Analytical and Bioanalytical Chemistry

, Volume 406, Issue 19, pp 4715–4724 | Cite as

Quantifying silica in filter-deposited mine dusts using infrared spectra and partial least squares regression

  • Andrew Todd WeakleyEmail author
  • Arthur L. Miller
  • Peter R. Griffiths
  • Sean J. Bayman
Research Paper


The feasibility of measuring airborne crystalline silica (α-quartz) in noncoal mine dusts using a direct-on-filter method of analysis is demonstrated. Respirable α-quartz was quantified by applying a partial least squares (PLS) regression to the infrared transmission spectra of mine-dust samples deposited on porous polymeric filters. This direct-on-filter method deviates from the current regulatory determination of respirable α-quartz by refraining from ashing the sampling filter and redepositing the analyte prior to quantification using either infrared spectrometry for coal mines or x-ray diffraction (XRD) from noncoal mines. Since XRD is not field portable, this study evaluated the efficacy of Fourier transform infrared spectrometry for silica determination in noncoal mine dusts. PLS regressions were performed using select regions of the spectra from nonashed samples with important wavenumbers selected using a novel modification to the Monte Carlo unimportant variable elimination procedure. Wavenumber selection helped to improve PLS prediction, reduce the number of required PLS factors, and identify additional silica bands distinct from those currently used in regulatory enforcement. PLS regression appeared robust against the influence of residual filter and extraneous mineral absorptions while outperforming ordinary least squares calibration. These results support the quantification of respirable silica in noncoal mines using field-portable infrared spectrometers.


Partial least square's predicted (Yfit) vs. observed (Yobs) reparable silica using infrared absorbance from the α-quartz doublet region of filter-deposited mine dust sample spectra. predictive features selected via backward Monte Carlo unimportant variable elimination (lower right hand corner) are also shown


Partial least squares Monte Carlo unimportant variable elimination Silica measurement FT-IR Mine dust 

Supplementary material

216_2014_7856_MOESM1_ESM.pdf (44 kb)
ESM 1 (PDF 163 kb)


