C H A P T E R
42
Lanthanum
RICHARD P. WEDEEN, BALAZS BERLINGER, AND JAN AASETH
ABSTRACT
Lanthanum (La) is a nonessential element. In its pure
form, it is a rather soft, silvery-white metal, which tar-
nishes rapidly in air. Its atomic weight is 138.9055 and
its atomic number is 57. Rare earth elements includ-
ing La are relatively abundant in the Earth’s crust, but
finding them where they can be economically mined
and processed presents a challenge. China is presumed
to be responsible for over 95% of the world’s mine
production. The chemistry of La primarily concerns
its formation of the ionic +3 oxidation state. Lantha-
num oxide improves the alkali resistance of glass: it is
used in making special optical glasses, such as infra-
red-absorbing glass, as well as camera and telescope
lenses, because of the high refractive index and the low
dispersion of rare earth glass. Small amounts of lantha-
num added to steel improve its malleability.
Microelement fertilizers with lanthanum as a main
component have been used in Chinese plant produc-
tion for about 30 years to improve yield and quality. In
the general population the mean dietary intake of La
and lanthanides is estimated to be below 150 μg, which
is less than 5% of the estimated acceptable daily intake.
Lanthanum in drinking water samples is reported to
be below 10 μg/L. Lanthanum carbonate as a drug was
approved for human use by the U.S. Food and Drug
Administration in 2004 and by the European Union
in 2006 to reduce serum phosphate levels in chronic
kidney failure. For its administration to patients with
end-stage renal failure, the lanthanum salt is given
in the form of chewable tablets, at a maximal dose of
3000 mg per day. The absorption of La salts from the
gut, as well as from the lungs, of humans is negligible
Handbook on the Toxicology of Metals 4E
http://dx.doi.org/10.1016/B978-0-444-59453-2.00042-1
or very small. Few side effects have been reported after
oral intake of lanthanum carbonate as a drug. Gastro-
intestinal disturbances such as diarrhea, vomiting,
and abdominal pain may occur. Myalgia, hypoten-
sion, and occasional cases of mental confusion have
also been reported. Therapeutic administration of lan-
thanum salt will interact with the absorption of some
other drugs, since the lanthanum cation can react with
anionic forms of some compounds such as tetracy-
clines and quinolones.
1  PHYSICAL AND CHEMICAL PROPERTIES
Lanthanum, La [Chemical Abstracts Service (CAS)
number 7439-91-0] in pure form is a rather soft, silvery-
white metal, which tarnishes rapidly in air. Its atomic
weight is 138.9055; atomic number, 57; and density at
20°C, 6.17 g/cm3. The melting point of La is 920°C and
its boiling point is 3420°C. La has two stable isotopes,
138La and 139La, with natural abundances of 0.09% and
99.91%, respectively.
The chemistry of La primarily concerns the forma-
tion of the predominant +3 oxidation state. Lantha-
num oxide, La2O3 (CAS number 1312-81-8) can be
prepared directly from the element. When water is
added to La2O3 it “slakes” like lime, with the evolu-
tion of much heat and a hissing sound. Dissolution
of the oxide or hydroxide, La(OH)3 (CAS number
14507-19-8) in the appropriate acid provides the most
convenient method for producing the salts of the col-
orless, diamagnetic La3+ ions. With the exception of
lanthanum fluoride, LaF3 (CAS number 13709-38-1),
the halides are very water soluble and deliquescent.
903 Copyright © 2015 Elsevier B.V. All rights reserved.
904 Richard P. Wedeen, Balazs Berlinger, and Jan Aaseth
Lanthanum sulfate, La2(SO4)3 (CAS number 10099-60-2)
and nitrate, La(NO3)3 (CAS number 10099-59-9) are
known to exist, and they decompose to La2O3 on heat-
ing. Reaction of La with hydrogen produces highly
conducting material with the composition LaH2 (CAS
number 13823-36-4). Further H2 can be absorbed caus-
ing loss of electrical conductivity until material with
the limiting composition LaH3 (CAS number 13864-
01-2) is produced. Another example of the “divalent”
state of La, which is probably analogous to the dihy-
dride, is LaI2 (CAS number 13813-22-4) (Greenwood
and Earnshaw, 1984). Lanthanum nitrate and sulfate
are soluble, and carbonate, phosphate, and hydroxide
are insoluble in water (Möller, 1963).
