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HydrobiohJ,q, ia 304: 197-207, 1995.

197
@ 1995 Kluwer Academic Publishers. Printed in Belgium.

Geochemical partitioning and bioavailability of copper to aquatic plants in
an artificial oxide-organic sediment

L. A. Warren I, E M. Outridge 2 & A. R Z i m m e r m a n 1
IDepartment ofZoolog3; UniversiO, of Toronto, Toronto, Ontario M5S 1A 1, Canada
2Environmental and Resource Studies Program, Trent UniversiO; Peterborough, Ontario K9J 7B8, Canada

Received 4 August 1993; in revised form 24 February 1994; accepted 2I April 1994

Key words." copper, bioavailability, toxicity, sediments, partitioning, macrophytes

Abstract

This study investigated the effects of competition between binding substrates (organic matter and iron oxide) and
between metals (cadmium and copper), on the partitioning of sedimentary copper and its subsequent bioavailability
to an aquatic plant. Organic matter and a synthesized iron oxide, ferrihydrite, were added singly and in combination
to a series of sand sediments, which were then dosed with environmentally realistic concentrations of cadmium and
copper and planted with rice, O0'za sativa.
Organic matter controlled copper partitioning and bioavailability, whereas the synthetic ferrihydrite bound
negligible amounts of either metal, even in the absence of organic matter. As organic matter concentrations
increased, operationally-defined leachable copper decreased, organic-associated copper increased and the survival
of rice plants improved in an approximately linear fashion. At a nominal starting copper concentration of 5.8 F~g g
dry wt -I , plant survival after four weeks averaged 0-8% in sediments without organic matter, 25% in a sediment
containing 0.18% organic matter and 58% in a sediment containing 0.36% organic matter. These results suggest
that organic-associated forms of copper are unavailable to plants, and that the operational definition of 'leachable'
copper (extracted with dilute ammonium acetate) adequately represents the species of copper that is (are) available
to plants. Our study using a well-characterized artificial sediment supports the copper fractionation patterns and
correlations between copper partitioning and bioavailability reported from the heterogeneous, poorly characterized
sediments of natural lake and river sediments.

Introduction ligands (Cahnano et al., 1988; Fulghum et al., 1988;
Tessier et al., 1985).
Aquatic systems constitute the largest sink for heavy Beyond these broad generalizations, however, a
metals mobilized by anthropogenic activities (Nriagu number of specific questions remain unresolved. One
& Pacyna 1988). Currently, a prevalent paradigm for issue concerns the relative sorptive affinities of particu-
metal toxicology and biogeochemistry is that geo- late organic matter and metal oxides for different trace
chemical partitioning between solid (sediment) and metals. For example, in oxidized, organic-rich natural
solution phases is the key factor controlling the avail- sediments, copper is usually most strongly associat-
ability, and hence toxicity, of metals to biota in aquatic ed with organic matter (Warren & Zimmerman, 1993;
environments (Campbell et al., 1988; Luoma, 1989). Chen et at., 1989; Tessier et al., 1980), although this
Furthex'more, the partitioning of metals in sediments association may be less important in sediments that are
(i.e. their distribution among different geochemical relatively high in iron oxides and low in organic mat-
substrates), is influenced by environmental factors ter (Luoma & Bryan, 1981; Luoma, 1986). In contrast,
such as pH and Eh, the abundance of organic and inor- metals such as cadmium tend to be associated only
ganic materials (clays and hydrous metal oxides), and weakly with organic matter, favouring the carbonate
the concentrations of competing cations and solution and 'exchangeable' fractions (Warren & Zimmerman,
198

