates

In recent years the determination of

sedimentation rates in the estuarine
environment has become an increasingly
important source of data for calculating
sediment budgets, determining the fluxes of
anthropogenic materials between the
sediments and water column, and identifying
potential sites of accumulation of toxic
materials. Sedimentation rate information
is also important from a geologic
perspective, because it has often been
stated that estuaries are short lived,
rapidly filling with sediments once they are
formed. In order to adequately describe the
resulting stratigraphy and characteristics
of the estuarine sedimentary fill, the
spatial variations in accumulation rates
must be established.
In the Chesapeake Bay, as in most
estuaries, sedimentation rates have been
determined by radionuclide dating of
sediment cores returned from the bottom.
Pb-210 rates have been obtained by three
separate research groups at 22 locations
(Schubel and Hirschberg, 1977; Goldberg et
al., 1978; Hirschberg and Schubel, 1979; and
Helz et al., 1982). The rates range from a
low of 0.07 cm/yr to a high of 8.0 cm/yr
(Figure 6). Rates determined by this method
assume that the sedimentation rate is
relatively constant. Events or processes
which cannot be accounted for by this method

FIGURE 6 Compilation of all published 210-Pb

determined sedimentation rates (cm/yr) in
Chesapeake Bay. Data from Helz et al.,
1982; Hirschberg and Schubel, 1979; Goldberg
et al., 1978; and Schubel and Hirschberg,
1977. Bold boundaries and numbers denote
the physiographic segments within which
sedimentation rates were determined by
bathymetric comparisons (see text and Figure
7).