2  METHODS AND PROBLEMS OF
ANALYSIS
Nowadays, inductively coupled plasma mass spec-
trometry (ICP-MS) is the analytical technique most
commonly used for the determination of lantha-
num—usually together with other rare earth elements
(REEs)—from biological samples, like human blood,
serum, or tissues (Rodushkin et al., 2000; Rodushkin
and Axelsson, 2000; Engström et al., 2004; Fujimori
et al., 1999; Inagaki and Haraguchi, 2000; Li et al.,
2001). While double-focusing sector field ICP-MS
is sensitive enough for the measurement of the very
low levels of lanthanum and REEs in these kinds of
samples (Rodushkin et al., 2000; Rodushkin and Axels-
son, 2000; Engström et al., 2004), use of the quadrupole
ICP-MS technique with a preconcentration procedure
is often required (Fujimori et al., 1999; Inagaki and
Haraguchi, 2000; Li et al., 2001). Ion chromatography
(IC) and inductively coupled plasma atomic emis-
sion spectrometry (ICP-AES) has been used for the
determination of lanthanum in biological samples
(Dybczynski et al., 2007; Qin et al., 1996), and zero and
first derivative spectrophotometry have been used
for the determination of lanthanum in human blood
serum (Chamsaz et al., 2005), but the application of the
latter techniques compared to ICP-MS is negligible.
3  PRODUCTION AND USES
3.1 Production
Lanthanum is always found together with other
REEs; taken together as a group, these elements are
often called lanthanides. REEs are relatively abundant
in the Earth’s crust, but finding them where they can
be economically mined and processed presents a chal-
lenge. World resources are contained primarily in
bastnäsite and monazite. Bastnäsite deposits in China
and the United States constitute the largest percentage
of the world’s REE economic resources, while monazite
deposits in Australia, Brazil, China, India, Malaysia,
South Africa, Sri Lanka, Thailand, and the United States
constitute the second largest segment. The Mountain
Pass rare earth mine in California was once the largest
rare earth supplier in the world. Throughout the 1990s,
however, China’s mine production grew very rapidly
and in 2009 China was believed to be responsible for
over 95% of the world’s mine production (Hedrick,
2010). The United States Geological Survey reports
that significant exploration and new mining activity
is expected from Canada and Australia (Cordier and
Hedrick, 2010). La is usually associated with lighter or
“cerium group” lanthanides in monazite, MPO4, and
bastnäsite, MCO3F (M represents La, Ce, and Nd). In
La (and lanthanides) production, the minerals are con-
centrated by processes such as flotation to increase the
lanthanide oxide content from about 7-10% to 60%. The
method of extraction depends on the particular min-
eral involved. Digestion with sulfuric acid or sodium
hydroxide and acid leaching with dilute hydrochloric
acid are used to extract the mixture of metal salts from
monazite and bastnäsite, respectively. Until around
1950, most separation of these mixtures revolved
around hundreds of tedious fractional crystallizations
of compounds like bromates, double sulfates, or dou-
ble nitrates. Ion exchange methods, a spin-off from the
Manhattan project, greatly simplified the separation:
the mixed lanthanide compounds were loaded on to a
cation exchange resin and then eluted with a suitable
complexing agent like ethylenediaminetetraacetic acid
(known as EDTA). Since the 1960s, solvent extraction
has been the favored process, employing complexing
agents like tributylphosphate or di(2-ethylhexyl)phos-
phoric acid in a covalent solvent such as kerosene.
Free La metal can be prepared by reduction of LaF3 or
lanthanum chloride (LaCl3) with metallic calcium at
1450°C in an argon atmosphere (Cotton, 1991).
