Environ. Sci. Technol.
1909, 23, 1475-1481
Plutonium, Lead-210, and Carbon Isotopes in the Savannah Estuary:
Riverborne versus Marine Sources
Curtis R. Olsen,'*+Myint Thein,$ Ingvar L. Lawen,+ Philip D. Lowry,§Patrick J. Mulholland,t
Norman H. Cutshall,+James 1.Byrd) and Herbert L. WindomII
Environmental Sciences Division and Environmental Compliance and Health Protection Division, Oak Ridge National Laboratory,
Oak Ridge, Tennessee 3783 1, Department of Anesthesiology, Emory University School of Medicine, Atlanta, Georgia 30322,
and Skidaway Institute of Oceanography, Savannah, Georgia 31415
W Plutonium-238 from the Savannah River Plant labels
riverborne particles, providing a unique opportunity for
tracing river-ocean exchange processes. Results indicate
that plutonium and lead-210 are enriched on estuarine
particles and that inputs of plutonium from oceanic sources
greatly exceed inputs from riverborne or drainage-basin
sources as far upstream as 30 km in the Savannah River
estuary. This is near the landward limit of seawater
penetration. Sediment resuspension in dynamic coastal
areas, sorption onto fine particles, and landward transport
of particulate material along the bottom are the primary
mechanisms for removing dissolved plutonium and lead-
210 from oceanic water and for concentrating these two
radionuclides in estuarine areas. Since estuaries, bays, and
intertidal areas serve as effective traps for fine particles
and associated substances, this landward transport from
the ocean has important implications concerning the dis-
posal of chemically reactive substances in oceanic waters
off coastlines affected by a rising sea level.
Introduction
It has been well established that deposition in estuaries
traps particles, nutrients, trace substances, and contami-
nants from land-based sources (1-4). Less well-defined
is the role of coastal estuaries in removing and trapping
materials from the oceanic water column (5-7). At the
estuarine interface, where fresh water mixes with seawater,
the fate of substances can be affected by river flow, tidal
flow, wave activity, currents, and a nontidal estuarine
circulation pattern. Estuarine circulation along submer-
gent coastlines is characterized by a lower salinity surface
layer with a net seaward flow and a denser, more saline
bottom layer with a net landward flow. This upstream or
landward flow along the bottom causes estuaries to trap
materials from both riverine and marine sources and to
serve as major deposition and accumulation sites for
particles and particle-associated substances (2, 6-9).
Although there is a general understanding of the pro-
cesses that affect the fate of chemically or particle-reactive
contaminants in estuarine systems, it has been very dif-
ficult to quantify net exchange between rivers and the
ocean because (1)contaminant source terms are diffuse
and poorly defined, (2) contaminant transport with par-
ticles usually involves numerous episodes of deposition and
resuspension in association with short-term events over
long periods of time, and (3) a complex suite of physical
and biogeochemical interactions take place when fresh
water mixes with seawater. In this paper, we present data
on plutonium (23aPuand 2399240Pu) concentrations in the
Savannah River estuary and compare its distribution with
Environmental Sciences Division, Oak Ridge National Labora-
tory.
* Environmental Compliance and Health Protection Division, Oak
Ridge National Laboratory.
5 Emory University School of Medicine.
'1 Skidaway Institute of Oceanography.
0013-936X/89/0923-1475$01.50/0 0 1989 American Chemical Society
radiocesium (137Cs)and two naturally occurring radionu-
clides, 210Pband 7Be. We show that the isotopic compo-
sition of plutonium released from the Savannah River
Plant (SRP) and of plutonium attached to suspended
particles in the Savannah River is different from that of
oceanic (fallout) plutonium, and we have used this dif-
ferente to determine that inputs of oceanic plutonium to
the Savannah estuary greatly exceed inputs from river-
borne sources. In addition, we have used the ratio of
short-lived 'Be to long-lived 210Pbas a new tool for
quantifying sediment resuspension in estuarine areas and
for examining the mechanisms responsible for enriching
radionuclides and, by analogy, other chemically reactive
contaminants on estuarine particles. Finally, we have used
particulate 13'Cs concentrations and carbon isotopic [a-
(13C)]data to identify the contribution of inorganic and
organic particles from riverborne and estuarine or marine
sources. These results help provide a rational for the
elevated plutonium and 210Pbconcentrations and inven-
tories that have been found to occur in fine-grained es-
tuarine and coastal sediments throughout the world
(10-20).
Locality Information and Geochemical Tracer
Methodology
Plutonium. The SRP, located -256 km upstream from
the mouth of the Savannah River (Figure l),is the prin-
cipal plutonium production facility for the United States
Department of Energy. Between 1954 and 1974, -1.4 X
loll Bq (3.7 Ci) of plutonium has been released into the
atmosphere from fuel reprocessing operations, and 1.1
X 1O'O Bq (0.3 Ci) has been released to surface waters,
-
which ultimately drain into the Savannah River (21).
Although concentrations of %Pu and 239v240Pu in SRP soils
exhibit large variations as a result of proximity to points
of release, microtopographicalheterogeneity in deposition,
and sampling error, mean soil concentrations have been
reported as 18 and 83 mBq/g, respectively (22). The re-
sultant mean 238Puto 239p240Pu ratio for soils on the SRP
reservation is -0.22. Concentrations of 238Puand 2391240Pu
in stream and pond sediments on the SRP reservation also
show large variations, ranging from 0.003 to 14 mBq/g for
238Puand 0.014 to 52 mBq/g for 239,240Pu (23). Measured
238Puto 2399240Pu ratios in these samples were often greater
than 0.12 and were as high as 3.3 in the sediments of Four
Mile Creek (23).
