Platinum, palladium and rhodium release from powder particles

exposed to simulated lung fluids

Claudia Colombo*, A. John Monhemius, Jane A. Plant

Department of Earth Science and Engineering, Imperial College London, London

SW7 2AZ, UK

*Corresponding author. Tel.: +44 (0)207 759 41362; Fax: +44 (0)207 594 7444 ; E-

mail address: claudia.colombo@ic.ac.uk

AbstractIncreases in platinum-group element (PGE) concentrations in ambient air and dust since the introduction of vehicle exhaust catalysts (VECs) is a cause of concerns. To assess the risks associated with the inhalation of VEC-emitted PGEs, extraction experiments on PGE-containing materials (i.e. road dust, auto catalyst and hydroxide samples) exposed to simulated lung fluids were performed. The aim of this study was to measure the release of PGEs in an inhalation scenario. Two synthetic lung fluids were used as surrogates for different areas of potential exposure in the human lungs: Gamble’s solution is representative of the interstitial fluid of the deep lung and artificial lysosomal fluid (ALF) is representative of the more acidic environment following phagocytosis by alveolar and interstitial macrophages within the lung. The results showed a higher PGE release for samples exposed to the acidic ALF compared to the neutral Gamble’s solution, implying that the inhaled particles would have to be phagocytized before a considerable solubilization of PGEs took place. The greatest percentage of released PGEs (up to 88%) was associated with road dust samples, most likely because of the transformations undertaken by these metals once deposited from VECs in the environment (i.e. formation of soluble and mobile species through complexation by inorganic and organic ligands common in the roadside environment). Pd and Rh showed higher % of metal release compared with Pt, probably due to differences in their mobilities and tendencies to form soluble complexes. The highest absolute bioavailability is observed for Pt however, because of its greater concentration in environmental samples. The elevated solubilization of Pt, Pd and Rh observed in the respiratory tract could involve the formation of PGE-chloride complexes. This observation merits particular attention considering the powerful toxic and allergenic effects of PGE-chloride salts on human beings and living organisms and the ever-increasing levels of PGEs in the environment due to VEC emissions.

Keywords: Platinum; palladium; rhodium; environment; lung fluids; health risk.

1

1. Introduction

Human exposure to particulate matter originating from traffic is finding

increasing interest and the widespread use of platinum, palladium and rhodium in

vehicle exhaust catalysts (VECs) has stimulated various scientists to study the

concentration of these metals in airborne samples at different urban sites and working

places {Gomez, 2001 #62}{Alt, 1993 #100}{Zereini, 2001 #113}{Bocca, 2004 #60}.

Platinum group elements (PGEs) are emitted in the exhaust gas from VECs with

emission rates in the ng/km range and their concentrations in urban air have increased

by more than two orders of magnitude in the last 20 years (up to approximately 110

pg/m3 {Merget, 2001 #72}). PGE emissions are thought to be mainly as fine

particulate material that originates from the abrasion and deterioration of the surface

of the catalyst. The annual Pt emission from VECs has been estimated at 0.5–1.4 ton

per year {Barbante, 2001 #102}. Pt, Pd and Rh are deposited along roadways, on

adjacent vegetation and soil, may be dispersed in silt, water and plants. Although

PGEs are mostly released in metallic and oxide form {Konig, 1992 #56;Artelt, 2000

#170;Schlogl, 1987 #188}, there is evidence that, following their deposition in the

environment, they can be transformed into soluble species by complexation with

ligands commonly found in nature, providing compounds able to enter the food chain

{Alt, 1993 #100}{Freiesleben, 1993 #133}{Lustig, 1996 #68}{Lustig, 1998 #131}

{Zimmermann, 2003 #85}{colombo, #246}{Wood, 2004 #138}.