3.2 Uses
China is the dominant consumer of lanthanum and
lanthanides, using the elements mainly in manufactur-
ing electronics products for domestic and export mar-
kets. Japan and the United States were the second and
third largest consumers of rare earth materials in 2009
(Cordier and Hedrick, 2010). In 2008 approximately
30% of the total amount of REEs used was lanthanum.
As REE congeners, La compounds are used as catalysts
for fluid cracking in petroleum refining and automo-
bile catalytic converters. In the glass industry, La and
other REE compounds are used as additives to glass to
 42 Lanthanum
absorb ultraviolet light; alter the refractive index and
colorizing or decolorizing; and as components of spin-
ning glass polishing powders. Lanthanum is added
in small quantities to aluminum, iron, steel, or other
host metals to improve selected physical properties of
the resulting alloys. La is added as a ferroalloy, master
alloy, mischmetal (a mix of mostly cerium and lantha-
num oxides), or as pure metal. La compounds are used
in phosphors in cathode ray tube displays, fluores-
cent lamps, and in other applications that require the
production of colored light. There is also an increas-
ing application of lanthanum in the high-technology
industry. It is added to some ceramic glazes for color
control in electronic applications, and La is used in
larger amounts in the negative electrodes of some
types of nickel-metal-hydride rechargeable batteries,
where the principal function of La is to store hydrogen.
In the rare earth-Ni battery class, the main REE used
is lanthanum or cerium, with small amounts of other
REEs (Goonan, 2011). Some lanthanum compounds are
used in water treatment. Lanthanum hydroxide can be
used for defluoridation (Na and Park, 2010) or for the
removal of arsenate from aqueous solutions (Tokunaga
et al., 1997).
Lanthanum carbonate (Fosrenol, from Shire Phar-
maceuticals) was approved for human use by the U.S.
Food and Drug Administration in 2004 and by the
European Union in 2006 to reduce serum phosphate
levels in chronic kidney failure (Finn, 2006).
4  ENVIRONMENTAL LEVELS AND
EXPOSURE
4.1  Food and Daily Intake
It is quite difficult to estimate the daily intake of
lanthanum from food because only a few studies have
reported concentrations of lanthanum and other REEs
in foodstuffs. There have been, however, some investi-
gations in China (Sun et al., 1994; Zhou and Liu, 1997;
Zhang et al., 2007; Jiang et al., 2012) in which REEs
were directly applied to plants. Microelement fertil-
izers with lanthanum and cerium as their main com-
ponents have been used in Chinese plant production
for about 30 years to improve yield and quality (Pang
et al., 2002). Based upon their performance-enhancing
properties, REEs have also been applied in animal hus-
bandry in China and they may also be of interest as
new, safe, and inexpensive performance enhancers in
Western countries (He and Rambeck, 2000; He et al.,
2001; He et al., 2010). According to a recent Chinese
study (Jiang et al., 2012), the average, median, and
90th percentile concentrations of La in cereals, fresh
vegetables, fresh aquatic products, fresh meats, and
905
eggs were 28.9, 1.1, and 28.7 μg/kg, respectively. The
dietary intake was calculated only for total rare earth
oxides (REOs). The mean dietary intake of total REOs
for an average Chinese adult was 133 μg, which was
only 3% of the estimated acceptable daily intake of
REOs. There are also few reports of investigations of
lanthanum in drinking water samples. La concentra-
tions between 8 ng/L and 8.7 μg/L were reported from
18 groundwater and two surface water stations in the
Netherlands in a Dutch study (de Boer et al., 1996). As
to the presence of La and other REEs in groundwater,
two origins were considered: (1) REEs already present
in the soil may dissolve in groundwater and (2) REEs
deposited onto the surface may migrate into ground-
water. Lower concentration levels (0.1-100 ng/L) were
found in groundwater from different Alpine aquifers
(Biddau et al., 2009).
4.2  Water, Soil, and Ambient Air
Lanthanum and other REEs were investigated in
rivers, estuaries, and costal seas in a study that deter-
mined lanthanum in the range of 20-600, 5-200, and
5-40 ng/L in different rivers, their estuaries, and costal
seas, respectively (Elderfield et al., 1990). Slightly lower
levels (3-100 ng/L) were reported by other authors in
Chinese and South Korean rivers (Han and Liu, 2007;
Ryu et al., 2007). An inverse correlation between the
concentration of both La and total RREs and pH was
found in river water (Goldstein and Jacobsen, 1988).
