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Source and Nature of Inhaled Atmospheric Dust from Trace Element

Analyses of Human Bronchial Fluids

Article · August 2011

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Published: June 21, 2011

r 2011 American Chemical Society 6262 dx.doi.org/10.1021/es200539p | Environ. Sci. Technol. 2011, 45, 6262–6267

ARTICLE

pubs.acs.org/est

Source and Nature of Inhaled Atmospheric Dust from Trace ElementAnalyses of Human Bronchial FluidsPaolo Censi,*,†,‡ Pierpaolo Zuddas,§ Loredana A. Randazzo,†,§ Elisa Tamburo,† Sergio Speziale,||

Angela Cuttitta,‡ Rosalda Punturo,^ Pietro Aric�o,† and Roberta Santagata#

†Dipartimento DiSTeM, Universit�a di Palermo, Via Archirafi, 36 90123 - Palermo, Italy‡I.A.M.C.-CNR �UOS di Capo Granitola, Via del mare, 3 - 91026 Torretta Granitola, Campobello di Mazara (TP), Italy§Institut de G�enie de l0Environnement Ecod�eveloppement and D�epartement Sciences de la Terre, UMR 5125,Universit�e Claude Bernard Lyon 1, 2 rue R. Dubois, Bat GEODE 69622 Villeurbanne Cedex, France

)Deutsches GeoForschungsZentrum, Telegrafenberg, Potsdam 14473, Germany^Dipartimento di Scienze Geologiche, Universit�a di Catania, Corso Italia, 57 - 95129 Catania, Italy#Dipartimento Biomedico di Medicina Interna e Specialistica, sezione di Pneumologia (DI.BI.M.I.S.),Universit�a degli Studi di Palermo - Via Trabucco n� 180, 90146 Palermo, Italy

bS Supporting Information

’ INTRODUCTION

Suspended atmospheric dust is a very heterogeneous assort-ment of particles derived from several sources, characterized bydifferent compositions and reactivity as regards of fluid phase. Inanthropized areas people are exposed to the almost constantinhalation of lithogenic and anthropogenic atmospheric dustdelivered from natural sources, automotive traffic, and/or in-dustrial activities. Effects on human health related to the inhala-tion of these atmospheric particulates are mainly recognized asprecursors of silicosis, asbestosis, and cancers, whereas only ascarce literature is available focused on effects of the dissolutionof atmospheric dust in the presence of human bronchial fluids.1�3

This represents a lack of knowledge since environmental solidsare often a source of concentrated metallic elements that can bereleased in biological fluids, and the amplitude of trace elementsleachable from these solids depends from their composition andnature.4,5

The research presented in this study is based on a newapproach to the identification of source materials of inhaled dustparticles. The new method is based on geochemical treatment of

trace element concentrations in bronchoalveolar fluids collectedfrom people exposed to the inhalation of a wide mixture ofatmospheric dust particles formed during summer 2001 in Cataniaas a consequence of eruption of Mount Etna.

In Catania, the second largest town in Sicily, located at the footof Mount Etna, people were exposed to the effects of intensefallout of atmospheric particulate matter induced by the pyr-oclastic activity of Mount Etna, the largest active Europeanvolcano. Moreover, Catania is characterized by a wide range ofindustrial activities (two of the largest chemical industrial areas inthe Central Mediterranean area are located in Gela and Augusta,about 50 km far from Catania), and traffic usually constitutes themajor source of air pollution in the area. These circumstancesenabled us to test a geochemical method focused on the sourcerecognition of inhaled atmospheric particulates from people

Received: February 22, 2011Accepted: June 21, 2011Revised: June 14, 2011

ABSTRACT: Rapid volcanic eruptions quickly ejecting large amounts of dustprovoke the accumulation of heavy metals in people living in surrounding areas.Analyses of bronchoalveolar lavage samples (BAL) collected from people exposedto the paroxysmal 2001 Etna eruption revealed a strong enrichment of many toxicheavy metals. Comparing the BAL to the dust composition of southeastern Sicily,we found that only V, Cr, Mn, Fe, Co, and U enrichment could be related to thevolcanic event, whereas Ni, Cu, Cd, and Pb contents come from the dissolution ofparticles of anthropogenic origin. Furthermore, the nature of these inhaledanthropogenic particles was revealed by anomalous La and partially Ce concentra-tions in BAL that were consistent with a mixture of road dust and petroleumrefinery emissions. Our results indicate that trace element distribution in BAL is asuitable tracer of human exposure to different sources of inhaled atmosphericparticulates, allowing investigations into the origin of source materials inhaled bypeople subjected to atmospheric fallout.

