Environmental Pollution 112 (2001) 329±337
www.elsevier.com/locate/envpol
In¯uence of organic amendments on copper distribution among
particle-size and density fractions in Champagne vineyard soils
E. Besnard, C. Chenu *, M. Robert
INRA, Unite de Science du Sol, Route de St Cyr, 78026 Versailles Cedex, France
Received 27 July 1999; accepted 30 May 2000
``Capsule'': Soil particle-size composition can be used to assess distribution of copper in soils.
Abstract
The intensive use for over 100 years of copper sulfate (Bordeaux mixture) to ®ght against mildew in vineyard soils has led to an
important, widespread accumulation of Cu (100 to 1500 mg Cu kgÿ1 soil). In Champagne vineyards, organic amendments are used
currently to increase soil fertility and to limit soil erosion. Organic amendments may have a direct e€ect on the retention of Cu in
the soil. To assess the in¯uence of the organic management on the fate of Cu in calcareous Champagne vineyard soils, we studied
Cu distribution (1) in the soil pro®le and (2) among primary soil particles, in vineyard parcels with di€erent amendments.
Amendments were oak-bark, vine-shoots and urban compost. The results were compared with the amount and the distribution of
Cu in an unamended calcareous soil. Physical soil fractionations were carried out to separate soil primary particles according to
their size and density. Cu has a heterogeneous distribution among soil particle fractions. Two fractions were mainly responsible for
Cu retention in soils: the organic debris larger than 50 mm or coarse particulate organic matter (POM) issued from the organic
amendments, and the clay-sized fraction <2 mm. The POM contained up to 2000 mg Cu kgÿ1 fraction and the clay fraction contained up to 500 mg Cu kgÿ1 fraction. The clay-sized fraction was responsible for almost 40% of the total amount of Cu in the four
parcels. POM was predominantly responsible for the di€erences in Cu contents between the unamended and the three amended
parcels. Our results attested that methods of soil particle-size fractionation can be successfully used to assess the distribution of
metal elements in soils. # 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Copper; Vineyard; Calcareous soils; Particulate organic matter; Particle-size fractionation
1. Introduction
An intensive use for more than 100 years of copper
sulfate (Bordeaux mixture) to ®ght against mildew in
vineyard soils led to an important, widespread accumulation of Cu. Arable land usually presents quantities of
Cu between 5 and 30 mg kgÿ1 soil, whereas concentrations ranging from 100 to 1500 mg Cu kgÿ1 soil are
frequently observed in vineyard soils (Drouineau and
Mazoyer, 1962; Delas, 1963; Geo€rion, 1975; Deluisa
et al., 1996; Flores-Velez et al., 1996). In Champagne,
wine growing is the main agricultural activity and vineyards cover an extensive portion of arable land. Contents and vertical distribution of Cu in these soils are
largely unknown. Furthermore, vineyards are located
on steep slopes, 10 to 35% on average, leading to
* Corresponding author. Tel.: +33-1-30-83-32-40; fax: +33-1-3083-32-59.
E-mail address: [email protected] (C. Chenu).
extensive soil-erosion processes. Ballif (1995) estimated
that 1.7 Mg soil haÿ1 yearÿ1 were removed by erosion in
Champagne vineyard soils between 1985 and 1994, corresponding to the removal of an 8-mm thick soil layer
during this period. A substantial proportion of added
copper sulfate sprayed annually on the vines reaches the
soil where it often remains ®xed in surface layers (Merry
et al., 1983; Deluisa et al., 1996; Flores-Velez et al.,
1996, Brun et al., 1998). Therefore, Cu is likely to be
disseminated in the environment by run-o€ (Ballif,
1995). Thus, major risks for environmental pollution are
generated, in particular with regards to water quality.
Bioavailability and mobility of Cu in soils largely depend
on its chemical forms and, consequently, on the nature of
the ``carrier'' constituents (Miller and McFee, 1983; Tessier and Campbell, 1988). The anity of Cu towards
humic substances is well described in literature, but few
studies deal with other soil organic matter components,
such as plant debris or bio-polymers (Kerndor€ and
Schnitzer, 1980; Schnitzer and Kodama, 1992; Spark et al.,
0269-7491/01/$ - see front matter # 2001 Elsevier Science Ltd. All rights reserved.