These plutonium isotope ratios are significantly higher
than the 238Puto 2399240Pu ratio in fallout from atmospheric
testing of nuclear weapons. On the basis of soil samples
collected in Raleigh, NC, Hardy and others (24) have es-
timated that -0.105 mCi/km2 (3.9 X lo6 Bq/km2) of =Pu
and 2.4 mCi/km2 (8.9 X lo7 Bq/km2) of 239,240Pu were
deposited as fallout to the southeastern United States.
When extrapolated over the Savannah River drainage
-
basin (27400 km2)this amounts to a total fallout delivery
of 1.07 X 10" Bq of 23aPuand 2.4 X 10l2Bq of 2397240Pu.
The recent nuclear accident at Chernobyl in the Soviet
Environ. Sci. Technol., Vol. 23, No. 12, 1989 1475
 I
_ - - - \
I 137Cscan substitute for K+ in (illitic) micaceous minerals
33'00'
0 occurring radionuclides with half-lives of 22.3 yr and 53.3
32'00' L days, respectively. zloPbis one of the daughters in the
82'00' 81000'
Flgure 1. Large-volume water sample collection sites in the Savannah
River estuary during June 1986. The freshwater sample downstream
from the U.S. Department of Energy's Savannah River Plant (S-301)
-
was collected from the river bank. All other samples were collected
in the rlver channel, 1 m below the surface. A sediment box core
was also collected near S-0102.
Union has not significantlyadded to this fallout plutonium
burden. The fallout 238Puto 239p240Pu ratio calculated from
these data is -0.046, which is similar to ratios that have
been measured in estuarine and coastal sediments along
the eastern United States (3, 7, 9, 10, 15, 18, 19). This
suggests that the 238Puto 239,240Pu ratio on riverborne
particles (affected by releases from the SRP) may be
different from the fallout plutonium ratio on coastal
particles and thus may provide a unique opportunity for
separating materials transported into the Savannah River
estuary from riverborne versus marine sources.
Radiocesium. Global fallout from atmospheric nuclear
weapons testing has also introduced 137Cs(30-yr half-life)
to the Savannah River watershed, with the major influx
occurring during the years 1962-1964. The 1950-1985
integrated and decay-corrected input of fallout 137Csto
mid-latitude areas in the United States is -95 mCi/km2
or 3.5 X lo9 Bq/km2 (25). When extrapolated over the
Savannah River drainage basin (27 400 km2)this amounts
to a total fallout delivery of -9.6 X 1013Bq of 137Cs. In
addition to global fallout, 137Cshas been introduced into
the Savannah River watershed via operations at the SRP.
It has been estimated that -500 Ci (1.9 x 1013Bq) of 137Cs
has been released into surface waters on the SRP reser-
vation between 1961and 1973, and that -18% of this total
release or 90 Ci (0.3 X 1013Bq)has drained into the Sa-
vannah River (26).
Previous work has shown that 137Csis rapidly sorbed to
clay minerals in drainage basin soils and freshwater sed-
iments (3) and exhibits a particle to water distribution
coefficient or sorption ratio of -1 X lo5 (25). Cesium
sorption on inorganic clay particles can occur at several
sites, including (1)easily exchangeable sites on the particle
surface, (2) fixed sites at the edges of the clay-mineral
lattice, and (3) nonexchangeable, interlayer sites where
1476 Environ. Sci. Technol., Vol. 23, No. 12, 1989
(25). Although little is known about the kinetics of 137Cs
fixation into clay interlayer sites, previous work in the
Susquehanna River-Chesapeake Bay system has indicated
that >90% of the 137Cson bottom sediments and >70%
of the 137Cson suspended particles was irreversibly sorbed
into mineral lattices (25).
In ocean waters, however, 137Cshas a tendency to remain
in solution because of its competition with other cations
(especiallyK+) for sorption sites on particles, and because
of the paucity of inorganic particles in the marine water
column. Consequently, 13'Cs concentrations on coastal
particles and the resulting 137Csparticle to water sorption
ratios in seawater are several orders of magnitude lower
than respective concentrations and ratios in freshwater
systems. This difference in the 137Cscontent of particles
derived from the land and those derived from the marine
environment suggests that 137Csmay serve as a tracer for
the origin of recent inorganic particles at the land/ocean
interface if its desorption from riverborne particles is
relatively insignificant (27).
Lead-210 and Beryllium-7. 21Pband 'Be are naturally
naturally occurring 238U-226Ra-222Rn-214Pb decay series.
As an inert gas, some z2zRnmay emanate into the atmo-
sphere before its decay to zlOPb.The removal of 21Pbfrom
the atmosphere via washout by precipitation forms a
measurable flux of "excess" 210Pb(210Pb-ex)back to the
earth's surface. This flux ranges from -0.2 to 2.6
mBq/cm2 on a monthly basis and annually averages 15 -
mBq/cm2 along the eastern coastline of the United States
(25,28). Over the 32-yr mean life of 210Pb,this annual flux
would support an expected steady-state 210Pb-exinventory
of -480 mBq/cm2 in soils and sediments. Previous work
has shown that zloPbis chemically and particle-reactive
in both fresh and marine waters, and as a consequence,
its distribution has been widely used to quantify physical
and biogeochemical processes in estuarine and coastal
systems (13, 14, 17, 20, 25, 28).
Beryllium-7 is produced by cosmic-ray spallation of
nitrogen and oxygen within the earth's atmosphere. Like
fallout radionuclides and 210Pb-ex,7Be is primarily re-
moved from the atmosphere via washout by precipitation.
Previous work has shown that 7Be is rapidly sorbed by
particulate material in aquatic systems, and exhibits a
particle to water sorption ratio similar to that of plutonium
and 210Pb-ex(25,28,29). Because of its short-half life, 7Be
is a powerful tracer for evaluating processes that occur on
short time scales (weeks to months), relative to the longer
time scales (months to decades) traced by 210Pb-ex,plu-
tonium, and radiocesium.
