Next Article in Journal
The Machine Learning-Based Dropout Early Warning System for Improving the Performance of Dropout Prediction
Next Article in Special Issue
DNA-Related Modifications in a Mixture of Human Lympho-Monocyte Exposed to Radiofrequency Fields and Detected by Raman Microspectroscopy Analysis
Previous Article in Journal
Complex and Hypercomplex-Valued Support Vector Machines: A Survey
Previous Article in Special Issue
Comparison of Raman and Mid-Infrared Spectroscopy for Real-Time Monitoring of Yeast Fermentations: A Proof-of-Concept for Multi-Channel Photometric Sensors
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Applied Sciences
Volume 9
Issue 15
10.3390/app9153092
applsci-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Review

Micro-Raman Spectroscopy, a Powerful Technique Allowing Sure Identification and Complete Characterization of Asbestiform Minerals

by
Caterina Rinaudo
* and
Alessandro Croce
*
Department of Science and Technological Innovation, University of Eastern Piedmont, Viale T. Michel 11, 15121 Alessandria, Italy
*
Authors to whom correspondence should be addressed.
Appl. Sci. 2019, 9(15), 3092; https://doi.org/10.3390/app9153092
Submission received: 10 July 2019 / Revised: 22 July 2019 / Accepted: 25 July 2019 / Published: 31 July 2019
(This article belongs to the Special Issue Novel Insights to Raman Spectroscopy: Advances and Prospects)
Browse Figures
Versions Notes

Abstract

:

Featured Application

Featured Application: Micro-Raman spectroscopy has been proved to be a quick technique for the study of minerals showing asbestiform morphology, in particular for identification of those ascribing to the phases defined by Law “asbestos”. Moreover, information about the crystal surface—free or occupied by crystalline or amorphous particles—can be at the same time obtained, being this last feature important for the interaction of the fibers with the biological medium.

Abstract

Micro-Raman spectroscopy has been applied to fibrous minerals regulated as “asbestos”—anthophyllite, actinolite, amosite, crocidolite, tremolite, and chrysotile—responsible of severe diseases affecting mainly, but not only, the respiratory system. The technique proved to be powerful in the identification of the mineral phase and in the recognition of particles of carbonaceous materials (CMs) lying on the “asbestos” fibers surface. Also, erionite, a zeolite mineral, from different outcrops has been analyzed. To erionite has been ascribed the peak of mesothelioma noticed in Cappadocia (Turkey) during the 1970s. On the fibers, micro-Raman spectroscopy allowed to recognize many grains, micrometric in size, of iron oxy-hydroxides or potassium iron sulphate, in erionite from Oregon, or particles of CMs, in erionite from North Dakota, lying on the crystal surface. Raman spectroscopy appears therefore to be the technique allowing, without preparation of the sample, a complete characterization of the minerals and of the associated phases.

