Chemosphere 147 (2016) 155e162

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

A sequential extraction procedure to evaluate the mobilization

behavior of rare earth elements in soils and tailings materials
Marc Mittermüller, Jessica Saatz, Birgit Daus*
UFZ e Helmholtz Centre for Environmental Research, Department of Analytical Chemistry, Permoserstrasse 15, 04318 Leipzig, Germany

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Novel sequential extraction method

for rare earth elements is presented.

Detailed differentiation of bioavail-
able REE fractions is enabled.

Better results for REE's are yield than
by the common BCR procedure.

a r t i c l e i n f o a b s t r a c t

Article history: A novel sequential extraction method for evaluation of the mobilization behavior of rare earth elements
Received 12 June 2015 in soils and mine tailings materials is presented. The sequence consists of the following four steps:
Received in revised form 0.05 mol L1 calcium nitrate (easily soluble and ion exchange fraction), 0.1 mol L1 citric acid (fraction
10 November 2015
mobilized by complexation and carbonate bound), 0.05 mol L1 hydroxylamine hydrochloride (pH ¼ 2)
Accepted 23 December 2015
Available online xxx
(reducible fraction), 1.4 mol L1 nitric acid (acid soluble fraction). The procedure was optimized with a
certified soil material and a mine tailings material and was applied to eight samples of a soil profile. The
Handling Editor: Martine Leermakers different results obtained by using either the developed method or the widespread used BCR-Method for
comparison are discussed. There were clear advantages using the newly created sequential extraction
Keywords: procedure in getting more detailed information about the bioavailable fraction and a fraction addressing
Leachability REE phosphates.
Fractionation © 2015 Elsevier Ltd. All rights reserved.
Bioavailability
ICP-MS
REE
BCR sequential extraction procedure

1. Introduction
Rare earth elements (REE) are mainly used for high-tech appli-
cations, e.g. light emitting devices, optical glasses and lenses, high
performance magnets (Nd2Fe14B), catalysts and medical
* Corresponding author.
E-mail address: birgit.daus@ufz.de (B. Daus).
applications like MRI contrast agents (Natrajan and Langford Paden,
2013). The discharge of gadolinium (Gd) into the environment is
estimated to be more than 1000 kg per year in Germany
(Kümmerer and Helmers, 2000). As a consequence, elevated con-
centrations of Gd are observed in sewage and surface water all over
the world (Kulaksız and Bau, 2011) and might be a source of soil
contamination. Furthermore, contamination by cerium (Ce) is re-
ported from broken automotive catalytic converters (Helmers,

http://dx.doi.org/10.1016/j.chemosphere.2015.12.101
0045-6535/© 2015 Elsevier Ltd. All rights reserved.
156 M. Mittermüller et al. / Chemosphere 147 (2016) 155e162
1996). Low levels of the REE are able to stimulate organisms as a
short-term effect, but higher levels result in toxicity symptoms, due
to their similarity to calcium (Hirano and Suzuki, 1996). Stimulation
of vegetable and animal organisms is the main reason for usage of
REE as fertilizer or food supplements in animal production,
respectively (Xu et al., 2002; Miller, 2006). Recent findings
contradict stimulation of plants by REE (Saatz et al., 2015), but large
amounts of REE were applied in China into the environment (Tyler,
2004). Chronic effects of long-term exposure with REE are hard to
estimate and still lacking research. Other anthropogenic sources for
REE input into the environment could be mining activities, espe-
cially dumped tailings materials from mines where REE occur but
are not in the focus of the activity.
Sequential extraction methods are used to estimate the mobi-
lization behavior of interesting elements from soils, sludge and
sediments simulating different leaching conditions. Especially the
mobilization behavior of heavy metals is in the focus to assess the
risk potential of contaminated media. Hardly mobile or inertly
bound elements pose a lower risk compared to easily soluble
fractions. In sequential extraction methods the sample is succes-
sively suspended in extraction solutions of increasing strength and
the mobilized amount of analytes is quantified. The assignment to
different chemical surroundings and species is thereby operation-
ally defined (Gleyzes et al., 2002; Hass and Fine, 2010).
Only a few studies have dealt with the mobilization behavior of
REE from soils and sediments. Most studies adopt methods for REE
which were developed for heavy metals, mainly the BCR method (Li
et al., 1998; Rauret et al., 1999; Wang et al., 2003; Rao et al., 2010;
Mihajlovic et al., 2014) and the sequence proposed by Tessier
et al. (1979) (Zhang et al., 1998; Xinde et al., 2000; Wang et al.,