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exposed to complicated environmental conditions where differ-ent concurrent sources of atmospheric dust can be present. Forthe first time, a study was carried out on bronchoalveolar fluidscollected from exposed people, rather than a direct study ofatmospheric dust, to test whether or not lung fluids record theeffects of interactions with atmospheric dust. Thus, a novel typeof environmental research study was undertaken to simulta-neously evaluate the amplitudes of exposure of involved peopleto major, minor, and trace metal components of atmosphericparticulates, the bioavailability of these elements in lung fluids,and the recognition of source materials present in the air columnof the studied area.

’EXPERIMENTAL SECTION

Characteristics of fine particulate matter emitted from theMount Etna volcano in the summer of 2001: Volcanic ejectaduring the summer of 2001 fromMount Etna typically consistedof amixture of several solid phases ranging from particles made ofsilicate minerals and volcanic glass to soluble salts adsorbed ontothese particles.6�8 The solid fraction of ejected materials mainlyconsisted of glass fragments (about 70%) with smaller amountsof clinopyroxene (about 15%) and minor amounts of olivine andspinel.9,10 Furthermore, a soluble ash fraction (SAF) coated thesurfaces of solid particles. More recently, Delmelle et al.8 demon-strated that this coating represents the effect of reactionsoccurring between gases/aerosols and silicate ash particles involcanic eruption plumes and consisted of highly soluble sub-limates of acids, metal salts, and adsorbed fluids formed duringthe uprising in the volcanic eruptive plume.6

Bronchoalveolar lavage (BAL) extraction and chemical sam-ple processing: Six patients of the Department of InternalMedicine of Catania University were subjected (after giving theirwritten informed consent) to the BAL procedure during thesummer of 2001, when the city of Catania was exposed to thesevere delivery of atmospheric particulate matter produced bythe pyroclastic activity of Mount Etna, the largest active Eur-opean volcano. Due to the closeness of Catania to the source ofthe eruption, this densely populated urban area was subjected toan intense delivery of volcanic particulate matter mainly consist-ing of mineral, glass, and rock fragments between 1 and 500 μmdiameter, with the most frequent grain size within the range of5�10 μm diameter.9�12

The BAL samples were obtained via instillation of four lavageswith 30 mL aliquots of a sterile solution of 0.9% w/v NaCl, usinga fibrobronchoscope,13 where each aliquot was immediately andgently aspirated. From each 20 mL lavage sample collected, only10 mL was used for chemical investigations. After filtrationthrough a 0.22 μm Nalgene membrane, each BAL sample wastreated with 15 mL of hydrogen peroxide, 5 mL of 30% HNO3

solution, 30% HCl solution, and 0.1 g of solid NH4F in a poly-tetrafluoroethylene (TFM) reactor. The reactors were sealed andheated in a microwave oven (MARS 5, CEM Corporation, UK)at 3 � 105 Pa and 200 �C for 30 min. Excess acid was removedfrom each solution up to incipient dryness using a CEM microvapapparatus, and an HNO3 solution (5% v/v) was added to attainfinal solution volumes of 20 mL. The solutions were finallytransferred to previously cleaned polycarbonate vials. The sam-ples were treated under a clean laminar airflow to minimizecontamination risks.

Trace element analyses were carried out using a sector fieldSF-ICP-MS Thermo-Fisher Element 2 using an external calibration

approach. The calibration for each element was based on sevenstandard solutions at known concentrations prepared by diluting1 g/L of a single-element solution (Merck ICP standard), similarto the procedure used by Rodushkin and Odman.14

The accuracy of the different procedures was evaluated byanalyzing five aliquots of CASS-4 and NASS-5 certified referenceseawaters (National Research Council of Canada; Ottawa,Ontario, Canada), which are reported in Table S2 in the SupportingInformation (SI). Analytical precision was evaluated using thesame sterile solution as used for the collection of BAL samples.The same quantities of chemicals used in the treatment of BALsamples were added to five aliquots of sterile solution (SS).These solutions were subject to mineralization procedures andrepresent our procedural blanks, which were used to determinecritical values (LC) and detection limits (LD) for the traceelements investigated according to the expressions

LC ¼ 2:33�σPBs

LD ¼ 4:65�σPBsð1Þ

where σPBs is the standard deviation of the procedural blankmeasurements, and quantification limit (LQ) was calculated asten times the amount of σPB, according to EPA procedures.15

The results obtained are reported in Table S3 in the SupportingInformation (SI). The low LQ values (see Supporting Information)indicated that the amounts of trace metals lost and/or addedduring sample collection and preparation were negligible withrespect to the trace element contents of the BAL samples.