T231: 7

..
1.0............- - -.....
,--.
>-
E
..........
0.8
(J
'-'
CD
-....""--
.. ~
c; 0.6
'.
c::
c
~ 0.4
...
(U
C
CD
E 0.2
"'C
CD
en o. O.........-----.,~----:-==-_T--==--~-=----~----_r_----~----_..,
300 250
FIGURE 7 Bathymetrically determined sedimentation rates (heavy
lines) within each of the geomorphic segments delineated on the
accompanying map. Rates are connected by light lines to show
trends. In segments 1-7 rates for both muddy sediments are
shown by solid lines and for sandy sediments by dashed lines.
Only a single overall rate could be determined in segments 8-12.
All rates in cm/yr.
are; periods of erosion or non-deposition,
remobilization of the radionuclide, and
reworking the sediment by either physical
processes or biogenic activity. Radio-
nuclide derived sedimentation rates can only
be determined for fine grained sediments
which sorb the isotope, and results cannot
be extrapolated to adjacent sediments which
contain little or no silt and clay sized
particles. Because sandy bottom sediments
are areally extensive in the Chesapeake Bay
the calculated rates are probably not valid
for much of the system.
Some generalizations may be made from
examination of Figure 6. The rate of
sediment accumulation tends to be higher in
the northern portion of the Bay, north of
Kent Island, and close to the Potomac River.
In the central portion the lowest rates are
observed. Also, rates have a tendency to be
higher in the axial channel than on the
adjacent channel flanks. However, the range
of values observed even between cores
located close together indicates that in
this highly heterogeneous system, and
extrapolation of the results from an
individual core over wide areas of the
estuary is risky.
In an attempt to overcome the limitations
inherent in the radionuclide methodology
sedimentation rates for the mainstem of the
Bay have been determined by the method of
bathymetric comparisons, with the initial
Number
6
----1IIIIIIIL---....--.....-----.....--~- .............--.-~
_.~..•.•~
.... -
-~-
- ....
'
......
.
~,.
",
200 150 100 50 o
Distance from Bay Mouth (km)
data derived from Byrne and others (1982)
and Kerhin and others (1988). The
bathymetric comparison technique provides a
better overview of the sedimentation rates
than the nuclide dating because of its
ability to provide measurements in the sandy
sediments of the Bay, and the capability of
developing rate estimates which are
representative of large areas of the Bay
floor. Due to the nature of the data
available from the original sources the Bay
was divided into 12 segments based upon
basin morphology and bathymetry with the
averaged sedimentation rate determined
within each segment (Figure 7). In Maryland
the average rate of accumulation per year
was calculated for both the muddy and sandy
sediments within each segment. In Virginia
only an average sedimentation rate could be
calculated for each segment due to the
characteristics of the original data set.
The averaged rates shown on Figure 6 are
highest in the northern portion of the Bay,
decline to a low in the upper middle
reaches, and rise again in the vicinity of
the Bay mouth.
The highest sedimentation rate of nearly
0.8 cm/yr occurs in the muddy sediments of
the northernmost segment of the Bay (Figure
7). In this area suspended sediments
supplied by the Susquehanna River are
rapidly deposited on the Bay bottom forming
the mixed sand-silt-clays and clayey silts
T231: 8
shown on Figure 3. This section of the Bay
is very shallow where almost complete
infilling of the axial channel has occurred.
Rates decline southward through segments 2
and 3 to a minimum approaching zero in
segment 4. The sediment distribution map
(Figure 5) reflects this trend with a broad
expanse of silty clays present in segments 2
and 3 where sedimentation rates are still
relatively high. In segment 4 where rates
are low the sediment distribution begins to
show a more discontinuous and patchy nature
with many isolated pockets of relatively
coarse bottom sediments located in deep
waters where little modern sediment is
accumulating. Maximum depths increase
dramatically from segment 2, where the high
volume of sediment accumulated has filled
the axial channel to segment 4 where the
channel attains some of its greatest depths
(Figure 2). Rates rise again in segments 5
and 6, though the sediment distribution map
continues to show many isolated and
discontinuous sediment types and the axial
channel is quite deep. This suggests that
the sites of sediment accumulation are
localized in this area. Southward through
segment 7 to the Bay mouth rates are
variable but remain high reflecting the
increasing influence of both the Atlantic
coastal sediment source and resuspension due
to tidal currents and wind driven waves in
an area where the Bay is relatively wide.
The axial channel becomes discontinuous
across this area where tidal and wind driven
currents have deposited differing amounts of
fill during the Holocene. The modern tidal
channels of the Bay mouth are unrelated to
the Susquehanna River paleochannel (Colman
et al., 1985).
Trace Metals
Trace metals in environmental systems are
important because of their affect on the
health of plants, animals, and man (Bowen,
1966; Keith and Tilliard, 1979; Forstner and
Wittman, 1979), as indicators of sediment
transport (Eaton et al., 1980), and their
participation in redox processes (see
Garrels and Christ, 1965). The first
Baywide survey of the trace element
composition of the bottom sediments was
performed by Sinex and Helz (1981) and Sinex
et ale (1981). The samples analyzed were
200 surficial grab samples. Information on
trace metal variation as a function of depth
in the sediments was obtained by Cantillo
(1982) on 17 one-meter long cores, taken
throughout the main stem of the Bay.
Generally it was found that the variation
in trace metal content of the sediments can
T231: 9
be explained by a combination of three
factors (Cantillo, 1982). These factors, or
associations are:
1) Association with clay (AI, Ga, Cr and
C);
2) Association with heavy minerals (Ti,
Zr, and the Rare Earth Elements, and;
3) Association with oxyhydroxide grain
coatings (Fe, Mn, Ni, Cu, and Co).
The first two factors are directly
related to the sediment distribution
patterns; clay minerals are exclusively
found in the clay-sized grain fraction,
while the heavy minerals are found with the
coarser grained sediment. The oxyhydroxide
grain coatings, on the other hand, are
chemical precipitates, which are dependent
on the source of the material and the
depositional environment. The predominant
occurrence of this factor is in the area
north of the Choptank River, dependent on
the input from the Susquehanna River.
Figure 8 shows a north-south axial
transect of core samples taken along the
length of the Bay (adapted from Cantillo,
1982). The concentration of three metals,
representative of each of the factors, is
shown. Zirconium is representative of the
heavy mineral fraction; the highest
concentrations of this element are found in
the sandy southern portion of the Bay and
coarser sediments of the northernmost Bay.
Aluminum is the element representing the
clay association; the lowest levels are
found in the ~outhern Bay, while the highest
are found in the, upper middle Bay, where
clay pockets are found. The oxyhydroxide
grain coating association is best shown by
the concentration of Mn in the sediment, and
as mentioned previously the highest levels
are found proximal to the mouth of the
Susquehanna River.
Carbon and Sulfur Distributions
Organic carbon is an important component
of the estuarine system. Physically, it is a
binder that aids in the agglomeration of
suspended sediment (Zabawa, 1978).
Chemically, organic carbon is the primary
reduced chemical species which, through
bacterial action, depletes the sediments of
oxidized species thus producing the reduced,
anoxic state of the system.
The distribution of carbon in the
sediment varies in direct relation to the
proportion of clay-sized grain fraction
(Figure 9a). Concentrations of carbon'range
from 0 to 5%, corresponding to Sand to Clay
sediment types respectively. The major
exception to this behavior is in the
sediments found in the area north of the Bay
Bridge, shown in Figure 9b. In this area consideration of the chemical equilibria
reduced carbon concentrations are much involved, based on the parameters of Eh and
higher, reaching concentrations of 10.5%. pH (see Krumbein and Garrels, 1952), or upon
These high values have been attributed to the characteristic concentrations of
sewage, coal, and/or terrestrial carbon specific components (i.e. 02 or H2S) in the
input (Ryan, 1953; Folger, 1972b; Goldberg aqueous media associated with environments
et al., 1978; Helz et al., 1982; Spiker et of concern (Berner, 1981 a&b).
al ., 1982). It is believed currently that
these high carbon levels are attributable to (c:-
coal (Hennessee et al., 1984, Hill and ':Y~ ,C:-
~~
Halka, 1988). It is clear that the nature ~
?:}:> ":<::'~
of the carbon differs from the rest of the
Bay. This is indicated by o13C values and
c§
~ 05- ~~ ~Q.;
9.Q.
" Q-0
6)
Y..v

C/N ratios which differ from values ..::> "yo

characteristic for marine sources (Hunt,

1966; Shimoyama and Ponnamperuma, 1975; Helz
·· --- ..
•
-...
-w •••
10
et al., 1982; Spiker et al., 1982). · =: • :
Reduced sulfur found in sediments of the
Bay is a by-product of the oxidation of
reduced· carbon by S042- (Hennessee et al.,
1984). As such~ sulfur concentrations are
related to the concentration of carbon in
~ ..::20~:
..·· .. ...
..
. .:·0
200~ .•.
.. ·· .. . :,~
..
30