1. Introduction

Identification and characterization of the minerals constituting rocks, soils or dispersed in different matrixes has been at all times object of study for researchers working in the earth sciences. Mineralogists in particular applied optical microscopy (OM), scanning electron microscopy coupled with electron dispersive spectroscopy (SEM/EDS), X-ray powder diffraction (XRPD), transmission electron microscopy (TEM), etc., to obtain a complete characterization of the mineral phases. The normally used techniques often require preparation of the sample before analysis. Considering that the samples are often constituted by different crystalline phases, in variable amounts, which can be sometimes mixed with amorphous phases, it is obvious that the preparation of the samples for analysis may induce changes, loss of important information, and difficulties in the identification of phases in very low amounts. Micro-Raman spectroscopy, where an OM is coupled with the spectroscope, allows overcoming these inconveniences, mainly when OM is equipped with crossed nicols. In fact, the technique can be applied directly on the samples, in a non-invasive way, and directing the laser beam in areas selected by the OM and characterized by optical peculiarities, heterogeneity in the sample can be easily highlighted. Moreover, Raman spectroscopy, supplying information on the vibrational modes of the chemical bonds, allows studying also materials in amorphous, gaseous, or liquid states.
Our research group operates in Alessandria, where the minerals regulated as “asbestos” have been, and are up till now, a serious problem consequent to the presence of an Eternit factory in Casale Monferrato, Alessandria (Italy), producing large quantities of asbestos-cement since the beginning of the last century until 1985 [1,2]. The asbestos are fibrous minerals with a high impact on the human health. In fact, to the inhalation of the asbestos fibers has been ascribed the development of severe respiratory diseases, in particular mesothelioma, asbestosis, and pulmonary carcinoma [3,4]. Other malignancies affecting extra-respiratory systems have been recognized as related to inhaled/ingested asbestos fibers. In particular, IARC recognized that the larynx and ovary tumors can be related to asbestos exposure [5] and various researchers are developing studies to verify the relationships between gastrointestinal cancers (GI) and asbestos [6,7,8,9,10].
We have been therefore interested in the identification of a technique able to identify surely fibers of asbestos, even when they are present in very low amounts. On the mineralogical point of view, the minerals regulated as “asbestos” [5,11,12] are:
  • actinolite, theoretical chemical formula Ca2(Mg, Fe2+)5[Si8O22](OH)2;
  • amosite, theoretical chemical formula (Fe2+, Mg)7[Si8O22](OH)2;
  • anthophyllite, theoretical chemical formula (Mg, Fe2+)7[Si8O22](OH)2;
  • crocidolite, theoretical chemical formula Na2Fe2+3Fe3+2[Si8O22](OH)2;
  • tremolite, theoretical chemical formula Ca2Mg5[Si8O22](OH)2,
when they exhibit fibrous habit. All these phases belong to amphibole group of silicates, where double chains of [SiO4] tetrahedra are each other linked by Na, Ca, Mg, Fe2+, or Fe3+ cations, Figure 1a [12,13]. Being phases growing in a natural system, then with complex chemical composition of the mother solutions, very often homo- and etero-valent diadochy in the different crystallographic sites may occur. The real chemical formula therefore can differ from the theoretical one. As an example, in tremolite iron is not foreseen but substitutions of Mg by Fe2+ in the octahedral sites can be frequently observed.
The last mineral regulated as “asbestos” is:
  • chrysotile, theoretical chemical formula Mg3Si2O5(OH)4.
This is a serpentine mineral [14], whose crystal structure is constituted by tetrahedra [SiO4] layers (T layer) and octahedra (Mg O, OH)6 layers (O layer), where Mg2+ are linked to the [SiO4] tetrahedra and to OH- ions, Figure 1b. Chrysotile exhibits a fibrous habit consequent to the rolling up of the T and the O layers around a hole, Figure 1c [15].
In this work, we describe the application of micro-Raman spectroscopy to fibers of the different “asbestos”, proving its reliability not only in the identification of the minerals, but also of other phases lying on the fiber surfaces. In fact, the spectral range 4000–100 cm−1 has been recorded and presence on the fiber surfaces of particles, not necessarily crystalline, could be demonstrated.
The reasons of the carcinogenic effects of the “asbestos” has been extensively studied by different authors [4,16,17,18] and the dose of the inhaled fibers but also their morphology and the iron in the chemical formula have been described as factors determining their harmfulness [19,20]. As described before, growing these compounds in natural environment, iron can be present also in phases theoretically iron free. In vitro studies proved that, among “asbestos”, the phases richest in iron, crocidolite and amosite, showed higher carcinogenic effects [21]. In addition to “asbestos”, other minerals exhibiting fibrous habit have been proved to be responsible of asbestos-related diseases. Among all, erionite, a zeolite mineral showing an average chemical formula K2(Na, Ca0.5)8[Al10Si26O72]·30H2O has been considered responsible of the peak of mesothelioma, detected in Cappadocia (Turkey) during the 1970s [22,23,24]. On this, mineral iron is not a main chemical component, but erionite has been defined by the International Agency for Research on Cancer (IARC) more carcinogenic than asbestos [25].
Micro-Raman spectroscopy has therefore been applied also to samples of erionite from different localities (Oregon and North Dakota- USA- and Karlik- Cappadocia).

2. Materials and Methods

All the samples were analyzed under a HORIBA JobinYvon HR800 LabRam μ-spectrometer (HORIBA Jobin Yvon, Paris, France), coupled with an Olympus BX41 microscope (Olympus, Tokyo, Japan). The used excitation source was a HeNe laser, 20 mW, working at 632.8 nm, and the detector was an air-cooled charge-coupled device (CCD). Spectrometer calibration was obtained checking position and intensity of the Si band at 520.65 ± 0.05 cm−1. The analyses were performed with a timing of at least 2 cycles of 200 s, after introduction of D06 filter to prevent sample modification, and a confocal hole set at 200 μm. ORIGIN software v 6.0 was applied on the recorded spectra. The asymmetric bands were treated with OPUS software to obtain fitting process after 13 points FFT smoothing of the spectrum and selecting a Lorentzian function and minimum number of component bands to obtain reproducible results with the minimal residual error.
SEM analyses were carried out using an environmental SEM (E-SEM; model Quanta 200, FEI Company, Hillsboro, OR, USA), with a pressure of 90 Pa, an accelerating voltage of 20 kV, and a working distance of 10 mm. Observation of phases with different chemical composition on the fiber surface was easy thanks to the back-scattered electron detector (BSED) and the generated white-black contrasts, not so evident using secondary electrons (SE).
For the six minerals, regulated as “asbestos”, the studied samples were:
  • amosite from South Africa;
  • UICC crocidolite reference sample from South Africa;
  • tremolite from Brachiello (Val d’Ala, Piedmont region);
  • anthophyllite from Bresimo mine (Trentino Alto Adige, Italy);
  • actinolite certified by IOM (Institute of Occupational Medicine);
  • UICC chrysotile reference sample “B” Canadian (NB #4173-111-1) from Quebec, Canada.
The a.–d. minerals have been previously characterized with the traditionally used techniques (XRPD, SEM/EDS, TEM/EDS, and Analytical Electron Microscopy- AEM) and stated in Rinaudo et al. 2004 [26], whereas for chrysotile, the crystal structure and chemistry was described in Pollastri et al. 2016 [27].
Oregon and Cappadocia erionite chemicals were determined by Dogan et al. 2006 [28], while North Dakota chemical composition was compared with Turkish samples in Carbone et al. 2011 [22].
For each studied mineral phase, different spectra from various bundles of fibers were recorded in the spectral range 4000–100 cm−1. When particles were observed on the fiber surface by means of the OM annexed to spectrometer, micro-Raman spectra were recorded directing the laser beam onto the grains.