All of the solutions studied were prepared using Milliporeultrapure water (18.2 MΩ). All chemicals used in the samplepreparation and analysis were Merck ULTRAPUR (VWR Inter-national, West Chester PA). All materials used to sample andmanipulate the water samples were plasticware, acid cleaned withhot 1:10 HNO3 aqueous solutions.

’RESULTS AND DISCUSSION

BAL Composition. The amplitude of Etna’s eruption duringJuly-August 2001 was large enough to expose all people living insoutheastern Sicily to volcanic particle inhalation. This fact madea typical comparative study of BAL composition in exposedpeople and control subjects virtually impossible to carry out.Therefore, the results of minor and trace element compositionsin the BAL samples of people exposed to volcanic particleinhalation were compared with the few minor and trace elementanalyses carried out for BAL lavage samples in other studies.16

The amounts of minor and trace elements measured in thisstudy, reported in Table S1 in the Supporting Information (SI),ranged between 0.2 μg L�1 for U and 229.36 mg L�1 for Al. Thelatter, together with Fe, was the most abundant of the elementsstudied in the BAL solutions. Concentrations of Y, La, andlanthanides (i.e., rare earth elements) were previously reportedby Censi et al.17 Variation coefficients of the minor and traceelements investigated, calculated as the ratio between the stan-dard deviation and average values of each element, were larger forCu, Cd, Ni, As, and U, ranging from 69% to 114%, and lower forthe other investigated elements, falling between 22.5% (Fe and Co)and 48.5% (V). Many of these values were different both interms of concentration and the observed variability when com-pared to analogous data recently reported by Bargagli et al.,16 asshown by the descriptive statistics of BAL analyses shown inFigure 1. Due the good quality of analyzed data evidenced in

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Tables S2 and S3 of Supporting Information, we attribute thevariability of elemental concentrations in BAL to different level ofexposure of investigated subjects to inhalation of atmosphericparticles. This hypothesis is corroborated by lower trace elementconcentrations reported by Bargagli et al.16 with respect to thoseanalyzed in BAL, especially for iron, which is the most enrichedelement in their data. Moreover also smaller ranges of traceelement variations in BAL fluids with respect to those

observed by Bargagli et al.16 agree to this hypothesis due tothe amplitude of the delivery of atmospheric particulatematter during pyroclastic activity of Mount Etna. In order toclarify whether or not the inhaled particles came from atmo-spheric fallout of the volcano alone, a typical geochemicalapproach based on an investigation of the amplitudes ofenrichment factors of the trace elements in the BAL fluidsstudied was carried out.

Figure 1. Descriptive statistics of the concentrations analyzed in BAL solutions compared to reference values (red numbers) given as averages byBargagli et al.16 The green areas represent values from 25% and 75% quartiles. The dashed red lines represent maximum and minimum values of eachelement. All concentrations are given as μg L�1.

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Enrichment Factors (EFs). Elemental enrichment factors inthe lung fluids were estimated for the elements investigated withrespect to the contents of Al, according to the following equation18

EFðREFÞ ¼½X�BAL½Al�BAL½X�REF½Al�REF

ð2,Þ

where [X] is the concentration of a given element in the BALsample (BAL) or in a hypothetical source material used as thereference.19 In general, EF values smaller than 5 indicate that theelement under consideration is not significantly enriched in the BALsample with respect to the hypothesized source, whereas EFs largerthan 5 imply an enrichment of the element under investigation inthe materials being studied with respect to the chosen source.20

In order to establish what was a suitable source for trace elementsrecognized in BAL fluids EF values for investigated elements werecalculated as regards of the most suitable source materials:i soluble ash fraction occurring as coating of solid ash particles(SAF) consisted of highly soluble sublimates of acids, metalsalts, and adsorbed halogen-rich fluids (formed during theuprising of the volcanic eruptive plume;6

ii parent magma (PM) of Etna eruption in summer 2001.Both SAF and PM concentrations are given in Aiuppa et al.21

Otherwise, also the hypothesis that an atmospheric particulatefraction from automotive traffic could inhaled by studied sub-jects, EF values were also calculated with respect to a suitableroad dust composition (RD). It was recognized from data ofDongarr�a et al.22 who studied atmospheric pollution in Messina,a town characterized by a dense automotive traffic, located atabout 60 far from Catania and characterized by similar climaticconditions occur.22