50
the sediment. This is shown in Figure 10,
· 20@·: :. -...
. ~
.:.
.:
:lOO
which depicts the average ratio of carbon to 70
sulfur proceeding from north to south. The
ratio is relatively uniform for most of the
Bay with the same value as modern marine 10
sediments. However, the northern Bay ~4
sediments show a markedly higher CiS ratio, E
30
one closer to freshwater ratios. In this 0

area carbon concentrations are quite high J:

even when the coal component is removed, the SO a.
l-

low concentrations of s~~fur are due to the lLI

a
low availability of S04 in the water column
(Hill, 1984; Hennessee et al., 1984). 70
Another feature to note about sulfur
chemistry is the distribution of sulfur .....
...
'

...
...
species in the sediment. In the northern .! : fO
Bay, north of 39° latitude, iron monosul- Q.5 :
fides are the dominant sulfur species. Their ...
...
concentration in the sediment is linearly .. . 30

related to the average overlying water

Mn :: .
..;:1
\j .•
column salinity (Hill, 1987). In the rest (p.g/g) j: 50
of the Bay pyrite tends to be the dominant x100 .:
sulfur species in the sediment, however the :~
speciation is more dependent on the local ......""--....-.."'"""--I-"'"---i.~....:....--" --'- 70
environmental conditions. o, zoo 300

KILOMETeRS FROtA THE MOUTH OF

INTERSTITIAL WATER CHEMISTRY TH£ SUSQUeHANNA RIVER

Interstitial water compositions are from Canti 110 (1983)

sensitive indicators of the chemical
reactions and transport mechanisms active in
sediments. This sensitivity of water
compositions has been used as the basis of FIGURE 8 North south transect of cores taken
methods for defining geochemical environ- along Bay axis showing the concentrations of
ments. These methods rely either upon zirconium, aluminum and manganese.

T231: 10
 18
8

m = 0.0368a
b = 0.249 15
c
8
r 0.917
0 UJ
..a "- 12
L. en
eo
U a .,./
'-
0
u 9
U 0 .......
·rl 0
C .r-f
eo
(J) a/O . .o... -+J
co 6
0
L. /
a:
2
~ 3

0
o
0 20 40 60 80 iOO
o 50 100 150 200 250 300

% Clay Distance From Susquehanna (km)

FIGURE 9a Plot of organic carbon as a FIGURE 10 Plot of the average organic carbon
function of clay in all samples south of to sulfur ratio as a function of distance
39°N. from the mouth of the Susquehanna River.

12

a
transport mechanisms active in the sediments
10 D a are non-equilibrium processes (Berner,
c e 1980). Equilibria in sediments which
o
..a involved r~dox s~~cies (such as dissolved
Fe, Mn, S2 ,C0
3 ,etc.) are secondary in
'- 8
CO
U
a
nature, working in tandem with the primary
u 6
o D
D
kinetically controlled reactions to provide
.r-f
c
a
the overall systems' conditions and reactive
eo chemical species. When equilibrium
~ 4 parameters, such as Eh, are used to define
o or describe a geochemical environment, it is
assumed the equilibria measured accurately
2 D
reflect the -major processes and reactions
occurring. This is seldom the case (Sayles
and Manheim, 1975; Stumm and Morgan, 1981).
Generally, because of the complexity of the
o 20 40 60 80 100 system, _it is difficult to define the
% Clay equilibria occurring in the sediment, and
more difficult to substantiate it by
FIGURE 9b Plot of organic carbon as a mineralogical corroboration (for related
function of clay in all samples north of discussion see Mackenzie et al~, 1979).
39°N. Table 2 shows the criteria which Berner uses
to distinguish between environments. These
criteria circumvents some of the problems
encountered in equilibria based classifica-
The classification scheme which relies on tion.
oxidant and metabolite concentrations has The primary kinetic reactions affecting
advantages over the equilibria based the redox conditions of the sediment are
classification. Major reactions and organic carbon degradation reactions. These

T231: 11
reactions require oxidants as terminal
electron acceptors. The sequence of
preference of oxidant is based on free
energy yield. Table 3 shows organic matter
decomposition reactions listing the oxidants
used in descending order of free energy
yield (Krumbein and Swart, 1983). Sulfate
reduction and methanogenesis (denoted by the
dashed line in the oxidant column) are the
two most important reactions occurring in
the sediments of the Bay. Generally, the
carbon rich sediments of the Bay are anoxic
just below the sediment water interface,
with sUlfate reduction commencing with the
0-2 cm interval.
Once sulfate is depleted from the
sediments methanogenesis is the primary
decomposition mode (see Claypool and Kaplan,
1974). Few direct measurements of CH4 have
been made in the Bay (Reeburgh, 1969;
Reeburgh and Heggie, 1974), though seismic
evidence indicates that methanogenesis is
wide-spread (Halka et al., 1988).
The other oxidants (02' Mn0 2 , N0 3 -, and
FeO(OH)) are consumed by organic matter
oxidation at the sediment-water interface in
organic rich sediments. However, these
oxidants may also be important in the very
carbon-poor sediments of the Bay, where the
reaction rates are lower than the rates of
oxidant transport into the sediment
(Froelich et al., 1979).
Parameters of interest are sulfate
(S042-) ion, sulfide species (HS-), and
amm~nium ion iNH4+). The sulfur species
(HS and S042 ) are important due to sulfate
reduction. Ammonium is used as an indicator
of bacterial action. In addition to these
species, two other parameters, iron (Fe 2+)
and Eh, relate to secondary, equilibrium
controlled reactions. A summary of the
behavior of these parameters is given in
Table 4.
The most significant aspect of the data,
summarized in Table 4, is the correspondence
of the chemical data with the major
influences in the Bay. Physiographically,
the Northern Bay is a shallow region
dominated by fluvial inputs. This is shown
in the pore water data by the seasonal
variation of the pore water data and the
abs~~ce of dissolved sulfide (due to low
S04 availability).
The middle Bay is dominated by the axial
channel and characterized by circulation and
salinity patterns indicative of estuarine
mixing processes. The upper Middle Bay has
distinguishing characteristics based on
sedimentation patterns, trace metal data,
and interstitial water data which indicate
this region represents the furthest extent
of the predominant influence of the
Susquehanna River. The chemical data show
that the upper middle Bay is transitional
between the highly variable, sulfide-free
northern Bay and the stable, sulfidic lower
middle Bay.
The Southern Bay is dominated by marine
tidal influences. In this high energy
setting, fine-grained material is winnowed
out, leaving coarser-grained, low-carbon
sediments. The low availability of carbon
is reflected by the limited extent of
s042-reduction, with the resulting lowered
level of dissolved sUlfide, and the absence
of NH 4+ .

