Chemical Geology 278 (2010) 1–14

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Chemical Geology
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c h e m g e o

Research paper

Rare earth element release from phosphate minerals in the presence of organic acids
Keith W. Goyne a,b,⁎, Susan L. Brantley c, Jon Chorover a
a
Department of Soil, Water and Environmental Science, University of Arizona, 429 Shantz Bldg., Tucson, AZ 85721, United States
b
Department of Soil, Environmental and Atmospheric Sciences, University of Missouri, 302 ABNR Bldg., Columbia, MO 65211, United States
c
Department of Geosciences, The Pennsylvania State University, 2217 Earth and Engineering Building, University Park, PA 16802, United States

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

Article history: The primary objective of this research was to investigate the effects of aliphatic and aromatic low molecular
Received 24 November 2009 weight organic acids (LMWOAs) on rare earth element and yttrium (REY) release from the phosphate
Received in revised form 2 March 2010 minerals apatite and monazite. Since prior studies have shown that redox status can affect REY partitioning
Accepted 9 March 2010
during incongruent dissolution, a secondary objective was to assess the influence of dissolved O2 con-
Editor: J.D. Blum centration. Increasing LMWOA concentrations from 0 to 10 mM resulted in enhanced REY release. In general,
REY release increased in the order: no ligand ≈ salicylate b phthalate ≈ oxalate b citrate. REY–ligand stability
Keywords: constants were only useful for predicting REY release for oxalate reacted with apatite and phthalate reacted
Apatite with monazite. The role of dissolved oxygen in dissolution of the phosphate minerals was mixed and
Dissolution inconsistent. Mineral type was observed to significantly affect REY pattern development. REY release
Monazite patterns for apatite range from nearly flat to those exhibiting the lanthanide contraction effect (radius-
Organic acids dependent fractionation); whereas, monazite REY release patterns are best described as exhibiting an M-
Rare earth elements
type lanthanide tetrad effect (radius-independent fractionation). Weathering of apatite in the presence of
Yttrium
aliphatic LMWOAs resulted in development of the lanthanide contraction effect fractionation pattern, and
the aliphatic LMWOAs further developed MREE and radius-independent fractionation during monazite
dissolution. Geochemical and mineral-specific REY signatures may, therefore, have utility for distinguishing
the impacts of biota on soil weathering processes on early Earth. The development of such signatures may be
mitigated, in part, by accessory mineral composition, the types and concentration of LMWOAs present, and
precipitation of secondary minerals.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction reduce the relative solution saturation with respect to minerals

Low-molecular weight organic acids (LMWOAs) in soil are mainly
comprised of aliphatic compounds with 1–3 carboxylic acid functional
groups and methoxy, hydroxy, carboxylic acid substituted benzoic and
cinnamic (aromatic) acids (Strobel, 2001). In soil solutions, these
compounds normally exist in the µM to mM concentration range, with
half-lives of ca. 1 to 6 h (Fox and Comerford, 1990; Stevenson, 1991;
Baziramakenga et al., 1995; Krzyszowska et al., 1996; Jones, 1998;
Strobel, 2001; van Hees et al., 2005). Because they form stable complexes
with lithogenic metals, LMWOAs play a significant role in pedogenic
mineral transformations and the amelioration of Al toxicity to plants.
Organic acids promote mineral dissolution by (1) donating H+ to proton-
promoted dissolution processes (Furrer and Stumm, 1986; Tan, 1986),
(2) forming inner-sphere surface complexes that dislodge structural
metals from the mineral surface (Furrer and Stumm, 1986; Stumm,
1997), and (3) the formation of aqueous metal–ligand complexes that
⁎ Corresponding author. Department of Soil, Environmental and Atmospheric
Sciences, University of Missouri, 302 ABNR Bldg., Columbia, MO 65211, United States.
Tel.: + 1 573 882 0090; fax: + 1 573 884 5070.
E-mail address: goynek@missouri.edu (K.W. Goyne).
undergoing dissolution (Drever and Stillings, 1997; Ganor et al., 2009).
The origin of LMWOAs in soil is primarily attributed to microbial
processing of biomolecules and humic substances (Tan, 1986; Steven-
son, 1994; Jones, 1998; Jones et al., 2003; Neaman et al., 2005a), as well
as plant root exudation and leaching of surficial plant detritus (Fox,
1995; Jones, 1998; Jones et al., 2003). The concentration and aromaticity
of LMWOAs in porewaters have likely increased over geologic time
due to the progressive colonization of weathering environments by
prokaryotes and later by vascular plants (Neaman et al., 2005a). Given
the variation in magnitude of metal–ligand stability constants charac-
teristic of LMWOAs, we have suggested that these compounds may
leave biosignatures in geomedia (e.g., paleosols) that indicate the
presence/absence of biogenic ligands and/or molecular oxygen during
weathering (Neaman et al., 2005a,b, 2006; Goyne et al., 2006).
The rare earth elements or lanthanides include lanthanum (La),
cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm),
samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb),
dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium
(Yb), and lutetium (Lu). Yttrium (Y) is often included with these ele-
ments because it has a valence and ionic radius similar to Ho (Tyler,
2004a). Bau and Dulski (2003) described three types of rare earth

0009-2541/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemgeo.2010.03.011
2 K.W. Goyne et al. / Chemical Geology 278 (2010) 1–14
element and yttrium (REY) fractionation patterns observed in rock–
water systems, including (1) the lanthanide contraction effect, (2)
redox-induced REY anomalies, and (3) electron-structure-induced REY
anomalies. Smooth, radius-dependent fractionation, which reflects the
fact that lanthanides possess progressively smaller ionic radii with
increasing atomic mass (i.e., the lanthanide contraction effect), could
potentially result from LMWOA-promoted dissolution, since REY
stability constants are observed in some well-known cases to increase
as a function of atomic mass. However, as shown in Fig. 1, metal–ligand
stability constant trends are dependent on ligand type; smooth
fractionation might be expected for citrate and oxalate (aliphatic
ligands) but not for phthalate and salicylate (aromatic ligands). Redox-
induced fractionation may give rise to Ce and/or Eu anomalies because
of Ce(III to IV) oxidation and/or Eu(III to II) reduction. The third REY
fractionation type, resulting from differences in REY electronic struc-
tures (radius-independent fractionation), may manifest as Y, La, and Gd
anomalies. Hence, fractionation patterns may enhance our understand-
ing of geochemical systems because they result not only from inherent
properties of REY themselves, but also from how these properties are
superimposed with geochemical conditions.
REY have potential utility as tracers in rock/water interaction
processes, groundwater flow and mixing, soil genesis, and as proxies
for evaluating paleoceanographic and paleoclimatic change (Braun
et al., 1998; Land et al., 1999; Ingri et al., 2000; Dia, et al., 2000; Aubert
et al., 2001; Aide and Pavich, 2002; Aide and Smith-Aide, 2003;
Compton et al., 2003; Gruau et al., 2004; Tyler, 2004b; Haley et al.,
2005; Andersson et al., 2006). A more thorough understanding of
organic compound—REE interactions is particularly important for
developing and evaluating these proxies based on previous studies
noting strong positive correlations between REY and dissolved or-
ganic carbon concentrations (Dupré et al., 1996; Land et al., 1999; Dia
et al., 2000; Tyler, 2004a). Laboratory studies further elucidating the
effect of redox status on REY fractionation are also warranted.
In this study, we explored whether REY dissolution from phos-
phate minerals is altered in the presence of LMWOAs. We postulated
that fractionation of REY in the presence of these ligands would follow
trends in metal–ligand stability (Fig. 1). Apatite and monazite were
chosen because they are a principal source of REY in natural systems,
and they are found as accessory minerals in a variety of rock types
(Gromet and Silver, 1983; Grauch, 1989; McLennan, 1989). The work
was driven by an overarching interest in establishing the utility of
trace element signatures as possible “organomarkers”, i.e., as indi-
Fig. 1. Stability constants (log β1) for REY complexation with organic acids. Data were
obtained from: Byrne and Li (1995), I = 0.10 M and T = 20–25 °C; Schijf and Byrne (2001),
I = 0.05 M and T = 25 °C; Wood (1993), I = 0 M and T = 25 °C. (β1 = [ML] [M3+]−1 [L]−1,
where M is the metal, L is the ligand, and ML is the metal–ligand complex).
cators of weathering in the presence of biogenic organic molecules.
In addition, since REY contain redox active species, we sought to
determine whether dissolution patterns might be diagnostic of weath-
ering in the presence versus absence of molecular oxygen. In either
case, REY could then prove useful to establishing the geochemical
conditions (presence/absence of biota and/or oxygen) dominant in
weathering systems, as would be relevant to studies of paleosols.
2. Materials and methods
2.1. Specimen mineral preparation
Research grade apatite (Durango, Mexico) was purchased from
Ward's Natural Science (Rochester, N.Y.) and monazite (New Mexico,
U.S.) was obtained from Minerals Unlimited (Ridgecrest, CA). Min-
erals were fractured using a zirconia ceramic vial/ ball set and ball mill
(SPEX Certiprep, Metuchen, NJ), and sieved to obtain the 75–150 μm
(100–200 mesh) particle size fraction. Fine particles were removed
through repeated ultrasonication in Barnstead Nanopure water fol-
lowed by repeated ultrasonication in HPLC-grade acetone until super-
natant solutions were clear, and then samples were dried for 12 h
at 60 °C. Powder X-ray diffraction (XRD) analyses were conducted
on randomly-oriented, back-filled 15 mm × 5 mm circular samples
mounted in spinning holders to confirm mineral composition. All
patterns were collected using a Philips X'pert MPD diffractometer
equipped with spinning stage and X'Celerator multiple strip detector
using Ni-filtered CuKα radiation at 50 kV and 40 mA. A continuous
scan mode was used to collect 2θ data from 3 to 80° with a step size of
approximately 0.017°. The divergent slit size was 0.1250°.
Total elemental composition of the isolated particle size fraction
was determined using lithium metaborate/tetraborate fusion fol-
lowed by aqueous phase analyses by inductively coupled plasma
(ICP)–optical emission spectrometry (OES) and ICP–mass spectrom-
etry (MS) for major and trace elements, respectively (Activation
Laboratories Ltd., Tucson, AZ). Analyses were performed in quadru-
plicate. These data, normalized to 100% volatile free mass (Table 1),
were used to calculate chemical formulae of Ca5(PO4)2.82(F,Cl,OH)1.54
and (La0.12Ce0.32Pr0.04Nd0.16Sm0.05 Gd0.02Y0.08Th0.09)P0.81Si0.30O4
for apatite and monazite, respectively. Analyses also indicated that
Zr concentrations (9.1 and 136 mg kg−1 for apatite and monazite,
respectively) in fractured samples were generally lower than REY
concentrations. Thus, suggesting insignificant contamination of
samples from the Zirconia vial and ball set.
2.2. Organic acids
Mineral dissolution was investigated in the absence and presence
of aliphatic (citrate and oxalate) and aromatic (phthalate and salic-
ylate) organic acids. Neaman et al. (2005a, 2006) noted that these
organic acids significantly enhance basalt and granite dissolution
during batch reaction. Neaman et al. (2005a) observed that gallic
acid enhanced rock dissolution to a greater extent than the aromatic
compounds used in the present study, but gallate was found to be
unstable in the presence of Li+, which was used here as a background
electrolyte cation. Kekulé structures and acid dissociation constants
(I = 0 M and 298 K) of the organic acids studied are shown in Fig. 2.
2.3. Oxic and anoxic dissolution experiments
Dissolution experiments were conducted in batch reaction under
oxic and anoxic conditions using acid-washed, 50 mL Teflon centri-
fuge tubes. A mineral mass of 0.3 g was added to each tube and
measured to 0.001 g. Reaction vessels with and without mineral (i.e.,
mineral-free controls) were autoclaved to eliminate microbial growth.
Organic acid stock solutions were prepared 24 h prior to each ex-
periment by dissolving individual organic acids (Fluka and Sigma,
 K.W. Goyne et al. / Chemical Geology 278 (2010) 1–14 3