1993; Pardo et al., 1990; Tessier et al., 1980), or metal cations, and realistic concentrations of metals. Tile
oxides (Reuther et al., 1981 ). objective of our laboratory-based study is two-fold.
Another primary area of interest is the nature of the First, we examine the geochemical partitioning of cop-
relationship between metal partitioning and bioavail- per in a series of sandy sediments containing varying
ability. Key questions include the identity of the proportions of a synthesized iron oxide (ferrihydrite)
'bioavailable" fo,ms of metals, how they are quanti- and organic matter (peat). The effect of another cation,
tatively influenced by sediment constituents, and the cadmium, on the partitioning of copper was also inves-
most appropriate means of measuring these forms tigated. Second, we relate tile observed differences in
(Luoma, 1989: Campbell & Tessier, 1989). One partitioning to the availability of copper to an aquatic
approach used to address these questions has been macrophyte, O0'za sativa, that was grown in the sedi-
to test for correlations between various operationally- ments. Specifically, we test the hypothesis that increas-
defined metal fractions in sediments and either the met- ing amounts of organic matter in sediments will lower
al concentrations in or toxicity to sediment-associated the bioavailability of copper to the macrophyte.
biota such as macrophytes, bivalves and other benthic
invertebrates (e.g. Campbell et al., 1985; Thompson
et al., 1984: Luoma & Bryan, 1978). A positive corre- Materials and methods
lation between the concentrations in a given sediment
fraction and ill biota would suggest that the fraction E x p e r i m e n t a l design
in question is "bioavailable'. Most studies of this type
have been carried out on natural systems, analysing The experimental design was an unbalanced two-way
sediments and biota collected from the field. factorial analysis of variance (Table 1), set up as a
In contrast, a second approach, which has produced sand culture experiment (Hewitt, 1966). Two different
most of our current theoretical knowledge regarding metal treatments, Cu alone or a mixture of Cu + Cd,
metal sorption onto solid phases, has largely involved were added to each of 4 sediment types: the sand sed-
laboratory model systems using well-defined "artifi- iment, 700 g of fine silica sand (SAND): oxide sedi-
cial' particles, predominantly metal oxides (Honey- ment, 2.5 g of ferrihydrite added to 700 g sand (OX);
man & Santschi, 1988). Because of the complexi- organic sediment, 2.5 g of peat added to 700 g sand
ty of metal-particle interactions, two common fea- (OM); and mixed sediment, 1.25 g each of ferrihydrite
tures of this type of study are single metal-substrate and peat added to 700 g sand (MIX). To account for
experimental designs, and the use of synthetically- any differences in partitioning due to the presence of
derived goethite (a-FeOOH), a crystalline Fe oxide plants, a sediment control (Cd +Cu treatment with no
(e.g. Ankomah, 1992; Barrow et al., 1989). In nat- plants) was included for each sediment type. Similarly,
ural sediments, however, other oxides such as ferri- to account for any differences in plant growth due to
hydrite and lepidocrocite have been identified (Fortin sediment type, a plant control (no metal treatment) was
et al., 1993: Tessier et al., 1993), which are more also included for each sediment type.
amorphous than goethite and consequently may have Ferrihydrite binding capacity was assumed to be
quite different sorption characteristics (Schwertmann 0.005 tool metal per tool Fe at a pH of 6.5 to 7,5
& Cornell, 1991). Natural systems may also contain (Dzombak & Morel, [990), so that 2.5 g of ferrihydrite
multiple binding substrates in potential competition for should theoretically be able to complex 2.6 × 10 - 4
metals. Thus, the degree to which the laboratory-based moles of metal ions. An initial experiment was car-
literature has direct relevance to questions of metal ried out with the peat to determine its binding capacity.
bioavailability in natural systems remains unclear. Rel- A 200 rnl volume of 5 mg 1- I Cu was added to a
atively few studies of metal-particulate associations in series of beakers containing fiom 0.25 to 3.0 g of peat,
natural systems (e.g. Tessier et al., 1993, 1989, 1985, and porewater Cu concentrations were measured after
1980; Warren & Zimmerman, 1994; Bendell-Young one week. This experiment revealed that 2.5 g of peat
& Harvey, 1992) are available for comparison with was able to complex 2 x 10 - 4 moles of Cu, rough-
laboratory-derived literature. ly equivalent to that for the same mass of Fe oxide.
This study aims to link these two different Both the Cu and the Cu + Cd treatments employed the
approaches, by employing a well defined artificial sed- same total molar concentration of metal (8.9 × 10 - s
inaent that has environmentally relevant characteris- M) in each sediment type. In the Cu + Cd treatment,
tics, namely, competing binding substrates and metal this was achieved by adding 3.12 × 10 -5 moles each
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Oxide and organic matter in amounts appropriate
Table 1. Experimental design
for each sediment type were individually mixed with
Sediment type 700 g of air dried silica sand in plastic bags. The
Metal Sand Oxide Mixed Organic metal treatments were added in solution (50 ml vol-
Treatments Matter ume diluted from BDH 1000 ppm Atomic Absorption
Standard), and the sediment again thoroughly mixed
Sediment
before being transferred to 100 mm Standard plastic
control
(no plants, 11=4 n=4 n=4 n=4
plant pots. Each pot was acid washed prior to use, and
Cu+Cd)
contained an acid-washed circle of nitex mesh (I #m
pore size) at the bottom to retain sediments and allow
Plant for water movement into the pots. The pots were then
control n = 6 n = 6 n= 6 n= 6 kept immersed in deionized ultrapure water buffered
(no metal ) to pH 6.5 to allow for development of a partitioning
equilibrium over a two week period. An initial sedi-
Cu 5.8 Fzg g - 1 n = 4 11 = 4 n= 4 n= 4 ment sample was collected for fractionation prior to
rice seedlings being planted in the pots at the start
Cu + Cd of the experiment (see below). Samples were collect-
5 # g g - I Cd + ed from three replicates from each of the sand sed-
2 . 9 / z g g - t Cu n=4 n=4 n=4 n=4 iments (SAND column, Table 1), and from all four
sediment types in the Cu + Cd treatment (bottom row,
Table I ).