Stable Carbon Isotopes. Stable carbon isotope ratios
have been widely used as biogeochemical tracers in systems
with two or more isotopically distinguishable sources of
carbon (30-33). The stable carbon isotope imprint is the
ratio of carbon-13 to carbon-12 and is generally expressed
in the 6 notation:
6(13C) (per mil) = (Rsamp/Rstd- 1) X 1000
where R,, is the 13C/12Cratio in the sample and RsU is
the 13C/128ratioin a PDB standard. Because the 6(13C)
value for plankton from surface ocean waters off the
southeastern United States (-21 per mil is heavier than
the value for soil or plant carbon (-26 per mil from ter-
restrial sources, the W3C) value on estuarine organic
materials can be used to help discern carbon derived from
terrestrial drainage-basin sources from carbon produced
in situ in the estuarine water column or derived from
Table I. Dissolved and Suspended-Particulate Plutonium in the Savannah River Estuarya
dissol susp part. dissol susp part. sorptn ratio part.
salinity, susp part., 238Pu, Z38Pu, 239,240pu, 239,240pu, 2aS,240pu,b Zapu to Z39,240pu
sample L mg/L rBq/L mBq/kg &/L mB,/kg L/kg ratioc
S-301 fresh 7.5 0.7 f 0.4 93 f 11 1.9 f 0.4 285 f 26 2x 106 0.33 f 0.05
S-0101 fresh 21.9 1.5 f 0.4 100 f 15 5.2 f 0.7 235 f 30 5x 104 0.43 f 0.08
S-0107 2.1 16.4 1.9 f 0.4 44 & 7 4.8 f 0.7 350 f 30 7x 104 0.13 f 0.02
S-0102 14.5 19.0 0.4 f 0.2 26 & 4 2.2 f 0.4 545 f 44 2x 105 0.05 f 0.01
S-0116 24.6 22.0 0.4 f 0.1 30 f 4 2.2 f 0.4 665 f 52 3x 106 0.05 f 0.01
S-HH8 32.5 0.9 0.4 f 0.4 30 f 6 3.3 f 0.4 400 f 35 1x 106 0.07 f 0.02
Surface Sediment at Station S-0102 (Figure 1)
0-2 cm 14.5 sediment 15 f 4 300 f 26 0.05 f 0.01
a Statistical counting errors are expressed in terms of la. Sorption ratio, 2aS*240Pu
concentration per kg of particles/239*240Pu concentration
per L of water. CParticulatePu isotope ratio, 2aPu concentration per kg of p a r t i ~ l e s / ~ ~ ~concentration
* ~ ~ ~ P u per kg of particles.

marine sources via landward transport (34).

PLUTONIUM-238
Sample Collection and Analysis
We measured the particulate and dissolved distribution
of 239*240Pu and 23aPuin six large-volume (850-L) water
samples collected along the salinity gradient of the Sa-
vannah River, the estuary, and the adjacent coastal marine
environment (Figure 1). Suspended-particulatematter was
removed from these samples by continuous-flowcentrifu-
gation. Dissolved plutonium was concentrated and re- a
moved from the water phase by coprecipitation with Fe- - - *O0 IPL:TONl~M-23$,240 I I fb)
(OH),. Radionuclide concentrations on the suspended
matter and in the water phase [Fe(OH), precipitate] were
analyzed separately. In addition, a sediment box core was
w m 600
k g 400 -
- g,i'2,- 6 z g qg
6
Z a
3
z -42;
collected in the Savannah estuary near station S-0102
3:- 200 - p 4 4 -2E{
(Figure 1).
The plutonium analyses involved dissolution with hy-
a:
m2l
' I I I I I - 0
s!?
drochloric acid, coprecipitation with calcium oxalate, ra- 0
diochemical separation with ion-exchange columns, elec-
trodeposition onto stainless steel disks, and a spectrometry
with silicon surface-barrier detectors (35). The samples
were CY counted for -21 days and yields were evaluated
with a 242Putracer. 2391240Pu activities are collectively re-
ported because the energies of the CY particles produced
by the decay of 240Pu(6580-yr half-life) cannot be resolved
from those produced by the decay of 239Pu(24400-yr
half-life) by CY spectrometry.
The concentrations of 13'Cs, 210Pb,and 7Be on the sus-
pended-particulate and bottom-sediment samples were
measured by y spectrometry using low-background,high-
resolution, germanium detectors equipped with a Nuclear
Data Model 9900 microprocessor system programmed to
record y spectra in 4096 channels. All samples were
packed in 90-cm3aluminum cans or 15-cm3plastic Petri
dishes, depending on the amount of material analyzed.
The detectors were calibrated for the respective geometries
with a certified mixed standard and the calibration pro-
cedures are described elsewhere (25). The low-energy (46.5
keV) zloPb y-ray was analyzed by use of a planar in-
trinsic-germanium detector and correction for self-ab-
sorption (36). This technique has a great advantage in that
it does not require sample leaching or radiochemical sep-
aration and allows for the simultaneous determination of
both the total zloPband the 214Pb-supportedlevel. Excess
zloPb (210Pb-ex)was calculated by subtracting the 214Pb-
supported level from the total 210Pbactivity. y-Emitting
radionuclide data are reported in milliBequere1per gram
dry weight (1mBq = 0.06 dpm = 0.027 pCi) and counting
errors are f l standard deviation.
The suspended-matter and sediment samples were also
analyzed for stable carbon isotopes at Coastal Science
Laboratories Inc. (Austin, TX), by standard mass spec-
trometric procedures (27).
