Geochimica et Cosmochimica Acta, Vol. 58, No. 2, pp.

695-703, 1994
Copyright 0 1994 Elsevier Science Ltd
Pergamon Printed in theUSA. All rights reserved
0016-7037/94 $6.00 + .OO

A radiotracer study of cerium and manganese uptake onto suspended particles

in Chesapeake Bay

JAMES W. MOFFETT
Woods Hole Oceanographic Institution, Woods Hole, MA 02543, USA

(Received December 16, 1992; accepted in revisedform September 14, 1993)

Abstract-The oxidation kinetics of Ce( III) and Mn( II) were studied in Chesapeake Bay in March and
July 1990 to establish the role of water column redox processes in contributing to Ce anomalies observed
in this estuary ( SHOLKOVITZ and ELDERFIELD,1988; SHOLKOVITZet al., 1992). Oxidation was measured
by adding Mn(II) and Ce(II1) to freshly collected water samples as radiotracers and measuring their
uptake onto the ambient suspended particle assemblage. Mn( II) oxidation was measured by following
the uptake of 54Mn (II) onto suspended particles and utilizing protocols established by other workers to
distinguish oxidation from Mn(I1) adsorption. The same protocols were applicable to Ce(III), using
‘39Ce( III), and were supported by the use of ‘52Eu( III) as a nonredox reactive control.
Specific rates of Ce( III) and Mn( II) oxidation measured at a station in the North Bay (depth = 4 m)
in July were 2016% per day and 4032% per day, respectively. In March at the same station, the specific
rate of Mn( II) oxidation was only 10% per day, and Ce( III) oxidation was undetectable. Both Ce( III)
and Mn( II) oxidation processes were inhibited by azide, indicating that they were microbially mediated.
The seasonal differences probably reflect strong seasonal variation in the abundance of Mn oxidizing
bacteria. No Ce( III) oxidation occurred in samples collected below the oxic/anoxic interface in July.
The specific rates of oxidation for both elements were over 1000 times higher than those measured in
the Sargasso Sea. However, the specific rates for Ce(II1) and Mn(I1) were very similar to each other.
This fact, coupled with similar spatial and temporal trends for specific oxidation rates, suggests a common
mechanism of oxidation of both elements which may be significant in a wide range of marine environments.

INTRODUCTION estuarine and riverine systems have appeared which have

provided insight into their behavior at the sea interface
THE GEOCHEMISTRYOF cerium presents an opportunity to (GOLDSTEIN and JACOBSEN,1987; SHOLKOVITZand ELDER-
study the role of redox reactions which lead to its enrichment FIELD, 1988; SHOLKOVITZ et al., 1992). In both the Amazon
or depletion with respect to its nonredox reactive lanthanide
River estuary and Chesapeake Bay, these studies show that
neighbors ( ELDERFIELD, 1988 and references therein ).
significant preferential Ce removal occurs so that the overall
Ce( III) exhibits typical trivalent lanthanide solution chem-
riverine source of cerium to the oceans already has a strong
istry, with properties intermediate between La(II1) and
negative Ce anomaly. In contrast, atmospheric depositional
Pr( III), but it undergoes oxidation to Ce( IV), which is in- fluxes of rare earths show no Ce anomaly (SCHNEIDER, 1985).
soluble in seawater and is probably associated exclusively Assessment of these sources is critical to understanding the
with particles. This leads to the preferential removal of Ce
significance of Ce anomaly data in the oceans and to devel-
in oxidizing environments and its preferential enrichment in
oping a Ce scavenging model ( ELDERFIELDet al., 1990).
reducing environments. This fraction is usually characterized Ce(II1) oxidation must occur on a short timescale with
quantitatively by the cerium anomaly, equal to the ratio of
respect to transport processes in the estuary (i.e., physical
its concentration to the hypothetical concentration that a
mixing and removal by scavenging on settling particles) in
strictly trivalent Ce (Ce * ), with properties intermediate be-
order to account for these results. This is consistent with the
tween La and Pr, would have. It is defined by the expression
observations of MOFFETT ( 1990) which indicate that Ce( III)
is oxidized to Ce(IV) by a microbial process on shorter
timescales than previously supposed, particularly in coastal
waters. Oxidation rates measured in that study in Vineyard
where SW = seawater and sh = shale, a standard reference Sound, a coastal environment, were 100 times higher than
material. Comparison of Ce distribution with its neighbors in the Sargasso Sea.
can be used to distinguish redox from nonredox transport MOFFETT (1990) showed that Ce(II1) and Mn(I1) oxi-
processes. dation rates covaried throughout the environments studied,
There are now considerable data for rare earth distributions with Mn( II) oxidation always 3-4 times faster. This implied
in the open ocean ( ELDERFIELD and GREAVES, 1982; DE a common mechanism, supported by the fact that both were
BAAR et al., 1985; SHOLKOVITZ and SCHNEIDER, 199 1; GER- inhibited by azide. Microbial oxidation is now considered to
MAN and ELDERFIELD, 1990; PIEPGRAS and JACOBSEN, be the predominant oxidative pathway for Mn(I1) in the
1992). However, determination of oceanic residence times marine water column (EMERSON et al., 1982; TEBO and
and budgets depends on more knowledge of their sources. EMERSON, 1986; SUNDA and HUNTSMAN, 1987). However,
Recently, several studies on the distribution of rare earths in Ce( III) can be abiotically oxidized on Mn oxides ( KOEPPEN-

