Beruflich Dokumente
Kultur Dokumente
197
@ 1995 Kluwer Academic Publishers. Printed in Belgium.
Received 4 August 1993; in revised form 24 February 1994; accepted 2I April 1994
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.
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
199
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
.............................,,:_ ..................
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
100'
Table 2. Finalbiomass and copper content of plants surviving to end
of the experiment+ .
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
Discussion
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
• t
/
\
, !
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
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