TABLE 2 Classification of Geochemical Sedimentary Environments

(from Berner (1981))

Environment Characteristic Solid Phases

Hematite, geothite, Mn0 2-type minerals;

no organic matter

II. Anoxic (02~10-6M)

a) Sulfidic (H2ST~10-6M) Pyrite, marcasite, rhodochrosite,

alabanite; organic matter

b) Non-Sulf~giC
(H 2ST<10 M)

1) Post-Oxic Glauconite and other Fe++ -Fe+++ silicates

(also siderite, vivianite, rhodochrosite);
no sulfide minerals; minor organic matter

2) Methanic Siderite, vivianite, rhodochrosite; earlier

formed sulfide minerals; organic matter

T231: 12
 TABLE 3 A listing of the oxidants which react with organic matter in the sediment, in order
of decreasing free energy yield. Also listed are the associated metabolites
produced by the reactions.

Carbon Nitrogen Phosphorus Other

Organic Matter + Oxidant Species Species Species Species ~G(k J/mol)

02 ------------~ CO 2 HN0 3 -3190

Mn02 ----------~ CO 2 N2 H3 P04 Mn++ -3050

(CH20)'06(NH3)16(H3P04)+ HN0 3 ------~---~ CO 2 N2 , NH 3 H3 P0 4 -2750

FeOOH ---------~ CO 2 NH 3 H3 P04 Fe++ -1330

H2S04 ---------~ CO 2 NH 3 H3P04 H2 S - 380

---------~ CO 2 , CH4 NH 3 H3 P0 4 - 350

t-3
I'\)
w

LA> TABLE 4 Summary of the interstitial water data for the physiographic regions of the Bay.

Eh NH + %SOLl2- reduced pS2- Fe

Ll

Northern Bay most positive High (similar All cores >80% Below Detection Highest
(seasonally distributions
variable) each season)

Upper Middle Bay Transitional High (similar All cores >80% Broad Transi- High (Trans-
(seasonally distributions tional distri- itional)
variable) each season) bution

Lower Middle Bay most negative High (similar Variable Highest S2- Low
(seasonally distributions concentrations
stable) each season)

Upper Southern Bay Intermediate Below Detection Most cores <20% High S2- Low
concentrations