Table 11. Savannah Estuary Box Core LPT Collected at Station 5-0102 in J u n e 1986
radioactivity, mBq/g radioactivitv. mBo /cm2
depth: cm weight,b gm IBe '37CS 210Pb 214Pb 210Pb-ex 40K IBe 137Cs zlOP b-ex
0-2 697 17 f 1 2.8 f 0.2 92 f 5 45 f 1 46 f 5 359 f 3 18.9 3.2 52.0
2-4 65 7 f 4 2.8 f 0.4 76 f 4 40 f 1 36 f 5 388 f 9 10.1 4.0 52.6
4-6 69 1.5 f 0.4 52 f 4 23 f 1 29 f 4 400 f 10 2.4 45.2
6-8 65 3.6 f 0.5 70 f 4 27 f 1 43 f 4 407 f 11 5.2 62.4
8-10 90 4.2 f 0.3 43 f 3 21 f 1 22 f 3 391 f 9 2.5 44.7
10-12 64 2.6 f 0.4 72 f 5 24 f 1 48 f 5 375 f 9 3.7 67.7
12-14 102 0.5 f 0.2 29 f 3 17 f 1 11 f 3 329 f 6 1.1 25.7
14-16 86 1.5 f 0.3 38 f 3 16 f 1 21 f 3 336 f 6 3.0 40.7
16-18 57 3.5 f 0.5 80 f 4 32 f 1 48 f 4 447 f 1 2 4.4 60.8
18-20A 46 5.2 f 0.6 71 f 5 28 f 1 42 f 5 448 f 14 5.3 43.7
18-20B 49 5.3 f 0.4 98 f 5 32 f 1 66 f 5 421 f 7 5.8 71.9
20-24 58 4.6 f 0.5 75 f 5 30 f 1 45 f 5 410 f 11 5.9 57.3
24-28 73 4.3 f 0.4 33 f 3 23 f 1 10 f 3 371 f 10 7.0 16.4
28-32 94 1.7 f 0.3 36 f 3 21 f 1 15 f 3 347 f 8 3.5 30.2
32-36 73 2.0 f 0.4 46 f 3 23 f 1 24 f 3 376 f 10 3.3 38.3
36-40 95 0.2 f 0.3 31 f 3 19 f 1 11 f 3 304 f 7 0.4 23.8
40-44 111 0.2 f 0.3 36 f 3 18 f 1 18 f 3 304 f 7 0.6 44.3
44-48 76 3.2 f 0.4 67 f 4 28 f 1 39 f 4 393 f 7 5.4 66.4
48-52 74 1.9 f O . 4 65 1 4 21 f 1 44 =k 5 388 f 10 3.1 71.9
52-56 63 1.8 f 0.4 68 f 5 36 f 1 33 f 5 418 f 7 2.5 45.8
56-61 56 3.8 f 0.6 95 f 5 30 f 1 65 f 6 395 f 11 4.8 81.3
61-66 67 3.0 f 0.4 67 f 4 24 f 1 43 f 4 365 f 10 - 4
.4 64.3
29 >82 >1107

expected inventory from atmospheric deposition or fallout 33 320 480

aTwo samples were accidently labeled 18-20 cm. These were not supposed to be duplicate samples and we suspect that the measured
depth increments below 20 cm are off by 2 cm. A large surface sample (620 cm2) was collected from the top of the box core for plutonium
analvses.

with 238Pu(Figure 2a) and that estuarine suspended par-
ticles are enriched in 239,240Pu (by a factor of -3) relative
to respective concentrations on riverborne particles and
on suspended matter in the surface waters of the ocean
(Figure 2b).
Plutonium isotopic ratios (238Puto 2399240Pu) for sus-
pended particles throughout the Savannah River estuary
and shelf system are also listed in Table I. In the Sa-
vannah River, the ratio of 238Puto 239@ Pu' is -0.4 (Table
I). This ratio is significantly higher than the 238Puto
239,240Pu ratio in fallout (0.05),but is similar to ratios that
have been measured previously in the soils and sediments
around the SRP, in the Savannah River downstream from
the SRP, and in some freshwater sediment cores (21-23).
The 238Puto 2399240Pu ratio on suspended particles abruptly
decreases to -0.13 at 2 ppt salinity (Table I). Since our
data do not indicate any differential behavior between
238Puand 239p240Pu, this decrease implies that riverborne
plutonium accounts for only -25% of the total plutonium
on suspended particles as far as 30 km upstream from the
river mouth. In the estuary, the 238Puto 239p240Pu ratio on
both the suspended matter and surface sediments is similar
to the ratio in fallout and on particles in the adjacent shelf
environment (Table I). This is conclusive evidence that
the plutonium presently enriching estuarine particles
(Figure 2) comes from oceanic sources rather than river-
borne sources. We suggest that dissolved plutonium is
being directly removed from oceanic water by sorption onto
particles within the estuary, or that coastal particulate
material (containing marine plutonium) is being trans-
ported landward (upstream) along the estuarine bottom.
This present-day (water-column) picture for the Sa-
vannah estuary also appears to be valid for the past as
indicated by the vertical distribution of 238Puto 239,240Pu
ratios in the sedimentary record. Goldberg and others (9)
showed that only one out of five sediment cores collected
in the Savannah estuary and adjacent marsh environment
contained elevated 238Puto 2399240Pu ratios at depth in the
1478 Environ. Sci. Technol., Vol. 23, No. 12, 1989
sediment. The other sediment cores contained 238Puto
239,240Pu ratios typical of fallout (or oceanic) plutonium
throughout their entire length; however, inventories were
often greater than the level expected from direct fallout
to the estuary surface (9). Although a 66-cm-longbox core
of fine-grained estuarine sediments was also collected at
S-0102 (Figure 1)during this study, only the surface (0-2
cm) was analyzed for plutonium (Table I), because the
vertical profiles for 137Csand 210Pb-exwere relatively
constant over the entire core length and did not decrease
to nondetectable and supported levels, respectively (Table
11). As a consequence, only minimum estimates for the
rate of sediment accumulation (>1cm/yr) and the 210Pb-ex
inventory (>1100 mBq/cm2) could be made (Table 11).