3. Results and Discussion

Considering the “asbestos” minerals, more or less numerous particles, mostly rounded and micrometric in size, were observed on their fiber surface under OM, Figure 2. The phenomenon was particularly evident on amosite, Figure 2a, where the fibers were practically recovered both by fine fibrils and by small particles. Also crocidolite, Figure 2b, and chrysotile, Figure 2f, exhibited many dark particles on their surface, but also areas free from these foreign phases could be observed. On tremolite, anthophyllite and actinolite, the presence of round grains was less frequently noticed, Figure 2c–e.
The data from micro-Raman spectroscopy can be analyzed for the spectral region where lie the vibrational modes ascribed to the three-dimensional lattice of the mineral phases, 1200–100 cm−1, and for the spectral range, 4000–1200 cm−1, where lie the non-reticular vibrational modes. As it concerns the first spectral region, the results are shown in Figure 3. The Raman spectra appeared very rich in bands, especially in amphiboles, as a consequence of the different chemical bonds in the crystal structure (Si-Ob-Si, Si-O, bonds between various cations and tetrahedral oxygens or OH− groups…), therefore the attribution of each band to a single vibrational mode is very hard and in any case beyond the aim of this work. A discussion about the vibrational modes produced by the stretching modes, both symmetric (νs) and antisymmetric (νas), of the different Si-O linkages has been proposed in Rinaudo et al. 2004 [26], and recently determination of the chemical formulae of various amphiboles by Raman spectroscopy has been suggested by Waeselmann et al. 2019 [29]. On the contrary, the Raman spectrum from chrysotile appeared poorer in bands, consequence of a crystal structure formed by only two types of polyhedra—SiO4 and Mg(O, OH)6. For the serpentine minerals, an attribution of the detected Raman bands to the different vibrational modes has been described in Rinaudo et al. 2003 [30].
Being interested in the identification of the mineral phase, it can be achieved considering the region where lie the symmetric stretching modes (νs), 700–600 cm−1, and antisymmetric stretching modes (νas), 1100–1000 cm−1, of the Si-Ob-Si linkages, Figure 3. In fact, the difference in wavenumbers where lie the νs modes is higher than the instrumental error, 2 cm−1. A particular situation involves tremolite and anthophyllite, where the νs modes vibrate very close. In this case, considering also the wavenumbers of the νas stretching modes (1044 cm−1 in anthophyllite and 1062 and 1031 cm−1 in tremolite), a sure identification can be achieved. As it concerns chrysotile, the νs modes vibrate at higher wavenumber, about 694 cm−1, with respect to all the amphibole asbestos phases. Concerning the νas stretching modes, lying at 1105 cm−1, it is often undetectable for the presence of intense bands produced by carbonaceous materials (CMs) lying on the crystal surface [31], Figure 3f, as will be after discussed.
In the spectral region 4000–1200 cm−1 on amosite, appearing under OM practically recovered by round dark particles, Figure 2a, bands ascribing to carbonaceous materials have been almost always detected, Figure 4a. In fact, bands at 1332, 1582, and 2663 cm−1 have been observed and they can be ascribed respectively to D (diamond like), G (graphite like) and G’ (second order Raman scattering) vibrations of CMs [31].
Also on crocidolite, showing often under OM dark particles on the crystal surface, Figure 2b, bands ascribed to CMs were identified when the laser beam was directed onto the grains, Figure 4b. On the spectra, the bands at 1333, 1600, 2660, and 2914 cm−1 can be ascribed respectively to D, G, G’, and C-H vibrations. The fact that on crocidolite the band at 1333 cm−1 showed higher intensity with respect to the band near 1600 cm−1, which appears large, proves a higher disorder in the CM particles lying on the crystal structure. On the other hand, applying fitting program to the 1600 cm−1 band, two underlying bands at 1591 (G vibrations) and 1621 (D’ vibrations) cm−1 were identified (box in Figure 4b), confirming carbonaceous grains rich in defects.
On the other amphibole phases, especially on actinolite and anthophyllite, bands ascribed to CMs were very rarely observed, confirming the data from OM observations, Figure 2c–e. On tremolite, at wavenumbers higher than 1200 cm−1, an intense and large hump produced by fluorescence effects was always detected. This fact avoided detection of Raman bands in this spectral range.
On chrysotile, in the 4000–1100 cm−1 spectral range, different bands ascribing to carbonaceous materials were detected, Figure 4f. In particular the band at 1118 cm−1 may be ascribed to symmetric stretching of C-O-C bonds, the band at 1273 cm−1 to disordered C-H, the band at 1340 cm−1 produced by D vibrations, the band at 1613 cm−1 by G + D’ vibrations, and the band at 1690 cm−1 due to C=O bonds [31,32].
With the laser wavelength used, 632.8 nm, the OH- vibrations were detected only on amosite, bands at 3618 and 3637 cm−1, anthophyllite at 3666 and 3671 cm−1, actinolite at 3643 and 3660 cm−1, and chrysotile, bands at 3688 and 3699 cm−1.
The position of the obtained Raman bands are summarized in Table 1 and Table 2.
Considering now the erionite samples, the spectral range where lie the lattice vibrational modes appeared poorer in Raman bands. In fact, only an intense band at about 485 cm−1, with an evident component at about 470 cm−1, and weaker bands at about 570, 330–345, and 127–140 cm−1 characterized the Raman spectrum, Figure 5.
Nevertheless, all the studied erionite fibers exhibited, under SEM, particles, sub-micrometric in size, lying on the crystal surface, Figure 6.
Directing the laser beam onto the observed grains, different results were obtained on erionite from the various outcrops. In particular on the erionite from Oregon, the Raman spectra recorded on the grains identified:
  • Goethite, chemical formula FeO(OH), Raman spectra as that shown in Figure 7a. In this case the band at 395 cm−1 resulted, with respect to the value, 385 cm−1, normally observed on this mineral, shifted of 10 cm−1 as consequence of a poor crystallinity of the grains [33,34];
  • Hematite, chemical formula Fe2O3, spectra as that shown in Figure 7b [34,35];
  • Jarosite, KFe33+(SO4)2(OH)6, an iron-potassium sulphate [35,36], Figure 7c. On the Raman spectrum recorded on the grains of jarosite, the presence of a band at 387 cm−1, not ascribing to this mineral phase, indicated a contemporaneous crystallization of small amounts of goethite [34,35].
Therefore, the described results indicated many iron particles lying on the surface of the erionite fibers. Considering that iron is a co-factor in the fiber carcinogenicity [21] and that the IARC indicated this mineral phase more carcinogenic than asbestos [25], the role of the iron particles on the fiber surface may play a synergic role in the pathogenicity of this mineral.
On the fibers from North Dakota, the Raman spectrum more frequently recorded is shown in Figure 6c. In this case, the Raman bands in the spectral region corresponding to lattice vibrations agree with the data obtained on erionite from Oregon and Karlik, but in the part of the spectrum 4000–1200 cm−1 bands ascribed to carbonaceous materials were almost always observed, Figure 8. On this mineral the D band lies at 1336 cm−1, the G + D’ band at 1604 cm−1, the G’ band at 2655 cm−1, whereas the bands at 1450, 2878 and 2914 cm−1 can be ascribed to C-H bonds.
Carbonaceous materials have been detected very rarely on erionite from Oregon and from Karlik.