Table 1
Mean elemental composition of apatite and monazitea.

Element Apatite Monazite Element Apatite Monazite Element Apatite Monazite

Mean (g kg−1) Mean (mg kg−1) Mean (g kg−1) Mean (mg kg−1) Mean (g kg−1)

Si 3.2 ± 0.3b 34 ± 3 La 4200 ± 110 66 ± 2 Ho 30.3 ± 0.6 0.7 ± 0.1

Al 0.30 ± 0.05 22.2 ± 0.4 Ce 5370 ± 40 174 ± 9 Er 95 ± 3 2.5 ± 0.3
Fe 0.5 ± 0.2 7.2 ± 0.6 Pr 470 ± 10 23 ± 1 Tm 12.3 ± 0.4 0.47 ± 0.07
Mn 0.101 ± 0.01 0.02 ± 0.01 Nd 1610 ± 30 89 ± 3 Yb 60 ± 1 3.6 ± 0.6
Mg 0.1 ± 0.1 b0.001 Sm 248 ± 6 30 ± 1 Lu 6.5 ± 0.4 0.50 ± 0.07
Ca 395.2 ± 0.9 b0.001 Eu 20.6 ± 0.5 0.05 ± 0.00 Th 370 ± 34 78 ± 2
Na 1.7 ± 0.3 1.6 ± 0.2 Gd 225 ± 4 15.3 ± 0.6
K 0.1 ± 0.1 2.0 ± 0.1 Tb 32.4 ± 0.5 1.69 ± 0.09
Ti 0.01 ± 0.02 0.04 ± 0.08 Dy 164 ± 2 5.4 ± 0.4
P 172 ± 3 98.5 ± 0.9 Y 1030 ± 5 28 ± 4
a
Structural formulas: apatite, (Ca5)(PO4)2.82(F,Cl,OH)1.54; monazite, (La0.12Ce0.32Pr0.04Nd0.16Sm0.05 Gd0.02Y0.08Th0.09)P0.81Si0.30O4. Apatite data obtained from Goyne et al. (2006).
b
Error represents 95% confidence interval.

≥ 99% purity) in amber glass jars containing 0.01 M LiCl (Sigma,
99.99 + % purity), and adding 0.01 M HCl (EM Science, OmniTrace
Ultrapure) or 0.1 M LiOH (Sigma, ≥ 99% purity) as needed to achieve
pH 5. An ionic strength of 0.01 M and pH 5 were chosen because they
are representative of natural soil solution conditions (Harter and
Naidu, 2001). Reactions were performed in the absence of pH buffers
to minimize elemental contamination and sorption artifacts. Amber
glass jars and LiCl solutions were autoclaved prior to use, and Al foil
was wrapped around amber jars containing organic acid solutions
to prevent photodegradation. Organic acid stock solutions were
filter-sterilized (Corning, sterilized 0.2 µm polyethersulfone filtra-
tion units) within a sterile laminar flow-hood immediately prior to
start of an experiment.
Dissolution experiments were initiated by adding to reaction
vessels appropriate quantities of organic acid stock solutions and/or
0.01 M LiCl to achieve initial organic acid concentrations of 0, 1, 5, and
10 mM at pH 5 and a solid to solution mass ratio of 1:100 (0.3 g per
30 mL). Solutions were added via pipette using sterilized pipette tips.
Mineral-free blanks were prepared concurrently, and all experiments
were conducted in triplicate. Reaction vessels were wrapped in Al
foil and placed in end-over-end shakers (8 rpm) at 23 ± 2 °C for 28 d.
At the end of the reaction period, samples were centrifuged at
26,000 rcf for 15 min and supernatant solutions were removed by
pipette. Mineral pellets were washed twice in ethanol and once in
water prior to freeze-drying. A Barnstead NANOpure ultrafiltration/
ultraviolet water unit served as the water source throughout the
experiments.
As noted previously, experiments were conducted in the presence
and absence of O2. Although all experiments followed the general
protocol outlined above, there were some differences between the
two types of experiments. In the case of oxic experiments, reaction
vessels were exposed to the ambient atmosphere (within a sterile
laminar flow-hood) three times per week to maintain equilibrium
with atmospheric O2 (g). For anoxic experiments, autoclaved reaction
vessels and 0.01 M LiCl solution (purged 30 min with filter sterilized
N2 (g)) were placed in a Coy (Grass Lake, MI) oxygen-free (b1 ppm)
anaerobic chamber one week prior to starting an experiment. Pre-
liminary trials indicated that one week was sufficient time for oxygen
to diffuse from vessels and solutions into the chamber's atmosphere
where it was removed by reaction with a palladium catalyst. Organic
acid stock solutions were prepared outside the anaerobic chamber
using deoxygenated 0.01 M LiCl, followed by a 30 min purge with
N2 (g). Stock solutions (loosely capped) were placed on a stir plate
within the anaerobic chamber and allowed to mix for 24 h prior
to filter-sterilization. All solution additions to reaction vessels were
conducted within the anaerobic chamber, and centrifuged samples
were opened only after reintroduction to the oxygen-free atmosphere.

2.4. Aqueous phase analyses

After centrifugation, supernatant solutions were partitioned into

Fig. 2. Kekulé structures and acid dissociation constants (pKa) of aliphatic and aromatic
organic acids used in dissolution experiments (Martell and Smith, 2003).
four separate vials for aqueous phase analyses. Aliquots taken for
subsequent elemental analysis were added to acid-washed polypro-
pylene tubes, acidified to bpH 2 with 6 M HCl (OmniTrace Ultrapure),
and stored at 4 °C. Aqueous phase element concentrations were
determined by a Perkin-Elmer Elan DRC II ICP-MS. Precautions were
taken to investigate multiple isotopes to ensure that polyatomic
interferences did not compromise accuracy of analyte measurements.
Non-acidified samples taken for subsequent organic acid and anion
analysis by ion chromatography (IC; Dionex DX-600) were stored in
4 mL glass amber vials, wrapped in aluminum foil, and analyzed
within 48 h. Measurement of pH (Orion, Ross semi-micro combina-
tion electrode), Eh (Orion, Redox/ORP combination electrode), and
dissolved oxygen (D.O.; VWR Model 4000) was conducted immedi-
ately following the end of the experiment using samples stored in
40 mL glass amber vials (Table 2). Anoxic samples used for ICP-MS
4 K.W. Goyne et al. / Chemical Geology 278 (2010) 1–14

Table 2
Mean pH, Eh, and dissolved oxygen (D.O.) measured at end of apatite and monazite dissolution experiments.