PII: S0269-7491(00)00151-2
330
E. Besnard et al. / Environmental Pollution 112 (2001) 329±337
1997). Studies on Cu behavior in vineyard soils are rather
scarce in calcareous environments in comparison with
acid, siliceous soils. In calcareous soils, an important part
of the Cu is supposed to be retained by CaCO3 (McBride
and Bouldin, 1984; Madrid and Diaz-Barrientos, 1992).
Except for CaCO3, the relative importance of other
mineral constituents regarding Cu retention was much less
assessed. In chemical extraction studies on calcareous soils,
Shuman (1986) and Saha et al. (1991) observed that less Cu
was retained by CaCO3 when organic matter contents of
these soils increased, suggesting a competition between
these two components for Cu retention. Nowadays, no
satisfactory method permits an unambiguous determination of the forms of association of trace metals with a given
soil fraction (McGrath and Cegarra, 1992). Chemical
methods become increasingly criticized because of technical limitations such as non-selectivity of the chemical
reactants or artifacts due to Cu re-distribution during
extraction procedures (Etcheber et al., 1983).
Another approach for studying relations between copper and soil constituents is physical fractionation. Over the
last decade, these methods were used successfully for
studying soil organic matter dynamics (Christensen, 1992).
More recently, particle-size fractionation has been used to
analyze the distribution of metal elements among soil primary particles. These studies emphasized the importance
of two main soil-fractions, i.e. the clay-sized fraction and
the coarse plant residues >50 mm forming the particulate
organic matter (POM) fraction. The role of particulate
organic matter in the retention of metals was highlighted in
the case of (1) soils amended with sewage sludge (Ducaroir
and Lamy, 1995), (2) soils polluted by industrial waste
(Balabane et al., 1999), and (3) acidic vineyard soils contaminated by Cu (Flores-Velez et al., 1996).
In Champagne vineyards, organic soil amendments
were introduced in the mid 1970s to increase soil fertility
and to limit soil erosion by run-o€. The most current
organic amendments are bark, vine shoots, and urban
compost (Ballif, 1995). We anticipate that these amendments modify the soil composition and thus, in¯uence
the retention and the distribution of Cu in vineyard
soils. Furthermore, these amendments are hypothesized
to limit Cu dissemination towards the environment.
In order to assess the in¯uence of organic management on the retention of Cu in calcareous Champagne
vineyard soils, we studied Cu distribution (1) in the soil
pro®le and (2) among primary soil particles, in vineyard
parcels with di€erent amendments.
2. Material and methods
2.1. Site and soils
Soil samples were taken from the site of Reuil sur
Marne, near Reims. The surface of the vineyard area
was about 160 ha, including 3326 parcels. After inquiries based on agro-historical questionnaires, four parcels were selected with comparable slopes of about 10%.
They received similar amounts of Cu each year, ranging
from 3 to 5 kg Cu haÿ1, depending on the humidity and
temperature of the summer period, which determined
the risks of mildew attacks. The ®rst parcel, which was
the control parcel, never received any organic amendment. The three other parcels received a single type of
organic amendment over the last 12 years: vine shoots,
each year after cutting (accounting for about 2 to 5 Mg
haÿ1 yearÿ1), bark (oak bark) or urban compost. For
oak bark and urban compost one single amendment of
about 100 Mg haÿ1 was performed 12 years ago. The
urban compost contained about 90 mg Cu kgÿ1 primary
product and was ®nely crushed. The parcels did not
receive any organic amendment before this 12 years
period. Organic amendments were applied to the soil
surfaces, but soils were not ploughed. The last vineplantation occurred in 1968 for the vine shoots parcel,
1969 for the oak-bark parcel, 1972 for the urban compost parcel and 1987 for the unamended parcel. Prior to
the vine plantation, the soils were ploughed to 40 cm
depth. Soils were calcaric cambisols (FAO, 1994) or
calcosols (AFES, 1995) (Table 1). The natural Cu content (i.e. from geochemical background) of the Champagne soils is about 20 mg Cu kgÿ1 (Baize, 1997).