2009; Smuc et al., 2012; Xu et al., 2012). Sanematsu et al. (2011)
developed a method especially for REE in rock minerals, focussing
on differences in the binding to mineral phases.
Regarding tailings materials and soils, there are natural pro-
cesses for REE mobilization; firstly, rain water or pore water will
make REE mobile by dissolution of REE-bearing minerals or ion
exchange. Secondly, plants will make REE bioavailable by root
exudation of low molecular organic acids (Ryan et al., 2001).
Dividing the first step of the BCR-Sequence into the fractions easily
soluble and ion exchangeable and a fraction mobilized by
complexation and carbonate bound will allow determining these
separately. A third important process is the mobilization under
reducing conditions by changing either the oxidation state of the
element or the host mineral elements (like iron ore manganese
hydroxides), which will promote mobility. This process can be
caused by weathering as well as microbial and root activities
(Marschner, 1995). Typical REE-bearing minerals are the phos-
phates. These minerals have a very low solubility, and mobilization
will only occur under strong acidic conditions. (Oelkers and
Poitrasson, 2002; Cetiner et al., 2005) Under acidic mine drainage
large quantities of REE might be mobilized (Nordstrom, 2011).
These amounts of REE will therefore not be available for plants
under usual environmental conditions, but may be important
regarding acid mine drainage and other strong acidic conditions.
The aim of this study was to develop a sequential extraction
procedure directed to the mobilization of REE from tailing materials
and soils which allows prediction of their environmental behavior
with special emphasis on the bioavailability.
2. Materials and methods
2.1. Chemicals and apparatus
The following chemicals were used to prepare the leaching so-
lution in p.a. or higher purity: 0.05 mol L1 calcium nitrate
(Ca(NO3)2 $ 4H2O; MERCK), 1 mol L1 ammonium acetate (MERCK),
1 mol L1 acetic acid (Th. Geyer), 0.05 mol L1 EDTA (Na2EDTA $
2H2O; MERCK), 0.1 mol L1 malic acid (Th. Geyer), 0.1 mol L1 citric
acid (MERCK), 0.1 mol L1 oxalic acid pH ¼ 3 ((NH4)2oxalate,
MERCK), 0.05 mol L1 hydroxylamine hydrochloride, pH ¼ 2
(MERCK) and nitric acid in concentrations of 0.1 and 1 mol L1 (1 M
FIXANAL, FLUKA) and 1.4 mol L1 (diluted by a factor of 10 from
65%, MERCK). The pH value of the extraction solutions was adjusted
as named before with nitric acid.
All extraction solutions were freshly prepared using de-ionized
water (Milli-Q, Millipore).
All laboratory-ware were soaked overnight in 4% nitric acid,
rinsed repeatedly with distilled water and dried before being used.
Extractions were performed using a horizontal shaker (HS-250
basic, IKA Labortechnik; Germany) at 90 rpm and at room tem-
perature. Centrifugation was carried out at 4000 rpm for 10 min
(Rotana 460, Hettich Zentrifugen; Germany). Samples were stored
prior to analysis in a fridge at 4  C or they were measured
immediately.
2.2. Sample materials
The certified reference material SRM 2710 (National Institute of
Standards and Technology; USA) was chosen as soil sample for the
optimization of the procedure. Additionally a tailings material with
elevated REE concentrations was tested.
Several soil samples were collected from a weathering profile in
2012 from a lead contaminated forest soil at Teutoburger Wald;
Germany (Lorz et al., 2010). The profile reached from þ10 cm
to 70 cm and could be divided into the horizons Oh1, Oh2, Aeh,
Ahc, Bh, Bs and Cv. Soils at the investigation site are extremely poor,
shallow podzols. The organic layers are raw humus. The sample
materials from every horizon were dried and milled (Retsch MM
200, with zircon oxide materials) before usage.
2.3. Microwave assisted aqua-regia digestion
An aliquot of the dried and ground samples of 250 mg were
weighed into the digestion vessels and 4.5 mL fuming hydrochloric
acid (MERCK) and 1.5 mL concentrated nitric acid (MERCK) was
added. The microwave digestion device (Multiwave, Anton Paar;
Austria) was used to enhance the yield of digestion. The following
program was used: 0e8 min from 500 to 800 W, 8e11 min from
800 to 1000 W and finally for another 20 min at 1000 W. After
cooling down to room temperature the volume was adjusted to
50 mL using deionized water. The made-up solution was centri-
fuged to separate remaining particles from the supernatant, which
was used for analysis without further treatment.
2.4. Single batch extractions
Single batch extractions were performed with the sample ma-
terials SRM 2710 and the tailings material using a sample-to-
solvent-ratio (SSR) of 1:200 and the solutions listed in chapter
2.1. To 50 mg of sample material, 10 mL of extraction solution was
added and shaken for 24 h at room temperature. Samples were
centrifuged before the supernatant was analysed by ICP-MS. Before
and after extraction, the pH-value was controlled using a pH-
Electrode (pH-Meter pH 539 equipped with Sentix Mic®-Elec-
trode, WTW; Germany). In case suspended particles were visible,
the extractant was filtered using 45 mm syringe filters from re-
generated celluloses (Minisart RC 15, Sartorius; Germany). All ex-
tractions were performed as triplicates.
 M. Mittermüller et al. / Chemosphere 147 (2016) 155e162 157

2.5. Extraction kinetics
Extraction kinetic experiments were performed analogously to
the single batch extractions. The only difference was the extraction
durations, which were 2, 4, 8, 16, 24, 48, and 96 h.
2.6. Sequential BCR-extraction procedure
The following m/z values were used for analysis: 89 (Y), 139 (La),
140 (Ce), 141 (Pr), 143 (Nd), 147 (Sm), 151 (Eu corrected for BaOþ),
157 (Gd corrected for CeOþ), 159 (Tb), 163 (Dy), 165 (Ho), 166 (Er),
169 (Tm), 172 (Yb), 175 (Lu).
Dwell time was 100 ms for every m/z-ratio analysed. The limits
of quantification calculated from the calibration lines were below
0.02 mg L1 for each element.