of Cu and Cd to the 700 g of sediment in each pot, Plant material and culture
giving nominal concentrations of 5 #g g dry weight-I
Cd and 2.9 pg g dry wt - I Cu, while in the Cu treat- Seedlings of rice (Oryza sativa var. M 101 ) were grown
ment, 6.23 x 10 -5 moles of Cu was added (giving a in a soil/peat mixture under combined natural and flu-
concentration of 5.8 Ftg g - l ) . The metal concentra- orescent light in a greenhouse for five weeks, at which
tions added approximately an order of magnitude less time they were approximately 20 cm high. The plants
cations than could theoretically be complexed by the were carefully separated from the soil, and the shoots
number of particulate binding sites available, thus pro- and roots trimmed to 5 cm and I cm respectively. Six
moting competition between geochemical fractions for plants were collected for initial dry wt and copper and
metal ions. In addition, the metal concentrations are in cadmium analyses. Three seedlings were transplant-
the range reported for sediments in lakes near Sudbury, ed into each of the pots containing the experimental
Ontario (Tessier et al., 1993, 1985), with the Cd con- sediments, and placed in the greenhouse under natu-
centration well below the threshold toxicity level of ral light supplemented by fluorescent lights on a 14:10
30 Itg g dry w t - I reported for rice (Muramoto et al., light:dark cycle. Each pot was placed in a larger con-
1990). tainer that acted as a water reservoir, ensuring the sedi-
ment remained saturated during the experiment. Ambi-
Sediment preparation ent temperatures in the greenhouse varied daily from
approximately 23 to 35 °C.
Ferrihydrite was prepared by precipitation with alkali At intervals of four days, each pot received 40 ml
following the protocol of Schwertmann and Cornell of nutrient medium in its external water reservoir. The
(1991). Briefly, 1M KOH was added to Fe(NO3)3 • nutrient was Peter's Professional 20/20/20 Medium,
9H20 dissolved in distilled water, until the pH of the added at a rate of 5 g l-I distilled water, and was
solution was between 7 and 8. The resulting slurry was adjusted to pH 6.5 with 1 M HNO3 and NaOH. Dis-
then centrifuged (12000 × g , 10 minutes) to remove tilled water that was adjusted to pH 6.5 was added as
the supernatant, dialyzed over 2-3 days to remove elec- necessary to maintain sediment saturation. Plant mor-
trolytes, and freeze dried. The peat (Canada Brand, tality was noted every second day, and dead plants
Annapolis Valley Peat Moss Co., Nova Scotia) was removed.
sieved to retain only particles less than 2 mm in diam- The experiment was terminated after 28 days, when
eter. approximately 10 g of sediment for metal fractionation
200

