1. UK Dust Network – 2nd Workshop Claire Horwell 14 th March 2008 Mineralogy & Volcanology

2. Objectives of field: To use mineralogy and geochemistry to make rapid assessments of the potential health hazard of natural mineral particles. To understand WHY a mineral or dust may trigger a pathogenic respiratory response.

3. Sources: Volcanoes –Volcanic ash –Aerosols (liquid & solid) Dust storms –Sourced from: Glacial forelands Debris fans Deserts Exposed lake beds Biogenic dust –bacteria, pollen, diatoms (silica) Quarrying and mining of rock 15 µm Phytolith (bacterium) Beijing, China, 2003

4. Questions to be answered: Is the dust small enough to enter the lungs? What is the composition of the dust? Is shape a relevant factor (e.g. fibrous)? Is the surface of the dust reactive? Are individual particles ‘pure’? Is the crystalline structure of the mineral relevant?

5. Grain size Is the dust small enough to enter the lungs? Grain size analysis techniques: –Laser diffraction –SEM with image analysis –Sieving > 63  m only New predictive technique Malvern Mastersizer 2000 Horwell, 2007, JEM

6. Grain size - volcanoes Horwell, 2007, JEM

7. Composition of heterogeneous dusts SEM image of volcanic ash Volcanic ash and eroded dusts are often composed of tens of minerals. Some are considered toxic e.g. crystalline silica. Analytical techniques: –SEM-EDX gives individual particle compositions but not polymorphs. –XRD-PSD gives quantity of minerals in a bulk sample. High res. so no overlap between plagioclase and cristobalite. –Raman-SEM allows polymorphic determination of individual crystals/particles.

8. Reactivity of surfaces Electron Spin Resonance detects free and surface radicals. Radicals formed by breaking bonds during fragmentation Radicals are highly reactive, damaging DNA, proteins, lipids etc. Likely to be one of several triggering mechanisms for chronic lung disease.

9. Production of silica surface radicals Horwell et al. Environmental Research, 2003 Soufrière Hills dome-collapse ash shows no generation of silica radicals (peaks expected at point A). Distinctive curve and peak (at point B) shows interaction of iron. Crystalline silica alone (Talvitie residue) has less iron but no significant generation of silica radicals.

10. Production of hydroxyl radicals: Fenton Reaction: Fe 2+ + H 2 O 2 Fe 3+ + OH - + HO Horwell et al. Environmental Research, 2003

11. Production of hydroxyl radicals Basaltic Andesitic/ Dacitic Tephritic/ Phonolitic Minusil 5 Quartz standard Horwell, Fenoglio & Fubini, in review

12. Purity of crystalline silica One could say that if a dust is respirable and contains x-silica then it is a potential health hazard. BUT toxicological and epidemiological evidence appears to suggest that volcanic silica isn’t very toxic. We can use mineralogy to determine WHY x-silica is/ is not toxic. The problem: Difficult to analyse differences in composition at the nano- scale. Timeliness: New technology for high resolution micro-analysis e.g. TEM-EDX, FIB thinning etc.

13. How pure is volcanic x-silica? SEM-EDX spectrum of cristobalite 1 mm Crystalline silica in volcanic ash may be modified by more-inert components. E.g. it is known that Al ameliorates silica toxicity. Evidence: SEM-EDX work indicates that silica particles are impure. The silica particles may be modified by: –occlusion by glass –intergrowth with glass or plagioclase –substitution of Si from atomic structure by Al & Na.

14. Results – dome rock Cristobalite in dome rock vugh 1 mm –In dome rock we see euhedral and platey crystals which have grown in cracks and vesicles by vapour-phase deposition. –Raman-SEM confirms these are cristobalite. Horwell, Williamson & Le Blond, in prep. Raman spectra from cristobalite in dome rock

15. Cristobalite composition – dome rock 1 mm Electron microprobe shows that the cristobalite is compositionally distinct from volcanic quartz, containing impurities of Al and Na. Horwell, Williamson & Le Blond (in prep.) quartz euhedral cris. platey cris.

16. Case Study 1 – Volcanic ash Early results 1 mm SEM-EDX Elemental maps In thin section, cracked appearance. Devitrification of glass also produces crystalline silica. Blue = Si Pink = K Green = Al

17. Case Study 1 – Volcanic ash Early results 1 mm SEM-EDX Elemental maps In thin section, cracked appearance. Devitrification of glass also produces crystalline silica. Would not fragment as microlites. Blue = Si Pink = K Green = Al ?

18. Where do we go from here? 1 mm Could alpha and beta forms of cristobalite and quartz have different toxicities? –Leverhulme proposal: Horwell, Williamson, Donaldson, Cressey (Fubini, Carpenter, Parman) Integration of work with toxicology. –Leverhulme proposal –Michnowicz PhD (April 2008) Application of techniques to other natural dusts e.g. coal and desert. –Horwell NERC Fellowship.

19. A useful tool for predicting the respirable fraction: Data collected by Malvern Mastersizer 2000 laser diffractometer. n = 65 samples from volcanoes worldwide.