Biogeochemistry 10: 237-255, 1990

1990 Kluwer Academic Publishers. Printedin the Netherlands

Radium in the Suwannee River and Estuary

Spring and river input to the Gulf of Mexico
WILLIAM C. BURNETT,' JAMES B. COWART 2 &
SUCHINT DEETAE 3
'Dept. of Oceanography, Florida State University, Tallahassee, FL 32306; USA; 2 Dept. of
Geology, Florida State University, Tallahassee, FL 32306; U.S.A.; 3Dept. of Marine
Science, Faculty of Fisheries, Kasetsart University, Bangkok, Thailand

Key words: radium, Suwannee River, Gulf of Mexico, submarine springs, isotopes, Florida
Abstract. A two-year study of radium in the Suwannee River has shown that groundwater
discharge, via springs, is a very important source of radium both to the river and to offshore
Gulf of Mexico waters. Dissolved radium is maintained within relatively narrow limits in the
river by uptake into suspended particles. In the estuary, dissolved radium versus salinity
profiles show distinctive nonconservative behavior with radium in significant excess of its
linear mixing value at mid-salinities. Unlike the situation in many other estuaries, however,
desorption of radium from particles cannot account for most of the observed excess. Thus, the
anomalously high radium characteristic of much of the west Florida shelf apparently does not
have a riverine source. Direct effusion of high-radium groundwater into these coastal waters
is thought to be the major supplier of radium, and perhaps other elements as well.

Introduction
The principal delivery pathways of uranium-series isotopes to the oceans
are: atmospheric deposition, river runoff, and in situ production in ocean
water (Krishnaswami & Lal 1982). In the case of radium, there appears to
be two significant pathways, river input and diffusion from bottom sediments (Cochran 1982). In some situations, it is possible that other sources
are important as well. The waters of the west Florida shelf have been
documented as an area where 22 6Ra and 222Rn concentrations are in significant excess of their open-ocean values as well as having concentrations
higher than typical of other shelf areas (Fanning et al. 1982). These excess
values were attributed by Fanning and his colleagues to input of radium-rich
waters from rivers that drain the uranium-rich phosphatic strata of Florida.
A later study by the same group showed that the radium and radon enrichments extend far to the north of their original study area, including areas

238
which should not be influenced by the occurrence of phosphate mineralization (Fanning et al. 1987). The possibilities for radionuclide enrichment of
the shelf waters were thus limited to diffusion from bottom sediment and
direct discharge of groundwater into the waters of the continental shelf.
We have made a study of radium in the Suwannee River and estuary, one
of the most important rivers in Florida in terms of discharge and radium
input into the Gulf of Mexico. This paper summarizes the results of two
years of monthly sampling at seven stations in the river and several sampling
profiles within the estuary. Our study included measurements of particulate
as well as soluble radium, thus allowing us to evaluate the contribution of
not only the 'river-borne radium', but 'desorbed-radium' as well. Our results
will show that although desorption of radium apparently does occur within
the estuary, it is insufficient to account for the high concentrations found in
the offshore waters. We conclude, based on this evidence, and the nature of
the offshore sediment, that the only plausible source for the excess radium
in this area is from submarine springs and seeps. If this is the case in the
other offshore areas around Florida, as we suspect that it is, the direct
effusion of groundwater into nearshore waters may constitute an important
source, not only of radionuclides, but of several other classes of elements as
well. Uranium-series isotopes, therefore, may be useful tracers of the influence of groundwater on the coastal ocean.

Radium in ground and surface waters

The occurrence of radium isotopes in natural waters is a function of the
content of their parents in the host matrix, the geochemistry of radium and
its parent isotopes, and the half-lives of the various radium isotopes. When
the aquifer matrix is weathered and leached by groundwater, uranium and
radium can be readily mobilized, transported, and deposited quite far from
their source. Radium may enter groundwater more readily than its radioactive parents, uranium and thorium, due to chemical and crystallographic
differences between these radionuclides.
The mechanisms that cause radium to enter groundwater are:
- dissolution of aquifer solids;
- direct alpha recoil across the solid-liquid boundaries during its formation by radioactive decay; and
- by desorption from particle surfaces.
The alpha recoil process is a prime factor in the higher activity of progeny
isotopes compared with their parents (Osmond & Cowart 1982; Hess et al.