Because of the toxic, cytotoxic and allergenic effects of some PGE species

(especially the chloride ones) and the increasing concentrations of VEC-emitted Pt,

Pd and Rh in the environment, there is growing concern over human health and

environmental risks resulting from PGE emissions. One of the major concerns for

exposure to VEC-emitted PGEs is sensitization of the airways caused by soluble PGE

2

compounds {Merget, 2000 #212}{Cristaudo, 2005 #162}. Many PGE compounds are

known as potent respiratory allergens leading to rhinitis, conjunctivitis, asthma and

urticaria {WHO, 1991 #189}{WHO, 2002 #190}. Signs of acute toxicity of several

PGE salts (such as H2[PtCl6], RhCl3, and PdCl2) in rats or rabbits included deaths,

decrease in feed and water uptake, emaciation, cardiovascular effects, peritonitis and

biochemical changes. There were also hemorrhages of lungs and the small intestine.

Moreover interactions with DNA were observed in vitro and an inhibition of DNA

synthesis were demonstrated both in vitro and in vivo {WHO, 2002 #190}. A study

on cell viability and oxidative stress in human bronchial epithelial cells {schmid, 2007

#292} showed that Pt and Pd had considerable toxic effects that are comparable if not

even exceeding the damage induced by heavy metal species such as Cd and Cr. The

mode of action of PGE ions and of elemental PGEs as dispersed dust in biological

systems is not fully clear. Similar to other transition metals, PGE ions follow a few

basic principles in their mode of action. Due to their ability to form strong complexes

with both organic and inorganic ligands, they have the potential not only to disturb

cellular equilibria or replace other essential ions but also to interact with functional

groups of macromolecules, such as proteins, enzymes and DNA/RNA, thereby

disrupting a variety of cellular processes. From occupational studies conducted in

VEC production, a no-effect level “critical range” of 15-150 ng/m3 has been

suggested {Merget, 2001 #72}. Higher concentrations could potentially induce

hypersensitivity reactions if halogenated PGE salts are present in VEC emissions or

are formed through transformation processes in the environment.

Very little information is available on the bioavailability of VEC-emitted PGEs

after inhalation. A study by Artelt et al. {Artelt, 1999 #54} provided bioavailability

measurements of a model platinum substance, similar to that emitted by VECs. This

3

substance was applied to Lewis rats during a 90 day inhalation study. The study

showed that the percentage of bioavailable platinum was up to 30%. The authors

concluded that the elevated in vivo solubility was most likely due to the ultrafine

structure of the platinum particles.

Data on PGE release into lung fluids relevant for human exposure are non-

existent in the literature. The inhaled particles may interact with cells and tissues in

the lung compartment in many different fashions. The mechanisms of these

interactions include the release of PGE species that may have a particular effect on the

human body. Reliable information on PGE-release from the inhaled particles in the

respiratory tract is crucial when assessing the potential risk for adverse effects arising

from exposure to these substances. The solubility of metal compounds in simulated

body fluids is commonly used for determining human health risk from exposure to

specific substances of concerns {midander, 2007 #277}{herting, 2006 #275}{herting,

2007 #276}{shi, 2006 #274}{stopford, 2003 #273}. Therefore, in this study, PGE-

containing materials, such as road dust and milled recycled catalyst have been

exposed to various simulated lung fluids to provide quantitative estimates of Pt, Pd

and Rh release in an inhalation scenario representative of a human being. Synthetic

hydroxide species have also been included serving as reference materials for

comparison of data. Artificial lysosomal fluid (ALF) and Gamble’s solution have

been used to simulate different interstitial conditions in the lung. ALF is analogous to

the fluid with which inhaled particles would come into contact after phagocytosis by

alveolar and interstitial macrophages within the lung. Gamble’s solution represents

the interstitial fluid deep within the lung. These fluids have previously been used to

investigate the bioaccessibility of cobalt compounds {stopford, 2003 #273}, the

4

copper release from powder particles {midander, 2007 #277} and metal release from

stainless steel {herting, 2007 #276}.

2. Experimental procedure

2.1. Test materials

Substrates evaluated for PGE release in the lung fluid experiments included two

-Certified Reference Materials (CRM) representative of (i) road dust with a

maximum particle size of 90 µm, from the Institute of Reference Materials and

Measurements, and (ii) powdered auto catalyst with a maximum particle size of 74

µm, from the National Institute of Standards and Technology (Table 1),

- Synthetic PGE-hydroxide species Pt(OH)2, Pd(OH)2 and Rh(OH)3 prepared

from the appropriate nitrate complexes (Johnson-Matthey) by precipitation with

NaOH, were also tested.