analysis was sampled from the upper three cm of each Results
pot. All plants were then carefully excavated, washed
with distilled water to remove adhering sediment par- Initial concentrations and partitioning of metals
ticles, and dried at 60 °C overnight. After cooling,
they were weighed, and digested with hot concentrat- Tile total Cu concentration in the plant control sand
ed HNO3. The digestate was cooled and made up to sediment (i.e. no added metal) at the start of the exper-
constant volume with deionized-distilled water. iment was 0.67-1-0.03 ttg g dry wt - I . By compari-
son, the sand sediment of the Cu treatment contained
Sediment extraction 1.9 #g g - i Cu (Fig. la), which was markedly low-
er than expected (nominally 5.8 #g g - i ) . Mean Cu
All glassware, centrifuge tubes, vials and pipettes were concentrations recovered initially from the C u + C d
acid washed in 10% HNO3 and rinsed with deionized treatment ranged from 2.26 to 3.10 #g g - I , which
water five times prior to use. A sequential extraction were close to the nominal concentration of 2.9 #g g-~,
procedure, modified from Tessier et al. (1979), was and showed no significant differences between sedi-
used to extract metals in four operationally defined ment types (/?>0.88; Fig. lb). Therefore, the relative
phases: leachable (exchangeable and carbonate associ- proportions of Cu in each geochemical fraction were
ated: 1M NH4OAc, room temperature for 5 hours with compared across all four sediment types in the Cu + Cd
continuous agitation); reducible (oxide associated; treatment. The leachable and oxidizable forms of Cu
0.04M NH~OH.HCL in 25% HOAc, heated to 96 °C., dominated in different sediment types. In the sand sed-
with occasional agitation for 6 hours); oxidizable iment, the proportion of leachable Cu (68%) was sig-
(organic associated; 0.02M HNO3, 30%H202, heat- nificantly higher than in other sediment types, while
ed to 85 °C with occasional agitation for 3 hours); and the organic sediment (OM) had a significantly high-
residual (resistate mineral phases; 4: l HNO3 + HCIO4 er proportion of oxidizable, i.e. organic-associated,
digestion, extracted with 4:1 deionized water+ warm Cu (69%). Surprisingly, reducible Cu (i.e. oxide-
6M HC1). A 20:1 ratio of reagents to dry weight of associated) was significantly higher in the mixed (29%)
sediment was used (see Warren & Zimmerman (1993) than in the oxide sediment (12%), which contained
for a complete set of reagents and conditions). about the same relatively small amount of reducible
The supernatants from each extraction step were Cu as the sand and organic sediments. The fractiona-
analyzed for Cu and Cd using flame atomic absorption tion patterns in the sand sediment were not significant-
spectroscopy (Laboratory Instruments Spectropho- ly different between the Cu and Cu +Cd treatments
tometer, Model 351 ). Blanks and NBS reference mate- (cf. Figs la, lb; p>0.10), suggesting that the presence
rial (NBS 2704, Buffalo River Sediment) were also of Cd had no effect on the partitioning of Cu.
run through the extraction; the total concentrations of The total concentrations of Cd recovered initially
metal recovered from the latter samples were within in the Cu +Cd treatment were similar to the nominal
the certified ranges. level of 5 #g ~o.--I , and showed no significant differ-
ences between sediment types (p>0.70; Fig. lc). In
Statistical procedure terms of fractionation, the leachable form of Cd was
dominant. Similarly as for Cu, the sand sediment had
Data on metal concentrations were log transformed, a significantly higher leachable fraction of Cd (91%)
and proportional metals and plant survival data arc- than other sediment types, while the OM sediment had
sine transformed, prior to statistical analysis. Plant the lowest (61%). Reducible Cd was significantly high-
survival was analysed by analysis of variance with er in the oxide, mixed and organic sediments compared
repeated measures, followed by Duncan's multi-range to sand.
test for differences between sediment types. All other
data were analysed by ANOVA followed by Duncan's Plant survival, growth and metal accumulation
test for differences between sediment types and metal
treatments. Data in figures and the text are shown as The concentrations of Cu and Cd used in these treat-
mean+standard error. Significance levels in the text ments were far more toxic to the rice plants than was
are at p<0.05 unless stated otherwise. expected, based on previous studies with rice. Both Cu
and Cu + Cd treatments resulted in rapid mortality of
plants in most sediment types, with <20% survival by
201