239
1985). The transport of radium is apparently retarded, however, by adsorption onto aquifer surfaces. For example, in spite of the much longer half-life
of 226Ra (1620 years), the transport distance of this isotope is usually
considerably shorter than its daughter, 222 Rn, with a half-life of only 3.8 days
(King et al. 1982). Radium removal from waters of Connecticut aquifers was
shown to be rapid, as short as a few minutes, with equilibrium between
adsorption and desorption being quickly established (Krishnaswami et al.
1982). Although the partition coefficient of radium in normal aquifer conditions strongly favors the solid phase, groundwater generally has radium
concentrations several times to orders of magnitude higher than surface
waters and seawater.
Groundwater in central and north Florida has been reported as having a
total range of 0.1-200dpmL - ' 22 6Ra (Irwin & Hutchinson 1976). The
geometric mean of 22 6Ra in groundwater outside the central Florida mining
district has been reported at about 2dpmL - ', several times the U.S.
geometric mean of 0.3dpmL-' (Kaufman & Bliss 1977). Within the
phosphate area, the values are higher yet, with a range of 3.3-33 dpm L - '.
The high activity of 226 Ra in central Florida groundwaters has been
attributed by Humphreys (1984) as due to secondary accumulation of
uranium within the aquifer and to the high content of total dissolved solids
in those waters.
The data available for radium in river water suggest that activities are
normally less than about 0.1 dpmL- ' (Rona & Urry 1952; Moore 1967;
Bhat & Krishnaswami 1969). A compilation of previously published data on
radium in world rivers, including several of those which discharge into the
Gulf of Mexico (Scott 1982), showed that rivers which drain arid areas (Rio
Grande and Pecos), or traverse uranium-enriched matrix strata (South
Texas rivers), and phosphate deposits (Suwannee River), are enriched in
radium 2 to 3 times the world average. Our study of the Suwannee River,
reported here and in more detail in Deetae (1986) and Deetae & Burnett
(1987), suggests that while radium in the river is indeed high, there is no
direct relationship to surface drainage of the phosphate deposits.

Hydrogeology of the Suwannee River and estuary system

The Suwannee River is the second largest river in Florida (Fig. 1) with an
average flow of about 311 m3 s- ' to the Gulf of Mexico (Kenner et al. 1975).
As one of the few remaining free-flowing rivers in the southeastern United
States, the Suwannee is still relatively pristine because of the generally
undeveloped nature of its drainage basin (FDER 1985). The river originates

240

,f
O0

Coc

WIDTH OF DOTTED RIBBON SHOWS

AVERAGE STREAM FLOW

FrTf
Kin.
40 80

Fig. 1. Major Florida rivers which drain into the Gulf of Mexico. All of these rivers were
sampled and analyzed for 226Ra during this study.

in the Okefenokee Swamp in southern Georgia and flows southward to the

Gulf of Mexico with a river length of approximately 380 km. The primary
economy within the drainage basin is agriculture although a significant portion of the work force is also involved in construction, mining, and manufacturing (FDER 1985). One of the largest phosphate mining and processing complexes in Florida is located near the banks of the northern part of the Suwannee
River in Hamilton County. Two of our river stations were located just
upstream and downstream of the principal drainage from these operations.
The flow of the Suwannee River increases systematically downstream,
being fed by three tributaries (Alapaha, Withlacoochee, and Santa Fe
Rivers) and a series of at least 50 springs. The largest of these springs are
represented by 9 first magnitude springs, each having an average discharge
greater than 2.8m 3 s - ' (100 cubic feet per second). These springs act as a
direct connection between underground aquifers and the Suwannee River
(Rosenau et al. 1977). By the time the waters of the river reach the Gulf of
Mexico, a very significant fraction has been contributed via spring input.