These minimum estimates, nevertheless, indicate that
sediments are rapidly accumulating at this site in the es-
tuary and that the sediment inventory of 210Pb-exis at least
2 times greater than the 210Pb-exinventory expected from
its atmospheric flux to the estuary surface (Table 11).
Concentrations of 210Pb-exand 7Be and 13'Cs on sus-
pended particles as a function of salinity and location in
the Savannah estuary are listed in Table I11 and illustrated
in Figure 3. As in the case for 239*240Pu, Savannah estuary
particles are also enriched in 210Pb-exrelative to concen-
trations on suspended matter in the Savannah River or
in the surface waters of the coastal ocean (Figure 3a).
Since the ratio of 210Pb-exto 239~240Pu is relatively uniform
on suspended matter throughout the Savannah River-
estuary-shelf system (Table 111),it would appear that most
of the 210Pb-exon estuarine particles also comes from
oceanic sources. Input of 210Pb-exfrom the marine en-
vironment may help explain the larger than expected in-
ventory of 210Pb-exmeasured in the estuarine sediment
box core (Table 11).
In contrast to zloPband 2397240Pu, the concentration of
short-lived 7Be is depleted on suspended particles in the
Savannah estuary (Figure 3b). Since the particle to water
sorption ratio for 7Beis similar to respective sorption ratios
Table 111. Suspended-Particulate Radionuclide and Carbon Isotope Data in the Savannah River Estuary"

radioactivity, mBq/g ratio

salinity, total supported excess 210Pb-ex/
sample %a zloPb ZlOpbb zloPb 'Be 137cs V3C), %a 239,uoPu 'Be/*loPb-ex
S-301 fresh 130 f 7 95 f 3 35 f 7 130 f 7 160 f 4 -26.6 f 0.2 125 f 27 3.7 f 0.9
s-0101 fresh 135 f 8 85 f 3 50f 8 115 f 4 120 f 2 -26.8 f 0.2 215 f 45 2.2 f 0.4
S-0107 2.1 125 f 6 55 f 2 70f7 80f6 55 f 1 -26.8 f 0.2 200 f 45 1.1 f 0.1
s-0102 14.5 115 f 7 35 f 2 80f7 90f7 15 f 1 -22.8 f 0.2 145 f 18 1.1 f 0.1
S-0116 24.6 125 f 9 35 f 3 90 f 9 105 f 9 9f1 -20.8 f 0.2 135 f 17 1.2 f 0.1
S-HH8 32.5 80 f 8 40 f 2 40 f 8 150 f 12 10 f 2 -21.2 f 0.2 100 f 38 3.8 f 0.8
Surface Sediment at Station S-0102 (Figure 1)
0-2 cm 14.5 90 *5 45 f 1 45 f 5 17 f 1 3f1 -21.2 f 0.2 150 f 22 0.4 & 0.1
astatistical counting errors are expressed in terms of lu. Radionuclide activities have been rounded to the nearest 5 mBq if the rounding
was within the statistical counting error. bThe supported zloPbwas determined from the 214Pb activity in the sample.

systems along the eastern coastline of the United States

(2, 3, 25), the trend of decreasing particulate 137Cscon-
centrations with increasing salinity (Figure 3c) is typical
of most estuarine systems throughout the world. The
relatively high concentration of 13Tson Savannah River
particles is probably a result of 13Ts releases from SRP
and the strong affinity for 13'Cs to become irreversibly
sorbed within clay mineral lattices in freshwater systems.
BERYLLIUM-7
Although the kinetics for irreversible sorption are still
unknown, previous work in Chesapeake Bay suggests that
desorption of 137Csfrom riverborne particles during
transport into estuarine areas is not significant enough to
m
m account for the order of magnitude decrease illustrated in
IC 50
Figure 3c (25). We suggest that this decreasing trend in
particulate 137Csconcentrations with increasing salinity
results from the dilution of riverborne particles with
200
1 (Cl CESIUM-137
i particles produced in situ in the estuary, eroded from the
e estuarine margins, or transported landward from marine
8
-$
E
150

100
I
50
0
NEAR' FRESH 10 20 30 40
SRP SALINITY '1-
Flgure 3. Plot of the concentrations of 210Pb-ex,'Be, and 137Cson
suspended particles as a function of salinity and location within the
Savannah River estuary. (a) As for 23e*240P~ (Figure 2b), 210Pb-exis
enriched on estuarine particles relative to its concentration on sus-
pended matter in the Savannah River or in the surface waters of the
coastal ocean. (b) In contrast, the concentration of short-lived 'Be
on estuarine suspended matter is depleted rattier than enriched. Since
the sorption behavior of 7Be is simHar to that of 239-240Pu and 210Pkx,
the enrichment of the latter two radionuclides must be a relatively
long-term process (years to decades), and the depletion of 7Be may
reflect the resuspension of aged bottom sedlments. (c) The sharp
decrease in ls7Csconcentration indicates that as much as 95% of the
137Cson riverborne particles may be desorbed during transport into
the estuary or that riverborne particles are highly diluted with particulate
material produced in situ in the estuary or transported landward from
marginal and marine sources.
for 210Pband 2399240Pu (3, 7, 25, 28, 29), this depletion of
7Be implies that the process responsible for enriching
239*240Puand 210Pb-exon estuarine particles is a relatively
long-term one and does not reflect short-term processes
such as coagulation of dissolved radionuclides during fresh
water and seawater mixing (38) or changes in particle
characteristics (composition or grain size) during transport
through the estuary.