Lower Southern Bay Intermediate Below Detection All cores <20% Intermediate Intermediate
GOALS
We will examine three transects in the
upper mesohaline portion of the estuarine
system in the transitional area between
sulfidic and non-sulfidic environments. The
platform for this field trip is the Research
Vessel Discovery, operated by the Maryland
Geological Survey for the State of Maryland.
We will depart from Sandy Point State Park
located near Annapolis on the Chesapeake Bay
and steam to three sampling stations (Figure
2). One station is located to the north of
the Park in the upper mesohaline portion of
the Bay, and the other two are located to
the south in the middle mesohaline portion.
At each station an initial survey of the
area will be conducted by traversing the
sampling station and immediate vicinity
while towing a high-resolution acoustic
subbottom profiling system. Following
retrieval of the towed acoustic array, a
bottom core will be obtained using a gravity
type coring device. Examples of core X-rays
from each station will be exhibited during
the cruise. On the cores we collect, we
will examine physical characteristics
(color, texture, biogenic and physical
structure, smell, etc.) and measure Eh and
sulfide to show the geochemical environment
of the sediments.
The following sections outline the
principles of the techniques and measure-
ments that will be used during this trip.
Principles of High Resolution Acoustic
Profiling
High resolution acoustic reflection
profiles, also called subbottom profiles,
are produced through the generation of short
duration acoustic pulses from a device towed
behind the research vessel. Acoustic energy
reflected from the sea floor and subsurface
horizons is received, electronically
processed and sent to a graphic recorder
which produces a hard copy output. The
device which will be operated on this field
trip uses piezoelectric transducers carried
in a towable catamaran. Each transducer
produces a sound pulse at a specified
frequency and time interval and operates as
both the sending and receiving device for
the acoustic energy.
When these sound pUlses are produced the
acoustic energy spreads through the
transmitting medium (water or sediments) as
a compressional wave in a spherical fashion
from the point of generation. The speed
with which the sound propagates is dependent
upon the density and elastic properties of
the medium, and is virtually independent of
T231: 14
sound frequency. In water the speed of sound
approximates 1500 m/sec and varies as the
salinity, temperature and pressure cause
changes in the density of the water. For
shallow waters such as the Chesapeake Bay
changes due to pressure are negligible. The
speed of sound can range from a low of 1400
m/sec at OOC and 0 ppt salinity to 1535
m/sec at 30°C 25 ppt. In water saturated
shallow sediments the speed of sound
commonly ranges from the speed in water
upwards to 1700 m/sec. The relationship
between sound speed (V), frequency (f) and
wavelength (A) is determined by the
following equation:
V = A/f (1)
Because the transducer fixes the frequency
of the sound pulse, it follows that the
change in velocity which occurs as the sound
pulse passes from the water column to the
sediment results in a change in wavelength.
As the acoustic energy travels along the
transmission path it is attenuated by wave
front spreading (a function of the cube root
of the distance), absorption, scattering,
and reflection. Absorption occurs as the
passing wave front rearranges the molecules
in the transmitting medium producing heat.
Within the frequencies commonly utilized for
subbottom profiling absorption is greater
the higher the frequency. Scattering occurs
off of elements in the medium which have a
smaller size than the wavelength of the
sound. Reflection returns sound to the
transmitter producing images of the seafloor
and horizons in the sediments. Each
successive reflection reduces the amount of
energy available for transmission through
the medium.
Due to the attenuation the recorded
profiles will show a progressive decrease in
signal amplitude with time (depth) of the
recording. The attenuation can be partially
compensated for through the use of
time-varying electronic gain amplification
(TVG). Eventually the energy is reduced to
the point that no further amplification of
the returning acoustic energy will produce
an image. Because sound wave absorption is
much greater for the higher frequencies than
for the lower, the lower frequencies will
travel a greater distance and provide better
penetration of the subbottom sediments which
are water saturated. A 5.0 kHz signal will
commonly produce 20 to 35 meters of
penetration below the sediment water
interface although under ideal conditions
50-60 meters is achieved. In contrast the 27
kHz commonly produces a maximum of 8 meters
of penetration.
 When sound waves cross an interface,
where there is a change in the density of
the medium or a change in the speed of sound
or both, a certain amount of the acoustic
energy is reflected. The amount of energy
reflected is a function of the magnitude of
the difference in the density-velocity
product (termed the acoustic impedence)
across the boundary. This is expressed in
the following relationship:
PIVI-P2 V2
R =
Plvl+P2 v 2
where Px the bulk density of the medium,
V
x the velocity of sound in the
medium.
R is a dimensionless quantity ranging
from -1 to +1.
Using equation 2 and the following values,
an estimate of R can be made for various
interfaces encountered in the estuarine
environment.
MEDIUM VELOCITY DENSITY
(m/sec) (g/cc)
Air 330 0.0012
S~a water* 1500 1.025
Flne*sand 1660 1.96
Clay 1452 1.28
* data from Anderson and Hampton, 1980
INTERFACE CALCULATED R
Air/sea water 0.999
Sea water/fine sand 0.358
Sea water/clay 0.094
Fine sand/clay 0.273
The air/sea interface is one of the
strongest acoustic reflectors in nature.
This accounts for the fact that reflected
energy returning from the sea floor or the
subsurface reflectors is re-reflected back
down from the sea surface causing multiples
in the subbottom records. It also should be
noted that while the sand/water and
sand/clay interfaces have strong reflec-
tivities the water/clay interface has a
significantly lower ability to reflect the
acoustic energy. Both of these effects will
be shown in the records collected during the
field trip. Also note that the sound
velocity measured in clayey sediments is
lower than that of the overlying water. This
effect may, in part, be due to the presence
of gas voids in the fine sediments which
further confounds the stratigraphic
interpretation of the records, although it
