Source and Nature of Inhaled Atmospheric Dust from Trace Element

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Source and Nature of Inhaled Atmospheric Dust from Trace Element Analyses of Human Bronchial Fluids Paolo 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 Genie de l0 Environnement Ecodeveloppement and Departement Sciences de la Terre, UMR 5125, Universite 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 ABSTRACT: Rapid volcanic eruptions quickly ejecting large amounts of dust provoke the accumulation of heavy metals in people living in surrounding areas. Analyses of bronchoalveolar lavage samples (BAL) collected from people exposed to the paroxysmal 2001 Etna eruption revealed a strong enrichment of many toxic heavy 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 the volcanic event, whereas Ni, Cu, Cd, and Pb contents come from the dissolution of particles of anthropogenic origin. Furthermore, the nature of these inhaled anthropogenic particles was revealed by anomalous La and partially Ce concentrations in BAL that were consistent with a mixture of road dust and petroleum refinery emissions. Our results indicate that trace element distribution in BAL is a suitable tracer of human exposure to different sources of inhaled atmospheric particulates, allowing investigations into the origin of source materials inhaled by people subjected to atmospheric fallout.

’ INTRODUCTION Suspended atmospheric dust is a very heterogeneous assortment of particles derived from several sources, characterized by different compositions and reactivity as regards of fluid phase. In anthropized areas people are exposed to the almost constant inhalation of lithogenic and anthropogenic atmospheric dust delivered from natural sources, automotive traffic, and/or industrial activities. Effects on human health related to the inhalation of these atmospheric particulates are mainly recognized as precursors of silicosis, asbestosis, and cancers, whereas only a scarce literature is available focused on effects of the dissolution of atmospheric dust in the presence of human bronchial fluids.1
3 This represents a lack of knowledge since environmental solids are often a source of concentrated metallic elements that can be released in biological fluids, and the amplitude of trace elements leachable from these solids depends from their composition and nature.4,5 The research presented in this study is based on a new approach to the identification of source materials of inhaled dust particles. The new method is based on geochemical treatment of r 2011 American Chemical Society

trace element concentrations in bronchoalveolar fluids collected from people exposed to the inhalation of a wide mixture of atmospheric dust particles formed during summer 2001 in Catania as a consequence of eruption of Mount Etna. In Catania, the second largest town in Sicily, located at the foot of Mount Etna, people were exposed to the effects of intense fallout of atmospheric particulate matter induced by the pyroclastic activity of Mount Etna, the largest active European volcano. Moreover, Catania is characterized by a wide range of industrial activities (two of the largest chemical industrial areas in the Central Mediterranean area are located in Gela and Augusta, about 50 km far from Catania), and traffic usually constitutes the major source of air pollution in the area. These circumstances enabled us to test a geochemical method focused on the source recognition of inhaled atmospheric particulates from people Received: February 22, 2011 Accepted: June 21, 2011 Revised: June 14, 2011 Published: June 21, 2011 6262

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Environmental Science & Technology exposed to complicated environmental conditions where different concurrent sources of atmospheric dust can be present. For the first time, a study was carried out on bronchoalveolar fluids collected from exposed people, rather than a direct study of atmospheric dust, to test whether or not lung fluids record the effects of interactions with atmospheric dust. Thus, a novel type of environmental research study was undertaken to simultaneously evaluate the amplitudes of exposure of involved people to major, minor, and trace metal components of atmospheric particulates, the bioavailability of these elements in lung fluids, and the recognition of source materials present in the air column of the studied area.