Test material Pt Pd Rh

Road dust (BCR-723) 81.3 µg/kg 6.0 µg/kg 12.8 µg/kg

Recycled catalyst (SRM-2557) 1131 mg/kg 233.2 mg/kg 135.1 mg/kg

Table 1: PGE content of Certified Reference Materials employed in the lung fluid

experiments.

1g road dust, 1g catalyst and 0.1g hydroxide sample (composed of 0.033g

Pt(OH)2, 0.033g Pd(OH)2 and 0.033g Rh(OH)3) were employed in the lung fluid

experiments.

2.2. Composition of simulated lung fluids

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The chemical composition of each ALF and Gamble’s solution is presented in

Table 2.

Chemicals (g/L) ALF

pH = 4.5

Gamble’s solution

pH = 7.4

MgCl2 0.050 0.095

NaCl 3.21 6.019

KCl — 0.298

Na2HPO4 0.071 0.126

Na2SO4 0.039 0.063

CaCl2·2H2O 0.128 0.368

C2H3O2Na — 0.574

NaHCO3 — 2.604

C6H5Na3O7·2H2O 0.077 0.097

NaOH 6.00 —

C6H8O7 20.8 —

H2NCH2COOH 0.059 —

C4H4O6Na2·2H2O 0.090 —

C3H5NaO3 0.085 —

C3H3O3Na 0.086 —

Table 2: Composition (g/L) of extraction fluids {midander, 2007 #277}{stopford,

2003 #273}.

The components of Gamble’s solution were added following the order in Table

2 to avoid precipitation of salts. Citrate was used in place of proteins and acetate to

6

replace organic acids. All chemicals were of analytical grades and both solutions were

prepared using ultra-pure water. Except for differences in salt composition, the main

difference between Gamble’s solution and ALF is the acidity: the former has pH = 7.4

whereas the latter has pH = 4.5. The ALF acidity may explain the higher level of

solubility for metals that are phagocytized compared to those that remain extracellular

{Costa, 1995 #278}.

2.3. Extraction method

The extraction experiments were performed by mixing the test material (1.0 g

for road dust and recycled catalyst or 0.1 g for the hydroxide species) with 100mL of

simulated lung fluid. The experiments were carried out in sealed containers to

minimize interactions between the reaction fluid and atmospheric oxygen and the

potential for cross contamination. Each experiment was conducted in duplicate and

blanks (containing only simulated lung fluids) were used. Each sample was placed

under dark conditions in a shaking incubator keeping the temperature at 37°C.

Extracts were filtered through a 0.2 µm filter to avoid any solid carry over. Different

extraction periods (up to 30 days) were investigated. The pH of each sample was

controlled at every extraction time and no variation superior to 0.2 units was

observed.

2.4. PGE analysis

All the extracts were analyzed for PGE content by inductively coupled plasma

mass spectrometry (ICP-MS), using an ICP-MS Varian model 810. The operating

conditions are given in Table 3.

Plasma

7

Plasma flow: 18.00 L/min

Auxiliary flow: 1.80 L/min

Sheath gas flow: 0.30 L/min

Nebulizer flow: 1.07 L/min

Sampling depth: 5.00 mm

Power: 1.40 kW

Pump rate: 5 rpm

Stabilization delay: 10 sec

Analysis Modes

Analysis type: Quantitative

Acquisition mode: Steady state

Scan mode: Peak hopping

Dwell time: 10000 µsec

Replicates/sample: 3

Scans/replicates: 30

Analytes: 63Cu, 65Cu, 87Rb, 87Sr, 88Sr, 89Y,

103Rh, 105Pd, 179Hf, 195Pt, 206Pb

Table 3: ICP-MS operating conditions.

ICP-MS is often used for the determination of PGEs in environmental samples

{Barefoot, 1997 #26;Ek, 2004 #33;Ravindra, 2004 #57} because of its excellent

detection limits that allow accurate determination of PGEs in the ppt range. The

determination of PGEs by ICP-MS is, however, hampered by spectral interferences

8

from monatomic and polyatomic ions produced in the argon plasma by the matrix

constituents: elements such as Cu, Y, Hf, Sr, Rb and Pb from road dust and catalyst

samples cause interferences with the PGE signals (Table 4).