EF(SAF) values in BAL fluids are lower than 1 for V, Mn, Co,Cu, and Cd (highlighted by green ellipses); close to 1 or slightlylower for Cr, Fe, As, Pb, and U; larger than 1 for Ni (Figure 2A).These results suggest that a Ni contribution from a differentsource with respect to SAF occurred. Cr, Fe, As, Pb, and U couldbe released during dissolution of the soluble fraction of volcanicmaterials, but it is hard to accept that soluble salt coatings remainundissolved during interactions with lung clearance fluids. There-fore the leaching of V, Mn, Co, Ni, Cu, and Cd from PM oranother source is suggested. To clarify this hypothesis EF(PM)

values for the latter elements were also calculated and reported inFigure 2B.These EF(PM) values were lower than 1 for V, Mn, and Co,

close to 1 or slightly lower for Ni and Cu (highlighted by greenellipses), whereas the Cd EF(RD) value was higher than 1. Theseevidences indicate that both Ni and Cu were released from PMinteracting with lung fluids, whereas V,Mn, andCo are leached inBAL fluids from partially dissolved glass ash fraction particles.The observed Cd EF(RD) value probably indicates their releasefrom a further anthropogenic RD source. It is confirmed bythe calculation of Cd EF(RD) in BAL fluids that produced a widerange of values centered on 1 probably due to the variableexposure of investigated subjects to the inhalation of road dustduring eruption of Mount Etna in summer 2001 (Figure 2C).To clarify whether the low values of EFs of Co, Mn, Ni, Cu,

and Cd were induced by partial dissolution of inhaled atmo-spheric particles, the EF(PM) and EF(RD) of these elements werecompared in Figure 3 to the amount of labile trace elementfractions occurring in atmospheric dust particles interacting with

simulated biological fluids.23 The increase of the EF(PM) of Co,Mn, Ni, Cu, and Cd is related to the bioaccessibility of theseelements contained in PM10 particles interacting with simulatedbiological fluids. Similarly, amplitudes of EF(RD) of Co, Mn, Ni,and Cd are correlated to the increase of the bioaccessibility of the

Figure 2. Enrichment factors (EF) calculated for studied elements withrespect to different possible parent materials: A, soluble fraction oferupted ash (ASF); B, Etna’s parentmagma (PM) of 2001 eruption; andC,road dust (RD). Pale green ellipses highlight elements whose source issuggested. Gray areas represent values falling 1 and 5. Black dots aremedians, and red segments link maximum to minimum EF values foreach measured element. Data on Etna’s parent magma and the solubleash fraction (SAF) are reported in Aiuppa et al.21 For further details,please see the text.

Figure 3. Relationship between the EF values calculated with respect tothe Etna’s parent magma (PM) (black dots) and road dust referencecomposition (RD) (circles) for elements with EFs < 1 in Figure 2B and C.Mn, Co, Ni, Cu, and CdEF(PM) values reported in Figure 2Bwere used tocalculate the curve (1), whereas Mn, Co, Ni, and Cd EF(RD) valuesreported in Figure 2C were used to calculate the curve (2). Values ofbioaccessible trace element fractions were reported in Falta et al.23Red dotrepresents Cu EF(RD) value not used for calculation of curve (2).

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latter elements in PM2.5 particles (Figure 3). Being bioaccessi-bility calculated from kinetic experiments carried out by Faltaet al.23 it is a time-dependent parameter. Therefore relationshipsreported in Figure 3 assume an exponential form because alsoEFs values have a kinetic significance, confirming that amplitudesof EF values are related to the trace element leaching frominhaled particles in lungs fluids.Y, La, and lanthanides, usually named Rare Earth Elements

(REE), released from inhaled solids interact with lung fluids andcoprecipitate as phosphates in bronchoalveolar spaces, allowingto several health diseases.24 The behavior of these elements,recently investigated in this particular environment, is character-ized by strong elemental fractionations that involve enrichmentsof elements from Nd to Ho in newly formed precipitates,whereas Y, La, Ce, and lanthanides from Er to Lu preferentiallyremain in dissolved phase.17 Being REE contents reported byCensi et al.17 influenced by phosphate crystallization in bronchialspaces their EF values were not calculated. Otherwise Censiet al.17 observed a large enrichment of Y and La in BAL fluids,also taking into account the phosphate crystallization, andhypothesized that Y and La could be delivered by a La-enrichedanthropogenic source, apart from the volcanic ash. Being La-richcarbonates and zeolites employed as catalytic converters in hydro-carbon refinery industry, La enrichments are considered typicalenvironmental signatures of the delivery of atmospheric particulatesduring hydrocarbon combustion in power stations.25�27 Thereforein order to verify this hypothesis we compared compositions of BALfluids with compositions of erupted ash particles using La �2�Ce-Sm � 10 and La � 3.1-Ce � 1.54-V triangular diagrams(Figure 4A and B, respectively).In Figure 4A the BAL samples closely fell around particulate