c,, (o) ,oo,\_ ..... ...............................................
(Cu Treatment)

.............................,,:_ ..................
i %
d~ S
{;~f,:3 RESIDdAL
U
OX~DIZASIE R
I I REOUCIBLE V
LEACHABLE I
1
V
O
R 40 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

0 S
H
I
P

Cu (b)
(Ou+Od Treatment)

3 0 5 10 15 20 25 30
7 ELAPSED TIME (DAYS)
Cu

- - SAND o OX o MiX - ~ - OM
1 Fig. 2. Plant survivorship in the Cu treatment.

0 100~

od (c) 80
(Cu+Od Treatment)
%

S
U 60
q~ R
V
I
V
O
R 40
S
H
t
SAND OX MIX Old P

Fig. 1. The total concentrations and proportions in each extracted 20
fraction of (a) Cu in the Cu treatment, (b) Cu in the Cu +Cd treat-
ment, and (c) Cd in the Cu + Cd treatment, at the start of the exper-
iment. Concentrations are shown as mean totals-t-standard error;
proportional data are shown as means, represented within each bar. 0
0 5 10 15 20 25 30
ELAPSED TIME (DAYS)
Cu + Cd
the end of the experiment (Figs 2, 3). The majority of Fig. 3. Plant survivorship in the Cu + Cd treatment. Symbols as in
plants in the plant control survived (Fig. 4), although Fig. 2.
mortality (22%) in the oxide sediment was significant-
ly greater than in other sediments.
The exception to the pattern of high mortality was (organic-oxide) sediment also had significantly elevat-
in Cu treatments with sediments containing organic ed survival compared with the oxide sediment. The
matter (Fig. 2). Plants grown in the organic sediment differences in survival between sediment types were
exhibited significantly higher survival than in any oth- roughly proportional to their levels of organic matter,
er sediment throughout the experiment. The mixed since survival averaged 58% in OM pots containing
202

100'
Table 2. Finalbiomass and copper content of plants surviving to end
of the experiment+ .

80 ............................................ Metal Sediment
type
treatments Sand Oxide Mixture Organic
%
manet
S
U 60 .....................................................
A) Biomass (g dry wt)x
R
V
I Plant 0.024 0.022 0.033 0.029
V
0 Control -4-0.003 + 0.005 4- 0.022 + 0.011
R 40 . . . . . . . . . . . . . . . . . . . . . .
S
H
1
Copper 0.036 - 0.036 0.045
P (n = 1) 4- 0.009 4- 0.037
20 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Copper + - 0.032
Cadmium (n = I)

0 I I I t I I
B) Copper content (#g g dry wt- I)~
0 5 10 15 20 25 30
ELAPSED TIME (DAYS)
Plant 79 q-- 1l A 90 4- 35A 74 4- 37A 38 4- l0 B
CONTROL
Control
Fig. 4. Plantsurvivorshipin the control treatment(no added metal).
Symbols as in Fig. 2.
Copper I. 195 165 4- 81 328 4- 134
01 = 1)