Apatitea

pH Eh (mV) D.O. (mg L−1)

Ligand concentration (mM)

Oxygen status Ligand 0 1 5 10 0 1 5 10 0 1 5 10

Oxic No Ligand 6.84 537 3.29

Citrate 5.46 5.25 5.18 552 538 528 3.84 3.76 3.74
Oxalate 6.72 6.67 6.61 471 459 455 3.76 3.88 4.03
Phthalate 5.31 5.07 4.98 589 577 567 3.83 3.67 3.73
Salicylate 6.80 6.69 6.42 578 554 544 4.11 4.19 4.12
Anoxic No Ligand 7.34 −355 0.00
Citrate 5.45 5.25 5.18 −269 −258 − 254 0.00 0.00 0.00
Oxalate 6.89 6.78 6.64 −359 −351 −343 0.00 0.00 0.00
Phthalate 5.28 5.06 5.01 −264 −250 −247 0.00 0.00 0.00
Salicylate 7.24 6.91 6.67 −359 −352 −341 0.00 0.00 0.00

Monazite

pH Eh (mV) D.O. (mg L−1)

Ligand concentration (mM)

Oxygen status Ligand 0 1 5 10 0 1 5 10 0 1 5 10

Oxic No ligand 5.91 518.9 3.33

Citrate 5.44 5.23 5.16 513.5 527.2 528.9 3.98 3.84 3.74
Oxalate 6.48 6.48 6.39 440.4 438.9 439.1 3.93 3.86 3.93
Phthalate 5.14 5.05 4.99 464.0 477.5 496.3 3.32 3.15 3.27
Salicylate 6.02 6.01 5.75 529.0 520.3 523.8 3.79 3.70 3.71
Anoxic No ligand 6.15 −309.2 0.00
Citrate 5.44 5.24 5.17 −260.2 −247.0 −239.2 0.00 0.00 0.00
Oxalate 6.63 6.58 6.45 −336.5 −332.7 −322.3 0.00 0.00 0.00
Phthalate 5.16 5.05 5.01 −255.6 −247.2 −246.0 0.00 0.00 0.00
Salicylate 5.94 6.00 5.76 −308.7 −317.4 −296.9 0.00 0.00 0.00
a
Apatite data obtained from Goyne et al. (2006).

analyses were acidified in the anaerobic chamber prior to removal and
storage at 4 °C, and all other anoxic samples were stored and analyzed
(except IC analysis) within the chamber.
2.5. Post-reaction solid phase analysis
After centrifugation and removal of supernatant solution, mineral
pellets were washed twice with ethanol and once with Barnstead
Nanopure water. Pellets were stored in a −20 °C freezer and freeze-
dried prior analysis. Diffuse reflectance infrared Fourier transform
(DRIFT) spectroscopy and an HCl selective extraction technique were
employed to investigate formation of secondary mineral phases.
Spectra of minerals were collected on neat samples (no KBr diluent)
by averaging 400 scans at 4 cm−1 resolution collected with a Nicolet
Magna 560 spectrometer. The HCl selective extraction was performed
by reacting 0.1 g of mineral in 2 mL of 0.5 M HCl for 2 h on an end-
over-end shaker (8 rpm). Following reaction, samples were centri-
fuged at 10,300 g and supernatant solutions removed by pipette prior
to ICP-MS analysis for element concentrations.
3. Results and discussion
3.1. REY release from apatite
3.1.1. Effects of ligands
The release of REY and major elements from apatite in the pres-
ence and absence of LMWOAs is impacted by both ligand type and
concentration (Figs. 3 and 4 and Table 3). Sum of the REY release
(Fig. 3) increases linearly from 0 to 10 mM concentrations of oxa-
late and phthalate. Citrate induces a dramatic increase in ∑REY in
solution between 0 and 1 mM concentrations, followed by a linear
increase as the concentration of citrate in solution increases from 1
to 10 mM. In contrast, the impact of salicylate on ∑REY release
is minimal and similar to ligand-free experiments in most instances.
Additionally, the ∑REY release is greater for apatite reacted with
aliphatic relative to aromatic LMWOAs. This trend is consistent with
REY–LMWOA stability constants (Fig. 1).
The general order of ligand-promoted REY release from apatite
is citrate N oxalate N phthalate N salicylate ≈ no ligand, and this order
follows that for P release from apatite observed in our previous work
(Goyne et al., 2006). The weaker acidity of aromatic acids is expected
to diminish surface cation complexation (and hence ligand-promoted
dissolution) at the experimental pH (Furrer and Stumm, 1986). Con-
sideration of pH is also warranted when evaluating the general ligand
order (Drever, 1994), because we intentionally did not use pH buffers
in our experiments as discussed in Materials and methods. Final
suspension pH values for ligand-free, oxalate, and salicylate (Table 2)
are comparable (pH 6.5–7.5) and fall within a range where apatite
dissolution is relatively invariant (Welch et al., 2002; Guidry and
Mackenzie, 2003; Harouiya et al., 2007). Solution pH at the end of
citrate and phthalate experiments was likewise similar (pH 5.0–5.5).
As shown in Fig. 4, the patterns of REY release from apatite in the
presence of organic ligands, irrespective of ligand type or concentration,
appear to be similar to those in ligand-free controls. Changes in REY
patterns were investigated by comparing light, middle and heavy rare
earth element release (LREE, MREE, and HREE, respectively), and dis-
solution behavior of REEs that sometimes exhibit anomalous fraction-
ation (La, Ce, Eu, Gd, and Y). Ratios of LREE/MREE, LREE/HREE, and
MREE/HREE in the presence and absence of organic ligands are shown
in Table 4. Because of low release rates in the ligand-free controls,
and the resulting relatively high coefficients of variation for REY ratios
for those samples, the data indicate few significant differences between
the release ratios in presence or absence of LMWOAs.
It is interesting to note, however, the large decreases in LREE/
MREE, LREE/HREE and MREE/HREE for apatite reacted with oxalate
under oxic conditions. These ratios suggest that oxalate preferentially
 K.W. Goyne et al. / Chemical Geology 278 (2010) 1–14
Fig. 3. Effect of (a) oxic and (b) anoxic condition and ligand concentration on the sum of
rare earth element and yttrium release (∑ REY) from apatite. Values are expressed as
grams of elements released (ER) per kilogram of element in the structure (ES) of
unweathered mineral. Error bars represent one standard deviation from triplicate
aqueous phase sample analyses (when not visible, they are smaller than symbol size).
releases MREE and HREE (consistent with Fig. 1) and/or LREE—and
MREE—oxalate complexes are precipitating under oxic conditions.
REY release in the presence of 5 mM and 10 mM oxalate (oxic con-
ditions) is evidently correlated with REY–ligand stability constant
values (Schijf and Byrne, 2001) (Fig. 5). Slope and intercept values
for the predictive equations at oxalate concentrations of 5 mM (REY
release = −0.477 + 0.109 log β1; r2 = 0.76; p = 2.09 × 10−4) and
10 mM (REY release = −0.663 + 0.155 log β1; r2 = 0.76; p = 2.04 ×
10−4) are not significantly different, based on 95% CI, when apparent
outlying data (i.e., La and Eu) are removed.
Similarly, LREE/MREE and LREE/HREE release ratios for citrate
solutions (oxic conditions) are lower than ligand-free values, suggesting
preferential release of elements with smaller ionic radii (higher atom-
ic mass), consistent with Fig. 1. However, the citrate data exhibit greater
MREE/HREE ratios at 5 and 10 mM citrate concentrations, relative to
ligand-free samples, counter to prediction from REY–ligand stability
constant values. The correlation between REY release in the presence
of citrate and log β1 stability constants was weak even at a 10 mM
citrate concentration (r2 b 0.15). Phthalate data appear to be generally
consistent with stability constants for REE–phthalate complexes (Fig. 1;
Wood, 1993). However, the REY release patterns in the presence of
phthalate are not a mirror image of REE-phthalate stability complexes,
as reflected by poor correlation (r2 b 0.13). Similarly, poor correlation
(r2 b 0.20) was observed for REY release and stability constants for
salicylate.
5
Overall, we observe that increasing aliphatic ligand concentrations
transforms REY patterns for apatite into those that exhibit the lan-
thanide contraction effect. The development of this REY pattern is in
agreement with bond-valence sums for REE in apatite. Hughes et al.
(1991) showed that Gd to Lu are underbonded within apatite in either
seven- or nine-fold coordination, which leads to a concentration of
light REE during mineral formation. We presume that poor compat-
ibility of heavy REE with apatite polyhedra also contributes to their
preferential release during aliphatic ligand-promoted dissolution.
Thus, development of a REY release pattern that exhibits the lan-
thanide contraction effect is likely the result of superimposed in-
fluences of mineral bond-strength and REY complex stability of the
aliphatic ligands.
Investigation of element release ratios commonly used to
characterize REY partitioning-La/Pr, La/Yb, Ce/Pr, Eu/Eu* (Eu* = 0.67
(Sm) + 0.33(Tb)), Gd/Gd* (Gd* = 0.33(Sm) + 0.67(Tb)), and Y/Ho
(Bau et al., 1997)—for apatite reacted in presence of the four LMWOAs
show no significant differences from ligand-free solutions (Table 5).
However, the elemental ratios La/Pr and La/Yb do show lower mean
values for citrate and oxalate reaction relative to phthalate; thus,
indicating a preferential release of Pr and Yb relative to La in presence
of aliphatic ligands. Blank corrected concentrations of Ce in solution
after oxalate reaction with apatite were approximately zero, and
examination of Ce/Pr release ratios further accentuates this observa-
tion. Cerium is known to form aqueous complexes with PO3− 4 and
oxalate that may precipitate from solution as rhabdophane (CePO4 •
H2O (s)) and cerium oxalate (Ce2(C2O4)3 (s)), respectively (Banfield
and Eggleton, 1989; Cervini-Silva et al., 2005). Jonasson et al. (1985)
and Cervini-Silva et al. (2008) report solubility product constants
(Ksp) for REE-phosphate minerals, including rhabdophane, on the
order of 10−25.
Diffuse reflectance infrared Fourier transformed (DRIFT) spectros-
copy confirms the presence of oxalate precipitates in powder samples
after reaction (Fig. 6b and d). Bands associated with precipitates
are clearly observed in Fig. 6b at 3330–3500 cm−1 (OH stretching
associated with water of crystallization), 1644 cm−1 (HOH bending),
1620 cm−1 (asymmetric stretch of COO−), and 1315 cm−1 (symmet-
ric stretch of COO−). However, not all of these vibrations are present
in 6d and peak intensity is greatly diminished. These spectral features
are consistent with the formation of calcium oxalate hydrate (CaC2O4 •
nH2O (s)) and REE-oxalate crystals (John and Ittyachen, 2001;
Bouropoulos et al., 2004), thus confirming our previous geochemical
modeling results that predicted formation of CaC2O4 • nH2O (s)
(Goyne et al., 2006). The lack of soluble Ce and the detection of
oxalate precipitates suggests the formation of Ce2(C2O4)3 (s) and
perhaps other REE-oxalate complexes that may be co-precipitated
with CaC2O4 • nH2O (s).
3.1.2. Effects of oxic/anoxic conditions
Patterns of REY release from apatite are similar under oxic and
anoxic conditions (Fig. 4). However, the sum of REY released is
significantly greater in the presence of O2(g), irrespective of citrate
concentration (0 to 10 mM) (Fig. 3) . In contrast, REY release in the
presence of oxalate is significantly greater under anoxic conditions,
irrespective of ligand concentration. Although this latter result seems
to suggest REY scavenging during precipitation of Fe and/or Mn oxides
in oxic apatite experiments, REY concentrations in HCl extracts are
not significantly different (data not shown). Presence or absence of
O2(g) had no significant effect on the sum of REY released in 1 mM
phthalate or salicylate, or at a 5 mM salicylate. However, at phthalate
concentrations of 5 and 10 mM, oxic conditions promoted greater
REY release. The opposite is true at 10 mM salicylate concentration.
Dissolved O2(g) concentration had no consistent influence on release
of Ce or Eu, the redox active REEs (Table 5). The overall lack of
consistent dissolved O2(g) effect on REY release from apatite is in
6 K.W. Goyne et al. / Chemical Geology 278 (2010) 1–14