4. Conclusions

It is now universally accepted the noxious role of the asbestos on the human health. Asbestos fibers in the human body can be detected not only in the respiratory system, when inhaled [18,37,38], but also in other organs or tissues [39,40,41,42,43], attained by translocation or ingestion processes. Considering that recent studies demonstrated its presence in unexpected places, in paintings as an example [44], it is therefore very important to find a technique allowing an easy identification of the fibers in different matrixes.
From all the above described data, micro-Raman spectroscopy appears the good technique for identification of mineral phase associated with fibers or bundle of fibers. It is a technique allowing to record spectra directly on the samples and on materials in crystalline and amorphous state. On asbestos it allowed not only to identify the phase, but also to highlight carbonaceous materials lying on the crystal surface, never recognized with the traditionally used techniques. It is known that carbonaceous particles, when inhaled, may constitute a problem for the human health [45,46]. Being stuck on the asbestos fibers, especially on amosite, crocidolite, and chrysotile, the most commonly used in the industry in the past, they may contribute to increase the noxious effects of these asbestiform minerals.
Also on erionite, a mineral phase not regulated but recognized more carcinogenic than asbestos, micro-Raman spectroscopy allowed to recognize, mainly on Oregon erionite fibers [35], many particles of iron oxy-hydroxides or sulphates. The role of iron in the pathogenicity of the fibers has been demonstrated. On erionite fibers from North Dakota, dark grains lying on the crystal surface have been recognized as carbonaceous particles, as those detected on the “asbestos”.
Although in this work micro-Raman spectroscopy has been applied on asbestiform phases, the technique contribution in an in-depth characterization of the minerals, of the mineral association, and generally of materials appears un-doubted. Moreover, the possibility of studies in a non-destructive way, maintaining unaltered the relationship among the different components of the analyzed samples, appears a very interesting peculiarity of the technique.

Author Contributions

conceptualization, C.R. and A.C.; methodology, C.R. and A.C.; software, C.R. and A.C.; validation, C.R. and A.C.; formal analysis, C.R. and A.C.; investigation, C.R. and A.C.; resources, C.R.; data curation, C.R. and A.C.; writing—original draft preparation, C.R. and A.C.; writing—review and editing, C.R. and A.C.; visualization, C.R. and A.C.; supervision, C.R. and A.C.; project administration, C.R.; funding acquisition, C.R.

Funding

The work was supported by ASL AL (“Progetto globale di ricerca in tema di cure e di prevenzione per la diagnosi e la terapia del mesotelioma–CUP C68F14000270005”).

