Chemical Geology 175 Ž2001.

249–258
www.elsevier.comrlocaterchemgeo

Abundance and fractionation patterns of rare earth elements in

streams affected by acid sulphate soils
˚ ¨ )
Mats Astrom
˚ Akademi UniÕersity, Domkyrkotorget 1, 20500 Abo,
Department of Geology and Mineralogy, Abo ˚ Finland
Received 4 October 1999; accepted 11 May 2000

Abstract

The abundance and shale-normalised fractionation patterns of rare earth elements ŽREEs. were studied in 121 streams of
first and second order in an area where acid sulphate soils, developed on oxidised sulphide-bearing marine sediments, are
abundant. During high-water flow events in autumn, on which this study focuses, the leaching of REEs from the acid
sulphate soils is extensive, resulting in high total REE concentrations Žup to ) 1 mgrl. in streams draining such soils
exclusively. In these streams, there is a general depletion of the heavy REEs explained by preferential scavenging of the
latter by oxyhydroxides in the deepest soil-profile horizons. In streams draining areas of glacial till and peat, the REE
concentrations are several orders of magnitude lower. In these streams, in contrast to the REE-enriched streams, there is a
depletion of light REEs explained most likely by preferential complexation of the middle and heavy REEs by dissolved
humic substances. q 2001 Elsevier Science B.V. All rights reserved.

Keywords: Rare earth elements; Fractionation; Stream; Acidity; Acid sulphate soil; Leaching

1. Introduction While this has had positive effects on both the

In coastal regions of western Finland, large areas
are covered with metal-sulphide bearing fine-grained
sediments Žaverage S concentrations 0.5%; Astrom ˚ ¨
¨
and Bjorklund, 1997., which until a few decades
ago, were poorly drained and were therefore water-
logged and chemically inert. In recent decades, how-
ever, the artificial drainage of these sediments, which
are largely in agricultural use, has strongly increased
with the aim of increasing runoff and thereby im-
proving the conditions for agricultural activities.
)
Fax: q358-50-3033905.
˚ ¨ ..
E-mail address: mats.astrom@abo.fi ŽM. Astrom
quality and yield of the cultivated crops, an environ-
mentally hazardous side effect has been the develop-
ment of acidic soils ŽpH s 2.5–5., caused by the
oxidation of the naturally occurring sulphides to
sulphuric acid Že.g., Hartikainen and Yli-halla, 1986;
˚ ¨ 1998a.. While the upper
Yli-Halla, 1997; Astrom,
horizon in these soils Žabout 0–30 cm. is extensively
limed and therefore has a near neutral pH ŽPalko,
1994., the subsoil Žfrom a depth of about 30 to
) 100 cm. remains strongly acidic and is classified
as Sulfic Cryaquept or Typic Sulfaquept ŽYli-Halla,
1997; Yli-Halla et al., 1999., but is commonly re-
ferred to as Aacid sulphate soilB. Because of their
present-day large spatial extent Žapproximately 3000
km2 . and substantial vertical depth, the acid sulphate