  1. 1.
    Mine Safety and Health Administratsion (2013) Infrared Determination of Quartz in Respirable Coal Mine Dust - Method No. MSHA P7. Pittsburgh Safety and Health Technology Center, PittsburghGoogle Scholar
  2. 2.
    World Health Organization (1997) Silica Volume 68. In: Monographs on the Evaluation of Carcinogenic Risks to Humans. Lyon, FranceGoogle Scholar
  3. 3.
    Steenland K, Mannetje A, Boffetta P, Stayner L, Attfield M, Chen J et al (2001) Cancer Causes Control 12:773–784CrossRefGoogle Scholar
  4. 4.
    Weeks JL, Rose C (2006) Am J Ind Med 49:523–534CrossRefGoogle Scholar
  5. 5.
    Hochgatterer K, Moshammer H, Haluza D (2013) Lung 191:257–263CrossRefGoogle Scholar
  6. 6.
    Calvert GM, Rice FL, Boiano JM, Sheehy JW, Sanderson WT (2003) Occup Environ Med 60:122–129CrossRefGoogle Scholar
  7. 7.
    Mannetje A, Steenland K, Attfield M, Boffetta P, Checkoway H, DeKlerk N et al (2002) Occup Environ Med 59:723–728CrossRefGoogle Scholar
  8. 8.
    Mazurek JM, Attfield MD (2008) Am J Ind Med 51:568–578CrossRefGoogle Scholar
  9. 9.
    Leung CC, Yu ITS, Chen W (2011) Lancet 379:2008–2018CrossRefGoogle Scholar
  10. 10.
    National Institute of Occupational Safety and Health (2003) Silica, Crystalline by IR (KBr pellet)- Method 7602 In: NIOSH Manual of Analytical Methods (NMAM), 4th edn. Center for Disease Control and Prevention, AtlantaGoogle Scholar
  11. 11.
    National Institute of Occupational Safety and Health (2003) Silica, Crystalline, by XRD (filter redeposition)- Method 7500 In: NIOSH Manual of Analytical Methods (NMAM), 4th edn. Center for Disease Control and Prevention, AtlantaGoogle Scholar
  12. 12.
    Madsen FA, Rose MC, Cee R (1995) Appl Occup Environ Hyg 10:991–1002CrossRefGoogle Scholar
  13. 13.
    Miller AL, Drake PL, Murphy NC, Noll JD, Volkwein JC (2012) J Environ Monit 14:48–55CrossRefGoogle Scholar
  14. 14.
    Miller AL, Drake PL, Murphy NC, Cauda EG, LeBouf RF, Markevicius G (2013) Aerosol Sci Technol 47:724–733CrossRefGoogle Scholar
  15. 15.
    Kauffer E, Masson A, Moulut JC, Lecaque T, Protois JC (2005) Ann Occup Hyg 49:661–671CrossRefGoogle Scholar
  16. 16.
    Eller PM, Feng HA, Song RS, Key-Schwartz RJ, Esche CA, Groff JH (1999) Am Ind Hyg Assoc J 60:533–539CrossRefGoogle Scholar
  17. 17.
    Schwerha DJ, Orr CS, Chen BT, Soderholm SC (2002) Anal Chim Acta 457:257–264CrossRefGoogle Scholar
  18. 18.
    Health and Safety Executive (2005) Crystalline silica in respirable airborne dusts Direct-on-filter analyses by infrared spectroscopy and X-ray diffraction In: Methods for the Determination of Hazerdous Substances. HSE Books, SudburyGoogle Scholar
  19. 19.
    Chen CH, Tsaia PJ, Lai CY, Peng YL, Soo JC, Chen CY et al (2010) J Hazard Mater 176:389–394CrossRefGoogle Scholar
  20. 20.
    Nayak P, Singh BK (2007) Bull Mater Sci 30:235–238CrossRefGoogle Scholar
  21. 21.
    Painter PC, Coleman MM, Jenkins RG, Whang PW, Walker PL (1978) Fuel 57:337–344CrossRefGoogle Scholar
  22. 22.
    Scott JF, Porto SPS (1967) Phys Rev 161:903–910CrossRefGoogle Scholar
  23. 23.
    Lee T, Chisholm WP, Kashon M, Key-Schwartz RJ, Harper M (2013) J Occup Environ Hyg 10:425–434CrossRefGoogle Scholar
  24. 24.
    Abdi H (2010) Wiley Interdiscip Rev Comput Stat 2:97–106CrossRefGoogle Scholar
  25. 25.
    Næs T, Isaksson T, Fearn T, Davies T (2002) A User-friendly Guide to Multivariate Calibration and Classification. NIR Publications, ChichesterGoogle Scholar
  26. 26.
    Wold S, Sjöström M, Eriksson L (2001) Chemom Intell Lab Syst 58:109–130CrossRefGoogle Scholar
  27. 27.
    Kalivas JH, Gemperline PJ (2006) In: Gemperline PJ (ed) Practical Guide to Chemometrics, 2nd edn. CRC/Taylor & Francis, Boca RatonGoogle Scholar
  28. 28.
    Bye E (1992) Chemom Intell Lab Syst 14:413–417CrossRefGoogle Scholar
  29. 29.