241
South of the Okefenokee Swamp, Suwannee River water is acidic, soft,
and tea-colored as it flows into Florida. Up until the approximate location
of White Springs, Florida, the river is superimposed on thick (up to 100 m)
Miocene deposits of sandy clay, clayey sand (including phosphorite), sandstone and limestone. The flow for this upstream portion of the river is
essentially derived from surface runoff. Beginning at White Springs, the river
channel deepens, its banks become steeper and higher as it cuts into the
Suwannee Limestone of the Floridan aquifer. Between White Springs and
Ellaville, the Alapaha and Withlacoochee Rivers contribute about 15 and
24%, respectively, to the average flow. From this point downstream, the
Suwannee River receives significant amounts of spring water input although
during high stages, the river water may provide direct recharge to the
Floridan aquifer. Below Ellaville, the river enters a region of thin sandy soil
overlying the Ocala Limestone, also part of the Floridan aquifer. This region
is characterized by low relief, few tributaries and increasingly numerous
springs that significantly change the flow and quality of the river water. Near
the town of Branford, the river channel broadens between low, marshy
banks, typical of the river from this point to the Gulf of Mexico. The third
major tributary, the Santa Fe River, enters the river approximately 16 km
below Branford and contributes about 15% of its flow. Manatee Springs,
the last first magnitude spring which contributes to the Suwannee River, is
located about 37 km from the Gulf of Mexico. At the river mouth, the river
separates into two main channels (East and West Pass) and the river enters
the Gulf of Mexico through these channels and numerous tidal creeks.

Methods
In the river portion of this study, water samples were collected just under the
surface at fixed station locations (Fig. 2) which were part of a sampling
network for a two-year environmental assessment of the river by the State
of Florida (FDER 1985). Samples were collected at all stations on a monthly
basis for two years beginning in January, 1982. For estuarine samples,
collection was based on the prevailing salinity gradient. A hand-held refractometer and a portable inductive salinometer were used to measure the
salinity in the field. More precise analyses of salinity were performed later
in the laboratory.
River samples (about 20 liters for 226Ra analysis) were returned to the
laboratory the same day as collected and each sample was filtered through
three in-line filters consisting of a Whatman glass microfiber (934-AH),
GF/F, and Millipore AA (0.45 #m), respectively. Filtering of the estuarine

242
.1

GEORGIA

WtE
S

* Major spring
o Other springs
0

10
i

20

Station number

~ 30'

Km

Fig. 2. Index map of the Suwannee River showing sampling stations and locations of known
springs.

samples followed a similar procedure but was performed in the field. All of
the particulate data in this study were derived from the combined amount
of particulate material remaining on all filters used during the filtering
process.
The activity of 2 26Ra was determined by three different techniques. Two
of these methods were based on the quantitative extraction of radium from
water by Mn-impregnated acrylic fiber. For samples from the January-May,
1982 sampling period, a slightly modified method based on gamma-counting
peaks of 22 6Ra daughters from a BaSO 4 precipitate was used (Michel et al.
1981; Kim & Burnett 1983). Although this method gave satisfactory results,
we found that processing time was reduced by collecting Mn-fibers as above,
and then sealing the still wet fibers in 125 ml Erlenmeyer flasks which were
later used for direct radon emanation after an appropriate ingrowth period
of about 3 weeks (Moore 1981).
The third method of 2 26Ra analysis, used for a few subsets of the samples

243
analyzed as above, was also based on randon emanation, but radon was
purged directly from the samples rather than from Mn-fiber. For these
'whole bottle' analyses, approximately 20 liters of unfiltered water were
sealed in large glass wine-making bottles and purged with helium to remove
any excess radon initially present. After about a 3-week ingrowth period, the
supported radon gas was purged, collected and loaded into a Lucas cell for
alpha scintillation counting. The 'whole bottle' measurements reported here
should include some particulate as well as soluble radium.

