C H A P T E R
40
Iridium
IVO IAVICOLI AND VERUSCKA LESO
ABSTRACT
Iridium (Ir) belongs to the platinum group elements
and is one of the rarest elements in the Earth’s crust.
Since Ir is a hard metal with good resistance to corro-
sion, it is widely used in the electronic, chemical, and
automotive industries. In the latter sector, Ir is pres-
ent as an impurity or is found in alloys together with
platinum, palladium, and rhodium in automobile cata-
lytic converters. These devices are continuously sub-
jected to physical and chemical stress that leads to Ir
release in airborne particulate matter and a consequent
increase in metal levels in the general environment.
Current data relating to environmental Ir concen-
trations in air, soil, roadside dust, water, and foods
indicate quite low levels that are not thought to pose a
serious threat to human health. However, the increase
in general exposure levels and the widespread indus-
trial use of this metal have raised concern in the sci-
entific community regarding potential adverse health
effects for the general and occupationally exposed
populations.
Limited knowledge of the toxicological mechanisms
of Ir in different physical and biological systems pre-
vents researchers from making a correct evaluation
of the risks derived from exposure to this metal and
also from reaching definite conclusions regarding the
potential adverse effects of low-“dose,” long-term
exposures.
Recently, the in vitro cytotoxic and genotoxic poten-
tial of Ir, mediated by oxidative stress reactions and the
induction of direct DNA damage, was demonstrated in
rat fibroblasts. Interestingly, in vivo results showed that
oral Ir exposure in rats induced nephrotoxic effects, as
Handbook on the Toxicology of Metals 4E
http://dx.doi.org/10.1016/B978-0-444-59453-2.00040-8
indicated by increased levels in a series of urinary pro-
teins and an immunological imbalance with a skew
toward a T helper 2 (Th2) cytokine pattern. Hypersen-
sitivity and allergic reactions were described in occu-
pationally and nonoccupationally exposed subjects
with symptoms including rhinorrhea, asthma, contact
dermatitis, and urticaria, indicating the sensitizing
potential of Ir, albeit at a relatively low level.
Overall, little is known of the toxicological charac-
teristics of Ir and further research is needed to define
its potentially hazardous properties and their princi-
pal toxicological mechanisms so that an appropriate
evaluation and management of Ir risk can be made
with regard to the general and occupationally exposed
populations.
1  PHYSICAL AND CHEMICAL PROPERTIES
Iridium (Ir); Chemical Abstracts Service number,
7439-88-5; atomic mass, 192.2; atomic number, 77; den-
sity at 20°C, 22.4 g/cm3; melting point, 2446°C; boiling
point, 4428°C; modulus of elasticity, E, 516 × 103 MN/
m2; modulus of rigidity, G, 210 × 103 MN/m2; silver-
white metal; oxidation states, from −3 to +6, most com-
mon oxidation states are +3 and +4; natural and stable
isotopes, 191Ir and 193Ir (Hunt, 1987; Royal Society of
Chemistry, 2013).
Ir belongs to the platinum group elements (PGEs).
Discovered by Smithson Tennant in 1803 among
insoluble impurities in natural platinum (Pt), this
metal was named iridium after the goddess Iris, the
personification of the rainbow, because of the strik-
ing and diverse colors of its salts (Argonne National
855 Copyright © 2015 Elsevier B.V. All rights reserved.
856 Ivo Iavicoli and Veruscka Leso
Laboratory, 2005). Ir is the second densest element
after osmium (Os), and is the most corrosion-resistant
metal. It is insoluble in all mineral acids including
aqua regia and is not attacked by other molten met-
als or by silicates at high temperatures. Ir has a very
high melting point and is the only metal to maintain
good mechanical properties in air at temperatures
above 1600°C (Hunt, 1987; Emsley, 2003). It can, how-
ever, be attacked by some molten salts such as sodium
cyanide and potassium cyanide (Emsley, 2003), as well
as by oxygen and the halogens at higher temperatures
(Lagowski, 2004). Since Ir is not only extremely hard,
brittle, very stiff, and resistant to deformation but also
has low ductility and a very high melting point, the
solid metal is difficult to machine, shape, or work. For
this reason, Ir is commonly employed in powder form
(Greenwood and Earnshaw, 1997). Ir has a very high
boiling point—the tenth highest of all elements—and
becomes a superconductor at temperatures below
0.14K (Kittel, 2004). Ir forms compounds in oxida-
tion states between −3 and +6. Hexachloroiridic(IV)
acid (H2IrCl6) and its ammonium salt are the most
important Ir compounds used in industry (Crabtree,
1979). Ir trichloride (IrCl3) is often used as a starting
material for the synthesis of other Ir(III) compounds
(Greenwood and Earnshaw, 1997). Organoiridium
compounds contain Ir-carbon bonds, where the metal
is usually in lower oxidation states (Greenwood and
Earnshaw, 1997). 191Ir and 193Ir are the only two natu-
rally occurring stable isotopes (Audi, 2003). At least 34
radioisotopes have also been synthesized, ranging in
mass number from 164 to 199. 192Ir, which falls between
the two stable isotopes, is the most stable radioisotope
with a half-life of 74 days. It decays by beta emissions
to stable 192Pt and 192Os. It is used in brachytherapy
(Stellman, 1998) and industrial radiography, and 192Ir
sources have been responsible for a number of radio-
logical accidents. 192Ir metastable isomer (192m Ir) has
a half-life of 240 years, and decays to 192Ir by isomeric
transition and by relatively low-energy gamma emis-
sion (Argonne National Laboratory, 2005).
2  ANALYSIS: METHODS AND PROBLEMS
The presence of Ir in the environment is currently
the subject of great interest (Locatelli, 2011). From a
geological point of view, PGEs have been significant
tracers for decoding the Earth’s late accretional his-
tory (Morgan et al., 2001) and deep mantle processes
(Puchtel et al., 2004), and for assessing the contribution
of impact materials in the breccias from impact craters
(Koeberl and Reimold, 2003; Shinotsuka and Suzuki,
2007). Moreover, more and more frequently in the
2000s, Ir has been alloyed (10-20% w/w) with Pt, pal-
ladium (Pd), and rhodium (Rh) in the manufacture of
autocatalytic converters. The compulsory use of these
devices has led to an increase in Ir concentrations in the
environment (Locatelli, 2011). In fact, during the release
of exhaust gases from the engine, the surface of the cata-
lyzer washcoat is chemically and physically stressed by
rapidly changing oxidative/reductive conditions, high
temperature, and mechanical abrasion. This results
in the emission of particulate matter (PM) containing
PGEs (Ravindra et al., 2004).
Recently, several papers have reported analytical
procedures for determining Ir levels in environmental
matrices. Researchers have mainly used spectroscopic
techniques (Rao and Reddi, 2000; Ely et al., 2001; Meisel
et al., 2001, 2003; Pretorius et al., 2003; Djingova et al.,
2003a,b; Fritsche and Meisel, 2004; Petrucci et al., 2004;
Cristaudo et al., 2007), whereas less frequent use has
been made of neutron activation analysis (NAA) (Dai
et al., 2001; Takeda et al., 2007) and chromatography
(Sánchez et al., 2000; Sommer and Vlasankova, 2000;
Wang et al., 1999; Locatelli, 2011). Regardless of the
analytical method used, the general difficulty in deter-
mining PGEs, including Ir, is due to low concentrations
(especially background ones) and the lack of reference
materials (RMs) for quality control (Balcerzak, 1997,
2011; Barefoot, 1997; Schramel et al., 2000; Djingova
et al., 2003a). Most available RMs consist of different
types of minerals in which the concentrations of Ir are
considerably higher than in environmental materials
(e.g. all CANMET-CCRM PGE RMs TDB-1, UMT-1,
WGB-1, WMG-1, and WPR-1). Furthermore, the matrix
composition and the PGE forms can differ significantly
(Schramel et al., 2000; Meisel and Moser, 2004). Thus,
the methods validated against these RMs may not nec-
essarily provide reliable data in the case of road dust,
soils, sediments, and plants.
Sample preparation for PGE analysis varies accord-
ing to the method and material used. For example,
classic silicate analysis with HF and HClO4, and alkali
fusion, widely used for geological and pedologi-
cal samples (Balcerzak, 1997; Djingova et al., 2003a),
require larger samples, are very time-consuming, are
prone to either loss or contamination of samples, and
depend on the analytical skill of researchers (Jarvis
et al., 1997; Totland et al., 1993, 1995). They are there-
fore not very well suited for environmental analysis.
Inductively coupled plasma quadrupole mass
spectrometry (Q-ICP-MS) is one of the most promis-
ing techniques for PGE determination at trace levels
(Balcerzak, 1997; Barefoot, 1997). Using this technique,
Djingova et al. (2003a,b) reported a detection limit
(3σ criterion) of 0.015 ng/g for 191Ir. However, a very
serious problem in this case is the spectral overlap of
 40 Iridium
177Hf16O+ and 175Lu16O+ ions with 193Ir and 191Ir iso-
topes, respectively. These interferences may also be
totally different depending on the matrix, the equip-
ment, and the measurement conditions, and underlines
the idea that validation of a method using only one
type of material does not automatically mean that the
procedure is correct. Ir analysis should be done using
191Ir; in fact, the error introduced by the spectral over-
lap of HfO+ on 193Ir is too high (Djingova et al., 2003a).
This method provides reliable determination of PGEs
in many environmental matrices. Although isotope
dilution (ID)-ICP-MS, high resolution (HR)-ICP-MS,
and sector field (SF)-ICP-MS are deemed to be more
efficient than Q-ICP-MS in determining PGEs, they are
subject to the same interferences and are also much
more expensive. To overcome these interferences, off-
or on-line matrix separation is usually done with ID-
ICP-MS (Müller and Heumann, 2000; Köllensperger
et al., 2000). In the case of HR-ICP-MS, resolutions of
over 10,000 are sometimes necessary in order to elimi-
nate interferences (Müller and Heumann, 2000).
For voltammetric determinations, prevalence is
given to high-pressure ashing with nitric and hydro-
chloric acid because this destroys any organic mate-
rial in the samples (Balcerzak, 1997; Barefoot, 1997).
Although voltammetric measurement is seldom used
(Ezerskaya and Kiseleva, 2001; Svancara et al., 2007),
it is nevertheless a valid and simple analytical tech-
nique that is suitable for multicomponent metal deter-
minations and ultratrace Ir measurements in complex
matrices (Baur and Spaine, 1998; Bobrowski and
Zarebski, 2000; Zaitsev et al., 1999; Locatelli, 2011).
Very low limits of detection can be obtained using this
technique because it is precise, accurate, and offers a
high degree of selectivity and sensitivity. Voltammetry
can also be a good alternative to spectroscopy due to
its lower running costs and the less costly equipment
needed to measure very low metal concentrations
(Locatelli, 2011).
To assess human exposure to Ir and study cor-
relations with possible health effects, it is important
to measure Ir in body fluids such as blood and other
biological matrices (Begerow et al., 1997). Powerful
and reliable analytical procedures are needed to mea-
sure extremely low concentrations of precious metal
samples in such complex matrices. Several analytical
methods such as NAA (Minoia et al., 1990), SF-ICP-
MS (Begerow et al., 1997; Rodushkin and Odman,
2001; Petrucci et al., 2004; Cristaudo et al., 2007), and
Q-ICP-MS (Petrucci et al., 2004; Cristaudo et al., 2007)
have been used to perform quantitative analyses of
biological matrices. SF-ICP-MS is a powerful tech-
nique for the ultratrace analysis of human body flu-
ids because it offers high sensitivity, a larger dynamic
857
range, and the possibility of a rapid multielement anal-
ysis accompanied by excellent lower detection limits
(Bocca et al., 2010a,b). Moreover, for noninterfered
isotopes, SF-ICP-MS yields far better detection lim-
its than quadrupole instruments when a comparable
sample introduction system is used (Moens et al., 1995;
Begerow et al., 1996). For complex matrices such as
blood, the removal of organic sample matrix and dilu-
tion to reduce the content of total dissolved solids are
recommended to avoid carbon deposition that could
result in blockage of the sampling cone and severe sig-
nal instability (Begerow et al., 1997). Strong mineral
acids are frequently utilized for matrix decomposi-
tion. However, this digestion technique could result
in solutions containing relatively high acid concentra-
tions that are not tolerated when using conventional
pneumatic nebulizers for sample introduction. For
urine and serum digestion, ultraviolet (UV) photoly-
sis has been found to be more advantageous than con-
ventional mineral acid digestion techniques (Begerow
et al., 1996; Ensslin et al., 1994). Since reagent addition
is minimal, blank values can be kept extremely low,
and compared to digestion by mineral acids, a large
dilution of the sample solution is not strictly necessary.
When applied on blood (Begerow et al., 1997), UV pho-
tolysis and magnetic SF-ICP-MS yielded an 193Ir practi-
cal detection limit of 0.03 ng/L, which is comparable to
the value determined by means of adsorptive voltam-
metry and lower than that obtained by Q-ICP-MS. Nev-
ertheless, such sophisticated instrumentation does not
necessarily guarantee high-quality data. Current rec-
ommendations underline the importance of develop-
ing a validated procedure that includes an uncertainty
estimate expressing the range of values within which
the true value is deemed to lie (ISO, 2005; Thompson
and Wood, 1995; Thompson et al., 2002; Bocca et al.,
2010b). Unfortunately, researchers often neglect vali-
dation and uncertainty estimation, possibly because it
is difficult to apply a rigorous mathematical model due
to variability in test matrices, the complexity of ana-
lytical methods, the lack of certified RMs guaranteeing
the traceability of measurements, the high instrument
costs, and the need for qualified and trained personnel
(Bocca et al., 2010b).