Copper + - 124
2.5 g (0.36%) of organic matter, 25% in MIX pots that
Cadmium (n = I)
had 1.25 g (0.18%) organic matter and 0 - 8 % in the
OX and SAND sediments that contained no organic
matter. +: data shown as mean 4- standard deviation
In terms of plant growth, there was no significant =: initial biomass was 0.014 4- 0.002 g dry wt (n = 6)
difference between sediment types in any metal treat- (~:initial copper content of plants was 36 4- 12 ttg g dry wt- J
Different superscripted letters indicate differences between sediment
ment (Table 2a.). However, plants that survived in the types significantat p<0.01.
Cu treatment produced markedly more biomass than
those in the control. Plants in the Cu-treated sediments
grew an average of 2.6- to 3.2-fold during the study
period, compared to only 1.7- to 2.4-fold in the con- Changes in metal partitioning during the
trol, suggesting that Cu deficiency was limiting growth experiment
in the control treatment. This suggestion is supported
by the Cu content data on the plants. The Cu-treatment Sediment samples taken at the end of the experiment
plants contained significantly higher Cu concentrations enable changes in the sedimentary partitioning and
than control plants (Table 2b), which no doubt reflects concentrations of metals during the experiment to be
the higher Cu concentrations in the treated sediments. identified. A c o m m o n feature of oxide sediments in all
An interesting result from the plant control was that metal treatments was a loss of most of the added metal
plants grown in the organic sediment exhibited sig- from the pots. In the Cu + Cd treatment, for example,
nificantly lower Cu concentrations than those in other this loss amounted to approximately 63% (1.13 g) of
sediments (p<0.01). In fact, the plants in OM sedi- the Cu and 85% (2.53 g) of the Cd present at the start
ment contained virtually the same concentration of Cu of the experiment. The mixed oxide-organic sediment
(38/~g g - i ) as seedlings at the start of the experiment showed smaller losses of Cu and Cd, and the sand
(36 #g g-X), while plants in other control sediments sediment exhibited similar losses of Cd. Presumably,
more than doubled their Cu contents during the exper- this metal flowed out of the sediments into the external
iment. reservoirs. The following discussion will therefore be
203

confined to those treatments which did not show sig-
nificant losses of total metal during the experiment.
In the Cu-treated sand sediment, the total Cu con- 4
v///J/////.4(Cu Cu
Treatment)

centration increased slightly during the experiment
27 70
(p>0.18, Fig. 5a cf. Fig. la), probably due to Cu T 3
added in the nutrient medium. Across sediment types,
the proportion of leachable Cu decreased, and oxidiz- 2
able Cu increased in an approximately linear fashion,
as the amount of organic matter increased (Fig. 5a). 1
The organic sediment had a significantly lower pro-
portion of leachable Cu (9%) than the sand (35%), and o

a significantly higher proportion of organic-associated
Cu (70%) than either the mixed (47%) or sand (27%)
sediments at the end of the study. ou (b)
(Cu+Cd Treatment)
In the Cu +Cd treatment, total recoverable con-
centrations of Cu again increased significantly in the
organic sediment, and decreased significantly in the
T
oxide sediment, but did not change appreciably in the c~
mixed or sand sediments (Fig. 5b). In terms of parti- ::L
tioning, a decrease in leachable Cu was observed in
the mixed sediment during the experiment (leachable
Cu initially 21%, final 8%; p<0.01). In the sand sed- 10

iment, reducible Cu increased during the experiment ;;ii~ii;iii

(initially 12%, final 34%; p<0.01) while there was no
change in the proportion of leachable forms. The losses
10
of total Cd observed in the mixed and sand sediments 9 Od (C)
over the study period were due to significant decreases 8 (Cu+Cd Treatment)
in leachable forms (p<0.01; Fig. 5c, cf. Fig. lc). No 7
significant difference was observed between initial and T 6 7""
final partitioning of Cd in the organic sediment. 5 a4
Cr~
::L 4