0009-2541r01r$ - see front matter q 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 9 - 2 5 4 1 Ž 0 0 . 0 0 2 9 4 - 1
250 ˚ ¨ Chemical Geology 175 (2001) 249–258
M. Astromr
soils have a large influence on the aquatic environ-
ment ŽEden ´ and Bjorklund,
¨ 1993; Lahermo et al.,
1996., particularly during heavy rains in autumn
ŽOctober–November. and snowmelt in spring ŽApril.,
when large amounts of H 3 Oq and metals are leached
from the acidic soil horizons into drains ŽWeppling,
˚ ¨ and Bjorklund,
1993; Astrom ¨ ˚ ¨
1995, 1996; Astrom
˚ ¨ 1997; Eden
and Astrom, ´ et al., 1999.. The other
common sediment types in the region are till, peat
and glaciofluvial deposits, which are largely forested
and from which occasionally acidic, but dilute waters
˚ ¨ and Astrom,
are discharged ŽAstrom ˚ ¨ 1997.. The
major aims of this study were to characterise the
behaviour of rare earth elements ŽREEs. in catch-
ments underlain by acid sulphate soils, and to assess
the overall impact of soilrsediment types on REE
hydrochemistry.
It has previously been suggested that the abun-
dance of REEs in river waters is inversely related to
pH ŽKeasler and Loveland, 1982; Goldstein and
Jacobsen, 1988., and while pH evidently is responsi-
ble for variations in REE concentrations among
streams with similar water type ŽElderfield et al.,
1990., a more important control of REE abundance
in rivers in general, is the amount of particulate and
colloidal-sized material commonly carrying the ma-
jor load of REEs ŽSholkovitz, 1992; Ingri et al.,
2000; Zhang et al., 1998.. The solution phase of
REEs in river waters is commonly characterised by
shale-normalised heavy REE ŽHREE. enrichment
ŽHoyle et al., 1984; Elderfield et al., 1990;
Sholkovitz, 1992, 1995; Ingri et al., 2000., as in
sea-water Že.g., Sholkovitz et al., 1994., due to the
increase in solution-complexation constants with the
important ligands ŽFy, CO 32y, OHy, HPO42y . across
the lanthanide series ŽCantrell and Byrne, 1987;
Wood, 1990; Millero, 1992; Johannesson et al.,
1997.. In contrast, the colloidal and particulate phases
tend to be enriched in the light REEs ŽLREEs.
andror middle REEs ŽMREEs. ŽHoyle et al., 1984;
Sholkovitz, 1992, 1995; Zhang et al., 1998; Land et
al., 1999; Ingri et al., 2000.. As a consequence, the
amount and nature of the particulatercolloidal mate-
rial, the type and proportions of ligands in solution
and a possible non-linear fractionation from La to Lu
ŽElderfield et al., 1990. affect REE hydrochemistry,
resulting in a variety of REE fractionation patterns in
river waters ranging from LREE, MREE to HREE
enrichment ŽElderfield et al., 1990.. While the be-
haviour of REEs has been characterised for a number
of major rivers, which commonly have a neutral or
weakly acidicralkaline water, little information ex-
ists on REE behaviour in catchments composed of
young, acidic and S-rich soils. This paper reports the
behaviour of REEs in streams in an area where such
soils are abundant.
2. Methods
A total of 121 streams mainly of first and second
order, affected to varying extent by acid sulphate
soils, were sampled during high-water flows in au-
tumn in western Finland: of these, 86 were sampled
in the Petalax area in October 1994, 12 in the
Munsala area in November 1996 and 23 in the
Rintala area in October 1997 ŽFig. 1.. During the
high-flow events in autumn, when the discharge is
approximately 50 times higher than during baseflow,
the acid sulphate soils are more strongly leached
than during any other period of the year Že.g., Palko,
˚ ¨ and Bjorklund,
1994; Astrom ¨ 1996.. All samplings
were therefore done on such events. The studied
areas ŽFig. 1. were selected as they are regionally
representative, consist of a range of sedimentrsoil
types including acid sulphate soils, and as in these
˚ ¨
areas stream-water acidification is common ŽAstrom
¨
and Bjorklund, ˚ ¨ and Astrom,
1996; Astrom ˚ ¨ 1997..
Electric conductivity and pH were determined
immediately after the sampling. For element analy-
ses, water samples were collected unfiltered in the
Petalax and Munsala areas and filtered Ž0.45 mm
polycarbonate screen filters. in the Rintala area.
These samples were acidified to pH - 2 with con-
centrated HNO 3 Žsuprapur quality, Merck., and anal-
ysed for a number of major and trace elements with
ICP-MS ŽPerkin Elmer-Sciex ELAN 6000.. The re-
sults of REEs, Fe, Al and Mn are presented in this
study. An analysis of variance, based on duplicate
samples ŽGarrett, 1969, 1973., showed that the ratio
of the overall data variance to error variance Žsample
inhomogeneity, analytical error. was ) 2000 for
Mn, between 40 and 950 for the REEs and Al, and
11 for Fe. Since these ratios were much larger than
the critical ratio at the 99% level of confidence Ž2.6.,
any patterns and trends of these metals in the data set
 ˚ ¨ Chemical Geology 175 (2001) 249–258
M. Astromr 251