The BCR procedure was used as described (Rauret et al., 1999) 3. Results and discussion
and is briefly summarised in the following.
Step 1. Add 40 mL of 0.11 mol L1 acetic acid to 1 g sample in a 3.1. REE concentrations in the materials employing microwave
50 mL centrifuge tube. Extract for 16 h at room temperature using assisted aqua-regia digestion
the horizontal shaker. Separate the extract from the sample mate-
rial by centrifugation. Decant the supernatant fresh centrifuge The sample materials under investigation were high in light REE
tubes and use for analysis. (La, Ce, Pr, Nd, Sm) and yttrium while being comparably low in
Step 2. Add 40 mL of 0.5 mol L1 hydroxylamine hydrochloride heavy ones (Table 1). For the certified reference material, SRM 2710,
in 0.05 mol L1 nitric acid to the residue from step 1 and re-suspend only noncertified values were listed for the REE. Therefore, our own
the sample by manual shaking. Extract for 16 h at room tempera- results, which were in good accordance with the given values, were
ture using the horizontal shaker and separate the extract. used for balance calculations. In all materials, cerium was the most
Step 3. Carefully add 10 mL of hydrogen peroxide in small ali- abundant element, having a share of 37e40%, whereas the most
quots to the residue. Digest for 1 h at room temperature before abundant heavy REE, yttrium, had 9e12%. All materials showed the
digesting at 85  C in a water bath for another hour. Reduce the natural occurring negative europium anomaly typical for felsic
volume by heating the uncovered tube before adding 10 mL of rocks due to processes during the magmatic formation of the rocks
hydrogen peroxide again. Digest again at 85  C for 1 h and after- (Weill and Drake, 1973).
wards reduce the volume to few millilitres. Allow the samples to These two samples with a wide range of REE concentrations
cool down to room temperature before making up to 50 mL using were used for the testing and optimization of the sequential
1 mol L1 ammonium acetate adjusted to pH ¼ 2 by nitric acid. leaching procedure. The aqua regia dissolution was used as indi-
Shake for 16 h and separate the extract as described above. cator for the maximum of REE being aware of possibly not analysing
The usual 4th step of an aqua regia digestion is not used in this the total REE concentration with this procedure. The so called
study. pseudo-total content is widely used in environmental science,
covering the relevant part for the evaluation of environmental
2.7. REE sequential batch extraction procedure behaviour. Therefore, it is used in this case to balance the extraction
yields of the tested fractions.
Based on the results of the single extraction procedures, a novel
sequential scheme for REE was developed, consisting of the 3.2. Single step extractions
following steps:
Step 1. Add to 250 mg sample, in a 50 mL centrifuge tube, 50 mL To evaluate the extractability of the REE from the soil and tail-
of 0.05 mol L1 calcium nitrate and extract for 6 h. Separate the ings material, single step extractions in a group of extractant
extract from the sample material by centrifugation. Decant the strength (easily soluble and exchangeable REE, bound to carbonates
supernatant into fresh centrifuge tubes and use for analysis. and mobilizable by complexation, and stronger bound REE) were
Step 2. Add 50 mL of 0.1 mol L1 citric acid to the residue from carried out.
step 1 and re-suspend the sample by manual shaking. Extract by
mechanical shaking for 24 h and retain the extract as in the step
3.2.1. Step 1 e Easily soluble and exchangeable fraction
before.
In the group of weak extractants deionized water, 0.05 mol L1
Step 3. Add 50 mL of 0.5 mol L1 hydroxylamine hydrochloride,
calcium nitrate, and 1 mol L1 of ammonium acetate were chosen.
adjusted to pH 2 using HNO3, to the residue from the step before
and re-suspend the sample by manual shaking. Extract by me-
chanical shaking for 24 h and retain the extract as before. This step Table 1
is similar to step 2 of BCR procedure. Average amounts of REE in the materials (±standard deviation) used for the leaching
tests after aqua regia digestion [mg kg1].
Step 4. Add 50 mL of 6.5% nitric acid (1.4 mol L1) to the residue
and re-suspend the sample by manual shaking. Extract by me- Soil (SRM 2710) Tailings material
chanical shaking for 24 h and retain the extract as before. Y 16.8 ± 0.2 1250 ± 39
All extractions were performed as triplicates. La 26.3 ± 0.3 1890 ± 40
Ce 51.5 ± 0.4 5200 ± 114
2.8. REE analysis using ICP-MS Pr 5.98 ± 0.03 704 ± 11
Nd 22.0 ± 0.2 2650 ± 44
Sm 4.17 ± 0.03 538 ± 11
Quadrupole based inductively coupled plasma mass spectrom- Eu 0.81 ± 0.01 11.2 ± 0.1
etry (Agilent 7700, Agilent Technologies Inc.; USA) was used to Gd 3.98 ± 0.02 369 ± 8
determine the concentrations of REE in all solutions. For calibration Tb 0.56 ± 0.01 42.8 ± 1.0
± ±
ICP-MS reference standard “Multi-element Solution 1” (Certiprep®, Dy 3.06 0.03 205 6
Ho 0.63 ± 0.01 39.7 ± 1.0
SPEX, 10 mg L1 of each REE) was diluted with 1% (v/v) nitric acid to Er 1.86 ± 0.03 125 ± 3.7
calibrate the REE's from 0.05 to 10 mg L1. Before measurement, the Tm 0.27 ± 0.01 17.1 ± 0.7
samples were diluted at least 1:10 with 1% (v/v) nitric acid to Yb 1.78 ± 0.02 107 ± 3.8
reduce the high matrix concentrations. A calibration standard was Lu 0.27 ± 0.07 12.3 ± 0.3
Sum 140 ± 1 13,170 ± 384
measured after every six samples to control the instrumental drift.
158 M. Mittermüller et al. / Chemosphere 147 (2016) 155e162

