Chemical Geology 197 (2003) 271 – 285

www.elsevier.com/locate/chemgeo

The Amazon River: behaviour of metals (Fe, Al, Mn)

and dissolved organic matter in the initial mixing at the
Rio Negro/Solimões confluence
A.-M. Aucour a,*, F.-X. Tao a,f, P. Moreira-Turcq b, P. Seyler c,
S. Sheppard d, M.F. Benedetti e,*
a
CNRS-UMR 5125, Université Lyon 1, 69622 Villeurbanne, France
b
IRD, Centre d’Ile de France, 32 av. H. Varagnat 93143-Bondy Cedex, France
c
IRD, UMR LMTG Université P. Sabatier, 38 rue des 36 ponts, 31000 Toulouse, France
d
CNRS-UMR 5570, Ecole Normale Supérieure de Lyon, 69622 Villeurbanne, France
e
LGM-UMR 7047, Université P. & M. Curie, Case 124, 4 place Jussieu, 75252 Paris Cedex 05, France
f
State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550002, PR China
Received 20 November 2001; accepted 11 November 2002

Abstract

We studied the changes in major elements and organic carbon concentrations during the initial stage of the mixing of the black
(Rio Negro) and the White (Rio Solimões) waters in the Amazon River basin to understand the geochemical processes that could
control the redistribution between particulate and dissolved fractions. Water samples were collected at six stations including the
Rio Negro and the Rio Solimões and four stations downstream from the confluence. The relative contributions of the two
tributaries were determined using a triple tracer approach (d18O, dD, Cl
). Particulate (>0.2 Am) and dissolved ( < 0.2 Am)
concentrations of major elements (Ca, Mg, Fe, Al, Si) and organic carbon (POC and DOC) were measured. Major elements in the
particulate fraction were found to have a nonconservative behaviour in the initial stage of the mixing due to mineral removal. In
the dissolved fraction, only the DOC, Fe, and Mn behaved nonconservatively. The Fe losses could be due to preferential removal
of Fe bound to N-rich organic matter (OM) and/or to preferential removal of Fe oxyhydroxides. The increasing dissolved
manganese content in the dissolved phase is explained by a reductive dissolution of manganese oxides due to massive inputs of
phenolic-rich OM from the Rio Negro. The amount of DOC removed from the water column in the initial stage of the mixing
would represent 4% of the total annual DOC flux of the Amazon River at the reference gauging station of Obidos.
D 2002 Elsevier Science B.V. All rights reserved.

Keywords: Amazon; Mixing zone; Isotopic tracer; Organic matter; Iron; Manganese; Sorption

1. Introduction

The Amazon River ranks first among the world

* Corresponding authors. A.-M. Aucour is to be contacted at
Fax: +33-72-44-8382.
E-mail addresses: anne-marie.aucour@univ-lyon1.fr
(A.-M. Aucour), benedett@cicrp.jussieu.fr (M.F. Benedetti).
rivers due to its drainage area of 6  106 km2 and its
yearly discharge of 5.5  109 m3 year
1. It represents
about 20% of the world fresh water flux from land to
ocean (Molinier et al., 1997). Dissolved and partic-

0009-2541/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0009-2541(02)00398-4
272 A.-M. Aucour et al. / Chemical Geology 197 (2003) 271–285

ulate fluxes carried by the Amazon River are therefore Table 1

of prime importance in biogeochemical cycling Processes affecting the cycling of organic matter (OM), manganese
(Mn) and iron (Fe) in aquatic systems
between land and ocean. Tributaries of the Amazon
OM Mn Fe
River exhibit a range of chemical characteristics. They
have long been classified into three types on the basis OM consumption: Reductive Photo-reduction
dissolution of dissolved
of their appearance as ‘‘white waters’’, ‘‘clear waters’’
of MnO2 Fe (III) by OM
and ‘‘black waters’’ (Gibbs, 1972). The Rio Solimões colloids with OM via ligand to
and Rio Negro combine at Manaus to form the metal charge
Amazon River. The ‘‘black waters’’ from the Rio transfert reaction
Negro are relatively acid, low in total cations and rich Bacterial Indirect Photo-reductive
photo-reduction dissolution of Fe
in dissolved organic carbon. The ‘‘white waters’’ from
of MnO2 oxides by ligand to
Rio Solimões show a near neutral pH and are rela- metal charge transfert
tively rich in total cations and in suspended sediments. reaction
In the Solimões River, the clay minerals of the river Photochemical Oxidation Fe(II) sorption
suspensions consist of smectites, illite and a minor UV, Vis light of Mn2 + to oxides
absorption by
amount of kaolinite, which are also present in the
chromophore
floodplain sediments, together with quartz and Na- or Sorption to Sedimentation Fe(III) precipitation
Ca-plagioclases (Irion, 1983; Martinelli et al., 1993). minerals via: of MnO2
In the Negro River, kaolinite dominates the clay Anion exchange Sedimentation
fraction of the suspension. of Fe oxide
Ligand exchange-
The marked difference in water chemistry between
surface complex
the two rivers and inputs of other sources such as Cation bridging,
varzea lakes (Junk, 1997) raises the issue of conser- hydrogen
vative or nonconservative behaviour of elements in bonding
the mixing zone. Does some of the dissolved fraction Van der Waals
forces
become part of the particulate phase through adsorp-
Physical
tion or flocculation during mixing? Is some of the adsorption
particulate phase mobilized? This issue has been Sedimentation
extensively documented in estuaries, in mixing zone
between river and sea water (e.g. Sholkowitz, 1976;
Santschi et al., 1997; Kraepiel et al., 1997) but has kampe et al., 2001) have shown appreciable sorption
been less frequently investigated at river confluences of DOM on mineral surfaces.
(McKnight et al., 1992). Several processes may affect Our objective was to investigate the transfers
the geochemistry of organic matter (OM), manganese between the dissolved fraction, the particulate fraction
and iron (Table 1). For OM, consumption (i.e. bacte- and the sediments at the interface of ‘‘black waters’’
rial or photochemical) and/or sorption to minerals and ‘‘white waters’’, in the first 25 km below the
(Table 1) are two major processes responsible for confluence of the Rio Solimões and Rio Negro. We
changes in OM concentrations in aquatic systems focused on both potentially conservative species (Ca,
(Stumm and Morgan, 1981). Precipitation and/or dis- Mg, K, Na) and reactive constituents (Fe, Al, Si, Mn,
solution of Mn oxides could be important. Table 1 organic carbon). Sorption experiments performed dur-
summarizes major processes that have been studied to ing our sampling cruise (Moreira-Turcq et al., in
understand Mn cycling (Scott et al., 2002). Similarly press) with DOC and alumina indicated a potential
to Mn, precipitation and/or dissolution of iron oxides for DOC removal in the Rio Negro waters. We report
are important processes (Table 1) that may affect the here elemental concentrations measured in the dis-
chemistry of iron during the mixing of waters solved and particulate fractions. The concentrations in
(Voelker et al., 1997). Experiments made with dis- the mixing zone were compared with those predicted
solved organic matter (DOM), suspended sediments by mixing the ‘‘black waters’’ from Rio Negro and
from the Amazon River and clay mineral (Aufden- ‘‘white waters’’ from Rio Solimões, in order to
 A.-M. Aucour et al. / Chemical Geology 197 (2003) 271–285
decipher conservative or nonconservative behaviour
in the mixing zone. This approach requires that inputs
from the Rio Negro and Rio Solimões are the only
end-members occurring in the confluence zone and,
ideally, that elemental concentrations in each end-
members are uniform and constant over the course
of the sampling cruise. We therefore used three con-
servative tracers to follow the process of water mixing
and to check whether two end-members or more occur
in the system: 18O, D, and Cl ions. The elemental
concentrations in the Negro and Solimões were meas-
ured at varying depths in a river section in order to
determine the magnitude of variation with depth.
They were also investigated at the beginning and
end of the cruise in order to evaluate the temporal
variation. The element behaviour (i.e. conservative
versus reactive) will be interpreted with the help of
onboard sorption experiments when possible.
Fig. 1. Study area and sampling stations. River sections with flow rates are yielded by ADCP transect. A vertical bar indicates location of the
vertical profiles.
273
2. Materials and methods
2.1. Sampling
The sampling cruise, in October 1997, spanned
over 10 days and took place during the period of
minimum discharge, more precisely at the end of the
falling stage. The discharge and the suspended sedi-
ments distribution were measured along several trans-
ects with an Acoustic Doppler Current Profiler (RDI
Instruments). On each transect, water samples were
taken at one station at three or four different depths
(Fig. 1, Table 2). The water samples were collected
with a clean sampling device, built by the Institut de
Recherche pour le Développement (IRD), which
allows sampling of 5 l along horizontal flow lines.
The water column is up to 35 – 40 m deep. The water
samples were collected (1) in the Rio Negro and
274 A.-M. Aucour et al. / Chemical Geology 197 (2003) 271–285

Table 2
d18O, dD and element concentration (in AM) of unfiltered waters and of the permeates < 0.2 Am obtained by TTF as well as FF dissolved
fraction ( < 0.22 Am) for samples of the Negro – Solimões confluence zone
Sta.* River Date Dis.* Depth pH f Unfiltered
no. (m3/s) (m) d18O dD Cl Ca Mg K Na Fe
(x ) (x )
G1 Negro 16/9 24,700 1 5.65
3.28
14.6 13 8.2 5.8 7.4 29.6 6.8
6 5.70
3.37
14.8 10 7.7 5.8 7.2 27.0 7.4
12 5.50
3.24
13.9 13 7.7 5.8 11.3 26.5 7.5
25 5.60
3.23
14.2 14 8.7 6.6 10.5 25.6 7.2
G2 Solimões 17/9 61,300 1 7.09
4.96
26.8 120 208.0 43.2 27.9 181.7 25.8
6 7.03
4.90
26.4 117 213.7 43.2 25.6 184.8 54.0
12 7.00
4.94
26.8 116 209.7 43.2 26.2 182.2 23.9
25 7.00
4.95
26.6 116 221.5 43.2 28.2 193.0 39.7
G3 Amazon 18/9 82,100 5 6.45 1
3.27
14.3 15 14.5 7.8 8.7 32.2 7.2
15 6.99 0.68
3.73
18.8 47 61.7 17.7 10.5 63.9 12.4
25 6.80 0.43
4.22
21.3 72 121.7 30.9 16.9 95.6 17.9
35 6.80 0.41
4.26
21.8 74 122.2 30.9 16.9 98.3 19.1
G4 Amazon 20/9 74,300 6 6.31 0.67
3.84
18.5 46 74.0 21.4 11.0 72.6 17.3
10 6.25 0.64
3.85
18.9 51 72.0 20.8 10.0 69.6 15.2
15 6.43 0.62
3.92
18.3 57 84.7 23.7 11.5 79.6 14.3
G5 Amazon 21/9 76,000 0.5 6.36 0.68
3.80
18.4 45 79.0 21.4 17.9 79.6 13.9
20 6.43 0.68
3.81
17.7 51 75.5 21.0 12.8 76.5 16.4
35 6.53 0.61
3.94
19.2 53 81.5 21.0 14.4 84.8 17.0
G6 Amazon 22/9 74,200 1 6.61 0.25
4.51
23.6 92 177.5 42.0 28.2 172.6 22.3
20 6.83 0.25
4.55
23.4 91 181.2 43.2 28.5 181.0 24.8
40 7.14 0.27
4.58
22.9 87 166.7 40.3 23.8 163.0 23.7
G1 Negro 26/9 – 1 5.40
3.05
12.6 21 6.7 4.9 10.0 14.6 7.0
G2 Solimões 27/0 – 1 7.06
4.68
25.8 131 264.0 94.6 33.3 106.9 54.8
*: Sta. for station, Dis. for discharge.
– : not determined.

Solimões above the confluence at stations G1 and G2
at the beginning and at the end of the cruise and (2) at
four stations (G3 –G6) downstream from the conflu-
ence (Fig. 1). Below the confluence, sampling loca-
tions were chosen based on conductivity profile
recorded by a CTD profiler (SBE19, Seabird) and
yield a progressive range between the two end-mem-
bers (Rio Negro and Solimões). The point furthest
downstream is located about 25 km from the con-
fluence. More details about the hydrodynamics pro-
cesses occurring in the Negro –Solimões mixing zone
are given in Laraque et al. (submitted for publication).
2.2. Filtration
0.2 Am. The membranes were cleaned with 50 l of
Milli-Q water. The first 5 l were systematically dis-
carded in the field to prevent sample contamination.
Water samples were also processed with frontal filtra-
tion (FF). Five hundred millilitres of water was
filtered using durapore filters (Millipore GVWP fil-
ters, 0.22 Am). The filters were cleaned with HNO3
5% and pre-weighed. To separate dissolved organic
(DOC) and particulate organic carbon (POC), 1 l of
water was filtered with a glass filter holder, on glass
fibre filters (Whatman GF/F), which had been pre-
weighed and pre-combusted overnight at 450 jC.
Glass fibre and durapore filters were than dried for
24 h at 50 jC after filtration.

Water samples were processed on board in two 2.3. Unfiltered waters and dissolved load
ways. Fifty litres of water was processed with tangen-
tial-flow filtration (TFF) (Ultrasart, Sartorius) using a The hydrogen and oxygen isotope compositions
clean ultrafiltration membrane with nominal cut-off of were measured on unfiltered water samples. The hydro-
 A.-M. Aucour et al. / Chemical Geology 197 (2003) 271–285 275

Unfiltered Dissolved TFF < 0.2 Am Dissolved FF (0.22 Am)

Al Mn TOC Cl Ca Mg K Na Fe Al Mn DOC Ca Mg K Na Mn DOC

5.7 0.220 538 14 8.0 6.2 11.8 30.9 2.22 2.89 0.177 483 8.45 6.71 7.54 24.09 155 542
5.7 0.222 538 13 7.5 5.3 8.2 27.4 2.90 3.19 0.173 491 10.70 8.64 9.05 27.30 149 566
5.7 0.220 517 13 7.5 5.8 7.9 27.4 2.47 2.85 0.178 500 – – – – – 528
6.6 0.228 560 13 8.0 5.8 10.3 27.4 3.42 2.96 0.177 495 – – – – – 511
40.0 0.555 248 120 212.5 43.6 27.4 190.9 0.86 0.70 0.95 218 203.38 50.37 21.15 179.91 102 278
91.2 1.403 257 116 210.8 43.6 27.9 182.2 0.93 0.78 0.100 219 201.43 49.79 22.85 178.00 62 250
36.6 0.584 230 115 211.3 43.6 26.4 180.4 0.89 0.59 0.100 222 – – – – – 244
63.0 1.110 250 115 209.3 43.6 23.3 189.1 0.95 0.70 0.102 222 – – – – – 231
8.9 0.224 529 15 12.0 6.2 6.4 30.9 3.51 3.48 0.167 480 16.58 8.23 8.10 28.74 173 –
18.5 0.366 482 47 59.3 17.3 9.2 64.8 2.58 2.59 0.191 395 65.10 18.44 11.54 68.26 178 454
26.7 0.519 395 71 116.8 30.0 15.9 93.5 1.77 1.93 0.189 336 117.50 30.29 15.10 110.35 164 –
28.2 0.533 372 74 115.5 30.0 16.1 96.5 1.70 1.56 0.208 319 123.70 31.48 15.56 113.17 184 395
26.3 0.499 469 42 74.2 21.4 11.5 70.4 2.27 2.11 0.213 460 74.53 20.49 12.21 74.91 182 490
23.3 0.437 470 51 69.0 20.3 12.0 67.8 2.29 2.08 0.215 434 74.70 20.74 12.23 75.74 180 396
19.6 0.486 437 52 83.7 23.6 12.3 79.1 2.02 1.82 0.206 427 87.48 23.62 13.05 84.48 167 386
21.1 0.420 456 – 72.0 20.2 12.8 77.8 1.86 2.41 0.233 405 71.65 20.29 12.26 73.74 191 454
26.3 0.477 447 – 74.5 20.6 15.4 80.4 1.90 2.45 0.266 410 78.20 21.73 12.62 78.09 180 –
26.7 0.495 438 – 80.2 21.8 15.9 83.9 1.68 2.41 0.213 394 84.18 23.21 13.05 83.48 172 –
37.1 0.581 188 91 173.3 40.3 23.6 182.2 0.82 1.11 0.166 179 167.70 41.73 19.00 146.70 132 313
44.1 0.673 192 90 170.5 39.3 26.1 165.7 0.98 1.19 0.164 183 153.43 37.78 16.74 131.65 119 224
39.3 0.633 191 86 175.0 40.7 24.9 163.5 0.82 1.30 0.162 175 165.23 41.23 19.03 144.52 116 183
28.9 0.213 213 22 4.2 3.7 10.8 15.1 2.33 3.00 0.171 281 – – – – – –
123.4 1.625 1625 129 263.0 66.3 24.6 115.1 0.34 0.67 0.224 127 – – – – – –

gen isotope composition of the water was determined
on triplicate measurements by reaction with uranium at
800 jC (Bigeleisen et al., 1952). The oxygen isotopic
composition of the water was determined by equilibra-
tion of water with CO2 (Epstein and Mayeda, 1953).
The isotopic ratios were determined on a VG Prism
mass spectrometer with the data presented using the
conventional d relative to SMOW (Table 1). The
precision is F 1xfor dD and F 0.05xfor d18O.
The concentration of Cl ions was measured by
ionic chromatography with a precision of F 1%. The
concentrations of Ca, Mg, Na and K were measured
by flame atomic absorption spectrometry and ICP-
AES (precision F 1%). Concentrations of Al and Fe
were measured by ICP-AES (unfiltered waters) or GF-
AAS (permeate < 0.2 Am). The detection limit was 10
nM for each metal ion and the precision range from
F 5% to 15%. Concentrations of Mn and Si were
measured by ICP-MS (precision F 2 – 3%). Total
organic carbon (unfiltered waters) and dissolved
organic carbon from TFF were determined with a
Dorhman DC analyser. The detection limit is 25 AM
and the precision is F 2%. Dissolved organic carbon
from FF was determined by high-temperature catalytic
oxidation method using a Shimadzu TOC-5000
Instrument (precision F 2%).
2.4. Suspended load
The suspended sediments collected on the durapore
filters were subject to a HNO3 –HF – HClO4 treatment
(Voinovitch et al., 1962). The filters were then
removed and the solution was evaporated to dryness.
The residue was dissolved in sub-boiling HNO3 and
then diluted with Milli-Q water. Ca, K, Mg, Na, Fe
and Al were measured by ICP-AES. POC collected on
the glass fibre filters was measured with an elemental
C/H/N Perkin-Elmer analyser.
276 A.-M. Aucour et al. / Chemical Geology 197 (2003) 271–285

3. Results

3.1. dD – d18O and Cl
tracing of the mixing process

The dD and d18O values and the concentration of

Cl of the water samples, which were collected in the
Negro and in the Solimões, are shown in Table 2. The
isotopic composition and the concentration of Cl
did
not significantly vary with depth, indicating homoge-
neous water masses in the Negro and in the Solimões.
There was a marked difference between the two
rivers. Compared with the Rio Solimões, the Rio
Negro was more enriched in heavy isotopes and more
diluted in Cl
. All three tracers can therefore be used
to follow the mixing process. A small enrichment in
heavy isotopes and Cl is found in the samples col-
lected at the end of the cruise. This change corre-
sponds to the decrease of the discharge of the Amazon
River by about 13% between the beginning and the
end of the cruise (Table 2). It was taken into account
into further calculations of mass balances below the
Negro –Solimões confluence.
In the mixing zone, the isotopic compositions and Fig. 2. (a) dD versus d18O and (b) Cl
concentrations versus d18O
the concentration of Cl
indicate that the sampled of water samples in the mixing zone between the Rio Negro and the
water columns presented a vertically homogeneous Rio Solimões.
distribution at stations G4, G5, G6 and that waters
from the Rio Negro preferentially flowed over those and Rio Solimões (either mixing line 1 or 2)
from the Rio Solimões at station G3 (Table 2). indicates no marked input from other sources such
Theoretical mixing lines between waters from Rio as varzea lakes and groundwaters.
Negro and Rio Solimões are shown in Fig. 2. Because of the marked difference between the Rio
Mixing line 1 is defined by the composition of Negro and the Rio Solimões, the contribution f of the
two end-members at the beginning of the cruise. Negro waters in the mixing zone was calculated from
Estimation of the end-member compositions of mix- the mass balances of oxygen isotopes, hydrogen
ing line 2 was calculated for the date of sampling of isotopes or Cl
:
station G6, which is the station located further
cM ¼ cN f þ cS ð1
f Þ
downstream. It uses the compositions of the Rio
Negro and of the Rio Solimões at the beginning and where cM is the composition of the water sample in
at the end of the cruise, sampling dates of G1, G2, the mixing zone; cN and cS are the composition from
and G6, and the expected transit between G1 and G6 Rio Negro and Solimões, respectively (as measured at
and between G2 and G6. Transit time was estimated the beginning of the cruise). Water samples in the
from the flow rates yielded by ADCP on the studied mixing zone align well on mixing line 1 (see above)
transects to be 1 – 3 days from G1 to G6 and 1 –2 and the compositions of the end-members were there-
days between G2 and G6. Travel time between the fore taken as those measured at the beginning of the
confluence and G6 was estimated to be 5 –10 h. The cruise. d18O, dD and Cl
yield three independent
two mixing lines are quite close. Water samples from estimates of the Rio Negro contribution, with preci-
the mixing zone align well on mixing line 1 (see sion of F 0.03, F 0.01 and 0.02, respectively. The
above). The fact that they do not significantly averaged f value will be considered further. The Rio
deviate from the mixing lines between Rio Negro Negro contribution is similar to that based on dis-
 A.-M. Aucour et al. / Chemical Geology 197 (2003) 271–285 277

charge (0.26/0.27) only at the station located furthest
downstream (G6). This indicates that complete mixing
of the waters occurred at this station only. The other
stations yield a progressive range from the Rio Negro
pole towards complete mixing.
3.2. Distribution among the dissolved and particulate
fractions
The concentrations of major elements in unfiltered
waters, in the dissolved fraction obtained by TFF and
FF, are presented in Table 2. Table 3 shows the
results for the particulate fractions. For the dissolved
load, there is a good agreement between the results
obtained by TFF and FF (Table 2). Comparison
between the two datasets, for Ca, Mg, K, Na,
indicate that the overall uncertainty linked to water
sub-sampling, filtration and analytical measurement
is of less than 10%. An underestimation of DOC and
an overestimation of Mn seem to occur in the TFF
procedure as the slopes of regression lines between
TFF and FF dissolved concentrations are 0.91 for
DOC and 1.19 for Mn, respectively. After correction
for this bias, the two datasets agree within less than
10%. Bulk concentrations measured directly on the
unfiltered waters were compared with the sum of
concentrations in the dissolved and suspended loads,
which were measured after FF, for Ca, Mg, K, Na
and organic carbon. For Al and Fe, the difference
between the bulk concentration and that of dissolved
species (TFF) was compared with the concentration
of particulate species (FF). TFF data would lead to a
large underestimation of the concentration of the
suspended load. Concentrations of particulate species
have a large uncertainty due to the problem of
sampling heterogeneous distributions ( F 10%). The
underestimation of the concentration of particulate
species in the TFF is however large (>10%) and
systematic and may be partly due to the analytical
procedure. Measurements on the suspended load

Table 3
Element concentration in the particulate fractions obtained dissolved and particulate fractions obtained after FF for samples of the Negro –
Solimões confluence zone
Sta. River Date Depths TSSa TSSb f Particulate (>0.22 Am) in wt.% Particulate (>0.22 Am) in AM
no (m) (mg l ) (mg l
1)

1
Ca Mg K Na Fe Al POC Ca Mg K Na Fe Al POC
G1 Negro 16/9 1 13.8 8.7 0.23 0.11 0.24 0.09 2.33 4.64 11.8 0.8 0.6 0.9 1.4 5.8 23.7 86
6 30.6 7.8 0.17 0.06 0.15 0.09 1.14 2.60 9.17 1.3 0.8 1.2 2.0 6.3 29.5 60
12 – 9.7 – – – – – – 8.51 – – – – – – 69
25 – 8.6 – – – – – – 11.3 – – – – – – 81
G2 Solimões 17/9 1 90.3 70.4 0.75 0.72 1.53 0.66 3.59 7.81 2.25 17.0 26.6 35.5 60.1 58.1 261.4 132
6 99.1 92.9 0.85 0.86 1.87 0.83 3.92 8.50 1.92 21.0 35.1 47.4 80.6 69.6 312.2 149
12 – 86.5 – – – – – – 2.11 – – – – – – 152
25 – 75.8 – – – – – – 1.66 – – – – – – 105
G3 Amazon 18/9 5 27.2 – 1 0.53 0.32 0.62 0.28 3.80 7.76 – 3.6 3.6 4.3 3.8 18.5 78.2 –
15 10.2 24.0 0.68 0.60 0.39 0.94 0.32 1.96 5.91 2.92 1.5 1.6 2.5 4.2 3.6 22.3 58
25 56.3 – 0.43 0.52 0.39 1.24 0.58 3.16 6.85 – 7.3 9.0 17.9 30.4 31.9 142.9 –
35 47.7 37.2 0.41 0.31 0.28 0.90 0.32 1.69 4.88 2.43 3.7 5.5 11.0 18.7 14.4 86.3 75
G4 Amazon 20/9 6 47.2 23.3 0.67 0.78 0.75 1.44 0.64 3.66 7.70 3.64 9.2 14.5 17.4 29.6 30.9 134.7 71
10 33.8 35.4 0.64 0.35 0.22 0.78 0.29 2.34 5.10 3.20 2.9 3.0 6.8 11.5 14.2 63.9 94
15 46.2 28.9 0.62 0.51 0.45 1.43 0.47 3.47 7.09 3.71 5.9 8.5 17.0 28.7 28.7 121.4 89
G5 Amazon 21/9 0.5 47.5 19.5 0.68 0.65 0.61 1.27 0.54 3.48 6.78 3.52 7.7 11.9 15.5 26.2 29.6 119.4 57
20 19.8 36.3 0.68 0.82 0.68 1.95 0.85 4.65 10.92 2.85 4.1 5.5 9.9 16.8 16.5 80.1 86
35 43.2 37.4 0.61 0.52 0.46 1.16 0.47 3.14 6.15 2.84 5.6 8.2 12.8 21.8 24.3 98.5 –
G6 Amazon 22/9 1 56.8 34.1 0.25 0.59 0.56 1.35 0.46 3.47 6.86 3.29 8.4 13.0 19.7 33.3 35.3 144.4 93
20 51.3 43.8 0.25 0.59 0.55 1.46 0.55 3.60 7.33 2.44 7.6 11.6 19.2 32.6 33.1 139.4 89
40 52.7 46.5 0.27 0.48 0.37 1.25 0.48 3.40 7.00 2.91 6.3 8.0 16.9 28.6 32.5 136.7 113
– : not determined.
a
Suspended sediment collected on durapore filters.
b
Suspended sediment collected on glass fibre filters.
278 A.-M. Aucour et al. / Chemical Geology 197 (2003) 271–285
after FF involve a complete dissolution by a HNO3 –
HF – HClO4 mixture while those on the unfiltered
waters were made directly. For Al and Fe, the
discrepancy between the bulk concentration and the
sum of dissolved and particulate phases may be due
to sorption of particles on the TFF membranes since
mass balances for those elements are quite poor
( < 60%). For organic carbon, discrepancies could
be due to un-complete oxidation of refractory carbon.
The sum of dissolved and particulate phases will
therefore be used to estimate the total load rather
than the measured bulk concentration, except for Mn
and Si because these elements were not analysed in
the suspended sediments.
3.3. Elemental budget in the mixing zone
Diagrams showing the elemental concentration
versus the Rio Negro contribution are used to infer
the conservative or nonconservative behaviour of the
elements Ca, Mg, K, Na, Al, Fe, Mn and organic
carbon in the mixing zone. Mixing line 1 is defined by
the composition of the two end-members at the
beginning of the cruise. An envelope of mixing lines
is given, when the composition of the end-member
varies within the sampled reference section for each
end-member. Mixing line 2 was calculated for the date
of sampling of station G6. The contribution f of the
Rio Negro waters in the mixing zone was estimated as
explained above.
3.3.1. Ca, Mg, K and Na
There is a clear contrast in concentrations of dis-
solved Ca, Mg, K, Na between the Rio Negro and Rio
Solimões, the latter being enriched relative to the Rio
Negro (Table 2). The concentrations measured for the
dissolved load were homogeneous in the studied sec-
tion of each river. The compositions of the end-mem-
ber, which were estimated for the date of sampling of
station G6 (see above), indicate a significant enrich-
ment of Mg (15%) in the Rio Solimões, over the course
of cruise sampling, which fits with the evolution of Cl,
dD and d18O and of discharge. The water samples from
the mixing zone present concentrations falling on the
theoretical mixing lines for K, Ca, Mg (not shown here)
which indicates a conservative behaviour for these
elements. Input of dissolved Na at station G6 is
indicated by the TFF data (20%) and not by the FF
data. The nonconservative behaviour of Na is consid-
ered as an artefact of the water processing.
In the suspended load, mixing lines between the
Rio Negro and Rio Solimões would define a large
envelop of mixing lines, due to the heterogeneous
distribution of the suspended sediments and the par-
ticulate species, rendering it hard to infer any source
or sink of the particulate species.
3.3.2. Organic carbon
DOC accounts for 90% of the total organic carbon
(TOC) in the Rio Negro and accounts 65% of the
TOC in the Rio Solimões. Water samples from the Rio
Negro have DOC concentrations (493 AM by TFF and
566 AM by FF) about two-fold higher than those of
the Rio Solimões (221 AM by TFF and 278 AM by
FF) (Fig. 3). In contrast, particulate organic carbon
(POC) concentrations were smaller in the Rio Negro
(74 AM by TFF and 86 AM by FF) than in the Rio
Solimões (134 AM by TFF and 152 AM by FF), where
maximum concentrations were found. Within the
rather large envelop of conservative mixing lines
between the Rio Negro and Rio Solimões, POC
presents an apparent conservative behaviour (Fig. 4).
In the mixing zone, the observed DOC concen-
trations (TFF) fall on the theoretical mixing lines at
stations G3 – G5 and below at station G6 (Fig. 3). The
station G6 is located further downstream and repre-
sents complete mixing between the two end-members.
The apparent loss of DOC at station G6 is of 30% (70
AM). The FF data yield a similar loss (30%).
A mass-balance calculation can be done for the
DOC losses. According to Fig. 3, the loss of DOC at
G6 is 70 AM and corresponds to a loss of 1.93 Terag C
year
1 or 5.3 Gigag C day
1, using the same water
discharge value as before. This amount represents
8.3% of the total annual DOC flux at the station G6
using a mean DOC concentration of 2.16 mg l
1. The
DOC sink is apparently not balanced by generation of
POC. A similar conclusion is reached with the bulk
carbon concentrations of unfiltered waters that show a
carbon loss at station G6. This would mean that, either
there is no input to POC, or that it is balanced by a
POC sink.
3.3.3. Aluminium, iron, manganese
The Rio Negro and Rio Solimões present quite
different distribution between the particulate and dis-
 A.-M. Aucour et al. / Chemical Geology 197 (2003) 271–285
Fig. 3. Comparison between observed concentration in dissolved Mn, Al, Fe and DOC and those predicted by a conservative mixing model
between the Negro and Solimões Rivers.
solved fractions. In the Rio Solimões, iron, aluminium,
and manganese are essentially present in the size
fraction >0.2 Am (Figs. 3 and 4). The distribution of
particulate Al and Fe within the water column is very
heterogeneous. Concentrations in the Rio Solimões are
about 10-fold higher than those of the Rio Negro.
The distribution of dissolved Fe and Al within the
water column is homogeneous (Table 2), except for
Fe in the Rio Negro. There was no significant drift of
the concentrations over the course of the cruise. The
concentration of dissolved Fe was 3.4 AM in the Rio
Negro and 0.9 AM in the Rio Solimões, i.e. three-fold
higher in the Rio Negro than in the Rio Solimões.
The concentration of dissolved Al was about five-
fold higher in the Rio Negro, with values of 2.8 and
0.6 AM, respectively. Dissolved Mn presented a less
systematic pattern between the two rivers. Over the
course of the cruise, the concentration remained at
279
180 AM in the Rio Negro and increased from 100 to
more than 200 AM in the Rio Solimões.
In the mixing zone, in the suspended load, Al, Fe
and Mn presented a wide envelop of theoretical
mixing lines between the Rio Negro and Rio Sol-
imões and subtraction of particulate species below the
confluence (Fig. 4). The dissolved Al data indicate an
apparent conservative behaviour (Fig. 3). Concentra-
tions of dissolved Fe indicate a significant loss at
station G6 that amounted to 20 –65%, depending on
the value of Rio Solimões concentration used in the
mixing model (Fig. 3). Al and Fe losses are not
balanced in the suspended load. The Mn data indicate
a significant apparent input of dissolved Mn (TFF) in
the mixing zone (Fig. 3). The level of dissolved Mn
remained >180 nM at stations G3 –G5 and at 165 nM
at station G6. This behaviour is confirmed by the FF
data. In opposition to Fe and Al, Mn losses in the
280 A.-M. Aucour et al. / Chemical Geology 197 (2003) 271–285

Fig. 4. Comparison between observed concentration in particulate Mn, Al, Fe and POC and those predicted by a conservative mixing model
between the Negro and Solimões Rivers. The grey field represents the envelop of mixing lines.

suspended load could be balanced by the increase in
the dissolved fraction.
4. Discussion
4.1. Particulate major elements removal during the
initial mixing
Major and trace elements (Na, Ca, Fe, Mn. . .)
show a systematic removal of particulate species
below the confluence (at station G6 in Fig. 4). Al
and Fe also show a strong correlation with Si (Fig. 5).
Similar correlations are obtained for Ca, Mg, Na and
K (not shown here). This is in agreement with the
previous mineralogical studies of the composition of
Amazon River basin suspended material and flood-
plain sediments consisting of smectites, illite and a
minor amount of kaolinite, together with quartz and
Na- or Ca-plagioclases (Irion, 1983; Martinelli et al.,
1993). In the Rio Negro, kaolinite dominates the clay
fraction of the suspension. During the early stage of
the mixing, we have already significant removal of
those minerals. It is difficult to say if this removal is
associated with POC removal since the POC concen-
trations stay within the envelop of the theoretical
mixing lines and present an apparent conservative
behaviour (Fig. 4). The mineral removal could be
due to preferential sorption of a specific fraction of the
DOC on particles (see below). This would explain the
lack of POC increase while we observe a large DOC
decrease.
We can calculate the amount of particulate Si (mol)
lost each year or day during the early stage of the
mixing. According to Table 2, we have a loss of 130
AM of Si at station G6. The measured water discharge
at this station was 74,200 m3 s
1. The calculated
annual loss is 0.3 Gmol of Si or a daily loss of
22.5  106 t of Si. A similar calculation can be done
with the suspended particulate matter (SPM) data in
Table 3. If we assume that the loss of SPM is roughly
20 mg l
1, it corresponds to 46.5  106 t year
1 of
 A.-M. Aucour et al. / Chemical Geology 197 (2003) 271–285 281

Fig. 5. Correlations between Fe, Al, Si, Mn and DOC. Plot (a) shows the correlation between Si, Fe and Al in the particulate fraction. Open
symbols correspond to Al (scale on the right axis) and dark symbols to Fe (scale on the left axis). Plot (b) shows the correlation between Fe, Al
and Mn in the particulate fraction. Plot (c) shows the correlation between Al, (or Fe) and OC in the dissolved fraction ( < 0.2 Am). Best fit line is
shown for Al (R2 = 0.8654).

SPM lost within 25 km after the initial mixing of the
two major Amazon tributaries, which can be com-
pared with the sedimentation rate of 37  106 t year
1
calculated by Filizola et al. (in press) for the low
Amazon River reach between the Solimões –Negro
confluence and Óbidos station.
4.2. Behaviour of organic matter in the initial mixing
zone
Processes involved in the organic carbon dynamic
in the mixing zone are numerous (Table 1). Flow rate
data yield transit, and reaction times, of about 5– 10 h
between the confluence and station G6. The mixing
zone presents conditions for OM sorption to mineral
surfaces: i.e. much higher concentrations of the OM
and much lower concentrations of suspended sedi-
ments in the Rio Negro than in the Rio Solimões.
Adsorption experiments have been made with DOM
collected in rivers and wetlands of the Amazon water-
shed, using kaolinite or river suspended sediments as
mineral surfaces (Aufdenkampe et al., 2001). These
experiments have shown that appreciable sorption of
DOM occurs on mineral surfaces under these condi-
tions, with newly sorbed organic matter ranging from
0.1 to 3 wt.% OC (mg OC/100 mg sediment). Moreira-
Turcq et al. (in press) showed that the removal of DOC
from solution by adsorption onto alumina particles can
represent up to 45% of the total DOC below the most
downstream station. They however do not exactly
reproduce the reactants involved below the conflu-
ence, where clay minerals (smectites, kaolinite, illite)
are major aluminium-bearing phases of the Rio Sol-
imões suspensions. At station G6, the observed DOC
282 A.-M. Aucour et al. / Chemical Geology 197 (2003) 271–285
loss would correspond to a gain of 1– 1.5 wt.% OC, all
lost DOC being newly sorbed on suspended sedi-
ments. Such a gain is consistent with the results of
sorption experiments, but is not indicated by the POC
mass balance below the confluence. This suggests that
additional withdrawal process occurs in the mixing
zone either by sedimentation or degradation of organic
matter. Extent of removal by sedimentation is hard to
infer because of the heterogeneous distribution of
suspended sediments (and of particulate species) in
the Rio Solimões and because of the large uncertainty
on the concentration in particulate species. Figs. 3 and
4 suggest a loss of particulate species as the water
samples from the mixing zone generally fall in the
lower part of the envelop predicted for conservative
mixing between the Rio Solimões and Negro or even
below this envelop. Respiration rates have been esti-
mated by bottle incubation of Amazon River waters
(Richey et al., 1990). At station G2, they vary by an
order of magnitude from 0.17 to 1.73 Amol O2 l
1 h
1
in October, over the period 1983 – 1993 (Devol et al.,
1995), yielding an upper estimate of respiration loss of
17 Amol l
1 during the time of transit between the
confluence and station G6. Fig. 6 allows the compar-
ison of the evolution of POC with that of the total
sediment concentration. Paths A and B would corre-
spond to removal of POC by sedimentation at station
G6, respectively, without sorption of DOM on mineral
surfaces and, with a gain of 1 wt.% OC. Oxidation of
Fig. 6. POC concentration versus TSS. Mixing line calculated for
average compositions of the Negro and Solimões Rivers, without
DOM sorption: – – – , taking a DOM sorption of 1 wt.% OC on
suspended sediments of the Solimões River: - - -. x: predicted
compositions for stations G6 (assuming conservative mixing).
organic matter (Path C) corresponds to a maximum O2
consumption of 17 Amol l
1. The amount of carbon
lost per day at the initial stage of the mixing (see above
in Results) is twice the amount of DOC that could be
lost via photochemical reactions in the Amazon River
plume as calculated by Amon and Benner (1996).
4.3. Behaviour of Fe and Al in the early stage mixing
There is a good correlation between Fe and DOC
and Al and DOC (Fig. 5) suggesting a control of both
elements by organic carbon. However, Fe, Al and
DOC have different behaviours in the initial stage of
the mixing. Aluminium behaves conservatively dur-
ing the mixing while 30% of iron is lost. Two
processes can explain this behaviour. The first one is
that Fe and Al are bound to two different pools of OM
and are fractionated during the mixing processes. One
pool would contain more Fe and much less Al. It
would be the most reactive pool in the mixing process
(i.e. losses of OM). This pool would react preferen-
tially with the particulate material removed during the
mixing. For instance, McKnight et al. (1992) showed
the fulvic acid, which was more aromatic and con-
tained more nitrogen reactive groups (i.e. amino
acids) strongly bounds Fe via ligand exchange inter-
actions. It was found to be preferentially adsorbed
(enriched) on the particulate fraction compared to the
dissolved fraction, during the mixing of two small
rivers with contrasted chemistries (McKnight et al.,
1992). Supporting this hypothesis for the initial mix-
ing of the Rio Negro and the Rio Solimões is the
recent result published by Gadel et al. (2000) and
Moreira-Turcq et al. (in press) showing that the
particulate fraction at stations G3, G4 and G6 and
further downstream was enriched in N-rich com-
pounds during the mixing. Also, Rocha et al. (1999)
showed by NMR that the OM from the Rio Negro was
highly aromatic with little substitution. Thus, the part
of the Fe pool bound to this fraction would be
controlled during the mixing by the preferential
removal of this OM fraction. Al would be mainly
present in a second pool of OM containing less
nitrogen-rich compounds and being less aromatic.
This idea is also supported by the work of Aitkenhead
and McDowell (2000) who report a good inverse
relationship between the C/N ratio and DOC fluxes
for a series of watersheds located all over the world.
 A.-M. Aucour et al. / Chemical Geology 197 (2003) 271–285
This correlation suggests also a preferential retention
of N-rich compounds on the particles during the water
transfer form the soil to the sea. The second pool of
OM would contain both elements as suggested by
Benedetti et al. (2002). In this work, they show, that in
the Rio Negro, Fe and Al are not distributed equally in
the colloidal fraction (5000 Db0.2 Am). Fe is found
in a fraction of colloids with nominal sizes ranging
from 0.2 Am to 100 kD where Al is not detected.
While both Fe and Al are detected in the smaller
fraction (5 kDb100 kD) (Benedetti et al., 2002).
The second simultaneous process is prompted by the
observation made by Allard et al. (2002). They have