Fig. 1. Location of investigated areas Žmap a. and the occurrence of sulphide-bearing fine-grained sediments Žmap b., on which acid
sulphate soils have developed, in the coastal areas of western Finland.

were not due to sampling or analytical error. Stan-
dards and blanks were also repeatedly run to control
analytical quality.
Aquatic REE concentrations should preferably be
normalised to the REE abundance pattern of the
geological source material in the catchments, but
since such data is unavailable, the North American
Shale Composite ŽNASC., which is often used to
normalise aquatic REE concentrations, was utilised
in the study. The NASC values are taken from
Haskin et al. Ž1968. and Gromet et al. Ž1984..
The results of La analyses of a regionally repre-
sentative and well-developed acid sulphate soil pro-
file for which transition metal and major element
252 ˚ ¨ Chemical Geology 175 (2001) 249–258
M. Astromr
˚ ¨ 1998a,b. are pre-
data are given elsewhere ŽAstrom,
sented in this paper. The chemical analyses were
˚ ¨ 1998a,b.: half a gram
performed as follows ŽAstrom,
of each sample Žcollected from each vertical 10-cm
section of the soil profile. was analysed for La Žand
other elements. with ICP–AES after partial digestion
in 3 ml 3:1:2 HClrHNO3rH 2 O Žaqua regia. for 1 h
at 958C and dilution to 10 ml with water. Approxi-
mately 75% of the total La in the samples is ex-
pected to have been extracted with this leach ŽDeng
et al., 1997..
3. Results and discussion
3.1. La in the soil profile
In the studied profile ŽFig. 2., the La concentra-
tions are 25–28 ppm in the reduced zone Žbelow a
depth of about 180 cm.. In this zone, where pH ) 6,
the sediment is chemically inert and La is immobile.
In the upper and middle part of the acid sulphate soil
Ž30–120 cm., the La concentrations are only be-
tween 13 and 23 ppm, while in the lower part of the
soil Ž130–170 cm., the La concentrations are as high
as 29–45 ppm. This concentration variation pattern,
˚ ¨
which is similar to that for Co, Ni and Zn ŽAstrom,
Fig. 2. Vertical variation in pH and the aqua regia extractable
concentrations of La in an acid sulphate soil profile.
1998a., is explained by first, extensive losses of La
from the upperrmiddle part of the acid sulphate soils
due partly to leaching and partly to transport down
the profile, and, second, to secondary immobilisation
of La in the lower parts of the acid sulphate soil ŽFig.
2.. Previous chemical work on samples from the
latter horizon Ženrichment horizon. has shown that
excess Co, Ni and Zn are largely scavenged by
amorphous oxyhydroxides of Fe and Mn ŽAstrom, ˚ ¨
1998a.. A similar enrichment mechanism of La Žand
other REEs., i.e. by sorption onto or coprecipitation
with amorphous Fe and Mn oxyhydroxides, is likely
as the REEs are substantially scavenged by Fe oxy-
hydroxides even at pH values as low as 4 ŽBau,
1999..
3.2. General classification of the streams
The classification of the streams Ž n s 121. in the
pH-conductivity plot ŽFig. 3a. is based on previous
hydrogeochemical work in the region ŽEden ´ and
¨
Bjorklund, 1993; Weppling, 1993; Palko, 1994;
˚ ¨ and Bjorklund,
Astrom ¨ ˚ ¨ and
1995, 1996; Astrom
˚ ¨ 1997; Eden
Astrom, ´ et al., 1999.. In field A ŽFig.
3a., in which there is a strong correlation between
pH and conductivity, acid sulphate soils is the major
hydrochemical control, i.e. as the pH decreases from
6 to 3 and the conductivity increases from 100 to
3500 mSrcm ŽFig. 3a., the proportion of the catch-
ment cover of acid sulphate soils increases from 0%
to 100%. Acidity and ions are thus leached in con-
siderably larger quantities from the acid sulphate
soils than from other soilrsediment types in the
catchments Žtill, peat.. The streams encircled in field
B are characterised by a relatively low ratio of
H 3 Oq to total ion concentrations ŽFig. 3a.. These
streams drain acid sulphate soil areas to varying
extent, but their pH is increased mainly due to excess
liming of the cultivated acid sulphate soils in the
catchments. The streams encircled in field C are
characterised by low pH Ž4.1–5.4. and also low
conductivity Ž65–199 mSrcm.. In the catchments of
these streams, acid sulphate soils are either absent or
occur only as small and insignificant patches. The
acidity of these streams is derived mainly from
dissociated humic and fluvic acids, leached from
 ˚ ¨ Chemical Geology 175 (2001) 249–258
M. Astromr 253