provides information on the geochemical
processes operating in the sediments.
The ability to resolve horizons within
the bottom is dependent upon the relation-
ship between the wavelength of the sound and
the thickness of the horizon. Theoretically
resolution is limited to one~quarter
wavelength, however, in practice 0.33 - 0.5
wavelength is the best that can be achieved
(Trabant, 1984). The theoretical resolution
for a 5.0 kHz signal is 0.075 m; practi-
cally, the limit is 0.15 m (15 cm).
Similarly, the 27 kHz signal can resolve at
(2) a practical limit of 0.28 m (2.8 em).
Through this method a continuous record
of the seafloor and subsurface horizons is
produced along the travel path of the
vessel. Stratigraphic interpretations can be
made although no direct determinations of
lithology are possible because acoustic
reflection profiling is a remote sensing
technique. However, equivocal inferences of
lithology are possible given a knowledge of
basin processes and experience with the
characteristics of the acoustic reflections.
Lithologic interpretations can, of course,
be confirmed or refuted through the
collection of bottom cores. The combination
of remotely sensed acoustic data and site
specific core collection provides a powerfUl
technique for arriving at a greater
understanding of the subsurface geology of
an area. Due to the heterogeneity of the
estuarine system, we always collect and
interpret acoustic data before identifying a
coring location to insure that the core
location chosen is representative of the
local stratigraphic environment. This is the
case whether the core is collected for
geochemical, biological, or lithologic
studies.
Electrode Measurements
The most rapid and least labor intensive
chemical measurements which can be performed
on pore fluids are electrochemical
measurements. Eh, pH, and pS2- are the
three chemical parameters which are often
measured routinely by electrochemical
techniques. Within the sediments of the Bay
pH changes very little. The sediments are a
highly buffered system with an average pH of
7.25 (based on an arithmetic average of a H+)
and a range between 7.00-7.93, throughout
the Bay. Thus within the limited area of
this field trip pH will not be measured.
Emphasis will be placed on examining the Eh
and pS2- variations at two sites in the Bay.
Oxidation potential (Eh). Eh is a measure
of the overall oxidation potential of a
system as referenced to the standard
hydrogen electrode. It has been used as the
T231: 15
basis for discerning geochemical environ-
ments (Garrels and Christ, 1965). The
boundary between oxic and anoxic environ-
ments is defined at an Eh of zero (Krumbein
and Garrels, 1952; Jorgensen, 1977).
Field measurements of Eh are made by
using noble metal electrodes (such as Pt or
Au) which, in theory, are non-reactive and
provide good electrical contact between the
solution and the reference electrode. These
measurements should not interfere with the
chemical system in the solution. Thus, the
resulting measured potential difference
between the solution and reference electrode
should reflect the electrochemical potential
of the redox reactions occurring in the
solution. In practice, however, this is not
always the case (see Stumm, 1966; Berner,
1981). Some of the difficulties encountered
in the use of noble metal electrodes are:
1) The noble metal electrode influences
the system by reacting with the
solution, either by providing sites
that catalyze reactions in the
solution or by the metal itself
reacting;
2) The current induced by the electrodes
can alter the chemistry of the
solution where low levels of
electroactive species are present.
This produces drifting, unstable
readings, and;
3) Many redox species in natural systems
are not electroactive, i.e. will not
readily transfer electrons with the
noble metal electrodes.
Eh can be valuable, however, as a relative
indicator (Troup, 1974). The more positive
the Eh, the more oXidizing the system and,
conversely, the more negative the Eh
potential, the more reducing the system.
The measured electrochemical potential of
any redox reaction can be written according
to the Nernst Equation as follows:
For the reversible reaction,
aA + bB •.• ~ cC + dD •••• + ne-
The measured potential, E, is;
E = EO + RT 1n Q - Ref
nF
where:
EO - is the oxidation half cell of
the reaction where all
substances are at standard
state.
R - is the gas constant
T - is the temperature (OK)
n - the number of electrons
transferred in the reaction
F - is Faraday's constant
Q - is the reaction quotient
d c (5)
anac ·· .
Q
a a
aAa B •• •
where:
a Aa activity of the A species to
the a power.
Ref - is the reference potential
against which the reaction is
measured.
Eh is defined as the electrochemical
potential referenced to the standard
hydrogen electrode (SHE = Ref = 0 mV).
Therefore Eh is:
Eh = EO + RT 1n Q (6)
nF
In practice the SHE can not be used in the
field because it is extremely cumbersome.
The other more commonly used reference
electrodes are the silver-silver chloride
electrode (222.2 mV relative to the SHE) and
the calomel electrode (244.4 mV relative to
the SHE). The measured potential in the
field must be corrected for this additional
potential. For example, at the theoretical
oxic-anoxic boundary (Eh=O) using a Pt
electrode and a Ag/AgCI reference (the
reference utilized on this trip), the
measured potential would be -222.2 mV.
Sulfide (S2-). The measurement of S2- in
environmental conditions is a specific
application of the Nernst Equation
(Equation (4)). The electrode used is a
solid state ion selective electrode (ISE)
made of Ag 2S. The reaction at the electrode
surface is:
or,
(4)
E (8)
where - the activity of Ag and Ag 2S both
are assumed to equal 1.
Thus the measured potential is directly
T231: 16
related to the activity of the sulfide ion
concentration in solution. c:
o
Fi~~re 11 shows a calibration curve of .,...... 8
+J
the S ISE as a function of measured mV, co
using a Ag/AgCl reference electrode. Noted L
+J
on the curve is the boundary used by Berner c:
(1981 a&b) to separate non-sulfidic from ~6--------
sulfidic environments. c:
o
An interestin~_apPlication on the use of u
the Pt and the S ISE can yield unique W
environmental information. This method is TI
.,......
4
based on the presence of elemental sulfur 4-
(so)/S2- couple in the system. The presence ,.....-t
:::::J
of this half-cell has been noted in other
estuarine and marine sediments (see Sweeney,
1972). The half-cell reaction for this
couple is written:
~2/
o
r-
508 mV (9)
o01 0 L......L.---L...-L..-..L-L-...L---L---L-~...L.-....L.-.L..-J.--L---L..--L--I--..L..--IL--I--L..--&......01