Fig. 4. Effect of ligand concentration and dissolved oxygen on individual rare earth element and yttrium release from apatite: (a) oxic—0 and 10 mM ligand, (b) anoxic—0 and 10 mM
ligand, (c) oxic—5 mM ligand, (d) anoxic—5 mM ligand, (e) oxic—1 mM ligand, and (f) anoxic—1 mM ligand. The release of each element is expressed as milligrams of element
released (ER) per kilogram of element in the structure (ES) of unweathered mineral. Error bars represent one standard deviation from triplicate aqueous phase sample analyses
(when not visible, they are smaller than symbol size).

agreement with our previous study investigating Ca and P release concentrations in solution generally increase as a function of ligand
(Goyne et al., 2006). concentration (Figs. 7 and 8 and Table 6). Similar to the apatite
experiments, ligand presence in solution increases REY release one to
3.2. REY release from monazite two orders of magnitude, with the exception of salicylate which
reduced monazite dissolution relative to ligand-free controls. The
3.2.1. Effects of ligands order of REY release, based on the ∑REY, is citrate N oxalate ≈
Rare earth element, yttrium, and other major element release phthalate N no ligand N salicylate. This order deviates slightly from
from monazite is enhanced by citrate, oxalate, and phthalate, and REY the ligand order observed in the apatite experiments. Final solution
 K.W. Goyne et al. / Chemical Geology 278 (2010) 1–14 7

Table 3
Major element release from apatite.

Ligand Ligand conc. Caa Oxic Anoxic P Oxic Anoxic

−1 b
mM g ER kg ES

No ligand 0 0.26 ± 0.02c 0.20 ± 0.02 0.43 ± 0.02 0.26 ± 0.01

Citrate 1 0.993 ± 0.008 1.47 ± 0.02 2.26 ± 0.02 2.29 ± 0.03
5 2.6 ± 0.1 3.69 ± 0.09 6.22 ± 0.08 6.3 ± 0.2
10 3.78 ± 0.05 5.44 ± 0.07 9.89 ± 0.03 10.2 ± 0.1
Oxalate 1 0.072 ± 0.02 0.13 ± 0.02 1.15 ± 0.01 1.27 ± 0.07
5 0.09 ± 0.03 0.16 ± 0.01 4.58 ± 0.05 4.83 ± 0.09
10 0.10 ± 0.01 0.2 ± 0.1 8.63 ± 0.02 9.13 ± 0.09
Phthalate 1 1.060 ± 0.004 0.95 ± 0.04 1.17 ± 0.01 1.23 ± 0.04
5 1.18 ± 0.02 1.08 ± 0.04 1.240 ± 0.004 1.34 ± 0.02
10 1.22 ± 0.06 1.19 ± 0.07 1.33 ± 0.02 1.38 ± 0.037
Salicylate 1 0.26 ± 0.07 0.12 ± 0.08 0.38 ± 0.02 1.08 ± 0.05
5 0.42 ± 0.02 0.06 ± 0.05 0.55 ± 0.02 0.7 ± 0.6
10 0.50 ± 0.01 0.26 ± 0.04 0.58 ± 0.02 1.4 ± 0.1
a
Data obtained from Goyne et al. (2006).
b
g ER kg − 1
ES , milligrams of elements released (ER) per kilogram of elements in the
mineral structure (ES).
c
Error represents 95% confidence interval.
Fig. 5. Relationship between REY–ligand stability constants (log β1; Schijf and Byrne,
2001) and REY release from apatite in the presence of 5 and 10 mM oxalate under oxic
conditions. The apparent outliers La and Eu were excluded from linear regression
analysis.
pH values (Table 2) were comparable for citrate and phthalate
(pH 5.0–5.5), although slightly higher for salicylate (pH 5.8–6.0),
ligand-free (pH 5.9–6.2), and oxalate (pH 6.4–6.6). These pH values all the generally inverse relationship between REY release and oxalate
fall within a range where monazite dissolution is relatively insensitive concentration (Fig. 7).
to pH (Oelkers and Poitrasson, 2002), indicating that ligand-promoted Presence of organic ligands during monazite dissolution not
dissolution enhances REY release. It should also be noted that large only increases REY (aq) concentrations, but also changes REY release
variability associated with REY release in presence of oxalate (Fig. 8) patterns (Fig. 8). Observed REY release patterns also differ sub-
may be attributed to precipitation of REE-oxalate complexes based on stantially from those of stability constant values (Fig. 1), with the

Table 4
Release from apatite of light, middle, and heavy REE and associated release ratios for oxic and anoxic conditions.

Ligand Ligand conc. LREEa Oxic Anoxic MREEb Oxic Anoxic HREEc Oxic Anoxic
−1 d
mM g ER kg ES

No ligand 0 0.05 ± 0.01e 0.019 ± 0.004 0.03 ± 0.01 0.04 ± 0.04 0.04 ± 0.02 0.005 ± 0.003
Citrate 1 7.90 ± 0.08 7.3 ± 0.1 8.6 ± 0.4 8.9 ± 0.2 10.4 ± 0.2 9.5 ± 0.1
5 26.8 ± 0.1 23.8 ± 0.3 28.4 ± 0.3 24.9 ± 0.4 29.5 ± 0.4 25.8 ± 0.4
10 42 ± 1 37.7 ± 0.1 44.6 ± 0.4 39.2 ± 0.5 45.2 ± 0.5 39.5 ± 0.3
Oxalate 1 0.11 ± 0.05 0.23 ± 0.03 0.11 ± 0.05 0.4 ± 0.1 0.17 ± 0.06 0.31 ± 0.03
5 0.33 ± 0.04 0.508 ± 0.010 0.4 ± 0.2 0.8 ± 0.4 0.7 ± 0.3 1.0 ± 0.5
10 0.53 ± 0.03 1.1 ± 0.4 0.57 ± 0.05 1.6 ± 0.5 1.05 ± 0.04 1.9 ± 0.5
Phthalate 1 0.101 ± 0.003 0.1 ± 0.02 0.068 ± 0.005 0.2 ± 0.2 0.044 ± 0.007 0.06 ± 0.02
5 0.56 ± 0.02 0.37 ± 0.01 0.6 ± 0.1 0.4 ± 0.03 0.46 ± 0.04 0.33 ± 0.03
10 1.15 ± 0.03 0.84 ± 0.02 1.21 ± 0.06 0.92 ± 0.07 1.13 ± 0.04 0.81 ± 0.04
Salicylate 1 0.011 ± 0.010 0.012 ± 0.002 0.007 ± 0.008 0.04 ± 0.03 0.015 ± 0.009 0.012 ± 0.007
5 0.007 ± 0.003 0.03 ± 0.02 0.1 ± 0.2 0.05 ± 0.03 0.004 ± 0.002 0.03 ± 0.02
10 0.009 ± 0.003 0.13 ± 0.07 0.003 ± 0.004 0.2 ± 0.1 0.009 ± 0.005 0.07 ± 0.02