695
696 J. W. Moffett
KASTROP et al., 1991; BIDOGLIO et al., 1992), so it is im-
portant to establish which reactions are important in estuaries
with high Mn oxide concentrations.
In this work, cerium redox experiments were carried out
in Chesapeake Bay, where lanthanide geochemistry has been
studied extensively by Sholkovitz and coworkers ( SHOLKOV-
ITZ and ELDERFIELD, 1988; SHOLKOVITZ et al., 1992). Their
data showed strong Ce anomalies associated with seasonal
redox cycling. In particular, certain basins within the Bay are
seasonally anoxic, and they become enriched in Ce relative
to the other lanthanides below the oxic/anoxic interface. This
suggests that Ce oxidation in the overlying oxic waters occurs,
leading to its preferential scavenging and subsequent remo-
bilization in the anoxic zone. Preferential enrichment of Ce
has also been observed in the Saanich Inlet, another seasonally
anoxic basin (GERMAN and ELDERFIELD, 1990). The sea-
sonal timescales associated with this process are short relative
to previous indirect estimates of Ce oxidation rates (ELDER-
FIELD, 1988), but they are consistent with the findings of
MOFFETT ( 1990) that Ce oxidation can be microbially me-
diated and rates are higher in coastal waters. The objective
of this investigation was to determine Ce oxidation rates in
Chesapeake Bay at different times of the year using the ra-
diotracer methodology developed in MOFFETT ( 1990) and
to study the remobilization of Ce oxidized in situ under dif-
ferent conditions. The results are coupled with the data re-
ported in SHOLKOVITZ and ELDERFIELD ( 1988) and SHOL-
KOVITZ et al. ( 1992) to assess the importance of water column
redox transformations on Ce distribution in Chesapeake Bay.
EXPERIMENTAL
Determination of Oxidation State
The basic experiment involved adding Mn and Ce radiotracers to
freshly collected seawater samples and following their uptake onto
filterable particles as a function of time. Manganese and cerium ox-
idation states were not directly measured, so a protocol had to be
established for determining oxidation from the particle uptake data.
It is assumed that all dissolved Ce is present as Ce( III). Therefore,
it is necessary to distinguish particulate Ce(II1) from particulate
Ce( IV). The approach was to utilize protocols developed by earlier
workers to distinguish particulate Mn( II) from Mn oxides. SUNDA
and HUNTSMAN ( 1987, 1988) distinguished Mn oxides from partic-
ulate Mn( II) in tracer studies by treating incubated samples with
ascorbate at seawater pH. Ascorbate rapidly dissolves Mn oxides but
does not affect particulate Mn(I1) since it is not a chelator and the
pH is unchanged. Therefore, the 54Mn oxide formed is equal to the
difference in particulate 54Mn between ascorbate-treated and non-
treated samples. Ascorbate will also reduce Ce( IV) oxides to Ce( III)
in seawater at pH 8 at the same concentration (0.4 mM) used by
SUNDA and HUNTSMAN ( 1987, 1988). This was determined in the
following experiment. Ascorbate (0.4 mM) was added to a suspension
of Ce( IV) oxide particles (Aldrich Chemical Co.) in seawater, and
the formation of Ce( III) followed spectrofluorimetrically. Ce( III) is
strongly luminescent in seawater, but Ce(IV) is not (CARPENTER
and GRANT, 1967). Results indicate complete reduction of Ce(IV)
on the timescale of the measurement (30 s-60 s). The difference
between particulate ‘j9Ce in ascorbate-treated and nontreated samples
can be attributed to Ce( IV). However, this fraction could also include
Ce( III) adsorbed onto Mn oxide surfaces which are dissolved by
ascorbate. Therefore, this approach is not unequivocal, so a second
approach was also used. Another lanthanide, 15’Eu, was added to the
solutions as a nonredox reactive control. Ideally, either La or Pr
isotopes would be used as a control, but Eu, separated from Ce by
four other elements, is the nearest Ianthanide with a long lived, carrier
free, isotope. It is important to establish experimentally that Eu( III)
partitioning is comparable to Ce(III) partitioning in seawater because
systematic differences in trivalent coordination chemistry are observed
within the lanthanide series (CANTRELL and BYRNE, 1987) which
may make their behavior significantly different. There is considerable
data for lanthanide partitioning onto a variety of surfaces in seawater.
Surfaces include Fe and Mn oxides, Al oxide, calcite, aragonite and
diatomite, algal surfaces, and glass beads with natural organic surface
films (BYRNE and KIM, 1990; KOEPPENKASTROP et al., 1991). For
all these surfaces, distribution coefficients for Ce and Eu are extremely
similar (within .05 log units) except for Mn oxides, where Ce oxidation
is probably occurring ( BYRNE and KIM, 1990; KOEPPENKASTROP et
al., 1991). These data indicate that Eu is a valid nonredox reactive
control for Ce. MOF’FETT ( 1990, 1993) has shown that ‘39Ce and
“‘Eu behave identically when oxidation is not occurring in coastal
and oligotrophic waters, even when relative concentrations of Mn( II)
and Ianthanides are varied by a factor of I 04.
In this study, the approach was to use both methods to determine
Ce oxidation. In the original study ( MOF’FETT, 1990), good agreement
between the two were observed in the Sargasso Sea. Differences be-
tween the two methods in Vineyard Sound were attributed to ad-
sorption of some Ce(II1) and Eu( III) onto Mn oxides.
The role of bacteria in Ce and Mn oxidation was investigated by
incubating some samples in the presence of azide. Azide is an effective
inhibitor of microbial Mn oxidation (NEALSONet al., 1988), and in
the original study it was found to completely inhibit Ce oxidation
( MOFFETT, 1990). Azide is not a reducing agent or a chelator and
it does not interfere with the nonbiological oxidation of Ce( III) on
Mn oxides (Moffett, unpubl. data), One caveat is that azide is not
an inhibitor of all biological activity. Therefore, oxidation which is
inhibited by azide is probably biological, but oxidation which is not
inhibited by azide is not necessarily abiotic.
Sampling Locations
Data reported in this paper were obtained using samples collected
in March and July 1990 on the R.V. Ridgely Warfield at three stations
in Chesapeake Bay. Most of the work was carried out at station I in
the North Bay, a 30 m deep basin east of Annapolis, Md. (38”56’N,
76”23’W). This site was selected because it is seasonally anoxic and
rare earth measurements had already been taken at the station by
SHOLKOVITZ et al. ( 1992). Samples were collected from the mouth
ofthe Susquehanna River (39”35’N, 76”06’W) in March. This river
was selected because SHOLKOVITZ and ELDERFIELD (1988) had
measured lanthanide concentrations there and because it is the major
source of particulate matter to the upper bay (EATONet al., 1980).
Samples were also collected at station 4, in the south Bay (37”55’N,
76’12’W) for the photochemical experiments.
Sample Collection
Samples were collected using a pumping system comprising a
Masterflex pump with polypropylene tubing for sampling down to
25 m. The system has been used previously for measurements of rare
earths, Fe, and Mn in Chesapeake Bay and does not contaminate
the samples (SHOLKOVITZ and ELDERFIELD, 1988; SHOLKOVITZ et
al., 1992). Corresponding hydrographic data was obtained using a
Seabird CTD system.
Incubation Experiments
Within I h of collection, 2-L unfiltered samples were each spiked
with the following radioisotopes: “‘Ce, 15’Eu, and 54Mn. The radio-
tracers had been previously added to aliquots of filtered water from
the same station ( 100 ml) and allowed to equilibrate with inorganic
and organic ligands present in solution for I h prior to coming in
contact with particles. It was important to minimize sample pertur-
bation due to increasing the total concentration of each element with
the added isotopes. For instance, MOFFETT ( 1993) has shown that
Ce additions as low as 1 nM can inhibit Mn oxidation. Carrier-free
tracers were used, so their final concentrations in solution were ap-
proximately 2 pM. ‘39Ce was approximately 5% ofthe typical natural
Ce levels ( SHOLKOVITZ et al., 1992), so it could be considered a
tracer. However. 15’Eu was roughly equivalent to dissolved Eu levels
 Adsorption of Ce’+ and Mn’+ on particulates in the Chesapeake Bay 697