Discussion

Copper fractionation in these artificial laboratory sed- o
SAND OX MIX OM
iments was strongly influenced by the presence of Fig. 5. The total concentrations and proportions in each extracted
organic matter, with the fraction of oxidizable (organic- fractionof(a) Cu in the Cu treatment, (b) Cu in the Cu + Cd treatment,
associated) Cu increasing proportionally with organic and (c) Cd in the Cu + Cd treatment, at the end of the experiment.
matter content. Our data are consistent with the strong Legend as in Fig. 1.
association of Cu with organic matter that is well
documented across a variety of natural aquatic sedi-
ments: lake sediments (Pardo et al., 1990; Bendell- oxidizable-associated Cu in the presence of organic
Young & Harvey, 1992; Chen et al., 1989); fluvial matter.
suspended particulate matter (Warren & Zimmerman, These changes in fractionation among sediment
1993); river sediments (Tessier et al., 1980); and estu- types were associated with changes in copper bioavail-
arine sediments (Luoma & Bryan, 1981). Leachable ability and toxicity. The decrease in leachable Cu and
forms of Cu decreased as oxidizable Cu increased in increase in oxidizable Cu was accompanied by signifi-
this experiment, while the reducible and residual frac- cantly improved survival of the rice plants growing in
tions remained relatively constant, suggesting a con- the organic sediment. These results lead to two conclu-
version from leachable (more loosely associated) to sions. First, organic-associated Cu was less bioavail-
able to the plants than leachable Cu. This finding was
204

supported by data from tile control treatment in which Other potential influences on the partitioning of
plants grown in organic sediments accumulated signif- Cu, i.e. Cd as a competing cation, and the presence of
icantly less Cu than plants in sediments with lower or aquatic plants, were found to be negligible. There were
no organic matter. Similarly, Campbell et al. (1985) no significant differences in partitioning between the
reported a somewhat lower correlation between oxi- Cu + Cd (with plants) and sediment control (Cu + Cd
dizable Cu in river sediments and Cu in macrophyte without plants) treatments. It may be that plants are
tissues, than with extractable Cu, again indicating a only a factor in reduced sediments, in which plant
lower availability of oxidizable forms of Cu. The sec- roots can create an oxidized mizosphere that alters
ond conclusion is that the operational definition of metal partitioning relative to the surrounding reducing
'leachable' Cu employed here (i.e. dilute ammoni- conditions (Crowder et al., 1987; Crowder & Mac-
um acetate extraction) provides a good approximation fie, 1986). Here, the oxidized nature of the sediments
of the bioavailable forms of Cu. It appears that vari- would preclude an effect from the plants. While sedi-
ous extraction schemes may adequately represent the ment Eh was not measured, we are reasonably certain
bioavailable fraction of sedimentary Cu, since field that the sand-based sediments remained oxidized, as
studies of the fractionation of Cu in underlying sed- visual examination of sediment profiles at the end of
iments and concentrations in tissues of Nuphar lutea the experiment revealed no black precipitate indicating
(Aulio, 1980) and Nuphar variegatum (Campbell etal., the presence of iron sulphides i.e. reduced conditions.
1985) found similarly good agreement using different The absence of Cd competition for Cu binding sites was
reagents to define the 'extractable' or 'leachable' frac- indicated by the consistent similarities in Cu fraction-
tions. ation between the Cu and tile Cu + Cd treatments with
We saw no consistent evidence that the the sand sediment at the start of the study, and across
synthetically-derived iron oxide, ferrihydrite, bound all sediment types at the conclusion of the study. Our
Cu or Cd to an appreciable degree. The mixed organic- findings are in accord with tile concept of heterogene-
oxide sediment was found to contain a larger propor- ity of solid binding sites suggested by Benjamin and
tion of oxide-associated Cu than the organic (oxide- Leckie (1981), who showed that particulate binding
fiee) sediment, suggesting that competition for Cu sites that have a high affinity for Cu are not preferred
might have occurred between organic matter and oxide for Cd, and thus minimal competition between the two
in the mixed sediment. However, the oxide sediment metals could be expected.
contained negligible amounts of oxide-associated Cu, An unexpected result was the 'loss' of recoverable
whereas the majority of Cu in the organic sediment Cu and Cd from the oxide sediment during the experi-
was organic-associated. This indicates that under the ment. Sand culture experiments such as these are rou-
conditions of the experiment, organic matter was a tinely used in plant nutrition and phytotoxicity studies
more effective sink for Cu than the synthetic oxide (Hewitt, 1966), and no such loss of Cu occurred in the
on a unit weight basis, corroborating studies of Cu sand or organic sediments during this study, suggesting
partitioning in natural systems in which both organic an effect associated with the presence of the synthetic
matter and iron oxide were present (Warren & Zimmer- ferrihydrite. Strangely, the losses did not occur during
man, 1993; Bendell-Young & Harvey, 1992). It should the two week sediment equilibration period prior to
be noted that both the pH of the experimental medium the experiment. Scanning electron microscope (SEM)
(pH 6.5) and the type of organic matter used here (peat, images of the oxide sediment at the start of the exper-
a refractory organic substance) would favour the asso- iment indicated a relatively amorphous coating of Fe
ciation of Cu with organic matter (Inskeep & Baham, oxide on sand particles (Fig. 6). We hypothesize that
1983). Our findings differ from those of Luoma & this coating may account for the loss of metal, if it
Bryan (1981) and Luoma (1986) who reported that prevented metals from sorbing to sand grains. As dis-
organic-Cu associations in estuarine sediments were cussed, the oxide was ineffective at binding Cu or
less dominant in the presence of increasing amounts Cd from solution, in apparent contrast to naturally-
of iron oxides. While a definite explanation is elusive, occurring metal oxides. Diagenesis of the oxide was
the discrepancy between studies may reside in differ- also apparent, because SEM images taken one month
ences in ambient pH, the type (natural versus synthetic) after the experiment concluded revealed that the oxide
and concentrations of iron oxides in each system, or no longer coated sand particles as amorphous mate-
changes in organic behaviour at the relatively higher rial, but was more crystalline in appearance (Fig. 7).
ionic strength of estuarine waters. These age-related changes, which have been report-
205