The results from application of these solutions to the soil and the
tailings material are shown in Fig. 1.
Using deionized water, only the very easily soluble fraction was
mobilized. Due to the absence of any salts in the extraction solution
and the neutral starting pH-value, ion exchange processes and
disintegration of the solid materials were strongly hampered.
Extraction yields were therefore very low; being less than 0.05% for
the tailings material and for the soil only the concentration of
cerium was above the limit of quantification.
The ion exchange processes are activated by the isomorphic ion
exchange with Ca2þ using the calcium nitrate solution. The calcium
ion has a comparable ion radius to the light REE of 1.14 Å, which is
favoured compared to the larger ion radius of NHþ 4 with 1.43 Å.
Another reason for this behavior could be the elevated concentra-
tion of the calcium ion in the extraction solution. The surplus of
calcium ions in the solution, compared to the amount of REE in the
sample materials, shifts the equilibrium between Ca2þ and REE3þ
for the positions in e.g. apatite in favour of the calcium ions. Calcium
replaces the REE on their positions and removes the REE ions from
the surfaces of ion-exchangeable minerals, including clays. Fig. 2. Step 1 e Extraction kinetics for cerium from SRM 2710 and tailings material
Extraction yields between 2 and 3.5% for the soil and up to 0.2% for using 0.05 mol L1 calcium nitrate, error bars indicate the standard deviation of the
triplicate.
the tailing materials are mobilized in consequence. Higher extrac-
tion yields were achieved by ammonium acetate, with up to 7% for
the soil and 1.3% for the tailings material. This extraction solution mobilize cations in this fraction and highest extraction yields were
shows mobilization by exchange with the ammonium ion, despite achieved, it was not chosen for the extraction sequence. Addressing
the larger ion radius of 1.43 Å, and the complexation by the acetate the easily mobilizable fraction in this step, the effect of complexa-
anion to form REE-acetates. Due to the effect of complexation, the tion seems to dominate the leaching behavior when using ammo-
effective concentration of bare ions in the extraction solution is nium acetate, it would be better suited for step 2 of the newly
lowered, resulting in dissolution of increased amounts of REE from developed sequential extraction procedure. Therefore, 0.05 mol L1
the solid materials. Hence, although the ammonium acetate solu- calcium nitrate was selected having represented better the easily
tion is preferred (Gleyzes et al., 2002; Hass and Fine, 2010) to mobilizable and ion exchangeable fraction.