Ligand Ligand Conc. LREE/MREE Oxic Anoxic LREE/HREE Oxic Anoxic MREE/HREE Oxic Anoxic

mM

No ligand 0 1.4 ± 0.6 0.4 ± 0.4 1.2 ± 0.67 4±2 0.8 ± 0.5 9±9
Citrate 1 0.92 ± 0.04 0.82 ± 0.03 0.76 ± 0.02 0.77 ± 0.02 0.82 ± 0.04 0.93 ± 0.03
5 0.94 ± 0.01 0.95 ± 0.02 0.91 ± 0.01 0.92 ± 0.02 0.96 ± 0.02 0.97 ± 0.02
10 0.95 ± 0.02 0.96 ± 0.01 0.93 ± 0.02 0.956 ± 0.007 0.99 ± 0.01 0.99 ± 0.02
Oxalate 1 1.0 ± 0.7 0.6 ± 0.2 0.7 ± 0.4 0.8 ± 0.1 0.6 ± 0.4 1.2 ± 0.4
5 0.9 ± 0.5 0.7 ± 0.3 0.5 ± 0.2 0.5 ± 0.2 0.5 ± 0.4 0.8 ± 0.6
10 0.94 ± 0.1 0.7 ± 0.3 0.51 ± 0.034 0.6 ± 0.3 0.54 ± 0.05 0.8 ± 0.4
Phthalate 1 1.5 ± 0.1 0.5 ± 0.5 2.3 ± 0.4 1.7 ± 0.6 1.6 ± 0.3 3±3
5 1.0 ± 0.2 0.94 ± 0.08 1.2 ± 0.1 1.1 ± 0.1 1.2 ± 0.3 1.2 ± 0.2
10 0.95 ± 0.05 0.91 ± 0.08 1.02 ± 0.04 1.03 ± 0.05 1.07 ± 0.06 1.1 ± 0.1
Salicylate 1 2±2 0.3 ± 0.2 0.8 ± 0.8 0.9 ± 0.6 0.5 ± 0.6 3±3
5 0.1 ± 0.2 0.6 ± 0.5 1±1 0.9 ± 0.8 20 ± 50 1±1
10 3±4 0.6 ± 0.5 1.0 ± 0.6 2±1 0.3 ± 0.4 3±2
a
Sum of the light rare earth elements (LREE; La, Ce, Pr, and Nd).
b
Sum of the middle rare earth elements (MREE; Sm, Eu, Gd, and Tb).
c
Sum of the heavy rare earth elements (HREE; Er, Tm, Yb, and Lu).
d
g ER kg − 1
ES , milligrams of elements released (ER) per kilogram of elements in the mineral structure (ES).
e
Error represents 95% confidence interval.
8 K.W. Goyne et al. / Chemical Geology 278 (2010) 1–14

Table 5
Mean aqueous REY ratios following oxic and anoxic dissolution of apatite.

Ligand Ligand conc. La/Pr Oxic Anoxic La/Yb Oxic Anoxic Ce/Pr Oxic Anoxic

mM

No ligand 0 1 ± 0.8a 0.9 ± 0.6 1±2 4±5 1.0 ± 0.8 1.0 ± 0.7
Citrate 1 0.83 ± 0.02 0.85 ± 0.04 0.67 ± 0.02 0.7 ± 0.03 0.9 ± 0.03 0.92 ± 0.04
5 0.88 ± 0.01 0.94 ± 0.03 0.85 ± 0.02 0.89 ± 0.03 0.95 ± 0.01 1.00 ± 0.03
10 0.91 ± 0.01 0.931 ± 0.009 0.89 ± 0.02 0.92 ± 0.01 0.96 ± 0.02 1.019 ± 0.009
Oxalate 1 1±1 0.9 ± 0.2 0.8 ± 0.8 0.8 ± 0.3 – 0.2 ± 0.2
5 0.9 ± 0.3 0.88 ± 0.04 0.6 ± 0.1 0.64 ± 0.05 – –
10 1.0 ± 0.1 0.9 ± 0.8 0.69 ± 0.06 0.7 ± 0.6 – –
Phthalate 1 1.5 ± 0.1 1.3 ± 0.7 1.8 ± 0.6 1.9 ± 1.0 1.0 ± 0.1 1.0 ± 0.6
5 1.5 ± 0.1 1.6 ± 0.1 1.8 ± 0.2 1.5 ± 0.2 1.00 ± 0.09 1.0 ± 0.1
10 1.36 ± 0.09 1.4 ± 0.08 1.4 ± 0.09 1.4 ± 0.2 0.98 ± 0.06 1.00 ± 0.06
Salicylate 1 1±2 1.2 ± 0.4 1±2 0.7 ± 0.3 1±2 0.6 ± 0.2
5 1±2 1±1 1±1 1±2 1±1 1±2
10 0.9 ± 0.9 0.5 ± 0.6 1±1 1.0 ± 0.6 0.7 ± 0.9 1±1

Ligand Ligand Conc. Eu/Eu* b Oxic Anoxic Gd/Gd* c Oxic Anoxic Y/Ho Oxic Anoxic

mM

No ligand 0 – 6 ± 11 2±2 1±2 1±1 0.9 ± 0.6

Citrate 1 0.5 ± 0.2 0.95 ± 0.10 1.13 ± 0.08 1.1 ± 0.1 0.82 ± 0.04 0.97 ± 0.03
5 0.78 ± 0.03 0.90 ± 0.05 1.09 ± 0.03 1.11 ± 0.05 0.81 ± 0.03 0.96 ± 0.05
10 0.84 ± 0.02 0.90 ± 0.04 1.10 ± 0.03 1.10 ± 0.04 0.82 ± 0.02 0.96 ± 0.02
Oxalate 1 – 2±2 1±2 1.2 ± 0.5 0.9 ± 0.9 1.0 ± 0.3
5 2±1 0.9 ± 0.1 1.2 ± 0.4 1.0 ± 0.1 1 ± 0.2 1.04 ± 0.07
10 0 ± 0.2 1±1 1.2 ± 0.2 1±1 1.0 ± 0.1 1.0 ± 0.8
Phthalate 1 – 6 ± 10 1.2 ± 0.2 1±1 1.6 ± 0.3 1.3 ± 0.8
5 0.8 ± 1.0 1.0 ± 0.4 1.4 ± 0.2 1.3 ± 0.2 1.2 ± 0.1 1.3 ± 0.1
10 0.7 ± 0.2 1.1 ± 0.4 1.3 ± 0.1 1.3 ± 0.2 1.15 ± 0.08 1.22 ± 0.07
Salicylate 1 – – 1±4 3±3 2±6 0.7 ± 0.4
5 50 ± 190 3±7 1±2 1±2 2±2 1±1
10 – 1±2 5 ± 39 1±2 2±4 0.9 ± 0.5
a
Error represents 95% confidence interval.
b
Eu*0.67(Sm) + 0.33(Tb).
c
Gd*0.33(Sm) + 0.67(Tb).