Analyte Possible interfering species

195Pt

105Pd

103Rh

179Hf16O+

40Ar65Cu+ 89Y16O+ 88Sr17O+ 87Rb18O+

40Ar63Cu+ 87Sr16O+ 87Rb16O+ 206Pb2+

Table 4: Possible interferences in the ICP-MS determination of 195Pt, 105Pd and 103Rh.

All the experimental solutions were prepared daily in 2% HNO3 and matrix-

matched using simulated lung solutions. PGE calibration standards were prepared by

dilution of stock solutions of 1000 mg/L of Pt, Pd and Rh (all from Alfa Aesar,

Johnson Matthey). The linearity of the calibration plots (correlation coefficient >

0.99) was checked for Pt, Pd and Rh in the concentration range 0.1 – 100 ng/L and 0.1

– 100 µg/L. To compensate for instrumental drifts, 10 µg/L of internal standards (ISs)

were added to all samples. 115In for 105Pd and 103Rh and 191Ir for 195Pt were selected as

ISs because of their low abundance in the sample matrix, similar atomic mass and

chemical and physical properties to the PGEs. For the interference studies, single

element stock solutions (1000 mg/L) of Cu, Rb, Sr, Y, Hf and Pb (all from Alfa

Aesar, Johnson Matthey) were used.

3. Results

3.1. Interference correction

The isotopes 195Pt, 105Pd and 104Rh were used to determine the concentration of

Pt, Pd and Rh, respectively, in the samples because of their high natural abundance

9

and because they are subject to fewer interferences; possible interferences are reported

in Table 4.

Interferences were corrected mathematically by estimating the contribution of

interfering species to the PGE signal through the analysis of single element standard

solutions of interferents {Rauch, 2001 #47;Moldovan, 1999 #25;Gomez, 2000 #63}.

The concentrations of the interfering elements in the standard solutions were at

similar levels as those in the sample solutions. Corrections were calculated using the

following equation:

SA = SA,S – (SI,S RIO)

where SA is the corrected analyte (A) signal, SA,S is the interfered analyte signal

measured for the sample solution, SI,S is the signal for the interfering element (I) in the

sample solution, and RIO is the signal ratio IO+/I+ (ratio between the concentration of

the ions produced in the plasma that interfere on the PGE signal and the concentration

of the interfering element itself, i.e. 40Ar63Cu+/63Cu+). The signal ratio RIO for all the

interfering species needed in the correction equations were measured daily. This

mathematical correction method requires a linear dependence of the IO+ signal on the

I+ concentration. In this study, a linear dependence was observed for all the interfering

elements.

Considering all the interferences, the corrections for Pt, Pd and Rh were:

SPt = SA,S – (SHf,S RHfO)

SPd = SPd,S – (CCu,S RArCu + CY,S RYO + CSr,S RSrO + CRb,S RRbO)

SRh = SRh,S – (CCu,S RArCu + CSr,S RSrO + CRb,S RRbO + CPb,S RPb)

Unfortunately, the extremely low PGE concentrations in the extracted samples and the

high content of interfering elements in the matrixes hampered the determination of Pd

released by road dust exposed to ALF. Even lower PGE concentrations were

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observed in road dust samples exposed to Gamble’s solution, preventing the

determination of all the three PGEs (i.e. Pt, Rd and Rh).

3.2. PGE release

Reproducible results were observed for every duplicate experiment and the

blank analysis showed that neither of the simulated lung fluids interfered with the

PGE signal. The results on Pt, Pd and Rh release from the various test materials in

ALF and Gamble’s solution are illustrated in Figures 2 and 4 respectively. In Figures

3 and 5 results are represented in terms of % of PGE released to allow comparison

between compounds and between extraction fluids.

a

0

0.05

0.1

0.15

0.2

0.25

0.3

0 100 200 300 400 500 600 700

Time of exposure (hours)

Tota

l rel

ease

(ppb

)

PtRh

11

b

0

50

100

150

200

250

0 100 200 300 400 500 600 700

Time of exposure (hours)

Tota

l rel

ease

(ppb

)

PtPdRh

c

0

5

10

15

20

25

0 100 200 300 400 500 600 700

Time of exposure (hours)

Tota

l rel

ease

(ppm

)

PtPdRh

Figure 2: Total Pt, Pd and Rh release from road dust (a), auto catalyst (b) and

hydroxide samples (c) exposed to ALF.