shown that there are two forms of iron in the colloidal
material (5 kDb0.2 Am) of both the Rio Negro and the
Amazon. The ESR spectra of the colloidal fractions
show that Fe is present not only as Fe organic com-
plexes involving organic reactive groups evidenced by
FTIR but also as iron oxyhydroxides. The iron oxy-
hydroxides could react preferentially with the other
particles through coagulation during the initial stage of
the mixing. Surface complexes with OM as shown by
McKnight et al. (1992) could enhance coagulation and
explain the preferential removal of the iron oxides. A
similar behaviour was observed by Powell et al. (1996)
in a southeastern US estuary. They concluded that iron
exhibits nonconservative removal and is dominated by
high molecular weight components that consist mainly
of Fe-oxyhydroxides or nonlabile organic complexes.
The different forms of Fe (i.e. organic versus mineral)
would react differently and explain the partition and the
difference with Al. A second fraction of organic Fe and
Al complexes could behave conservatively during the
mixing. Because Al is only present as Al OM com-
plexes in the colloidal fraction (Küchler et al., 1994;
Benedetti et al., 2002), this difference in speciation
would explain the different behaviour of Fe and Al
during the mixing.
4.4. Manganese input during the initial mixing
The manganese is the only ion that shows an
increase in its dissolved concentration during the early
mixing of the Rio Negro and the Rio Solimões in the
dissolved fraction. All other elements show either a
nonconservative loss (C, Fe) or conservative behav-
iour (Al) in the dissolved fraction. A specific process
must be involved to explain the different behaviour of
283
Mn. The source of Mn could be the particulate
fraction, because Gibbs (1977) calculated that metallic
coatings account for 69% of the total available Mn
transported in the Amazon River. These coatings
could undergo reductive dissolution in the presence
of OM as shown by Sunda and Kieber (1994).
According to Stone and Morgan (1987), the process
would involve the phenolic groups of the OM. The
slow oxidation of the released Mn(II) would be
responsible of the temporary increase of the Mn
concentration in the early stage of the mixing. Bene-
detti et al. (2002) in agreement with the work of
Rocha et al. (1999) showed that the colloidal OM of
the Rio Negro was richer in phenolic groups when
compared to the OM of the Rio Solimões or the
Amazon River. A massive input of Rio Negro phe-
nolic-‘‘rich’’ water at the mixing zone would create
favourable conditions for the reductive dissolution of
the manganese coatings and/or indirect photo-reduc-
tion of manganese oxides (Scott et al., 2002).
A second source of manganese could be the OM
itself. Allard et al. (2002) showed by ESR spectro-
scopy that in the colloidal fraction part of the man-
ganese, ions were bound to the OM by outer-sphere
complexes. The photo-oxidation of the OM in the
Amazon River basin is important, because over a 75-h
period, 15% of the original DOC can be consumed by
photochemical processes (Amon and Benner, 1996).
Moreover, Amon and Benner (1996) calculated that at
least 15% of the OM from the Rio Negro is very
photo-reactive and suggested that the major photo-
reactive groups involved could be the carboxylic
groups. These groups are partly responsible of the
overall negative charge of the OM. A significant loss
of these groups via photochemical processes could
reduce the overall negative charge of the OM resulting
in the release into the solution of a part of the loosely
bound Mn ions (i.e. outer-sphere).
It is difficult to quantify the above processes but an
estimation of the amount of phenolic groups available
for reductive dissolution can be made assuming a 1 to 1
stoichiometry for the reaction (i.e. one Mn for one
phenolic group as proposed by Stone and Morgan,
1987). Based on the data from Benedetti et al. (2002),
the Rio Negro and the Rio Solimões contain 8 and 4
Aeq phenolic mg C
1, respectively. If we assume that
70% of the water comes from the Rio Solimões at the
mixing and the rest from the Rio Negro, using their
284 A.-M. Aucour et al. / Chemical Geology 197 (2003) 271–285
respective DOC concentration given in Table 2, we can
calculate the amount of phenolic groups transported by
each river. The total amount is equal to 25 Aeq l
1 with
16 and 9 Aeq l
1 brought by the Rio Negro and the Rio
Solimões, respectively. This number is similar to the
increase of the dissolved Mn concentration in the early
mixing (Fig. 3). The contribution of the second process
is even more difficult to estimate because we do not
know the amount of Mn bound to the OC.
5. Conclusion
In the present work, we have shown the usefulness
of a triple tracer approach to follow the mixing of the
two major tributaries of the Amazon River. It was
possible to see rapid changes in the chemical compo-
sition and the isotopic signature of the two end-
members (Rio Negro and Rio Solimões) during the
length of the cruise.
Our data show that within less then 25 km, massive
quantities of particulate Ca, Mg, Si, Fe, Al and Mn are
lost at the confluence of those two large rivers. Also,
we did not see lateral input due to ground waters or
varzea lakes.
In the dissolved fraction, we found that both DOC
and Fe behave in a nonconservative way during
mixing. This could be due to preferential interaction
of N-rich OM with iron oxyhydroxides.
In the dissolved fraction, Al has a conservative
behaviour, while Mn is not conservative and is
enriched. This enrichment in the initial stage of the
mixing could be due to reductive dissolution of Mn
oxides and/or photochemical decomposition of OM
input from the Rio Negro that would release into
solution Mn ions previously bound via outer-sphere
complexes.
The amount of DOC lost during the initial stage of
the mixing represents 4% of the total annual flux of
DOC of the Amazon River at Óbidos reference gaug-
ing station.
Acknowledgements
This work was financially supported by Pro-
gramme d’Etude de la Géosphère Intertropicale,
Programe Sol et Erosion from the Institut des Sciences
de l’Univers of the CNRS and the Institut de
Recherche et Développement. The authors express
their gratitude to the Hidrologia de Bacia Amazonica
(CNPq-IRD-ANEEL and UnB) project team. A.K.-C
Wong postdoctoral fellowship from the CNRS-France
to F.-X. Tao is also acknowledged. Comments from
D.M. McKnight and an anonymous reviewer help to
clarify several aspects of the manuscript. [LW]
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