    Ritz M, Vaculikova L, Plevová E, Matýsek D, Mališ J (2012) Acta Geodyn Geomater 9:511–520Google Scholar
  30. 30.
    Cai W, Li Y, Shao X (2008) Chemom Intell Lab Syst 90:188–194CrossRefGoogle Scholar
  31. 31.
    Isaksson T, Næs T (1988) Appl Spectrosc 42:1273–1284CrossRefGoogle Scholar
  32. 32.
    Galvão RKH, Araujo MCU, José GE, Pontes MJC, Silva EC, Saldanha TCB (2005) Talanta 67:736–740CrossRefGoogle Scholar
  33. 33.
    Abdi H, Williams LJ (2010) Wiley Interdiscip Rev Comput Stat 2:433–459CrossRefGoogle Scholar
  34. 34.
    Xu HS, Liang YZ (2001) Chemom Intell Lab Syst 56:1–11CrossRefGoogle Scholar
  35. 35.
    Höskuldsson A (2001) Chemom Intell Lab Syst 55:23–38CrossRefGoogle Scholar
  36. 36.
    Balabin RM, Smirnov SV (2011) Anal Chim Acta 692:63–72CrossRefGoogle Scholar
  37. 37.
    Shao J (1993) J Am Stat Assoc 88:486–494CrossRefGoogle Scholar
  38. 38.
    Centner V, Massart DL, de Noord OE, de Jong S, Vandeginste BM, Sterna C (1996) Anal Chem 68:3851–3858CrossRefGoogle Scholar
  39. 39.
    Ainsworth S (2005) J ASTM Int 2:1–14CrossRefGoogle Scholar
  40. 40.
    Saikia B, Parthasarathy G, Sarmah NC (2008) Bull Mater Sci 31:775–779CrossRefGoogle Scholar
  41. 41.
    Innocenzi P (2003) J Non-Cryst Solids 316:309–319CrossRefGoogle Scholar
  42. 42.
    Osswald J, Fehr KT (2006) J Mater Sci 41:1335–1339CrossRefGoogle Scholar
  43. 43.
    Hirata T (1999) Solid State Commun 111:421–426CrossRefGoogle Scholar
  44. 44.
    Piro OE, Castellano EE, González SR (1988) Phys Rev B Condens Matter Mater Phys 38:8437–8443CrossRefGoogle Scholar
  45. 45.
    Kirk CT (1988) Phys Rev B Condens Matter Mater Phys 38:1255–1273CrossRefGoogle Scholar
  46. 46.
    Spitzer WG, Kleinman DA (1961) Phys Rev 121:1324–1335CrossRefGoogle Scholar
  47. 47.
    Ocaña M, Fornes V, Garcia-Ramos JV, Serna CJ (1987) Phys Chem Miner 14:527–532CrossRefGoogle Scholar
  48. 48.
    Almeida RM, Pantano CG (1990) J Appl Phys 68:4225–4232CrossRefGoogle Scholar
  49. 49.
    Berreman DW (1963) Phys Rev 130:2193–2198CrossRefGoogle Scholar
  50. 50.
    Gallardo J, Durán A, Di Martino D, Almeida RM (2002) J Non-Cryst Solids 298:219–225CrossRefGoogle Scholar
  51. 51.
    Prost R, Dameme A, Huard E, Driard J, Leydecker JP (1989) Clays Clay Miner 37:464–468CrossRefGoogle Scholar
  52. 52.
    Efron B, Tibshirani RJ (1993) An Introduction to the Bootstrap. Chapman & Hall, Boca RatonCrossRefGoogle Scholar
  53. 53.
    Burnham KP, Anderson DR (2004) Sociol Methods Res 33:261–304CrossRefGoogle Scholar
  54. 54.
    Mehmood T, Liland KH, Snipen L, Sæbø S (2012) Chemom Intell Lab Syst 118:62–69CrossRefGoogle Scholar
  55. 55.
    Martens H, Høy M, Westad F, Folkenberg D, Martens M (2001) Chemom Intell Lab Syst 58:151–170CrossRefGoogle Scholar
  56. 56.
    Krimm S (1968) Pure Appl Chem 16:369–388CrossRefGoogle Scholar
  57. 57.
    Stromberg RR, Straus S, Achhammer BG (1958) J Res Natl Bur Stand 60:147–152CrossRefGoogle Scholar
  58. 58.
    Tabb DL, Koenig JL (1975) Macromolecules 8:929–934CrossRefGoogle Scholar
  59. 59.
    Ramesh S, Leen KH, Kumutha K, Arof AK (2007) Spectrochim Acta A 66:1237–1242CrossRefGoogle Scholar
  60. 60.
    Sato RK, McMillan PF (1987) J Phys Chem 91:3494–3498CrossRefGoogle Scholar
  61. 61.
    Francis S, Stephens WE, Richardson N (2009) Environ Health 8(S4):1–4Google Scholar
  62. 62.
    Weakley AT, Griffiths PR, Aston DE (2012) Appl Spectrosc 66:519–529CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Andrew Todd Weakley
    • 1
    Email author
  • Arthur L. Miller
    • 2
  • Peter R. Griffiths
    • 3
  • Sean J. Bayman
    • 2
  1. 1.Department of Chemical and Materials EngineeringUniversity of IdahoMoscowUSA
  2. 2.National Institute for Occupational Safety and HealthSpokaneUSA
  3. 3.Griffiths Consulting LLCOgdenUSA

Personalised recommendations