measured by SHOLKOVITZ et al. ( 1992). Nevertheless, it was only Fluorescence

0.0 5.0 10.0
l-2% of the total dissolved trivalent (i.e., excluding Ce) rare earth / I I I I I I I / I I
concentration in these waters. Since all of the trivalent rare earths Salinity (ppt)
are probably influenced by the same solution-particle processes, this 0.0 10.0 20.0
small increase in the overall pool is probably insignificant. 54Mn was
5-6 orders of magnitude lower than its ambient concentrations,
Samples were incubated under various conditions described below,
"">
and at specific times IOO-ml aliquots were withdrawn and filtered
through 0.2~pm Millipore filters. The radioactivity of the filters was
measured to determine the uptake of the isotopes onto filterable par-
ticles In the text, these samples are designated the controls. For each
lO.O-
experiment, additional 100 ml aliquots were withdrawn periodically
from the sample and spiked to 0.4 mM ascorbic acid in a l25-ml
polyethylene bottle. Fresh ascorbate solutions were prepared daily E
and brought up to pH 8 with ammonia. After incubating for I h, s
they were filtered and counted like a normal sample. For each sample, 0
0
a second sample was run in parallel to which I g I-’ azide was added
prior to spiking with tracer. Aliquots were withdrawn and filtered
20.0 -
from these samples periodically.

Gamma Counting

I[!,, , /
All of the isotopes used are gamma emitters, and activities on the
Millipore filters were determined using a Canberra GeLi detector
coupled to an Ortec multichannel analyzer interfaced with a personal
30.0 ' ' ' '
computer. The total activity in each sample was determined by adding 0.0 5.0
IO mg L-’ Mn oxide to a IOO-ml sample to adsorb 100% of the Oxygen (ml/l)
tracers and filtering that. Later, it was found that simply counting I I1 I I ) / 1 I ) I
0.0 5.0 10.0
the activity on 2 ml of the sample solution absorbed on a disc of
Temperature (deg. C)
adsorbent tissue roughly the size of our filters gave the same results.

Precision Fluorescence
0.0 5.0 10.0
I I I 1 I I I I / I
For uptake experiments, the standard deviation of replicates was
Salinity (ppt)
23% of the signal. Counting times (IO-20 min.) were sufficiently 10.0 15.0 20.0
long that counting errors were a negligible contribution to this vari- 0.0" , 1 I ! I

ability.