Fig. 1. Step 1 e Extraction yields of REE (relative to the content dissolved by aqua regia digestion) from SRM 2710 and tailings material using weak extraction solutions.
 M. Mittermüller et al. / Chemosphere 147 (2016) 155e162
Data for dissolution kinetics for the selected solutions are shown
in Fig. 2 for both materials for cerium as representative example.
Due to the very low concentrations in the extraction solutions,
small inhomogeneity's in the samples lead to comparatively large
error bars independent of the sample material and the extraction
time. Nevertheless, 6 h extraction time was sufficient to get a
representative extraction result for both materials.
3.2.2. Step 2 e Carbonate bound and mobilized by complexation
fraction
The extraction solutions for this step were chosen to simulate
the mobilization of REE by exudation of natural low molecular
organic acids into the rhizosphere of plant roots, while EDTA acted
as a reference. Acetic acid, malic acid and citric acid are the most
important acids for promoting mobilization and plant uptake of
mobilized ions (Jones, 1998). All acids were used without pH
adjustment at their own pH-value, leading to pH-values around 2.2
for the organic acids and of 4.7 for EDTA. Additionally, the acids are
able to dissolve carbonates and release the REE bound therein.
The extraction yields of the solutions tested in this step are
clearly higher than by the solutions of step 1 (Fig. 3). For both
sample materials the extraction yields of the organic acids gener-
ally increased with increasing complexation capacity in the order:
acetic acid < malic acid < citric acid.
For the soil, highest extraction yields were obtained by EDTA.
Soils retain ions by complexation on organic substances and
especially on humic substances. This could better be counteracted
by stronger complexation than by lowering the pH-value (Fig. 3).
This is the reason for the highest extraction yields by using EDTA. In
Fig. 3. Extraction yields (relative to the content dissolved by aqua regia) for soil (SRM 2710) and the tailings material using extraction solutions to mobilize by complexation and REE
bound to carbonates (step 2).
159
the case of the tailings material, the highest yields are observed
with citric acid. Here, the pH-value was the determining factor for
mobilization (cf. step 4).
With the focus on the bioavailability and bioaccessibility, even
though for the soil, EDTA was the most effective ligand for the
mobilization, citric acid was chosen as preferred extraction solu-
tion. Citric acid is naturally produced by plants and occurs in the
environment as root exsudate as a ligand for metal mobilization
and uptake into plants (Ryan et al., 2001). It should give a more
natural view, than anthropogenic EDTA, for the estimation of
bioavailability.
Kinetic experiments (see Fig. 5) showed, for the citric acid after
24 h, a stable average extraction yield. The extraction time for the
extraction with citric acid was therefore set to 24 h.
3.2.3. Step 3eReducible fraction
A reducible fraction typically mobilizes the elements associated
to iron or manganese oxides that can be released under reductive
conditions (Zimmerman and Weindorf, 2010). This was investi-
gated as 3rd fractionation step using oxalic acid (0.1 mol L1,
pH ¼ 3) and hydroxylamine hydrochloride (0.05 mol L1, pH ¼ 2).
Both reducing agents showed large differences in the extraction
yields (Fig. 4). Oxalic acid at pH 3 mobilized in all cases at least 5%
less REE than hydroxylamine hydrochloride at pH 2. The reason for
this behavior should be in the low solubility of REE oxalates (Chung
et al., 1998). Even if large quantities were mobilized under the
reductive conditions of oxalic acid, the REE-oxalate-complexes
formed in solution would precipitate when the solubility product
is exceeded. This will be especially the case for materials with high
160 M. Mittermüller et al. / Chemosphere 147 (2016) 155e162

Fig. 4. Extraction yields (relative to the content dissolved by aqua regia digestion) for the soil, SRM 2710, and the tailings material using either reductive conditions (oxalic acid and
hydroxylamine hydrochloride; step 3) or strong acidic conditions (different concentrations of HNO3, step 4).

Fig. 5. Extraction kinetics for cerium from SRM 2710 (left) and the tailings material (right) using either 1.4 mol L1 nitric acid, 0.1 mol L1 citric acid, or 0.5 mol L1 hydroxylamine
hydrochloride at pH 2. Error bars are the standard deviation of the triplicate.