The Nernst expression for Eh and for the S 2-

--J -650 -600 -550 -500 -450
I
ISE is written as follows: Su 1 f ide Measurement (mV)
FIGURE 11 Calibration curve of the sulfide
= E ° 5°/5 2 - - RT (5 2 -)
Eh 2F 1 n (10)
electrode; plot of log of total sulfide
concentration vs. measured millivolts. The
boundary between sulfidic and non-sulfidic
environments is shown by the dashed line.

the major influence controlling delta. This

The difference (~; delta) between these two
expressions is the ~ifference in the
electrochemical potential of the cells; the
dependency on the sulfide ion cancels out.
~ = EO so / S2 - - EO Ag/Ag2S
The va~ue of delta is -227 mV for HS (H 2S
and S2 species are not significant at
interstitial water pH values).
The data from the Bay can be grouped into
three millivolt ranges, allowing for ±50 mV
error around specific values. The first
range is +65 to -85 mV; empirically the data
show that in very low salinity conditions,
and in situations where active methano-
genesis is occurring, delta is equal to
zero; i.e. the sulfide electrode acts like
the Pt electrode (Hill et al., 1988). This
occurs generally where there is a strong
influence of freshwater, for example in the
northern Bay and dimninishing down-Bay.
The second range is -180 to-280 mV, the
range for elemental sulfur. Most of the data
falls within this range, however the
distribution of data is broad in the
northern and southern Bay regions. The
northern Bay distribution of data is bimodal
reflecting freshwater input and elemental
sulfur equilibrium. The southern Bay data
is spread to the more negative values of
delta; this will be discussed in the next
range. Equilibrium with elemental sulfur is
is important not only to reactions which
require elemental sulfur (e.g. pyrite
formation), but it indicates the geochemical
stability of the system. The redox state of
the system is buffered to some extent by
( 12) elemental sulfur.
The third range consists of samples with
delta more negative than -285 mV. Samples
which fall into this range have Eh values
more positive than the sulfide concentra-
tions should produce. The Eh readings of
these samples generally drift, indicating
very low concentrations of electroactive
species. These samples are found
predominantly in the Southern Bay. These
values are consistent with the slow rate of
S04 2 - reduction in the~e regions, as
indicated by the %S04 2 reduced and the
lower concentrations of NH4+. Sediments in
these regions are relatively the least
poised with respect to the redox state of
the sediment.
Color Banding
It has long been noticed that color
banding in sediment occurs in semi-euxinic
basins such as the Chesapeake Bay (see
Biggs, 1967). This banding is a chemical
imprint in the sediment which can cross
physical structures, and is unstable on
exposure to air. The color of the bands,
which ranges from a light gray to jet black,