’ EXPERIMENTAL SECTION Characteristics of fine particulate matter emitted from the Mount Etna volcano in the summer of 2001: Volcanic ejecta during the summer of 2001 from Mount Etna typically consisted of a mixture of several solid phases ranging from particles made of silicate minerals and volcanic glass to soluble salts adsorbed onto these particles.6
8 The solid fraction of ejected materials mainly consisted of glass fragments (about 70%) with smaller amounts of clinopyroxene (about 15%) and minor amounts of olivine and spinel.9,10 Furthermore, a soluble ash fraction (SAF) coated the surfaces of solid particles. More recently, Delmelle et al.8 demonstrated that this coating represents the effect of reactions occurring between gases/aerosols and silicate ash particles in volcanic eruption plumes and consisted of highly soluble sublimates of acids, metal salts, and adsorbed fluids formed during the uprising in the volcanic eruptive plume.6 Bronchoalveolar lavage (BAL) extraction and chemical sample processing: Six patients of the Department of Internal Medicine of Catania University were subjected (after giving their written informed consent) to the BAL procedure during the summer of 2001, when the city of Catania was exposed to the severe delivery of atmospheric particulate matter produced by the pyroclastic activity of Mount Etna, the largest active European volcano. Due to the closeness of Catania to the source of the eruption, this densely populated urban area was subjected to an intense delivery of volcanic particulate matter mainly consisting of mineral, glass, and rock fragments between 1 and 500 μm diameter, with the most frequent grain size within the range of 5
10 μm diameter.9
12 The BAL samples were obtained via instillation of four lavages with 30 mL aliquots of a sterile solution of 0.9% w/v NaCl, using a fibrobronchoscope,13 where each aliquot was immediately and gently aspirated. From each 20 mL lavage sample collected, only 10 mL was used for chemical investigations. After filtration through a 0.22 μm Nalgene membrane, each BAL sample was treated with 15 mL of hydrogen peroxide, 5 mL of 30% HNO3 solution, 30% HCl solution, and 0.1 g of solid NH4F in a polytetrafluoroethylene (TFM) reactor. The reactors were sealed and heated in a microwave oven (MARS 5, CEM Corporation, UK) at 3  105 Pa and 200 C for 30 min. Excess acid was removed from each solution up to incipient dryness using a CEM microvap apparatus, and an HNO3 solution (5% v/v) was added to attain final solution volumes of 20 mL. The solutions were finally transferred to previously cleaned polycarbonate vials. The samples were treated under a clean laminar airflow to minimize contamination risks. Trace element analyses were carried out using a sector field SF-ICP-MS Thermo-Fisher Element 2 using an external calibration

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approach. The calibration for each element was based on seven standard solutions at known concentrations prepared by diluting 1 g/L of a single-element solution (Merck ICP standard), similar to the procedure used by Rodushkin and Odman.14 The accuracy of the different procedures was evaluated by analyzing five aliquots of CASS-4 and NASS-5 certified reference seawaters (National Research Council of Canada; Ottawa, Ontario, Canada), which are reported in Table S2 in the Supporting Information (SI). Analytical precision was evaluated using the same sterile solution as used for the collection of BAL samples. The same quantities of chemicals used in the treatment of BAL samples were added to five aliquots of sterile solution (SS). These solutions were subject to mineralization procedures and represent our procedural blanks, which were used to determine critical values (LC) and detection limits (LD) for the trace elements investigated according to the expressions LC ¼ 2:33σPBs LD ¼ 4:65σ PBs

ð1Þ

where σPBs is the standard deviation of the procedural blank measurements, and quantification limit (LQ) was calculated as ten times the amount of σPB, according to EPA procedures.15 The results obtained are reported in Table S3 in the Supporting Information (SI). The low LQ values (see Supporting Information) indicated that the amounts of trace metals lost and/or added during sample collection and preparation were negligible with respect to the trace element contents of the BAL samples. All of the solutions studied were prepared using Millipore ultrapure water (18.2 MΩ). All chemicals used in the sample preparation and analysis were Merck ULTRAPUR (VWR International, West Chester PA). All materials used to sample and manipulate the water samples were plasticware, acid cleaned with hot 1:10 HNO3 aqueous solutions.

’ RESULTS AND DISCUSSION BAL Composition. The amplitude of Etna’s eruption during July-August 2001 was large enough to expose all people living in southeastern Sicily to volcanic particle inhalation. This fact made a typical comparative study of BAL composition in exposed people and control subjects virtually impossible to carry out. Therefore, the results of minor and trace element compositions in the BAL samples of people exposed to volcanic particle inhalation were compared with the few minor and trace element analyses carried out for BAL lavage samples in other studies.16 The amounts of minor and trace elements measured in this study, 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. The latter, together with Fe, was the most abundant of the elements studied in the BAL solutions. Concentrations of Y, La, and lanthanides (i.e., rare earth elements) were previously reported by Censi et al.17 Variation coefficients of the minor and trace elements investigated, calculated as the ratio between the standard deviation and average values of each element, were larger for Cu, Cd, Ni, As, and U, ranging from 69% to 114%, and lower for the other investigated elements, falling between 22.5% (Fe and Co) and 48.5% (V). Many of these values were different both in terms of concentration and the observed variability when compared to analogous data recently reported by Bargagli et al.,16 as shown by the descriptive statistics of BAL analyses shown in Figure 1. Due the good quality of analyzed data evidenced in 6263

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

Tables S2 and S3 of Supporting Information, we attribute the variability of elemental concentrations in BAL to different level of exposure of investigated subjects to inhalation of atmospheric particles. This hypothesis is corroborated by lower trace element concentrations reported by Bargagli et al.16 with respect to those analyzed in BAL, especially for iron, which is the most enriched element in their data. Moreover also smaller ranges of trace element variations in BAL fluids with respect to those

observed by Bargagli et al.16 agree to this hypothesis due to the amplitude of the delivery of atmospheric particulate matter during pyroclastic activity of Mount Etna. In order to clarify whether or not the inhaled particles came from atmospheric fallout of the volcano alone, a typical geochemical approach based on an investigation of the amplitudes of enrichment factors of the trace elements in the BAL fluids studied was carried out. 6264