Fig. 3. Plots between studied parameters. Circles and squares indicate unfiltered stream waters from the Munsala area Ž n s 12. and Petalax
area Ž n s 86., respectively, while triangles indicate filtered Ž0.45 mm. stream waters from the Rintala area Ž n s 23..The fields A, B and C
in the pHrEC Želectric conductivity. plot represent streams with similar hydrogeochemical controls Žsee text.. Those streams which are
encircled in field C in the pHrEC plot are indicated also in the pHrYb plot.
254 ˚ ¨ Chemical Geology 175 (2001) 249–258
M. Astromr

peat and the humus horizon of forest soils. In these
source materials, the contents of easily mobilised
major and trace elements are considerably lower than
in the acid sulphate soils, resulting in relatively low
ionic strength of the waters despite their low pH.
3.3. REE concentration leÕels in the streams
A strong inverse linear correlation exists between
pH and the REE concentrations Žthe plot of pH and
Yb is shown in Fig. 3b.. This shows that the REEs
are leached much more abundantly from the acid
sulphate soils than from other sediment types. This is
in agreement with the soil-profile data indicating
extensive leaching of La from the upperrmiddle part
of the acid sulphate soils ŽFig. 2.. Because the REE
concentrations were not lower in the filtered samples
from the Rintala area Ž n s 23. than in the unfiltered
ones from the Petalax Ž n s 86. and Munsala Ž n s 12.
areas at any pH level ŽFig. 3b., the REE concentra-
tions for the unfiltered samples are representative
also for the dissolved phase Ž- 0.45 mm..
Those streams that are to varying extent affected
by acid sulphate soils, but have a relatively high pH
caused by excess soil-liming Žfield B in the pHrEC
plot., do not appear as an individual group of streams
in the pHrYb ŽYb representative for REEs. plot
ŽFig. 3a and b.. This shows that while the extent of
leaching of major ions ŽSO42y, Ca2q, Naq, Mg 2q .
from the acid sulphate soils is not significantly re-
duced by the artificially increased pH, the REEs are
affected, either as a result of immobilisation of REEs
in the soil profile or due to subsequent precipitation
and removal in-stream. Those streams, which drain
till and peat areas and have relatively low pH due to
high loads of organic acids Žfield C in Fig. 3a., are
also anomalous in the pHrYb plot ŽFig. 3b., i.e. the
REE concentrations in these streams are not elevated
to the same extent as at corresponding pH levels in
the other streams.
As a result of the extensive leaching of REEs
from the acid sulphate soils, and as the percentage of
the catchment cover of these soils varied between
0% and 100%, there was a large range in REE
concentrations in the stream waters ŽTable 1., i.e. the
maximum concentrations for La–Er are between
3444 and 6469 times higher, and those of Tm–Lu
about 2000 times higher, than the minimum concen-
trations ŽTable 1.. In comparison with La concentra-
tions in natural waters elsewhere, the 95 percentile of
the La concentrations for the studied streams is
higher by the indicated factors: unfiltered and partic-
ulate-rich water from Yangtze River — 37 ŽZhang et
al., 1998., the Kalix river in northern Sweden during

Table 1
pH, electric conductivity ŽEC; mSrcm. and REE concentrations Žmgrl. in 121 streams, mainly of first and second order in mid-western
Finland during high-water flow in autumn ŽOctober–November.
dl Min 5 Percentile Median 95 Percentile Max Maxrmin
pH 2.9 3.6 4.7 6.0 7.0
EC 65 85 370 1729 3796
La 0.005 0.18 0.93 7.2 236 900 5000
Ce 0.01 0.36 1.85 15 355 2035 5653
Pr 0.002 0.048 0.255 2.1 61 231 4813
Nd 0.004 0.182 0.938 6.1 202 771 4236
Sm 0.005 0.033 0.17 1.074 33 164 4970
Eu 0.001 0.009 0.04 0.21 7.3 31 3444
Gd 0.002 0.032 0.222 1.63 51 207 6469
Tb 0.001 0.007 0.03 0.22 6.4 28 4000
Dy 0.002 0.03 0.19 1.44 39 168 5600
Ho 0.001 0.007 0.034 0.24 7.1 30 4286
Er 0.001 0.018 0.103 0.5 16 62 3444
Tm 0.001 0.004 0.01 0.11 2.0 8.4 2100
Yb 0.001 0.029 0.103 0.52 15 62 2138
Lu 0.001 0.005 0.017 0.11 2.2 8.9 1780