Acknowledgments

The authors thank the Associazione Familiari Vittime dell’Amianto (AFeVA) for their encouragement, the Editors and the anonymous reviewers for their work.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Martuzzi, M.; Comba, P.; De Santis, M.; Iavarone, I.; Di Paola, M.; Mastrantonio, M.; Pirastu, R. Asbestos-related lung cancer mortality in Piedmont, Italy. Am. J. Ind. Med. 1998, 33, 565–570. [Google Scholar] [CrossRef]
  2. Magnani, C.; Dalmasso, P.; Biggeri, A.; Ivaldi, C.; Mirabelli, D.; Terracini, B. Increased risk of malignant mesothelioma of the pleura after residential or domestic exposure to asbestos: A case-control study in Casale Monferrato, Italy. Environ. Health Perspect. 2001, 109, 915–919. [Google Scholar] [CrossRef] [PubMed]
  3. Bartrip, P.W.J. History of asbestos related disease. Postgrad. Med. J. 2004, 80, 72–76. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  4. Carbone, M.; Ly, B.H.; Dodson, R.F.; Pagano, I.; Morris, P.T.; Dogan, U.A.; Gazdar, A.F.; Pass, H.I.; Yang, H. Malignant mesothelioma: Facts, myths, and hypotheses. J. Cell. Physiol. 2012, 227, 44–58. [Google Scholar] [CrossRef]
  5. International Agency for Research on Cancer (IARC). Asbestos (chrysotile, amosite, crocidolite, tremolite, actinolite, and anthophyllite). In IARC Monographs on the Evaluation of Carcinogenic Risks to Humans; IARC: Lyon, France, 2012; Volume 100, pp. 219–309. [Google Scholar]
  6. Brandi, G.; Di Girolamo, S.; Belpoggi, F.; Grazi, G.; Ercolani, G.; Biasco, G. Asbestos exposure in patients affected by bile duct tumours. Eur. J. Oncol. 2008, 13, 171–179. [Google Scholar]
  7. Brandi, G.; Di Girolamo, S.; Farioli, A.; de Rosa, F.; Curti, S.; Pinna, A.D.; Ercolani, G.; Violante, F.S.; Biasco, G.; Mattioli, S. Asbestos: A hidden player behind the cholangiocarcinoma increase? Findings from a case–control analysis. Cancer Causes Control 2013, 24, 911–918. [Google Scholar] [CrossRef]
  8. Di Ciaula, A. Asbestos ingestion and gastrointestinal cancer: A possible underestimated hazard. Expert Rev. Gastroenterol. Hepatol. 2017, 11, 419–425. [Google Scholar] [CrossRef]
  9. Di Ciaula, A.; Gennaro, V. Possible health risks from asbestos in drinking water. Epidemiol. Prev. 2016, 40, 472–475. [Google Scholar]
  10. Farioli, A.; Straif, K.; Brandi, G.; Curti, S.; Kjaerheim, K.; Martinsen, J.I.; Sparen, P.; Tryggvadottir, L.; Weiderpass, E.; Biasco, G.; et al. Occupational exposure to asbestos and risk of cholangiocarcinoma: A population-based case–control study in four Nordic countries. Occup. Environ. Med. 2018, 75, 191–198. [Google Scholar] [CrossRef]
  11. Italian Government. Legislative Decree No. 277 of 15 August 1991, Implementing EU Directives No. 80/1107/EEC, No. 82/605/EEC, No. 83/477/EEC, No. 86/188/EEC, and No. 88/642/EEC, on the Protection of Workers from the Risks Related to Exposure to Chemical, Physical and Biological Agents at Work. Gazzetta Ufficiale Supplemento Ordinario No. 200. 27 August 1991. Available online: https://www.gazzettaufficiale.it/atto/serie_generale/caricaDettaglioAtto/originario?atto.dataPubblicazioneGazzetta=1991-08-27&atto.codiceRedazionale=091G0311&elenco30giorni=false (accessed on 4 July 2019).
  12. Leake, B.E.; Woolley, A.R.; Arps, C.E.S.; Birch, W.D.; Gilbert, M.C.; Grice, J.D.; Hawthorne, F.C.; Kato, A.; Kisch, H.J.; Krivovichev, V.G.; et al. Nomenclature of amphiboles: Report of the Subcommittee on amphiboles of the International Mineralogical Association, Commission on New Minerals and Mineral Names. Can. Mineral. 1997, 35, 219–246. [Google Scholar]
  13. Hawthorne, F.C.; Oberti, R.; Harlow, G.E.; Maresch, W.V.; Martin, R.F.; Schumacher, J.C.; Welch, M.D. Nomenclature of the amphibole supergroup. Am. Mineral. 2012, 97, 2031–2048. [Google Scholar] [CrossRef]
  14. Whittaker, E.J.W.; Zussman, J. The characterization of serpentine minerals by X-ray diffraction. Mineral. Mag. 1956, 233, 107–126. [Google Scholar] [CrossRef]
  15. Putnis, A. The crystal structure of minerals II—Silicates. In Introduction to Mineral Sciences; Cambridge University Press: Cambridge, UK, 1992; pp. 141–184. [Google Scholar]
  16. Aust, A.E.; Cook, P.M.; Dodson, R.F. Morphological and chemical mechanisms of elongated mineral particle toxicities. J. Toxicol. Environ. Health Part B 2011, 14, 40–75. [Google Scholar] [CrossRef] [PubMed]
  17. Fubini, B.; Mollo, L. Role of iron in the reactivity of mineral fibers. Toxicol. Lett. 1995, 82–83, 951–960. [Google Scholar] [CrossRef]