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

EFðREFÞ

½XBAL ½AlBAL ¼ ½XREF ½AlREF

ð2,Þ

where [X] is the concentration of a given element in the BAL sample (BAL) or in a hypothetical source material used as the reference.19 In general, EF values smaller than 5 indicate that the element under consideration is not significantly enriched in the BAL sample with respect to the hypothesized source, whereas EFs larger than 5 imply an enrichment of the element under investigation in the materials being studied with respect to the chosen source.20 In order to establish what was a suitable source for trace elements recognized in BAL fluids EF values for investigated elements were calculated 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, metal salts, and adsorbed halogen-rich fluids (formed during the uprising 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 particulate fraction from automotive traffic could inhaled by studied subjects, EF values were also calculated with respect to a suitable road dust composition (RD). It was recognized from data of Dongarr
a et al.22 who studied atmospheric pollution in Messina, a town characterized by a dense automotive traffic, located at about 60 far from Catania and characterized by similar climatic conditions 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 slightly lower for Cr, Fe, As, Pb, and U; larger than 1 for Ni (Figure 2A). These results suggest that a Ni contribution from a different source with respect to SAF occurred. Cr, Fe, As, Pb, and U could be released during dissolution of the soluble fraction of volcanic materials, but it is hard to accept that soluble salt coatings remain undissolved during interactions with lung clearance fluids. Therefore the leaching of V, Mn, Co, Ni, Cu, and Cd from PM or another source is suggested. To clarify this hypothesis EF(PM) values for the latter elements were also calculated and reported in Figure 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 green ellipses), whereas the Cd EF(RD) value was higher than 1. These evidences indicate that both Ni and Cu were released from PM interacting with lung fluids, whereas V, Mn, and Co are leached in BAL fluids from partially dissolved glass ash fraction particles. The observed Cd EF(RD) value probably indicates their release from a further anthropogenic RD source. It is confirmed by the calculation of Cd EF(RD) in BAL fluids that produced a wide range of values centered on 1 probably due to the variable exposure of investigated subjects to the inhalation of road dust during 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 atmospheric particles, the EF(PM) and EF(RD) of these elements were compared in Figure 3 to the amount of labile trace element fractions occurring in atmospheric dust particles interacting with

Figure 2. Enrichment factors (EF) calculated for studied elements with respect to different possible parent materials: A, soluble fraction of erupted ash (ASF); B, Etna’s parent magma (PM) of 2001 eruption; and C, road dust (RD). Pale green ellipses highlight elements whose source is suggested. Gray areas represent values falling 1 and 5. Black dots are medians, and red segments link maximum to minimum EF values for each measured element. Data on Etna’s parent magma and the soluble ash 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 to the Etna’s parent magma (PM) (black dots) and road dust reference composition (RD) (circles) for elements with EFs < 1 in Figure 2B and C. Mn, Co, Ni, Cu, and Cd EF(PM) values reported in Figure 2B were used to calculate the curve (1), whereas Mn, Co, Ni, and Cd EF(RD) values reported in Figure 2C were used to calculate the curve (2). Values of bioaccessible trace element fractions were reported in Falta et al.23 Red dot represents Cu EF(RD) value not used for calculation of curve (2).

simulated biological fluids.23 The increase of the EF(PM) of Co, Mn, Ni, Cu, and Cd is related to the bioaccessibility of these elements contained in PM10 particles interacting with simulated biological fluids. Similarly, amplitudes of EF(RD) of Co, Mn, Ni, and Cd are correlated to the increase of the bioaccessibility of the 6265

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Figure 4. Compositions of BAL (black dots) and SAF samples (black squares) reported from Aiuppa et al.21 compared with typical crustal and anthropogenic products in terms of La
Sm
Ce (A) and La
Ce
V signatures (B). RD: road dust from Dongarr
a et al.,22 PM: parent magma of Etna’s 2001 eruption from Aiuppa et al.,21 crustal materials from Taylor and McLennan,29 and oil refinery products from Moreno et al.26