dl s detection limit.
 ˚ ¨ Chemical Geology 175 (2001) 249–258
M. Astromr
REE peaks — 815 ŽIngri et al., 2000., the acidic and
humic-rich Luce river in Scotland — 1230 ŽHoyle et
al., 1984., the Connecticut River — 8850 ŽSholko-
vitz, 1992., the acidic Colour Lake on Axel Heiberg
Island in Canada — 119 ŽJohannesson and Lyons,
1995., REE-enriched acidic ground water from
metasediment in the Carnmenellis area in southwest
England — 2.5 ŽSmedley, 1991., sea water — 57 000
ŽLibes, 1992..
3.4. REE fractionation patterns in the stream waters
With increasing REE concentrations Že.g., La from
- 1 to ) 100 mgrl., there is a concomitant general
increase in the La SN rLu SN ratios from about 0.5 to
2.5 ŽFig. 4. as a result of HREE depletion at high
REE concentrations and LREE depletion at low REE
concentrations ŽFig. 5.. There are only a few excep-
tions to this overall pattern: in two streams with high
REE concentrations ŽLa s 108 and 382 mgrl., the
La SN rLu SN ratios are - 1 ŽFig. 4., and in a few
other streams, the ratio of La SN rLu SN to La concen-
trations is relatively high ŽFig. 4.. The origin of the
main trend in the data, i.e. the increase in La SN rLu SN
Fig. 4. Plot of La concentrations and the ratio of NASC-normal-
ised La ŽLa SN . to Lu ŽLu SN . for 121 streams in western Finland.
Circles and squares indicate unfiltered stream waters from the
Munsala Ž ns12. and Petalax Ž ns86. areas, respectively, while
triangles indicate filtered Ž0.45 mm. stream waters from the
Rintala area Ž ns 23..
255
ratios with increasing REE concentrations, is dis-
cussed below.
Shale-normalised light and middle REE enrich-
ment in river waters is a common phenomenon
ŽGoldstein and Jacobsen, 1988; Elderfield et al.,
1990; Zhang et al., 1998., commonly related to high
amounts of suspended particulatesrcolloids carrying
the main part of the river-transported REEs, and
being preferentially enriched in LREEs and MREEs
ŽHoyle et al., 1984; Sholkovitz, 1992; Zhang et al.,
1998; Land et al., 1999; Ingri et al., 2000.. The
similar REE-fractionation pattern found for a major-
ity of the studied streams, and in particular for those
having high REE concentrations ŽFigs. 4 and 5., is
thought not to be the result of this same phenomenon
for the following reasons: Ž1. the amount of sus-
pended particulates Ž) 0.45 mm. in stream waters in
the area are low Žup to a few mgrl. due to low relief
ratios, and thus limited erosion, of the catchments;
Ž2. the REE concentrations and the La SN rLu SN ra-
tios are not significantly different between the fil-
tered Ž0.45 mm. stream waters from the Rintala area
and the unfiltered ones from the Petalax and Mun-
sala areas ŽFig. 4., indicating that AlargeB particu-
lates are unimportant and do not control levels and
fractionation patterns of REEs; Ž3. there is no overall
correlation between the concentrations of REEs and
Fe ŽFig. 3c., and in the few samples with elevated
concentrations of both Fe and Yb ŽFig. 3c., pH is
- 3.5 and Fe thus expected mainly in ionic form; Ž4.
in 22% of the streams Ž27r121. the total molar REE
abundance is between 11% and 160% of the total Fe
concentrations, excluding the possibility of extensive
scavenging of REEs by colloidal Fe oxyhydroxides;
and Ž5. the strong correlation between the concentra-
tions of REEs and those of Mn ŽFig. 3d. and Al ŽFig.
3e., are not explained by scavenging of REEs by Al
and Mn oxyhydroxides, but are caused by extensive
leaching of Ln3q, Mn2q and Al 3q ions from the
acid sulphate soils. It is also unlikely that the identi-
fied LREErMREE-enrichment pattern Žat high REE
concentrations. is the result of solution-complexation
phenomena, since SO42y, which is by far the most
abundant anion in these streams Žup to 2000 mgrl;
˚ ¨ and Bjorklund,
Astrom ¨ 1995., does not preferentially
complex the LREEsrMREEs ŽWood, 1990., and as
Cly and NOy 3 , which do preferentially complex the
LREEs ŽWood, 1990; Millero, 1992., form overall
256 ˚ ¨ Chemical Geology 175 (2001) 249–258
M. Astromr
Fig. 5. Shale ŽNASC.-normalised REE patterns for some representative streams with high REE concentrations Žleft. and low REE
concentrations Žright..
weak complexes with the REEs ŽWood, 1990;
Millero, 1992. and are not abundant in the streams.
Hence, because the LREErMREE enrichment can-
not be explained by in-stream processes, it must be
inherent in the REE-rich soil waters leached from the
acid sulphate soils. The possible mechanisms are
discussed below.
It is unlikely that the REEs in the sulphide-bearing
fine-grained sediments, on which the acid sulphate
soils have developed, are significantly fractionated