Desorption Studies

Several experiments were also conducted to measure desorption

of tracers from natural particles. Samples were prepared as outlined
above, but the entire sample was filtered 36 h after spiking. Seawater 10.0

from the same sample which was not spiked was passed through the
filtration apparatus to remove dissolved or weakly adsorbed tracer ,,:.’T
s
from the filter, which was transferred to a bottle containing 100 ml
s
of seawater. The bottle was shaken vigorously to resuspend the par- 0
ticulate material. Most of the tracer came off the filter after 2-3 min. Q

of shaking. This solution was added to samples in 300 ml round

bottom quartz flasks. Samples were taken from these flasks and filtered 20.0

to determine particulate and dissolved tracer activities. For samples

with low or zero oxygen, the flasks were capped with no headspace
and only one sample per flask was used.

Experimental Conditions

Reactions were incubated in the dark in constant temperature in- 30.;

0
cubators at the temperature of the ambient water unless otherwise Oxygen (m/A)
noted. Sunlight experiments were carried out in quartz flasks on the / I I I I I I I 1
deck of the ship, in a water bath to maintain them at sea surface 20.0 25.0 30.0
temperature. Temperature (deg. C)

FIG. 1, Hydrographic data obtained at station I in (a) March and

RESULTS (b) July 1990.

Hydrographic data for station I are shown in Fig. 1. The

water column had a typically estuarine structure at both times Plots of uptake vs. time for ‘39Ce, 54Mn, and ‘52Eu mea-
with a salinity minimum at the surface. However, stratifi- sured at station I at 5 m and 20 m depth in March are shown
cation was more intense in the summer. Consequently, in in Figs. 2 and 3. Plots obtained at station 1 at 5 m and 4 m
March the station was fully oxygenated throughout the water in July are shown in Figs. 4 and 5. In both March and July,
column, but in July oxygen declined rapidly below the mixed rapid uptake of ‘39Ce and lS2Eu was observed. In March,
layer and was undetectable at 14 m. uptake for ‘39Ce in the presence and absence of azide was
698
0 1000 2000 3000
Time (minutes)
FIG. 2. The uptake of radiotracers onto filterable particles in
a sample collected on March 12, 1990, from station 1. Depth = 4
m. ‘39Ce (m); 139Ce + azide (+); ‘39Ce + ascorbate (e); 15*Eu (A);
54Mn (+); 54Mn + azide (a); ‘52E~ + ascorbate (0).
identical, indicating that no microbial oxidation of Ce was
occurring. Ascorbate-treated samples had 5- 10% less Ce than
the control, possibly due to nonbiological Ce oxidation. Al-
ternatively, the ‘39Ce could have been adsorbed on Mn oxides
as Ce(III) and dissolved by ascorbate. However, lS2Eu was
not affected by ascorbate, which would have been the case if
a significant fraction of trivalent lanthanides were associated
with Mn oxides. “*Eu uptake was slightly lower than ‘39Ce.
This fractionation could be explained by the slight Ce oxi-
dation suggested by the ascorbate data.
In July, ‘39Ce uptake was much faster (note different
timescales in figures), with essentially 100% uptake within 5
hours. In contrast to March, there was a large difference be-
tween ‘39Ce uptake in the control and ‘39Ce uptake in the
azide-treated sample, indicating biologically mediated uptake.
Moreover, ‘39Ce in the azide-treated samples and “‘Eu in
the control were all equivalent, indicating that the difference
was due to Ce oxidation. As in March, ‘39Ce and ls2Eu uptake
100
1
a0
i
0 300 600 900 1200 1500
Time (minutes)
FIG. 3. The uptake of radiotracers onto filterable particles in a
sample collected on March 12, 1990, from station 1. Depth = 20 m.
‘39Ce (m); ‘39Ce + azide (e); ‘39Ce + ascorbate (e); ‘52E~ (A);
s4Mn (+); 54Mn + azide (+#); 15*Eu + ascorbate (0).
J. W. Moffett
0 250 500 750
Time (minutes)
FIG. 4. The uptake of radiotracers onto filterable particles in
a sample collected on July 16, 1990 from station 1. Depth = 5
m. 139Ce (H); 139Ce + azide (+); ‘39Ce + ascorbate (0); “‘Eu (A);
j4Mn (+); 54Mn + azide (S); ‘52Eu + ascorbate (0). Lines represent
values for ‘39Ce uptake in the control and azide-treated samples
calculated using the constants in Table I and the integrated solutions
to the rate equations.
in ascorbate-treated samples was lower, possibly due to some
association with Mn oxides. ‘52Eu in the control and azide-
treated samples were the same in all samples (see Fig. 5 ) but
were omitted from the other figures for clarity.
54Mn also showed a strong seasonal effect, with virtually
complete uptake in 2-3 h in July, but a much slower uptake
in March. Uptake was due to microbial oxidation as it was
inhibited by azide and not detected in ascorbate-treated sam-
ples.
Rate constants for Mn( II) oxidation derived from radio-
tracer data are generally reported as specific rates (SUNDA
and HUNTSMAN, 1987, 1988; TEBO, 1991). In the Sargasso
Sea and Vineyard Sound, Massachusetts, rates were slow
enough that specific rate constants could be determined from
0 100 200 300
Time (minutes)
FIG. 5. The uptake of radiotracers onto filterable particles in
a sample collected on July 17, 1990 from station 1. Depth = 4
m. ‘39Ce (m); ‘39Ce + azide (+); ‘39Ce + ascorbate (0); ls2Eu (A);
54Mn (+); 54Mn + azide (%); 15*Eu + ascorbate (0); 15*Eu + azide
(0). Lines represent values for ‘39Ce uptake in the control and azide-
treated samples calculated using the constants in Table 1 and the
integrated solutions to the rate equations.
 Adsorption of Ce 31 and M n 2+ on particulates in the Chesapeake Bay 699

the initial slopes ( MOFFETT,1990).In the Sargasso Sea, these The integrated solution is
slopes were linear for 4 days. In Chesapeake Bay samples,
Mn(I1) and Ce(II1) uptake deviated from linearity almost
immediately, so estimation of rate constants from initial rates
is not accurate. This is especially true for Ce( III), where the
initial rate ofoxidation is difficult to distinguish from Ce( III) + (kr- “) exp(pyzt), (5)
(r, - Yz)
adsorption in the azide treated control. An alternative ap-
proach was to propose a mechanism for the uptake process, where y, and yz are negative roots of the quadratic equation
derive a rate equation for the mechanism. and fit the inte-
grated solution to the rate equation to the entire data set.
y’ + y( k, + k, + k,,) + k,k,, = 0. (6)

rather than just using the initial points. This approach has It was desirable to constrain k, and k, first in order to obtain
been used by NYFELLER et al. ( 1984) and JANNASCH et al. the best estimate of k,, These constants were determined by
( 1988) to model radiotracer data. The simplest plausible fitting data obtained in the azide-treated samples to the in-
mechanism is rapid, reversible uptake of Ce( III) onto par- tegrated solution to the rate equation for step ( I ) alone.
ticles, competing with slower, irreversible Ce( III) oxidation:
[Ce(III) S”l”tlon
I(I1 _ k
fart
Ce( III LOiUtl””- Ce( III )pall,cu~atc (1) tCe(III)so,ut,onl~r=o, 4 + k
faas1 SIOW
CW 111)solutlon+ Cd 111)panlcu~ale*
-+ Ce( IV)part,culate. (2 1
+(1-&j exp(-(k,+ k,)t). (7)

In this scheme, Ce( III)panlcula,e* represents the particulate ad-

The equations were fit to the data using the program RS/ I
sorption sites where Ce( III) oxidation actually occurs. This
(BBN Software Products Corp.), which utilizes an iterative
is probably a small fraction of the total particulate Ce( III)
fitting technique known as Marquardt’s compromise method.
in these experiments, given the high affinity Ce( III) has for
Rate constants obtained for the July samples are shown in
many solids on which oxidation does not occur. Assuming
Table I, along with the standard errors calculated by the
that this is the case, and that the steady-state condition for
program. Curves generated from these equations are shown
these oxidatively active sites is attained rapidly, step (2) can
in Figs. 4 and 5. Mn( II) oxidation rates were also determined.
be simplified to a one-step process
Plots of In (% oxidized) vs. time were linear, indicating
Sl”W
Ce( III )sO~UflOn
+ Ce( IV )panicu~atr, (3) pseudo-first-order behavior, so the rate constants were ob-
tained from the slopes.
which would yield pseudo-first-order kinetics in the absence The pseudo-first-order rate constants k,,, were converted
of the adsorption processes occurring in step ( 1). This is a into specific rate constants k,, according to the relationship
reasonable assumption because Mn (II) oxidation presumably
k,,(%: day-‘) = 100 X 60 X 241\,,(min.-‘). (8)
occurs via the same type of two-step process shown in (2)
and obeys pseudo-first-order kinetics. This assumption can This enabled the data to be compared with specific rate con-
be tested by fitting the data to the integrated solution of the stants measured in the earlier study ( MOFFET-I,1990)where
following rate equation: the reaction order was not determined. The results are sum-
marized in Table 2, along with data obtained in March and
= ACe( III)paniculate + dW
dCe( III )sO~UllOn IV)part,cubte from MOFFETT ( 1990).The ratio of Mn to Ce specific rate
dt dt dt constants is 2: I and I .3: 1 for the samples, respectively.
Absolute rates are determined by multiplying the specific
= kf[WIII)soh,,onl - k,[Ce(III),,,,,,,,,,l rates by dissolved concentrations of Ce and Mn. However.
+ k,,[Ce(lfl),,l,,,,,l. (4) Mn and Ce were not determined in these samples, so esti-
mated absolute rates were calculated from earlier data. Con-
where k, and k, are rate constants for the adsorption and centrations of 100 nM and 152 pM for Mn and Ce. respec-
desorption of Ce( III) onto suspended particles ( I ), and k,, tively,weretaken from SHOLKOVITZ~~~ ELDERFIELD(~~~~)
is the pseudo-first-order rate constant for Ce( III) oxida- for measurements made at 5 m at station I in July 1985.
tion (3). Time series measurements of dissolved rare earths in surface

TABLE 1. Pseudo-first-order rate constants determined for station 1 samples in July. 1990.

Date Depth kl(B) k,(=’ km

(m) (min.‘)

July 16, 1990 5 0.029 + ,007 0.012 * ,003 0.0092 k ,003

July 17, 1990 4 0.050 * .017 0.044 f .019 0.014 * ,003

(a) Determined from ‘39Ce uptake in azide-treated samples.

700 J. W. Moffett

TABLE 2. Speafic rates and cstmnkd absolute rates of Ce(III) and Mn(II) oxidauon with SUNDA and HUNTSMAN (1987) who showed that specific
Mn oxidation rates varied from 115.2% day-’ in July to 4%
spec1tic Rae
day-’ in March in the Newport estuary in North Carolina.
Sample
Tracer uptake was also studied for samples collected at 25
(% day+ Rat; (nM day-‘)
m at station 1, well below the oxic/anoxic interface. The
CC Mn Ce Mn concentration of H2S was 7.7 PM (Millero, pers. commun.).
Results are shown in Fig. 6. As expected, there was no Mn
oxidation. Also, there was no preferential uptake of Ce over
A. Chesapeake Bay, July (this study)
Eu. The uptake of Ce( III) and Eu( III) is somewhat less than
sta. 1.5 m 1325 1671 .93 1671(‘) at 5 m, but increased rapidly in the flasks kept for over 8 h.
Sm. 1.4 m 2016 4032 1.41 4032(a) This appeared to be associated with the oxidation of H2S and
Fe( II) (the latter forming ferric hydroxide which probably
B. Chesapeake Bay. March 1990 (IhIs study) scavenged both Ce and Eu), in spite of the flasks being capped.
Sw.l,4m ND. 10
Results are consistent with recent findings that Ce oxidation
@) @)
does not occur in samples stripped of oxygen (MOFFETT,
sla. 1.4 In(C) N.D. IO @) @)
1993) in agreement with previous studies of microbial Mn
sta. 1.20 m N.D. 2 @) @) oxidation (TEBO and EMERSON,~~~~;NEALSON~~ al.,1988).
No detectable Ce( III) or Mn( II) oxidation occurred in
C. Sqasso Sea, May 1989 (MOFFETT, 1990)
samples collected from the Susquehanna River in March (Fig.
120m .74 2.6 I.1 x lo-“(‘) .013(a) 7 ). This may have been due to low microbial activity at this
time of year, as observed for all the estuarine samples collected
D. Vineyard Sound, September 1989 (MOFFEIT,
1990) in March. However, Ce anomalies are generally not observed
SUAXC 31.2 93.6 @) 0) in freshwaters, including the Susquehanna ( SHOLKOVITZ and
ELDERFIELD, 1988),so thismay not be solely a seasonal
effect. The addition of ascorbate had no effect, indicating
(a)Absolule rates = specific rates X Cc- 01 Mn-dissolved concenuation. Conccnuauon that Mn oxides are not an important phase for rare earth
dam are from SHOLKOVITZ and ELDERFIELD (1988) and SHOLKOVIlZ and adsorption in the river.
SCHNEIDER (1991).
Desorption experiments were conducted on samples col-
lected at station 1. Radiolabelled particles were produced by
(b) No dssolved data available.
incubating surface waters collected 10 miles south of station
(c) Temperalure of sample mcreascd from 6°C to 26’C. 1 with tracers for 36 h prior to the experiment. They were
N.D. = Not dewcmble. resuspended in waters collected from the following depths:
8 m, 10 m, 12 m, 15 m, and 25 m. Results for Mn are shown
in Fig. 8. There was no significant redissolution of particulate
waters (Sholkovitz, unpubl. data) indicate that they do not Mn until 25 m, where dissolution was extremely rapid. Dis-
vary by more than a factor of 2-3 throughout the year, so solution at 25 m was to be expected ifall the particulate 54Mn
these calculations provide a reasonable estimate. Data from is in the oxide form, as our data indicate. For Ce and Eu, the
SHOLKOVITZ and SCHNEIDER( 1991)for Ce(15 pM)and results showed no trends other than an initial rapid desorption
Mn (0.5 nM) in the Sargasso Sea were used to calculate ab- of both isotopes (data not shown ). Subsequent re-adsorption
solute rates of Ce and Mn oxidation from specific oxidation seemed to occur at the same time, creating considerable scat-
rates reported by MOFFETT ( 1990). The results indicate that ter and making the data useless for any determination of
although the ratio of specific rates of Ce(II1) and Mn(I1)
covary, absolute rates do not because of the much higher
ratio of Mn to Ce dissolved concentrations in coastal waters.
In March, the Mn(I1) specific rate was only 10% per day,
400 times lower than in July. The Ce(Il1) oxidation rate
could not be determined in March because the difference
between Ce uptake in the presence and absence of azide was
not significant. Therefore, it was not possible to determine
the ratio of Mn to Ce oxidation in March.
The seasonal differences in oxidation rates could arise from
temperature differences. The surface temperature at station
1 was 6°C in March and 26.5”C in July, and both biological
and nonbiological reactions could be enhanced by temper-
ature. However, when the temperature of the March sample
was raised from 6°C to 25°C no increase in Mn( II) oxidation 0, +,___-r_*+i
rates occurred (Table 2), indicating that the difference in 0 200 400 600
rates between March and July was more likely due to seasonal Time (minutes)
differences in bacterial abundance rather than a direct thermal FIG.6.The uptake of radiotracers onto filterable particles at station
kinetic effect. The seasonal variability in results is consistent I (depth = 25 m) on July 18 1990.'j9Ce
(m):Eu (A);54Mn (+).
 Adsorption of Ce3+ and Mn’+ on particulates in the Chesapeake Bay 701

20 A-11
0 400 800 1200 0 100 200 300 400 500
Time (minutes) Time (minutes)
FIG. 7. The uptake of radiotracers onto filterable particles at the FIG. 9. The dissolution of particulate 54Mn resuspended in a sample
Susquehanna River station collected on March 13, 1990. pH = 7.5. collected from 3 m at station 4. Dark (0); Sunlight (0).
‘39Ce (m); Ce + azide (0); ‘39Ce + ascorbate (0); “‘Eu (A); S4Mn
(+); 54Mn + azide (+K).

for Ce and Eu could not be characterized because of this

desorption rates. Therefore, it was not possible to compare
Ce( IV) reduction and Mn( III, IV) reduction as a function
of depth, to see if the reductive mechanisms for each element
are related. Since the data for Mn show much less scatter,
the problem must be partly due to desorption of adsorbed
Ce( III) which overwhelmed dissolution associated with
Ce( IV) reduction.
In seawater, manganese oxides undergo photoreduction
when exposed to sunlight (SUNDA et al., 1983; SUNDA and
HUNTSMAN, 1988 ). To determine how fast this process was
compared with the other reactions in Chesapeake Bay, the
dissolution of particulate 54Mn that had been formed by in-
cubating 3 m water from station 4 with tracers for 36 h was
studied. The samples were placed in quartz flasks and exposed
to sunlight at 1100 h on a cloudless day. The results, shown
in Fig. 9, indicate that photochemical dissolution occurred
with a specific rate of about 10% per hour. Cerium and eu-
ropium showed no difference between light and dark within
the scatter of the data (data not shown). Desorption reactions
8
0 guished from nonbiological oxidation on freshly formed mi-
01 I , I , , , , ,
0 100 200 300 400
Time (minutes)
FIG. 8. The dissolution of particulate 54Mn resuspended in samples
collected from different depths at station I. 8 m (0); 10 m (w); 12
m (A); 15 m (+); 25 m (+).
scatter. Manganese showed significant desorption at t = 0
(Figs. 8 and 9) making it difficult to follow dissolution by
measuring small increases in dissolved Mn. Consequently,
no estimates of Mn dissolution in oxic waters (except in sun-
light) or in suboxic waters were obtained. SUNDA and
HUNTSMAN ( 1988) have been successful in measuring low
rates of photochemical dissolution of particulate 54Mn they
formed naturally, but in their experiments they irradiated
the entire filter in fresh solution rather than trying to resus-
pend the particles. In this study, agitating the filter to get the
particles off may have broken the particles up into small,
filterable particles. This is plausible given the complex, fibrous
morphology of bacteria ( COWEN, 1992).
DISCUSSION
The data from Chesapeake Bay, coupled with the earlier
study ( MOFFETT, 1990), show that there is a close relationship
between Ce and Mn redox chemistry, with oxidation rates
covarying spatially and temporally. This covariance, coupled
with the fact that rates differ by only a factor of 1.3 to 3 over
a thousand-fold range in specific rates, contribute to simi-
larities in the elements’ geochemistries.
The inhibition of Ce oxidation by azide indicates that it is
microbially mediated. This observation alone does not enable
direct enzymatically mediated Ce oxidation to be distin-
crobial oxides. However, the latter mechanism is less plausible
for several reasons. It requires that Ce oxidation occurs on
fresh oxides but not pre-formed ones (present in azide-treated
samples). However, there are no data to support this premise.
Furthermore, the specific rates of Ce oxidation would be pro-
portional to the absolute rate of Mn oxidation (= formation
+ of fresh Mn oxide surface), rather than specific rates. Yet the
data in Table 2 indicate that this is not the case. For instance,
500 Ce specific oxidation rates were approximately 300 times
greater in Chesapeake Bay (station I,4 m) than the Sargasso
Sea ( 120 m). Specific oxidation rates of Mn were about 160
times greater in Chesapeake Bay, but the absolute rate of Mn
oxidation (i.e., the rate of freshly formed oxides) was 10’
702 J. W. Moffett
times greater, owing to the much higher dissolved Mn con-
centrations relative to Ce.
Ce(III) specific rates covary with Mn specific rates, not
absolute rates, which are consistent with oxidation via a
common or similar mechanism. An investigation of the re-
lationship between Ce( III) and Mn( II) oxidation in seawater
as a function of Mn (II) and Ce( III) concentrations, pH and
pOZ, supports the hypothesis that both elements are oxidized
by a common enzymatic pathway ( MOFFETT, 1993).
The significant fraction (5- 15%) of Ce( III) associated with
Mn oxides did not undergo detectable non-biological oxi-
dation, in contrast to previous studies using synthetic Mn
oxides ( BIDOGLIOet al., 1992; KOEPPENKASTROP et al., 1991;
BYRNEand KIM, 1990). Possible explanations are differences
in mineralogy between synthetic and natural oxides, the
presence of surface coatings, or differences in the solution
chemistry of the tracers.
Ce( III) oxidation rates in Chesapeake Bay in July are faster
than those measured in any other environment (Table 1).
They are clearly fast enough to account for the strong gra-
dients in Ce anomalies with depth measured at the station 1
location by SHOLKOVITZet al. ( 1992). Rapid oxidative re-
moval in the oxic zone, coupled with reduction and prefer-
ential enrichment in the anoxic zone, would give rise to the
features they observed.
Manganese and cerium have similar redox chemistries,
yet their depth profile features are not identical. From SHOL-
KOVITZ and ELDERFIELD( 1988), Mn concentrations increase
by a factor of 30 between 5 and 20 m, but Ce increases by
only a factor of 3. This is clearly related to the fact that Ce( III)
is much more particle reactive than Mn( II). In the anoxic
samples studied, less than 5% of the added 54Mn was adsorbed
onto particles, but 50-60% of ‘39Ce was; therefore, less Ce
accumulation occurs in the anoxic water because it is still
strongly scavenged. The slower oxidation rate of Ce( III) in
the oxic region should also contribute to the different con-
centration gradients.
Seasonal trends reported here for Mn( II) oxidation are in
good agreement with those of SUNDAand HUNTSMAN( 1988)
for a North Carolina estuary. They also observed much higher
rates in summer than in winter. The corresponding season-
ality in Ce( III) oxidation is consistent with a common oxi-
dative pathway for both elements. From these seasonal trends,
one would expect much more depletion of Ce relative to its
neighbors in surface waters in summer than in winter. Data
obtained by Sholkovitz (unpubl. data) in 1988 indicate that
this is the case, but Ce anomalies in the upper 2 m only vary
by a factor of two between seasons ( .35-.45 in winter vs. .18
in June). Clearly, other processes occur which maintain Ce
depletion relative to its neighbors in winter. Mixing with the
Ce depleted marine endmember contributes to this trend,
because dissolved Ce concentrations are comparable in sur-
face ocean waters and Chesapeake Bay. However, in the bay
the dissolved fraction is probably in equilibrium with some
component of the very much larger particulate fraction, which
is likely to mask the influence of the marine endmember. In
addition, there are no Ce anomalies associated with riverine
inputs if the Susquehanna river data are representative
( SHOLKOVITZand ELDERFIELD, 1988). Most likely, other
oxidative processes are occurring. There are at least three
possibilities. Firstly, microbial oxidation may be occurring
on a slower timescale than our experiments. Microbial Mn
oxidation was occurring with a specific rate of 10% per day.
It is, therefore, reasonable that some Ce oxidation was oc-
curring, although since it was not detectable, it must be at
least 1000 times lower than in summer. Secondly, nonbio-
logical oxidation of Ce adsorbed on Mn oxides may be oc-
curring. Results reported here, which show that a significant
fraction of Ce(II1) is adsorbed on Mn oxides indicate the
potential for this reaction, albeit at a rate too slow to measure.
Finally, either biological or nonbiological oxidation at the
sediment water interface may be occurring at rates higher
than in the water column.
The high rates of Ce oxidation in this study should lead
to much larger negative Ce anomalies in surface waters than
0.18. However, seasonal variability in the reduction and re-
cycling of Ce( IV) may also offset the seasonal variability in
oxidation. SHOLKOVITZet al. ( 1992 ) reported large positive
Ce anomalies in porewaters at station 1 in summer, which
would provide a strong source of Ce to the water column.
Values in the winter were much lower suggesting that recy-
cling would be less important. Under those conditions, even
slow oxidative processes could maintain the wintertime Ce
anomaly.
Photoreductive dissolution of Mn oxides is also a poten-
tially important process in recycling dissolved Mn back into
the oxic zone as proposed by Sunda (SUNDA et al., 1983;
SUNDA and HUNTSMAN, 1988). However, specific photo-
reduction rates are still only about 10% of microbial oxidation
rates at sea-surface midday-light intensities, and probably
drop off rapidly with depth owing to the high light attenuation
of bay waters.
The variation in specific Mn and Ce oxidation rates by a
factor of two at station 1 in July between the two samples
shown in Figs. 4 and 5 cannot be explained by the limited
data set. However, microbial Mn(I1) oxidation is photo-
inhibited and shows a pronounced die1 cycle in some coastal
environments ( SUNDAand HUNTSMAN, 1988 ). The sample
from July 16 was collected at 1100 h and the sample from
July 17 was collected at 0900 h, so progressive photo-inhi-
bition of oxidation during the morning could account for
the variability. The difference in depth (4 m vs. 5 m) is un-
likely to be a factor, since hydrographic features were constant
over this range.
Eu( III) and Ce( III) behave similarly when oxidation does
not occur. Consequently, it would be expected that La, Nd.
and Eu should behave similarly in Chesapeake Bay. This is
generally the case, as shown by SHOLKOVITZet al. ( 1992) at
station 1 in July 1988. Fractionation among the trivalent
rare earths only becomes significant between the light to
middle rare earths and the heaviest rare earths. This is con-
sistent with data for distribution coefficients measured for
La, Nd, and Eu on various surfaces (KOEPPENKASTROPet
al., 1991; BYRNEand KIM, 1990) which show little fraction-
ation between light and medium rare earths, but significant
fractionation between these elements and the heaviest rare
earths.
Ascorbate-treated samples showed that 5-15% of Eu( III)
and Ce(II1) were probably associated with Mn oxides in
March and July. Manganese oxides are proposed to be im-
 Adsorption of Ce 3+and Mn *+ on particulates in the Chesapeake Bay
portant in lanthanide scavenging across the oxic/anoxic in-
terface in the Cariaco Trench (DE BAAR et al., 1988) and
the Black Sea ( SCHIJF et al., 199 1). However, porewater data
from Chesapeake Bay show that Ce (and other rare earths)
are correlated more closely with Fe than Mn ( SHOLKOVITZ
et al., 1992). This is not necessarily inconsistent, as Mn oxides
may be important in the transport of rare earths to the sed-
iments, but subsequent diagenetic processes may result in
rare earth incorporation into iron oxides.
Acknowledgments-Technical assistance was provided by Carla
Zimmerman. Thanks to E. Sholkovitz and N. Blough for their in-
valuable contributions to this work. Thanks also to three anonymous
reviewers for their careful and detailed criticisms. This work was
supported by National Science Foundation contract OCE-88 1740 1.
This is Contribution No. 8227 from the Woods Hole Oceanographic
Institution.
Editoriul handling: L. S. Balistrieri
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