Concentrations of 13'Cs on suspended particles in the
Savannah River estuary are listed in Table I11 and are
illustrated in Figure 3c. Although the 13Tsconcentration
on riverborne suspended particles is a factor of -2 higher
than respective concentrations in other river-estuarine
sources. Assuming that 137Csdesorption from riverborne
particles is relatively insignificant, it would appear that
estuarine or marine sources contribute -40% of the
particulate material in the upper estuary to 100% in the
lower estuary (27).
Dilution of riverborne particles by estuarine or marine
materials is also supported by the stable carbon isotope
data in Table 111. The 6(13C) signature of freshwater
particles (-27 %o) clearly indicates a terrestrial watershed
source, whereas particles in the estuary have 6(13C)values
typical of marine phytoplankton (-21 $Ti). Estimates for
the extent of dilution of riverborne organic materials by
in situ productivity within the estuarine or coastal envi-
ronment are complicated, because V3C) values for C-4
plants, such as Spartina alternaflora, which dominate the
flora of salt marshes, are considerably heavier (-15 %o) than
marine or estuarine phytoplankton. Consequently, we
cannot discount the possibility that a combination of
terrestrial and salt marsh detritus could be responsible for
the particulate 8(13C)values in the Savannah estuary. A
much more detailed discussion on the sources for organic
and inorganic particles in the Savannah River estuary is
presented elsewhere, based on many more lNCs, 6(13C),and
6(15N)analyses for sediment samples recently collected in
the estuary (27).
Sediment Resuspension and Radionuclide
Enrichment Mechanisms
One possible mechanism for depleting the concentration
of 7Be and enriching the concentration of oceanic m*240Pu
and 210Pb-exon estuarine particles involves radionuclide
sorption onto resuspended bottom materials during land-
ward transport into or within estuarine systems. Although
plutonium, 210Pb,and 7Be are chemically and particle-re-
Environ. Sci. Technol., Vol. 23, No. 12, 1989 1479
active in oceanic water, the paucity of suspended matter
causes these nuclides to remain in solution. For example,
when suspended-matter concentrations are less than 1
mg/L (typical of the marine environment), there is lo6
-
times more water than suspended matter in a liter. As a
consequence, only 10% of a particle-reactive radionu-
clide (having particle to water distribution coefficient or
sorption ratio of -lo5) will be associated with the sus-
pended matter and the remaining 90% will be in the water
phase. Previous work has shown that more than 90% of
the fallout plutonium delivered (primarily in the mid-
1960s) to the surface ocean is still in the water column, but
that dissolved concentrations of plutonium decrease
sharply as you approach the coastal zone (10,18). Nutrient
loading, and wave and current action in estuarine and
coastal areas, increase suspended-matter concentrations
by 1-2 orders of magnitude by enhancing biological pro-
duction and sediment resuspension. We suggest that
plutonium, 210Pb,and 7Be are being continually removed
from the oceanic water phase by sorption onto particles
in turbid estuarine and coastal areas. This removal
probably occurs over long time periods as bottom sedi-
mentary materials undergo repeated episodes of resus-
pension during landward transport on the inner shelf and
upstream transport in the estuary. Sorption onto particles
during repeated episodes of sediment resuspension would
enrich the concentration of long-lived 239i240puand 210Pb-ex
on estuarine particles (Figures 2b and 3a) but would dilute
the concentration of short-lived 7Be (Figure 3b) by re-
suspending older materials from the bottom that have been
depleted in 7Be by radioactive decay.
These results also imply that the ratio of short-lived 7Be
to long-lived 210Pb-ex(Table 111)can be used as a new tool
for quantifying the amount of resuspended material in the
estuarine water column. Because of its short half-life and
because of its dilution with older sediment particles, the
concentration of 7Be on surface bottom sediments is much
less than its concentration on suspended particles, whereas
the concentration of long-lived 210Pb-exis nearly the same
on fine-grained sediments and suspended matter. The 7Be
to 210Pb-exratio on surface bottom sediments in the Sa-
vannah estuary is 0.4, which is an order of magnitude lower
than the 7Beto 21”Pb-exratio on planktonic-rich suspended
matter (-3.8) in the Savannah River and in surface water
on the inner shelf (Table 111). Suspended matter in the
Savannah estuary has a 7Be to 210Pbratio of 1.0 (Table
111). If we assume that the suspended particles in the
- River Inputs to Ocean S y s t e m ; Martin, J.-M., Burton, J.
estuary is a mixture of plankton (with a 7Be to 210Pbratio
of -4.0) and resuspended bottom material (with a ratio,
of 0.4),then the measured ratio of 7Be to 210Pb-exon es-
tuarine suspended particles (Table 111) suggests that re-
suspended bottom material may account for more than
80% of the suspended matter in the estuarine water col-
umn. Although this is certainly a rough estimate, it nev-
ertheless illustrates the potential use of this natural ra-
dionuclide technique for quantifying the amount of par-
ticles produced in the surface water from the amount of
particles resuspended from the bottom. In addition, these
results illustrate the important contribution that sediment
resuspension makes to turbidity within estuarine systems.