REE amounts like the tailings material. The lower amount of REE in
the soil material lead to higher extraction yields before solubility of
REE oxalates became problematic. Thus, oxalic acid is a non-
suitable reagent for the REE extraction and hydroxylamine hydro-
chloride was chosen.
Regarding the extraction kinetics in Fig. 5, the soil reached stable
dissolution equilibrium after 24 h; the extraction yield for the
tailings material increased over 96 h and seemed not to reach
equilibrium in this time frame.
3.2.4. Step 4 e Acid soluble fraction
Another binding form of REE are barely soluble phosphates, like
apatite which can only be dissolved by strong acids, while REE-
bearing minerals like monazite can hardly be leached even by
strong acids. Therefore, in this case leaching employing different
concentrations of nitric acid was selected.
Extraction yields increased with the concentration of the acid
(Fig. 4). For soil extraction, on the one hand, yields mobilized with
nitric acid were on average 20e25% higher than with organic acids;
for tailings material, on the other hand, the acid soluble fraction led
to the highest extraction yields (>15%) compared to all preceding
fractions. Kinetic experiments Fig. 5 illustrated again the slow
dissolution for this material, while for the soil the maximal amount
was already leached within a few hours. Oelkers and Poitrasson
 M. Mittermüller et al. / Chemosphere 147 (2016) 155e162
(2002) determined the dissolution rate of monazite at pH 2 and
70  C to be as small as 4.3$1017 mol cm2 sec1, which is several
magnitudes below the dissolution rates of common REE bearing
minerals such as fluoroapatite [6.9$107 mol cm2 sec1 (Guidry
and Mackenzie, 2003). Dissolution of REE-phosphates were inten-
sively studied by Cetiner et al. (2005), showing that reaching
dissolution equilibrium requires 15e20 days. During this time REE-
phosphates continuously dissolve and REE concentrations increase
in the solution. Additionally, the dissolution kinetic is dependent on
the nature of the phosphate. Smaller, already hydrated and poorly
crystallised phosphates such as freshly precipitated phosphates
dissolve faster than well-crystallised, non-hydrated phosphates
(Cetiner et al., 2005). Again, extraction times of more than 24 h are
not suitable for an extraction sequence and therefore this fraction
will be in the sequence extracted with 1.4 mol L1 nitric acid for
24 h. If materials with high REE-phosphate content are investi-
gated, this should be considered and longer extraction times are
advised. However, for a wide range of materials like soils without
high content in REE-bearing phosphates, 24 h are sufficient.
Since the extraction is non-exhaustive, determination of the
residual fraction using aqua regia digestion is recommended.
3.3. Sequential extractions
In the course of preparing the sequential extraction scheme, one
extraction solution proved superior to all others in each extraction
step. Table 2 summarizes the optimized scheme, considering also
the findings of the kinetics experiments.
To test the developed procedure, it was applied to the soil, SRM
2710, and compared with the often used BCR procedure. Selected
elements are shown in Fig. 6.
The easily soluble and exchangeable fraction (step 1) seems to be
of minor importance for the tested soil. Step 1 of the BCR procedure
(acetic acid) was not remarkably higher. For the yttrium from the
soil material, 1.8% leached by step 1 of the BCR method opposes 1%
leached by the calcium nitrate-solution of the new created
extraction scheme. Taking into account that the calcium nitrate
solution leaches without any complexation properties, the result
seems to be plausible. The mobilization by low molecular organic
acids is covered by the second step of the suggested procedure to
distinguish between both mobilization processes.
Remarkable amounts and much more than step 1 of the BCR
scheme were mobilized within the 2nd step of the new method. Up
to one-third of the aqua regia dissoluble content of yttrium is found
in this fraction, and for the other REE a bit less than one-third.
Both sequences use solutions in comparably strong concentra-
tions (0.1 mol L1 citric acid and 0.11 mol L1 acetic acid), but the
pH-values differed significantly. The acetic acid solution had a pH
value of 2.9; while the citric acid solution was at pH 2.1. Next to the
difference in pH-value complex formation constants were higher
for citric acid (NIST, 2004) and as a consequence citric acid mobi-
lized a much higher amount from all materials than acetic acid.
Taking this into account, the 0.11 M acetic acid (step 1) used in the
BCR method underestimated the available amount.
The 3rd step of the new scheme is identical to step 2 of the BCR
method. The results of step 3 in the new method were clearly lower
than the amount yield with step 2 of the BCR scheme. However, the
Table 2
Overview of the developed extraction sequence for REE.
Step
1 Easily soluble and ion exchangeable fraction
2 Fraction mobilized by complexation and carbonate bound
3 Reducible fraction
4 Acid soluble fraction
161
Fig. 6. Extraction yields (relative to the content dissolved by aqua regia digestion) of
the original BCR sequential extraction procedure (3 steps) and the newly developed
sequence for selected elements from the soil (SRM 2710).
sum of the first three steps of the new method was in good
accordance with the sum of step 1 and 2 of the BCR method.
Fraction 3 of the BCR method addresses metals which are mobilized
under strongly oxidizing conditions. The soil sample has noncer-
tified total carbon mass fraction of 3% (SRM 2710), while sulphur is
0.24%. For this material, the oxidizable fraction mobilized REE
bound to organic matter by degrading it. The oxidizable fraction
was in the soil sample <18% and in the tailings material <1.5% (data
not shown). These amounts will be leached also in step 4 of the new
procedure.
The BCR-Method, like all other sequential extraction methods,
does not consider soluble REE-phosphates separately. These are
included within the residual fraction after aqua regia digestion. In
this newly developed sequence, though, these soluble phosphates
are separately determined in the acid soluble fraction by application
of 1.4 M nitric acid, as they have high abundances especially in the
tailings material (cf. Fig. 4). However, the total yields of all extrac-
tions are by trend increased by this fraction in comparison to the
sum of the 3 BCR-steps for the soil material. Roughly 60% of the
aqua-regia soluble (pseudo-total) content of the soil could be
categorized by using differences in its mobilization behavior. This
was for both materials significantly more than for the BCR proce-
dure, when leaving out the final aqua regia digestion of the residue.
3.4. Application to a soil profile
A soil profile with different soil properties with depth was used
to demonstrate the capabilities of the new sequential extraction
scheme. In Fig. 7 the profile of the element cerium is shown as an
example to demonstrate the different extraction pattern in
dependence on the soil type (representative for all REE's, Ce con-