3  PRODUCTION AND USES
3.1 Production
With an average concentration of 0.05 ng/g in the
continental crust, Ir is one of the least abundant ele-
ments in the Earth’s crust (Wedepohl, 1995). It is
thought that the overall concentration of Ir on Earth
858 Ivo Iavicoli and Veruscka Leso
is much higher than that observed in crustal rocks
but, because of its density and siderophilic character,
Ir descended below the crust and into the Earth’s core
when the planet was still molten (Renner et al., 2002). Ir
is found in nature as an uncombined element. The most
dominant species are Ir4+ and Ir3+ (the latter is usually
found in soluble form), or those in natural alloys, espe-
cially the Ir-Os alloys, but it is also found in raw nickel
or raw copper (Emsley, 2003; Xiao and Laplante, 2004;
Martín-Peinado and Rodríguez-Tovar, 2010). In seawa-
ter, the commonest Ir species are the oxy-hydroxyl and
chloro-complex ion forms (Dai et al., 2000a,b).
The highest concentrations of Ir within the Earth’s
crust are found in igneous deposits and impact cra-
ters. The largest known primary deposits are in the
Bushveld Igneous Complex in South Africa (Seymour
and O’Farrelly, 2001), although the large copper (Cu)-
nickel (Ni) deposits near Norilsk in Russia and the
Sudbury Basin in Canada are also significant sources
of Ir. Smaller deposits are found in the United States
(Seymour and O’Farrelly, 2001). Ir is also found com-
bined with PGEs in secondary alluvial deposits. Mined
production of Ir declined in 2011 in accordance with
lower mined Pt output in South Africa. Industrial pur-
chases of Ir exceeded primary mined supply and metal
was drawn from above-ground stocks in order to bal-
ance the market (Johnson Matthey Publications, 2012).
Ir is obtained commercially as a by-product from Ni
and Cu mining and processing. Noble metals such as
silver, gold, and the PGEs settle during electrorefin-
ing of copper and nickel (George, 2006, 2008). Subse-
quently, the metals are brought into solution by fusion
with sodium peroxide followed by dissolution in aqua
regia or by dissolution in a mixture of chlorine with
hydrochloric acid to be separated (Renner et al., 2002;
Seymour and O’Farrelly, 2001). Ir is separated from the
other PGEs by precipitating (NH4)2IrCl6 or by extract-
ing IrCl62− with organic amines (George, 2006, 2008).
3.2 Uses
The principal use of Ir is as a hardening agent in Pt
alloys. Ir, and especially Ir-Pt or Os-Ir alloys, are hard-
wearing and are used, for example, for multipored
spinnerets, through which a plastic polymer melt is
extruded to form fibers such as rayon (Egorova et al.,
1979). Os-Ir alloys are used for tipping fountain pen
nibs and for compass bearings (Emsley, 2003; Handley,
1986; Stallforth and Revell, 2000). Because of its corro-
sion resistance, an Ir alloy is used for certain long-life
aircraft engine parts, and deep-water pipes are made
from an Ir-titanium alloy (Emsley, 2003). Ir compounds
are used as catalysts in the carbonylation of methanol
to produce acetic acid (Cheung et al., 2000) and in the
electrocatalytic hydrogenation of organic compounds
(Hindle et al., 2005; Andersson, 2011; Diéguez et al.,
2012). Moreover, Ir was recently introduced in the
autocatalyst sector as the so-called ‘DeNOx’ cataly-
sator in order to drastically reduce NOx emission in
the exhausts of lean burning engines (Emsley, 2003;
Ravindra et al., 2004).
Nowadays, demand for Ir comes mainly from the
electronic, automotive, and chemical industry. In 2010,
there was a quadruple increase in Ir demand that
suddenly and rapidly rose to 9469 kg compared to
the 2296 kg of the previous year. The extra 7173 kg of
demand came mainly from the electrical sector (Johnson
Matthey Publications, 2011), where Ir is principally used
in the manufacture of crucibles utilized for growing sin-
gle crystal sapphire, which is the substrate for gallium
nitride, the inorganic semiconductor material used to
make blue and green light-emitting diodes for TV and
the smartphone and tablet computer markets. Ir has
good properties for this application, including a high
melting point and resistance to chemical attack (Johnson
Matthey Publications, 2012). The refitting of the Chinese
chloralkali industry generated additional demand for Ir.
Growth in the worldwide automotive sector in 2010 also
led to increased demand for Ir-tipped spark plugs.
In 2011, total demand for Ir was 8533 kg, with the
electronic sector accounting for 4678 kg, 18% less than in
2010, but still over half of total global purchasing of the
metal. Interestingly, in 2011, some Ir was purchased for
use as phosphorescent emitter materials in organic light-
emitting diodes, suggesting a future use for Ir in display
technology. Ir continues to be used widely in electrodes
for high-performance spark plugs in the automotive sec-
tor and also in the medical sector in the Pt-Ir alloys of
devices designed to be implanted in the human body
(Johnson Matthey Publications, 2012).
4  ENVIRONMENTAL LEVELS AND
EXPOSURE
4.1  Iridium Levels in Geological Samples
Since the mid-1990s, we have seen a dramatic
increase in the quantity of data available on PGE con-
centrations in different types of geological materials.
This is largely due to the development of analytical
equipment capable of detecting PGEs at the range
found in most rocks, i.e. 0.1-10 ng/g (Barnes et al.,
1985; McDonald, 1998). Moreover, since PGE concen-
trations and the distribution of these metals in rocks
are important tracers of mantle processes and extrater-
restrial input into the crustal environment, PGE data
have been used in some high profile studies, notably
 40 Iridium
the debate over events at the Cretaceous-Tertiary (K-T)
boundary (Alvarez et al., 1980; Tredoux et al., 1989;
Evans et al., 1993a; McDonald, 1998).
Average PGE concentrations in oceanic basalts dif-
fer greatly from those in rocks from different tectonic
environments (Crocket, 2000). Surveys indicate that
mid-ocean ridge basalt (MORB) is much lower in PGE
content than basalt from intraplate environments,
especially those associated with plume or hotspot vol-
canism (Crocket, 1981; Barnes et al., 1988; Greenough
and Fryer, 1991). Ir is approximately six times higher
in intraplate basalt (Crocket, 1981), with averages of
0.06 and 0.36 ng/g in MORB and ocean island basalt,
respectively. The same group (Crocket, 2000) investi-
gated the Ir content in fresh unaltered tholeiite basalt
collected from the Kilauea Volcano, Hawaii, showing a
mean (±SD) level of 0.38 ± 0.14 ng/g. When compared
to basalts subjected to hydrothermal alteration, minor
changes in Ir concentrations were detected, suggest-
ing that the metal was relatively inert to alteration
processes and stable in the primary host phase. Con-
versely, high-temperature sulfate-dominated conden-
sates generated incrustations 50 times enriched in Ir,
with concentrations ranging from 10.7 to 30.7 ng/g.
The same study (Crocket, 2000) reported that most of
the Ir in fresh rocks was hosted by chromite. This find-
ing was also confirmed in other investigations carried
out on chromite layers from El Tigre, San Cristobal, and
Juan mines, Vizcaino Peninsula, Baja California Sur,
Mexico (Vatin-Perignon et al., 2000). These deposits,
belonging to the lower > 600 m lithostratigraphic zone,
had the highest absolute Ir abundance, with concen-
trations ranging from 97 to 557 ng/g. Analysis of the
other silicate rocks from the upper zones showed prac-
tically no Ir content, with a maximum concentration
of 2.51 ng/g, suggesting that precipitation of the metal
occurred during the earliest stages of fractional crys-
tallization and was concentrated in chromitites. Singh
et al. (2013), comparably, found a greater Ir content
in chromitites (9.8-84.4 ng/g) than in peridotites (2.2-
4.0 ng/g) of the Manipur Ophiolitic Complex, which
is part of the Indo-Myanmar Orogenic Belt, Northeast
India. Interestingly, the Ir distribution pattern in chro-
mitites showed enrichment of the metal in the high-
chromium (Cr) samples (22.8-84.4 ng/g) compared to
the high-aluminum ones (9.8-30.8 ng/g), suggesting
that differences in the chemistry of magma involved in
chromitite formation could influence the nonhomoge-
nous Ir distribution. Some researchers have suggested
that the PGE enrichments in chromitites are largely
driven by mechanical processes such as the formation
of clusters where PGEs preferably bond with other
metals (Tredoux et al., 1995; Fiorentini et al., 2004),
while, according to other researchers, PGEs primarily
859
form platinum group minerals on which chromite
grains nucleate and grow (Brenan and Andrews, 2001;
Sattari et al., 2002; Fiorentini et al., 2004).
However, in this context, the discrepancy between
experimental studies in the literature could be due
to an overestimation of the partition coefficients for
PGEs between silicate melts and Cr spinels (Pagé et al.,
2012). In situ analysis of Cr spinels from the Merensky
Reef, a sulfide-bearing, PGE-rich cumulate horizon in
the upper critical zone of the Bushveld Igneous Com-
plex, South Africa (Ballhaus and Sylvester, 2000), and
the evaluation of the komatiitic basalts, ferropicritic
basalts, and tholeiitic basalt from the Abitibi greenstone
belt, Canada (Fiorentini et al., 2004), failed to reveal
detectable Ir concentrations. Ir analysis of chromites
from Ni sulfide mineralized and unmineralized kom-
atiite flows in the Archaean Agnew-Wiluna greenstone
belt in the Yilgarn Craton, Western Australia, showed
levels ranging from 0.75 to 7.21 ng/g (Fiorentini et al.,
2004). Pagé et al. (2012) reported Ir levels of ∼20 ng/g
in Cr spinels from komatiites collected from the south
of the Main Alexo Mine, northern Ontario, Canada.
Park et al. (2012) found an Ir abundance of ∼10 ng/g in
Cr spinels from the reduced Jimberlana layered intru-
sion, Western Australia, while higher Ir contents, rang-
ing from 13 ± 15 to 104 ± 76 ng/g, were detected in Cr
spinels from the oxidized lavas of the Ambae Volcano,
Vanuatu, southwestern Pacific. This interesting find-
ing suggests that Ir was highly compatible in Cr spinel
when crystallized under oxidized conditions.
In the Yilgarn Craton region, Barnes et al. (2012)
found Ir levels ranging from 6.7 to 20.4 ng/g in a 250-m
continuous drill core of the Mount Keith magmatic sul-
fide-hosted Ni ore body. PGEs are important constitu-
ents of magmatic sulfide ores and their concentrations
are useful indicators of ore-forming processes. When
different chemostratigraphic zones were analyzed, the
uppermost zone with the lowest Ni level (1500 ppm)
was found to have a declining sulfur and PGE content
with a very low Ir content. This could be due to wan-
ing of the magma flux and temperature in the upper-
most zones responsible for the gradual decrease in the
rate of accumulation of cumulus sulfide liquid and a
progressive decrease in Ni and PGE tenors.
The Deccan flood volcanism of India has generated
interest in the influence that PGE geochemistry has
had on terminal Cretaceous extinctions. Rocchia et al.
(1988) found the Ir content in basalt or interflow ash
beds or boles to be below the detection limit of the ana-
lytical method employed (0.04-0.3 ng/g). A set of 18
flow and dyke basalt samples subsequently collected
in the same region showed an average (±SD) Ir concen-
tration of 0.065 ± 0.12 ng/g with a small subset of these
samples (n = 4) demonstrating a positive skew of the Ir
860 Ivo Iavicoli and Veruscka Leso
distribution with a mean value of 0.24 ng/g (Crocket
and Paul, 2004). The highest Ir group samples were
characterized by a higher proportion of Cr relative to
Ni and magnesium oxide (MgO). This observation and
the occasional occurrence of chromite inclusions in
some of these samples confirmed that chromite was a
sink for Ir. Interestingly, a strong positive Ir correlation
with MgO was detected, suggesting a possible relation
between Ir levels and the fractional crystallization of
basic magma, as was subsequently confirmed (Jamais
et al., 2008). In this latter study, Ir concentrations were
determined in fractionated lavas erupted during two
stages of volcanic activity, named the Pololu (455-
260 ka old) and Hawi (232-62 ka old) volcanics, after the
Kohala Volcano, Hawaii. The metal levels ranged from
0.003 to 0.213 ng/g in Pololu basalts, where more prim-
itive lavas (> 8 wt% MgO) showed a rather constant Ir
abundance, while the metal content decreased rapidly
with increasing fractional crystallization in lavas with
< 8 wt% MgO. An Ir concentration of 0.003 ng/g was
found in the highly differentiated Hawi lavas.
Ir content was also investigated in the mafic igne-
ous alkaline rocks from the Kutch region, Gujarat, of
the Deccan Volcanic Province. These represented the
earliest phases of the Deccan volcanic activity (Crocket
and Paul, 2008). Compared to the tholeiites, a substan-
tially lower PGE level was found in the alkaline rocks,
with significantly different Ir PGE (including Ir and
ruthenium) proportion compared to the other PGEs. In
fact, Ir PGEs accounted for 17% of the total PGEs in the
alkaline rocks and only 1% of the PGEs in tholeiites.
For flood basalts in general, Pd:Ir ratios correlate posi-
tively with Mg, confirming that PGEs are governed to
some extent by processes such as fractional crystalli-
zation that control major element composition. When
Dai et al. (2001) measured Ir content in impact breccias
and target rocks from the Lake Bosumtwi impact crater
in Ghana using NAA and the ultrasonic nebulization-
ICP-MS analytical techniques, they found comparable
levels that ranged from 0.29 to 3.7 and from 0.15 to
1.9 ng/g, respectively.
Anbar et al. (2001) measured extremely low Ir con-
centrations, < 3 × 10−12 g/g rock powder, in metasedi-
ments older than 3.8 Gyr sampled from Akilia Island,
southern West Greenland, resembling a geochrono-
logical period of heavy terrestrial mass bombardment.
These concentrations were well below those predicted
from mixing terrigenous sediments and extraterrestrial
material contributions, suggesting that metasediments
contained negligible Ir contributions from the weather-
ing of emergent landforms or their sedimentary detri-
tus. Moreover, low Ir levels could be a consequence of
undersampling the extraterrestrial contribution due to
the rapid accumulation of sediments.
Considerable research has also been carried out
on the geochemical behavior of PGEs in laterites (e.g.
Bowles et al., 1994; Traoré et al., 2006; Cornelius et al.,
2008; Ndjigui, 2008; Ndjigui et al., 2008). When ana-
lyzed in serpentinite samples collected in the Kongo-
Nkamouna ultramafic massif, Lomié region, Southeast
Cameroon, a low Ir content was found ranging from
4.83 to 5.00 ng/g. Interestingly, the weathering pro-
files located in the southern (Nkamouna), the middle
(Napene), and the northern (West and East Mada) part
of the massif indicated that Ir content increased with
depth as concentrations ranged from 5.52 to 41, 10.9 to
34, and 5 to 17 ng/g, respectively (Ndjigui and Bilong,
2010). Higher levels were always found in the deeper
saprolite zone, supporting the theory of permanent Ir
enrichment due to the weathering process or to copre-
cipitation of Ir-rich alloys with iron and manganese
oxides (Wimpenny et al., 2007). The low Ir content
in the upper part of the lateritic profiles might be the
result either of late neoformation of Ir-bearing minerals
within the laterites or of their dissolution in laterites.
4.2  Iridium Levels in Air
An initial study to investigate Ir levels in the atmo-
sphere was conducted by Tuncel and Zoller (1987). The
authors analyzed Ir concentrations in 30 atmospheric
particulate samples collected at the geographical South
Pole in 1979. Ir concentration ranged from 2 × 10−17 to
13.4 × 10−17 g/m3 and was higher during the austral
summer than in winter, with average concentrations of
9.1 × 10−17 and 7.2 × 10−17 g/m3, respectively. A strong
correlation was reported between Ir concentrations
and beryllium-7 (7Be) activity in the South Pole atmo-
sphere. On the basis of this correlation and 7Be produc-
tion in the stratosphere due to the interaction of cosmic
rays with atmospheric nitrogen, Tuncel and Zoller
(1987) hypothesized the existence of a stratospheric
source of Ir (possibly extraterrestrial material). Earlier
studies at the South Pole had demonstrated that the
flux of crustal dust is one-to-two orders of magnitude
less than a similar flux at midlatitudes, thus reduc-
ing the contribution of terrestrial Ir to the atmosphere
(Cunningham and Zoller, 1981).
Although it has been suggested, that the use of Ir
in the most recent catalytic converters produces an
increase in the atmospheric levels of this element,
especially in high-density vehicle traffic areas, only a
few studies have investigated environmental Ir pol-
lution (Rauch et al., 2006; Botrè et al., 2007; Iavicoli
et al., 2008). The first study (Rauch et al., 2006) mea-
sured Ir concentrations in airborne PM with a mean
diameter of 10 μm (PM10) that was collected in the
Mexico City Metropolitan Area (MCMA). The aim of
 40 Iridium
the authors was to ascertain the eventual variations
in Ir airborne concentrations over time between 1991,
the year in which catalysts became compulsory in new
vehicles in Mexico City, and 2003. No evidence of an
increasing trend was found for this element between
1991 and 2003; in fact, average airborne concentrations
remained in the same order of magnitude—0.010 pg/
m3 in 1991 and 0.07 pg/m3 in 2003. Concentrations rel-
ative to sampled PM10 mass also remained relatively
constant, with a mean Ir level of 0.13 ng/g in 1991
and 0.5 ng/g in 2003. These results contrast with the
increasing trend detected for other PGEs such as Pt,
Pd, and Rh over the same period. The lack of a clear
temporal trend for this element compared to the other
PGEs could be due to the small amount of Ir used in
catalysts, and the use of Ir-containing devices in a non-
significant fraction of the vehicle fleet. Furthermore, no
spatial variability in Ir levels was demonstrated when
an evaluation was made of Ir concentration in PM10
samples collected in 2003 from five different sites in
the MCMA. Results showed a mean (±SD) airborne
Ir concentration of 0.08 ± 0.05 pg/m3 and an average
(±SD) concentration relative to sampled PM10 mass of
1.3 ± 0.8 ng/g. This result is probably due to the lim-
ited dataset, day-to-day variations, and PM10 particle
dispersion. It raises some questions about the potential
catalytic source of Ir contamination because areas of
medium traffic density have Ir levels that are compa-
rable to those with higher vehicle density. It therefore
seems necessary to investigate how (1) Ir mobility in
PM10 particles due to wind patterns and (2) possible
regional industrial emissions and volcanic activity can
influence air Ir concentration.
Higher levels of Ir contamination were detected
during PM10 environmental monitoring performed by
Botrè et al. (2007) in two heavy traffic sites of Rome
in the winter months between 2004 and 2005. Ir con-
centrations ranged from 0.28 to 3.73 pg/m3, with an
average (±SD) level of 0.85 ± 0.59 pg/m3. Comparable
results were obtained in a subsequent study that eval-
uated Ir levels in the total suspended particle (TSP),
PM10, and PM2.5 fractions sampled inside a tram run-
ning along Rome city streets with medium-high traf-
fic during the first week of November 2005 (Iavicoli
et al., 2008). Airborne collection was performed close
to the seat of the tram driver and lasted about 6 h per
day in order to obtain a good estimate of Ir exposure
during the work shift. Samplings were also carried
out close to the open window of the driver cabin so
as to collect information on outdoor Ir pollution in the
urban air. Mean (±SD) Ir levels were 1.43 ± 1.66 pg/m3
in TSP, 0.44 ± 0.27 pg/m3 in PM10, and 0.36 ± 0.19 pg/m3
in PM2.5. Since authorities such as the Occupational
Safety and Health Administration, the National
861
Institute for Occupational Safety and Health, and the
Deutsche Forschungsgemeinshaft (German Research
Foundation) have not yet established threshold values
for airborne Ir, no clear interpretation of these findings
can be made. This study also detected typical Ir dis-
tribution in the particulate fraction: in fact, about 30%
of the total amount of the metal was bound to parti-
cles < 10 μm diameter, with about 80% of this portion
found in the fraction < 2.5 μm. Only a small percentage
seemed to be associated with particles between 2.5 and
10 μm. These data are of great importance on account
of the potentially greater toxicity of the finest particles,
which can easily penetrate the deeper part of the respi-
ratory tract. Unfortunately, this phenomenon is not yet
fully understood and no comparisons can be made due
to a lack of data in the literature. In fact, there is a need
for further research into the Ir content in finer fractions
so that a better assessment can be made of the poten-
tial risks of respiratory exposure and so that air quality
policy can be adapted to regulate and monitor increas-
ingly smaller airborne PM size fractions (Iavicoli et al.,
2008; Wiseman and Zereini, 2009).
Only two studies have monitored Ir concentration
in indoor airborne PM10 sampled in the same indus-
trial plant engaged in the production and recycling
of PGEs (Petrucci et al., 2004; Cristaudo et al., 2007).
Ir concentrations were detected in different sectors of
the plant, including the salt and solution department
(SSD), the chemical and catalyst department (CCD),
the coating department (CD), and the recycling depart-
ment (RD). Values of 2 × 10−3, 0.6 × 10−4, 0.7 × 10−4, and
0.9 × 10−4 μg/m3 were reported in the aforementioned
departments, respectively. These data were compared
with values of 0.5 × 10−4 μg/m3 in the administrative
service (AS) and of 6 × 10−6 μg/m3 in sites away from
the plant, used as control areas (Petrucci et al., 2004;
Cristaudo et al., 2007). When assessed by means of per-
sonal sampler devices, Ir exposure levels were 2 × 10−3,
0.2 × 10−3, 0.8 × 10−3, 1.0 × 10−3, and 0.06 × 10−3 μg/m3
in the SSD, CD, CCD, RD, and in AS, respectively
(Cristaudo et al., 2007). In all sites investigated, the
levels of Ir were very low because this element is very
rarely used in production processes. However, Ir level
in indoor production sectors were higher than in areas
assumed to be unexposed. Even if it is difficult to com-
pare data resulting from indoor and outdoor airborne
monitoring, it should be noted that indoor environ-
mental Ir concentration is greater than in an external
environment (Rauch et al., 2006; Botrè et al., 2007;
Iavicoli et al., 2008). Surprisingly, the highest Ir concen-
tration was detected in the SSD, where all processes are
completed in a closed reactor and the dissolved PGEs
are transferred to other departments by means of pipes.
This suggests that although all equipment is effectively
862 Ivo Iavicoli and Veruscka Leso
fitted with hoods and extraction vents and the oven
plant is self-contained, aerosols and dust powder are
nevertheless able to spread in the indoor environment.
This could be an interesting point to investigate in
future research in order to clarify the health risk for
occupationally exposed subjects.
In conclusion, there are only limited data on air-
borne Ir pollution in the literature. In the studies
reviewed, there are few attempts at evaluating the
level of a “new kind” of air contamination resulting
from the relatively recent introduction of Ir as a cata-
lyzing agent in converters. Although the studies differ
with regard to sites, sampling seasons, vehicle traffic
density, and methodological design, all found average
outdoor Ir levels to be quite low. The limited use of
Ir in catalysts in some new diesel devices or as PGE
impurities in the older ones may explain these low lev-
els. Nevertheless, the potentially rising trend of envi-
ronmental Ir emission due to a more widespread use
of this metal in newer catalysts and the growing num-
ber of vehicles fitted with these devices are a source of
concern for the near future. To this end, the monitoring
of Ir in urban air could indicate appropriate measures
for catalyst introduction and provide information on
how the complex apparatus needed for automobile
catalysts can function efficiently. An extended airborne
Ir database could be useful for establishing standard
levels so that abnormally high concentrations would
signal an inadequate use of catalysts (Kojima and
Lovei, 2001). Moreover, environmental monitoring of
airborne Ir levels should be systematically performed
to follow-up time and spatial Ir variability. Lastly, par-
ticular attention should be given to Ir concentrations in
the different PM fractions so as to clarify the toxicolog-
ical profile of this metal and the potential health effects
resulting from general and occupational exposure.
4.3  Iridium Levels in Soils and Roadside Soils
Only three studies have been carried out to quan-
tify the Ir content of roadside soils located near local
roads, interstates, and urban highways. These stud-
ies investigated the anthropogenic contribution to
roadside Ir enrichment as a result of environmental Ir
release caused by the attrition of catalysts (Ely et al.,
2001; Müller and Heumann, 2000; Fritsche and Meisel,
2004). Ely et al. (2001) collected soil samples from inter-
state highways, urban roads, and side streets in and
around South Bend, Indiana, USA. A South Bend local
background sample was also taken. For a comparative
purpose, three soils were collected from Perth, Western
Australia, immediately adjacent to one rural and one
urban highway. The background South Bend Ir content
(±SD) of 0.06 ± 0.04 ng/g was similar to the literature
values for the upper crust, which ranged from 0.025
to 0.05 ng/g (Wedepohl, 1995; McDonald, 1998). In line
with the fact that Ir is supposedly not widely present
in catalytic converters but possibly present as impu-
rities or contained in some new diesel catalysts, all
soils showed levels of less than 1 ng/g [values (±SD)
ranging from 0.09 ± 0.06 to 0.43 ± 0.07 ng/g], with no
significant differences related to road traffic inten-
sity. Somewhat surprisingly, when Ir concentrations
were normalized to the local background, all soils
showed levels significantly higher than those of the
background, and Ir enrichments in some soil samples
was as much as five to seven times the background.
Considering the distance from road edges, relatively
constant abundances were detected across the length
of the two sampling traverses conducted perpendicu-
lar to the two major roads investigated. The Austra-
lian roadside soils, with contents (±SD) ranging from
0.59 ± 0.17 to 0.73 ± 0.30 ng/g, also exhibited Ir enrich-
ment compared to the general upper crust levels.
However, interpretations are limited because a local
background soil sample was not collected. Australian
and U.S. levels were comparable, although caution
should be exercised in trying to compare roadside Ir
concentrations from different regions. In fact, a large
number of variables affecting the production, accu-
mulation, and subsequent transformation of metals in
the roadside environment could lead to inappropriate
conclusions. Soil characteristics such as composition,
mineralogy, grain size, and underlying bedrocks can
also play a role in influencing Ir abundance.
In contrast to the results of the previous study (Ely
et al., 2001), a distance-related Ir decrease was demon-
strated in a study investigating Ir concentrations in soil
samples collected at different distances from a high-
way near Mainz, Germany (Müller and Heumann,
2000). Ir concentrations decreased with increasing dis-
tance from the highway, showing levels of 0.37 ± 0.09,
0.16 ± 0.07, and 0.13 ± 0.07 ng/g at 0.6, 1.8, and 3 m from
the road, respectively. Compared to the 0.03-0.05 ng/g
average Ir abundance in the Earth’s crust (Wedepohl,
1995, Schmidt et al., 1997), the concentrations detected
significantly exceeded the assumed background con-
tent. A similar distribution pattern was observed in the
soils along three Austrian motorways, with a signifi-
cant decrease in Ir concentration according to the dis-
tance from the edge of the roads (Fritsche and Meisel,
2004). Ir content was more than 20 times the natural
background at 0.20 m from the road and decreased to
the background level at a distance of 3 m. Compared
to natural alpine background concentrations, cor-
responding to continental crust mean values of 0.03-
0.05 ng/g (Wedepohl, 1995), the Ir values sampled
were significantly higher, with levels ranging from
 40 Iridium
0.04 to 1.1 ng/g. Interestingly, this study showed that
multiple factors could affect Ir roadside soil concentra-
tions because the highest Ir concentration was found in
the immediate vicinity of a road impacted by frequent
traffic jams (1.1 ng/g) and a lower level was observed
along another street with higher traffic density but less
precipitation (0.09 ng/g).
The coexistence of multiple factors must be taken
in consideration when evaluating potential sources
of Ir contamination. When analyzed according to
soil depth distribution, Ir content showed a less dra-
matic decrease compared to the perpendicular profile
because concentrations in the second depth range ana-
lyzed (5–10 cm next to the road edge) were still signifi-
cantly elevated. In order to demonstrate that vehicle
traffic is the primary emission source of Ir to the sur-
rounding urban environment, the content of this metal
was compared with those of other traffic-borne heavy
metals such as nickel (Ni), copper (Cu), zinc (Zn), lead
(Pb) (Ely et al., 2001), cobalt (Co), Zn, and antimony
(Sb) (Fritsche and Meisel, 2004; DeMiguel et al., 1999;
Hares and Ward, 1999). In the first study (Ely et al.,
2001), no consistent positive correlation between Ir and
Ni, Cu, Zn, and Pb was found; the same was true for Ir
and yttrium and gallium, two lithophile elements that
are generally constant in all soils and for which there
is no documented anthropogenic input. In the second
study, inconsistent results were obtained (Fritsche and
Meisel, 2004). In fact, on the one hand, correlations of
Ir levels with the aforementioned heavy metals are
ambiguous (Fritsche and Meisel, 2004) and geochemi-
cal data cannot confirm traffic as the primary source
(Ely et al., 2001); also the influence of industrial emis-
sions is not clear (Müller and Heumann, 2000). On the
other hand, Ir content considerably above the local
background (Ely et al., 2001; Fritsche and Meisel, 2004;
Müller and Heumann, 2000) and most likely depos-
ited along with Pt, Pd, Rh (Ely et al., 2001), and the
considerable decrease in concentration with distance
from the highways (Fritsche and Meisel, 2004; Müller
and Heumann, 2000) make it impossible to exclude
the possibility of Ir emission from catalytic convert-
ers. The limited number of studies on Ir deposition in
roadside soils and the relatively recent employment of
this metal in the catalytic industry point to the need
to focus future research on determining the anthropo-
genic sources that truly influence Ir levels in environ-
mental samples. Interestingly, only some soil samples
in the Ely et al. study (2001) were processed both as
bulk samples and as samples separated according
to grain size. Although attrition studies on catalytic
converters indicated that the finest < 0.25 mm frac-
tion was the richest in PGE particles, Ely et al. (2001)
failed to demonstrate differences in Ir content between
863
the finest fraction (< 0.25 mm) and the coarser fraction
(< 0.5 mm) compared to the background level. How-
ever, in the near future, with the widespread use of Ir
in catalytic converters and the growing number of cars
fitted with these devices, differences could become
evident and this approach to soil deposition analysis
should be taken into careful consideration. It should
be noted that although the limited number of studies,
different dates for the compulsory introduction of cat-
alytic converters, variable composition of each coun-
try’s car population according to car manufacturer and
model, and differences in the age of catalytic convert-
ers, speed of cars, volume of traffic, climate, rainfall,
and soil type all make accurate comparisons difficult,
comparable levels of Ir were found in different coun-
tries (Ely et al., 2001). Studies on Ir transformation in
the roadside environment, its mobility and the bio-
availability, and the toxicity of Ir from catalytic con-
verters are still in the early stages and require deeper
analysis. In fact, the behavior of Ir in depositional and
postdepositional conditions is not well established and
this introduces significant uncertainty regarding varia-
tions in the original Ir concentrations. Ir is considered
one of the less mobile of the PGEs (Colodner et al.,
1992; Evans et al., 1993b). There is evidence of postde-
positional mobilization after changes in sedimentary
conditions (Izett, 1990; Wallace et al., 1990; Evans et al.,
1995), but little is known about Ir mobility in terres-
trial environments. In this context, Ir concentration in
a soil covered by a layer of tailings after a catastrophic
mining spill in Seville, Spain, was determined from
1998 up to 10 years after deposition (Martín-Peinado
and Rodríguez-Tovar, 2010). The tailing layer had an Ir
concentration of 0.349 mg/kg. The oxidative weather-
ing of the tailings caused the release of Ir and infiltra-
tion into the soil. Ir distribution in soil samples taken
from different depths indicated the ability of the metal
to redistribute throughout the profile according to the
changing physicochemical properties of the soil, par-
ticularly in relation to the sulfur, iron, and clay con-
tent, and pH. Anomalous Ir values (0.129 mg/kg) were
detected in the first 11 cm below the layer of tailings
10 years after the spill. The maximum concentration
was found in the uppermost 2 cm next to the layer of
tailings (0.192 mg/kg). The residual/insoluble fraction
was > 90% of the total Ir concentration in the soil.
4.4  Road Dusts and Sediments
Djingova et al. (2003b) examined the Ir content in
dust samples collected along three highways and
a road in Germany in September 1999. The authors
found the greatest Ir concentrations in samples col-
lected from sites with the highest traffic and speed of
864 Ivo Iavicoli and Veruscka Leso
cars, particularly along two highways with values of
3.5 ± 0.2 and 3.5 ± 0.3 ng/g. Twofold lower levels were
detected in sites with lower vehicular traffic: 1.2 ± 0.1
and 1.6 ± 0.2 ng/g. These results confirmed that higher
traffic density and speed leads to an increase in envi-
ronmental Ir release.
Interestingly, a previous study (Müller and
Heumann, 2000) had investigated Ir content in road
dusts collected in a highway tunnel in Austria and
homogenized to different grain sizes: < 1000 μm and
< 90 μm. Comparable Ir levels (±SD) of 0.16 ± 0.06 and
0.15 ± 0.06 ng/g, respectively, were detected in the two
different granulometric fractions. These results differed
significantly from those of 5.69 ± 5.27 ng/g described in
the literature for dust samples sized < 1000 μm (Lustig,
1997) and those of 4 ± 1.8 ng/g recently reported by
Jackson et al. (2010) in samples of road dusts collected
in the center of Sheffield, UK. When examining metal
levels in samples of this type, it should be remembered
that road dust is constantly removed from the street and
concentrations are therefore not cumulative. Indeed,
a temporal and spatial comparison of the detected
values might not be an adequate analysis of results
(Djingova et al., 2003b). These differences demonstrate
the need to develop a standardized, highly sensitive,
and accurate method of measuring trace metals in the
environment so that researchers can make an adequate
comparison of findings from different studies (Müller
and Heumann, 2000).
Road sediments contain materials directly emit-
ted or worn away from vehicles, atmospheric deposi-
tion, and soil eroded from roadside areas (Sutherland
et al., 2008). Moreover, road-deposited sediments are
an important archive in urban areas for assessing the
degree of contamination of solid PM entering the
subsurface storm sewer system and potentially the
river network (Wei and Morrison, 1994; Sutherland
and Tolosa, 2000; Sutherland, 2003). In June 1999,
De Vos et al. (2002) found average (±SD) Ir levels of
1.40 ± 0.56 ng/g in road sediments sampled from a
sediment retention lagoon that collected runoff from
a motorway in east Kent, England. Since this catchpit
drained directly into the River Stour, it was able to
directly influence Ir fluvial sediment levels.
To date, Ir levels in roadside sediments are avail-
able for three urban watersheds, Manoa, Palolo, and
Nuuanu in Honolulu, Hawaii (Sutherland et al., 2007;
2008). Ir levels were determined in the < 63-μm fraction
road-deposited sediments representative of all residen-
tial traffic levels collected in the period from 1999 to
2002. A Hawaiian baseline concentration of 0.268 ng/g
was computed as a background reference value
(Tatsumi et al.,1999; Crocket, 2000; Meisel and Moser,
2004). Ir concentrations never exceeded 1 ng/g, with
levels ranging from 0.040 to 0.59 and 0.090 to 0.96 ng/g
in road-deposited sediments in Manoa and Palolo,
respectively. No statistically significant differences
were detected between the two systems. The average Ir
concentrations, 0.25 ng/g for both sample sites, did not
significantly exceed the aforementioned baseline con-
centration in Hawaii (Sutherland et al., 2007). Compa-
rable results were obtained in the Nuuanu watershed.
In fact, Ir levels did not differ significantly from the
computed regional baseline level of 0.268 ng/g, with
concentrations ranging from 0.04 to 1.27 ng/g and an
average (±SD) level of 0.22 ± 0.34 ng/g (Sutherland
et al., 2008). To assess metal contamination, researchers
calculated the Ir enrichment ratio, i.e. the ratio between
the trace element concentration of the sample and the
baseline concentration for the same element. No Ir
enrichment was found in any of the sites examined
(Sutherland et al., 2007, 2008), with ERs of 0.95 ± 0.62,
0.93 ± 0.7, and 0.8 ± 1.3 in Manoa, Palolo, and Nuuanu,
respectively. These values indicate that Ir was primar-
ily controlled by geogenic inputs particularly related to
the proximity of the Koolau Volcano, characterized by
tholeiite basalts with high metal content. Overall, data
from the three watersheds examined in Hawaii reveal
comparable Ir levels, indicating a common contempo-
raneous source of this metal in the road environment
of this country (Sutherland et al., 2007, 2008). The lack
of Ir enrichment reinforces the absence of a significant
anthropogenic signal for Ir and the fundamental role
of geogenic contributions. However, it should be noted
that these data reflect residential street traffic and not
highways, as typically reported in the literature. Addi-
tionally, Ir abundance comparisons between studies is
complicated by different sampling methodologies, the
grain size fractions analyzed, digestion procedures,
analytical approaches, traffic densities, and fleet com-
positions. Further research is required to enlarge the
Ir sediment concentration database and to examine Ir
mass loading in different grain size fractions in depth
so as to reach a better understanding of Ir transport
pathways in urban environments and their potential
consequences.
4.5  Water Ecosystem
PGE levels in marine seawater and sediments were
studied in 1986 by Hodge et al. in order to clarify
their oceanic chemistry and reveal the nature of envi-
ronmental chemical reactions. Samples of seawater,
sediments, and manganese nodules collected off the
California coast were analyzed. The Ir level in seawater
was 0.0009 ng/L. This was the lowest reported concen-
tration for a stable element in seawater and was in line
with subsequent determinations of the metal in 100-L
 40 Iridium
samples that revealed a concentration of < 2pg/kg
(Date et al., 1987). Sediment levels ranged from 0.2 to
1.2 ng/g, while in manganese nodules collected at a
water depth ranging from 1409 to 4200 m, Ir concentra-
tions ranged from 2.2 to 7.4 ng/g, respectively (Hodge
et al., 1986).
The Pacific Ocean seawater from depths of 60,
1500, and 4500 m gave upper limits of less than 5 pg/L
(Goldberg et al., 1986). When investigated in pelagic
sediments, Ir content ranged from 0.2 to 1.2 ng/g and
seemed to be strongly governed by Mg concentra-
tions. Higher Ir values were found in the ferroman-
ganese concretions, where its levels ranged from 0.4
to 7.4 ng/g. Colodner et al. (1993) determined Ir con-
centrations of 1.5 ± 0.1 and 2.1 ± 0.1 ng/g in abyssal
pelagic sediments from the northwest Atlantic Ocean
at depths of 1440–1442 and 1420–1422 cm, respectively;
there results are in line with those previously reported
by Kyte and Wasson (1986).
Anbar et al. (1996; 1997) evaluated Ir levels in 4-kg
water samples from the Pacific and Atlantic Oceans, the
Baltic Sea, and rivers draining into the Baltic. In the open
ocean, Ir concentration was essentially depth indepen-
dent and was comparable in the Pacific (4.4 ± 0.6 × 108
atoms/kg at 1000 m depth) and Atlantic Oceans (range
from 2.5 ± 0.6 × 108 to 5.1 ± 0.8 × 108 atoms/kg at depths
ranging from 200 to 4200 m). The latter data, examined
at depths ranging from 200 to 4200 m, indicated small
but significant variations in Ir concentrations that may
be evidence of a minor redistribution of this element in
near-surface waters resulting from the adsorption of Ir
to particles or to uptake of Ir in the marine biological
cycle. Moreover, surface water Ir content was shown
to be influenced by aeolian inputs, as demonstrated by
the different enrichment in the Atlantic (17.6 ± 0.9 × 108
atoms/kg) compared to the Pacific (15.7  ± 0.8 
× 108
atoms/kg) surface water at the same 25-m depth. In
the rivers that feed the Baltic Sea, Ir concentrations
were 10-20 times higher than in the open oceans and
were much more variable, ranging from 17.4 ± 0.9 × 108
atoms/kg for a pristine river to 92.9 ± 2.2 × 108 atoms/
kg for a polluted one (Ponter et al.,1992). The shallow,
oxic waters of the Baltic Sea have concentrations rang-
ing between the average river concentration and seawa-
ter (range from 10.7 ± 1.0 × 108 to 38.9 ± 2.2 × 108 atoms/
kg at depths ranging from 5 to 225 m). These levels can
be explained in terms of mixing and removal of Ir into
oxic Baltic sediments (Anbar et al., 1996).
At closely spaced intervals, Lee et al. (2003) investi-
gated Ir concentrations in pelagic sediment cores from
the South Pacific Ocean, including the K-T boundary
(KTB; thought to represent the fallout of a large mete-
oric impact), and in the KTB clay from a pelagic North
Pacific site. Two European hemipelagic KTB sediments
865
now exposed on land in Caravaca, Spain, and Stevns
Klint, Denmark, were also examined. In the first sample,
Ir ranged from 0.269 to 13.8 ng/g. The highest values
detected at the KTB were 30-fold greater than the pre-
and post-KTB sediments. Interestingly, the elevated
levels were approximately symmetrically distributed
over a distance of ∼1.8 m from the KTB, supporting
postdepositional Ir redistribution. A concentration of
12.8 ng/g was observed in the North Pacific site, while
the other two locations showed near chondritic adun-
dances of 50.9 and 42.0 ng/g, respectively.
Significant quantities of PGEs enter fluvial, estuarine,
and coastal sediment systems via road runoff, storm
drains, wastewater, and sewage treatment systems and
may accumulate in fluvial sediments by physical and
chemical processes. Fluvial systems are ideal systems
to document the sources and distribution of anthro-
pogenic PGE in an attempt to determine some of the
physical and chemical parameters that may influence
the distribution of these elements because they contain
tidal and nontidal components and drain catchments in
which land use and potential PGE inputs change (e.g.
Lee, 1983; Hodge et al., 1986; Koide et al., 1991; Esser
and Turekian, 1993; Wei and Morrison, 1994; Ravizza
and Bothner, 1996). In this context, in June 1999 De Vos
et al. (2002) carried out a baseline survey of contempo-
rary fluvial sediments in the Stour River in east Kent,
England. The Ir content (±SD) of the river sediments,
sieved to a ≤ 2-mm sized fraction, ranged from < 0.03
to 2.69 ± 2.03 ng/g. Interestingly, analysis of the sedi-
ment sample sites revealed that the lowest Ir concen-
trations occurred at tributary sites and rural sites little
affected by discharge from sewage works, whereas the
highest concentrations were found at urban sites with
heavy traffic and at urban and rural sites affected by
discharge from sewage works. Although these data
suggest that anthropogenic sources play an important
role in Ir contamination, it is difficult to distinguish
between the possible catalytic converter Ir source and
sewage works. However, further confirmation of this
anthropogenic Ir source is provided by the fact that
the abundance and distribution of Ir in the river sedi-
ment samples did not correspond to potential geologic
inputs to the Stour River. In fact, no systematic corre-
lation was found between the Ir levels (±SD) ranging
from < 0.03 to 0.89 ± 0.13 ng/g in the samples of major
sedimentary rocks traversed by the Stour and the Ir
concentration detected in river sediments. However,
the absence of a pure catalytic converter signature in
the river sediments suggests that there may be a vari-
ety of Ir sources, possibly mixed in sewage works, or
that PGEs may undergo chemical fractionation in the
fluvial environment, possibly in response to changes
in redox potential.
866 Ivo Iavicoli and Veruscka Leso
Three river bed locations were sampled in a head-
water area of the Palolo watershed in Honolulu,
Hawaii at a distance of about 20 m from a road with
restricted traffic access (Sutherland et al., 2007). The
average (±SD) Ir level was 0.207 ± 0.205 ng/g in the
sediment material passed through a < 63-μm sieve.
Unfortunately, as in the case of road dusts, the different
methodologies and environmental context prevented
any comparison with previous studies.
Rauch et al. (2004a) presented evidence of recent
changes in the Ir accumulation rate by studying sedi-
ments collected in 2002 from the Upper Mystic Lake,
Boston, MA, USA. These demonstrated that the Ir
accumulation rate had significantly increased, ranging
from 0.034 ± 0.015 μg/m2/year in the period 1948-1971
to 0.69 ±  0.018 μg/m2/year in the period 1992-2002.
The relatively higher accumulation rates detected for
Ir in the second period might be related to Ir released
from automobile catalysts. Measurement of Ir accu-
mulation rates may provide a better understanding
of PGE transport on a regional scale and help identify
the source of Ir in the environment. Moreover, restrict-
ing the processes that give rise to Ir variations in water
sediments is vital to understanding the geochemical
behavior of Ir in this complex ecosystem.
Some PGEs are carried downstream in natu-
ral watercourses (de Vos et al., 2002; Whiteley and
Murray, 2005; Jackson et al, 2007; Prichard et al., 2008)
and some are washed off the roads into artificial drain-
age systems and into sewage. Unfortunately, analysis
of Ir in sewage is rare and only Jackson et al. (2010) has
analyzed such samples, collected between 2004 and
2006 from the sewage treatment facilities in Sheffield
and Birmingham, UK. Results yielded a maximum Ir
concentration of 3 and 4 ng/g in the two sites, respec-
tively. Ir concentrations in sewage sludge samples
from all locations were generally comparable to those
found in road dust from central Sheffield.
Compared to data available for PGE pollution levels
close to source regions, there are relatively few time
records of changes in PGEs at remote and polar loca-
tions because of the extremely low concentrations and
associated analytical challenges (Soyol-Erdene et al.,
2011a). It is therefore difficult to evaluate the impact
of increasing PGE levels on the global environment
over time. Currently, data on Ir are available for the
snow layers of Greenland (Gabrielli et al., 2008) and
Antarctica (Soyol-Erdene et al., 2011a,b), and for the
ancient ice of the same regions (Gabrielli et al., 2004,
2006; Takahashi et al., 1978; Soyol-Erdene et al., 2011a).
To determine changes in the global background atmo-
spheric Ir level, Soyol-Erdene et al. (2011a) reported
atmospheric Ir deposition rates in Antarctica over
the last ∼50 years by measuring Ir in snow samples
collected in December 2007. The 50-year average (±SD)
Ir concentration was 0.12 ± 0.08 × 10−15  g/g, with a
minimum concentration < 0.05 × 10−15 g/g and a maxi-
mum one of 0.34 × 10−15 g/g. Peak Ir concentration was
observed at depths corresponding to volcanic eruption
periods, thus indicating that Ir can be used to trace
past volcanic activity. Estimated average Ir flux was
0.003 ± 0.002 ng/m2/year. These data were compara-
ble with those observed in the Antarctic Dome C ice
sample (Takahashi et al., 1978), with an average (±SD)
concentration of 0.31 ±  0.12 × 10−15 g/g and a flux of
0.010 ± 0.004 ng/m2/year. However, these results were
approximately one or two orders of magnitude lower
than those of another study (Gabrielli et al., 2006) of
Antarctic ice core samples from the Holocene period
(average fluxes: 0.18 ng/m2/year for Dome C, 0.04 ng/
m2/year for Vostok), and two or three orders of mag-
nitude lower than the Ir flux registered in Greenland
snow (Gabrielli et al., 2008). Surprisingly, the study
carried out by Gabrielli et al. (2006) found a relatively
high Ir concentration (averages were 6 × 10−15 g/g for
Dome C and 2 × 10−15 g/g for Vostok), with high Ir:Pt
ratios of close to or greater than 1. This value was sig-
nificantly higher than the average Ir:Pt ratio of 0.006
determined by Soyol-Erdene et al. (2011a) and was dif-
ficult to explain solely in terms of natural contributions
such as volcanic (Yudovskaya et al., 2008; Puchtel and
Humayun, 2001; Bockrath et al., 2004; Rilling, 2009),
crustal (Wedepohl, 1995; Peucker-Ehrenbrink and Jahn,
2001; Schmidt et al., 1997), and cosmic dust (Anders
and Grevesse, 1989).
4.6  Other Environmental Matrices
Ombrotrophic peat bogs receive nutrients and
trace elements only from atmospheric deposition; the
peat cores of ombrotrophic bogs have therefore been
used to investigate historical change in atmospheric
trace metal concentrations and to determine rates
of atmospheric deposition (Shotyk et al., 1998, 2003;
Weiss et al., 1997). Rauch et al. (2004b) investigated
changes in Ir deposition in two peat cores collected
in October 2002 from Thoreau’s Bog, an ombrotrophic
peat bog located near Concord, MA, USA. Similar Ir
levels were observed in the two peat samples, with
a mean (±SD) concentration calculated on the two
cores of 0.05 ± 0.08 ng/g. Lithogenic atmospheric soil
dust, which has a composition similar to that of the
upper continental crust, is the major source of natu-
rally occurring particles in ombrotrophic bogs. How-
ever, an estimated enrichment factor (ER) of 129 for
Ir indicated an enrichment of this element above the
atmospheric soil dust. This result was further con-
firmed by the levels of lithogenic and nonlithogenic
 40 Iridium
Ir fractions corresponding to 0.0003 ng/g (0.8%) and
0.04 ng/g (99.2%), respectively. The analyzed cores
corresponded to peat accumulation from 1980 to 2002.
Catalysts were introduced in the U.S. in the mid-1970s
and their number increased sharply until approxi-
mately 1990 (Rauch and Hemond, 2003). However,
compared to the previous evidence of an increase in
Ir deposition in the Upper Mystic Lake in the period
between 1948-1971 and 1992-2002, possibly as a result
of atmospheric Ir emissions released from impurities
present in catalysts (Rauch et al., 2004a), time variabil-
ity in Ir concentration in Thoreau’s Bog did not follow
a similar trend. The absence of a clear trend follow-
ing the introduction of catalysts indicated that Ir was
not quantitatively preserved in peat. This may have
been due to postdepositional mobility of the metal, in
which downward leaching and plants play an impor-
tant role. The average Ir value reported by Rauch
et al. (2004b) was comparable to the 0.070 ng/g level
reported in a subsequent study that evaluated Ir con-
centration in a minerotrophic peat deposit near a his-
toric Pb-Ag mining district in Příbram, Czech Republic
(Strnad et al., 2008). This value, which was similar or
slightly elevated in absolute comparison with values
for the upper continental crust, did not indicate any
substantial enrichment. However, when the Ir EF was
calculated, an increasing trend was observed toward
the upper part of the peat profile, possibly due to min-
ing and smelting activity and also to automotive emis-
sions. These findings indicate the need for a deeper
understanding of the potential role that anthropogenic
sources such as automotive emissions or other human
industrial activities play in elevating Ir concentrations
even in areas where increased environmental pollu-
tion is not expected.
Jackson et al. (2010) compared the Ir content in
sewage sludge and incinerator ash sampled between
2004 and 2006 in Sheffield and Birmingham. Ir concen-
trations in incinerator ash were greater than in sew-
age sludge, suggesting that the incineration process
increases the Ir concentration, possibly due to the loss
of PGE-barren material. The highest concentration
(33 ng/g) was found in the Sheffield raw incinerator
ash, while a lower level (11 ng/g) was detected at the
other site. Ir concentrations were all below 20 ng/g in
samples of stored ash from Sheffield. Ir concentrations
in the incinerator ash samples were 10-fold higher than
those found in road dust.
4.7  Plant Organisms
Because of the limited data available on how Ir
behaves in the environment, its distribution in the dif-
ferent PM fractions, and its mobility and capacity to
867
be solubilized by various environmental components,
as well as its potential transformation into more toxic
species after uptake by organisms, researchers have
investigated Ir levels in plants (Wiseman and Zereini,
2009; Petrucci et al., 2000; Pino et al., 2010). In recent
decades, terrestrial plants, grasses, and lichens have
been used to assess the bioaccumulation and bioavail-
ability of Ir as a function of environmental pollution in
and around areas with heavy vehicle traffic, but also
in areas considered to be relatively unpolluted (Conti
and Cecchetti, 2001). When interpreting the findings
of these studies, consideration must be given to the
fact that the accumulation of metals in plants is influ-
enced by a number of factors such as the availability
of elements, the characteristics of the plants (species,
age, state of health, type of reproduction), and other
parameters, e.g. temperature, available moisture, and
substratum characteristics (Conti and Cecchetti, 2001;
Baker, 1983).
Ely et al. (2001) demonstrated that Ir was taken up
by grass. The authors reported mean Ir values (±SD)
ranging from 0.07 ± 0.04 to 0.09 ± 0.04 ng/g and from
0.07 ± 0.05 to 0.06 ± 0.04 ng/g in washed and unwashed
grasses, respectively, collected at a distance of 0 and
18 m from the Interstate 80/90 (Indiana Toll Road),
South Bend, Indiana, USA. Interestingly, the amount of
Ir in all samples was influenced neither by local back-
ground soil nor by distance from the road edge.
To provide another bioindicator, Ir levels were
evaluated in sphagnum moss located in the top sec-
tion of a peat core collected from Thoreau’s Bog, where
concentrations reached levels of 0.021 ng/g (Rauch
et al., 2004b). The utility of mosses as environmental
bioindicators depends on their ability to trap airborne
pollution and accumulate persistent metals to concen-
trations far greater than those in air (Pino et al., 2010).
Ir concentrations detected by Rauch et al. (2004b) were
lower than those found in urban mosses collected in
Germany in September 1999 by Djingova et al. (2003b).
This decrease in Ir deposition may have been linked to
the increasing distance from traffic emissions. Among
plant samples collected in a urban site where traffic
density was low, the highest Ir concentration (±SD)
of 0.10 ± 0.03 ng/g was found in Rhytidiadelphus squar-
rosus (moss), while mean Ir levels (±SD) of 0.08 ± 0.02,
0.010 ± 0.003, and < 0.004 ng/g were detected in Taraxa-
cum officinale (dandelion), Plantago lanceolata (plantain),
and Vascellum pratense (mushrooms), respectively.
In the same study, Ir content was measured in plant
samples collected at a distance of less than 1 m from
the road edge of two high traffic highways and a road.
The highest Ir concentration was found in T. officinale
(0.4 ± 0.2 ng/g) followed by P. lanceolata (0.3 ± 0.2 ng/g).
These results were twice the values reported by
868 Ivo Iavicoli and Veruscka Leso
Ely et al. (2001). Further comparison can be made
using the PGE analysis of samples of T. officinale and
P. lanceolata collected 15 years previously in Bulgaria,
Germany, and the Netherlands (Djingova and Kuleff,
1993) in which researchers found concentrations below
the detection limits (< 0.01 ng/g), indicating a clear
accumulation of the metals in plants along highways.
Comparisons of Ir levels in washed and unwashed
grasses yielded conflicting results (Ely et al., 2001;
Djingova et al., 2003b): no differences were detected
in the first study (Ely et al., 2001), demonstrating that
almost all Ir was incorporated into the leaves and
stems, while the second revealed a twofold decrease
in Ir content after washing (Djingova et al., 2003b). As
current data on Ir levels in plants are limited, future
research should focus on investigating Ir distribution
in different plants in a specific location, on compar-
ing behavior between sites, and on the transfer factor
between soil and plants so as to clarify possible metal
distribution in ecosystems and its effect on the food
chain (Djingova et al., 2003b).
Nazarov et al. (1995) carried out an initial study to
investigate Ir content in Pinus Sivestris needles, col-
lected in the Tver Region and in the Kola Peninsula,
and also in Usnea spp. lichens obtained in Franz Josef
Land, Russia. Ir levels were 0.0007 and < 0.0002 ng/g in
pine needles and lichens, respectively.
Few studies have measured the amount of Ir in
uncontaminated areas, probably because the back-
ground concentrations of PGE are very low and
remain outside the resolution of routinely used
analytical methods. However, in order to assess air
quality in the remote area of Tierra del Fuego, Pata-
gonia, Argentina, in 2006 Pino et al. (2010) investi-
gated Ir levels in lichen samples of Usnea barbata.
The global Ir concentration in lichen samples ranged
from 0.05 to 1.011 ng/g, with a mean (±SD) level of
0.192 ± 0.258 ng/g and no difference between trans-
planted and native samples. When correlations
between Pt and Ir, and Rh and Ir were calculated, low
correlation factors were obtained, suggesting that a
common local source of emission (e.g. vehicle traffic)
did not exist. The presence of Ir in this uncontami-
nated environment, where the impact of anthropo-
genic activities is very low, could be ascribed to the
influence of air mass movement that results in the
long-range atmospheric transport of metals to remote
areas (Moldovan et al., 2007; Barbante et al., 2001).
This is further confirmed by the comparable Ir lev-
els detected in plants collected in highly urbanized
areas, 0.3-0.4 ng/g (Djingova et al., 2003b), and those
found in Tierra del Fuego. However caution must be
used when making a straight comparison of these
results due to differences ascribable to the substrate
(lichen, grass, or other plants) selected as a biomoni-
tor. These may regard accumulation, distribution,
and complexation ability, as well as parameters such
as weather conditions, site morphology, number of
vehicles, distance from roads, and analytical meth-
odology that might affect Ir content in the analyzed
samples.
4.8  Food and Drugs
The Total Diet Study (TDS) is an important part
of the UK Government’s surveillance program for
chemicals in food and has been carried out on a con-
tinual yearly basis since 1996. Results from the TDS
are used to estimate the dietary exposure of the gen-
eral UK population to chemicals in 20 groups of food
(e.g. nutrients and contaminants) to identify trends
in exposure and make assessments on the safety and
quality of the food supply. In 1994, the TDS started
reporting average Ir concentrations in food. These
were generally low, and for many groups were under
0.001 mg/kg fresh weight (f.w.), the limit of detec-
tion, in foods such as bread, carcass meat, offal, milk,
and nuts (Ysart et al., 1999). In miscellaneous cere-
als, levels reached 0.002 mg/kg f.w. Total Ir dietary
exposure for the general population was 0.002 mg/
day; the mean estimated total exposure for an adult
consumer was 0.002 mg/day, with un upper range of
0.003 mg/day.
With regard to pharmaceutical products, in Sep-
tember 2008, the European Medicines Agency (EMEA,
2008) adopted maximum acceptable concentration
limits for metal catalyst residues present in pharma-
ceutical substances or in drugs. Interestingly, due to
the risk to human health, together with Rh, Ru, and Os,
Ir was classified among the 1B category that includes
metals of significant safety concern. However, since
current toxicity data for these metals are rather lim-
ited, a conservative approach was adopted in estab-
lishing the acceptable permitted daily exposure (PDE)
and concentration limits for the four-metal group. In
fact, for the listed metals, the oral PDE should not
exceed 100 μg/day and a concentration limit of 10 mg/
kg, while the parenteral PDE and concentration limit
should not exceed the 10 μg/day and 1 ppm values,
respectively.
Bocca et al. (2007) investigated the content of 13
metals in 11 types of moisturizing cream available
on the Italian market to provide a basis for assess-
ing their safety for consumers. The maximum (±SD)
Ir level detected was 0.20 ± 0.03 ng/g, but for most of
the samples concentrations were below the limit of
quantification (0.003 ng/g) by the analytical method
employed.
 40 Iridium
5  KINETICS AND METABOLISM
5.1 Absorption
Ir can be taken into the body by eating food, drink-
ing water, or breathing air. Most of the studies on the
toxicokinetics of Ir have been conducted in animal
models, principally with rats (Hamilton, 1951a,b). Gen-
erally, the absorption of a metal seems to depend on its
chemical form, its route of administration, and particu-
larly its solubility in aqueous media. The presence of
Ir in several secondary target organs after inhalation
or endotracheal or intrapulmonary administration is a
clear demonstration of the absorption capacity of this
metal (Kreyling et al., 2002, 2009; Semmler et al., 2004;
Semmler-Behnke et al., 2007).
There are conflicting data in the literature with
regard to the oral route (Hamilton, 1951a,b; Kreyling
et al., 2002; Iavicoli et al., 2012a). Hamilton (1951a,b)
clearly demonstrated gastrointestinal absorption of Ir
in the chloride or oxychloride form. He estimated that
total overall absorption from the gastrointestinal tract
was about 10% of the administered dose. Subchronic
oral exposure to IrCl3 hydrate in rats induced a clear
systemic absorption of the metal (Iavicoli et al., 2012a).
On the other hand, another study found no detectable
ultrafine insoluble 192Ir particles in any rat organ or
tissue after oral gavage, suggesting that there was no
uptake and/or absorption from the gastrointestinal
tract (Kreyling et al., 2002). The diverse solubility of the
metal forms administered and the different size of the
metallic particles with consequent variations in reactiv-
ity in biological fluids may explain these discrepancies.
5.2 Distribution
Hamilton (1951a,b) demonstrated that 2 h after a
single intravenous administration of Ir chloride or
oxychloride in rats the metal was found principally in
liver and blood, although measurable amounts were
detected in other soft tissues such as the spleen and
the kidneys (Hamilton, 1951a,b). This finding was con-
firmed by Kreyling et al. (2002), who demonstrated
that the main fraction of intravenously administered
192Ir ultrafine particles remained in the liver and the
spleen of treated rats.
When metallic-Ir aqueous aerosols were inhaled,
the metal was deposited in the upper respiratory tract
and the pulmonary parenchymal regions of treated
animals (Casarett et al., 1960). Ir deposited at bron-
chial and bronchiole level in an amount exceeding 95%
of the administered dose was subsequently rapidly
eliminated by lungs, with a half-life of approximately
2-4 h. The first fecal samples after 24 h from inhalation
869
contained almost all the metal deposited in the upper
respiratory tract. On the other hand, the metal parti-
cles accumulated in the pulmonary parenchyma had
a considerably slower clearance, with a half-life of
22-24 days. The redistribution of Ir to other tissues of
the body was negligible. The translocation of ultrafine
insoluble 192Ir particles from the lungs to extrapulmo-
nary organs using different routes of administration
was assessed by Kreyling et al. (2002). Male WKY/
NCrl BR rats exposed via aerosol to 15- and 80-nm
sized ultrafine particles showed a deposited fraction
(±SD) in the lungs of 0.49 ± 0.12 and 0.28 ± 0.10, respec-
tively. Lung retention decreased very slowly for both
particles. A predominant part of the deposited particles
was cleared through the gastrointestinal tract; how-
ever, during the 7-day postexposure period, there was
also a small amount of translocation from the lungs to
the blood and to secondary target organs such as liver,
spleen, kidneys, heart, brain, and carcass. Interestingly,
extrapulmonary translocation was significantly greater
for 15-nm particles than for 80-nm particles, suggest-
ing inverse particle size-dependent transport into the
blood. Similar results were determined after 192Ir ultra-
fine particle endotracheal instillation and also after
intrapulmonary administration of a solution of soluble
192IrCl , while no detectable 192Ir in any rat organ or tis-
3
sue was found following particle gavage. Long-term
retention data showed that no further accumulation
occurred, but net clearance from these target organs
was found with time (Semmler et al., 2004). In fact, male
WKY rats exposed via inhalation to 192Ir ultrafine 15- to
20-nm particles, showed a prominent decrease in the
particle fraction retained in the lungs at all three time
points of sacrifice (3 weeks, 2 months, and 6 months),
i.e. 26, 15, and 6%, respectively. Interestingly, the same
group (Semmler-Behnke et al., 2007) demonstrated
that 3 weeks after inhalation, 80% of the retained 192Ir
ultrafine particles was translocated into the intersti-
tium, and that from this site particles underwent alveo-
lar macrophage-mediated long-term clearance to the
larynx. Moreover, Kreyling et al. (2009) showed that
nanoparticle characteristics such as the material and
size of the chain-type aggregate determined transloca-
tion and accumulation in secondary target organs and
the skeleton after an inhalation exposure. In fact, 24 h
after exposure, a small fraction of the 192Ir ultrafine par-
ticles administered was found in liver, spleen, kidneys,
heart, brain, and carcass. Interestingly, the fractions
of 192Ir carried with the carbon nanoparticles retained
in secondary target organs, the skeleton, and soft tis-
sues were significantly lower than with particles made
from pure Ir. Furthermore, there was significantly less
translocation and accumulation with 80-nm than with
20-nm nanoparticle aggregates of Ir.
870 Ivo Iavicoli and Veruscka Leso
The presence of small but detectable quantities of
Ir that had entered by the oral route was found after
7 days in the kidney, liver, lungs, and spleen. On the
basis of animal studies, it has been suggested that 4%
of the Ir that reaches the blood after administration is
deposited in the kidney (Peterson et al., 2007). After
treating female Wistar rats with increasing concentra-
tions of IrCl3 hydrate (0-1 mg/L) in drinking water,
Iavicoli et al. (2012a) demonstrated a significant dose-
dependent increase in Ir levels in serum and in several
analyzed organs. The greatest amount was found in
kidney and spleen, but high levels of the metal were
also observed in the liver, lung, and brain. The high
kidney uptake might explain the renal tubule dysfunc-
tion observed in a previous study (Iavicoli et al., 2011)
and calls for further study to ascertain whether the
kidney is the critical organ of toxicological Ir action.
5.3 Excretion
After a single intravenous administration of Ir chlo-
ride or oxychloride in rats, the metal was principally
excreted through the renal system (Hamilton, 1951a,b).
Significant amounts of the metal were determined in
the urine at short intervals after injection. Although
the urinary content decreased markedly after 24 h,
detectable levels of Ir were present for 33 days follow-
ing administration. Studies after systemic injection of
ultrafine 192Ir particles showed that negligible fractions
passed through glomerular filters of the kidneys into
the urine (Kreyling et al., 2002). This may indicate that
injected particles were either (1) rapidly and tightly
bound to proteins or other structures in blood or (2)
agglomerated to larger aggregates that were not able
to penetrate the kidneys toward the bladder. No Ir was
found in feces (Kreyling et al., 2002).
When metallic-Ir aqueous aerosols were inhaled, the
major route of excretion was by the feces, amounting
to a total of about 96% of the excreted dose (Casarett
et al., 1960). Only a small amount (4%) appeared in the
urine. In this study, the quantities of Ir redistributed to
organs and excreted in the urine were much smaller
than those observed by Hamilton (1951a,b) after intra-
venous injection and oral administration of Ir chloride,
probably due to the greater insolubility of the metal-
lic form of Ir administered in this study compared to
the chloride or oxychloride form used in the previous
work. Studies performed with 192Ir ultrafine particles
demonstrated that Ir clearance occurred through the
gastrointestinal tract. From 1 day to 1 week after inha-
lation, 192Ir ultrafine particles were cleared predomi-
nantly from the peripheral lung via thoracic airways
to the larynx into the gastrointestinal tract and feces,
regardless of their size (Kreyling et al., 2002). Particle
dissolution estimated from urinary excretion appeared
to be very low (Kreyling et al., 2002). Comparable
results were obtained with endotracheal instillation.
Intrapulmonary administration of soluble 192IrCl3 par-
ticles resulted in greater excretion through the renal
system, while a smaller amount was excreted via feces,
possibly due to their greater solubility (Kreyling et al.,
2002).
There are conflicting results in the literature con-
cerning Ir excretion after administration by the oral
route (Kreyling et al., 2002; Iavicoli et al., 2012a).
Kreyling et al. (2002) reported that almost all of
the esophageal administered 192Ir suspension was
found in fecal excretion within 2–3 days. 192Ir was
not observed in urine at any day of observation. A
dose-dependent urinary excretion of Ir was detected
in rats subchronically administered increasing doses
of the metal (0-1 mg/L) as IrCl3 hydrate via the oral
route (Iavicoli et al., 2011). In a subsequent work, the
same authors confirmed these findings and also dem-
onstrated gastrointestinal elimination of the metal,
assessed by the increase in fecal Ir concentration
in accordance with a dose-dependent relationship
(Iavicoli et al., 2012a). However, these results cannot
be compared with other findings owing to the differ-
ent solution administered, the route of treatment, and
time points assessed.
6  LEVELS IN HUMAN TISSUES AND
BIOLOGICAL FLUIDS
Biological monitoring plays a key role in determin-
ing individual human exposure to Ir and in evaluating
the health risks associated with this exposure.
6.1  General Population
6.1.1  Blood and Serum
Minoia et al. (1990) measured Ir levels in the blood
samples of 22 nonexposed healthy Italian volunteers
living in the province of Varese in the Lombard region
of Italy. Elemental concentration ranged from 0.2 to
35 ng/L, with a mean level of 7.4 ± 4 ng/L. When the
serum samples of eight volunteers were investigated
for Ir content, the latter ranged from 0.2 to 40 ng/L,
with a mean value of 5 ± 1 ng/L. These values were
clearly higher than those found by Begerow et al.
(1997) in blood samples from seven healthy German
volunteers with no known exposure to precious met-
als. In this group, Ir concentrations ranged from 0.1 to
0.4 ng/L, with an average value of 0.3 ng/L.
As assessed by Rodushkin et al. (2000), Ir contamina-
tion owing to leaching from glass collection tubes was
 40 Iridium
negligible for this element. In fact, Ir values assessed
by SF-ICP-MS were comparable in glass and plastic
tubes, with mean values (±SD) of 0.0002 ± 0.0001 and
< 0.0002 ng/mL, respectively. Interestingly, the Ir con-
tent in three pooled human blood samples analyzed
by ICP-MS confirmed the previous results by reveal-
ing Ir concentrations lower than the detection limit of
0.0002 ng/mL. In 2004, the same group found Ir con-
centrations ranging from 0.16 to 0.24 ng/L in serum
samples collected from adults living in different parts
of Sweden (Rodushkin et al., 2004).
Twenty years after the data from the Lombard
region (Minoia et al., 1990), Bocca et al. (2010a) quan-
tified Ir concentrations in serum collected from non-
occupationally exposed subjects living in two Italian
regions: Calabria and Umbria. Comparable results
were found from the two regions; in fact, mean concen-
trations (±SD) of 3.20 ± 0.14 and 3.76 ± 0.12 ng/L were
determined in 283 Umbrian and 218 Calabrian valid
samples, with values ranging from 0.50 to 11.7 ng/L
and from 0.63 to 10.8 ng/L, respectively. Subsequently,
a mean blood Ir concentration of 10.2 ng/L was mea-
sured on a population of 1423 healthy Italian subjects
composed of 953 males and 470 females (Alimonti et al.,
2011). Male Ir blood concentrations were significantly
higher (mean, 10.7 ng/L) than female levels (mean,
9.18 ng/L). When analyzed in serum, the mean Ir con-
centration in a total population of 1344 subjects was
3.08 ng/L. Significantly higher levels were observed
in the youngest group in comparison with the older
groups. In fact, mean levels in subjects aged 18-35,
36-50, and 51-65 years were 3.15, 3.17, and 2.80 ng/L,
respectively. Serum Ir levels were higher in alcohol
abstainers (mean, 3.35 ng/L) than in alcohol drinkers
(mean, 2.90 ng/L). The large number of subjects evalu-
ated in this study could provide a basis for establishing
reference values in adults exposed to an urban envi-
ronment. However, it is not clear to what extent the
experimentally determined range of values for Ir is
representative of “normal values,” and how an upper
limit can be set above which the onset of metabolic
alterations or pathological states might be expected.
This difficult topic can be influenced by a number of
factors such as the interrelationships between differ-
ent elements, analytical inconsistencies due to prob-
lems of sensitivity and inaccuracy, and the selection
criteria of the population investigated, which should
attempt to avoid physiological anomalies, pathologi-
cal states, or exceptional exposure conditions (Minoia
et al., 1990). Moreover, other crucial factors depend on
biological variability that can affect the concentrations
to be evaluated: these include the route of absorption,
the presence of sources of environmental pollution in
certain residential areas, physiological variables, and
871
lifestyles. These aspects are frequently disregarded or
only partially explored (Bocca et al., 2010a).
6.1.2 Urine
Urine samples collected from the aforementioned
Italian volunteers were analyzed for Ir content. Find-
ings ranged from 0.7 to 70 ng/L, with an average con-
centration (±SD) of 18 ± 9 ng/L (Minoia et al., 1990).
In 1998, the German Environmental Survey analyzed
Ir concentrations in 1080 urine samples of subjects
randomly selected from the German National Health
Survey bank and representative of the total national
population. Mean Ir concentration related to volume
of urine and amount of creatinine was 0.24 ng/L and
0.19 ng/g creatinine, respectively (Becker et al., 2003).
A mean Ir concentration of 0.6 ng/L was detected in
samples collected from 19 male and female nonsmok-
ing, nonoccupationally exposed healthy subjects living
in Sweden (Rodushkin and Odman, 2001). In another
set of 30 samples obtained from Swedish nonoccupa-
tionally exposed subjects, Ir levels ranged from 0.04
to 0.05 ng/L (Rodushkin et al., 2004). Moreover, in the
same study, a set of pooled urine samples supplied for
a round-robin study was also investigated for Ir con-
tent. Samples were analyzed both in 2001 and in 2004,
with results (±SD) of 1.05 ± 0.04 and 0.35 ± 0.04 ng/L, in
the first and second measurement, respectively, with a
mean value (±SD) of 0.75 ± 0.42 ng/L (Rodushkin et al.,
2004).
6.2  Occupationally Exposed Population
6.2.1  Blood and Serum
With regard to the occupationally exposed popu-
lation, biological samples of blood and serum were
collected from three subjects employed in the differ-
ent production sectors (SSD, CD, CCD, and RD; see
Section 4.2 for definitions) of an industrial PGE plant
(Petrucci et al., 2004), from three subjects in the AS, and
10 control subjects not employed in the plant. SF-ICP-
MS revealed blood Ir concentrations of 0.02, 2.05, 0.03,
0.15, 0.04, and 0.001 μg/L in the SSD, CD, CCD, RD,
and AS subjects, and in controls, respectively. In the
same departments, serum Ir levels were 0.02, 0.74, 0.03,
0.16, 0.02, and 0.001 μg/L, respectively. Albeit interest-
ing, the Ir values reported in this study cannot be used
for establishing reliable reference values on account of
the limited number of subjects involved in the investi-
gation. In a subsequent work (Cristaudo et al., 2007),
the same group enrolled 122 subjects employed in the
production sectors of the factory, 16 employed in the
AS as internal controls, and 25 unexposed subjects for
biomonitoring evaluation. Ir concentrations in blood
872 Ivo Iavicoli and Veruscka Leso
were 0.02 ± 0.001, 0.21 ± 0.015, 0.03 ± 0.002, 0.16 ± 0.01,
0.05 ± 0.003, 0.04 ± 0.002, and 0.001 ± 0.0008μg/L in the
SSD, CD, CCD, RD, quality control (QC) department,
and AS, and controls, respectively. The highest mean Ir
level was found in workers in the CD, while the lowest
was detected in the samples taken in the SSD. Unfortu-
nately, these data did not confirm the environmental Ir
levels previously described.
6.3 Urine
Only limited data are available regarding Ir expo-
sure in the occupationally exposed population. Urine
samples collected during one work week from 15
Finnish workers engaged in the refining of noble
metals, manufacturing of catalysts, and repairing of
car exhaust systems were analyzed by Kiilunen et al.
(2004). A tentative Ir reference value for urine in non-
exposed Finns was set at 1 nmol/L. The highest mean
urinary metal concentrations (2.3  nmol Ir/L) were
measured in the manufacturing of car catalysts. Ir con-
centrations increased during the work shift.
Ir levels measured in three urine samples collected
from subjects employed in the previously described
industrial production and recycling PGE plant were
0.015, 0.01, 0.01, 0.01, 0.01, and 0.001 μg/L in the SSD, CD,
CCD, RD, AD, and nonexposed controls, respectively
(Petrucci et al., 2004). Comparable results were obtained
in a larger group of workers from the same plant by
Cristaudo et al. (2007), who found concentrations (±SD)
of 0.015 ± 0.002, 0.005 ± 0.001, 0.005 ± 0.001, 0.01 ± 0.001,
0.008 ± 0.002, 0.001 ± 0.0004, and 0.001 ± 0.0004 μg/L in
the SSD, CD, CCD, RD, QC, AD, and nonoccupation-
ally exposed controls, respectively. The lowest Ir values
were detected in the CD and CCD and, as assessed for
blood samples, the urine findings did not confirm the
environmental monitoring scenario.
Urinary Ir content was measured in another occupa-
tionally exposed population when urine samples were
collected in November 2005 from 64 tram drivers oper-
ating in the city of Rome (Iavicoli et al., 2008). Mean
Ir values (±SD) were 13.8 ± 15.7 and 13.4 ± 10.8 ng/L in
tram drivers and controls, respectively, indicating no
significant differences between the two groups. Inter-
estingly, these results suggest that tram drivers who
are occupationally exposed to vehicular traffic, are not
more exposed to Ir than the general population living
in an urban environment.
6.4  Other Matrices
A further matrix was investigated in an occupa-
tionally exposed population when Petrucci et al.,
(2004) and Cristaudo et al. (2007) determined Ir levels
in hair. Values of 0.0044, 0.204, 0.0005, 0.0042, 0.0005,
and 0.0002 μg/g were detected by Petrucci et al. (2004)
in workers in the SSD, CD, CCD, RD, AD, and con-
trols, respectively. Comparable results were deter-
mined by Cristaudo et al. (2007), with levels (±SD) of
0.0044 ± 0.0011, 0.20 ± 0.011, 0.0009 ± 0.001, 0.0001 ± .001,
0.004 ± 0.0001, 0.0005 ± 0.0001, and 0.0002 ± 0.0001 μg/g
in workers in the SSD, CD, CCD, RD, QC, AD, and con-
trols, respectively. On the whole, workers employed in
the CD had the highest body load of Ir. However this
finding was not in agreement with data obtained with
area samplers that revealed higher airborne Ir con-
centrations in the SSD (Petrucci et al., 2004; Cristaudo
et al., 2007).
7  EFFECTS AND DOSE-RESPONSE
RELATIONSHIPS
7.1  In Vitro Studies
Iavicoli et al. (2012b) demonstrated that IrCl3 hydrate
had cytotoxic effects on RAT-1 rat embryo fibroblasts
exposed for 48 h, with a concentration inhibiting the
growth of fibroblasts by 50% of 0.5 mM. A dose- and
time-dependent inhibition of cell proliferation was
determined after 48 and 72 h of exposure to 0.1 and
0.3 mM Ir, and a significant increase in apoptotic cells
was detected after a 72-h treatment. Inhibition of cell
growth was mainly associated with a reduction in
the percentage of cells in the G0/G1 phase of the cell
cycle and an accumulation of cells in the S and G2/M
phases. These findings suggest that Ir may have a toxic
effect that is probably linked to an inhibition of the
DNA synthesis process or to alterations in the S-G2/M
transition due to a block in cell division activities. The
authors found that the Ir salt was able to induce oxida-
tive stress, with accumulation of intracellular radical
oxygen species and DNA fragmentation as assessed by
Comet test.
7.2  Ex Vivo Studies
In an ex vivo study (Meiring et al., 2005), lungs
isolated from Wistar-Kyoto rats were ventilated with
120-min aerosols of ultrafine 17-20-nm sized 192Ir par-
ticles to achieve a lung burden of 100-200 μg. Inhalation
exposure was performed with and without prior lumi-
nal instillation of H2O2 or histamine in the perfusate.
No particle translocation, as assessed by radioactivity
in the perfusate, was found in the group treated only
with 192Ir, while there was an increase in 192Ir particles
in the perfusate in lungs pretreated with histamine
on the endothelial side (1 μM) or H2O2 in the alveolar
lumen (0.5 mM). These findings support the idea that
 40 Iridium
particle translocation is influenced by increased lung
and endothelial permeability induced by H2O2 oxi-
dative stress and histamine vasoactive action, respec-
tively. These alterations could explain 192Ir particle
passage into the interstitium via lung epithelium and
through the endothelium into the perfusate.
7.3  In Vivo Studies
Casarett et al. (1960) were the first to evaluate the
toxic effects of Ir exposure on animal models when they
treated 30 male rats with an 192Ir aerosol at a mean con-
centration of 1.2410−4 μg/L. Only the respiratory tract
was affected by exposure to 192Ir. In fact, the lungs of
two animals, sacrificed at 1 and 6 days postexposure,
respectively, exhibited foci of chronic bronchitis, bron-
chiectasias, and pneumonia. Chronic ulcerative bron-
chitis was observed in the major bronchi of an animal
sacrificed 6 days after inhalation. No other significant
pathological effects were observed during a 6-month
follow-up period.
Since Ir compounds had previously been shown to
cause immune sensitization in humans, the effects of
Ir subchronic exposure on the animal immune system
were investigated by Iavicoli et al. (2010). Increasing
doses of IrCl3 hydrate ranging from 0 to 1 mg/L were
administered to adult female Wistar rats via drink-
ing water for 90 days. Quantitative serum alterations
in the levels of two Th1 cytokines [interleukin-2 (IL-2
and interferon gamma (IFN-γ)] and one Th2 cytokine
(IL-4) were evaluated. Interestingly, Ir exposure dose-
dependently decreased the IL-2 and IFN-γ serum lev-
els, while increasing those of the IL-4. This finding
demonstrates that Ir exposure was able to induce an
immunological imbalance with a skewing toward a
Th2 bias, a known risk factor for asthma onset. More-
over, using the same methodology, Iavicoli et al. (2011)
also demonstrated nephrotoxic Ir effects evaluated by
alterations in the levels of a series of urinary proteins.
In fact, albumin levels increased in a dose-dependent
manner. In low-molecular-weight proteins, a signifi-
cant dose-related increase was detected in retinol-
binding protein (RBP), while no alteration compared
to controls was reported for β2-microglobulin. These
data demonstrate that renal tubule function is affected
by Ir exposure and also suggest that the metal may
have an effect on renal glomerular filtration capacity.
Moreover, they provide evidence for the role of RBP
as a sensitive biological marker of Ir-induced renal
damage.
Alessandrini et al. (2008) analyzed the poten-
tial effects of allergen sensitization and challenge on
total and regional deposition of 2-4-nm sized pri-
mary 192Ir ultrafine particles in the lung. Ovalbumin
873
(OVA)-sensitized and nonsensitized female BALB/c
mice were exposed for 1 h to ultrafine Ir particles
radiolabeled with 192Ir at a concentration of 0.2 mg/
m3 at two different time points, either before or after
allergen (OVA) challenge. Other sensitized and non-
sensitized mice were exposed to ultrafine Ir without
allergen challenge. Three days after Ir inhalation, a 21%
increase in the total ultrafine Ir deposited fraction was
observed in OVA-sensitized mice compared to nonsen-
sitized mice. Surprisingly, no differences in total and
regional deposition were detected in the two groups
during the elicitation phase of the allergic response.
This suggested that allergen sensitization alone can
affect ultrafine particle deposition in the lungs. Fur-
ther research is needed to establish whether higher
ultrafine particle deposition in sensitized individuals
compared to nonsensitized individuals or other fac-
tors such as alterations in long-term clearance kinetics
make a substantial contribution to the susceptibility of
allergic individuals to particle exposure.
7.4 Humans
7.4.1  Nonoccupationally Exposed Subjects
7.4.1.1  Hypersensitivity and Allergic Reactions
In 1955, a case report indicated a Pt alloy with a 10%
Ir metal content as a possible cause of contact derma-
titis (Sheard, 1955; Iavicoli et al., 2008). Ir can be recov-
ered in currently used dental amalgams as well as in
white gold onto which porcelain is fused for dental
crowns and/or bridges (Marcusson et al., 1998). Only
a few studies (Marcusson, 1996; ­Marcusson et al., 1998)
have focused on the role of Ir metal salts in dental
restoration materials that might lead to a hypersen-
sitivity mechanism causing local mucosal reactiv-
ity and systemic side effects. A short communication
(Marcusson et al., 1998) reported positive reactions
to IrCl3 in three Swedish subjects sporadically patch
tested for suspected hypersensitivity to dental mate-
rials during the period 1990-1995. One patient was
positive to all three test concentrations utilized: 0.1%,
0.32%, and 1% IrCl3. Another patient had positive
reactions to the two higher concentrations tested and
the third had a positive reaction only to the high-
est IrCl3 concentration. No reactions were obtained
with ammonium hexachloroiridate. Interestingly, the
patient positive to all three concentrations showed a
concomitant allergy to Ni and Pd metals. In the same
period (1992-1993), Marcusson (1996) used a standard
patch test procedure to investigate the presence of a
metal allergy in 397 patients who had reported sub-
jective symptoms related to dental restoration materi-
als. These ranged from oral symptoms (20-40% cases)
874 Ivo Iavicoli and Veruscka Leso
and muscle and joint disorders (52%) to pronounced
fatigue (62%). Only two patients (< 1% of the examined
population) tested positive to IrCl3. From 1995 to 1996,
in order to systematically investigate the presence of
metal hypersensitivity in subjects implanted with
metallic dental materials, Marcusson et al. (1998) con-
secutively tested 0.32 and 1% concentrated IrCl3 solu-
tions on 205 patients who had complained not only of
oral mucosal reactions but also of the aforementioned
systemic symptoms (Marcusson, 1996). Two patients
had positive reactions to both IrCl3 concentrations,
although only weak nonvesicular reactions were
observed in one subject. The patient who manifested
an extremely strong edematous vesicular reaction was
also allergic to gold.
Between March 2001 and September 2002, 720
eczematous patients were patch tested with 1% IrCl3
(Stingeni et al., 2004). No positive or irritant reactions
were observed in the subjects examined. Similarly,
no positive IrCl3 patch test reaction was detected in
a set of 25 patients with oral lichenoid manifestations
(Ditrichova et al., 2007).
Unfortunately, since no analysis was performed to
investigate Ir content in dental alloys, a clear causal
relationship could not be established between positive
patch test results and the metal recovered in dental
alloys, even if the onset of symptoms was temporally
related to the fixing of a variety of dental materials.
It should be noted that local symptoms such as cuta-
neous and mucosal alterations were not predominant
in this subgroup. Delayed hypersensitivity seemed to
be related to the presence of sensitized lymphocytes.
Hypothetically, the liberation of metallic material from
dental alloys might activate lymphocytes in vivo,
causing the release of cytokines that results in distant
effects (Marcusson, 1996). Forsell et al. (1996) have
developed a method for establishing the qualitative
composition of dental alloys that will facilitate fur-
ther studies of the possible side effects of these alloys.
Meanwhile, IrCl3 should be added to dental screen-
ing series (Marcusson et al., 1998). Another interesting
point of discussion is the concomitant presence of mul-
tiple metal allergies. There may be a kind of propen-
sity to develop allergy to metals. The high prevalence
of Ni allergy in the population (Marcusson 1996) may
be due to the overwhelming exposure in the environ-
ment and could make individuals prone to develop-
ing allergies to other metals such as PGEs when they
are exposed (Marcusson, 1996). In conclusion, despite
their low sensitization potential, Ir salts should prob-
ably be included in the screening series when subjects
who work in the jewelry and precious metals indus-
tries or who suffer from gingivostomatitis are patch
tested (Stingeni et al., 2004).
7.4.2  Occupationally Exposed Subjects
In the occupational setting, cases of sensitization to
Ir are known but rare (IUPAC, 2004). A nonatopic male
subject, employed in an electrochemical factory and
occupationally exposed for 3 years to IrCl3 aerosols,
developed contact urticaria and respiratory symptoms
such as rhinitis, a dry cough, and dyspnea (Bergman
et al., 1995). Clinical examination, chest X-ray, general
prick tests, and lung function and methacholine tests
proved normal on all occasions. When four solutions
from the workplace were tested on the forearm in a
scratch test, two produced extensive weal and flare
reactions within minutes. A congested nose, coughing,
and generalized urticaria were observed after 15 min.
This allergic reaction required prompt treatment with
steroids, antihistamine, and epinephrine to recede.
The two solutions that had produced the reaction were
found to contain Ir chloride (H2IrCl6); Ir was absent
from the other two solutions. In order to investigate the
presence of a possible specific immediate-type reaction
to Ir, a H2IrCl6 prick test was performed. The patient
showed a positive reaction only to the highest concen-
tration applied, corresponding to 5.0 × 10−4 g/mL. This
same concentration applied to the normal skin with-
out pricking caused follicular urtications and flare.
The patient did not react on testing with Pt, a common
impurity in solutions of all other PGMs, including Ir.
One year after occupational exposure ceased, a prick
test with H2IrCl6 solution of 5.8 × 10−4 g/mL gave a
weak positive reaction, while the scratch test produced
a positive reaction, and after 30 min the patient began
coughing and developed itching and conjunctival red-
ness. These results demonstrate that an Ir salt allergy
diminishes over time, but can persist for at least 1 year
after exposure ceases. Prick tests applied to 14 out of
the 16 persons who worked in the same factory as the
patient were negative, indicating that Ir salts do not
give a nonspecific positive reaction. This was the first
case report in which an individual simultaneously had
a positive prick test reaction to Ir salts and a negative
one to Pt salts.
Conversely, in previous studies carried out on
workers in a platinum refinery, Murdoch and cowork-
ers (Murdoch et al., 1986; Murdoch and Pepys, 1987)
observed some positive prick test reactions to Ir
salts. However, all of these workers simultaneously
responded positively to Pt salt, and the interpretation
was that Pt and other metals could be cross-acting.
However, the case presented by Bergman et al. (1995)
cannot be explained by cross-reactivity since the Ir salt
prick test was positive, while the Pt salt test was nega-
tive. Interestingly, application of Ir salt to normal skin
elicited contact urticaria and the scratch test caused
 40 Iridium
anaphylactic reactions. These reactions had not previ-
ously been described for Ir salts but are well known for
Pt salts. In this case, the patient may have been sensi-
tized through the airways, and the immediate strong
hypersensitivity reaction may have been due to a type
1 allergy.
From March to May 1999, 153 subjects variably
exposed in a plant producing all PGMs from primary
and secondary materials were patch and prick tested
with IrCl3 1% (Santucci et al., 2000; Cristaudo et al.,
2005). Some of these patients suffered from rhinitis
(28%), asthma (9%), urticaria (5.8%), and dermatitis
(5.8%). As controls, 800 nonoccupationally exposed
subjects affected by different forms of eczema or urti-
caria were consecutively enrolled and subjected to the
same analysis. Among exposed workers, positive prick
tests were detected in two subjects affected by asthma
and urticaria and in a third worker with rhinitis and
asthma. No positive results were observed with the
15 μL IrCl3 patch examination. IrCl3 never elicited irri-
tant or urticarial reactions in control subjects. All of the
positive workers manifested concomitant reactions to
hexachloroplatinic acid [H2(PtCl6)], and two had con-
comitant positive results also for Rh chloride (RhCl3),
potassium tetrachloroplatinate [K2(PtCl4)], and RhCl3,
and for sodium hexachloroplatinate [Na2(PtCl6)],
respectively. Comparable results were obtained in a
subsequent study (Cristaudo et al., 2007) in which the
authors performed prick and patch tests with 16 com-
mon inhalants and solutions of H2(PtCl6), IrCl3, RhCl3,
and Pd chloride (PdCl2) on 103 workers employed in a
catalyst production and refining plant. Three subjects
were simultaneously positive to the skin prick tests
with IrCl3, H2(PtCl6), and RhCl3 and developed one or
more respiratory symptoms such as wheezing, cough-
ing, and shortness of breath. These results lend sup-
port to the theory that refinery workers are exposed to
more than one of the PGM salts and that the concomi-
tant reactions might be due to a mechanism of cross-
reactivity, as suggested in previous studies (Murdoch
et al.,1986; Murdoch and Pepys 1987).
Exposure to Ir salts may cause acute toxicity or
hypersensitivity with respiratory symptoms, urti-
caria, and contact dermatitis. More in-depth studies
are needed to investigate the role played by the inten-
sity of exposure and the chemical forms of the metals
(International Programme of Chemical Safety, 1991).
Exposure intensity (e.g. in urban areas) could be vital
for determining the health risks of the general popula-
tion. At present, even if data on biological monitoring
show detectable Ir levels in the general population,
only two studies (Santucci et al., 2000; Cristaudo et al.,
2005) have evaluated the potential effects of IrCl3
hypersensitivity at a general, nonoccupational level
875
of exposure to this salt. No positive correlations were
found in either study. It is not clear which hypersensi-
tivity mechanism leads to these allergic reactions. Sen-
sitization routes may pass through the airways (aerosol
and dust) and minor skin lesions (Bergman et al. 1995).
Insufficient ventilation and poor enclosure of the
process equipment may have contributed to the spread-
ing of aerosols into the operators’ work zone; therefore,
it is important to take these aspects into consideration
when evaluating a suspected case of occupational sen-
sitization and when programming primary prevention
activity in plants.
The role of smoking and atopy should also be inves-
tigated to understand which factors may predispose
some exposed workers to Ir hypersensitivity (Santucci
et al., 2000). More attention should be given to the
possible effects of concomitant exposure to different
PGEs in occupational environments, since these are
all present in the workplace, all belong to the transi-
tional metal group, and are all highly reactive ele-
ments capable of causing inflammation and mediating
immunological effects (Cristaudo et al., 2005). None of
the reviewed studies have established a clear correla-
tion between environmental levels of Ir exposure and
sensitivity reactions. A careful evaluation needs to be
made of interactions between length of exposure, the
characteristics of occupational tasks, the atopic con-
dition of workers and other influencing factors, and
sensitivity to Ir salt. Furthermore, attention should be
given to the trend toward a continual increase in envi-
ronmental PGE emissions. If the average level of envi-
ronmental PGE emissions approaches those existing
in industrial settings, we will probably observe more
frequent health effects (Santucci et al., 2000).
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