2.2. Sampling
Soil samples were collected in June 1997, prior to
copper treatments. The 0±3, 3±6 and 6±10 cm layers
were sampled to assess the distribution of Cu with
depth. In addition, the bulk of the 0±10 cm horizons of
each parcel was sampled in three locations, one in the
row, the other two between the rows. The 0 level was
®xed at the top of the organo-mineral soil layer, under
the organic residues issued from the amendments. The
three samples were homogenized to obtain one average
sample. Samples were air-dried, sieved to 2-mm diameter, and stored in plastic boxes at room temperature.
The samples were used for current pedological and chemical analyses, as well as for physical fractionation. At
the same sites, undisturbed soil samples were sampled
with cylindars for bulk density determinations.
2.3. Soil fractionation
Samples from the 0±10 cm depth layer of each parcel
were mechanically dispersed prior to size and density
separation of primary particles. We used the procedure
described by Balesdent et al. (1991), except that fractions <50 mm were separated by centrifugation, rather
than by sedimentation. The soluble and <2 mm fractions were freeze dried and other fractions were oven
dried at 55 C.
E. Besnard et al. / Environmental Pollution 112 (2001) 329±337
331
Table 1
Physical and physico-chemical data of the 0±10 cm horizons of the di€erent soilsa
Organic
amendment
Texture (%)
No amendment
Vine shoots
Oak bark
Urban compost
27.0
35.0
50.3
24.1
a
Sand
(0.6)
(0.3)
(0.4)
(0.1)
Elements
Silt
clay
pH
water
Bulk
CEC
CaCO3
density (Mg mÿ3) (cmol kg1) (g kgÿ1)
Organic C C/N
(g kgÿ1)
Total Cu
(mg kgÿ1)
36.8 (0.2)
34.5 (0.3)
20.6 (0.3)
46.2 (0.3)
36.2 (0.5)
30.5 (0.4)
29.1 (0.2)
29.7 (0.2)
8 (0.1)
7.8 (0.1)
7.1 (0.1)
7.7 (0.02)
1.26 (0.16)
1.40 (0.09)
1.80 (0.05)
1.53 (0.05)
15.2 (0.7)
25.9 (0.9)
52.2 (0.9)
28.5 (1.3)
248 (4)
378 (9)
377 (12)
341 (24)
25.2 (1.8)
23.9 (2)
34.1 (1.5)
24.1 (2)
253.9 (7.6)
205.3 (5.6)
92.9 (2.6)
296.3 (13.3)
9.8 (0.1)
11.5 (0.2)
16.5 (0.2)
10.8 (0.2)
Standard deviations shown in parentheses.
2.4. Chemical analysis
3. Results and discussion
Chemical analysis were performed according to standard procedures of the French Normalization Association (AFNOR, 1996). Soil pH was measured in soil
water suspension 1:2.5 (AFNOR X31-117). Total C and
N contents were measured by dry combustion (C±N
autoanalyzer 1500 Carlo Erba) (AFNOR X31-409). As
the soil was calcareous, the organic C content was
determined by wet oxidation (AFNOR X31-109),
CaCO3 by HCl attack (AFNOR X31-105) and the
cation exchange capacity (CEC) of the bulk samples
using cobaltihexamine (AFNOR X31-130). Total Cu
contents were determined by atomic absorption spectrometry after acid digestion (¯uorhydric and perchloric
acids) of the solid sample (AFNOR X31-147).
3.1. Cu and organic carbon contents in soil
Cu concentrations decreased as the depth increased
up to 60 cm (Fig. 1). Cu was to a large extent located in
the 0±10 cm horizon. In the upper layer 0±3 cm, Cu
concentrations ranged from 264 (unamended parcel) to
519 mg kgÿ1 soil (vine-shoots parcel) suggesting a high
anity of Cu towards plant debris. Layers deeper than
10 cm showed distinctly lower Cu contents, decreasing
from 149 mg kgÿ1 soil at 15 cm depth to 18 mg kgÿ1 soil
at 60 cm depth.
When 0±10 cm layers were considered, Cu contents
were in the following order: urban compost < oak bark
2.5. Calculation
To improve the correlation between laboratory results
and actual ®eld conditions (Ellert and Bettany, 1995),
we calculated the mass of Cu and organic C per unit
area in the 0±40 cm horizon, i.e. the stock of these two
elements in the horizon. We ®rst calculated stocks in the
0±10 cm horizon and in the 10±40 cm, using the corresponding bulk density of the horizon:
Melement ˆ ‰EŠ FBD T 10;
…1†
where Melement=element stock in the considered horizon per unit area (kg haÿ1), [E]=element concentration
in the considered horizon (mg kgÿ1), FBD=®eld bulk
density of the considered horizon (Mg mÿ3) and
T=thickness of the horizon (m). Then, we added up all
of them to obtain stocks in the 0±40 cm horizon.
Bulk soil analyses, physical fractionations and chemical analyses were carried out in three replicates. The
fractions obtained from these three replicates were analyzed independently. All element concentrations, i.e.
element mass per unit mass of soil sample or soil fraction, were expressed on a 105 C dry mass base. Statistically analysis of the data was conducted by using
ANOVA.
Fig. 1. Vertical distribution of copper in soil pro®les.
332
E. Besnard et al. / Environmental Pollution 112 (2001) 329±337
< vine shoots (Table 1). Cu contents of all four parcels
exceeded 100 mg kgÿ1 soil in the surface layers, indicating that soils were Cu-contaminated, i.e. they were
above the permissible limit to allow sewage sludge
application according to the French standard NFU 44041 (AFNOR, 1985) (Table 1).
The organic C was much higher in amended parcels
than in the unamended one (Table 1). The oak-bark
parcel exhibited the highest organic C content and C/N
of all four parcels.
In the 0±10 cm layer the bulk density was higher in
parcels that received organic amendments than in the
unamended parcel (Table 1). The higher density was
ascribed to the absence of soil ploughing and to
mechanical compaction. Bulk densities of 0±10 cm and
10±40 cm layers allowed calculating stocks of Cu to 40cm depth. Stocks were about 870 kg haÿ1 in the unamended parcel, 910 kg haÿ1 in the vine-shoots parcel,
1420 kg haÿ1 in the oak-bark parcel and 1870 kg haÿ1 in
the urban compost parcel.
One single application of Bordeaux mixture introduced 3 to 5 kg Cu haÿ1. Three to 10 applications were
performed annually until the 1970s, with only one to
three per year since then. This would correspond to
applications of 1500±3000 kg haÿ1 over the last century
(Geo€rion, 1975). Cu in the 0±40 cm soil horizons ranged 870±1870 kg haÿ1 in the studied parcels. Considering that grape harvesting removed a negligible fraction
of Cu sprayed on the vine and that leaf fall restored the
rest (Flores Velez et al., 1996), only about 60% of the
applied Cu were recovered in the soil. Thus, Cu must
have been removed from the parcels by soil leaching or
erosion. Retention of Cu in the deeper layers of soil
shows that leaching is limited. Erosion takes place in the
vineyards of Reuil sur Marne. Hence, the loss of Cu in
the soils is mainly caused by erosion. Such phenomena
have already been observed after sludge applications to
soils (McGrath and Lane, 1989; Yingming and Corey,
1993).
Each year, the di€erent parcels received the same
input of Cu with Bordeaux mixture treatments, either
sprayed directly on the soil surface or returned to soil by
means of leaves and shoots each winter. Inputs for the
last 12 years can be estimated to be 4 kg haÿ1 2
treatments 12 years=96 kg Cu haÿ1 on average. The
vine shoots represented 1±2.5 Mg haÿ1 each year; they
contained about 250 mg Cu kgÿ1 of dry material. Vine
shoots cutting in the unamended, the urban compost
and the oak bark parcels thus decreased the input of Cu
by 6 kg haÿ1 at the maximum in those 12 years. The
urban compost contained about 90 mg Cu kgÿ1. A single application of 100 Mg haÿ1, 12 years ago, brought
about 9 kg Cu haÿ1 in the top horizon of this parcel.
Hence, in 12 years, the parcels have received quite
comparable inputs of Cu whatever the amendment:
about 90 kg Cu haÿ1 (unamended and oak bark par-
cels), 96 kg Cu haÿ1 (vine shoots parcel) and 99 kg Cu
haÿ1 (urban compost parcel). The stocks of Cu in the 0±
40 cm layer of soil were 870 kg haÿ1 (unamended parcel), 910 kg haÿ1 (vine-shoots parcel), 1420 kg haÿ1
(oak-bark parcel) and 1870 kg haÿ1 (urban compost
parcel). Since the parcels had similar slopes, agro-historics, and quite similar inputs of Cu over the last 12
years, the variations in Cu stocks was attributed to the
amendment treatments. The amounts of Cu retained
due to the amendments, i.e. di€erences in Cu stocks,
were as high as 1000 kg haÿ1 in 12 years, which is much
larger than the amounts of Cu applied during these 12
years. Hence, the amendments not only retained the Cu
applied during the last 12 years in the soil pro®le, but
they also prevented the loss of ``older'' Cu by erosion.
Indeed, Ballif (1995) showed that compost and oak bark
reduced soil erosion.
3.2. Particle size fractionation
Particle size fractionation of soil samples resulted in
the recovery of 98.90.5% of the initial sample mass.
The four parcels had di€erent POM contents (Fig. 2) in
relation with their organic management. POM masses
represented only 1.3% of the mass of the soil in the
unamended parcel, 4% in vine-shoots and urban compost parcels, and 6.8% in the parcel receiving oak-bark.
In all parcels, ®ne POM 50±200 mm was the dominant
POM fraction. Fine POM accounted for 53 (oak-bark
parcel) to 76.5% (unamended parcel) of the total POM.
3.3. Organic carbon and Cu in particle size fractions
Results of organic C and C/N ratio of particle-size
fractions are given in Table 2. The mass balance of
organic C recovered from the di€erent fractions was
96.94.6% of the organic C measured on bulk soils.
Soluble organic C ranged from 1% (unamended parcel)
to 4% (oak-bark parcel) of the organic C measured on
bulk soils. The distribution of organic C among soil
Fig. 2. Size distribution of particulate organic matter in the 0±10 cm
horizons.
E. Besnard et al. / Environmental Pollution 112 (2001) 329±337
333
Table 2
Organic C and C/N ratio of particle-size fractions in super®cial 0±10 cm layers of the di€erent soilsa
Organic control
Fractions (mm)
Dry weight (g kgÿ1)
Organic C (g kgÿ1 fraction)
C/N
No amendment
POM>1000
POM 500±1000
POM 200±500
POM 50±200
Total Mineral>50
20±50
2±20
<2
0.6 (0.1)
0.7 (0.1)
2 (0.1)
10 (1)
251 (6)
100 (2)
23.8 (8)
383 (13)
429.1
419.1
353.1
206.1
1.2
4.8
13.1
21.6
(5.4)
(3.2)
(9.4)
(12.9)
(0.16)
(0.12)
(0.6)
(0.7)
25.8
20.2
16.3
13.3
Vine shoots
POM>1000
POM 500±1000
POM 200±500
POM 50±200
Total Mineral>50
20±50
2±20
<2
4
3
9
23
349
95
200
303
(0.6)
(0.2)
(0.7)
(4)
(4)
(5)
(4)
(4)
432.6
403.2
325.3
246.2
0.8
11.5
20.8
26.4
(12.1)
(9.3)
(12.4)
(18.7)
(0.15)
(2.8)
(0.8)
(0.3)
18.4
17.4
14.6
13.6
POM>1000
POM 500±1000
POM 200±500
POM 50±200
Total Mineral>50
20±50
2±20
<2
12
7
13
36
437
63
129
287
(2)
(1)
(3)
(5)
(5)
(2)
(1)
(2)
446.4
433.2
409.9
333.9
1.3
33.1
57.0
39.1
(5.5)
(9.0)
(13.7)
(11.4)
(0.06)
(3.7)
(1.4)
(1.3)
25.0
22.6
20.1
17.2
POM>1000
POM 500±1000
POM 200±500
POM 50±200
Total Mineral>50
20±50
2±20
<2
5
3
5
27
246
166
203
339
(1)
(1)
(0.8)
(4)
(4)
(2)
(9)
(16)
576.3
529.7
403.0
263.2
1.2
7.1
14.0
27.9
(40.1)
(19.7)
(29.7)
(9.5)
(0.2)
(2.44)
(2.0)
(1.0)
30.7
25.1
16.1
13.6
Oak-bark
Urban compost
a
(2.4)
(0.5)
(0.6)
(1.2)
7.7 (0.1)
(1.3)
(0.8)
(0.1)
(0.2)
7.2 (0.2)
(0.6)
(0.4)
(0.7)
(0.3)
11.0 (0.06)
(4.9)
(2.5)
(1.4)
(0.2)
7.8 (0.4)
Standard deviations shown in parentheses.
particle-size fractions was heterogeneous. POM fractions
showed the highest organic C contents, ranging from
248 (unamended parcel) to 377 g C kgÿ1 total POM
(oak-bark parcel). In all parcels, organic C contents in
POM fractions decreased with decreasing POM size
(Table 2). C/N ratio in POM also decreased with
decreasing POM size. Total POM accounted for 46±
54% of organic C present in the 0±10 cm horizon of the
three amended parcels in contrast with only 20% in the
case of the unamended parcel. For both amended and
unamended parcels, ®ne POM 50±200 mm contributed
to about 50% of the organic C of the total POM.
The distribution of Cu among particle-size fractions
was also heterogeneous (Fig. 3). In all four 0±10 cm soil
horizons, the highest Cu contents were detected in POM
fractions. Cu contents of the total POM fraction in the
unamended parcel, the vine-shoots parcel and the urban
compost parcel were similar, of about 2000 mg kgÿ1
total POM (P< 0.05), whereas the total POM fraction
in the oak-bark parcel contained only about 1200 mg
kgÿ1 fraction. Thus, in non-amended, vine-shoots and
urban compost parcels, the total POM fraction was
nearly 6 times richer in Cu than the bulk soil versus only
3 times in the oak-barks parcel. Comparing the four
parcels, Cu contents in POM fractions were as follows:
oak-barks < unamended=urban compost=vineshoots. Cu contents in POM fractions increased with
decreasing POM size, ranging from 517 to 2430 mg kgÿ1
fraction considering the four parcels. Nevertheless,
except in the oak-barks parcel, the ®nest POM 50-200
mm were slightly less rich in Cu than coarser POM 200±
500 mm, which was caused by the presence of some
mineral particles in the ®ner POM fraction (50±200 mm)
due to the diculty to separate e€ectively such ®ne
fractions by ¯otation-sedimentation in water.
In organo-mineral fractions <50 mm, Cu contents
ranged from 54 to 631 mg kgÿ1 fraction and increased
with a decreasing size fraction. Cu contents in clay-sized
fractions <2 mm ranged from 420 to 631 mg kgÿ1 fraction. Comparing the four soils, Cu contents in fractions
<50 mm were as follows: unamended < urban compost
< vine-shoots < oak-bark. In fractions <50 mm, Cu
334
E. Besnard et al. / Environmental Pollution 112 (2001) 329±337
Fig. 3. Copper concentrations in soil particle-size fractions.
contents were correlated positively with organic C contents, especially in clay-sized fractions <2 mm
(r2=0.74).
Cu contents in sand-sized mineral fractions ranged
from 20 to 190 mg kgÿ1 in the di€erent parcels. There
was no signi®cant relation between Cu concentrations
of these mineral fractions with the size of the fractions.
In vine-shoots and oak-barks parcels, some mineral
fractions coarser than 1000 mm exhibited very high Cu
contents [Fig. 3: (M)]. Such Cu contents in mineral
fractions were ascribed to the presence of Cu sulfate
trapped in the porosity of mineral grains.
We calculated the contribution of each particle size
fraction to the total Cu content of the di€erent 0±10 cm
soil horizons by multiplying the Cu content of the fraction by its mass percentage in each soil. The mass balance of Cu recovered from the di€erent fractions was
98.510.2% of the Cu measured in bulk soils. Soluble
Cu ranged from 0.1 (unamended soil) to 2.3% (urban
compost soil) of total Cu. Cu was predominantly found
in the ®nest soil fractions, in particular in the clay-sized
fraction <2 mm (Fig. 4), that contained from 40 (vineshoots soil) up to 67% (unamended soil) of the total Cu
in 0±10 cm soil horizons. In spite of their very high Cu
contents, POM fractions did not contribute to more
than 10 to 26% of the total Cu of the 0±10 cm soil
horizons. Nonetheless, di€erences in Cu retention
among the di€erent parcels were mostly due to POM,
and especially to ®ne POM 50±200 mm. These POM
represented 8% of the total Cu content in the unamended parcel, and about 15% in the amended parcels.
Our results revealed that the distribution of Cu
among particle-size and density fractions in soils was
heterogeneous, thus arousing the interest of the physical
soil fractionation methods for assessing the localization
of pollutants in soils.
Cu and organic C were both concentrated in the same
fractions: <2 mm and POM fractions (Table 2 and Fig.
3). High concentrations of Cu and other metals in the
clay-sized fraction have already been reported (FloresVelez et al., 1996). It was put down to the high reactivity
of the mineral constituents and organo-mineral associations present in these fractions (Essington and Mattigod, 1990), and possibly also, to natural pedogenetic
processes resulting in clay neo-formation (i.e. pedogenetic Cu). Comparing the four parcels, high Cu contents
in fractions <50 mm, and particularly in clay-sized
fractions <2 mm, were related to high organic C contents. Accumulation of metals in coarse plant residues
was very recently described for other metals and for
di€erent types of pollution (Ducaroir and Lamy, 1995;
Flores-Velez et al., 1996; Balabane et al., 1999). In the
four situations studied here, POM, i.e. leaves, vineshoots, and organic amendments were directly exposed
to Cu sulfate spraying, which explains why high quantities of Cu were deposited on POM surfaces. However,
little is known of the precise nature of the associations
between Cu and POM (Flores-Velez et al., 1996). Cu
may thus occur as surface deposits on POM, or correspond to leaves or vine-shoots that have accumulated
Cu in their tissues during growth. Organic particles rich
in Cu may be inherited from the compost itself. Furthermore, POM are organic materials that contain
reactive groups which are able to complex metals (Harter and Naidu, 1995; Mackey et al., 1996) and can
actively complex Cu. Finally, accumulation of Cu in
POM may also be due to a selective ®xation of Cu by
actinomycetes, bacteria or fungi associated to POM
(Aoyama and Nagumo, 1997).
Very small amounts of Cu were recovered in the
soluble fraction. Little Cu was thus desorbed or solubilised from POM during dispersion and sedimentation of
the soil samples and Cu can be assumed to be tightly
bound to POM. Concentrations of Cu in POM fractions
may re¯ect di€erences in exposure to Cu or di€erences
in reactivity with Cu. In the unamended parcel, the vine
shoots parcel and the parcel amended with compost,
POM had similar Cu contents. The low Cu concentrations in POM from the oak-bark soil are probably due
to a low reactivity of the oak barks towards Cu. However, the high mass percentage of the POM fraction in
this soil may result in a dilution e€ect.
Considering that all four parcels received similar
quantities of Cu and POM from leaf fall, we estimated,
by di€erence between Cu contents in total POM from
the unamended parcel and Cu contents in total POM
fraction from the amended parcels, the amounts of Cu
bound to POM deriving from the amendments, i.e. vine
shoots, urban compost or oak-bark. These POM had
similar Cu contents (P<0.05): 50 to 60 mg Cu kgÿ1
fraction, suggesting that there were no di€erences in the
reactivity of these POM towards Cu. Nevertheless, vine
shoots probably received more Cu than oak barks or
compost particles, i.e. a ®rst time when they were living
parts of the vine, and a second time after cutting when
E. Besnard et al. / Environmental Pollution 112 (2001) 329±337
335
Fig. 4. Amounts of Cu in the di€erent 0±10 cm soil horizons.
they lay at the surface of the soil. In the three amended
soils, about 67% of the Cu present in the total POM
fraction was thus attributed to the POM from the
organic amendment itself.