Results and discussion

Soluble and particulate radium in the river
The overall mean soluble 226Ra activity at all stations for the 2-year study
period was 22.4 + 8.4 dpm 100 L-'. No measurable change in radium concentration was observed at the stations located just upstream from and
downstream from the phosphate mining operations near White Springs.
Although there was no systematic trend with location, the upstream stations
did tend to be lower (18.9 dpm 100 L-' mean for stations upstream of White
Springs) compared to downstream locations (27.0 dpm 100 L-' mean for
stations south of Branford). This increase is probably due to the increased
importance of spring input further downstream. Radium analyses of several
of the first-magnitude springs which flow into the Suwannee River showed
that these springs contain relatively high 2 26Ra (Table 1). The concentrations
in these springs progressively increased in a downstream (southwest) direction as deeper aquifers become more important in supplying spring water to
the river. If this trend continues out onto the continental shelf, the waters
would be expected to be relatively rich in radium.
Since soluble radium in the Suwannee River is a consequence of mixing
of surface drainage (low radium) and spring water (high radium), variations
in radium activity related to discharge may be expected. In fact, although
there is some relationship (Fig. 3a), it is obviously not the only controlling
mechanism. We observed that radium concentrations remain in relatively
narrow limits even during extreme fluctuations of flow. The range in 22 6Ra
at station 6, for example, was 13.9 to 37.2dpm100L-', about a 3-fold
variation. Discharge at the same station during the same period varied by
well over 2 orders of magnitude. When plotted as a time-series diagram, the
data of station 6 appear to show a cyclicity with a period of approximately
6-7 months (Fig. 3b). High radium occurs in the early winter and summer,
while low values appear in the early spring and fall. The cycles are not

244
Table 1. Concentration of 226 Ra and discharge to the Suwannee River in first magnitude
springs measured during this study.

Blue
Falmouth
Troy
Ichetucknee
Fannin
Manatee

Flow
m3 s-1

Location

Spring

Lat
Long
Lat

30
83
30

28'
14'
21'

49"
40"
40"

N.
W.
N.

Long

830

08'

07"

W.

Lat

300

00'

21"

N.

Long

820

59'

51"

W.

Lat

290

59'

02"

N.

Long

82

45'

43"

W.

Lat
Long
Lat

29
82
29

35'
56'
29'

15"
08"
22"

N.
W.
N.

Long

82

58'

37"

W.

226

Ra
dpm 100 L-`

226Ra
Discharge
1010 dpm yr-

3.3

15.5 + 0.7

1.59

4.5

34.9 + 1.1

4.92

4.7

34.8 + 0.9

5.16

10.2

30.0 + 0.9

9.64

2.9

53.9 + 1.3

4.96

5.1

91.7 + 1.6

14.80

Total

41.10

obviously related to rainfall or discharge patterns in the drainage basin and

may be related to some other process.
Analysis of Suwannee River suspended particulates for 226 Ra showed
them to be quite high in radium from stations with a small amount of total
suspended sediment (Fig. 4). The fraction of radium contained in the
particulate, as opposed to the soluble fraction was fairly constant at all
stations, usually varying between 25-35%. Thus, the distribution of radium
between the soluble and particulate phases may be controlled by particle
interaction processes. The distribution coefficient, KD, shows that 226 Ra is
more favored in the solid phase by 0.5-1.5 x 105 compared to the solution
phase. Although we were unable to positively identify the solid phases in
these particulate samples because of diffuse X-ray diffraction patterns, it is
likely that the principal carrier phase for radium is a clay mineral with high
adsorption and/or ion-exchange capacities. The difficulties identifying and
analyzing the high-radium particulates were compounded by their very low
abundance, usually less than about 2-3 mg L-' in the down-stream locations.
A sample of sandy sediment recovered from the junction of the East and
West Passes at the mouth of the river was size fractionated by sieving
techniques and radiochemically analyzed. Results show that although the
fine (< 0.63p m) fraction constitutes a very small amount (0.06%) of the
total sediment, it is very concentrated in 226 Ra and 2 0Pb, having many times
the equilibrium activity of 238U (Fig. 5). This is internally consistent with the

245
fl

0
0
o

E
ct

C'

Nr

Discharge (m 3 /sec.)
'

b
0
0

gI

E
0
0

0
To

cu
c.

MONTHS
Fig. 3. (a) Dissolved 22 6Ra versus discharge at station 6 based on monthly sampling for two
years beginning January, 1982. (b) Time-series plot of same results as in (a).

river particulate data, and suggests that fine-grained particles are an important transport path of radium to the estuary. The activity of 226 Ra on
Suwannee River particulates are consistently greater than 10 dpm g-', and

246
346

E
O

c14

10

20

30

40

Suspended Load ( mg / I )
Fig. 4. Specific activity of 226Ra in suspended particles versus concentration of suspended
sediment in the Suwannee River. Results are for all stations collected in June, 1983 and July,
1984.