T231: 17
is related to the sulfur chemistry, hence
the biogeochemical environment of the
sediments. Commonly in organic rich coastal
and marine sediments the color of the
sediment is black in the upper sediment
grading downward into a light gray. This
color change reflects the formation of acid
volatile iron sulfides (AVS), the sulfur in
these minerals is primarily in the -2
oxidation state at the surface, which is
converted through time to pyrite (Berner,
1967). The overall reactions occurring in
the sediments are:
Fe 2+ + HS e FeS + H+
(black)
FeS + So e FeS 2 (14)
(light gray)
In these reactions the source of sulfur
species (HS- and SO) is from sulfate
reduction (see Table 3); elemental sulfur
(SO) is formed from mild oxidation of HS-
which can occur via several pathways. The
reduced iron (Fe 2+) forms either by
reduction of goethite directly by iron
reducing bacteria or by reaction with HS-.
Although the mechanisms which produce color
banding is currently unknown, it would be
expected that the banding results from
oscillations between which of the reactions
dominate.
Reaction (14) is limited by the
availability of sulfur. This limitation is
reflected in the linear dependence of the
FeS fraction of the total inorganic sulfur
content on the mean water column sulfate
concentrations in the northern Bay (Hill,
1987). Variations in freshwater flow may be
a significant factor in the northern and
upper middle Bay in controlling color band
formation. However sulfur availability is
substantially greater in the lower middle
and upper southern Bay, so that water column
hypoxia/anoxia may be the principal
environmental factor effecting the sulfur
chemistry in the surficial sediments. As
the surficial sediments are buried,
mono-sulfides are subject to conversion to
pyrite. This conversion will continue until
the sediment is buried deep enough to be
removed from the source of sUlfur, into the
region of methanogenesis. It might be
expected that the banding which enters the
methanic zone would be preserved as long as
transport through the sediment is limited.
T231: 18
REFERENCES
Anderson, Aubrey L. and Lloyd D. Hampton,
1980, Acoustics of gas-bearing sediments
1. Background: Jour. Acoustic Soc. Amer.,
v. 67, pp. 1865-1889.
Berner, R.A., 1967, Diagenesis of iron
sulfide in Recent marine sediments. (in)
Estuaries, (AAAS), pp. 268-272.
Berner, R.A., 1970, Sedimentary pyrite
formation. Am. Journal Sci., v. 258, pp.
1-23.
Berner, R.A., 1980, Early Diagenesis: A
Theoretical Approach, Princeton Series in
Geochemistry, Princeton University Press,
241 pp.
Berner, R.A., 1981a, Authigenic mineral
formation resulting from organic matter
decomposition in modern sediments.
Fortschr. Miner., v. 59(1), pp. 117-135.
Berner, R.A., 1981b, A new geochemical
classification of sedimentary environ-
ments, Journal Sed. Pet., v. 51, pp.
359-365.
Biggs, R.B., 1967, Sediments of the
Chesapeake Bay. (in) Lauff G.H.,
Estuaries, Publication #83, American
Association for the Advancement of
Science: Washington, D.C., pp. 239-260.
Bowen, H.J.M., 1966, Trace Elements in
Biochemistry, Academic Press.
Byrne, R.S., Hobbs, C.H., and Carron, M.J.,
1982, Baseline sediment studies to
determine distribution, physical
properties, sedimentation budgets, and
rates in the Virginia portion of the
Chesapeake Bay. Virginia Institute of
Marine Science, Final Report to the U.S.
Environmental Protection Agency, 155 pp.
Cantillo, A.Y., 1982, Trace element
deposition histories in the Chesapeake
Bay. Unpubl. Ph.D. Thesis, Chemistry
Dept., University of Maryland, College
Park, MD, 298 pp.
Claypool, G. and Kaplan, I.R., 1974, The
origin and distribution of methane in
marine seidments. (in) Natural Gases in
Marine Sediments (ed. Kaplan, I.R.),
Plenum, NY, pp. 99-139.
Colman, S.M., C.H. Hobbs III, and J.P.
Halka, 1985, Late Quaternary History of
Southern Chesapeake Bay: Geol. Soc. Amer.
Abst. with Programs, v. 17, p. 551.
Eaton, A., Grant, V., and Gross, M.G., 1980,
Chemical tracers for particle transport in
the Chesapeake Bay. Est. Coastal Mar.
Sci., v. 10, pp. 75-83.
Folger, D.W., 1972a, Characteristics of
estuarine sediments of the United States.
Geological Survey Professional Paper 742,
94 pp.
is related to the sulfur chemistry, hence
the biogeochemical environment of the
sediments. Commonly in organic rich coastal
and marine sediments the color of the
sediment is black in the upper sediment
grading downward into a light gray. This
color change reflects the formation of acid
volatile iron sulfides (AVS), the sulfur in
these minerals is primarily in the -2
oxidation state at the surface, which is
converted through time to pyrite (Berner,
1967). The overall reactions occurring in
the sediments are:
Fe 2+ + HS e FeS + H+
(black)
FeS + So e FeS 2 (14)
(light gray)
In these reactions the source of sulfur
species (HS- and SO) is from sulfate
reduction (see Table 3); elemental sulfur
(SO) is formed from mild oxidation of HS-
which can occur via several pathways. The
reduced iron (Fe 2+) forms either by
reduction of goethite directly by iron
reducing bacteria or by reaction with HS-.
Although the mechanisms which produce color
banding is currently unknown, it would be
expected that the banding results from
oscillations between which of the reactions
dominate.
Reaction (14) is limited by the
availability of sulfur. This limitation is
reflected in the linear dependence of the
FeS fraction of the total inorganic sulfur
content on the mean water column sulfate
concentrations in the northern Bay (Hill,
1987). Variations in freshwater flow may be
a significant factor in the northern and
upper middle Bay in controlling color band
formation. However sulfur availability is
substantially greater in the lower middle
and upper southern Bay, so that water column
hypoxia/anoxia may be the principal
environmental factor effecting the sulfur
chemistry in the surficial sediments. As
the surficial sediments are buried,
mono-sulfides are subject to conversion to
pyrite. This conversion will continue until
the sediment is buried deep enough to be
removed from the source of sUlfur, into the
region of methanogenesis. It might be
expected that the banding which enters the
methanic zone would be preserved as long as
transport through the sediment is limited.
T231: 18
REFERENCES
Anderson, Aubrey L. and Lloyd D. Hampton,
1980, Acoustics of gas-bearing sediments
1. Background: Jour. Acoustic Soc. Amer.,
v. 67, pp. 1865-1889.
Berner, R.A., 1967, Diagenesis of iron
sulfide in Recent marine sediments. (in)
Estuaries, (AAAS), pp. 268-272.
Berner, R.A., 1970, Sedimentary pyrite
formation. Am. Journal Sci., v. 258, pp.
1-23.
Berner, R.A., 1980, Early Diagenesis: A
Theoretical Approach, Princeton Series in
Geochemistry, Princeton University Press,
241 pp.
Berner, R.A., 1981a, Authigenic mineral
formation resulting from organic matter
decomposition in modern sediments.
Fortschr. Miner., v. 59(1), pp. 117-135.
Berner, R.A., 1981b, A new geochemical
classification of sedimentary environ-
ments, Journal Sed. Pet., v. 51, pp.
359-365.
Biggs, R.B., 1967, Sediments of the
Chesapeake Bay. (in) Lauff G.H.,
Estuaries, Publication #83, American
Association for the Advancement of
Science: Washington, D.C., pp. 239-260.
Bowen, H.J.M., 1966, Trace Elements in
Biochemistry, Academic Press.
Byrne, R.S., Hobbs, C.H., and Carron, M.J.,
1982, Baseline sediment studies to
determine distribution, physical
properties, sedimentation budgets, and
rates in the Virginia portion of the
Chesapeake Bay. Virginia Institute of
Marine Science, Final Report to the U.S.
Environmental Protection Agency, 155 pp.
Cantillo, A.Y., 1982, Trace element
deposition histories in the Chesapeake
Bay. Unpubl. Ph.D. Thesis, Chemistry
Dept., University of Maryland, College
Park, MD, 298 pp.
Claypool, G. and Kaplan, I.R., 1974, The
origin and distribution of methane in
marine seidments. (in) Natural Gases in
Marine Sediments (ed. Kaplan, I.R.),
Plenum, NY, pp. 99-139.
Colman, S.M., C.H. Hobbs III, and J.P.
Halka, 1985, Late Quaternary History of
Southern Chesapeake Bay: Geol. Soc. Amer.
Abst. with Programs, v. 17, p. 551.
Eaton, A., Grant, V., and Gross, M.G., 1980,
Chemical tracers for particle transport in
the Chesapeake Bay. Est. Coastal Mar.
Sci., v. 10, pp. 75-83.
Folger, D.W., 1972a, Characteristics of
estuarine sediments of the United States.
Geological Survey Professional Paper 742,
94 pp.