centrations between 1 and 5 mg kg1). As can be seen from this
figure, the proportion of step 1 (calcium nitrate-solution) was much
higher than in the reference material. This demonstrates the
importance of this first step for such kinds of samples. The surface
soil horizons Oh1 and Oh2 could be characterized by decomposing
organic matter with remarkable concentrations of easily mobiliz-
able cerium (up to 15% of the total amount). The horizon Bs was
Extractant Concentration Duration
Calcium nitrate 0.05 mol L1 6h
Citric acid 0.1 mol L1 24 h
Hydroxylamine hydrochloride, pH ¼ 2 0.5 mol L1 24 h
Nitric acid 1.4 mol L1 24 h
162 M. Mittermüller et al. / Chemosphere 147 (2016) 155e162
Fig. 7. Vertical distribution of cerium along the soil horizons relative to the amount
analysed after aqua regia digestion of cerium in each horizon.
characterized by adsorbed sesquioxides that where moved from
higher horizons. The REE were again easily mobilized during the
first extraction step in remarkably high proportions in this sample.
The contents of iron and manganese hydroxides were very low
in these samples, due to the low soil pH in this region. Conse-
quently, the yields of step 3 are rather low, especially in the deeper
samples. And again, step 4 seems to give important information
which is different from the aqua-regia digestion (as reference set to
100%). The difference between the sum of the 4 steps and the 100%
of the aqua regia digestion is an indicator for strongly bound
cerium.
Generally, the leachable proportion seems to depend on the soil
type with high mobility in the surface layers rich in organic matter
(around 30% in samples Of, Oh1, and Oh2) and much lower mobility
in the other samples.
4. Conclusion
The extraction procedure developed in this study allows clas-
sifying REE in solid materials (soils and tailings materials) into well
separated fractions. This is very important regarding the evaluation
of processes which potentially lead to bioavailable REE. The
selected extraction solutions were able to distinguish between
easily mobilizable fraction by ion-exchange-processes, mobiliza-
tion by complexation, mobilization under reducing conditions and
an acid soluble fraction. The first three steps can be summarized to
quantify a bioavailable fraction which is split off in the three major
processes regarding plant-availability (easily soluble and ion ex-
change, mobilized by complexation or under reducing conditions).
Compared to the widely used BCR method, the new fraction-
ation scheme provides more detailed insight into how REE are
bound in a particulate material, either soil or tailings material. The
importance of determining REE-phosphates in tailings materials as
well as in soils, which is not included in the BCR method, is also an
advantage of the newly developed method. Application of the
developed sequence to a soil profile demonstrates the usefulness of
the defined fractions.
References
Cetiner, Z.S., Wood, S.A., Gammons, C.H., 2005. The aqueous geochemistry of the
rare earth elements. Part XIV. The solubility of rare earth element phosphates
from 23 to 150 degrees C. Chem. Geol. 217, 147e169.
Chung, D.-Y., Kim, E.-H., Lee, E.-H., Yoo, J.-H., 1998. Solubility of rare earth oxalate in
oxalic and nitric acid media. J. Ind. Eng. Chem. 4, 277e284.
Gleyzes, C., Tellier, S., Astruc, M., 2002. Fractionation studies of trace elements in
contaminated soils and sediments: a review of sequential extraction pro-
cedures. TrAC Trends Anal. Chem. 21, 451e467.
Guidry, M.W., Mackenzie, F.T., 2003. Experimental study of igneous and sedimen-
tary apatite dissolution: control of pH, distance from equilibrium, and tem-
perature on dissolution rates. Geochim. Cosmochim. Acta 67, 2949e2963.
Hass, A., Fine, P., 2010. Sequential selective extraction procedures for the study of
heavy metals in soils, sediments, and waste materialsda critical review. Crit.
Rev. Environ. Sci. Technol. 40, 365e399.
Helmers, E., 1996. Elements accompanying platinum emitted from automobile
catalyst's. Chemosphere 33, 405e419.
Hirano, S., Suzuki, K.T., 1996. Exposure, metabolism, and toxicity of rare earths and
related compounds. Environ. Health Perspect. 104, 85e95.
Jones, D., 1998. Organic acids in the rhizosphere e a critical review. Plant Soil 205,
25e44.
Kulaksız, S., Bau, M., 2011. Anthropogenic gadolinium as a microcontaminant in tap
water used as drinking water in urban areas and megacities. Appl. Geochem. 26,
1877e1885.
Kümmerer, K., Helmers, E., 2000. Hospital effluents as a source of gadolinium in the
aquatic environment. Environ. Sci. Technol. 34, 573e577.
Li, F., Shan, X., Zhang, T., Zhang, S., 1998. Evaluation of plant availability of rare earth
elements in soils by chemical fractionation and multiple regression analysis.
Environ. Pollut. 102, 269e277.
Lorz, C., Eissner, C., Lethmate, J., Schneider, B., 2010. Spatial and temporal small-
scale variability of nitrogen mobilization in a forest ecosystem with high N
deposition in NW-Germany. Environ. Pollut. 158, 424e439.
Marschner, H., 1995. Mineral Nutrition of Higher Plants. Academic Press.
Mihajlovic, J., Giani, L., Sta €rk, H.-J., Rinklebe, J., 2014. Concentrations and
geochemical fractions of rare earth elements in two different marsh soil profiles
at the North Sea. Ger. J. Soils Sediments 14, 1417e1433.
Miller, T., 2006. Einfluss Seltener Erden in der Schweine- und Ka €lbermast. Ludwig-
Maximilians-Universit€ at München.
Natrajan, L.S., Langford Paden, M.H., 2013. F-block Elements Recovery. Royal Society
of Chemistry, RSC Green Chemistry Series.
NIST, 2004. Standard Reference Database 46: NIST Critically Selected Stability
Constants of Metal Complexes, 8.0 ed. Version 8.0.
Nordstrom, D.K., 2011. Hydrogeochemical processes governing the origin, transport
and fate of major and trace elements from mine wastes and mineralized rock to
surface waters. Appl. Geochem. 26, 1777e1791.
Oelkers, E.H., Poitrasson, F., 2002. An experimental study of the dissolution stoi-
chiometry and rates of a natural monazite as a function of temperature from 50
to 230  C and pH from 1.5 to 10. Chem. Geol. 191, 73e87.
Rao, C.R.M., Sahuquillo, A., Lopez-Sanchez, J.F., 2010. Comparison of single and
sequential extraction procedures for the study of rare earth elements remobi-
lisation in different types of soils. Anal. Chim. Acta 662, 128e136.
Rauret, G., Lopez-Sanchez, J.F., Sahuquillo, A., Rubio, R., Davidson, C., Ure, A.,
Quevauviller, P., 1999. Improvement of the BCR three step sequential extraction
procedure prior to the certification of new sediment and soil reference mate-
rials. J. Environ. Monit. 1, 57e61.
Ryan, P., Delhaize, E., Jones, D., 2001. Function and mechanism of organic anion
exudation from plant roots. Annu. Rev. Plant Physiol. Plant Mol. Biol. 52,
527e560.
Saatz, J., Vetterlein, D., Mattusch, J., Otto, M., Daus, B., 2015. The influence of gad-
olinium and yttrium on biomass production and nutrient balance of maize
plants. Environ. Pollut. 204, 32e38.
Sanematsu, K., Moriyama, T., Sotouky, L., Watanabe, Y., 2011. Mobility of rare earth
elements in Basalt-Derived Laterite at the Bolaven Plateau, Southern Laos.
Resour. Geol. 61, 140e158.