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\

, !

Fig. 7. SEM images of the OX sediment taken one month after the
Fig. 6. SEM images of the OX sediment after the two week
experiment concluded, i.e. oxides were kept in an aqueous state for
equilibration period, prior to the introduction of the plants. A sand
8 weeks. A sand grain coated by Fe oxide appears in the middle of
grain coated by Fe oxides can be seen in the middle of (a), and this
(a), and this same sand grain shown at higher magnification in (b).
same sand grain shown at higher magnification in (b). Fe oxides
Fe oxides appear more crystalline in comparison to the images in
appear as a relatively amorphous coating on the sand grains.
Fig. 6.
206

ed p r e v i o u s l y in h y d r o u s ferric o x i d e s , are e n h a n c e d Campbell, E G. C. & A. Tessier, 1989. Geochemistry and bioavail-
b y h i g h e r t e m p e r a t u r e s ( 2 0 - 3 0 °C; D z o m b a k & M o r e l , ability of trace metals in sediments, In Boudou A. & F. Ribeyre
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f a v o u r the a g i n g p r o c e s s . T h e a p p a r e n t d i a g e n e s i s o f Accumulation of copper and zinc in the yellow water lily, Nuphar
the F e o x i d e p r e c l u d e d t e s t i n g t h e a b o v e h y p o t h e s i s in variegcmcm: Relationships to metal p,'utitioning in the adjacent
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Chert, J., L. Dong & B. Deng, 1989. A study on heavy metal parti-
o x i d e c o u l d h a v e also a l t e r e d ( S c h w e r t m a n n & C o r - tioning in sediments from Poyang Lake in China. Hydrobiologia
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m e n t a l l y realistic o x i d e than g o e t h i t e (Tessier et al., 2120-2124.
1993; F o r t i n et al., 1993) s h o u l d take into a c c o u n t Crowder, A. A., S. Macfie, T. Conlin, L. St. Cyr & S. Greipsson,
d i a g e n e t i c e f f e c t s that m a y alter t h e o x i d e ' s b i n d i n g 1987. Iron hydroxide plaques on roots of wetland plants. Proc.
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Fortin, D., G. G. Leppard & A. Tessier, 1993. Characteristics of
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