latter elements in PM2.5 particles (Figure 3). Being bioaccessibility calculated from kinetic experiments carried out by Falta et al.23 it is a time-dependent parameter. Therefore relationships reported in Figure 3 assume an exponential form because also EFs values have a kinetic significance, confirming that amplitudes of EF values are related to the trace element leaching from inhaled particles in lungs fluids. Y, La, and lanthanides, usually named Rare Earth Elements (REE), released from inhaled solids interact with lung fluids and coprecipitate as phosphates in bronchoalveolar spaces, allowing to several health diseases.24 The behavior of these elements, recently investigated in this particular environment, is characterized by strong elemental fractionations that involve enrichments of elements from Nd to Ho in newly formed precipitates, whereas Y, La, Ce, and lanthanides from Er to Lu preferentially remain in dissolved phase.17 Being REE contents reported by Censi et al.17 influenced by phosphate crystallization in bronchial spaces their EF values were not calculated. Otherwise Censi et al.17 observed a large enrichment of Y and La in BAL fluids, also taking into account the phosphate crystallization, and hypothesized that Y and La could be delivered by a La-enriched anthropogenic source, apart from the volcanic ash. Being La-rich carbonates and zeolites employed as catalytic converters in hydrocarbon refinery industry, La enrichments are considered typical environmental signatures of the delivery of atmospheric particulates during hydrocarbon combustion in power stations.25
27 Therefore in order to verify this hypothesis we compared compositions of BAL fluids 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 the Augusta-Priolo area had an impact on the air column in Catania. Further confirmation of a partially nonlithogenic nature of La is also provided in Figure 4B where the BAL solutions are clustered between the linear arrays identifying crustal materials and products

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from the oil refinery industry, as reported by Moreno et al.26 These evidence confirm the double origin, lithogenic and anthropogenic, of La contained in atmospheric particulates inhaled by studied subjects. In particular, Figure 4A also shows that this anthropogenic source material influences also the SAF composition reported by Aiuppa et al.21 allowing some SAF sample to fall in the area usually considered typical of anthropogenic sources.26 The data collected indicate that Cr, Fe, As, Pb, and U had a lithogenic origin due to the dissolution of soluble fraction of erupted ash. Ni and Cu were released from volcanic glass particles, whereas Cd was probably leached from a road dust component of inhaled solids. The partial dissolution of volcanic glass and road dust particles was mainly responsible for the observed V, Mn, and Co concentrations in BAL fluids in agreement with relationships evidenced by EF values of these elements and their bioaccessibility in the presence of simulated biological fluids, as deduced by reference data.23 Lanthanum enrichments were able to evidence anthropogenic industrial contributions to the budget of the atmospheric dust interacting with biological fluids, demonstrating as the REE distribution in dissolved phase can be a powerful environmental probe also during metabolic reactions. Therefore analyses of trace element contents of biological fluids can allow us to recognize the origin and nature of inhaled solids by means of a geochemical treatment of trace element data. The application of this geochemical technique to biological fluids was shown to be suitable for determining the origin of trace elements from prolonged exposures to anthropogenic source materials with respect to interactions between human fluids and lithogenic solids that originated from paroxystic, short-term, geological events. As suggested by our data the difference between lithogenic and anthropogenic sources is important because the chemical fluxes originated from anthropogenic solids are different from those released from lithogenic materials. Since chemical toxicity for humans is an effect of metallic elements and their compounds on biological systems, it changes from one element or group of elements to another (see Nordberg et al.28 and references therein), inducing different health effects on humans due to elemental accumulation in the organs. Moreover, concentrations of the trace elements analyzed in bronchial fluids have been shown to be sensitive to the partial or total dissolution of inhaled atmospheric particles. This demonstrates the power of this geochemical approach when applied to solid
liquid interactions and also when occurring in nonconventional environments such as the human body. The study of minor and trace element distributions in bronchoalveolar lavages collected from people who inhaled atmospheric dust particles of different origins can represent a powerful tool for environmental research, giving direct information about the nature of these materials and related exposures. The results of this study show that an approach based on the analysis of EF values calculated with respect to different suitable source materials is able to determine the nature of inhaled solids. Here we have presented a successful application of the new approach to the complex urban environmental system of the city of Catania, where in the summer of 2001 a one-month long intense episode of volcanic ash emission by Mount Etna was superimposed to a continuous “background” delivery of road dust and particulate from oil refineries nearby.

’ ASSOCIATED CONTENT

bS

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

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’ AUTHOR INFORMATION Corresponding Author

*Phone: +393479662844. E-mail: [email protected].

’ ACKNOWLEDGMENT This work was financially supported by the ICT-3E grant provided by the Italian C.I.P.E. We are indebted to N. Crimi, C. Mastruzzo, and P. Pistorio for the collection of samples. The authors are also very grateful to Dr. Thomas Darrah and two anonymous reviewers for their careful and dedicated revision of the early version of this manuscript. This paper reports scientific results belonging to the Ph.D. project of L. A. Randazzo. ’ REFERENCES (1) Takaya, M.; Shinohara, Y.; Serita, F.; Ono-Ogasawara, M.; Otaki, N.; Toya, T.; Takata, A.; Yoshida, K.; Kohyama, N. Dissolution of functional materials and rare earth oxides into pseudo alveolar fluid. Ind. Health 2006, 44 (4), 639–644. (2) Forde, S.; Hynes, M. J.; Jonson, B. Dissolution of glass compositions containing no added lead in simulated lung fluid. International. J. Hyg. Environ. Health 2008, 211 (3
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