Conclusions
Our results indicate that the input of plutonium and
210Pb-exinto the Savannah estuary via landward transport
from marine sources greatly exceeds the input of these two
radionuclides via river discharge from drainage-basin
sources. We suggest that these radionuclides are being
scavenged from oceanic water by sorption onto particles
in turbid estuarine and coastal areas. Scavenging, in as-
1480 Environ. Sci. Technol., Vol. 23, No. 12, 1989
sociation with repeated episodes of fine-particle deposition
and resuspension, will deplete the concentration of 7Beand
enrich the concentration of 239mPuand 21”Pb-ex(over long
time periods) on suspended particles and sediments. Net
landward transport along the bottom traps inorganic and
organic materials from marine sources and causes coastal
bays and estuaries to serve as major deposition and ac-
cumulation sites for marine, as well as riverborne sub-
stances. These results are consistent with previous studies
that have shown elevated 2399240P~ and 210Pb-exconcen-
trations and inventories in fine-grained sediments along
the coastlines of England (5), France (11), and various
other locations around the world (!9-20). Since other
chemically or particle-reactive trace substances may also
be scavenged from oceanic waters by sorption in turbid
coastal areas and, subsequently, transported landward to
accumulate within estuarine systems, it is important to
quantify the magnitude of this process in models that
simulate the transport and biogeochemical fate of river
inputs to the ocean. To date, inputs of carbon, synthetic
organic compounds, trace metals, and radionuclides from
oceanic sources have largely been ignored in models sim-
ulating the fate of contaminants in estuaries. In addition,
these results have extremely important implications for
the landward transport and accumulation of chemically
reactive substances disposed of in oceanic waters off
coastlines affected by a rising sea level.
Acknowledgments
We thank E. D. Goldberg of Scripps Institute of
Oceanography, G. R. Helz of the University of Maryland,
P. Santschi of Texas A&M University, K. L. Von Damm
and T.-H. Peng of Oak Ridge National Laboratory, and
G. Saunders of the U. S. Department of Energy for their
reviews and comments on earlier drafts of this paper.
C.R.O. would also like to thank H.J. Simpson of Columbia
University and R. F. Bopp of Barnard College for their
advice regarding the use of geochemical tracers for es-
tuarine processes.
Registry No. 238Pu,13981-16-3; 239Pu,15735-80-5; 240Pu,
14119-33-6;137Cs,10045-97-3;210Pb,14255-04-0;7Be,13966-02-4;
40K, 13966-00-2;13C,14762-74-4.
Literature Cited
D., Eisma, D., Eds.; United Nations Environment Pro-
gramme: Switzerland, 1981.
Bopp, R. F.; Simpson, H. J.; Olsen, C. R.; Trier, R. M.;
Kostyk, N. Enuiron. Sci. Technol. 1982, 16, 666-676.
Simpson, H. J.; Linsalata, P.; Olsen, C. R.; Cohen, N.; Trier,
R. M. In Environmental Research on Actinide Elements;
Pinder,J. E., 111,Alberta,J. J., McLeod, K. W., Schreckhise,
R. G., Eds.; U S . Department of Energy: Springfield,VA,
1987; CONF-841142, pp 273-297.
Smith, J. N.; Ellis, K. M.; Nelson, D. M. Chem. Geol. 1987,
63, 157-180.
Peirson, D. H.; Cambray, R. S.; Cawse, P. A.; Eakins,J. D.;
Pattenden, N. J. Nature 1982, 300,27-31.
Meade, R. H. In Framework of Coastal Plain Estuaries;
Nelson, B. W., Ed.; Geology -. Society of America: Boulder,
CO,1972; pp 91-120.
Olsen, C. R.; Simpson, H. J.; Trier, R. M. Earth Planet.
Sci. Lett. 1981. 55. 377-392.
Sinex, S. A.; Helz, G. R. Enuiron. Sci. Technol. 1982,16,
820-825.
Goldberg, E. D.; Griffin, J. J.; Hodge, V.; Koide, M.; Win-
dom, H. L. Enuiron. Sci. Technol. 1979, 13, 588-594.
Buesseler, K. 0.;Livingston, H. D.; Sholkovitz, E. R. Earth
Planet. Sci. Lett. 1986, 76, 10-22.
Jeandel, de C.; Martin, J.-M.; Thomas, A. J. C. R. Acad.
Sci. Paris, Ser. D 1980, 291, 125-128.
 Environ. Sci. Technol.
Aston, S. R.; Stanners, D. A. Nature 1981,289, 581-582.
Beasley, T. M.; Carpenter, R.; Jennings, D. C. Geochim.
Cosmochim. Acta 1982,46, 1931-1946.
Scott, M. R.; Salter, P. F.; Halverson, J. E. Earth Planet.
Sci. Lett. 1983, 63, 202-222.
Santachi, P. H.; Li, Y.-H.;Bell, J. J.; Trier, R. M.; Kawtaluk,
K. Earth Planet. Sci. Lett. 1980, 51, 248-265.
Aston, S. R.; Assinder, D. J.; Kelly, M. Estuarine, Coastal
Shelf Sci. 1985, 20, 761-771.
Smith, J. N.; Boudreau, B. P.; Noshkin, V. Earth Planet.
Sci. Lett. 1987, 81, 15-28.
Sholkovitz, E. R.; Mann, E. R. Estuarine, Coastal Shelf
Sci. 1987, 25, 413-434.
Linsalata, P.; Wrenn, M. E.; Cohen, N.; Singh, N. P. En-
uiron. Sci. Technol. 1980, 14, 1519-1523.
Kuehl, S. A.; DeMaster, D. J.; Nittrouer, C. A. Cont. Shelf
Res. 1986, 6 , 209-225.
Hayes, D. W.; Sackett, W. M. Estuarine, Coastal Shelf Sci.
1987, 25, 169-174.
Pinder, J. E., 111; Paine, D. In Transuranic Elements in
the Enuironment; Hanson, W. C., Ed.; U.S. Department
of Energy: Springfield,VA, 1980; pp 165-172.
Alberts, J. J.; Halverson, J. E.; Orlandini, K. A. J.Environ.
Radioact. 1986, 3, 249-271.