Cu contents in POM fractions increased with
decreasing POM size, i.e. with increasing POM age
(Balesdent, 1996) (Fig. 3). In laboratory experiments,
plant debris were shown to retain larger amounts of
heavy metals as the age of debris increased (Hughes et
al., 1980; Harter and Naidu, 1995). Increases of POM
reactivity with decomposition could simply be due to
increases in the surface area of the material with
decreasing size. They could also involve changes in the
chemical nature of POM with decomposition and
humi®cation. Time of exposure to Cu also increases
with the age of POM. Balabane et al. (1999) suggested
that a selective decomposition of POM in soils,
depending on their metal element contents, may also
explain high metal element contents in some POM
fractions. These authors observed an heterogeneous
localization of heavy metals in the metallophyte plants
living on the soils they were studying, and suggested
that plant debris or parts of plant debris with an initially
low metal element content were more rapidly mineralized than plant debris or parts of plant debris with
high metal element contents. We did not assess the
localization of Cu among the organic debris from our
soils (roots, leaves, shoots, barks, urban compost
fragments. . .). However, selective decomposition rates
depending on Cu content could account for our results.
In our study, POM organic C contents, POM C/N
and POM size distribution showed general trends in
agreement with classical characteristics of decomposing
plant debris (Balesdent, 1996). These results indicated
that even in such Cu contaminated soils, biological
activity occurred (Valsecchi et al., 1995; Aoyama and
Nagumo, 1997). An alteration of the decomposition of
organic matter was reported in other soils polluted with
metal elements (Berg et al., 1991; Cotrufo et al., 1995;
Balabane et al., 1999). However, in our case, the inputs
of fresh plant and organic debris and their chemical
nature were di€erent in the four parcels, and it was not
possible to assess the possible e€ect of high Cu contents
on soil organic matter dynamics.
4. Conclusion
This study showed that organic amendments strongly
modi®ed the retention and the distribution of Cu in soils
subject to annual inputs of this metal due to phytosanitary treatments of vineyards. Organic amendments had
a direct e€ect on the retention of Cu in soil, as shown by
the high Cu contents of particulate organic matter.
Furthermore, organic amendments may also limit erosion and thus the dispersion of Cu from the vineyards in
the environment and particularly in the surface waters.
Particle-size fractionation can be successfully used to
assess the distribution of metal elements in soils. We
showed that Cu has a heterogeneous distribution among
particle size and density fractions, i.e. among soil constituents. Main carrier phases for Cu were clay minerals
and organo-clay associations present in the < 2 mm
fractions, as well as particulate organic matter. POM
fractions were responsible for the di€erences in soil Cu
content between the unamended and the amended parcels.
In this study we characterized Cu retention by total
Cu contents. The mobility and bioavailability of Cu
associated to POM and to clay minerals are likely to be
336
E. Besnard et al. / Environmental Pollution 112 (2001) 329±337
di€erent, depending on the mechanisms of Cu retention
by these constituents. These aspects deserve detailed
studies. Furthermore, POM is a labile organic fraction
and POM associated Cu is likely to be freed upon POM
decomposition.
Acknowledgements
This study is part of an EUROPOL'AGRO research
program. The authors gratefully acknowledge (1) the
Conseil General of Champagne-Ardennes for its ®nancial
support, (2) winegrowers for their collaboration, especially
L. Lagache, (3) M. Pernes and J.P. PeÂtraud for ®eldwork,
and (4) M. Perrier for her precious help in fractionating
soils. The authors are also grateful to F. Oort for critical
reading of the manuscript, and G. Vernet and F. Arnoult
for constructive comments during this work.
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