The same concentration levels of La were reported in
the oceans as were determined in costal seas, with an
increasing concentration profile with increasing depth
(Elderfield and Greaves, 1982; Sotto and Nozaki, 1999).
La and other REE contents in the soils of different
countries have been determined in multiple studies
(Diatloff et al., 1996; Yoshida et al., 1998; Wyttenbach
et al., 1998; Ran and Liu, 1999). The concentration of La
in Australian (Diatloff et al., 1996), Japanese (Yoshida
et al., 1998), Swiss (Wyttenbach et al., 1998), and Chi-
nese (Ran and Liu, 1999) soils varied within a range of
1-50 μg/g, quite close to the value (32 μg/g) found in
the upper continental crust (Wedepohl, 1995). La con-
centration can be increased by pollution from industry
and agriculture, usually through the addition of sew-
age sludge, mining waste, and factory effluent (Jones,
1997). Many phosphate fertilizers, if derived from apa-
tite, contain appreciable amounts of REEs; this may
influence the La concentration in soils (Wyttenbach
et al., 1998). Regarding the use of REE-containing fer-
tilizers, it has been stated by Tyler (2004) that even if
all REEs end up and remain in the soil, thousands of
years are needed to double the natural total soil pool at
the recommended rates of application. REEs supplied
906 Richard P. Wedeen, Balazs Berlinger, and Jan Aaseth
as fertilizers are, however, much more soluble and
reactive than the average soil pool and are therefore
of more environmental interest. The transfer of lantha-
num and other REEs from the soil into plant material
is usually low, but extreme accumulators have been
found, e.g. among several species of ferns (Tyler, 2004).
Lanthanum concentrations in ambient air are usu-
ally very low (0.05-30 ng/m3) even in more polluted
urban areas (Wang et al., 2000, 2001; Perez et al., 2008;
Moreno et al., 2008). Recent studies have showed that
atmospheric lanthanum and lanthanides can be used
as markers for hydrocarbon combustion emissions
(Moreno et al., 2008; Kulkarni et al., 2007) because
some compounds of these elements are used as cata-
lysts in the petroleum refinery industry.
4.3  Working Environment
Lanthanum concentrations in the workplace atmo-
sphere cannot be found in the current literature,
although some cases were reported in which lantha-
num exposure from the working environment may
have occurred (Brune et al., 1980; Gerhardson et al.,
1984, Dufresne et al., 1994; Porru et al., 2000). Increased
levels of lanthanum were found in the kidney, liver,
and lungs of exposed smelter and refinery workers
compared to concentrations in the same tissues of non-
exposed referents (Brune et al., 1980; Gerhardson et al.,
1984). High amounts of La were found in the lungs of a
printer (Dufresne et al., 1994) and a movie projectionist
(Porru et al., 2000): both were exposed to REE-contain-
ing aerosols from cored carbon arc lamps.
5  METABOLISM AND METABOLIC
INTERACTIONS
The absorption of lanthanum salts after oral intake
or inhalation is minimal or negligible.
Administered orally, lanthanum carbonate is used
as a drug (Fosrenol, Shire Pharmaceuticals) to trap
phosphate in the gut in chronic advanced renal fail-
ure. The resulting lanthanum phosphate, like other
salts of lanthanum, is poorly absorbed in the gastro-
intestinal tract and excreted in the stool, along with
small amounts in bile, and the compound is not accu-
mulated in any organ (Curran and Robinson, 2009);
these characteristics explain the ability of the drug
to reduce phosphate levels in chronic kidney failure.
End-stage renal failure is otherwise characterized by
increased serum phosphate levels (Hruska et al., 2008).