Hardy, E. P.; Krey, P. W.; Volchok, H. L. Nature 1973,241,
444-445.
Olsen, C. R.; Larsen, I. L.; Lowry, P. D.; McLean, R. I.;
Domotor, S. L. Radionuclide Distributions and Sorption
Behavior in the Susquehanna-Chesapeake Bay System.
Maryland Power Plant and Environmental Review
PPER-R-12; Annapolis, MD, 1989.
Marter, W. L. Radioactivity from SRP Operations in a
Downstream Savannah River Swamp. Atomic Energy
Commission Report DP-1370. E. I. du Pont de Nemours
Co.: Aiken, SC, 1974.
Modeling and Field Evidence of Pressure-Driven Entry of Soil Gas into a
House through Permeable Below-Grade Walls
Karina Garbed' and Richard G. Sextro
Indoor Environment Program, Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720
Modeling and field evidence are presented that indicate
that soil gas can enter houses with basements at significant
rates through permeable below-grade walls. Entry via this
pathway could result in elevated indoor concentrations of
radon and other pollutants. By use of artificial depres-
surization of the basement (-25 to -30 Pa), field mea-
surements were made of pressure coupling between a
basement and the surrounding soil and of soil-gas entry
into the house. A two-dimensional, steady-state finite
element model of fluid flow through porous media was
used to simulate the experimental conditions, assuming
air flow occurs through permeable substructure walls.
Given a basement wall permeability consistent with prior
experimental research, the model predicts 32 5% pressure
coupling 0.5 m from the basement wall at a depth of 0.5
m, in agreement with pressure coupling measured a t the
site. Under the same conditions the model predicts a
soil-gas entry rate of 2.5 m3 h-l, within the range estimated
by tracer-gas measurements. The presence of a horizontal,
low-permeability soil layer just above basement floor level
explains the high pressure coupling observed at 3-m depth
even out to 14 m west of the house.
Introduction
Soil gas is an important source of indoor air pollution.
Research on sources of human exposure to radon indicate
0013-936X/89/0923-1481$01.50/0 0 1989 American Chemical Society
Mulholland, P. J.; Olsen, C. R. submitted for publication
in Estuarine, Coastal Shelf Sci.
Krishnaswami, S.; Benninger, L. K.; Aller, R. C.; Von
Damm, K. L. Earth Planet. Sci. Lett. 1980,47,307-318.
Olsen, C. R.; Larsen, I. L.; Lowry, P. D.; Cutshall, N. H.;
Nichols, M. M. J. Geophys. Res. 1986, 91, 896-908.
(30) Craig, H. Geochim. Cosmochim. Acta 1953, 3, 53-92.
(31) Gearing, J. N.; Gearing, P. J.; Rudnick, D. T.; Requejo, A.
G.; Hutchins, M. J. Geochim. Cosmochim. Acta 1984,48,
1089-1098.
(32) Hedges, J. I.; Parker, P. L. Geochim. Cosmochim. Acta 1976,
40, 1019-1030.
(33) Krom, M. D.; Bennett, J. T. Estuarine, Coastal Shelf Sci.
1985,21, 325-326.
(34) Turekian, K. K.; Benoit, G. J. In Flux of Organic Carbon
by Riuers to the Oceans. U S . Department of Energy:
Washington, DC, 1981; DOE/OER CONF-8009140, pp
314-330.
(35) Thein, M.; Ballestra, S.; Yamato, A.; Fukai, R. Geochim.
Cosmochim. Acta 1980, 44, 1091-1097.
(36) Cutshall, N. H.; Larsen, I. L.; Olsen, C. R. Nucl. Znstrum.
Methods 1983,206, 309-312.
(37) Hamilton-Taylor,J.; Kelly, M.; Mudge, S.; Bradshaw, K.
J. Environ. Radioact. 1987, 5, 409-423.
(38) Shen, G. T.; Sholkovitz,E. R.; Mann, E. R. Earth Planet.
Sci. Lett. 1983, 64, 437-444.
Received for review November 9,1988. Accepted June 29,1989.
This research was sponsored by the Ecological Research Division,
Officeof Health and Environmental Research, U S . Department
of Energy, under contract DE-AC05-840R21400 with the Martin
Marietta Energy Systems, Znc., and under contract DE-FGOS-
86-ER60435 with Skidaway Institute of Oceanography. Pub-
lication No. 3341, Environmental Sciences Division, Oak Ridge
National Laboratory.
that soil is the primary source of indoor radon in single-
family houses in the United States ( I ) . Pressure-driven
flow is a principal means by which soil gas enters houses;
it is expected to be the predominant source of radon in
houses with elevated concentrations (2-4). Recent studies
indicate that entry of volatile organic contaminants via the
soil-gas pathway could pose a public health risk in resi-
dences located near landfiis, even those designed to accept
only nonhazardous waste (5, 6 ) .
Pressure-driven flow of soil gas into houses results from
the depressurization of the substructure of the hquse with
respect to the surrounding soil. There are three principal
causes of basement depressurization: thermal differences
between indoors and outdoors, wind loading on the
building superstructure, and imbalanced building venti-
lation ( 2 , 4 ) . Field measurements have shown that under
normal operating conditions of houses during the winter
the temperature effect alone can result in consistent sub-
structure underpressures of between 2 and 6 Pa (7, 8).
Other factors being equal, pressure-driven entry is likely
to be most important in houses with basements because
they provide a large interface with the soil. Soil-gas entry
due to basement depressurization has been experimentally
demonstrated by Turk et al. (9) and Nazaroff et al. (10).
Significant pressure-driven entry of radon from soil has
also been reported for houses with crawl spaces (11). Entry
pathways have been assumed to be penetrations, gaps, or
Environ. Sci. Technol., Vol. 23, No. 12, 1989 1481