Sn
o

E
Q.

C
0

tL

<U

Size Class (m)

Fig. 5. Distribution of sediment mass and activities of 2 38U,

grain size in one sample of Suwannee River sediment.

22 6

Ra, and 2"0pb as a function of

247
is often considerably greater. This is high compared to an average activity
of only 3.4 dpm g-' in Mississippi River particles (Moore & Scott 1986) and
a range in the Amazon of 1.7-2.6dpmg-' (Dion 1983; Key et al. 1985).
However, the total amount of suspended material is far less in the
Suwannee, thus diminishing the overall effect of these particles as radium
transporters to the Gulf of Mexico.
All major Florida rivers that drain into the Gulf of Mexico (Fig. 1) were
sampled in May, 1986 and analyzed for soluble and particulate radium
(Table 2). These results show that rivers in Northwest Florida (Escambia,
Choctawhatchee, Apalachicola, and Ochlockonee) have low concentrations
of radium compared to those found in central and southwest Florida. This
is most likely a consequence of the higher contribution of springs to the flow
of the central and southern rivers although the presence of high-grade
phosphate ore in the region may be important in some cases.
Crude estimates of the radium discharge to the Gulf of Mexico for all the
rivers of Table 2 show that the Suwannee has the highest radium flux of the
rivers investigated. The Suwannee alone accounts for about 25% of the
riverine radium flux to the Gulf of Mexico from Florida. All Florida rivers
contribute an estimated 1.5 x 10t 3dpmyr- ' compared to about
3.1 x 1014dpmyr-' for the Mississippi River alone (Moore & Scott 1986).
In spite of this lesser input, radium concentrations are much higher on the
west Florida shelf than elsewhere (Fanning et al. 1982). Reasonable sources
for this excess radium include release from particles entering the Gulf,
diffusion from bottom sediments, and direct effusion of waters enriched in
radium via submarine springs and seeps.
Radium entry into the estuary
During our study, five sampling trips were made to the Suwannee estuary.
In addition, one profile was made for the estuary of the Ochlockonee River,
another coastal plain river in Northwest Florida (Fig. 1). When dissolved
(filtered Mn fiber) 22 6Ra is plotted against salinity, typical nonconservative
profiles result in most cases (Fig. 6). The only exceptions are the March and
June, 1983 profiles which show apparent conservative behavior. These
samplings were made during periods of relatively high discharge. A radium
maximum, if it does occur during these periods, may be located further
offshore. Conservative mixing curves were also observed in the Pee Dee
River-Estuary during a period of high discharge by Elsinger & Moore
(1980). Most of our profiles are similar to those observed in other estuaries
except that the maximum 22 6Ra concentrations are much higher, up to
125 dpm 100 L- '. The high concentrations are in agreement, however, with

248
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249
120 March

December 2, 1982

3, 1983

80
/

143
m3/! sec.

40

-j

612
m3/sec.

K.

120
120
October 6-9, 1983

June 22, 1983

0
0

m'sec88
m
3/sec.

80

173
3
m /sec.

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0.

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~Z~J
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fn
120

OCHLOCKONEE RIVER ESTUARY

January 4, 1984

July 10-12, 1984

286
3
m /sec.

80
.

_ A

40

10

20

I
30

10

20

30

Salinity (%.)
Fig. 6. Dissolved 226Ra versus salinity in the Suwannee River estuary for five sampling periods
and one profile of the Ochlockonee River estuary. The discharge, measured at the most
downstream station, is given for each Suwannee profile. Triangles represent stations located
in the East Pass while circles represent the West Pass portion of the estuary.

the observations of Fanning et al. (1982, 1987) of high radium in the waters
of the west Florida shelf.
The question we would like to examine here is the source of this radium.
Specifically, can the 'excess' radium observed in the Suwannee River estuary be
explained by desorption of 226Ra from particles entering the Gulf of Mexico?
This argument has been successfully applied to the study of radium in several
estuaries including the Pee Dee, Hudson, Amazon, and Mississippi Rivers (Elsinger & Moore 1980; Li & Chan 1979; Key et al. 1985; Moore & Scott 1986).
Basically, the concept states that radiumoccupying particle adsorption and/or
ion exchange sites will exchange with divalent cations encountered upon entering the sea. Thus, an enrichment in dissolved 226Ra is observed and data points
occur above an ideal conservative mixing line when plotted against salinity.