Serum phosphate concentration increases inexorably
as renal failure progresses, leading to the development
of secondary hyperparathyroidism (HPT). HPT leads
to hypercalcemia, severe bone disease (renal osteodys-
trophy), and life-threatening vascular, valvular, and
other soft tissue calcification (Goodman, 2001). Thera-
peutic lowering of serum phosphate levels above 3.5-
5.5 mg/dL is standard medical practice in advanced
renal failure because elevated phosphate levels are
associated with decreased survival (Block et al., 2004;
Kestenbaum et al., 2005; Tentori et al., 2008). Calcium
carbonate may be used to reduce phosphate levels in
chronic renal failure but has the disadvantage of some-
times causing hypercalcemia. The usual clinical substi-
tutes for calcium carbonate, i.e. lanthanum carbonate
or sevelamer, avoid the elevated calcium side effect but
are more expensive. However, it should also be taken
into account that the higher the plasma phosphate, the
more rapid is the decline in renal function (Voormolen
et al., 2007). Nevertheless, there is insufficient evidence
that treatment with phosphate binders increases sur-
vival time (Isakova et al., 2009).
Randomized clinical trials have shown that lantha-
num carbonate effectively and safely reduces serum
phosphate in patients with advanced renal failure
(Curran and Robinson, 2009; Finn, 2006; Joy and Finn,
2003; Sprague et al., 2009a; Wilson et al., 2009). Based
on the reduction in urinary excretion of phosphate,
Sprague et al. (2009b) estimated that lanthanum car-
bonate therapy reduces phosphate absorption by
one-third. A randomized, double-blind comparison
of lanthanum carbonate versus calcium carbonate
in 259 patients for 8 weeks found a similar efficacy
(Shigemetsu, 2008). A multicenter study of dialysis
patients comparing bone histomorphology following
treatment with lanthanum or calcium carbonate after
1 year showed improvements in bone structure with
lanthanum (D’Haese et al, 2003). Improvement in bone
morphology has been seen after 1 and 2 years of lan-
thanum therapy compared to standard therapy with
calcium salt in dialysis patients (Malluche et al., 2008).
In a comparison study, there was significantly less pro-
gression of aortic calcification over 18 months with
lanthanum carbonate than with calcium carbonate, as
assessed by spiral computed tomography (Toussaint
et al., 2011).
Coronary artery disease is a major cause of death in
hemodialysis patients. Elevated serum phosphate and
the associated raise in fibroblast growth factor 23 (FGF-23)
in renal failure suppresses renal 1-α-hydroxyvitamin D,
which reduces the ­conversion of 25-hydroxyvitamin D
to calcitriol (1,25-dihydroxycholecalciferol), the active
form of vitamin D (Hruska et al., 2008). The resulting
reduction in active vitamin D, in turn, reduces intestinal
calcium absorption and lowers serum c­ alcium concen­
tration, thereby stimulating the production of para-
thyroid hormone (PTH), leading to HPT. Lanthanum
 42 Lanthanum
treatment reduced FGF-23 levels in renal failure
stage 3 and increased phosphate excretion as well as
vitamin D production, thereby reducing the severity
­ bone histological morphology similar to those seen
of HPT (­Gonzalez et al., 2011). HPT promotes vascular
calcification by direct effects on smooth muscle cells
­ after long-term use of lanthanum (Brancaccio and
mediated by sodium-dependent phosphate cotrans-
porters and other genetically controlled mechanisms
(Giachelli, 2009; Finn and Joy, 2005). However, the role
of FGF-23 in HPT and renal osteodystrophy is not fully
understood (Isakova et al., 2009).
Bone deposition of lanthanum after 2 years of
treatment was low, averaging 1.9 μg/g wet weight
bone, while plasma lanthanum averaged 0.09 ng/mL
(Spasovski et al., 2006).
Many studies have indicated that reducing phos-
phate reduces PTH, which is a surrogate marker for
clinical outcomes (e.g. death, bone histomorphology,
fractures, and hospitalizations) (Spasovski et al., 2006;
D’Haese et al., 2003; Sprague et al., 2009a). In a long-
term study reported by Hutchison (2008a), PTH levels
averaging less than 408 mmol/L remained relatively
constant throughout the lanthanum salt treatment
period.