Smuc, N.R., Dolenec, T., Serafimovski, T., Dolenec, M., Vrhovnik, P., 2012.
Geochemical characteristics of rare earth elements (REEs) in the paddy soil and
rice (Oryza sativa L.) system of Ko
cani Field, Republic of Macedonia. Geoderma
183e184, 1e11.
Tessier, A., Campbell, P.G.C., Bisson, M., 1979. Sequential extraction procedure for
the speciation of particulate trace-metals. Anal. Chem. 51, 844e851.
Tyler, G., 2004. Rare earth elements in soil and plant systems e a review. Plant Soil
267, 191e206.
Wang, J., Zhang, C.B., Jin, Z.X., 2009. The distribution and phytoavailability of heavy
metal fractions in rhizosphere soils of Paulowniu fortunei (seem) Hems near a
Pb/Zn smelter in Guangdong, PR China. Geoderma 148, 299e306.
Wang, Z., Shan, X.-q., Zhang, S., 2003. Effect of exogenous rare earth elements on
fraction of heavy metals in soils and bioaccumulation by plants. Commun. Soil
Sci. Plant Anal. 34, 1573e1588.
Weill, D.F., Drake, M.J., 1973. Europium anomaly in Plagioclase Feldspar: experi-
mental results and semiquantitative model. Science 180, 1059e1060.
Xinde, C., Xiaorong, W., Guiwen, Z., 2000. Assessment of the bioavailability of rare
earth elements in soils by chemical fractionation and multiple regression
analysis. Chemosphere 40, 23e28.
Xu, X., Zhu, W., Wang, Z., Witkamp, G.-J., 2002. Distributions of rare earths and
heavy metals in field-grown maize after application of rare earth-containing
fertilizer. Sci. Total Environ. 293, 97e105.
Xu, Y., Song, J., Duan, L., Li, X., Yuan, H., Li, N., Zhang, P., Zhang, Y., Xu, S., Zhang, M.,
Wu, X., Yin, X., 2012. Fraction characteristics of rare earth elements in the
surface sediment of Bohai Bay, North China. Environ. Monit. Assess. 184,
7275e7292.
Zhang, C., Wang, L., Zhang, S., Li, X., 1998. Geochemistry of rare earth elements in
the mainstream of the Yangtze River, China. Appl. Geochem. 13, 451e462.
Zimmerman, A.J., Weindorf, D.C., 2010. Heavy metal and trace metal analysis in soil
by sequential extraction: a review of procedures. Int. J. Anal. Chem. 2010.