exception of phthalate. The release pattern reflects the M-type lan-
thanide tetrad effect (Masuda et al., 1987; Bau, 1999) or radius-
independent fractionation. The convex nature of the first three seg-
Fig. 6. Diffuse reflectance infrared Fourier transform (DRIFT) spectra of apatite reacted
with (a) 10 mM citrate, (b) 10 mM oxalate, (c) 1 mM citrate, (d) 1 mM oxalate, and
(e) 0.01 M LiCl (ligand-free) under oxic conditions. Spectrum (f) is unreacted apatite.
ments (I: La–Nd; II Nd–Gd; III: Gd–Ho) generally fits the first, second
and third tetrad effects; however, the fourth segment (IV: Ho–Lu)
exhibits a concave shape. Table 7 shows a comparison of LREE/MREE,
LREE/HREE, and MREE/HREE release ratios in the absence and pres-
ence of LMWOAs. In most instances, significant treatment effects are
observed. In contrast to the pattern for apatite, monazite dissolution
data clearly demonstrate an increase in MREE relative to LREE and
HREE release. The unusual behavior of LREE and increased error
associated with these particular REE in the presence of oxalate also
suggests precipitation of LREE-oxalate complexes. Indeed, DRIFT
characterization of the reacted solids (Fig. 9b and d) indicates pre-
cipitation of REE-oxalate complexes based on changes in vibrational
modes between 1260 and 1650 cm−1, particularly the greater inten-
sity of peaks at 1514 and 1641 cm−1.
The elements La, Eu, and Y appear to exhibit anomalous behavior,
particularly in the presence of citrate and phthalate (Table 8). Lan-
thanum release is diminished relative to Pr in the presence of these
ligands, but not in ligand-free experiments. In the presence of oxygen,
citrate and phthalate give Eu/Eu* values greater than one, whereas a
mean Eu/Eu* release ratio of one is observed in the absence of ligands.
Lastly, citrate and phthalate strongly fractionate the “geochemical
twins” Y and Ho through greater release of Ho into aqueous solution. As
discussed by Bau (1999), the specific electron configurations of Y3+
([Kr]4d0) and La3+ ([Xe] 4f0) result in greater covalency upon com-
plexation relative to 4f transition elements that exhibit greater ionic
character. This difference arises due to less effective nuclear charge
shielding by 4f electrons as compared to electrons residing in other
orbitals. Although the degree of covalent binding will be specified by
the complex formed (Bau, 1999), we postulate that Y and La strongly
complexed with phosphate within the crystal structure of monazite
may diminish the ability of organic ligands to break crystal lattice bonds
resulting, subsequently, in negative anomalies for these elements.
 K.W. Goyne et al. / Chemical Geology 278 (2010) 1–14
Fig. 7. Effect of (a) oxic and (b) anoxic conditions and ligand concentrations on the sum
of rare earth element and yttrium release from monazite (∑ REY). Values are expressed
as grams of elements released (ER) per kilogram of elements in the structure (ES) of
unweathered mineral. Error bars represent one standard deviation from triplicate
aqueous phase sample analyses (when not visible, they are smaller than symbol size).
The fact that citrate and phthalate generate a positive Eu anomaly
under oxic conditions is difficult to explain. Our observation of en-
hanced Eu release is in agreement with several samples studied by
Hannigan and Sholkovitz (2001) where it was demonstrated that the
weathering of phosphate minerals leads to MREE enrichment in
solution. Shibata et al. (2006) demonstrated the importance of Eu
compatibility to Eu anomalies within the host mineral by comparison
of plagioclase and pyroxene dissolution. However, monazite crystal
structure results in enrichment of REEs with larger ionic radius (La
to Gd) (Ni et al., 1995; Williams et al., 2007). Europium is the least
concentrated REE in the monazite sample studied perhaps lending
some credibility to the incompatibility hypothesis, but fluid compo-
sition at the time of mineral formation also controls stoichiometry.
With the exception of phthalate, REY release from monazite was
not well predicted by REY–ligand stability constants. Linear regression
analysis of REY release against stability constant values resulted in
poor correlation for citrate, oxalate and salicylate even at the highest
ligand concentrations (r2 b 0.26). REE-ligand stability constants (log
β1) were, however, a moderate to strong predictor of REE release for
phthalate (stability constant for Y-phthalate complex was excluded as
constant was not present in data compiled by Wood, 1993). Analyses
performed using the entire suite of REE release data at phthalate
concentrations of 1, 5 and 10 mM under oxic conditions yielded r2
values of 0.45, 0.51, and 0.54, respectively. Removal of the apparent
outliers Nd and Sm from the linear regression analyses improved the
data fits (Fig. 10). Listed below are the predictive equations developed
9
upon removal of the apparent outlying data (units associated with
REE release are g released per kg of element in the mineral structure):
1 mM phthalate-oxic
2 −4
REE release = −1:71 + 0:393 logβ1 ; r = 0:75; p = 2:69 × 10
5 mM phthalate-oxic
2
REE release = − 5:66 + 1:27 logβ1 ; r = 0:92; p = b 0:0001
10 mM phthalate-oxic
2
REE release = −7:43 + 1:67 logβ1 ; r = 0:92; p = b 0:0001
Thus, in the case of monazite and apatite, REY–ligand stability
constants for only one of the four ligands studied was a useful pre-
dictor of REY release.
Although the REE–ligand stability constants aid in explaining REE
release in the presence of phthalate and specific electron configura-
tions assist in understanding the anomalous behavior of Y and La,
the overall enhanced release of MREE from monazite remains to be
explained. Monazite preferentially concentrates lighter REE (La–Gd),
similar to apatite. Based on this information and the REY-stability
constants in Fig. 1, one might predict the development of a lanthanide
contraction effect pattern for monazite dissolution. The fact that this
pattern does not develop suggests a difference in energy associated
with ligand-promoted REY release from monazite as compared to
apatite, which is likely due to differences in mineral structure. In
apatite, lighter REEs are thought to favor seven-fold coordination sites,
thus leaving the heavier REEs to occupy nine-fold coordination sites
(Hughes et al., 1991). In contrast, lighter REE in monazite are found
within irregular nine-fold coordination (Ni et al., 1995; Williams et al.,
2007). Heavier REE (Tb–Lu) in the monazite sample studied are likely
contained within xenotime crystals or xenotime-like structures in the
larger sample matrix (Franz et al., 1996). Xenotime preferentially
incorporates heavier REE into eight-fold coordination, and Tb is
the largest REE that can be incorporated into this polyhedron (Ni
et al., 1995). If the MREE are approaching the lower limit for REEO9
polyhedra and the upper limit for xenotime REEO8 polyhedra, this
could explain greater MREE release in our dissolution experiments.
3.2.2. Effects of oxic/anoxic conditions
As for apatite, the patterns of REY release from monazite are
essentially independent of dissolved O2(g) (Figs. 7 and 8). The ex-
ceptions are positive anomalous behavior of redox active Ce and Eu
under anoxic conditions in organic ligand-free solutions. The Ce/Pr
release ratio is significantly greater under anoxic relative to oxic
conditions (Table 8), the latter being closer to the unit value expected
for stoichiometric release. These data suggest that Ce remains in the
+3 valence state under anoxic conditions and, therefore, remains
more soluble than under oxic conditions. Oxidation of Ce3+ (aq) to
Ce4+ (aq) in oxic solutions is not possible because the emf for the half
cell (1.74 V) is well above the upper stability limit for water (Brookins,
1989; Pourret et al., 2008). However, under oxic conditions, it is quite
possible that Ce3+ (aq) is released and oxidized to form of cerianite,
CeO2 (s) (Brookins, 1989; Pourret et al., 2008), or the element is being
oxidized at the mineral surface while remaining within the monazite
crystal structure. The lack of a negative Ce anomaly in the oxic ex-
periments and the fact that Cervini-Silva et al. (2008) did not observe
Ce oxidation at the surface of CePO4 • H2O (s) in oxic solutions in
absence of organic molecules seems to suggest that an alternative, but
as of yet unknown, mechanism of release may be occurring. Though
the mean Eu/Eu* ratio appears greater for anoxic conditions, this
effect is not statistically significant; the ratio for both anoxic and oxic
10 K.W. Goyne et al. / Chemical Geology 278 (2010) 1–14

Fig. 8. Effect of ligand concentration and dissolved oxygen on rare earth element and yttrium release from monazite: (a) oxic—0 and 10 mM ligand, (b) anoxic—0 and 10 mM ligand,
(c) oxic—5 mM ligand, (d) anoxic—5 mM ligand, (e) oxic—1 mM ligand, and (f) anoxic—1 mM ligand. The release of each element is expressed as milligrams of element released (ER)
per kilogram of element in the structure (ES) of unweathered mineral. Error bars represent one standard deviation from triplicate aqueous phase sample analyses (when not visible,
they are smaller than symbol size).

conditions is not significantly different from unity. Enhanced release
of Eu from the mineral surface via a reductive dissolution mechanism
in anoxic experiments may explain the elevated release of Eu relative
to neighboring REE. However, the pe-pH region where Eu2+ (aq)
predominates is rather narrow (Brookins, 1989) and others have
suggested that the Eu3+/Eu2+ redox boundary is below the lower
stability field of water at earth surface conditions (Elderfield, 1988).
The role of organic ligand as reductant also remains unclear, although
previous studies have demonstrated that organic acids serve as re-
ductants in various abiotic systems (Krumpolc and Roček, 1985;
Pohlman and McColl, 1989; Deng and Stone, 1996). More detailed
studies are required to elucidate the geochemical reactions resulting
in the anomalous behavior of Ce and Eu as they are released from
monazite.
Anoxia increases the sum of REY released from monazite in the
presence of all concentrations of citrate. Anoxic conditions also result
in significantly greater REY sums for some experiments conducted in
the presence of phthalate (1 mM) and salicylate (5 and 10 mM). Oxic
conditions induced significantly greater REY release in ligand-free,
5 mM phthalate, all three oxalate concentrations. Overall, mixed and
 K.W. Goyne et al. / Chemical Geology 278 (2010) 1–14 11

Table 6
Major element release from monazite (excluding rare earth elements and yttrium).