250

E
C.
o

cJ
-o
0

(n
C')

Salinity (%o)
226

Fig. 7. Specific activity of Ra in particles collected from estuarine samples versus salinity for
all Suwannee River estuary profiles.

Upon initial examination, our results of particulate radium in the Suwannee estuary appear to support the desorption hypothesis as there is a
significant drop in the 226Ra specific activity through the estuary (Fig. 7). The
22 6Ra concentration on particles at 0%o salinity (located at the junction
of the
East and West Passes, where the sediment sample of Fig. 5 was collected)
was extremely variable with higher activities occurring when the concentration of particles was lowest. The offshore particulates were consistently
lower. Although these results support the desorption mechanism, we feel
that this is not the dominant process here because:
- most desorption apparently occurs at low salinities whereas maximum
22 6Ra in the salinity profiles occurs at higher values,
between 15-20%o;
- there are not sufficient river-borne particles to account for the excess
observed.
Suspended matter in the Suwannee River estuary increases with salinity, an
opposite trend compared to most rivers. The river-end member suspended
load is only about 4mgL- ', much lower than the 10's to 100's of mgL- `
observed in many of the world's rivers.
Dissolved radium in the Suwannee River estuary is a composite from
several sources:
- dissolved radium in the river;
- dissolved radium in seawater;
- desorbed radium from river-derived particles;
addition from diffusive flux from bottom sediments; and
- direct effusion of radium from submarine springs and seeps.

251
Table 3. Results and parameters used to calculate the relative amounts of dissolved and
desorbed radium from the Suwannee River to the Gulf of Mexico. The March sampling was
not used because of an incomplete profile.
Parameters

Units

20 Dec 82 22 Jun 83 6 Oct 83 10 Jul 84 Overall

(m3 s i)
(mg L- ')
(dpm 100L- ')

142.7
0.97

288.2
2.60

172.5
1.50

286.0
2.30

311.1
1.84

33.1
98.8
99.3

32.2
103.8
125.4

31.6
11.1
81.1

31.1
44.3
87.1

32.0
64.5
98.2

50.4
22.6
27.8
7.2

102.9
5.2
97.7

39.2
1.5
37.7

76.6
7.6
69.0

(dpm 100 L-1 )

114.0
1.2
112.8
10.9

14.7

8.7

12.7

Yearly Discharge
Dissolved river 226 Ra (1012dpmyr-')
Desorbed river 226Ra (1012dpmyr ')
Total river 226Ra
(1012 dpm yr-')

1.5
0.5
2.0

1.7
0.8
2.5

2.8
0.8
3.6

Flow rate
Sampling day
Suspended load
Dissolved 226 Ra
River end
Max. Sal. end
Max. Conc.
Suspended 226Ra
River end
Max. Sal. end
Desorbed
Desorbed 226Ra

(dpm g-)

2.9
0.7
3.6

3.1
1.3
4.4

We evaluated the desorbed radium contribution to the estuary by subtracting the radium concentrations measured for particulates collected at the
high salinity end of our profiles from those measured in the river. This
'desorbable' radium concentration is then multiplied by the suspended
sediment concentration to arrive at an amount of desorbed radium which
may be directly compared to the contribution of soluble radium from the
river, either as a concentration or a flux (Table 3). Although we have drawn
our trend lines in the estuarine profiles (Fig. 6) through the low and high
salinity ends of each profile, it is more informative to consider open Gulf of
Mexico 226 Ra concentrations as the potential seawater contributor. An
average of six outer shelf and open Gulf of Mexico values reported by
Moore and Scott is 12.6dpm 100L - ', much lower than the high salinity
ends of most of our estuarine profiles. With a typical maximum concentration of radium in the estuary of 98.2 dpm 100 L - ', and mixing between a
river end-member at 32.0dpmlOOL ' and a 12.6dpmlO0L - ' offshore
component, an additional input of approximately 60dpm100L - ' is
required. The radium desorbed from river-borne particulates can only account for about 20% of this excess.
When expressed as a flux, our estimates (Table 3) show that the total river