6  BIOLOGICAL MONITORING
Blood plasma concentrations have been routinely
used in biological monitoring after exposure to lan-
thanum salts. Hutchison (2008a) reported 574 mea-
surements in 93 patients given lanthanum carbonate
treatment and followed for up to 6 years; he revealed
few cases of plasma lanthanum levels above 2 ng/mL.
Only 15 samples had such raised levels, which is com-
parable to the low levels in plasma found by D’Haese
et al. (2003) and Spasovski et al. (2006).
7  EFFECTS AND DOSE-RESPONSE
RELATIONSHIPS
For use as a drug in end-stage renal failure, lantha-
num carbonate is administered in chewable 500, 750,
or 1000 mg tablets, usually three times a day (Hutchi-
son et al., 2009). In a study in healthy volunteers
funded by Shire Pharmaceutics, lanthanum carbonate
decreased phosphorus absorption in a single meal by
45% (Martin et al., 2011). Few side effects have been
reported after oral intake of lanthanum carbonate.
Gastrointestinal disturbances such as diarrhea, vom-
iting, abdominal pain, constipation, and nausea have
been noted in some cases, but dose dependency has
not been observed. A follow-up study for up to 6 years
showed no increase in adverse events on liver function
907
compared to other phosphate binders in hemodialy-
sis patients (Hutchison et al., 2009). Side effects on
with aluminum hydroxide have rarely been observed
Cozzolino, 2007). Cases of myalgia and hypotension
have been reported with lanthanum carbonate treat-
ment (Finn and Joy, 2005; Hutchison, 2008b).
Occasional case reports of mental confusion associ-
ated with lanthanum carbonate use have raised con-
cern about the possibility of adverse cerebral effects,
but these episodes are difficult to distinguish from
the array of symptoms commonly seen in end-stage
renal disease and dialysis patients (Muller et al., 2009).
Adverse effects on cerebral function observed after
long-term use of lanthanum (Altman et al., 2007) may
be related to interference of the lanthanium cation with
GABA receptors, which has been observed in experi-
mental studies (Boldyreva, 2005). Experiments pur-
porting to show cerebral effects in animals have been
met with considerable skepticism with respect to the
clinical use of sevelamer (Damment et al., 2009).
The therapeutic administration of lanthanum inter-
feres with the absorption of some other drugs because
the lanthanum cation can interact, for example, with
anionic forms of antibiotics such as tetracyclines and
quinolones. The effect of calcium channel blockers
might also be influenced by lanthanum.
A case report of inhaled lanthanum describes X-ray
dense deposits in the lungs but no discernible adverse
systemic consequences. However, the development of
pneumoconiosis has been suspected after long-term
exposure from occupational environment, although
the occurrence of such cases apparently is extremely
rare (Dufresne et al., 1994).
8  TREATMENT OF LANTHANUM
POISONING AND ITS PREVENTION
Acute poisoning from lanthanum salts is extremely
rare. However, the side effects of long-term intake in
renal failure patients might necessitate a changed treat-
ment regimen, such as choosing another phosphate
binder. In particular, the noncalcium-containing syn-
thetic polymer resin, sevelamer (Renagel and Renvela,
Genzyme Corporation) is an alternative drug to reduce
phosphate absorption. Clinical experience indicates
comparable efficacy between the phosphate binders
lanthanum and severlamer (Toussaint et al., 2011).
Thus, severlamer appears to be the drug of choice if
lanthanum is not well tolerated. There is no efficient
therapeutic chelator to remove excess lanthanum from
the body.
908 Richard P. Wedeen, Balazs Berlinger, and Jan Aaseth
Drugs other than lanthanum or severlamer medi-
cation can also be used to control hyperparathyroid-
ism (HPT) in renal failure. Whereas dietary phosphate
restriction (Shineberger et al., 2008) and dialysis
removal of phosphate is insufficient to prevent hyper-
phosphatemia, the administration of vitamin D or its
analogs, metabolites, or precursors raises serum cal-
cium levels and suppresses PTH. The calcimimetic
agent, cinacalcet (Sensipar, Amgen), also blocks PTH
production at the parathyroid gland calcium receptor
level.
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