relative to average shale ŽNASC., since the bulk of
these sediments consists of material from Proterozoic
gneisses and granites, and as glacial till composed of
material from this bedrock type have flat NASC-nor-
¨
malised REE patterns ŽOhlander et al., 1996; Land et
al., 1999.. Hence, a direct relationship between the
REE patterns in the parent sediments and those in
the soil solutions leached from the acid sulphate soils
is unlikely. Fractionation of REEs during soil forma-
tion is however likely, since the soil data indicate
that a substantial proportion of the REEs mobilised
in the upperrmiddle part of the acid sulphate soil is
transported downward and is subsequently immo-
bilised in the lower soil horizon by sorption onto Fe
oxyhydroxides ŽFig. 2.. During this secondary im-
mobilisation, the HREEs are expected to be preferen-
tially retained for the following two reasons: Ž1. in
the soil solution in the acid sulphate soils, the LnSO4q
complex Žapproximately equally strong for all REEs.
and the free ion Ln3q are the major anticipated
aqueous REE species ŽWood, 1990; Johannesson and
Lyons, 1995; Johannesson et al., 1996; Johannesson
and Zhou, 1999., while the ligands Fy, CO 32y, OHy,
HPO42y and organic molecules, which preferentially
complex the HREEs ŽCantrell and Byrne, 1987;
Wood, 1990; Millero, 1992., are not abundant, thus
excluding the possibility of extensive REE fractiona-
tion caused by solution complexation; Ž2. as there
are no ligands capable of preferentially keeping the
HREEs in solution, the latter are instead likely to be
preferentially scavenged by oxyhydroxides in the
soils, a mechanism supported by experimental data
ŽBau, 1999. and the increase in the first hydroxide
binding constant across the lanthanide series ŽBau,
1999; Millero, 1992.. The overall result is that the
soil solution, which is ultimately discharged into
streams, becomes depleted in the HREEs, resulting
in HREE depletion in the stream waters ŽFigs. 4 and
5.. This mechanism is supported by glacial till data,
which show that the LREEs are more strongly de-
 ˚ ¨ Chemical Geology 175 (2001) 249–258
M. Astromr
pleted than the HREEs in the E-horizon, and that the
B-horizon can be enriched in REEs due to adsorption
¨
on oxyhydroxides ŽOhlander et al., 1996..
As indicated in Fig. 4, the La SN rLu SN ratio
decreases with decreasing REE concentrations, such
that in 81% of the streams having La concentrations
- 2.0 mgrl Ž26r32., this ratio is - 1.0. This phe-
nomenon is unlikely to be caused by inorganic solu-
tion complexation for the following reasons: Ž1. the
stability constant with the CO 32y anion increases
across the lanthanide series ŽCantrell and Byrne,
1987; Wood, 1990; Millero, 1992.; however, be-
cause the studied streams are acidic Žall but seven
had a pH - 6. and as limestone and dolomite are
absent in the local bedrock, CO 32y and HCOy 3 are
unimportant ligands in the streams, Ž2. the ligands
Fy and HPO42y, which preferentially complex the
MREEs and HREEs ŽWood, 1990; Millero, 1992.,
are not abundant in the waters and are expected to
form complexes mainly with A land Fe, Ž3. other
inorganic anions of some quantitative importance in
2y .
the low REE streams ŽCly, NOy 3 , SO4 do not
preferentially complex the MREEsrHREEs ŽWood,
1990; Millero, 1992.. Several previous studies have
indicated extensive association of REEs with organic
molecules ŽHoyle et al., 1984; Goldstein and Jacob-
sen, 1988; Sholkovitz, 1992., and an increase in
stability constants with such compounds across the
lanthanide series ŽWheelwright et al., 1953; Cantrell
and Byrne, 1987; Li and Byrne, 1997.. It is therefore
likely that in the low REE streams, which are charac-
terised by high concentrations of organic substances
Ž20–60 mgrl organic C., the REE hydrochemistry is
controlled by organic substances with preferential
binding of the middlerheavy REEs.
4. Conclusions
A large range in REE concentrations and a gen-
eral increase in the La SN rLu SN ratios with increas-
ing REE concentrations were observed in the studied
streams. Streams affected by acid sulphate soils are
characterised by high REE concentrations, and
shale-normalised HREE-depleted profiles explained
by a stronger tendency of the heavy than the LREEs
to be immobilised and retained in the deepest soil
horizons. In contrast, the streams with catchment
257
covers composed of glacial till and peat are charac-
terised by low REE concentrations, and shale-nor-
malised profiles that are LREE depleted most likely
due to preferential complexation of the heavier REEs
by the dissolved humic substances.
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