252
output (dissolved plus desorbed) of 226Ra varied from 2.0-3.6 x 10'2dpm
yr-'. An estimated long-term average of about 4.4 x 1012dpmyr -l ' is
higher because the river flow was generally below average during our study.
These calculations show that the contribution of desorbed radium to the
total river output is significant at about 20-30% of the total. However, this
is insufficient to account for the excess 22 6Ra measured in the estuary. The
only other reasonable sources for radium are diffusion from bottom sediments and/or input from direct groundwater discharge into the coastal zone.
The sediments in the Suwannee River estuary consist of quartz and carbonate sands and biogenic materials including oyster reefs. We have
analyzed several samples of this material and have found it to be uniformly
low (< 0.1 dpm/g 238U and 2 26Ra) in uranium-series nuclides. Diffusion from
this type of sediment would be negligible low compared to the required
fluxes. We conclude that the only reasonable source for the excess radium
measured in this estuary is from submarine springs and/or seeps which
discharge high-radium waters directly into the offshore waters in the vicinity
of the Suwannee River estuary.

Conclusions and implications

Study of spatial and temporal trends of dissolved and particulate radium in
the Suwannee River, springs that enter the river, and in the estuary show
that while interactions between suspended particles and dissolved radium is
significant, there is only a minor addition of radium from particles to
offshore waters. Thus, high radium waters in the Suwannee estuary and
offshore are largely the result of radium input from some other source, most
likely submarine springs or seeps. Thus, it seems very possible that the
anomalously high radium observed on the entire inner portion of the west
Florida shelf may be a result of a 'leaky' continental margin, with waters
from the Floridan and other aquifers supplying the excess radium.
Numerous submarine springs are known to occur on the west Florida
shelf. In fact, a map of the known submarine springs by Rosenau et al.
(1977) shows a concentration of springs occurs in the same two areas (off
northwest Florida and Tampa) where Fanning et al. (1987) documented
particularly high activities of near-bottom radium and radon. Conversations with other scientists as well as local fisherman and divers have convinced us that many more springs exist offshore than appear on Rosenau's
map. Assuming that the major portion of the excess radium observed in the
region is due to spring input, there must be important contributions of other
constituents as well. It is possible, for example, that these springs are an

253
important source of nutrients to the coastal ocean in this area. Detailed
study of a series of springs near 'Mudhole Springs' off Fort Myers, Florida
showed that these may contribute significant amounts of radium and radon
to the west Flordia shelf (Fanning et al. 1981). These particular springs,
however, were characterized by near marine salinities and a thermal
anomaly. Fanning and his co-workers concluded that they were dealing with
a recycled seawater hydrothermal system. Although radionuclides were
probably contributed from the bedrock, the fresh water aquifers of Florida
are apparently not directly involved in that case. It is not known if this type
of spring is typical of others on the west Florida shelf. Certainly many of the
springs mentioned in Rosenau et al. (1977) are known to be fresh water and
huge masses of fresh water have been documented as occurring under the
continental shelf under the southeastern United States. For example,
analysis of interstitial waters from the early JOIDES test holes, off Jacksonville, showed that a wedge of fresh water extends out approximately 120 km
from shore (Manheim 1967). It would be of interest, both from geochemical
and biogeochemical points of view, to investigate the elemental composition
of some of the fresh water springs on the Florida margin. Radionuclides
such as radium may serve as useful tracers of spring water input into the
ocean.
Acknowledgements
Much of the river and estuary sampling that this study is based upon was
accomplished using the R/V BELLOWS of the Florida Institute of Oceanography. Captain Millander and his crew were extremely helpful during
these cruises. The Suwannee River Water Management District also provided personnel and small boat support for sampling the estuary. Financial
support for this research was provided by contracts from the Florida
Department of Environmental regulation (LR 48) and the Florida Institute
of Phosphate Research (FIPR 83-05-016).
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