matter collected from refinery and oil power station emissions,26

suggesting that particulates emitted from oil refineries in theAugusta-Priolo area had an impact on the air column in Catania.Further confirmation of a partially nonlithogenic nature of La isalso provided in Figure 4B where the BAL solutions are clusteredbetween the linear arrays identifying crustal materials and products

from the oil refinery industry, as reported by Moreno et al.26 Theseevidence confirm the double origin, lithogenic and anthropogenic,of La contained in atmospheric particulates inhaled by studiedsubjects. In particular, Figure 4A also shows that this anthropogenicsource material influences also the SAF composition reported byAiuppa et al.21 allowing some SAF sample to fall in the area usuallyconsidered typical of anthropogenic sources.26

The data collected indicate that Cr, Fe, As, Pb, and U had alithogenic origin due to the dissolution of soluble fraction oferupted ash. Ni and Cu were released from volcanic glass particles,whereas Cdwas probably leached from a road dust component ofinhaled solids. The partial dissolution of volcanic glass and roaddust particles wasmainly responsible for the observed V,Mn, andCo concentrations in BAL fluids in agreement with relationshipsevidenced by EF values of these elements and their bioaccessi-bility in the presence of simulated biological fluids, as deduced byreference data.23 Lanthanum enrichments were able to evidenceanthropogenic industrial contributions to the budget of theatmospheric dust interacting with biological fluids, demonstrat-ing as the REE distribution in dissolved phase can be a powerfulenvironmental probe also during metabolic reactions. Thereforeanalyses of trace element contents of biological fluids can allow usto recognize the origin and nature of inhaled solids by means of ageochemical treatment of trace element data. The application ofthis geochemical technique to biological fluids was shown to besuitable for determining the origin of trace elements fromprolongedexposures to anthropogenic source materials with respect to inter-actions between human fluids and lithogenic solids that originatedfrom paroxystic, short-term, geological events. As suggested byour data the difference between lithogenic and anthropogenicsources is important because the chemical fluxes originated fromanthropogenic solids are different from those released fromlithogenic materials. Since chemical toxicity for humans is aneffect of metallic elements and their compounds on biologicalsystems, it changes from one element or group of elements toanother (see Nordberg et al.28 and references therein), inducingdifferent health effects on humans due to elemental accumulationin the organs. Moreover, concentrations of the trace elementsanalyzed in bronchial fluids have been shown to be sensitive tothe partial or total dissolution of inhaled atmospheric particles.This demonstrates the power of this geochemical approach whenapplied to solid�liquid interactions and also when occurring innonconventional environments such as the human body.The study of minor and trace element distributions in

bronchoalveolar lavages collected from people who inhaledatmospheric dust particles of different origins can represent apowerful tool for environmental research, giving direct informa-tion about the nature of these materials and related exposures.The results of this study show that an approach based on theanalysis of EF values calculated with respect to different suitablesource materials is able to determine the nature of inhaled solids.Here we have presented a successful application of the newapproach to the complex urban environmental system of the cityof Catania, where in the summer of 2001 a one-month longintense episode of volcanic ash emission by Mount Etna wassuperimposed to a continuous “background” delivery of roaddust and particulate from oil refineries nearby.

’ASSOCIATED CONTENT

bS Supporting Information. Tables S1-S3. This material isavailable free of charge via the Internet at http://pubs.acs.org.

Figure 4. Compositions of BAL (black dots) and SAF samples (blacksquares) reported from Aiuppa et al.21 compared with typical crustal andanthropogenic products in terms of La�Sm�Ce (A) and La�Ce�Vsignatures (B). RD: road dust fromDongarr�a et al.,22 PM: parent magmaof Etna’s 2001 eruption from Aiuppa et al.,21 crustal materials fromTaylor and McLennan,29 and oil refinery products from Moreno et al.26

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’AUTHOR INFORMATION

Corresponding Author*Phone: +393479662844. E-mail: censi@unipa.it.

’ACKNOWLEDGMENT

This work was financially supported by the ICT-3E grantprovided by the Italian C.I.P.E. We are indebted to N. Crimi, C.Mastruzzo, and P. Pistorio for the collection of samples. Theauthors are also very grateful to Dr. Thomas Darrah and twoanonymous reviewers for their careful and dedicated revision ofthe early version of this manuscript. This paper reports scientificresults belonging to the Ph.D. project of L. A. Randazzo.

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