  18. Yao, S.; Della Ventura, G.; Petibois, C. Analytical characterization of cell-asbestos fiber interactions in lung pathogenesis. Anal. Bioanal. Chem. 2010, 397, 2079–2089. [Google Scholar] [CrossRef]
  19. Stanton, M.F.; Layard, M.; Tegeris, A.; Miller, E.; May, M.; Morgan, E.; Smith, A. Relation of particle dimension to carcinogenicity in amphibole asbestoses and other fibrous minerals. J. Natl. Cancer Inst. 1981, 67, 965–975. [Google Scholar]
  20. Prandi, L.; Tomatis, M.; Penazzi, N.; Fubini, B. Iron cycling mechanisms and related modifications at the asbestos surface. Ann. Occup. Hyg. 2002, 46 (Suppl. I), 140–143. [Google Scholar]
  21. Lund, L.G.; Aust, A.E. Iron mobilization from crocidolite asbestos greatly enhances crocidolite-dependent formation of DNA single-strand breaks in ϕ X174 RFI DNA. Carcinogenesis 1992, 13, 637–642. [Google Scholar] [CrossRef]
  22. Carbone, M.; Baris, Y.I.; Bertino, P.; Brass, B.; Comertpay, S.; Dogan, A.U.; Gaudino, G.; Jube, S.; Kanodia, S.; Partridge, C.R.; et al. Erionite exposure in North Dakota and Turkish villages with mesothelioma. Proc. Natl. Acad. Sci. USA 2011, 108, 13618–13623. [Google Scholar] [CrossRef] [Green Version]
  23. Dogan, A.U.; Dogan, M.; Hoskins, J.A. Erionite and its Health Effects. In Encylopedia of Environmental Health; Nriagu, J.O., Ed.; Elsevier: Burlington, MA, USA, 2011; Volume 2, pp. 590–593. [Google Scholar]
  24. Emri, S.A. The Cappadocia mesothelioma epidemic: Its influence in Turkey and abroad. Ann. Transl. Med. 2017, 5, 239. [Google Scholar] [CrossRef]
  25. International Agency for Research on Cancer (IARC). Erionite. In IARC Monographs on the Evaluation of Carcinogenic Risks to Humans; IARC: Lyon, France, 2012; Volume 100, pp. 311–316. [Google Scholar]
  26. Rinaudo, C.; Belluso, E.; Gastaldi, D. Assessment of the use of Raman spectroscopy for the determination of amphibole asbestos. Mineral. Mag. 2004, 68, 455–465. [Google Scholar] [CrossRef]
  27. Pollastri, S.; Perchiazzi, N.; Lezzerini, M.; Plaisier, J.R.; Cavallo, A.; Dalconi, M.C.; Bursi Gandolfi, N.; Gualtieri, A.F. The crystal structure of mineral fibres 1. Chrysotile. Period. Mineral. 2016, 85, 249–259. [Google Scholar]
  28. Dogan, A.U.; Baris, Y.I.; Dogan, M.; Emri, S.; Steele, I.; Elmishad, A.G.; Carbone, M. Genetic predisposition to fiber carcinogenesis causes a mesothelioma epidemic in Turkey. Cancer Res. 2006, 66, 5063–5068. [Google Scholar] [CrossRef] [PubMed]
  29. Waeselmann, N.; Schlüter, J.; Malcherek, T.; Della Ventura, G.; Oberti, R.; Mihailova, B. Nondestructive determination of the amphibole crystal-chemical formulae by Raman spectroscopy: One step closer. J. Raman Spectrosc. 2019. [Google Scholar] [CrossRef]
  30. Rinaudo, C.; Gastaldi, D.; Belluso, E. Characterization of chrysotile, antigorite and lizardite by FT-Raman spectroscopy. Can. Mineral. 2003, 41, 883–890. [Google Scholar] [CrossRef]
  31. Croce, A.; Arrais, A.; Rinaudo, C. Raman micro-spectroscopy identifies carbonaceous particles lying on the surface of crocidolite, amosite, and chrysotile fibers. Minerals 2018, 8, 249. [Google Scholar] [CrossRef]
  32. Bonoldi, L.; Frigerio, F.; Di Paolo, L.; Savoini, A.; Barbieri, D.; Grigo, D. Organic matter maturity profile of a well case study by combination of Raman spectroscopy and principal component analysis−partial least squares regression (PCA−PLS) chemometric methods. Energy Fuels 2018, 32, 8955–8965. [Google Scholar] [CrossRef]
  33. Bourchand, M.; Smith, D.C. Catalogue of 45 reference Raman spectra of minerals concerning research in art history or archaeology, especially on corroded metals and coloured glass. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2003, 59, 2247–2266. [Google Scholar]
  34. Hanesch, M. Raman spectroscopy of iron oxides and (oxy)hydroxides at low laser power and possible applications in environmental magnetic studies. Geophys. J. Int. 2009, 177, 941–948. [Google Scholar] [CrossRef]
  35. Croce, A.; Allegrina, M.; Rinaudo, C.; Gaudino, G.; Yang, H.; Carbone, M. Numerous iron-rich particles lie on the surface of erionite fibers from Rome (Oregon, USA) and Karlik (Cappadocia, Turkey). Microsc. Microanal. 2015, 21, 1341–1347. [Google Scholar] [CrossRef]
  36. Sasaki, K.; Tanaike, O.; Konno, H. Distinction of jarosite-group compounds by Raman spectroscopy. Can. Mineral. 1998, 36, 1225–1235. [Google Scholar]