12

0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700

Time of exposure (hours)

% re

leas

ed

Pt (road dust)Rh (road dust)Pt(auto catalyst)Pd(auto catalyst)Rh(auto catalyst)Pt(hydroxide)Pd(hydroxide)Rh(hydroxide)

Figure 3: % of Pt, Pd and Rh released from road dust, auto catalyst and hydroxide

samples exposed to ALF.

a

0

2

4

6

8

10

12

14

16

0 100 200 300 400 500 600 700

Time of exposure (hours)

Tota

l rel

ease

(ppb

)

PtPdRh

13

b

0

50

100

150

200

250

300

350

400

0 100 200 300 400 500 600 700

Time of exposure (hours)

Tota

l rel

ease

(ppb

)

PtPdRh

Figure 4: Pt, Pd and Rh release from auto catalyst (a) and hydroxide samples (b)

exposed to Gamble’s solution.

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0.45

0.5

0 100 200 300 400 500 600 700

Time of exposure (hours)

% re

leas

ed

Pt(auto catalyst)Pd(auto catalyst)Rh(auto catalyst)Pt(hydroxide)Pd(hydroxide)Rh(hydroxide)

Figure 5: % of Pt, Pd and Rh released from auto catalyst and hydroxide samples

exposed to Gamble’s solution.

14

The results of the extraction experiments for the three different test materials

(road dust, auto catalyst and hydroxide) exposed to ALF showed that metal releases

changed with substrates, with the road dust samples showing much higher percentages

of released PGEs than either the catalyst or the hydroxide samples (Fig. 3). For road

dust samples, the percentage of released Pt was about 36% and released Rh about

88%, whereas for the auto catalyst and hydroxide samples, the percentage of released

PGEs was less than 8% and 10%, respectively (Fig. 3). The extraction experiments

conducted employing Gamble’s solution showed a low percentage of release for

PGEs: up to 0.45% for auto catalyst and 0.15% for hydroxide samples (Fig. 5).

The results also showed considerably lower metal release from samples exposed

to Gamble’s solution (pH 7.4) compared to ALF (pH 4.5) (Fig. 3 and 5).

For road dust samples exposed to ALF, the percentage of released Rh was

higher than the one for Pt in road dust samples exposed to ALF (Fig. 3). The auto

catalyst and hydroxide samples exposed to ALF and Gamble’s solution, showed

percentages of released PGEs in the following order: Pd > Rh > Pt (Fig. 3 and 5).

The results for the absolute PGE releases showed that for road dust samples the

amount of released Pt was greater than the amount of released Rh (Fig. 2a) and for

auto catalyst samples, the absolute release order was Pt > Pd > Rh (Fig. 2b and 4a).

Because the hydroxide sample contained the same amount of Pt, Pd and Rh (see

paragraph 2.1), the extraction experiments employing this material showed an

absolute release order identical to the percentage of release order (Fig. 2c and 4b).

4. Discussion

The elevate percentages (36% for Pt and 88% for Rh) of released PGEs

observed for road dust samples (Fig. 3 and 5) corroborate previous assumptions that

15

PGEs in road dust have been transformed from a metallic form to much more soluble

species, probably through complexation by inorganic ions {colombo, #246} and

humic substances commonly found in the environment {Wood, 1996 #222} {Lustig,

1998 #132;Lustig, 1996 #68;Lustig, 1998 #131}. Besides, the % of released Pt from

road dust observed in this study (36%) was in accordance with the results of Artelt et

al. {Artelt, 1999 #54} that exposed Lewis rats to a material resembling VEC-

emissions during a 90-day inhalation study and found that about 30% of the Pt

deposited in the lung was bioavailable.

The higher metal release observed from samples exposed to ALF compared to

Gamble’s solution (Fig. 3 and 5) is probably due to the acidity of the former

compared to the neutrality of the latter (ALF pH = 4.5 and Gamble pH = 7.4). This

suggestion is supported by various studies reporting increased PGE solubilities in

acidic environments {Nachtigall, 1996 #129}{Fuchs, 1974 #130}{Zereini, 1997

#22}. The higher PGE release observed in ALF implies that inhaled PGE particles

would have to be phagocytized before a significant solubilization occurred.

The different % of release for Rh and Pt from environmental samples (i.e. road

dust) (Fig. 3) can be attributed to different reactions the two metals undergo once

emitted by VECs and deposited in the environment. The more mobile nature of Rh

{Rauch, 2000 #106} and its higher tendency to form complexes with humic

substances than Pt {Wood, 1996 #222} support this assumption. The percentage of

released Pd in road dust samples (which could not be determined because of

interference issues, as discussed in paragraph 3.1) would probably be the greatest due

to the highly soluble and mobile nature of this element {Ravindra, 2004 #57;Ek, 2004

#33}. The percentage of release order observed in the extraction experiments

involving auto catalyst and hydroxide samples exposed to ALF and Gamble’s solution

16

(Fig. 3 and 5) was in agreement with the findings of several solubility studies {Ek,

2004 #33;Ravindra, 2004 #57} that reported the highest solubility for Pd followed by

Rh and eventually Pt. Pt/Pd and Pt/Rh concentration ratios in environmental and

biological samples indicate different transformation for the three metals once

deposited in the environment by VECs {Ek, 2004 #33}. Concentration ratios in VECs

are about 5 for Pt/Pd and 8 for Pt/Rh (Table 1) and they decrease further up the food

chain, indicating a higher mobility and biological uptake for Pd and Rh compared to

Pt: in airborne particles, road dust and soil the Pt/Pd ratio is about 3 and Pt/Rh about

6, in invertebrates and birds the ratios decrease to 0.5 for Pt/Pd and 1.3 for Pt/Rh and

both ratios are lower than 0.1 in human urine and blood.

The results for the absolute PGE release (Fig. 2a, 2b and 4a) reflected the

relative PGE concentrations in the environmental samples (i.e. road dust and catalyst)

employed in the extraction experiments (Table 1). It can therefore be concluded that,

despite Pd and Rh being more soluble and mobile than Pt (% of release is in the order

Pd > Rh > Pt), the higher amount of Pt present in the samples accounts for its highest

absolute release in the respiratory tract.

A crucial parameter to consider when assessing the risk associated with

inhalation of dusts is the particle size of the inhaled material. Research about the size

distribution of the PGEs emitted from modern three-way VECs {Artelt, 1999 #52}

{Gomez, 2002 #41}{Merget, 2001 #72} showed that the size fraction of particles with

a diameter > 10.2 µm ranged from ca. 43 to 71% and the small sized fraction of

particles (particle diameter < 3.1 µm) was between 11 and 36%. Importantly for this

study, the particle-size distribution of the reference material road dust (BCR-723) was

measured by laser diffraction spectroscopy {Zischka, 2002 #64}: the results showed a

particle top size of less than 90 μm, a median particle size of 13.2 μm, about 36% of

17

the particle (volume %) smaller than 10 μm and about 16% of the particle (volume %)

smaller than 4 μm. Particle size affects where inhaled particles may be deposited in

the respiratory tract. Small particles (Ø < 4 µm) and aggregates of nano-particles that

easily fragment are capable to penetrate the alveolar region of the respiratory system,

causing an inflammatory response {murr, 2004 #279}. Particles with a diameter > 10

µm and up to 100 µm are inhalable, but are mainly deposited in the upper respiratory

tract, whereas particles with a diameter < 10 µm have a likelihood of ≥ 50% to reach

the tracheobronchial region {Merget, 2001 #72}.

From the toxicological perspective, it is important to consider the possible

formation of PGE-chloride complexes in the respiratory environment due to the

presence of HCl. It has been shown that, in acidic conditions (ALF pH = 4.5) and in

presence of chloride ions, PGE-chloride species can be formed {colombo, #246}

{Fuchs, 1974 #130}{Zereini, 1997 #22}. Potent allergenic effects of PGE-chloride

salts on human beings, as well as acute toxicity in laboratory mammals, including

death, cardiovascular effects, reproductive toxicity and DNA mutagenicity {WHO,

1991 #189}{WHO, 2002 #190} suggest an increased health risk due to the presence

of these species. Topical exposure of mice to respiratory sensitizing Pt salts caused a

similar quality of immune response to that induced by epicutaneous application of

organic allergens, such as toluene diisocyanate or cyanuric chloride {dearman, 1998

#301}.

In a previous study, the bioavailabilities of PGEs from road dust, auto catalyst

and hydroxide samples were estimated using a physiologically based extraction test

(PBET) {colombo, #300}. In the PBET assay, digestive juices based on human

physiology are used to extract soil contaminants, in conditions that mimic those in the

human digestive tract. The PBET results supported the findings of this study: much

18

higher percentages of bioavailable PGEs were observed in road dust samples

compared to auto catalyst and hydroxide samples, Pd and Rh showed higher

bioavailabilities compared with Pt and the highest absolute release in environmental

samples was observed for Pt, because of its greater concentration. In order to evaluate

the potential pathways (inhalation and ingestion) of VEC-emitted PGEs into humans,

it is useful to compare the PGE release from road dust samples in the respiratory and

digestive environment: about 17% of Pt and 68% of Rh were solubilized during the

PBET experiments, whereas about 36% of Pt and 88% of Rh were solubilized during

extraction experiments with lung fluids. A higher PGE uptake was therefore observed

for the respiratory tract compared to the digestive tract.

5. Conclusion

VEC-emission of PGEs in populated urban areas has resulted in an increasing

concern about the hazardous effect of these new pollutants for people and other living

organisms. Very little information is available on the behaviour of PGEs after

exposure via inhalation. In order to address this information gap, a study of the release

of PGEs from road dust, auto catalyst and hydroxide samples was carried out.

Detailed data on Pt, Pd and Rh release from the various PGE-containing

materials were generated. The in-vitro extraction experiments were performed in ALF

(pH 4.5) and Gamble’s solution (pH 6.4), where the former represents conditions

occurring in conjunction with phagocytosis by alveolar and interstitial macrophages

and the latter represents the interstitial fluid deep within the lung. The acidity of ALF

is probably responsible for the higher PGE release observed in samples exposed to

this fluid compared to Gamble’s solution. This result implies that the inhaled particles

19

would have to be phagocytized before a considerable solubilization of PGEs took

place.

Road dust provided the greatest percentage of released PGEs: percentages of

release up to 88% were detected. This is most likely due to transformations that PGEs

undertook once deposited from VECs in the environment. These transformations

include complexation by inorganic and organic ligands common in the roadside

environment leading to the formation of more soluble and mobile species.

The different % of release of Pt, Pd and Rh observed in this study can be

attributed to differences in their mobilities, tendencies to form soluble complexes and

transformations in the environment. The results of the extraction experiments support

the assertion that Pd and Rh have higher mobilities and biological uptakes compared

with Pt: the % of metals release followed the order Pd > Rh > Pt. The highest absolute

release is observed for Pt, however, because of its greater content in the road dust and

auto catalyst samples.

A comparison of the results from the present study with a previous one

{colombo, #300} investigating the bioavailabilities of PGEs from road dust, auto

catalyst and hydroxide samples in fluids mimicking the human gastrointestinal tract

showed a higher PGE uptake by the respiratory tract compared to the digestive tract.

This study demonstrated that human beings can uptake up to 88% of VEC-

emitted PGEs via inhalation exposure. Owing to the presence of chloride in the lung

fluids, the solubilization of Pt, Pd and Rh in the respiratory tract could be in part due

to, or involve, the formation of PGE-chloride complexes. This information needs

particular attention in view of the powerful toxic and allergenic effects of PGE-

chloride salts on human beings and living organisms and of the ever-increasing levels

of PGEs in the environment due to VEC emissions.

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Acknowledgments

The research presented in this paper was partially supported by Anglo American

plc. We are grateful to Dr. Raquel Garcia-Sanchez and Dr. Eva Valsami-Jones at the

Natural History Museum for ICP/MS measurements. We would also like to thank

anonymous reviewers for critically reading the manuscript and suggesting

improvements to the text.

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