Ligand Ligand conc. P Oxic Anoxic Si Oxic Anoxic

−1 a
mM g ER kg ES

No ligand 0 0.01 ± 0.01b 0.008 ± 0.005 2.9 ± 0.7 2.3 ± 0.4

Citrate 1 3.5 ± 0.7 2.4 ± 0.4 6.2 ± 0.2 8.2 ± 0.8
5 4.8 ± 0.2 3.73 ± 0.09 8.6 ± 0.3 12.1 ± 0.5
10 5.7 ± 0.3 4.75 ± 0.07 10.0 ± 0.7 13 ± 1
Oxalate 1 0.16 ± 0.02 0.14 ± 0.07 3.3 ± 0.2 2.8 ± 0.1
5 0.65 ± 0.02 0.63 ± 0.08 8.13 ± 0.06 7.4 ± 0.2
10 2.00 ± 0.01 1.83 ± 0.06 13.0 ± 0.35 12.5 ± 0.7
Phthalate 1 0.007 ± 0.003 0.023 ± 0.001 2.3 ± 0.1 2.54 ± 0.04
5 0.07 ± 0.02 0.08 ± 0.01 2.17 ± 0.02 2.28 ± 0.01
10 0.12 ± 0.03 0.12 ± 0.02 2.26 ± 0.02 2.66 ± 0.08
Salicylate 1 0.048 ± 0.007 0.00 ± 0.01 2.0 ± 0.2 3±1
5 0.044 ± 0.007 0.02 ± 0.02 2.7 ± 0.2 3.9 ± 0.5
10 0.01 ± 0.01 0.008 ± 0.008 2.7 ± 0.2 4±1
a
g ER kg − 1
ES , grams of elements released (ER) per kilogram of elements in the mineral
structure (ES).
b
Error represents 95% confidence interval.

inconsistent effects suggest a weak role of O2(g) in monazite dis-

solution, similar to apatite experiments discussed previously.

3.3. Stoichiometry of element release and other potential factors

mitigating REY patterns
Fig. 9. Diffuse reflectance infrared Fourier transform (DRIFT) spectra of monazite
We reported previously that Ca and P release from apatite was reacted with (a) 10 mM citrate, (b) 10 mM oxalate, (c) 1 mM citrate, (d) 1 mM oxalate,
nonstoichiometric for all experiments as evidenced by mineral nor- and (e) 0.01 M LiCl (ligand-free) under oxic conditions. Spectrum (f) is unreacted
monazite.
malized molar Ca/P release ratios less than 1 (Goyne et al., 2006).
Using data from the present work, we can likewise calculate aqueous

Table 7
Release from monazite of light, middle, and heavy REE and associated release ratios for oxic and anoxic conditions.

Ligand Ligand conc. LREEa Oxic Anoxic MREEb Oxic Anoxic HREEc Oxic Anoxic
−1d
mM g ER kg ES

No ligand 0 0.20 ± 0.02e 0.24 ± 0.06 0.19 ± 0.02 0.19 ± 0.03 0.14 ± 0.01 0.07 ± 0.01
Citrate 1 6.99 ± 0.07 7.6 ± 0.2 12.2 ± 0.2 13.7 ± 0.4 4.1 ± 0.1 4.7 ± 0.2
5 11.8 ± 0.2 13.6 ± 0.24 18.9 ± 0.3 22.3 ± 0.4 5.2 ± 0.2 6.3 ± 0.1
10 13.7 ± 0.2 15.6 ± 0.1 21.5 ± 0.2 25.2 ± 0.3 5.4 ± 0.1 6.5 ± 0.2
Oxalate 1 0.93 ± 0.04 0.6 ± 0.1 1.66 ± 0.04 1.6 ± 0.1 1.96 ± 0.06 1.35 ± 0.04
5 0.33 ± 0.09 0.20 ± 0.06 0.6 ± 0.4 0.5 ± 0.2 0.6 ± 0.3 0.3 ± 0.2
10 1.0 ± 0.2 0.2 ± 0.1 6.4 ± 0.7 0.6 ± 0.1 3.2 ± 0.3 0.30 ± 0.05
Phthalate 1 0.50 ± 0.04 0.64 ± 0.02 0.65 ± 0.05 1.01 ± 0.02 0.47 ± 0.03 0.47 ± 0.01
5 1.24 ± 0.03 1.4 ± 0.2 2.22 ± 0.04 2.0 ± 0.1 1.04 ± 0.02 0.82 ± 0.06
10 1.73 ± 0.06 2.07 ± 0.08 3.0 ± 0.1 2.87 ± 0.04 1.42 ± 0.06 1.15 ± 0.01
Salicylate 1 0.06 ± 0.01 0.06 ± 0.01 0.050 ± 0.008 0.07 ± 0.01 0.028 ± 0.003 0.030 ± 0.004
5 0.054 ± 0.002 0.066 ± 0.010 0.089 ± 0.005 0.11 ± 0.02 0.025 ± 0.002 0.037 ± 0.004
10 0.102 ± 0.002 0.123 ± 0.005 0.104 ± 0.001 0.20 ± 0.03 0.048 ± 0.001 0.08 ± 0.003

Ligand Ligand conc. LREE/MREE Oxic Anoxic LREE/HREE Oxic Anoxic MREE/HREE Oxic Anoxic

mM

No ligand 0 1.0 ± 0.1 1.3 ± 0.4 1.4 ± 0.2 3.2 ± 0.9 1.4 ± 0.2 2.5 ± 0.5
Citrate 1 0.57 ± 0.01 0.55 ± 0.02 1.70 ± 0.05 1.62 ± 0.08 2.97 ± 0.10 2.9 ± 0.1
5 0.62 ± 0.01 0.61 ± 0.01 2.2 ± 0.1 2.18 ± 0.05 3.6 ± 0.2 3.56 ± 0.08
10 0.64 ± 0.01 0.620 ± 0.008 2.52 ± 0.06 2.4 ± 0.08 3.96 ± 0.10 3.9 ± 0.1
Oxalate 1 0.56 ± 0.03 0.41 ± 0.07 0.47 ± 0.02 0.48 ± 0.08 0.85 ± 0.03 1.2 ± 0.1
5 0.5 ± 0.3 0.4 ± 0.2 0.5 ± 0.3 0.6 ± 0.4 1.0 ± 0.8 1±1
10 0.15 ± 0.03 0.4 ± 0.2 0.29 ± 0.06 0.8 ± 0.4 2.0 ± 0.3 1.9 ± 0.5
Phthalate 1 0.77 ± 0.08 0.64 ± 0.02 1.1 ± 0.1 1.38 ± 0.06 1.4 ± 0.1 2.17 ± 0.08
5 0.56 ± 0.02 0.69 ± 0.09 1.19 ± 0.04 1.6 ± 0.2 2.13 ± 0.07 2.4 ± 0.2
10 0.58 ± 0.03 0.72 ± 0.03 1.22 ± 0.06 1.81 ± 0.08 2.1 ± 0.1 2.50 ± 0.05
Salicylate 1 1.2 ± 0.3 0.9 ± 0.2 2.2 ± 0.4 2.1 ± 0.5 1.8 ± 0.4 2.2 ± 0.5
5 0.61 ± 0.04 0.6 ± 0.2 2.2 ± 0.2 1.8 ± 0.3 3.6 ± 0.4 2.9 ± 0.7
10 0.98 ± 0.02 0.6 ± 0.1 2.12 ± 0.07 1.58 ± 0.09 2.17 ± 0.06 2.6 ± 0.4
a
Sum of the light rare earth elements (LREE; La, Ce, Pr, and Nd).
b
Sum of the middle rare earth elements (MREE; Sm, Eu, Gd, and Tb).
c
Sum of the heavy rare earth elements (HREE; Er, Tm, Yb, and Lu).
d
g ER kg ES−1, milligrams of elements released (ER) per kilogram of elements in the mineral structure (ES).
e
Error represents 95% confidence interval.
12 K.W. Goyne et al. / Chemical Geology 278 (2010) 1–14

Table 8
Mean aqueous REY ratios following oxic and anoxic dissolution of monazite.

Ligand Ligand conc. La/Pr Oxic Anoxic La/Yb Oxic Anoxic Ce/Pr Oxic Anoxic

mM

No ligand 0 1.0 ± 0.2 a 1.0 ± 0.5 1.8 ± 0.4 2±1 0.8 ± 0.2 4±2
Citrate 1 0.70 ± 0.02 0.70 ± 0.05 1.58 ± 0.05 1.5 ± 0.1 0.84 ± 0.02 0.82 ± 0.06
5 0.73 ± 0.04 0.73 ± 0.04 2.0 ± 0.4 2.1 ± 0.2 0.86 ± 0.04 0.84 ± 0.04
10 0.72 ± 0.03 0.75 ± 0.01 2.5 ± 0.2 2.5 ± 0.1 0.85 ± 0.03 0.87 ± 0.02
Oxalate 1 0.66 ± 0.07 0.7 ± 0.3 0.56 ± 0.03 0.4 ± 0.1 0.52 ± 0.06 0.8 ± 0.3
5 0.6 ± 0.4 0.8 ± 0.7 0.5 ± 0.3 0.7 ± 0.5 0.4 ± 0.2 0.8 ± 0.8
10 0.6 ± 0.2 0.8 ± 0.2 0.4 ± 0.1 0.8 ± 0.3 0.2 ± 0.1 0.7 ± 0.4
Phthalate 1 0.7 ± 0.1 0.92 ± 0.09 0.9 ± 0.2 1.31 ± 0.09 0.7 ± 0.1 0.96 ± 0.10
5 0.72 ± 0.05 0.8 ± 0.3 1.06 ± 0.07 1.6 ± 0.6 0.76 ± 0.04 0.8 ± 0.2
10 0.73 ± 0.08 0.82 ± 0.08 1.1 ± 0.1 1.6 ± 0.1 0.77 ± 0.07 0.9 ± 0.1
Salicylate 1 1.0 ± 0.4 0.9 ± 0.5 2.3 ± 0.9 2.4 ± 0.9 0.9 ± 0.4 0.8 ± 0.5
5 0.9 ± 0.1 1.0 ± 0.4 1.6 ± 0.3 2.2 ± 0.7 0.88 ± 0.08 0.8 ± 0.4
10 0.88 ± 0.03 0.9 ± 0.1 1.56 ± 0.08 1.7 ± 0.3 0.86 ± 0.06 0.82 ± 0.09

Ligand Ligand conc. Eu/Eu* b Oxic Anoxic Gd/Gd* c Oxic Anoxic Y/Ho Oxic Anoxic

mM

No ligand 0 1.0 ± 0.6 2±1 1.0 ± 0.3 1.0 ± 0.7 1.0 ± 0.2 0.9 ± 0.4
Citrate 1 1.38 ± 0.09 1.4 ± 0.1 1.02 ± 0.07 1.01 ± 0.09 0.7 ± 0.07 0.66 ± 0.04
5 1.28 ± 0.08 1.34 ± 0.08 1.01 ± 0.06 1.01 ± 0.06 0.7 ± 0.03 0.66 ± 0.02
10 1.29 ± 0.05 1.31 ± 0.05 1.00 ± 0.04 1.00 ± 0.04 0.69 ± 0.05 0.67 ± 0.02
Oxalate 1 1.2 ± 0.1 1.3 ± 0.4 0.89 ± 0.07 0.9 ± 0.2 0.8 ± 0.1 0.93 ± 0.10
5 1±1 1±1 0.8 ± 0.9 0.9 ± 0.9 0.9 ± 0.7 1.0 ± 0.7
10 0.9 ± 0.4 0.9 ± 0.5 0.8 ± 0.3 0.8 ± 0.5 0.7 ± 0.2 0.8 ± 0.4
Phthalate 1 1.0 ± 0.3 1.3 ± 0.1 1.0 ± 0.2 0.94 ± 0.06 0.7 ± 0.1 0.91 ± 0.08
5 1.44 ± 0.09 1.2 ± 0.3 0.98 ± 0.05 1.2 ± 0.3 0.67 ± 0.04 0.9 ± 0.2
10 1.4 ± 0.2 1.19 ± 0.06 1.01 ± 0.09 1.17 ± 0.05 0.66 ± 0.06 0.9 ± 0.1
Salicylate 1 – 2±1 0.9 ± 0.4 1.0 ± 0.6 1.8 ± 0.6 1.1 ± 0.4
5 2.1 ± 0.4 2±1 0.9 ± 0.2 1.0 ± 0.5 1.7 ± 0.4 1.1 ± 0.4
10 0.4 ± 1.0 2.1 ± 0.8 0.92 ± 0.04 1.0 ± 0.1 1.6 ± 0.1 1.1 ± 0.2
a
Error represents 95% confidence interval.
b
Eu* = 0.67(Sm) + 0.33(Tb).
c
Gd* = 0.33(Sm) + 0.67(Tb).

phase molar REY/P ratios and normalize them to the same ratios
in mineral solids to assess the extent to which REY release was
stoichiometric. Resulting values indicate that REY release for apatite
was nonstoichiometric (ratios b 1) in all cases except for citrate ex-
periments where REY/P ratios approach unity. Nonstoichiometric
release of REY/P was generally observed for monazite although un-
like the case for apatite, P release did not consistently equal or ex-
ceed that of the cations, rather the data indicate variation depending
on the ratio among the ligands and ligand concentrations. Despite
this variation, REY/P ratios were consistent between oxic and anoxic
experiments for both apatite and monazite. Of course, the REY trends
in preferential dissolution are also reflected directly in Figs. 3, 4 and
7, 8, since these data have been normalized to REY content of
the mineral solids.
The mechanisms of nonstoichiometric dissolution of apatite and
monazite are all not readily determined by the data collected in
this series of experiments. Potential explanations for nonstoichiome-
teric element release include: (1) preferential element release from
mineral surfaces due to differences in ligand-stability constants and
REY coordination environments within the minerals; (2) re-adsorption
of REY to mineral surfaces; (3) precipitation and co-precipitation of REY
in newly formed secondary minerals; and (4) precipitation of REY–
organic ligand complexes. In addition to information obtained from
previous REY studies, we used spectroscopic and extraction analyses to
identify particular instances where certain mechanisms influencing
nonstoichiometric dissolution were clearly evident or hypothesized to
be significant. However, we acknowledge that the techniques employed
may not have identified all potential explanations for the REY patterns
observed, and factors other than organic ligand type and concentration
may also be exerting an influence on the REY patterns developed in our
studies.

3.4. Implications for using REY as organomarkers

Apatite and monazite data clearly demonstrate that mineral dis-

Fig. 10. Relationship between REE-ligand stability constants (log β1; Wood, 1993) and
REE release from monazite in the presence of 1, 5, and 10 mM phthalate under oxic
conditions. The apparent outliers Nd and Sm were excluded from linear regression
analysis.
solution was enhanced by three out of the four LMWOAs studied—
salicylate being the exception. Thus, the presence of LMWOAs in soil
solutions should result in zones of eluviation and illuviation that can
be observed by studying REY content (Land et al., 1999; Tyler, 2004b).
 K.W. Goyne et al. / Chemical Geology 278 (2010) 1–14
REY release results indicate that aliphatic organic acid weathering
of apatite exhibits a lanthanide contraction effect (Bau-Dulski Type 1
REY fractionation pattern) and monazite dissolution shows greater
MREE release and radius-independent (Bau-Dulski Type 3) REY
fractionation. Therefore, ratios of La/Pr, Eu/Eu*, Y/Ho ratio and MREE
fractionation may be particularly useful for identifying biotic effects
in paleosol formation when monazite is the dominant REE-bearing
mineral present in soil parent material. In cases where soil is weath-
ering from parent materials containing apatite, it may be possible to
denote organic ligand effects through investigation of LREE/MREE,
LREE/HREE, and MREE/HREE ratios.
Distinctive REY release patterns of the two phosphate minerals
is particularly noteworthy, as they indicate that REY patterns may
more strongly reflect the source mineral undergoing dissolution than
the type of organic ligand present. Thus, our data suggest that REY
patterns in organic-rich natural waters may also facilitate identifica-
tion of REY source minerals (e.g., apatite versus monazite). Develop-
ment of larger data sets containing a greater variety of REY-host
minerals reacted with LMWOAs and humic substances, particularly
the more mobile fulvic acid fraction, would permit further evaluation
of using REY patterns as a tool to identify phosphate mineral weath-
ering in both contemporaneous and paleo environments. In addition,
future studies should address other factors that could also influence
REY fractionation including adsorption/desorption processes, mass
movement, solute migration, and secondary mineral formation. Nev-
ertheless, REY patterns are clearly sensitive to weathering environ-
ment and, therefore, represent a potential to complement measures of
major lithogenic element behavior to better understand weathering
phenomenon in contemporary soils or paleosols.
4. Conclusions
The presence of LMWOAs citrate, oxalate and phthalate enhanced
REY release from apatite and monazite relative to inorganic weath-
ering under comparable conditions. Aliphatic ligands promote REY
release to a greater extent than aromatic ligands and increasing li-
gand concentrations enhances mineral dissolution in nearly all cases.
Within the group of organic ligands investigated, citrate enhances
mineral dissolution to the greatest extent (40-fold or greater increase
relative to ligand-free samples) and salicylate reduced or had a neg-
ligible effect on dissolution, consistent with trends in stability con-
stant data. When aliphatic ligands were reacted with apatite, REY
release patterns exhibited the lanthanide contraction effect, where-
as aliphatic and aromatic ligands reacted with monazite induced
development of radius-independent REY fractionation patterns. REY
release was poorly predicted by REY–ligand stability constants with
the exceptions of oxalate and phthalate in experiments containing
apatite and monazite, respectively. This suggests that REY release
patterns from apatite and monazite are controlled to a large extent by
the specific crystal structure of the mineral undergoing dissolution.
The presence/absence of dissolved O2(g) did not result in consistent
effects on element release from the phosphate minerals. We conclude
that REY may have utility as organomarkers, e.g., for distinguishing
the presence of terrestrial organisms during soil weathering processes
on early earth, and REY fractionation patterns induced by organic
ligands may also permit determination of REY source mineralogy.
Acknowledgements
The authors wish to thank Mary Kay Amistadi for her assistance
with ICP-MS and IC analyses, Aaron Thompson for his thoughtful
comments and suggestions, Sanjai Parikh, and John Villinski for their
assistance in the laboratory, and Sunkyung Choi and Michael Carducci
for assisting with analysis and interpretation of XRD data. This study
was funded by NASA grant NAG5-12330.
13
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