  37. Rinaudo, C.; Allegrina, M.; Fornero, E.; Musa, M.; Croce, A.; Bellis, D. Micro-Raman spectroscopy and VP-SEM/EDS applied to the identification of mineral particles and fibres in histological sections. J. Raman Spectrosc. 2010, 41, 27–32. [Google Scholar] [CrossRef]
  38. Rinaudo, C.; Croce, A.; Musa, M.; Fornero, E.; Allegrina, M.; Trivero, P.; Bellis, D.; Sferch, D.; Toffalorio, F.; Veronesi, G.; et al. Study of inorganic particles, fibers, and asbestos bodies by variable pressure scanning electron microscopy with annexed energy dispersive spectroscopy and micro-Raman spectroscopy in thin sections of lung and pleural plaque. Appl. Spectrosc. 2010, 64, 571–577. [Google Scholar] [CrossRef] [PubMed]
  39. Croce, A.; Capella, S.; Belluso, E.; Grosso, F.; Mariani, N.; Libener, R.; Rinaudo, C. Asbestos fibre in gallbladder: A case study. Micron 2018, 105, 98–104. [Google Scholar] [CrossRef] [PubMed]
  40. Ehrlich, A.A.; Gordon, R.E.; Dikman, S.H. Carcinoma of the colon in asbestos-exposed workers: Analysis of asbestos content in colon tissue. Am. J. Ind. Med. 1991, 19, 629–636. [Google Scholar] [CrossRef] [PubMed]
  41. Grosso, F.; Croce, A.; Libener, R.; Mariani, N.; Pastormerlo, M.; Maconi, A.; Rinaudo, C. Asbestos fiber identification in liver from cholangiocarcinoma patients living in an asbestos polluted area: A preliminary study. Tumori J. 2019. [Google Scholar] [CrossRef] [PubMed]
  42. Grosso, F.; Croce, A.; Trincheri, N.F.; Mariani, N.; Libener, R.; Degiovanni, D.; Rinaudo, C. Asbestos fibres detected by scanning electron microscopy in the gallbladder of patients with malignant pleural mesothelioma (MPM). J. Microsc. 2017, 266, 48–54. [Google Scholar] [CrossRef] [PubMed]
  43. Grosso, F.; Randi, L.; Croce, A.; Mirabelli, D.; Libener, R.; Magnani, C.; Bellis, D.; Allegrina, M.; Bertolotti, M.; Degiovanni, D.; et al. Asbestos fibers in the gallbladder of patients affected by benign biliary tract diseases. Eur. J. Gastroenterol. Hepatol. 2015, 27, 660–664. [Google Scholar] [CrossRef]
  44. Kakoulli, I.; Prikhodko, S.V.; King, A.; Fischer, C. Earliest evidence for asbestos composites linked to Byzantine wall paintings production. J. Archaeol. Sci. 2014, 44, 148–153. [Google Scholar] [CrossRef]
  45. Donaldson, K.; Poland, C.A.; Murphy, F.A.; MacFarlane, M.; Chernova, T.; Schinwald, A. Pulmonary toxicity of carbon nanotubes and asbestos—Similarities and differences. Adv. Drug Deliv. Rev. 2013, 65, 2078–2086. [Google Scholar] [CrossRef]
  46. International Agency for Research on Cancer (IARC). Carbon black, titanium dioxide, and talc. In IARC Monographs on the Evaluation of Carcinogenic Risks to Humans; IARC: Lyon, France, 2010; Volume 93, pp. 43–191. [Google Scholar]
Applsci 09 03092 g001 550
Figure 1. (a) Crystal structure of amphibole minerals: in green the [SiO4] tetrahedra, in blue the (OH)- groups, in yellow and in violet the Na, Ca, Mg, Fe2+, or Fe3+ cations; (b) Crystal structure of serpentine minerals: in green the [SiO4] tetrahedra (T layers), in yellow the octahedral Mg cations (O layer), and in blue and white the OH- groups; (c) In chrysotile T and O layers roll up around a hole forming long fibers.
Figure 1. (a) Crystal structure of amphibole minerals: in green the [SiO4] tetrahedra, in blue the (OH)- groups, in yellow and in violet the Na, Ca, Mg, Fe2+, or Fe3+ cations; (b) Crystal structure of serpentine minerals: in green the [SiO4] tetrahedra (T layers), in yellow the octahedral Mg cations (O layer), and in blue and white the OH- groups; (c) In chrysotile T and O layers roll up around a hole forming long fibers.
Applsci 09 03092 g001
Applsci 09 03092 g002 550
Figure 2. Optical Microscopy images of the six regulated asbestos minerals: (a) amosite; (b) crocidolite; (c) tremolite; (d) anthophyllite; (e) actinolite; (f) chrysotile.
Figure 2. Optical Microscopy images of the six regulated asbestos minerals: (a) amosite; (b) crocidolite; (c) tremolite; (d) anthophyllite; (e) actinolite; (f) chrysotile.
Applsci 09 03092 g002
Applsci 09 03092 g003 550
Figure 3. Spectra obtained on the six regulated asbestos minerals in the spectral range 1200–100 cm−1: (a) amosite; (b) crocidolite; (c) tremolite; (d) anthophyllite; (e) actinolite; (f) chrysotile. Considering the νs and νas modes of the Si-Ob-Si bonds, a sure identification of the mineral phase can be obtained.
Figure 3. Spectra obtained on the six regulated asbestos minerals in the spectral range 1200–100 cm−1: (a) amosite; (b) crocidolite; (c) tremolite; (d) anthophyllite; (e) actinolite; (f) chrysotile. Considering the νs and νas modes of the Si-Ob-Si bonds, a sure identification of the mineral phase can be obtained.
Applsci 09 03092 g003
Applsci 09 03092 g004 550
Figure 4. Raman spectra of the 4000–100 cm−1 range obtained on the six regulated asbestos minerals: (a) amosite; (b) crocidolite; (c) tremolite; (d) anthophyllite; (e) actinolite; (f) chrysotile.
Figure 4. Raman spectra of the 4000–100 cm−1 range obtained on the six regulated asbestos minerals: (a) amosite; (b) crocidolite; (c) tremolite; (d) anthophyllite; (e) actinolite; (f) chrysotile.
Applsci 09 03092 g004
Applsci 09 03092 g005 550
Figure 5. Raman spectra in the 1200–100 cm−1 range obtained on erionite from (a) Oregon, (b) Karlik, and (c) North Dakota.
Figure 5. Raman spectra in the 1200–100 cm−1 range obtained on erionite from (a) Oregon, (b) Karlik, and (c) North Dakota.
Applsci 09 03092 g005
Applsci 09 03092 g006 550
Figure 6. Backscattered scanning electron microscopy (SEM) images of erionite fibers from (a) Oregon, (b) Karlik, and (c) North Dakota. The arrows indicate particles lying on the crystal surfaces.
Figure 6. Backscattered scanning electron microscopy (SEM) images of erionite fibers from (a) Oregon, (b) Karlik, and (c) North Dakota. The arrows indicate particles lying on the crystal surfaces.
Applsci 09 03092 g006
Applsci 09 03092 g007 550
Figure 7. Raman spectra of the 1200–100 cm−1 range obtained on different iron rich particles on erionite: (a) goethite, (b) hematite, and (c) jarosite. The band indicated by * in (c) may be ascribed to goethite.
Figure 7. Raman spectra of the 1200–100 cm−1 range obtained on different iron rich particles on erionite: (a) goethite, (b) hematite, and (c) jarosite. The band indicated by * in (c) may be ascribed to goethite.
Applsci 09 03092 g007
Applsci 09 03092 g008 550
Figure 8. Raman spectra obtained in the 4000–100 cm−1 range on a dark grain on the surface of North Dakota erionite fibers.
Figure 8. Raman spectra obtained in the 4000–100 cm−1 range on a dark grain on the surface of North Dakota erionite fibers.
Applsci 09 03092 g008
Table
Table 1. Raman bands observed on the mineral phases defined “asbestos” by the Law.
Table 1. Raman bands observed on the mineral phases defined “asbestos” by the Law.
Mineral PhaseAmosite
This Work		Amosite
Rinaudo et al. 2004 [26]		Crocidolite
This Work		Crocidolite
Rinaudo et al. 2004 [26]		Tremolite
This Work		Tremolite
Rinaudo et al. 2004 [26]
Mineral Raman Bands (cm−1)156155109 162162
184182134 180180
215216147 225
252166162234234
289197195252254
307 211 290
348348229 306
368368252246 335
400400274272 348
423423300300354355
507335331372373
528528365360396396
660659377374418418
904433428438438
970968472470516516
10211020510506531531
1093542537676676
580577738740
666664750751
733931932
771952950
89188910311031
97196710621062
1030
10891082
CM Raman Bands (cm−1)1332n.a. *1333n.a.-n.a.
1470-
15821591-
1621-
26632660-
2914-
OH- Raman Bands (cm−1)3618n.a.-n.a.-n.a.
3637--
* n.a.: not available.
Table
Table 2. Raman bands observed on the mineral phases defined “asbestos” by the Law.
Table 2. Raman bands observed on the mineral phases defined “asbestos” by the Law.
Mineral PhaseAnthophyllite
This Work		Anthophyllite
Rinaudo et al. 2004 [26]		Actinolite
This Work		Chrysotile
This Work		Chrysotile
Rinaudo et al. 2003 [30]
Mineral Raman Bands (cm−1)188188118132
222149203
254254175234231
265265221347345
304304386390389
342342532432
364670467
3883871064622620
414410 694692
432433 1105
503
539
675674
699
928
10441044
CM Raman Bands (cm−1)-n.a. *-1118n.a.
--1273
--1340
--1613
--1690
--
--
OH- Raman Bands (cm−1)3666n.a.36433688n.a.
367136603699
* n.a.: not available.

Share and Cite

MDPI and ACS Style

Rinaudo, C.; Croce, A. Micro-Raman Spectroscopy, a Powerful Technique Allowing Sure Identification and Complete Characterization of Asbestiform Minerals. Appl. Sci. 2019, 9, 3092. https://doi.org/10.3390/app9153092

AMA Style

Rinaudo C, Croce A. Micro-Raman Spectroscopy, a Powerful Technique Allowing Sure Identification and Complete Characterization of Asbestiform Minerals. Applied Sciences. 2019; 9(15):3092. https://doi.org/10.3390/app9153092

Chicago/Turabian Style

Rinaudo, Caterina, and Alessandro Croce. 2019. "Micro-Raman Spectroscopy, a Powerful Technique Allowing Sure Identification and Complete Characterization of Asbestiform Minerals" Applied Sciences 9, no. 15: 3092. https://doi.org/10.3390/app9153092

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop